Stuff 'n Stuff
Sci-Tech News & Olds
( April 2014 )
Molecular Music ( See also : J. STERNHEIMER : Protein
Music )
A. RABINOVICH : Plasmatron
Carburetor
Z. ZHONG : Graphene Infrared Lens
Glassesoff Vision Training App
D. DEUTSCH : Speech-Music
V. SCHAUBERGER : The Energy Evolution
( Translated & Edited by Callum Coates )
A. PERBELLINI / C. VENTURA :
Epigenetic Reprograming
A ALPEREN :
Power Extraction From pressure
D. CRAIK : Conotoxin Analgesic
Back Issues : January ... February ... March ...
Molecular Music
( See also : Joel
STERNHEIMER : Protein Music )
www.oursounduniverse.com
Susan
Alexjander
WATER -- Molecular water frequencies also correspond to
'some kind of an F# chord. Again, Dr. Deamer provided me with the
wave numbers of water which are:
1600 converted to hertz = 698 F/F#
2100 converted to hertz = 918 A#
3500 converted to hertz = 134.58 C#
SCHUMANN RESONANCE
'Octavise' the Schumann frequencies into our hearing range,
six of the seven tones are F#s, A#s and C#s. The seventh is a D#
F# - creates an unusual oscillating effect between the two
cavities of the brain, especially when generated by the tuned
resonant cavity of a quartz crystal bowl. It has a frequency of
5.8 kHz (5800 Hz)
F# References:
a. 360 is often referred to as Spherical Consciousness i.e.
expanded awareness.
b. 11.11 = F/F# an opening gateway for mind expansion.'
c. speed of light = 363.83 F# (186,282.3959Hz)
d. Gematria of Consciousness = 175 (F/F#)
e. Gematria of Zero Point Field = 174 (F/F#)
d. Gematrias of hate + love = 88
good + evil = 89
yin + yan = 88....all octaves of F/F#.
http://algoart.com/music.htm
Genetic Music From DNA and Protein
The music on this page was composed algorithmically with
Algorithmic Arts software from the raw genetic data that is
available as free downloads on the internet .
Currently there are 3 CD albums available, with more to follow. On
this page, you can either audition or download the full tracks as
free .mp3 files.
http://www.aber.ac.uk/~phiwww/pm/
ProteinMusic
ProteinMusic is a Java program converting DNA sequences into
music. The original idea for this project came from R. D. King
here at the University of Wales, Aberystwyth and C. G Angus from
the Shamen (King, R.D. & Angus, C.G. (1996)). They developed a
program written in C on an Apple Mac together with a MIDI
connection to a synthesizer in 1996. This program here is a
complete re-write of the original program in Java.
http://ndbserver.rutgers.edu/atlas/music/musical_atlas.html
ATLAS: The Musical Atlas
The Nucleic Acid Database has been developing different
musical algorithms to provide a unique look into the structure of
DNA.
http://www.botany.hawaii.edu/faculty/bridg...nflections/mp3/
Music from DNA by John Dunn and K. W.
Bridges
http://www.helenwhitehead.com/Dissert/genetic17.htm
You wouldn't think there was music in me. But beautiful and
strange music has been developed from the sequence of nucleotides
in my DNA.
Using special software John Dunn selected and/or developed
synthesizer sounds to be used to create music by translating the
individual DNA codons, the strings of guanine, adenine, cytosine
and thymine, into the proteins they form, taking account of
"start" and "stop" signals.
The amino acids of each protein sequence plus chemical properties
of the amino acids and the bases themselves were interpreted as
pitches, pan positions, transpose values, tempi, tone, colors and
so on. The realization of the piece was developed manually, until
the piece was right.
http://www.dnamusic.com/articles/music_and_metamusic.htm
Hidden right there in plain sight is one of the most profound
truths of our existence. From ancient Hindu mystics to modern
quantum physicists the collective wisdom of humankind has
repeatedly discovered that the universe is an immense energy field
vibrating on a score of frequencies. No matter how we separate the
individual notes, they all play together to create a single
harmonious song.[2]
The Bible, so central to the beliefs of many Western cultures,
tells us that "In the beginning was the Word." Yet many Eastern
and aboriginal cultures maintain that the world was not spoken,
but, rather, SUNG into existence. For a growing number of
scientists, their research into the impacts of music on the brain
and consciousness now favors the influence of song over speech. In
fact, quantum string theory describes our bodies, all physical
matter, and even the Earth itself, as cosmic instruments staying
in tune with a larger universal orchestra.
http://www.artic.edu/~pgena/genexs.html
http://www.artic.edu/~pgena/DNAmus.html
Peter Dena: DNA music for Genesis
The physio-musical conversion of DNA sequences occurs via a
series of formulae that were worked out in a manner based on
physical properties of DNA and musical parameters. Once the
sequences are converted by my custom algorithms they are played by
the DNA Mixer, which reads linearly much like the
ribosomes—organelles that read codons for amino acid
conversion—traverse the mRNA, mixing multiple sequences
simultaneously just like in our cells.
From the onset I believed that a musical reading of DNA ought to
be rendered literally. As the sequences represent life of many
sorts, I am reluctant to tamper with the “score.†The DNA
mixer can realize sequences as digital sound and/or print them out
in musical notation. Ideally, performances of the gene sequences
should be executed live from the computer as in an installation,
where the ribosome simulations can be positioned spontaneously
before playing. Red Blood Cells is a mix of five genes that are
present in human blood: alpha and beta globin, heme synthetase,
transaldolase, and glucose 6 phosphate. These are realized
simultaneously, just as they are produced in the body. The piece
was premiered in November, 1995 at the XI Colloquium on Musical
Informatics at the University of Bologna. In May, 1996 it was
aired over Icelandic National Radio during a series on American
Electronic Music, and in August of the same year it was presented
in Hong Kong at the 1996 International Computer Music Conference.
http://www.nslij-genetics.org/dnamusic/
DNA Music
DNA and music?? What is the connection? And why is it included
in a page on correlation structure of DNA sequences? Because: the
correlation stucture "1/f spectra" have been found in both musical
signals and DNA sequences.
Prof. Susumu Ohno (of Beckman Research Institute of the City of
Hope, who died on January 13, 2000, at the age of 71) proposed
years ago that the repetition process governs both the musical
composition and the DNA sequence construction . see this paper by
Ohno in Immunogenetics (1986) titled: "The all pervasive principle
of repetitious recurrence governs not only coding sequence
construction but also human endeavor in musical composition".
When DNA sequences are converted to music, it sounds musical!
Models with duplication and mutation operations, such as the
"expansion-modification model" are able to generate sequences with
1/f spectra.
http://whozoo.org/mac/Music/
http://whozoo.org/mac/Music/samples.htm
Human protein sequences from the Gene
Project Reports at Texas Wesleyan University
Note: all of the sequences from the links immediately above
are simple linear readouts of the amino acid sequences of the
proteins indicated. However some sense of the protein's higher
order structure emerges from the alternation between the
higher-pitched polar amino acids and the lower-pitched nonpolar
amino acids.
http://www.molecularmusic.com/
Welcome to the World of Molecular Music -- The site for music
derived from the molecules of life.
Created by award-winning biochemist and musician Dr. Linda Long,
Molecular Music provides a pioneering link between the seemingly
disparate worlds of music and biological science. It involves the
generation of music from three-dimensional biological molecules
called proteins. Dr. Linda Long has developed it as tool for
teaching molecular modelling of complex protein structures, and to
generate music from herbs, medicinal plants and the human body for
relaxation and therapeutic purposes.
Molecular Music is computer generated music that creates a gateway
into understanding life, allowing us to perceive nature in her
many forms through sound. Music is not limited by words or logic
and so may communicate with us on deeper levels, freeing us to
directly experience the essence of all living matter and giving us
an insight into the voice of nature.
Music of the Body
Music of the Body is a CD of music derived from protein
hormones found in the human body. Its soothing and uplifting
properties make it ideal for use by health professionals and
alternative medicine practitioners to accompany their therapeutic
work (e.g. massage therapy with essential oils, reiki and music
therapy), and by individuals to enhance meditation, mind-body
visualization techniques, and bodywork e.g. yoga. It may also be
used to promote relaxation in health clubs, health clinics, spas
and beauty salons, and induce calm in clinical settings such as
hospitals and dentists.
Computer generated note sequences, derived from protein hormones
found in the human body, have been arranged by Dr. Linda Long to
create complex 'multi-dimensional' musical pieces which contain
sequences describing both the secondary and tertiary features of
the individual hormones.
Thyrotropin .. Thyroid hormone .. Parathyroid hormone ..
Guanylin .. Somatostatin .. Growth hormone .. Progesterone
receptor protein ..Chorionic gonadotropin .. Follitropin ..
Crystals
Crystals arise in accordance with laws of symmetry, so they
have very simple orders which can be interpreted harmonically.
These properties are already expressed in the atomic structure of
the crystal. There are 32 crystal classes, covering all existing
specimens. Crystal symmetry is classed in terms of rotation and
mirroring. For rotational symmetry, the only possible values are
360’, 180’, 120’, 90' and 60', which corresponds to the fractional
series 1/1, 1/2, 1/3, 1/4, 1/6 (where 1/1 = 360'), and can in turn
be interpreted harmonically (c, c’, g’, c”, g”).
At the beginning of the 20th century, the German mineralogist
Victor Goldschmidt discovered a mathematical formula to classify
how crystals form surfaces. His table corresponds exactly to the
Pythagorean Lambdoma right up to the number 4 (or 1/4) – this is
particularly interesting because he was not familiar with the
Lambdoma.
Listen to mp3 clips of music derived from herbs, medicinal plants
and the human body. Visit our online education section with a
preview version of Molecular Music's first interactive exhibit
currently showing at Bristol.
http://algoart.com/music.htm
Dunn & Clark: Life Music (1998)
A collaboration with biologist Dr. Mary Anne Clark, produced
from the primary and secondary structure of protein sequences,
using BioSon software (built on KAM), and EMu Proteus (Clark) and
Morphius (Dunn) synths. In each piece, pitch is determined by
amino acid identity and instrumentation is chosen according to
protein folding pattern, with different instruments representing
regions of alpha-helix, beta-strands and turns. An article
detailing this work has been published in Leonardo On Line. The
title is: Life Music: The Sonification of Proteins : Beta-globin ,
Calmodulin, Gamma Lens Crystallin, Alcohol Dehydrogenase, Lysozyme
C, Spidroin, Collagen.) Life Music
http://sourceforge.net/projects/proteinmusic/
http://sourceforge.net/projects/proteinmusic/files/latest/download
Website : http://www.aber.ac.uk/~phiwww/pm/
ProteinMusic
ProteinMusic is a Java program converting DNA sequences into
music. The original idea for this project came from R. D. King at
the University of Wales, Aberystwyth and C. G Angus from the
Shamen (King, R.D. & Angus, C.G. (1996)).
http://brenthugh.com/audio/
Music of the genome 1-9
8:17 ( 2.92 Mb )
http://algoart.com/
ArtWonk4
ArtWonk4 produces music, visuals and wordplay based on
generative algorithms you interactively create by connecting
modules (graphical objects representing functions and processes)
in real time, adjusting the parameters as you go, in a drag &
drop environment especially designed to be fast to learn, fast to
use.
Source material can be anything at all: Fractals, DNA, EEGs, EKGs,
stock quotes, you name it. Built in data extraction reads data
from virtually any source, and an extensive DNA editor opens
mountains of public domain genetic sequences to explore.
ArtWonk v4.2 was released in September, 2010, but the algorithms
and generative processes in ArtWonk have been in development for
over 20 years, since the first release of MusicBox for MSDOS in
1986. It represents the ongoing life work of pioneer music and
graphics developer John Dunn. This makes ArtWonk vast, deep, and
comprehensive; but it is easy and playful to use because it is
always running, always live, and you get instant feedback on every
change you make.
Genetic Music From DNA and Protein -- The sound pieces on
this page were all composed using algorithmic music software
developed by me (John Dunn) over the past 25+ years. Except where
otherwise noted, the music is also by me, although often with help
from and in collaboration with others, for both the music and the
algorithms and software features that made the music what it is.
Most tracks are based on DNA and protein genetic data sequences
that are freely available on the Internet. Two excellent sources
of genetic sequences are the Swiss Protein Data Bank and the NIH
GenBank.
http://www.dnamusic.com/articles/music_and_metamusic.htm
Music and Metamusic—A Universal Bridge
by
Barbara Bullard and Matthew Joyce
YouTube : Professor Barbara Bullard - Metamusic :
http://www.youtube.com/watch?v=n_cXL7jr2-c&feature=mfu_in_order&list=UL
http://www.youtube.com/watch?v=4FtRcp6leJU
http://www.youtube.com/watch?v=LGlP0jFiAW8
http://www.youtube.com/watch?v=tRnXUs6aDj0
http://www.youtube.com/watch?v=i0wMTC3i2uU
http://www.petergena.com/genexs.html
http://www.petergena.com/DNAmus.html
Peter Gena DNA Music for Genesis
Red Blood Cells (1995), digitally synthesized DNA sequences --
The physio-musical conversion of DNA sequences occurs via a series
of formulae that were worked out in a manner based on physical
properties of DNA and musical parameters. Once the sequences are
converted by my custom algorithms they are played by the DNA
Mixer, which reads linearly much like the ribosomes—organelles
that read codons for amino acid conversion—traverse the mRNA,
mixing multiple sequences simultaneously just like in our cells.
From the onset I believed that a musical reading of DNA ought to
be rendered literally. As the sequences represent life of many
sorts, I am reluctant to tamper with the “score.” The DNA mixer
can realize sequences as digital sound and/or print them out in
musical notation. Ideally, performances of the gene sequences
should be executed live from the computer as in an installation,
where the ribosome simulations can be positioned spontaneously
before playing. Red Blood Cells is a mix of five genes that are
present in human blood: alpha and beta globin, heme synthetase,
transaldolase, and glucose 6 phosphate. These are realized
simultaneously, just as they are produced in the body...
Collagen and Bass Clarinet (1997), bass clarinet and five DNA
sequences -- Collagen is the main structural protein found
in animal connective tissue (it forms gelatin when boiled).
Collagen and Bass Clarinet, was commissioned by Italian
clarinetist Frederico Paci. He premiered it at the Aspekte Musik
Festival in Salzburg, Austria in 1997. The six parts (the bass
clarinet plus five computer tracks) are generated from two
collagen DNA sequences (three copies of each). Thus, one of the
six was outputted as musical notation (properly transposed) for
the bass clarinet, and the remaining five "channels" were realized
and played electronically by a DNA mixer, programmed by the
composer in MAX/MSP.
Prolation Collagen (2005) -- for disklavier uses the same
DNA sequence, but is set as a prolation canon for five voices,
where each subsequent voice augments the note values progressively
to simulate different meters.
Immunoglobulin (2005, revised '06), interactive installation --
Upon the major overhaul of the DNA programs during a residency
in Bellagio, my subsequent goal was to implement a sonic mapping
of the human immunoglobulin system. Our immune system is made up
of multiple random generators that continually produce billions of
unique DNA sequences that are put on call to fight off invading
diseases. Each immune gene consists of one of three fixed lead
sequences (Gamma, Kappa and Lambda), stitched at the head of a
variable region, or randomly generated string. The programming
effort requires an algorithm that initiates lead sequences and
generates the variable regions until an end codon is encountered.
GB2350469
A method of producing audibly discernible sounds
Inventor(s): Helen LONG
Means for producing an audibly discernable representation of a
three dimensional structure such as a biological structure
comprises a preliminary analysis of the structure to determine
three dimensional positional coordinate data, processing this data
to filter out large scale and small scale variations into
successive sets of data, combining this data into a single
sequence and generating audible sounds therefrom relating to the
positional coordinate data. The biological structure represented
are proteins whereby the CA carbon atoms of the amino acids of the
proteins are analysed by x-ray crystallography to produce the data
sets for generating the audible sounds.
The present invention relates generally to a method for producing
audibly discernible sounds, and particularly to a method in which
the sounds are representative of complex structures.
In the representation of complex structures occupying
three-dimensional space it has been conventional either to use
stylised models of the structures, themselves occupying the
three-dimensional space, or to represent the structures in
two-dimensions with an appropriate representational convention by
which the information concerning the third dimension is conveyed.
Each of these representational techniques has inherent drawbacks.
Threedimensional models, although they can be produced accurately,
are not readily transportable nor are is they indefinitely
extendable, so that, for example, a highly complex structure may
be limited to a representation of only a portion under immediate
examination. Although two-dimensional representations are more
readily portable, and can also be converted into a form suitable
for display on a screen such as a computer screen, the necessity
for a drawing convention to represent the third dimension results
in a degree of imprecision and uncertainty in the accuracy of the
representation. The present invention proposes a complete
departure from conventional representational techniques by
proposing to provide an audibly discernible representation of
spatial information.
The present invention finds particular (but not exclusive)
application in the 2 representation of naturally-occurring
structures such as biological structures, especially proteins.
Structure, pattern and form are inherent in naturally-occurring
biological material, and these features may be drawn upon to
provide parameters for audibly discernible representations. In the
representation of spatial information in audible form the audible
information may approximate to, or be considered as, music.
Culture and musical tradition has resulted in the evolution of
music consisting of references and structures often not
consciously appreciated by the listener but nevertheless having an
effect on the physiological perception of the music. Recent
developments in digital computing have made available to musicians
further means by which musical composition may be developed, and
it is not unknown for a digital computer to be used as a
compositional tool for developing new structures in music. This
new type of - music is sometimes called algorithmic, and such
music, developed with computer process rules, may combine tonal
and structural relationships which it would be difficult to
calculate by traditional means.
The audible representation of biological structures such as
proteins may, therefore, result in sounds which may be musical in
their form. Proteins are biological macro molecules which are the
fundamental building blocks in all life forms. Proteins are
composed of a plurality of sub units, amino acids, which are
arranged according to the individual amino acid properties to form
a three dimensional molecule. It is recognised that music is
defined by the intervals between notes rather than the absolute
pitches of the notes and, correspondingly, proteins may be
considered as being defined more by their overall patterns than by
their absolute or primary sequences. Proteins structures, may be
considered to comprise four mains elements or levels of
complexity, namely'a I w..
3 primary structure which is the linear order in which the amino
acid sub units occur. A secondary and a tertiary structure
determined by the properties of these amino acids which give rise
to structural features referred to by biologists as loops, turns,
alpha helices and beta strands or beta sheets depending on the
spatial arrangements of the sub units in the linear sequence.
Quaternary structures are recognisable as the quaternary structure
is the broadest structural level concerned with the'arrangement of
individual protein "blocks" which fit together to form the final
protein molecule.
At the primary level, alpha helices are uniform coil-like
structures in which the 10 functional groups or R-groups of the
amino acid project outward from the helix axis.
On the other hand secondary structures known as beta strands fold
back and forth with individual amino acid R-groups projecting from
the folded chain on alternate sides. Different beta strands may be
aligned with one another, adjacent strands forming weak bonds
which connect them into what are called beta-sheets. Also at the
secondary/tertiary level regions of the molecule referred to as
"tums' follow a difFerent directional path and are commonly found
connecting two regions of an alpha helix or beta strands. These
are structures spanning both the secondary and tertiary level in
that the folding patterns of the secondary structures are combined
to produce the overall tertiary structure of a protein.
Information concerning the relationship of these features is
usually considered at a visual level and represented visually. The
present invention provides an alternative means of representation
allowing other senses to be involved.
According to one aspect of the present invention, therefore, a
method of producing an 4 audibly discernible representation of a
three dimensional sti-ucture comprises the steps of:
generating numerical information concerning the spatial position
of identifiable components of the structure from analysis of the
structure, converting the numerical information into a derived
digital signal by forming moving averages of the numerical
information, subjecting the derived digital signal to a conversion
from the three- dimensional value to produce a signal having a
scalar value representing at least one of the properties of a
audibly discernible sound, and generating a sound having that or
those properties.
At a fundamental level it may be considered that each positional
coordinate representing the presence of a feature or structural
element of the structure may be allocated a unique discernible
sound. It is of course important that the same sound is repeatably
produced by the same feature, but it is not essential that only
one feature produce that sound.applied to the representation of a
naturally occurring structure, such as a protein the analysis may
be performed by x-ray crystallography to determine the relative
locations of the amino acids of which the protein is composed. In
its application to other stru ctures, however, different analysis
techniques may be used on order to generate the raw positional
data and, of course, the coordinate. information may represent the
positions of other significant elements in the structure. In an
engineering structure, for example, the positional coordinates may
represent the nodes in a load-bearing assembly and/or the stresses
applied to elements of a structure during operation or when
performing its function. For example, the stresses exerted on an
element of a building may be represented by pitch, variation of
which represents increases in the stress so that dynamic variation
of the stress pattern can be represented audibly which enables a
plurality of different signals to be perceived simultaneously even
in a structure in which, with a traditional visual representation,
certain 5 components may be masked or covered by others and
therefore not visible.
In the representation of structures such, as proteins the
resultant data of the x-ray crystallography analysis may comprise
a set of positional coordinates representing the relative
positions of at least some of the atoms of the amino acids of the
protein. In particular the positional coordinate data may
represent the three dimensional positions in space, with respect
to a given frame of reference, of the CA carbon atoms of the amino
acids of the protein.
Although individual unique sounds may be generated these sounds
may not necessarily be represented-by individual musical notes,
but could be other detectable sounds such as chords or discordant
sounds.
In the performance of the method of the invention the said moving
averages comprise at least a first moving average of the value of
the positional coordinate data scanned over successive groups of
carbon atoms to provide an approximate representation of the
secondary structure of the amino acids in the protein.
Likewise, a second moving average of the values of the first
moving average may be taken over a range of values thereof greater
than the range used to form the first 6 moving average. This
second moving average provides a further degree of "smoothing" to
act effectively to filter out the smaller scale variations,
without completely excluding larger scale variations.
Further sequences of digital signals may be derived from the said
first and second moving averages, for example by determining the
differences between the first moving average and the positional
coordinate data, whereby to provide a digital data signal in which
larger scale variations are not present and smaller scale
variations are amplified.
The second further sequences of digital signals may be derived
from the first and second moving averages by determining the
differences between the first and second moving averages whereby,
in effect, to act as a midfrequency filter on the data.
The method may include deriving a third further sequence of
digital signals by normallsing the second moving average values
about a selected origin to represent the large scale features of
the positional coordinate data stream. This, effectively, acts as
a low frequency filter to produce signal dependent on the large
scale features.
The said first, second and third further sequences of digital
signals may each be multiplied by a respective weighting factor
and summed to produce a single sequence of averaged and processed
three dimensional coordinate values which are then mapped onto a
sequence of one-dimensional values. This may be achieved via a
three dimensional wave form generated by spectral synthesis, using
a fourier synthesis technique, or by other techniques which
provide a repeatable mapping of a three- 7 dimensional point onto
a one-dimensional point which can be interpreted as a musical
parameter. A simple example might be to sum together the three
coordinate values to get a single one-dimensional value.
The one-dimensional value may be pitch or volume and other means
may be provided for varying the attack and decay of the sound in
order to generate musical notes.
The present invention also comprehends a method of producing an
audibly discernible representation of a three-dimensional
structure in which the identification of the details of secondary
structures in the positional coordinate data is obtained by means
of a filter.
In another aspect of the invention a method of producing audibly
recognisable sounds representing respective amino acids in a
protein structure comprises the steps of subjecting the protein
structure to an x-ray crystallography analysis to produce a series
of raw data signals representing the three-dimensional positional
coordinates of the CA carbon atoms of the amino acids of which the
protein is composed; filtering the said raw data signals to
generate a plurality of derived moving averages thereof whereby to
filter out large and small scale variations respectively;
generating from the derived moving averages a composite signal
including weighted moving averages as components thereof, and
generating from the said composite signal an audible signal in
which each amino acid is represented by an identifiable musical
note.
The present invention may be embodied in apparatus including
visual display means by 8 which the raw data positional coordinate
signals may be displayed graphically in synchronism with the
audible output signals such that visual and aural correspondence
is discernible.
The present invention also comprehends apparatus for producing an
audibly discernible representation of a three-dimensional
structure, comprising: means for analysing numerical information
to generate representations of the position of identifiable
components thereof, means for forming moving averages of the said
numerical information, means for converting the moving averages of
the numerical information into scalar values, and means for
allocating pitch or volume values to the said scalar values to
generate audible sounds related to the structure.
Various examples of the invention will now be more particularly
described.
Example I - for the generation of musical notes
representing the individual amino acids of a protein structure,
each x, y and z positional coordinate of the CA carbon atom from
each amino acid in an original protein sequence SO derived from
x-ray crystallography analysis is processed twice, once to extract
a first moving average SI, calculated by averaging the values of
the sequence SO over a range of five amino acids, and then a
second time to extract a second moving average S2 calculated by
averaging the values of the moving average S I over a range of
twenty five amino acids. The first moving average represents the
secondary structure of the protein and the second 9 moving average
represent the tertiary structure.
From these three digital data streams S 50, 51, 52 may be derived
three further sequences as follows:
1 ' SO- 1 is calculated by subtracting the first moving average S
1 from the original three dimensional data SO. This has the effect
of emphasising the small twists and turns of the protein and of
masking the larger scale curves over the protein structure as a
whole. This in effect acts as a high 6equency filter on the
three-dimensional structure of the protein and highlights the
spiral shape of the alpha helices. By subtracting the first moving
average from the original data all the short-term fluctuations are
maintained within the structure of the alpha helices without
interference from larger scale changes. By mapping this to pitch
variation an accurate sonic representation of the alpha helices is
obtained. This mapping results in the generation of sequences of
arpeggios when the alpha helices are traversed, and the same or a
slightly varying note is is heard when the beta sheets are
traversed. This latter results from the fact that a beta sheet
contains few small-scale changes.
SI-2 is created by subtracting the second moving average from the
first moving average. This has the effect of amplifying the medium
sized turns of the protein whilst attenuating the higher frequency
alpha helix turns and the lower frequency large scale curves. This
process acts as a medium frequency filter on the three-dimensional
structure.
Finally, S2-3 is derived by calculating the mean position of all
the amino acids in the raw data SO to create a second moving
average by subtracting this mean from each value of a coordinate
for an amino acid in the moving average S2. The resulting sequence
S2-3 is essentially identical to the sequence S2 but is normalised
about a central zero origin point. This sequence represents the
larger scale curves of the 5 original three-dimensional protein
structure, effectively acting as a low frequency filter.
Weighting factors are then applied to each sequence and the
weighted sequences summed to give a final sequence ST = a (SO-1) +
b(S 1-2) + c (S2-3). The magnitude of the weighting factor a
determines the proportion of the high frequency component of the
protein in the final sequence ST whilst b and c determine the mid
frequency and low frequency component.
The sequence ST is than mapped onto musical parameters such as
pitch via a threedimensional waveform generated by
three-dimensional spectral synthesis, thus creating is sequences
of notes which express visual features in musical form. The
waveform maps a three-dimensional coordinate value onto a
one-dimensional value, that is the value of that point in the
waveform. The three dimensional input values are a sequence of
coordinate values ftom ST and the output is a sequence of
one-dimensional values which are interpreted as notes in musical
scales or dynamic levels (volume). This mapping may be achieved as
follows. First a random number (ranging from 5 to 20 or more) of
vectors are provided which reside in a 2-dimensional
frequency-space (the frequency-space is the spectral analog to the
final 2 dimensional landscape). Each vector has a randomly
determined position in this frequency-space and has a randomly
determined phase and magnitude associated with it (represented by
a complex number).
11 For mathematical reasons, there must also exist for each vector
a 'mirror' vector with the same vector location but having a
complex number associated with it that is a complex conjugate of
the original vector's complex number. Therefore there must always
be an even number of these vectors.
Once these vectors with their associated complex numbers have been
generated it is a simple process of fourier synthesis so that
given a 2-dimensional coordinate in cartesian space, one can sum
the contributions of each vector (at the cartesian coordinate) to
end up with a scalar (1 -dimensional) value which can be
interpreted as a height value. Details are given by D. Saupe.
Since the resulting "landscape" is constructed from a combination
of waves, for a small list of vectors it has the property that two
points close to each other in 2-dimensions have similar resulting
height values (i.e. mathematically speaking, the landscape is
continuously differentiable everywhere.
is This process is extended to 3-dimensions by generating a list
of 3dimensional vectors in frequency -space. When given a point in
3-dimensional cartesian space, these vectors can be summed using
complex arithmetic to provide a 1 - dimensional scalar value. This
allows a 3-dimensional coordinate (i.e. 3-dimensional position of
a CA atom after the moving average process) to be turned into a 1
-dimensional scalar value.
In an analogous way to the 2-dimensional synthesis, two points
close to each other in 3-dimensional cartesian-space will have
close 1 -dimensional results ftom the mapping.
This means that close 3-dimensional positions will have close
(audibly related) pitch, amplitude or other such musical value.
12 Whilst this invention may make use of a fourier synthesis
technique, fourier synthesis by such is not new, and this
invention includes the use of any other method of mapping a
3-dimensional point, for example derived from filters or moving
averages of x-ray crystallography data to a 1dimensional point
which can be interpreted in a musical fashion. A simple example
might be simply to sum together the x, y, and z values of the
3-dimensional coordinate to get a single 1 -dimensional value.
Another alternative in the specific case of proteins may be to use
the coordinates of the second moving average as an "axis" and to
calculate "angular" offsets of the original data from that axis.
As the alpha helix twists around a sequence of angles averaging
around 360' may 10 then be derived.
This output is then written to a NMI text file for conversion into
music or a layer in a musical arrangement using known MIDI music
software to produce complex multi timbral musical pieces
containing melodies reflecting the large-scale tertiary structures
15 or small repetitive arpeggios expressing the structural nature
of the alpha helices.
Example 2: for the production of a musical representati-on
of a protein. This follows the same basic method as described in
relation to example I above, with the addition of tempo, rhythm
and key changes derived from the x-ray crystallography coordinate
20 data.
In this example positions in the original data sequence are
determined where the musical parameter changes are to take place
corresponding to visual transmission points in the secondary
structure of the protein, for example where an alpha helix, a 13
beta sheet, a loop or a turn begins or ends.
The secondary structure details are identified using a filter.
This filter outputs secondary structure features from an input
comprising the three-dimensional data.
Two filter techniques may be used in the identification of the
secondary structures, namely:
Filter technique 1. The three dimensional distance of each
CA carbon atom is taken from the mean position of the CA carbon
atoms of a particular section of the protein. The filter moves a
vrindow containing data covering approximately 10 CA carbon atoms
for different amino acids along a section of the crystallography
data looking at the distance of each CA carbon atom from the mean
value of all the carbon atoms in the current window. From these
distances it is possible to determine the likelihood of the
current window containing data from an alpha helix or a beta
sheet. The termination points of these features may thus be
identified.
Filter technique 2. In this technique matched filters are
used with parameters tuned to those found in protein alpha helices
and beta strands and the like. For example, alpha helices will
have an approximate pitch of 4.6 angstrom units, beta sheets will
have an approximate pitch of 13.5 angstrom units.
Example 3. This example may be embodied in a model giving
participants the opportunity to create their own pieces of music
from a range of onscreen three dimensional proteins. The three
dimensional x-ray crystallography x, y, z coordinate data is used
as the basis for an animated display of the progress of the
generated music 14 along the physical structure of the proteins as
displayed graphically on a computer screen. By choosing from a
selection of moving average operations the user can see how the
chosen proteins are converted into musical sounds. The weightings
a, b, c of example 1 may be made available to the user for
selection, and their combination by 5 the computer then results in
a sequence of notes.
Each note, corresponding to a specific arnino acid in the display,
is then sounded with the an-dno acid on the display, with the
visual representation of the protein being highlighted
simultaneously whereby to demonstrate and emphasise the
correspondence 10 between the musical notes and the protein
sequences.
Example 4: a display booth or exhibition kiosk may be
equipped with an interactive touch screen compute. system
containing both the audio and visual components described in
relation to examples 1 and 3. The screen may display graphics
generated is using a graphics processor depicting a traverse
through the biological material of a plant, animal, insect,
fungal, bacteria, yeast or human Iandscape". The protein molecules
are used to derive musical sounds identifying the proteins. This
may also have an educational value in, enabling aural recognition
of proteins.
Example 5. Another educational application may be developed
as a three dimensional tactile model of a protein containing a
plurality of switches connected to a computer system whereby the
display of an audio visual information device may be influenced.
On touching a particular amino acid (that is operating the
associated switch) the an-dno acid on the display screen would be
highlighted and the corresponding note, chord or is other musical
sound representing this amino acid generated for the user to hear.
The present invention thus expands and crosses the boundaries
between science and art, enabling new approaches to understanding
biological structure to be achieved as S well as the generation of
music for educational or purely entertainment purposes. Use of
this invention in protein homology modelling, where fast and
easily recognisable differences in proteins of similar structure
are required, may be developed as there is a currently unfulfilled
demand for such a tool in this widely used research technique.
Protein-derived music may be of therapeutic interest in the
treatment of conditions currently treated using music therapy. It
is believed that such specialised music may offer a focused and
precise application which optimises and hence is more cost
efFective than, known music therapies utilising music derived from
other sources.
Protein-derived music may be used to strengthen mind-body
connections. Likewise, protein-derived music may be used for
studying and modelling protein sequence data, complementing
existing techniques which have wide application in drug design.
Since alpha helices, beta strands and turns each have
characteristic combinations of hydrophobic and hydrophilic amino
acids, different structural categories of proteins, which combine
these secondary elements in different ways, also have different
musical characteristics. The sounds generated therefrorn may
therefore be used effectively in the discrimination and
demonstration of different protein types.
Protein music may also be used in sequence alignment and
structural homology determination as structural homology may be
heard when it might not easily be 16 perceived visually.
Alexander RABINOVICH, et al. :
Plasmatron Fuel Reformer
Science & Mechanics ( February 1970 )
http://connection.ebscohost.com/c/articles/2639544/plasmatron-device-can-cut-car-nox
Professional Engineering;12/08/99, Vol. 12 Issue 22, p50 (
December 1999 )
Plasmatron device can cut car NOx
by Diinah Greek
ABSTRACT -- Offers a look at the plasmatron device developed
by Alexander Rabinovich and colleagues in the plasma technology
division at the Massachusetts Institute of Technology. Ability to
cut emissions of pollutants such as nitrogen oxides; Mechanism;
Testing; Features.
http://worldwidescience.org/topicpages/p/plasmatron+fuel+reformer.html
Plasmatron-catalyst system
A plasmatron-catalyst system. The system generates
hydrogen-rich gas and comprises a plasmatron and at least one
catalyst for receiving an output from the plasmatron to produce
hydrogen-rich gas. In a preferred embodiment, the plasmatron
receives as an input air, fuel and water/steam for use in the
reforming process. The system increases the hydrogen yield and
decreases the amount of carbon monoxide.
HYDROGEN GENERATION FROM PLASMATRON
REFORMERS :
A PROMISING TECHNOLOGY FOR NOX ADSORBER REGENERATION AND OTHER
AUTOMOTIVE APPLICATIONS
Plasmatron reformers are being developed at MIT and
ArvinMeritor [1]. In these reformers a special low power
electrical discharge is used to promote partial oxidation
conversion of hydrocarbon fuels into hydrogen and CO. The partial
oxidation reaction of this very fuel rich mixture is difficult to
initiate. The plasmatron provides continuous enhanced volume
initiation. To minimize electrode erosion and electrical power
requirements, a low current, high voltage discharge with wide area
electrodes is used. The reformers operate at or slightly above
atmospheric pressure. Plasmatron reformers provide the advantages
of rapid startup and transient response; efficient conversion of
the fuel to hydrogen rich gas; compact size; relaxation or
elimination of reformer catalyst requirements; and capability to
process difficult to reform fuels, such as diesel and bio-oils.
These advantages facilitate use of onboard hydrogen-generation
technology for diesel exhaust after-treatment. Plasma-enhanced
reformer technology can provide substantial conversion even
without the use of a catalyst. Recent progress includes a
substantial decrease in electrical power consumption (to about 200
W), increased flow rate (above 1 g/s of diesel fuel corresponding
to approximately 40 kW of chemical energy), soot suppression and
improvements in other operational features.. Plasmatron reformer
technology has been evaluated for regeneration of NOx adsorber
after-treatment systems. At ArvinMeritor tests were performed on a
dual-leg NOx adsorber system using a Cummins 8.3L diesel engine
both in a test cell and on a vehicle. A NOx adsorber system was
tested using the plasmatron reformer as a regenerator and without
the reformer i.e., with straight diesel fuel based regeneration as
the baseline case. The plasmatron reformer was shown to improve
NOx regeneration significantly compared to the baseline diesel
case. The net result of these initial tests was a significant
decrease in fuel penalty, roughly 50% at moderate adsorber
temperatures. This fuel penalty improvement is accompanied by a
dramatic drop in slipped hydrocarbon emissions, which decreased by
90% or more. Significant advantages are demonstrated across a wide
range of engine conditions and temperatures. The study also
indicated the potential to regenerate NOx adsorbers at low
temperatures where diesel fuel based regeneration is not
effective, such as those typical of idle conditions. Two vehicles,
a bus and a light duty truck, have been equipped for plasmatron
reformer NOx adsorber regeneration tests.
Low current plasmatron fuel converter
having enlarged volume discharges
A novel apparatus and method is disclosed for a plasmatron
fuel converter ("plasmatron") that efficiently uses electrical
energy to produce hydrogen rich gas. The volume and shape of the
plasma discharge is controlled by a fluid flow established in a
plasma discharge volume. A plasmatron according to this invention
produces a substantially large effective plasma discharge volume
allowing for substantially greater volumetric efficiency in the
initiation of chemical reactions within a volume of bulk fluid
reactant flowing through the plasmatron.
Onboard Plasmatron Hydrogen Production for
Improved Vehicles
A plasmatron fuel reformer has been developed for onboard
hydrogen generation for vehicular applications. These applications
include hydrogen addition to spark-ignition internal combustion
engines, NOx trap and diesel particulate filter (DPF)
regeneration, and emissions reduction from spark ignition internal
combustion engines First, a thermal plasmatron fuel reformer was
developed. This plasmatron used an electric arc with relatively
high power to reform fuels such as gasoline, diesel and biofuels
at an oxygen to carbon ratio close to 1. The draw back of this
device was that it has a high electric consumption and limited
electrode lifetime due to the high temperature electric arc. A
second generation plasmatron fuel reformer was developed. It used
a low-current high-voltage electric discharge with a completely
new electrode continuation. This design uses two cylindrical
electrodes with a rotating discharge that produced low temperature
volumetric cold plasma., The lifetime of the electrodes was no
longer an issue and the device was tested on several fuels such as
gasoline, diesel, and biofuels at different flow rates and
different oxygen to carbon ratios. Hydrogen concentration and
yields were measured for both the thermal and non-thermal
plasmatron reformers for homogeneous (non-catalytic) and catalytic
reforming of several fuels. The technology was licensed to an
industrial auto part supplier (ArvinMeritor) and is being
implemented for some of the applications listed above. The
Plasmatron reformer has been successfully tested on a bus for NOx
trap regeneration. The successful development of the plasmatron
reformer and its implementation in commercial applications
including transportation will bring several benefits to the
nation. These benefits include the reduction of NOx emissions,
improving engine efficiency and reducing the nation's oil
consumption. The objective of this program has been to develop
attractive applications of plasmatron fuel reformer technology for
onboard applications in internal combustion engine vehicles using
diesel, gasoline and biofuels. This included the reduction of NOx
and particulate matter emissions from diesel engines using
plasmatron reformer generated hydrogen-rich gas, conversion of
ethanol and bio-oils into hydrogen rich gas, and the development
of new concepts for the use of plasmatron fuel reformers for
enablement of HCCI engines.
Onboard Plasmatron Generation of Hydrogen
rich Gas for Diesel Engine Exhaust Aftertreatment and Other
Applications
Plasmatron reformers can provide attractive means for
conversion of diesel fuel into hydrogen rich gas. The hydrogen
rich gas can be used for improved NOx trap technology and other
aftertreatment applications.
PATENTS
Alexander RABINOVICH : Plasmatron Fuel Reformer
LOW POWER COMPACT PLASMA FUEL CONVERTER
WO0114702
Plasmatron-internal combustion engine system
US5425332
Plasmatron-internal combustion engine system
US5437250
Apparatus and Method for NOx Reduction
US2007289291
Rapid response plasma fuel converter systems
US5887554
Integrated plasmatron-turbine system for the production and
utilization of hydrogen-rich gas
US5852927
Homogeneous charge compression ignition control utilizing
plasmatron fuel converter technology
US2004099226
PLASMATRON FUEL CONVERTER HAVING DECOUPLED AIR FLOW CONTROL
WO2004094795
WIDE DYNAMIC RANGE MULTISTAGE PLASMATRON REFORMER SYSTEM
WO2005094335
HYDROGEN AND CARBON MONOXIDE ENHANCED KNOCK RESISTANCE IN SPARK
IGNITION GASOLINE ENGINES
WO2004111417
Zhaohui ZHONG
, et al.
Graphene Infrared Lens
http://www.dailymail.co.uk/sciencetech/article-2584617/The-contact-lens-infrared-vision.html
19 March 2014
The contact lens that could let you
see in the dark: Researchers reveal graphene 'supervision'
sensor
By Mark Prigg
Researchers have unveiled plans for a smart contact lens that
could give its wearer infrared 'night vision'.
The team say that by sandwiching graphene inside the lens they can
build a sensor capable of capturing every from visible light to
infrared.
They have already built a prototype smaller than a fingernail, and
experts say it could one day be built into lenses for soldiers and
others who need to see in the dark.
WHAT IS GRAPHENE?
Graphene is made of a single layer of carbon atoms that are bonded
together in a repeating pattern of hexagons.
It is one million times thinner than paper, and Graphene’s flat
honeycomb pattern grants it many unusual characteristics,
including the status of strongest material in the world.
Zhaohui Zhong at the University of Michigan say their layered
approach can lead to ultrathin sensors.
'We can make the entire design super-thin,' said Zhong, assistant
professor of electrical and computer engineering.
'It can be stacked on a contact lens or integrated with a cell
phone.'
The prototype device created by Zhong is already 'smaller than a
pinky nail' and can be easily scaled down.
'If we integrate it with a contact lens or other wearable
electronics, it expands your vision,' Zhong said.
'It provides you another way of interacting with your
environment.'
It takes advantage of graphene's 'supersensor' properties.
The material shows a very strong effect when it’s struck by
photons (light energy).
It turns into what is known as a 'hot carrier' - an effect that
can be measured, processed, and turned into an image.
The team developed a way to sandwich the graphene to make it as
sensitive as CMOS silicon imaging sensors in commercial digital
cameras.
'Graphene is a promising candidate material for ultra-broadband
photodetectors, as its absorption spectrum covers the entire
ultraviolet to far-infrared range,' the team wrote in Nature.
The team are investigating using graphene to sandwich between two
layers of a lens, rather like this Google prototype for a glucose
monitoring lens for diabetics
'Here, we report an ultra-broadband photodetector design based on
a graphene double-layer heterostructure.
'The detector is a phototransistor consisting of a pair of stacked
graphene monolayers (top layer, gate; bottom layer, channel)
separated by a thin tunnel barrier.
'Under optical illumination, photoexcited hot carriers generated
in the top layer tunnel into the bottom layer, leading to a charge
build-up on the gate and a strong photogating effect on the
channel conductance.
'The devices demonstrated room-temperature photodetection from the
visible to the mid-infrared range, with mid-infrared responsivity
higher than 1 A W-1, as required by most applications'
US2012225296
UNIFORM MULTILAYER GRAPHENE BY CHEMICAL VAPOR
DEPOSITION
Inventor(s): ZHONG ZHAOHUI [US]; LEE
SEUNGHYUN [US]; LEE KYUNGHOON [US] +
Also published as: WO2012031238 (A2)
WO2012031238 (A3)
A method of producing uniform multilayer graphene by chemical
vapor deposition (CVD) is provided. The method is limited in size
only by CVD reaction chamber size and is scalable to produce
multilayer graphene films on a wafer scale that have the same
number of layers of graphene throughout substantially the entire
film. Uniform bilayer graphene may be produced using a method that
does not require assembly of independently produced single layer
graphene. The method includes a CVD process wherein a reaction gas
is flowed in the chamber at a relatively low pressure compared to
conventional processes and the temperature in the reaction chamber
is thereafter decreased relatively slowly compared to conventional
processes. One application for uniform multilayer graphene is
transparent conductors. In processes that require multiple
transfers of single layer graphene to achieve multilayer graphene
structures, the disclosed method can reduce the number of process
steps by at least half.
BACKGROUND OF THE INVENTION
[0003] Single and few-layer graphene has emerged as a
promising material for novel applications in electronics due to
certain advantageous optical and electrical properties and due to
its potential for integrating bottom-up nanomaterial synthesis
with top-down lithographic fabrication at a wafer size or macro
scale. Its semi-metallic nature with high carrier mobility and low
opacity also makes it a good candidate for use as transparent
conductors for photovoltaic devices, touch panels, and displays,
for example. Graphene structures also have high chemical
resistance, low manufacturing costs, and, being atomically thin,
are relatively flexible when compared to some other transparent
conductor materials such as indium tin oxide (ITO). Bilayer
graphene (BLG) in particular holds further promise for use in
post-silicon electronics applications because a bandgap up to 250
meV can be induced in the material using an electric field, which
is not possible with single or monolayer graphene (SLG), and
because exciton binding energies in BLG are tunable by electric
field- induced bandgap.
[0004] A monolayer or single layer graphene is a plane of carbon
atoms bonded in a hexagonal array. Several methods have been used
to synthesize graphene films including the reduction of graphene
oxide, liquid exfoliation using organic solvents, and chemical
vapor deposition (CVD). The CVD method has drawn much attention,
as this method can yield high quality graphene films. Homogeneous
single layer graphene has been synthesized on transition metal
substrates, such as copper, that have low carbon solubility using
low pressure CVD (LPCVD). But the sheet resistance of pristine or
undoped SLG is on the order of 2000-6000[Omega]-too large to for
use as a transparent conductor, for example. Stacking multiple
individually produced layers of SLG and individually doping each
layer is one method that has been used to achieve lower film
resistance for graphene structures. But fabrication of a
multi-sheet SLG stack can require a multitude of transfer
processes, depending on the number of SLG sheets desired in the
stack. This can lead to high processing time and cost, and a
higher likelihood of defects in the films.
[0005] Bilayer graphene has been fabricated by initially producing
two separate monolayers of graphene and subsequently using a
sacrificial carrier to physically stack one of the separate
monolayers on the other. BLG has also been fabricated via
mechanical exfoliation of graphite to produce SLG that is
subsequently stacked with another SLG, but the sheet size is
limited to the square-micron range and such processes are not
scalable to sizes large enough to be practical for use in many
electronics applications. The synthesis of wafer scale uniform
bilayer graphene product presents a tremendous challenge.
[0006] Graphene sheets having multiple layers of graphene with
lower sheet resistance than SLG have been directly synthesized
using an LPCVD method on other transition metals, such as nickel,
that have relatively high carbon solubility and on copper using
atmospheric pressure CVD (APCVD). Multiple layer graphene (MLG)
structures produced by these methods typically have non-uniform
thickness, with different numbers of graphene layers throughout
the structure, and rough surfaces compared to LPCVD-grown SLG.
Graphene sheet thickness variation can be problematic for use in
electronics applications because it causes the sheet resistance
and optical transmittance to vary among different areas of the
sheet. Additionally, APCVD processes that are used to produce MLG
can lead to higher numbers of defects compared to LPCVD SLG due to
particulate deposition resulting from APCVD conditions.
SUMMARY OF THE INVENTION
[0007] In accordance with one embodiment, a method of directly
synthesizing uniform multilayer graphene by chemical vapor
deposition is provided.
[0008] In accordance with another embodiment, a method of
producing multilayer graphene is provided. The method comprises
the steps of: (a) placing a substrate having a metal surface in a
reaction chamber of a furnace; (b) flowing H2 gas in the reaction
chamber; (c) increasing the temperature in the reaction chamber to
a desired level; (d) after the temperature in the reaction chamber
reaches the desired level, ceasing flow of the H2 gas, and flowing
reaction gas in the reaction chamber for a desired time; and (e)
after the desired time, decreasing the temperature in the reaction
chamber at a controlled rate.
[0009] In accordance with another embodiment, a method of
producing multilayer graphene is provided. The method comprises
the steps of: (a) placing a substrate having a metal surface in a
reaction chamber of a furnace; (b) evacuating the reaction
chamber; (c) purging the reaction chamber with a working gas; (d)
flowing H2 gas in the reaction chamber; (e) increasing the
temperature in the reaction chamber to a desired level; (f) after
the temperature in the reaction chamber reaches the desired level,
ceasing flow of the H2 gas so that the reaction chamber is free of
H2 gas, and flowing reaction gas in the reaction chamber at a
pressure in the reaction chamber of less than 0.5 Torr; and (g)
thereafter decreasing the temperature in the reaction chamber at a
rate of less than 100[deg.] C./min.
[0010] In accordance with another embodiment, a method of making a
multilayer graphene film is provided. The method comprises the
steps of: (a) synthesizing uniform multilayer graphene by chemical
vapor deposition; (b) providing a uniform graphene sheet having at
least one layer of graphene; and (c) stacking the uniform
multilayer graphene of step (a) together with the uniform graphene
sheet of step (b).
[0011] In accordance with another embodiment, a multilayer
graphene film is provided. The film has interlayer uniformity and
also has the same number of graphene layers throughout a major
portion of the sheet...
Experimental Sample Preparation
[0093] A 25 [mu]m thick copper foil (99.8%, Alfa Aesar) was
placed into an inner quartz tube reaction chamber inside a
three-inch horizontal tube furnace of a commercial CVD system
(First Nano EasyTube 3000). The system was purged with argon gas
and evacuated to a pressure of about 0.1 Torr. The chamber was
then heated to 1000[deg.] C. in an H2 (100 sccm) environment at a
pressure of about 0.35 Torr. When a chamber temperature of
1000[deg.] C. was reached, 70 sccm of CH4 was flowed through the
chamber for 15 minutes at a pressure of 0.45 Torr. The sample was
then cooled slowly to room temperature with a feedback loop to
control the cooling rate. The pressure was maintained at 0.5 Torr
with 100 sccm of argon flowing. A time vs. temperature plot from
the CVD growth process is shown in FIG. 5.
[0094] Two different methods were used to transfer the produced
uniform multilayer graphene from copper foil substrate to SiO2
substrates. The first method utilized thermal release tape (Nitto
Denko) to transfer the graphene from the copper foil. The tape was
applied to the copper surface and a force of 6.25 N/cm<2
>was applied to the copper/graphene/tape stack for 10 minutes
using a EVG EV520IS wafer bonder. The opposite side of the
substrate was exposed to O2 plasma for30 seconds to remove the
graphene on that side. The substrate was etched away using an iron
(III) nitrate (Sigma Aldrich) solution (0.05 g/ml) for 12 hours. A
4-inch silicon wafer with thermally grown SiO2 was precleaned with
nP12 nanoPREP using plasma power of 500W for 40 seconds to modify
the surface energy and produce a hydrophilic surface. The tape and
graphene stack was transferred to the pre-cleaned SiO2 wafer and a
force of 12.5N/cm<2 >was applied for 10 minutes. The
substrate was then heated to 120[deg.] C. to overcome the adhesion
of the thermal release tape. The tape was then peeled off and the
adhesive residue was removed with warm acetone.
[0095] Polymethylmethacrylate (PMMA) film may be used in another
method to transfer graphene. This method does not require a
bonding tool but the edge portion of the graphene film may be
rough due to uneven thickness of spin-coated PMMA at the edge. In
this method, the growth side of the CVD graphene sample was coated
with 950PMMA A6 (Microchem) resist and cured at 180[deg.] C. for 5
minutes. The other side of the substrate was exposed to O2 plasma
for 30 seconds to remove the graphene on that side. The sample was
then left in iron (III) nitrate (Sigma Aldrich) solution (0.05
g/ml) for at least 12 hours to completely dissolve away the copper
layer. The sample was transferred onto a silicon substrate with a
thermal oxide layer. The PMMA coating was removed with acetone and
the substrate was rinsed several times. Raman spectroscopy as well
as optical microscope were used to characterize the graphene films
from all transfers, and electrical transport measurement was done
with samples transferred by the PMMA method.
[0096] For the above-described electrical testing, graphene
devices were fabricated according to the following process. After
the multilayer graphene was transferred onto SiO2/Si substrate,
Ti/Au (5 nm/100 nm) was deposited to form the source/drain
electrodes. Bilayer graphene films were then patterned into 1
[mu]m*1 [mu]m, 1 [mu]m*2 [mu]m, and 2 [mu]m*2 [mu]m pieces using
conventional lithography and oxygen plasma etching. After 40 nm of
Al2O3 was deposited as the top gate dielectric by atomic layer
deposition (ALD), top gates were patterned and the metals were
evaporated (Ti/Au: 5 nm/100 nm). It is noted that the adhesion
between metal electrodes and graphene was not perfect, as some
metal peeled off. Gate leakage/breakdown at high field was also
observed for some devices. These devices are regarded as
fabrication defects, as described in conjunction with FIG. 4(a).
Glassesoff Vision Training App
http://www.dailymail.co.uk/sciencetech/article-2583746/The-app-let-throw-away-reading-glasses.html
18 March 2014
Could the 'eye training' app really let you
throw away your reading glasses?
By Mark Prigg
A new app that claims to be able to improve people's eyesight
by 'training' them with a series of exercises has become a hit.
Called GlassesOff, it uses a series of patterns to create 15
minutes exercises for users.
If done three times a week, its makers say it could mean they no
longer need reading glasses after three months.
The app uses a series of games, puzzles and tests to improve a
user's eyesight - if they can play for 15 minutes three times a
week for three months.
HOW IT WORKS
GlassesOff uses a completely different approach that is
exclusively aimed at teaching the visual system of the brain to
better use its potential.
This allows the brain to compensate for blurred information
captured by the eyes as we age.
The foundation for this technology is provided by the brain's
ability to adapt, the app makers say.
The app uses patterns designed to strengthen connections
within circuits relevant to a task, such as recognizing letters
when reading.
'Traditionally, near distance reading improvement solutions were
limited to optical corrections such as glasses, contact lenses and
refractive surgery,' said said Nimrod Madar, CEO of GlassesOff.
'However, human vision performance is in fact limited by two
factors: the quality of an image captured by the eye and the image
processing capability of the brain as it interprets such images.
'Our solution is designed to improve reading by enhancing the
image processing function of the visual cortex, demonstrating the
amazing potential of the human brain.
'We created this app because we wanted to empower people who
experienced natural age-related changes in reading ability to take
control of their vision and improve their quality of life.
'Our personalized app constantly adapts according to users’
progress, with the ultimate goal of freeing them from dependency
on magnifying devices such as reading glasses.”
The GlassesOff app is free to download from the App Store and
offer users access to a vision evaluation and the first segment of
the GlassesOff program.
After Using the GlassesOff app for approximately two weeks, users
will be given the option to subscribe to the full version, which
includes additional advanced segments, for $59.99.
However, during the launch, subscriptions will be offered at a
special price of just $9.99.
App claims exercise will improve eyesight
The app gives users regular tests to check their progress,
giving them a 'brain speed' ranking as they improve
The researchers have also published several studies backing up the
app's effectiveness.
In a study carried out at the University of California at Berkeley
and published in Nature Scientific Reports, all subjects who
completed the GlassesOff program were able to read standard
newspaper font size without the use of reading glasses, while
improving their 'Eye Age' by an average of 8.6 years.
A second study looks at the correlation between the fovea, which
is part of the retina, and crowding, processing speed and vision
sharpness.
The findings demonstrate that the GlassesOff technology may be
applicable to improved performance of daily tasks, such as sports,
reading, driving, and more.
'This study results reaffirm our product’s ability to help reading
by improving visual processing speed.
'The results are encouraging and relevant for our planned launch
of a series of pipeline products for mass market segments,
including those designed to improve visual functions in sports and
reading speed,' said Madar.
http://www.glassesoff.com/
Revolutionary science delivered
directly to your iPhone
Human vision is limited by two main factors:
The quality of an image captured by the eyes.
The image processing capabilities of the brain as it interprets an
image captured by the eyes.
GlassesOff scientists have developed a proprietary method for
improving near vision sharpness, by improving the image processing
function in the visual cortex of the brain.
eople can impact their vision by increasing the quality of images
captured by their eye (e.g., wearing glasses, going through
corrective eye surgery), or by enhancing their brain’s image
processing abilities.
At some point, every person will suffer from the inevitable
natural deterioration in near distance reading capabilities. This
deficiency has typically been addressed by traditional products
for improvement of reading capabilities, mainly magnification
devices such as reading glasses or contact lenses that support
reading.
GlassesOff scientists have developed a patented method for
boosting the image processing function in the visual cortex of the
brain, thereby improving a person’s near vision sharpness and
reading capabilities.
Scientifically Proven Solution
Our technology is based on extensive scientific research and
achievements that have been published in the leading scientific
publications, such as Nature, Science, PNAS, Vision Research,
Scientific Reports and others.
During the last two decades, scientists have demonstrated that
contrast-driven neural responses are robustly affected by lateral
propagations between neurons in the visual cortex. A positive
effect of this interaction is called “collinear facilitation”,
which amplifies weak and slow responses and their underlying
mechanism of neuronal excitations. This function strengthens
selective synapses to elevate weak stimuli above the noise, and is
the foundation of GlassesOff technology.
Weaker and slower neuronal responses in the visual cortex, either
as a consequence of blurred input from the eyes or abnormal
development, result in degraded basic visual functions both in the
spatial domain, e.g. contrast sensitivity, and the temporal
domain, e.g. processing speed. These changes eventually affect
high-level visual tasks, such as letter identification. GlassesOff
scientists have shown that using neuronal plasticity retained in
the adult brain, it is possible to increase collinear facilitation
to compensate for spatial and temporal deficiencies.
Selected peer-reviewed scientific publications and scientific
presentations:
http://uripolat.files.wordpress.com/2012/06/srep00278.pdf
Training the brain to overcome the effect
of aging on the human eye
The effectiveness of the GlassesOff product was examined in a
recent study conducted at the University of California at Berkeley
and published in Nature’s Scientific Reports. This study clearly
demonstrated the significant benefit of the GlassesOff training
program for reading abilities and eye age. Moreover, cutting-edge
optometric equipment allowed the scientists to unequivocally
determine that the actual source of the observed benefits is
solely in the brain and not in the optics of the eyes.
http://uripolat.files.wordpress.com/2011/05/2004-polat-pnas-amblyopia.pdf
Improving vision in adult amblyopia by
perceptual learning
Perceptual training was applied to an adult visual system with
abnormal development of the primary visual cortex of the brain
leading to amblyopia (“lazy eye”). Training yielded significant
benefits that transfer to higher visual tasks, resulting in a
two-fold improvement in contrast sensitivity and in
letter-recognition tasks in patients between 9 and 55 years old.
This is the first evidence for a remarkable vision improvement
following perceptual learning in a condition previously
acknowledged as untreatable in adults.
http://uripolat.files.wordpress.com/2012/06/2009-practical_pl.pdf
Making perceptual learning practical to
improve visual functions
Generalization, or transfer, of gains acquired on a trained
task to other functions is crucial for both understanding the
neural mechanisms and the practical values of the training. This
study describes a perceptual learning method applied to amblyopia
(“lazy eye”), myopia (near-sightedness) and presbyopia
(age-related near vision decline). The gains were transferred to
visual acuity, processing speed and reaction time. Thus,
perceptual learning can become a practical method for improving
visual functions in people with impaired or blurred vision.
http://uripolat.files.wordpress.com/2012/06/sterkin_yehezkel_polat_vr_2012.pdf
Learning to be fast: gain accuracy with
speed
The effectiveness of perceptual learning on contrast detection
in young adults was tested using behavioral and neurophysiological
(Event-Related Potentials, ERPs) measurements. A remarkable
improvement in all behavioral measurements, including sensitivity
and reaction time, along with shorter latency and increased
amplitude of an ERP marker of neuronal interactions within the
visual cortex of the brain. Thus, perceptual learning that
strengthens inter-neuronal interaction results in a faster
processing speed and higher contrast sensitivity.
http://www.glassesoff.com/wp-content/uploads/2013/05/ARVO_2013.pdf
Digital precise remote near vision
sharpness evaluation on mobile devices
GlassesOff developed a tool for precise remote evaluation of
near vision sharpness in order to accurately and remotely estimate
reading abilities. Tested on 73 volunteers on iPhone 4, the
application better predicts the functional reading acuity due to
the brief stimuli presentation, as opposed to single letter
detection used in golden standard reading chart measurements.
http://www.glassesoff.com/wp-content/uploads/2013/05/ARVO_2012.pdf
Perceptual training on mobile devices
improves near visual functions
The resolution and quality of smart phone screens are much
better than those of PC monitors, with an average pixel size
several times smaller in Apple’s retina display than in PC
screens. This enables one to achieve better contrast sensitivity
by a factor of 2-3, thus providing more prospect for training near
visual functions.
http://www.glassesoff.com/wp-content/uploads/2013/05/AAO_2012.pdf
Perceptual training on mobile devices for
the aging human eye
Training with GlassesOff on mobile devices is an effective
solution for improving near vision sharpness in presbyopia by
enhancing image processing in the brain, with better contrast
sensitivity compared to PC.
http://uripolat.files.wordpress.com/2011/05/2009-experreviews1.pdf
Neuroplasticity following perceptual
learning for visual improvement
The aim of this review is to show that perceptual learning can
be applied for practical purposes to improve visual functions of
people with special needs. Prof. Polat predicts that perceptual
learning methodology will be modified in the near future into
complementary or standalone procedures to aid care providers in
treating and improving a variety of visual functions that are not
addressed by conventional treatment.
Diana DEUTSCH, et al.
Illusory Transformation from Speech to Song
[ PDF ]
Repetition of a spoken phrase can be
perceptually transformed to sound like song rather than
speech...
Viktor SCHAUBERGER
The Energy Evolution
( Translated & Edited by Callum Coates )
[ PDF ]
Alberto PERBELLINI / Carlo VENTURA
Epigenetic Reprograming
Nonstem adult cells can be epigenetically reprogrammed backward to
a state where they can become neural, cardiac, skeletal, muscle or
insulin-producing cells:
Use of retinoic esters of hyaluronic acid
for the differentiation of totipotent stem cells
US2006216820
The present the invention relates to a new use of retinoic of
hyaluronic acid, that exhibit pre-differentiating activity on
totipotent stem cells. The invention also relates to a process to
differentiate said stem cells and to select molecules capable of
modulating the pro-differentiating activity of those esters.
Attila ALPEREN
POWER EXTRACTION FROM PRESSURE
PESWiki.com
Pure Energy Systems News
September 18, 2013
http://TurXotorDemo.com
2013 : TurXotor Demo
On October 24-27, the Turkish government will be holding a
four-day Turkish Innovation Fair in Istanbul featuring the best
Turkish technologies of the year, and that two of the Alperen
Group technologies will be among the three on display.
On September 7, Attila Alperen told me that his Alperen™ Group's
TurXotor® motor is poised to be among the top three featured at
the event. He said that the Turkish government wants to create a
large electric car industry in Turkey around this invention that
will enable electric vehicles to never have to be plugged in, and
to be able to operate with only a few batteries on board, because
the power source is onboard, pulling energy from the environment
somehow -- harnessing the wheelwork of nature, as Tesla coined it.
TurXotor® is a motor that works as a generator at the same time --
the only system like this in the world, as far as Mr. Alperen is
aware. So the TurXotor® motor powers the wheels of the electric
vehicle -- and produces electricity at the same time, both to
replenish the source battery and provide extra for the other
electrical needs of the vehicle such as lights, radio, heat,
windows, etc.
The Alperen™ Group doesn't describe their technology as a "free
energy" technology. They shy away from words like "overunity" as
well. They depict it as merely an efficient regeneration of the
used technology. But obviously, if they are propelling a vehicle
down the road, they have to be harvesting energy from somewhere
beside the battery, if they don't have to ever recharge the
battery from an external source.
Attila said this will solve two problems presently associated with
electric cars: range, and battery costs. The range will become
unlimited, and the battery costs will be significantly reduced,
because the vehicle will only need enough to serve as a buffer for
acceleration input and deceleration harvesting of regenerative
braking. They won't be needed for storage for duration travel.
You'll be able to travel as far as you want without ever stopping
for fuel or to recharge your batteries.
This will be the first time the TurXotor® will be publicly
demonstrated. The event will enable interested parties worldwide
to see the technology demonstrated as well as discuss licensing
manufacturing of the technology. Normally, Attila is not very
accommodating for people to come and see the technology
demonstrated, so this will be a rare opportunity.
Attila said that at the event, the TurXotor® motor-generator will
be demonstrated in isolation, showing its attributes of torque,
electricity generation, and efficiency. It will also be open to
inspection, not concealed in a "black box" of any kind.
Though such a technology has a myriad of applications, at present,
the only application that is being licensed is for manufacturing
the motor to fit electric vehicles, or trains, or ships.
WO2013048352
METHOD OF POWER EXTRACTION FROM PRESSURE
The method of invention consists of the extraction and utilization
of potential energy as usable energy contained in pressurized
liquid, air, and gas which is transferred via transfer lines such
as pipes without losing the pressure values of inlet and outlet of
the system.
DESCRIPTION
The method of invention consists of the extraction and utilization
of potential energy as usable energy contained in pressurized
liquid, air, and gas which is transferred via transfer lines such
as pipes without losing the pressure values of inlet and outlet of
the system.
Every pressurized liquid, air, and gas has a usable potential
energy. In the current systems, the need for additional inlet
pressure power increases at Inlet(3) in proportion to the amount
of usable energy in the Turbine Shaft(5). Thanks to this invention
this potential energy is converted into usable energy in the
Turbine Shaft(5). Contrary to the current systems, during the
utilization of this energy in the Turbine Shaft(5), the equality
of Outlet(4) pressure power and Inlet(3) pressure power is
preserved.
The sample system showing the operating principle of the invention
consists of eight parts. These are; Turbine(l), Pressure
Preservation Chamber(2), Inlet(3), Outlet(4), Turbine Shaft(5),
alternators, generators, and loads (6) Pressure Preservation
Chamber Spaces(7), and Pressure Direction Nozzle(8).
The operating principle of the invention is as follows: In order
to generate mechanical energy, any or some of the pressurized
liquid, air, and gas applied from Inlet(3) are directed to the
Turbine(l) blades positioned in the Pressure Preservation
Chamber(2) via Pressure Direction Nozzle(8). This mechanical
energy generated in the Turbine(l) is transferred to the outside
the system via the Turbine Shaft(5) and thus the generating of
mechanical power necessary for any alternators, generators, and
loads (6) is provided. The pressure power from Inlet(3), after
applied to the Turbine(l) inside the Pressure Preservation
Chamber(2) whose internal pressure is preserved and which is kept
closed, is transferred to the outside of the system from the
Outlet(4) without losing its (inlet's) own pressure power.
Since the turbine is positioned in the Pressure Preservation
Chamber(2), the counter power applied to the Turbine(l) via the
Turbine Shaft(5) by the alternators, generators, and loads (6) is
not reflected back to the Inlet(3).
Therefore, while the pressure from Inlet(3) is transferred to the
outside of the system without losing its pressure value at
Outlet(4), the potential energy contained in this pressure power
is extracted via the Turbine Shaft(5) as usable energy.
There are no Pressure Preservation Chamber(2) and spaces in the
current available systems. As a result, the counter power of the
alternators, generators, and loads (6) is reflected back to the
Inlet(3) via the Turbine Shaft(5) and the Turbine(l). However,
thanks to this invention, the counter power is not reflected back
to the Inlet(3) since the Turbine(l,) is positioned in the
Pressure Preservation Chamber Spaces(7).
Basinçtan güç ekstraksiyon (açiga çikartma)
yöntemi.
TR201109533
Yüksek verimli türbin.
TR201107424
David CRAIK : Conotoxin Analgesic
http://www.smh.com.au/national/chronic-pain-relief-scientists-trial-nonaddictive-drug-from-snail-venom-20140317-34y5l.html
March 18, 2014
Chronic pain relief: Scientists trial
non-addictive drug from snail venom
Lucy Carroll
Venom used to paralyse their prey: The carnivorous tropical
marine cone snail.
A new drug extracted from snail venom could provide a
breakthrough in treating severe chronic pain without the risk of
addiction and dangerous side effects, researchers have found.
The venom - considered 100 times stronger than morphine - could
lead to the development of a new class of oral drugs used to
relieve nerve pain associated with injury, cancer, AIDS and
other diseases.
''It's a very exciting discovery which has the potential to be a
blueprint for other protein-based medication,'' David Craik,
lead researcher and professor of biomolecular structure at the
University of Queensland, said.
The prototype drug, which has been tested on rats, is taken from
carnivorous tropical marine cone snails, which use their venom
to paralyse their prey. The venom contains hundreds of peptides,
or ''mini proteins'', known as conotoxins, which have a
pain-killing effect.
''Snails have had 60 million years of evolution to fine-tune
their venom, which contains some very powerful molecules,'' said
Professor Craik, who will present his findings at an American
Chemical Society meeting this week.
''If we can tap into that then it saves us having to do the hard
work that evolution has already done for us,'' he said.
A preliminary study using tiny proteins from the venom ''appears
to significantly reduce pain'' in lab rats, he said. ''Our
digestive system is designed to break down proteins. What we've
done is taken a protein and re-enginered it to make it stable
enough to work orally.''
Only one conotoxin-derived drug, ziconotide, has been approved
for human use but it must be injected into the spine.
PATENTS
Novel nucleic acid molecules
AU2006200422
Cyclised conotoxin peptides
AU6070599
A novel molecule
AU784222
CYCLISED ALPHA-CONOTOXIN PEPTIDES
US8354372
TYROSINE-RICH CONOPEPTIDES
US2010093620
Cyclised alpha-conotoxin peptides
CN101448516
CYCLISED CONOTOXIN PEPTIDES
ES2308847
CYSTINE KNOT MOLECULES
US2011244564
J-SUPERFAMILY CONOTOXIN PEPTIDES
US2011064668
NOVEL NUCLEIC ACID MOLECULES
AT482975
Brajendra SHARMA, et al.
Plastic to Diesel Fuel
http://news.illinois.edu/news/14/0212bags_oil_BrajendraKumarSharma.html
http://www.sciencedaily.com/releases/2014/02/140212132853.htm
February 12, 2014
Plastic shopping bags make a fine diesel
fuel
Used plastic shopping bags can be converted into petroleum
products that serve a multitude of purposes.
by Diana Yates
Plastic shopping bags, an abundant source of litter on land and at
sea, can be converted into diesel, natural gas and other useful
petroleum products, researchers report. The conversion produces
significantly more energy than it requires and results in
transportation fuels -- diesel, for example -- that can be blended
with existing ultra-low-sulfur diesels and biodiesels.
Used plastic shopping bags can be converted into petroleum
products that serve a multitude of purposes. Plastic shopping
bags, an abundant source of litter on land and at sea, can be
converted into diesel, natural gas and other useful petroleum
products, researchers report.
The conversion produces significantly more energy than it requires
and results in transportation fuels -- diesel, for example -- that
can be blended with existing ultra-low-sulfur diesels and
biodiesels. Other products, such as natural gas, naphtha (a
solvent), gasoline, waxes and lubricating oils such as engine oil
and hydraulic oil also can be obtained from shopping bags.
A report of the new study appears in the journal Fuel Processing
Technology.
There are other advantages to the approach, which involves heating
the bags in an oxygen-free chamber, a process called pyrolysis,
said Brajendra Kumar Sharma, a senior research scientist at the
Illinois Sustainable Technology Center who led the research. The
ISTC is a division of the Prairie Research Institute at the
University of Illinois.
"You can get only 50 to 55 percent fuel from the distillation of
petroleum crude oil," Sharma said. "But since this plastic is made
from petroleum in the first place, we can recover almost 80
percent fuel from it through distillation."
Americans throw away about 100 billion plastic shopping bags each
year, according to the Worldwatch Institute. The U.S.
Environmental Protection Agency reports that only about 13 percent
are recycled. The rest of the bags end up in landfills or escape
to the wild, blowing across the landscape and entering waterways.
Plastic bags make up a sizeable portion of the plastic debris in
giant ocean garbage patches that are killing wildlife and
littering beaches. Plastic bags "have been detected as far north
and south as the poles," the researchers wrote.
"Over a period of time, this material starts breaking into tiny
pieces, and is ingested along with plankton by aquatic animals,"
Sharma said. Fish, birds, ocean mammals and other creatures have
been found with a lot of plastic particles in their guts.
Whole shopping bags also threaten wildlife, Sharma said.
"Turtles, for example, think that the plastic grocery bags are
jellyfish and they try to eat them," he said. Other creatures
become entangled in the bags.
Previous studies have used pyrolysis to convert plastic bags into
crude oil. Sharma's team took the research further, however, by
fractionating the crude oil into different petroleum products and
testing the diesel fractions to see if they complied with national
standards for ultra-low-sulfur diesel and biodiesel fuels.
"A mixture of two distillate fractions, providing an equivalent of
U.S. diesel #2, met all of the specifications" required of other
diesel fuels in use today -- after addition of an antioxidant,
Sharma said.
"This diesel mixture had an equivalent energy content, a higher
cetane number (a measure of the combustion quality of diesel
requiring compression ignition) and better lubricity than
ultra-low-sulfur diesel," he said.
The researchers were able to blend up to 30 percent of their
plastic-derived diesel into regular diesel, "and found no
compatibility problems with biodiesel," Sharma said.
"It's perfect," he said. "We can just use it as a drop-in fuel in
the ultra-low-sulfur diesel without the need for any changes."
Journal Reference:
Fuel Processing Technology, 2014; 122: 79
DOI: 10.1016/j.fuproc.2014.01.019
Brajendra K. Sharma, Bryan R. Moser, Karl E. Vermillion,
Kenneth M. Doll, Nandakishore Rajagopalan : Production,
characterization and fuel properties of alternative diesel fuel
from pyrolysis of waste plastic grocery bags.
http://www.sciencedirect.com/science/article/pii/S0378382014000290?via=ihub
Fuel Processing Technology -- Volume 122, June 2014, Pages
79–90
http://dx.doi.org/10.1016/j.fuproc.2014.01.019
Production, characterization and fuel
properties of alternative diesel fuel from pyrolysis of waste
plastic grocery bags ?
Brajendra K. Sharmaa, Bryan R. Moserb, Karl E. Vermillionb,
Kenneth M. Dollb, Nandakishore Rajagopalana
Abstract
Pyrolysis of HDPE waste grocery bags followed by distillation
resulted in a liquid hydrocarbon mixture with average structure
consisting of saturated aliphatic paraffinic hydrogens (96.8%),
aliphatic olefinic hydrogens (2.6%) and aromatic hydrogens (0.6%)
that corresponded to the boiling range of conventional petroleum
diesel fuel (#1 diesel 190–290 °C and #2 diesel 290–340 °C).
Characterization of the liquid hydrocarbon mixture was
accomplished with gas chromatography–mass spectroscopy, infrared
and nuclear magnetic resonance spectroscopies, size exclusion
chromatography, and simulated distillation. No oxygenated species
such as carboxylic acids, aldehydes, ethers, ketones, or alcohols
were detected. Comparison of the fuel properties to the
petrodiesel fuel standards ASTM D975 and EN 590 revealed that the
synthetic product was within all specifications after addition of
antioxidants with the exception of density (802 kg/m3). Notably,
the derived cetane number (73.4) and lubricity (198 µm, 60 °C,
ASTM D6890) represented significant enhancements over those of
conventional petroleum diesel fuel. Other fuel properties included
a kinematic viscosity (40 °C) of 2.96 mm2/s, cloud point of 4.7
°C, flash point of 81.5 °C, and energy content of 46.16 MJ/kg. In
summary, liquid hydrocarbons with appropriate boiling range
produced from pyrolysis of waste plastic appear suitable as blend
components for conventional petroleum diesel fuel.
1. Introduction
Plastic retail bags are ubiquitous in modern society because they
represent a convenient means to transport purchased goods from the
supermarket to the home. Plastic bags are plentiful, inexpensive
to produce, sturdy yet low weight, and easy to store and
transport. However, the same properties that make them
commercially successful also contribute to their proliferation in
the environment. Although they are recyclable, the U.S. EPA noted
that only 13% of the approximately one trillion produced in 2009
were recycled in the U.S. [1]. The remainder were disposed of in
landfills, released into the environment as litter, or used in
secondary applications by end-users eventually ending in
landfills. Plastic bags may take centuries to naturally decompose
due to their stable chemical composition [2]. In addition to being
a source of litter in urbanized areas, plastic bags exacerbate
localized flooding by clogging municipal drainage systems and
constitute a significant portion of floating anthropogenic marine
debris [3], [4] and [5]. In fact, plastic bags contribute to the
so-called Great Pacific Garbage Patch of floating refuse in the
Pacific Ocean and have been detected as far north and south as the
poles [3], [4] and [5]. Once in the environment, plastic bags are
lethal to animals that ingest or become entangled in them [6], [7]
and [8]. Because of these and other factors, various regional and
national governments have banned or are contemplating bans or fees
on plastic bags [9].
Standard plastic bags consist of thin polyethylene (PE) sheets
produced commercially from polymerization of ethylene. PE is
divided into categories based on density and molecular branching
frequency. The two types most important to production of plastic
bags are low-density PE (LDPE) and high-density PE (HDPE). HDPE is
a copolymer with up to 1% 1-butene and is made historically with
either Cr or Ziegler catalysts at 1–16 MPa at temperatures as low
as 60 °C. More recently, single site catalysts such as
metallocenes have been employed [10]. LDPE is produced at high
temperatures (200–300 °C) and supercritical ethylene pressures
(130–260 MPa) using peroxide-free radical initiators [10]. HDPE is
a linear copolymer with a density range of 0.945–0.965 g/cm3
whereas LDPE is branched with densities ranging from 0.915 to
0.925 g/cm3[10]. Due to these differences in structure, the
crystalline melting point, softening point and tensile strength of
LDPE are considerably lower than the corresponding values for HDPE
[10]. However, LDPE shows higher elongation at break and higher
impact strength than does the more rigid HDPE [10]. It is also
translucent rather than opaque due its lower crystallinity (55%)
relative to HDPE (85–95%) [10]. HDPE is more commonly utilized for
production of plastic bags due to its greater tensile strength
coupled with its less energy-intensive production process.
Pyrolysis is defined as the irreversible anaerobic thermochemical
decomposition of material at elevated temperature (300 + °C). The
principal benefit of pyrolysis is conversion of low energy density
substrates into higher density liquid (bio-oil) and solid
(biochar) fractions. A low-density volatile (syngas) fraction is
also produced. Pyrolysis has been utilized for millennia to
produce charcoal and coal. More recently, pyrolysis is used to
produce charcoal, activated carbon, coke, carbon fiber, and
methanol, among others. The distribution of products (bio-oil,
biochar and syngas) is dependent on the type of pyrolysis,
reaction conditions and feedstock. Pyrolysis is classified into
four categories: slow, fast, flash, and gasification. Of these,
fast and flash pyrolysis maximizes bio-oil production, slow
pyrolysis augments the yield of biochar and gasification maximizes
syngas production. With regard to production of liquid
transportation fuels, fast or flash pyrolysis is employed to
produce bio-oil [11], [12], [13] and [14]. The properties and
composition of bio-oil such as high moisture and heteroatom
content, presence of oxygenates such as organic acids, and broad
distillation curve prevent its direct use as a transportation
fuel; thus upgrading such as hydroprocessing and distillation is
necessary [14], [15] and [16].
Fast or flash pyrolysis has been reported on biological materials
such as wood [13], triglycerides [17], grasses [18], shrubs [19],
corn cobs and stover [20], alfalfa [21], oilseed presscakes [22],
and pig compost [23], among others. Examples of fast pyrolysis on
non-biological feedstocks include scrap tires [24] and [25],
sewage sludge [25], general municipal solid waste [26], waste
electrical and electronic equipment [27], and various plastics
[25], [28], [29], [30], [31], [32], [33], [34], [35] and [36]. The
plastics include polystyrene [30], [31] and [32], poly(vinyl
chloride) [30] and [31], polypropylene [31], [32], [33] and [34],
PE terephthalate [32], acrylonitrile–butadiene–styrene [32], and
PE [30], [31], [32], [35] and [36]. In some cases plastics were
co-pyrolyzed with other materials such as waste motor oil [32].
With regard to fast pyrolysis of PE, pyrolysis of LDPE [30], HDPE
[35] and [36] and various mixtures [31] and [32] was reported. In
all PE studies, the properties of the resulting bio-oils were not
reported, nor were the upgrading to fuel-grade hydrocarbons and
subsequent fuel property determination.
The objective of our study was the production, characterization
and evaluation of alternative diesel fuel from pyrolysis of HDPE
waste grocery bags. Comparison of our pyrolyzed polyethylene
hydrocarbons (PPEH) with conventional petroleum-derived ultra-low
sulfur (< 15 ppm S) diesel (ULSD) fuel was a further objective,
along with a comparison to petrodiesel standards such as ASTM D975
and EN 590 (Table 1). Blends of PPEH with ULSD and biodiesel were
prepared and the resultant fuel properties measured. It is
anticipated that these results will further understanding of the
applicability and limitations of HDPE as a feedstock for the
production of alternative diesel fuel.
Table 1. Fuel properties of pyrolyzed polyethylene hydrocarbons
(PPEH) and ULSD along with a comparison to petrodiesel fuel
standards.a
2. Materials and methods
2.1. Materials
Plastic HDPE grocery bags were collected from local retailers and
represent the typical ones used in grocery stores. Summer grade
ULSD was donated by a major petrochemical company. With the
exception of conductivity and corrosion inhibitor additives, ULSD
contained no performance-enhancing additives. Soybean oil methyl
esters (SME) were donated by a BQ-9000 certified commercial
producer. All other chemicals were obtained from Sigma-Aldrich
Corp (St. Louis, MO). All materials were used as received.
2.2. Pyrolysis of HDPE to produce plastic crude oil
Thermochemical conversion of plastic grocery bags (HDPE) to oils
were conducted using a pyrolysis batch reactor in triplicate.
Pyrolysis was performed in a Be-h desktop plastic to oil system
(E-N-Ergy, LLC, Mercer Island, WA) containing a 2 L reactor and
oil collection system using approximately 500 g of plastic grocery
bags each time. The pyrolysis reactor has two heating zones (upper
and lower); the upper and lower temperatures were set to 420 and
440 °C, respectively. Once the reactor reached the set
temperatures, a reaction time of 2 h was employed from that point
on. Vapors produced as a result of pyrolysis were condensed over
water as plastic crude oil (PCO). The upper oil layer was
separated and weighed. The reactor lid was opened once the
temperature was below 50 °C to remove the remaining residual solid
material and weighed separately. The mass balance yields were
calculated as the ratio of the corresponding product phase (liquid
and solid) obtained in 12 batch experiments to the initial
feedstock mass. Lastly, the gas-phase yields were calculated based
on the resulting mass difference.
2.3. Distillation of plastic crude oil to yield diesel-range
hydrocarbons
Distillation of PCO was performed in a Be-h desktop plastic to oil
system. A known amount of PCO (1 L) was added to the Be-h reactor
vessel. The oil collection tank was cleaned by removing the water
and dried before starting distillation. For collecting the
gasoline equivalent fraction (< 190 °C), the upper and lower
temperatures were set to 175 and 190 °C, respectively. Once the
liquid stopped dripping into the collection vessel, the gasoline
equivalent fraction was removed, filtered, and weighed to provide
yield. The upper zone temperature was then raised to 275 °C and
lower zone to 290 °C to collect a #1 diesel equivalent fraction
(190–290 °C). The # 2 diesel equivalent fraction (290–340 °C) was
then collected by setting the upper zone temperature to 330 °C and
lower zone to 340 °C. The material remaining in the reactor vessel
was an atmospheric residue equivalent fraction (> 340 °C),
which was removed using a siphon pump once the reactor temperature
was below 50 °C. All fractions except the atmospheric residue
equivalent (> 340 °C) were filtered through Whatman filter
paper #4 to remove residual solid particles.
2.4. Chemical characterization of plastic oil fractions
2.4.1. Gas chromatography–mass spectroscopy (GC–MS)
2.4.2. Simulated distillation by GC–FID
2.4.3. Size exclusion chromatography (SEC) analysis
2.4.4. NMR and FT-IR spectroscopy
2.5. Fuel properties
2.6. Preparation of PPEH–petrodiesel blends
3. Results and discussion
3.1. Preparation and chemical composition of pyrolyzed
plastics
The pyrolysis temperature range of 420–440 °C was chosen based on
previous studies [34]. These temperatures resulted in
decomposition reactions of HDPE to provide hydrocarbons of
different chain lengths. Pyrolysis of waste plastic grocery bags
at temperatures of 420–440 °C provided 74% yield of liquid product
referred to as PCO, as shown in Fig. 1. Although not determined in
the present paper, literature data suggested gaseous product
obtained from pyrolysis of PE consisted primarily of ethane and
ethene (C2, 52%) and C4 (32%) compounds [34]. The higher solid
residue yield (17%) is likely due to the inorganic content and/or
char content and/or unconverted HDPE. As the pyrolysis of PE has
higher activation energy (280–320 kJ/mol) compared to
polypropylene (190–220 kJ/mol), therefore, increasing the
pyrolysis temperature to certain extent could result in increased
amounts of the liquid fraction [34]. Also, this residue may have
been the fraction boiling above 420 °C (analogous to the higher
boiling vacuum gas oil fraction, VGO from petroleum distillation).
Further thermal cracking of this product could have been achieved
by increasing pyrolysis temperature and/or time, which we
speculate would have resulted in higher yields of the desired PCO
fraction. This residue along with the VGO fraction from PCO have
potential to be used as lubricant basestocks, which upon further
refining such as dewaxing/wax isomerization may yield API Group
II/III lubricant base oils.
The PCO thus obtained after pyrolysis of waste plastic grocery
bags was distilled into four fractions (< 190; 190–290;
290–340; and 340 + °C equivalent of motor gasoline (MG), diesel#1
(PPEH-L), diesel#2 (PPEH-H) and VGO respectively. The product
yields are represented in Fig. 2. Similar results were obtained
from SimDist analysis of PCOs with maximum coefficient of
variation ranging from 0 to 7% (Table 2). In the absence of a
catalyst, the major product is PPEH-L (41%). The product
distribution can be changed with the use of zeolite catalysts such
as ZSM-5, which will increase conversion to more low boiling
products, such as MG and PPEH-L [34].
Fig. 2. Distillate fractions yield (%) on distillation.
Table 2. Distillate fraction yields (wt.%) of plastic crude
oils (PCO) using simulated distillation (HTGC–FID).
Elemental analysis of waste plastic grocery bags and PCO fractions
revealed less than 0.5% nitrogen content and less than 0.7% oxygen
content (Table 3). As expected, waste plastic grocery bags have an
empirical formula of CH2.1N0.005O0.007 quite similar to that of
polyethylene (CH2). Higher carbon and hydrogen content and lower
oxygen and nitrogen content resulted in a higher calculated HHV
[37], [38] and [39] of 49–50 MJ/kg for most of the fractions,
making these high energy liquid fuels
(Table 3). The calculated values were slightly higher than the
actual determinations (Table 1)...
The boiling point distribution of PCO fractions was obtained using
high temperature GC–FID. Table 2 shows that the method developed
for boiling point distribution was repeatable with a CV of less
than 7% for distribution of various fractions in PCO and was
similar to actual distillation data. All PCOs contained a large
percentage of fraction 2 (PPEH-L) followed by PPEH-H and MG.
Around 98% of the PCO was distilled under 400 °C, which is a good
range for producing various fuels such as naphtha,
gasoline, aviation fuel, diesel, and fuel oil. The boiling point
distribution of PCO and its four fractions is shown in Fig. 3. As
boiling point and MW distribution of PCO were similar to petroleum
fractions and contained negligible heteroatom content, therefore,
we speculate that these PCOs will be compatible with petroleum
crude oil for refining in a conventional refinery. The
compatibility is further depicted in 10–50% blends of PPEH in ULSD
as shown in Fig. 4. As the PPEH content increased in ULSD, the
boiling point distribution shifted towards the higher boiling
range, although overall the mixture remained within the boiling
range of diesel fuel...
Depicted in Table 7 and Table 8 are fuel properties of PPEH-L
(Table 7) and PPEH-H (Table 8) blended with ULSD. For each sample,
blends of 10 (P10), 20 (P20), 30 (P30), 40 (P40) and 50 (P50)
vol.% in ULSD were investigated. With regard to cold flow
properties, as the percentage of PPEH-L increased in blends with
ULSD, values for CP, CFPP and PP became progressively lower due to
the superior low temperature performance of PPEH-L relative to
ULSD. In the case of PPEH-H, the opposite trend was elucidated in
which cold flow properties (CP and PP) deteriorated as the
concentration of PPEH-H in ULSD increased. CFPP of PPEH-H was not
measured due to insufficient sample. Similarly, oxidative
stability decreased as the percentage of PPEH increased in blends
with ULSD. Comparison to the IP specification in EN 590 revealed
that only the P10–30 blends of PPEH-H were above the minimum
specification of 20 h. Results obtained from measurement of OT
corroborated those obtained for IP: deterioration of stability as
the concentration of PPEH increased in ULSD as indicated by
progressively lower OTs.
Table 7. Fuel properties of pyrolyzed polyethylene hydrocarbons
(PPEH-L) blended with ULSD.a
3.4. Influence of blending biodiesel with PPEH
...It was found that diesel obtained from pyrolysis of plastic is
as compatible with biodiesel as ULSD due to quite similar
hydrocarbon structures and chain length distribution of molecules.
4. Conclusions
Pyrolysis of HDPE waste plastic grocery bags followed by
distillation resulted in a major liquid hydrocarbon product
(PPEH-L) with average structure consisting primarily of saturated
aliphatic paraffinic hydrogens (94.0%) and smaller amounts of
aliphatic olefinic hydrogens (5.4%) and aromatic hydrogens (1.0%)
that corresponded to the boiling range typical of conventional
petroleum diesel fuel (190–290 °C). Negligible
heteroatom-containing species were detected from elemental
analysis. Also obtained was a heavier boiling fraction (290–340
°C) equivalent of diesel#2 from distillation of the crude
pyrolysis product, PPEH-H, which also consisted of paraffinic
protons (96.8%), olefinic protons (2.6%) and aromatic protons
(0.6%). Based on the results obtained after determination of fuel
properties and comparison to petrodiesel standards, the following
conclusions were made regarding the applicability of these
materials as alternative liquid transportation fuels:
1. PPEH-H is more appropriate as an alternative diesel fuel
because it exhibited higher values for FP, IP, KV, DCN, HHV,
density, and lubricity than PPEH-L.
2. PPEH-H, after addition of antioxidants, met all ASTM D975 and
EN 590 fuel specifications with the exception of density in the
case of EN 590.
3. PPEH-L did not meet EN 590 specifications for IP, KV, FP, and
density due to its higher content of lower MW constituents.
4. A 1:1 mixture of PPEH-H and PPEH-L met all ASTM D975 and EN 590
specifications with the exception of density and IP in case of EN
590, therefore PPEH-L and PPEH-H distillates can be collected
together to provide ~ 64% diesel equivalent fraction from
pyrolysis of plastic grocery bags.
5. P10–P30 blends of PPEH-H with ULSD met all ASTM D975
specifications whereas only the P20–P30 blends met all EN 590
limits. P40 and P50 blends require antioxidants to meet the
oxidative stability specification listed in EN 590.
6. P10 blend of PPEH-L with ULSD met all ASTM D975 specifications
except lubricity, while none of the blends of PPEH-L with ULSD met
EN 590 specifications primarily due to poor DCN, IP, FP, and KV.
7. Diesel obtained from pyrolysis of plastic is as compatible with
biodiesel as ULSD due to similar hydrocarbon structures and chain
length distribution of molecules.
8. Biodiesel blends with PPEH-H met the specifications for
lubricity and KV, while PPEH-L blends satisfied the lubricity
limits, but not KV limits. PPEH-L improved low temperature
properties of SME biodiesel whereas PPEH-H had the opposite
effect.
Based on these findings, PPEH-H and a mixture of PPEH-H/PPEH-L are
suitable blend components for ULSD in the P10–P50 blend range so
long as antioxidants are employed...
Zhe Liu, et al.
ZL-105 vs Cancer
http://www2.warwick.ac.uk/newsandevents/pressreleases/new_drug_raises/
New drug raises potential for cancer
treatment revolution
A revolution in cancer treatment could soon be underway following
a breakthrough that may lead to a dramatic improvement in cancer
survival rates.
A new study at the University of Warwick, published today in the
journal Angewandte Chemie International Edition, has developed a
new drug that can manipulate the body’s natural signalling and
energy systems, allowing the body to attack and shut down
cancerous cells.
Called ZL105, the drug is a compound based on the precious metal
iridium. The study has found ZL105 could potentially replace
currently used anticancer drugs, which become less effective over
time, cause a wide-range of side-effects and damage healthy cells
as well as cancerous.
Commenting on the breakthrough, University of Warwick researcher
and study co-author Dr Isolda Romero-Canelon said “The
energy-producing machinery in cancer cells works to the limit as
it attempts to keep up with quick proliferation and invasion. This
makes cancer cells susceptible to minor changes in the cell
‘power-house’. Our drug pushes cancer cells over the limit causing
them to slow and shut down, whilst normal cells can cope with its
effects”.
Preliminary data indicate that the novel drug may be ten times
more effective in treating ovarian, colon, melanoma, renal, and
some breast cancers, according to data obtained by the US National
Cancer Institute. The researchers now aim to expand the study to
cancers that are inherently resistant to existing drugs and to
those which have developed resistance after a first round of
chemotherapy treatments.
Study co-author Professor Peter J. Sadler said “Existing cancer
treatments often become less effective after the first course, as
cancer cells learn how they are being attacked. The drug we have
developed is a catalyst and is active at low doses. It can attack
cancer cells in multiple ways at the same time, so the cancer is
less able to adapt to the treatment. This means the new drugs
could be much more effective than existing treatments.”
“Platinum-based drugs are used in nearly 50% of all
chemotherapeutic regimens, exert their activity by damaging DNA
and cannot select between cancerous and non-cancerous cells,
leading to a wide-range of side-effects from renal failure to
neurotoxicity, ototoxicity, nausea and vomiting.
“In contrast, the new iridium-based drug is specifically designed
not to attack DNA, but to have a novel mechanism of action,
meaning that it could not only dramatically slow down and halt
cancer growth, but also significantly reduce the side effects
suffered by patients” argues Professor Sadler.
This research could also lead to substantial improvements in
cancer survival rates. “Current statistics indicate that one in
every three people will develop some kind of cancer during their
life time, moreover approximately one woman dies of ovarian cancer
every two hours in the UK according to Cancer Research UK .It is
clear that a new generation of drugs is necessary to save more
lives and our research points to a highly effective way of
defeating cancerous cells” said Dr Romero-Canelon.
http://onlinelibrary.wiley.com/doi/10.1002/anie.201311161/abstract;jsessionid=487D95E3B88B65F3288F6BC1F5D4638E.f01t03
Angewandte Chemie International Edition, Vol. 53 Issue 13
DOI: 10.1002/anie.201311161
11 MAR 201
The Potent Oxidant Anticancer Activity of
Organoiridium Catalysts
Dr. Zhe Liu, Dr. Isolda Romero-Canelón, Bushra Qamar, Jessica M.
Hearn, Dr. Abraha Habtemariam, Dr. Nicolas P. E. Barry, Dr. Ana M.
Pizarro, Dr. Guy J. Clarkson and Prof. Dr. Peter J. Sadler
Abstract
Platinum complexes are the most widely used anticancer drugs;
however, new generations of agents are needed. The
organoiridium(III) complex [(?5-Cpxbiph)Ir(phpy)(Cl)] (1-Cl),
which contains p-bonded biphenyltetramethylcyclopentadienyl
(Cpxbiph) and C^N-chelated phenylpyridine (phpy) ligands,
undergoes rapid hydrolysis of the chlorido ligand. In contrast,
the pyridine complex [(?5-Cpxbiph)Ir(phpy)(py)]+ (1-py) aquates
slowly, and is more potent (in nanomolar amounts) than both 1-Cl
and cisplatin towards a wide range of cancer cells. The pyridine
ligand protects 1-py from rapid reaction with intracellular
glutathione. The high potency of 1-py correlates with its ability
to increase substantially the level of reactive oxygen species
(ROS) in cancer cells. The unprecedented ability of these iridium
complexes to generate H2O2 by catalytic hydride transfer from the
coenzyme NADH to oxygen is demonstrated. Such organoiridium
complexes are promising as a new generation of anticancer drugs
for effective oxidant therapy.
NOVEL IRIDIUM/RHODIUM ANTI-CANCER COMPOUNDS
US2013065864
Inventor: HABTEMARIAM ABRAHA/LIU ZHE [GB] (+3)
Also published as: WO2011148124 / EP2575801
/ CN102905705 / CA2797921 / AU2011257002
The present invention relates to novel iridium and/or rhodium
containing complexes for use as a cytotoxic, such as an
anti-cancer agent. There is also provided a method of preparing
said compounds.
FIELD OF THE INVENTION
[0001] The present invention relates to novel iridium and/or
rhodium containing complexes for use as cytotoxic, such as
anti-cancer agents. There is also provided a method of preparing
said compounds.
BACKGROUND OF THE INVENTION
[0002] A significant development of organometallic chemistry in
recent years has been the increasing use of
pentamethylcyclopentadienyl compounds. Not only are such compounds
usually more soluble in organic solvents and more readily
crystallized than their unsubstituted cyclopentadienyl analogs,
but they are generally more stable as a result of the steric and
electron-donation effects of the five methyl groups. This is
particularly so for the
([eta]<5>-pentamethylcyclopentadienyl)iridium complexes,
where the [eta]<5>-C5Me5 acts as an excellent ligand toward
Ir(III) since it is displaced only with considerable
difficulty.<1 >
[0003] Sheldrick's group in Germany has studied the biological
activity of ([eta]<5>-pentamethyl cyclopentadienyl)iridium
complexes with polypyridyl ligands. Their work focuses on the
intercalative binding properties of polypyridyl (pp) ligands
(pp=dpq, dppz and dppn) into DNA. Recently they have showed that
[([eta]<5>-C5Me5)IrCl(dppz)](CF3SO3) and
[([eta]<5>-C5Me5)Ir((NMe2)2CS)(dppn)](CF3SO3)2 possess in
vitro cytotoxic activity towards MCF-7 and HT-29 cancer cell
lines, while [([eta]<5>-C5Me5)Ir(phen)Cl](CF3SO3) and
[([eta]<5>-C5Me5) Ir(en)Cl](CF3SO3) are inactive against
MCF-7 (breast cancer).<2 >Furthermore they have studied the
influence of polypyridyl ligands (pp=dpq, dppz and dppn) and
monodentate ligands (L-Cl, (NH2)2CS, (NMe2)2CS) on DNA
intercalation (see FIG. 1).<3 >They also found that the
complexes [IrCl3(DMSO)(pp)] (pp=phen, dpq, dppz, dppn), (FIG. 1),
are potent cytotoxic agents toward the human cell lines MCF-7 and
HT-29 and their IC50 values are dependent on the size of the
polypyridyl ligands.<4 >Their work on iridium and rhodium
polypyridyl complexes of general formula [Me(hal)3(sol)(pp)], in
which hal is a halogenide and sol is a solvent, is described in
EP2072521.
[0004] DNA binding of the type
[([eta]<5>-C5Me5)Ir(Aa)(dppz)](CF3SO3)n containing
S-coordinated amino acids has been studied and X-ray structure of
[([eta]<5>-C5Me5)Ir(9-EtG)(phen)](CF3SO3)2 has been
reported.<5 >
[0005] The biological activity of three novel indium(III)
complexes with 1,2-naphthoquinone-1-oximato ligand are also
described.<6 >The complex [([eta]<5>-C5Me5)Ir
(pyTz)Cl]<+ >containing the 2-(pyridine-2-yl)thiazole (pyTz)
N,N-chelating ligand is reported to be inactive towards human
ovarian cancer cell lines A2780 and A2780cisR
(cisplatin-resistant)...
[0072] Examples of cancers which may be treated by the active
compounds include, but are not limited to, a carcinoma, for
example a carcinoma of the bladder, breast, colon (e.g. colorectal
carcinomas such as colon adenocarcinoma and colon adenoma),
kidney, epidermal, liver, lung, for example adenocarcinoma, small
cell lung cancer and non-small cell lung carcinomas, oesophagus,
gall bladder, ovary, pancreas e.g. exocrine pancreatic carcinoma,
stomach, cervix, thyroid, prostate, or skin, for example squamous
cell carcinoma; a hematopoietic tumour of lymphoid lineage, for
example leukemia, acute lymphocytic leukemia, B-cell lymphoma,
T-cell lymphoma, Hodgkin's lymphoma, non-Hodgkin's lymphoma, hairy
cell lymphoma, or Burkett's lymphoma; a hematopoietic tumor of
myeloid lineage, for example acute and chronic myelogenous
leukemias, myelodysplastic syndrome, or promyelocytic leukemia;
thyroid follicular cancer; a tumour of mesenchymal origin, for
example fibrosarcoma or habdomyosarcoma; a tumor of the central or
peripheral nervous system, for example astrocytoma, neuroblastoma,
glioma or schwannoma; melanoma; seminoma; teratocarcinoma;
osteosarcoma; xenoderoma pigmentoum; keratoctanthoma; thyroid
follicular cancer; or Kaposi's sarcoma.
[0073] Preferred cancers include leukaemia, CNS cancer, melanoma,
prostrate cancer, colon cancer, breast cancer or any selection
thereof.
Osmium (ii) arene azo anti-cancer complexes
CN103108880
http://onlinelibrary.wiley.com/doi/10.1002/anie.201311161/abstract;jsessionid=487D95E3B88B65F3288F6BC1F5D4638E.f01t03
Angewandte Chemie International Edition, Vol. 53 Issue 13
DOI: 10.1002/anie.201311161
11 MAR 2014
The Potent Oxidant Anticancer Activity of Organoiridium
Catalysts†
Dr. Zhe Liu, Dr. Isolda Romero-Canelón, Bushra Qamar,
Jessica M. Hearn, Dr. Abraha Habtemariam, Dr. Nicolas P. E.
Barry, Dr. Ana M. Pizarro, Dr. Guy J. Clarkson and Prof. Dr.
Peter J. Sadler
Abstract
Platinum complexes are the most widely used anticancer drugs;
however, new generations of agents are needed. The
organoiridium(III) complex [(?5-Cpxbiph)Ir(phpy)(Cl)] (1-Cl),
which contains p-bonded biphenyltetramethylcyclopentadienyl
(Cpxbiph) and C^N-chelated phenylpyridine (phpy) ligands,
undergoes rapid hydrolysis of the chlorido ligand. In contrast,
the pyridine complex [(?5-Cpxbiph)Ir(phpy)(py)]+ (1-py) aquates
slowly, and is more potent (in nanomolar amounts) than both 1-Cl
and cisplatin towards a wide range of cancer cells. The pyridine
ligand protects 1-py from rapid reaction with intracellular
glutathione. The high potency of 1-py correlates with its ability
to increase substantially the level of reactive oxygen species
(ROS) in cancer cells. The unprecedented ability of these iridium
complexes to generate H2O2 by catalytic hydride transfer from the
coenzyme NADH to oxygen is demonstrated. Such organoiridium
complexes are promising as a new generation of anticancer drugs
for effective oxidant therapy.