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topics in chemsitry

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Timothy Sutter

unread,
Nov 19, 2012, 7:48:41 PM11/19/12
to
here's on e generalized educational website from
an organization called RCC "advances in chemical science"

this is a very wide ranging subject which addresses
a wide variety of interdsciplinary subjects and topics

quantum mechanics molecular biology evolutionary
biology genetics dna chemistry cosmology etc.
are all fair game in a chemical discussion.




==========

http://www.rsc.org/Education/EiC/topics/Free_to_access_articles.asp


Another brick in the whorl
Cross-examining the scientists on the inside of advanced fingerprinting
research


The International Chemistry Olympiad
This summer Washington DC eagerly awaited the world's finest sixth
form chemists to compete in the 44th International Chemistry Olympiad


Concluding a cosmic chemical census
Scientists are preparing to say goodbye to Herschel,
the largest ever space telescope


Dyeing for a place in the sun
Can dye-sensitised solar cells compete with silicon and emerging
alternatives? Performance and flexibility allow business to design for
light


Jump-starting lectures
There is an emerging trend towards using pre-lecture activities
to support tertiary level learning: the options investigated


Rise of the molecular machines
Chemists are putting molecules to work
in ways only limited by our imagination


Unlocking video: 24/7 learning for the iPod generation
The capability to produce high quality video is now literally
in the palm of your hand. Find out how video can be used to
enhance your teaching and support your students' learning....


The chemistry of pottery
Pottery vessels have been made for around 18,000 years. But how
does clay extracted from the earth become a colourful pot,
and what's the chemistry behind the process?


Chemistry with lasers
The Lasers for Science Facility in Harwell, UK, lets chemists see
and manipulate chemical and biological systems. This research has
a direct impact on our everyday lives.


Faster than a speeding bullet...
In 2014 a small team from the UK will dispatch a car to Africa with
the aim of it speeding across the desert at 1000 mph. We find out
how chemistry powers the car to success


What's in your strawberries?
Why are strawberries so irresistible? Do the strawberries you pick
in the wild really taste nicer than shop-bought ones?


Thermoelectric materials: efficiencies found in nanocomposites
Thermoelectric materials can be assembled into mechanical structures
which can transform heat to electrical energy. They can be used
for heat harvesting and refrigeration.


Podcasting: support and enrich chemistry education
Podcasts are an easy and cheap way to provide supporting resources
to enhance student learning. Find out why you should join in and
prepare your own with this useful 'how to' guide...


Nitrous oxide: are you having a laugh?
Since its discovery, laughing gas has played its part in our
dental surgeries, operating theatres and - more controversially
- at our parties


Trouble in the periodic table
As chemists we see the periodic table as an icon but its design
continues to evolve and is the source of much debate


Protecting chemical innovations
Researchers can protect their chemical inventions from competitors
with patents but this is a long and complex process which needs expert
guidance


Enhancing teaching using tactile objects
Kinaesthetic learners learn by doing rather than by seeing and hearing.
Introducing objects to examine and discuss in class can enhance
the learning experience


Ruthenium compounds as anticancer agents
New ruthenium-based compounds with fewer and less severe side effects,
could replace longstanding platinum-based anticancer drugs

2011

Research at ISIS
ISIS acts as a super-sensitive microscope. Researchers working at the
cutting edge of science use neutrons to find out where atoms are
inside materials and what they are doing


Teaching chemistry in 3D using crystal structure data
Fundamental topics such as stereochemistry are taught in 2 or 2.5 D
- the Cambridge Structural Database provides an interactive 3D solution


Did molybdenum control evolution on Earth?
Recent discoveries indicate that our atmosphere was not always oxygen
rich
- molybdenum could have been the limiting factor in the evolution of
life on earth


A healthy, wealthy, sustainable world
..won't happen without chemists. We need a new generation of young
chemists to avoid becoming an undernourished, impoverished,
unsustainable world.


Biomimetics
The next generation of functional materials will need to include
aniostropic (directionally dependent) crystals. But how has nature
been the source of inspiration for these?


Symmetry of buckminsterfullerene
Both Euler's formula and Descartes' theorem can be used to show
how buckyballs are made from closed cages of carbon pentagons and
hexagons


Chemical bonding
A masterclass in teaching the topic of bonding,
basing chemical explanation on physical forces


Diamond Light Source: illuminating chemistry
Synchrotron light allows chemists to see within structures
and individual atoms, without disrupting samples


Four Curie centennial elements
The four Curie elements provide us with an interesting tour
of the bottom of the periodic table for the International Year of
Chemistry


Giving fossil fuels the chop
Axe Valley Biodiesel - a case study on partnership
between school, university and business


Really cheesy chemistry
Stilton, camembert, limburger and cheddar - why, and
how, does cheese come in such a variety of smells and tastes?


Entropy - a masterclass
The concept of entropy might seem abstract, but
can be illustrated by a statistical interpretation

2010

The curious story of toxic ice
In 1944 a fake article was submitted and published as a
scientific paper. In the context of How Science Works,
can a hoax have educational value?


Two-step bromine attack
An experiment for the classroom to show that bromine
adds to an alkene by two-step electrophilic addition


Iron ocean seeding
Carbon sequestration - the removal of carbon dioxide
from the atmosphere - is an active area of research


Single molecule sequencing
The first draft sequence of the human genome,
announced 10 years ago, was time-consuming and expensive


The importance of weak forces
London dispersion forces - instantaneous dipole-induced
dipole attractions - are extremely short ranged


Black paper
Flexible carbon nanotube paper is now available
for use in high-tech electronics


Look who discovered caesium
Although Robert Bunsen and Gustav Kirchhoff are often
credited with the discovery of caesium, this honour
belongs to Carl Setterberg


Mass spectrometry - the early days
1912, physicist Joseph John (J. J.) Thomson discovers mass spectrometry


A problem shared - the Singapore experience
Problem-based learning (PBL) gives students opportunities
for collaborative as well as self-directed learning


Five rings good, four rings bad
Fifty years ago steroid abuse among sportsmen and women
was a serious problem. Today, thanks to the skills of
analytical chemists, the sporting cheats rarely win


New challenges for photocatalysts
Titania catalysts are being used to keep hospital
surfaces clean and to produce hydrogen in solar cells

2009

Potato packaging
Chemists design new plastics from natural carbohydrates


Chemical tornadoes
An alternative and inspirational way to demonstrate
acid-base reactions and fluorescence and chemiluminescence


Sonochemistry - beyond synthesis
Sonochemistry, the use of sound energy to induce physical
or chemical changes within a medium, has a growing number
of applications in fields such as medicine and nanotechnology


Survival of the fittest
Examples of natural products produced by organisms and
plants to overcome competing species and predators
provide chemical evidence for Darwin's legacy of natural selection


What is entropy?
What's the best way to introduce to your students
this most misunderstood of thermodynamic properties?


Biofuels: the next generation
Chemists look to develop second-generation biofuels made
from dead wood, algae and genetically-engineered microorganisms


Crop protection chemicals
By 2030, the world's population is expected to rise to over
eight billion - the need for safe and environmentally
friendly crop protection chemical has never been greater


Investigations get real
What real chemists do can be the basis of motivating
investigations and learning in school chemistry

2008

Radioactivity discovered
Centenary celebrations for the founding fathers of
radioactivity - Henri Becquerel and Ernest Rutherford.


The ambassadors
Undergraduate chemists get the opportunity to
teach as part of their degree course.


The power of NMR: in two and three dimensions
Over the past 30 years chemists have developed NMR experiments
in two and three dimensions that enable them to solve the
structure of complex organic compounds


Multiple-choice tests - are they fit for purpose?
Of what value are multiple-choice tests in the
new GCSE Science specifications?


The power of NMR: the beginnings
Originally a curiosity of the quantum world, NMR is
now an essential tool for chemists, biochemists and clinicians


From waxes to riches
Supercritical carbon dioxide can be used to remove valuable
chemicals, including waxes, from plants, the most widely
available and cheap source of biomass in the world


George III, indigo and the blue ring test
Can urine test offer insight into George III's insanity?


Battery power
Chemical reactions to power a host of different cells and batteries


CF3SF5 - a 'super' greenhouse gas
Trifluoromethyl sulfur pentafluoride - a byproduct of the
electronics industry - has been named a 'super' greenhouse
gas by physical chemists

Biosensors based on DNA
Chemists are developing new medical and environmental
sensors based on DNA sequences which have been selected
to bind certain targets such as cancer markers in blood

Halogenating enzymes in organic syntheses
The use of haloperoxidases, from seaweed, in organic syntheses is
simple and cost-effective and offers more environmentally-friendly
routes to a host of compounds


Experimental nanoscience for undergraduates
The recent development of low cost, user-friendly scanning
tunnelling microscopes has brought nanoscience experiments
into undergraduate laboratories


Good lab practice
Students who want to work as analytical chemists in industry need
to be introduced to the basic regulatory requirements of 'good
laboratory practice'


Photochromism in view
A context-based chemistry practical highlighting the importance
of chemical kinetics and spectroscopy in commercial photochromic dyes


Fighting cancer - the early years
Research and development of nitrogen mustards 60 years ago sets the
scene for new era in the treatment of cancer


Nanomedicine arrives
Nanoscale chemical entities target the building blocks of biology with
medicinal consequences


Antimony revisited
The intriguing chemistry of antimony, one of the earliest elements to be
discovered


E-learning in practice
Making the most of the Internet and ICT to support teaching and learning
in science


Librium and Valium - anxious times
This year marks the 100th anniversary of the birth of Leo Sternbach,
discoverer of the anti-anxiety drugs Librium and Valium


Deadly things come in small packages
Painstaking work by chemists to characterise deadly alkaloids exuded in
the skin of some brightly coloured poison arrow frogs has offered leads
for new and useful pharmaceuticals

Better than antibiotics?
Chemicals that make bacteria lose their hair could be a new weapon in
the fight against infections, and at the same time help to overcome the
problem of antibiotic resistance


Supercritical processing
Chemists at the University of Nottingham use supercritical fluids to
process polymers for drug delivery systems and for tissue engineering.


Magnetic resonance imaging (MRI)
Magnetic resonance imaging (MRI) is an invaluable tool in diagnostic
medicine.

2007

Fuelling the future: solid phase hydrogen storage
The portable and safe storage of hydrogen will be fundamental to the
success of fuel cell-powered cars


Polymers on the move
Fuel prices and the impact transport has on the environment are leading
car and aircraft manufacturers to use more lightweight plastics and
composites in their products


Harnessing solar energy with Grätzel cells
Chemists from the Universities of Loughborough and Bristol have teamed
up to take a research-based project into local schools


Build your own spectrophotometer
By designing and building their own visible-light spectrophotometers,
students get to grips with the underlying principles of this widely used
analytical tool


Experimenting with biodiesel
The synthesis of biodiesel is exploited to teach general chemistry
principles and as a way of fostering a 'green conscience' within
undergraduate chemistry students


Understanding our changing atmosphere
Research by chemists into the chemical processes occurring in the
troposphere could help to predict the likely impacts of climate change
upon atmospheric conditions


Fighting skin cancer with prodrugs
Prodrugs - selective chemical agents - are beginning to show potential
as a cure for skin cancer


Which chemistry course?
Selecting the right chemistry course and the right institution are
paramount in a prospective chemist's life


US chemical education going green
Kathryn Roberts meets Mary Kirchhoff, the new director of education at
the American Chemical Society (ACS) in Washington DC


Flu drugs - pathway to discovery
If bird flu ever starts to transmit from human to human, with no
effective vaccine available our only defence will be the antiviral drugs
Relenza and Tamiflu


Molecular computers - tomorrow's technology?
As the miniaturisation of silicon chips fast approaches its limit
chemists are copying Nature in attempt to build computers atom by atom,
molecule by molecule


Phenols in medicine
Phenol encountered in school or college chemistry laboratories demands
special respect on account of its toxic and corrosive nature. But phenol
and its derivatives do have a few me...


Who really discovered the Haber process?
Although Fritz Haber's name is now attached to the process for the
synthesis of ammonia from its constituent elements by using high
pressure, who was responsible for this reaction?...


Making triazoles, the green way
Triazole synthesis provides an excellent example of a reaction that has
the potential to illustrate principles of green chemistry to
undergraduates


Pesticides - keeping one step ahead
Organic chemists have developed myriad agents to kill pests


Historical highlights in organoarsenic chemistry
Organoarsenic compounds have given insight into important theoretical
topics in chemistry and proved to have beneficial pharmacological
effects


Investigating commercial sunscreens
Commercial sunscreens provide the basis of an industry-linked
investigation suitable for students at various levels


Nanotechnology update
The past 10 years have witnessed myriad R&D programmes in nanotechnology
around the world


Cocaine - a short trip in time
In the latter half of the 19th century chemists started to investigate
the properties of cocaine. Elucidation of its molecular structure
followed some 30 years later


I can see clearly now
Thanks to advances in polymer chemistry contact lenses are now more
comfortable and fashionable

2006

Drugs for dementia
About 10 per cent of men and women over 65, and nearly half of those
over 80, have Alzheimer's disease


Applied science: on course
Applied science has a key role in the 14-16 curriculum, and its
popularity is growing


Glass bones
'Bioactive' ceramic and glass alternatives could improve the quality of
life for millions of people suffering from osteoporosis


Making the most of starch
With some clever chemistry starch represents an enormous and sustainable
source of renewable carbon for non-food applications.


Artemisinin and a new generation of antimalarial drugs
Every year between one and two million people - mainly children - living
in the tropics and subtropics die of malaria.


Research in schools
Science for the 21st Century Initiative (SCI) aims to cultivate an
interest in, and knowledge of, the wider aspects of science and
technology among A-level students.


Spicing up chemistry
Spices have been used in cooking since Roman times, and were believed to
be important as antiparasitic agents and as gastrointestinal protectants
in the diet


In the steps of Markovnikov
The addition reactions of HCl and HBr to propene to give either
2-chloropropane or 2-bromopropane are often given as examples of
Markovnikov's Rule, but in his original 1870 paper,...


Chemistry, medicine and genetic analysis
In the near future, doctors will be able to carry out a 'while you wait'
test, using genetic analysis, for chlamydia, the silent disease that can
lead to infertility in women. This...


GM foods - addressing public concerns
Genetically modified (GM) foods continue to generate media attention and
concern among the public. How can analytical chemists help consumers
make informed choices


Rough science and homemade batteries
Investigations involving simple batteries made from items found in the
home or school laboratory can help KS3 pupils understand the origin of
current, voltage and power, and the ch...

Percivall Pott, chimney sweeps and cancer
Over 200 years ago, doctor and writer Percivall Pott made the astute
connection between soot and scrotal cancer, known then as the chimney
sweep's cancer.

Acid mine drainage - a legacy of an industrial past
The environmental damage caused by acid mine drainage (AMD) is a
worldwide and growing problem in those countries that once, or are
still, extracting coal and/or metals. What is AM...

The carbon dioxide problem
Measuring carbon dioxide from plant debris provides an opportunity for
an inquiry-based experiment aimed at 14-15 year olds. Similar
experiments are done by soil scientists and eco...


Titan - a museum of the Earth's atmosphere
Titan, the largest moon of the planet Saturn, has an atmosphere that is
predominantly nitrogen with a small amount of carbon present in the form
of methane and higher hydrocarbons....


Chlorpromazine - unlocks the asylums
The history of pharmaceuticals is enriched by accounts of drugs
developed for one therapeutic purpose that found application in another.
This is true for chlorpromazine, a treatmen...

Pioneering women chemists of Bedford College
In the early part of the 20th century, a few institutions seemed to have
been havens for women interested in chemistry.


Biting insects - a challenge for chemists
In many parts of the world biting insects are major disease vectors,
being the source of malaria and yellow fever for example, though in the
UK they are mainly just a nuisance.

Amedeo Avogadro 1776-1856
This year marks the 150th anniversary of the death of the Italian
chemical physicist, Amedeo Avogadro.


A forgotten anniversary?
Has the significance of William Henry Perkin's synthesis of the purple
dye mauveine begun to fade?


Dirty air
What constitutes ground-level air pollution and what are the impacts of
such pollutants on Man and the environment?


Chapattis and the English disease
In the early 1700s in England 'nothing was so much feared or talk'd of
as Rickets among Children'. We now know that this softening of the
bones, is caused by a deficiency of vitami...


Ancient coins
Chemistry has played its part in numismatics - in the manufacture,
analysis, aesthetics and conservation of coinage


Natural products - back in vogue
Chemists are once again turning to Nature to replenish the medicine
chest

2005

The Chemistry Olympiad - miss it, miss out
The international final of the Chemistry Olympiad - a chemistry
competition for sixthformers - was held this year in Taiwan. Some 225
students from 59 countries took part in this p...


The chemistry of self-healing polymers
A familiar example of a system with self-healing ability is the human
body. But could an analogous strategy be used for the self-repair of
polymeric composites?


Pain relief: from coal tar to paracetamol
Analgesics, ie pain-relieving drugs, fall into two categories: those
that also reduce body temperature in fevers (antipyretics), and those
that act mainly on the brain - typically ...


Investigating the secrets of the Stradivarius
For the past 200 years violin makers around the world have sought to
produce violins that would rival those of Stradivari and Guarneri made
during 1700-50.


Analytical chemistry makes the news
University departments traditionally divided chemistry into inorganic,
organic and physical subsets, with analytical chemistry sitting
somewhere in between. But this is changing. T...


The fight against food adulteration
Today's quality control of the food and drinks industry is thanks to
pioneering work started by chemist Frederick Accum and medic Arthur Hill
Hassall in the 19th century


Salty solvents - ionic really
Ionic compounds are usually high melting point solids. But mix together
a powdered organic salt with aluminium chloride and the result is a
clear, colourless, 'ionic liquid'.


Skeletal chemistry
What is the minimal core of an education in chemistry? What should
someone with a passing need to understand a bit of chemistry -
engineers, biologists, physicians, physicists - kn...

2003

Making ice cream - it's physical chemistry
An understanding of the physical chemistry of ice cream is the route to
a smooth, soft, creamy dessert

2002

The beginnings of Mössbauer spectroscopy
In 1958 Rudolf Ludwig Mössbauer, aged 29, published the results of an
experiment which gave rise to the branch of spectroscopy which now bears
his name.

=============

Timothy Sutter

unread,
Nov 19, 2012, 8:01:12 PM11/19/12
to
> here's on e generalized educational website from
> an organization called RCC "advances in chemical science"

> this is a very wide ranging subject which addresses
> a wide variety of interdsciplinary subjects and topics

> quantum mechanics molecular biology evolutionary
> biology genetics dna chemistry cosmology etc.
> are all fair game in a chemical discussion.


nothing i have posted in this place sci.chem
has been "off topic" in any manner.

i -am- a chemist and have a chemical viewpoint.

my cosmological worldview is a chemical one.

i have posted some duplicate messages here as of late

all of my posts are being anonymously
hidden in the gurgle archive.

no mention from anyone as to why they
are being hidden is ever given.

i realize that the gurgle archive is not
the only place these posts appear, but they ae housed
there for a long time and i have just as much right
to post here without interference as anyone else.

i will post reposts again if i see that
they are being hidden in the gurgle arhive.

i may flag some of those as "Repost"

it is not my interest to annoy people.

i think my posts are topical and relevant.

if anyone would like t tell me otherwise,
i may even liste to what they have to say.

but there is a comprehensive storyline here

and not one that constantly refers
to specific reaction sequences.

chemical engineering does not always refer to reaction
sequences as we saw lately with the person who was
having problems with oil in their compressed air.

that was not, stricly speaking a problem of
reaction mechanism but one of an engineering nature.

please excuse me as i carry out my feud
with the mad post flagger at gurgle groups.

yes, i mention "God"

this is not at all uncommon even in the sciences.

Gregor Mendel was a christian monastic.

etc. etc . etc.

i will post some of my posts again, and again, and again.

i do -not- do so to raise people's ire.

i do so because i feel they have relevant information in them.

if ifeel like posting messages -about- "God"

i will do so, and if they are flagged atguglegroups

i will postthem again, and not feel that
i am being "abusive" in any manner.


there, i've given a brief explanation of my actions...


feel free to ignore my posts

feel free to confront me on any of them.

feel free to flag them as abusive on gurgle groups...

and i feel free to repost them if and when i so desire.

thank you.







====
http://en.wikipedia.org/wiki/Chemistry
Subdisciplines
Chemistry is typically divided into several major sub-disciplines. There
are also several main cross-disciplinary and more specialized fields of
chemistry.[50]
Analytical chemistry is the analysis of material samples to gain an
understanding of their chemical composition and structure. Analytical
chemistry incorporates standardized experimental methods in chemistry.
These methods may be used in all subdisciplines of chemistry, excluding
purely theoretical chemistry.
Biochemistry is the study of the chemicals, chemical reactions and
chemical interactions that take place in living organisms. Biochemistry
and organic chemistry are closely related, as in medicinal chemistry or
neurochemistry. Biochemistry is also associated with molecular biology
and genetics.
Inorganic chemistry is the study of the properties and reactions of
inorganic compounds. The distinction between organic and inorganic
disciplines is not absolute and there is much overlap, most importantly
in the sub-discipline of organometallic chemistry.
Materials chemistry is the preparation, characterization, and
understanding of substances with a useful function. The field is a new
breadth of study in graduate programs, and it integrates elements from
all classical areas of chemistry with a focus on fundamental issues that
are unique to materials. Primary systems of study include the chemistry
of condensed phases (solids, liquids, polymers) and interfaces between
different phases.
Neurochemistry is the study of neurochemicals; including transmitters,
peptides, proteins, lipids, sugars, and nucleic acids; their
interactions, and the roles they play in forming, maintaining, and
modifying the nervous system.
Nuclear chemistry is the study of how subatomic particles come together
and make nuclei. Modern Transmutation is a large component of nuclear
chemistry, and the table of nuclides is an important result and tool for
this field.
Organic chemistry is the study of the structure, properties,
composition, mechanisms, and reactions of organic compounds. An organic
compound is defined as any compound based on a carbon skeleton.
Physical chemistry is the study of the physical and fundamental basis of
chemical systems and processes. In particular, the energetics and
dynamics of such systems and processes are of interest to physical
chemists. Important areas of study include chemical thermodynamics,
chemical kinetics, electrochemistry, statistical mechanics,
spectroscopy, and more recently, astrochemistry.[51] Physical chemistry
has large overlap with molecular physics. Physical chemistry involves
the use of infinitesimal calculus in deriving equations. It is usually
associated with quantum chemistry and theoretical chemistry. Physical
chemistry is a distinct discipline from chemical physics, but again,
there is very strong overlap.
Theoretical chemistry is the study of chemistry via fundamental
theoretical reasoning (usually within mathematics or physics). In
particular the application of quantum mechanics to chemistry is called
quantum chemistry. Since the end of the Second World War, the
development of computers has allowed a systematic development of
computational chemistry, which is the art of developing and applying
computer programs for solving chemical problems. Theoretical chemistry
has large overlap with (theoretical and experimental) condensed matter
physics and molecular physics.
Other disciplines within chemistry are traditionally grouped by the type
of matter being studied or the kind of study. These include inorganic
chemistry, the study of inorganic matter; organic chemistry, the study
of organic (carbon based) matter; biochemistry, the study of substances
found in biological organisms; physical chemistry, the study of chemical
processes using physical concepts such as thermodynamics and quantum
mechanics; and analytical chemistry, the analysis of material samples to
gain an understanding of their chemical composition and structure. Many
more specialized disciplines have emerged in recent years, e.g.
neurochemistry the chemical study of the nervous system (see
subdisciplines).
Other fields include agrochemistry, astrochemistry (and cosmochemistry),
atmospheric chemistry, chemical engineering, chemical biology,
chemo-informatics, electrochemistry, environmental chemistry,
femtochemistry, flavor chemistry, flow chemistry, geochemistry, green
chemistry, histochemistry, history of chemistry, hydrogenation
chemistry, immunochemistry, marine chemistry, materials science,
mathematical chemistry, mechanochemistry, medicinal chemistry, molecular
biology, molecular mechanics, nanotechnology, natural product chemistry,
oenology, organometallic chemistry, petrochemistry, pharmacology,
photochemistry, physical organic chemistry, phytochemistry, polymer
chemistry, radiochemistry, solid-state chemistry, sonochemistry,
supramolecular chemistry, surface chemistry, synthetic chemistry,
thermochemistry, and many others.




===========
> http://www.rsc.org/Education/EiC/topics/Free_to_access_articles.asp
===========

Timothy Sutter

unread,
Nov 19, 2012, 8:29:56 PM11/19/12
to
> i -am- a chemist and have a chemical viewpoint.

> my cosmological worldview is a chemical one.

i'v even managed to have work published in peer reviewed journals.

http://65.54.113.26/Author/20499163/timothy-p-g-sutter



==
"Kinetic and equilibrium studies on porphyrins, chlorins,
and isobacteriochlorins; basicities, zinc incorporation,
and acid catalyzed solution reactions in aqueous and nonaqueous
solutions," T.P.G. Sutter and P. Hambright,
Inorg. Chem., 1992, 31, 5089-5093.

http://pubs.acs.org/doi/abs/10.1021/ic00050a031


http://pubs3.acs.org/acs/journals/toc.page?incoden=inocaj&indecade=0&involume=31&inissue=24
http://pubs.acs.org/cgi-bin/abstract.cgi/inocaj/1992/31/i24/f-pdf/f_ic00050a031.pdf
==


==
"Mossbauer, magnetic susceptibility, radiolytic and photochemical
studies of europium and lutetium porphyrins," F.W. Oliver, C. Thomas,
E. Hoffman, D. Hill, T.P.G. Sutter, P.Hambright, S. Haye, A.N. Thorpe,
N. Quoc, A. Harriman, P. Neta, and S. Mosseri,
Inorg. Chim. Acta, 1991, 186, 119-124.

http://www.nist.gov/kinetics/neta/index.htm <== dead
http://www.sciencedirect.com/science/article/pii/S0020169300879402
224. Mössbauer, magnetic susceptibility, radiolytic and photochemical
studies of europium and lutetium porphyrins. F.W. Oliver, C. Thomas, E.
Hoffman,
D. Hill, T.P.G. Sutter, P. Hambright, S. Haye, A.N. Thorpe, N. Quoc, A.
Harriman,
P. Neta, and S. Mosseri. Inorg. Chim. Acta, 186, 119 (1991).
==


==
"Diamagnetic susceptibilities of porphyrins,"
T.P.G. Sutter, P. Hambright, A.N. Thorpe, and N. Quoc,
Inorg. Chim. Acta, 1992, 195, 131-132.
http://cat.inist.fr/?aModele=afficheN&cpsidt=5423525
==


==
"One-electron reduction and demetalation of copper porphyrins,"
M. Kumar, P. Neta, T.P.G. Sutter, and P. Hambright,
J. Phys. Chem., 1992, 96, 9571-9575.
Manmohan Kumar, P. Neta, T. P. G. Sutter, and P. Hambright
pp 9571 - 9575; DOI: 10.1021/j100202a091
http://pubs3.acs.org/acs/journals/toc.page?incoden=jpchax&indecade=&involume=96&inissue=23
http://pubs.acs.org/doi/abs/10.1021/j100202a091
==

==
"Steric and inductive effects on the basicity of porphyrins
and on the site of protonation of porphyrin dianions. Radiolytic
reduction of porphyrins and and metalloporphyrins to chlorins
and phlorins," T.P.G. Sutter, R. Rahimi, P. Hambright,
J.C. Bommer, M. Kumar, and P. Neta,
J. Chem. Soc., Faraday Trans., 1993, 89, 495-502.

241. Steric and inductive effects on the basicity of porphyrins and on
the site of protonation of porphyrin dianions. Radiolytic reduction of
porphyrins and metalloporphyrins to chlorins or phlorins. T.P.G. Sutter,
R. Rahimi, P. Hambright, J.C. Bommer, M. Kumar, and P. Neta,
J. Chem. Soc. Faraday Trans., 89, 495 (1993).
http://www.nist.gov/kinetics/neta/index.htm <==dead
http://www.uast.ac.ir/modules.php?name=treeview&op=viewnodepage&nid=1036
<==dead
http://pubs.rsc.org/en/Content/ArticleLanding/1993/FT/ft9938900495
==

==
"The effect of peripheral substituents on the kinetics of
zinc ion incorporation and acid catalyzed removal from
water soluble sulfonated porphyrins,"
T.P.G. Sutter and P.Hambright,
J. Coord. Chem., 1993, 30, 317-326.
http://cat.inist.fr/?aModele=afficheN&cpsidt=3859250
==

==
"Aqueous Solution Acid Catalyzed Solvolysis Kinetics
of Zinc(II), Cobalt(II), Copper(II) and Nickel(II)
N-Methyl-Tetra(4-sulfonatophenyl) Porphyrins,
"R. Rahimi, T.P.G. Sutter and P. Hambright,
J. Coord. Chem., 1995, 34, 283-288
http://www.uast.ac.ir/modules.php?name=treeview&op=viewnodepage&nid=1036

http://www.iust.ac.ir/page.php?slct_pg_id=3690&sid=20&slc_lang=en

can't find a good url on this one, but rahimi has one.

yeah, he was iranian.

no, he wasn't a mad bomber as far as i could tell.

==


i realize this isn't like a million publications and
i'm not claiming to be anything more than a chemist.


i did go through that by the numbers.

Timothy Sutter

unread,
Nov 19, 2012, 8:59:47 PM11/19/12
to
> > i -am- a chemist and have a chemical viewpoint.

> > my cosmological worldview is a chemical one.

> i'v even managed to have work published in peer reviewed journals.

> http://65.54.113.26/Author/20499163/timothy-p-g-sutter

calling my posts "abusive" is a libel

so, gurgle is sort of like an accomplice to a libel.

and that's not just a matter of petty annoyances.

Timothy Sutter

unread,
Nov 19, 2012, 9:15:26 PM11/19/12
to
i know the post flagger is a tiny nitwit

so, that doesn't bother me one little bit

i'm just saying, if you see duplicate posts,

and you wonder;

"why is he doing that?"


because i feel like it...

Martin Brown

unread,
Nov 20, 2012, 3:19:13 AM11/20/12
to
On 20/11/2012 01:01, Timothy Sutter wrote:
>> here's on e generalized educational website from
>> an organization called RCC "advances in chemical science"
>
>> this is a very wide ranging subject which addresses
>> a wide variety of interdsciplinary subjects and topics
>
>> quantum mechanics molecular biology evolutionary
>> biology genetics dna chemistry cosmology etc.
>> are all fair game in a chemical discussion.
>
>
> nothing i have posted in this place sci.chem
> has been "off topic" in any manner.
>
> i -am- a chemist and have a chemical viewpoint.
>
> my cosmological worldview is a chemical one.
>
> i have posted some duplicate messages here as of late
>
> all of my posts are being anonymously
> hidden in the gurgle archive.

Good for them. You post complete garbage.

Unfortunately what you say is *NOT* true your garbage is cluttering up
Google archives along with the many copy watch, handbag spammers dross.

Now stop morphing to escape my kill file you demented fuckwit.

> feel free to ignore my posts

I will do.

--
Regards,
Martin Brown

Timothy Sutter

unread,
Nov 20, 2012, 4:41:40 AM11/20/12
to
here's on e generalized educational website from
an organization called RCC "advances in chemical science"

this is a very wide ranging subject which addresses
a wide variety of interdsciplinary subjects and topics

quantum mechanics molecular biology evolutionary
biology genetics dna chemistry cosmology etc.
are all fair game in a chemical discussion.




Harnessing solar energy with Gr�tzel cells
The beginnings of M�ssbauer spectroscopy
In 1958 Rudolf Ludwig M�ssbauer, aged 29, published the results of an

dlzc

unread,
Nov 20, 2012, 9:01:56 AM11/20/12
to
Why this is marked as abuse? It has been marked as abuse.
Report not abuse
On Monday, November 19, 2012 6:59:30 PM UTC-7, Timothy Sutter wrote:
> > > i -am- a chemist and have a chemical viewpoint.
> > > my cosmological worldview is a chemical one.
> > i'v even managed to have work published in peer
> > reviewed journals.
>
> > http://65.54.113.26/Author/20499163/timothy-p-g-sutter
>
> calling my posts "abusive" is a libel

Calling your posts off topic spam in this newsgroup is truth. You are violating posting guidelines for this newsgroup. This is not your personal blog. This newsgroup is for discussion of chemistry news.

If you accidentally actually talk about chemistry, *I* am not flagging them. I didn't even bother when you posted over and over under the same title. I could at least see if there was something interesting that had been posted by someone that was less of an "artist".

David A. Smith

Timothy Sutter

unread,
Nov 20, 2012, 9:19:09 AM11/20/12
to
dlzc wrote:

> Timothy Sutter wrote:

> > > > i -am- a chemist and have a chemical viewpoint.
> > > > my cosmological worldview is a chemical one.
> > > i'v even managed to have work published in peer
> > > reviewed journals.

> > > http://65.54.113.26/Author/20499163/timothy-p-g-sutter

> > calling my posts "abusive" is a libel

> Calling your posts off topic spam in this newsgroup is truth.

no, this would be your opinion.
chemistry is not your own personal topic.
topicallity is not defined by you nor
by people who happen to agree with you.

> You are violating posting guidelines for this newsgroup.

show everyone these posting guidlies.

> This is not your personal blog.

show precisely how i am using this group as my personal "blog"

chemistry is not your own personal topic.
topicallity is not defined by you nor
by people who happen to agree with you.

> This newsgroup is for discussion of chemistry news.

my posts do discuss chemistry news.

> If you accidentally actually talk about chemistry, *I* am not flagging them.

from the google archive;

==
http://tinyurl.com/ctgtmv2
sci.chem
Chemistry and related sciences.
60436 members - 0 days ago
==

all of my recent posts have been directly
topical to chemistry and related sciences.


> I didn't even bother when you posted over and over under the same title.

chemistry is not your own personal topic.
topicallity is not defined by you nor
by people who happen to agree with you.


> I could at least see if there was something interesting
> that had been posted by someone that was less of an "artist".

chemistry is not your own personal topic.
topicallity is not defined by you nor
by people who happen to agree with you.

i suggest you draw a line where you feel comfortable

and stay on the other side.

Timothy Sutter

unread,
Nov 20, 2012, 11:20:19 AM11/20/12
to
Martin Brown wrote:

> Timothy Sutter wrote:

> >> here's on e generalized educational website from
> >> an organization called RCC "advances in chemical science"

> >> this is a very wide ranging subject which addresses
> >> a wide variety of interdsciplinary subjects and topics

> >> quantum mechanics molecular biology evolutionary
> >> biology genetics dna chemistry cosmology etc.
> >> are all fair game in a chemical discussion.

> > nothing i have posted in this place sci.chem
> > has been "off topic" in any manner.

> > i -am- a chemist and have a chemical viewpoint.
> > my cosmological worldview is a chemical one.
> > i have posted some duplicate messages here as of late

> > all of my posts are being anonymously
> > hidden in the gurgle archive.

> Good for them. You post complete garbage.

lock your own mind up and try not to place
your little padlocks on anyone else.


> Unfortunately what you say is *NOT* true your garbage is cluttering up
> Google archives along with the many copy watch, handbag spammers dross.


if there was even the remotest chance that i could post
too much for google to accomodate, i'm sure google
would tell me about it.

google hasn't complaind to me about my postings.


> Now stop morphing to escape my kill file you demented fuckwit.


i will post as i will post and my posting is not motivated

by you and your personl problems.


> > feel free to ignore my posts

> I will do.


then there's little chance of me hearing from you again, goodie goodie.

dlzc

unread,
Nov 20, 2012, 1:01:33 PM11/20/12
to
Dear Timothy Sutter:

On Tuesday, November 20, 2012 7:19:01 AM UTC-7, Timothy Sutter wrote:
> dlzc wrote:
> > Timothy Sutter wrote:
...
> > > calling my posts "abusive" is a libel
>
> > Calling your posts off topic spam in this
> > newsgroup is truth.
>
> no, this would be your opinion.

Your off topic posts are spam according to posting guidelines. No opinion required, however apparently others agree with me.

Either you stick to one thread title, so I can easily ignore your off-topic musings, or reporting continues.

David A. Smith

Timothy Sutter

unread,
Nov 20, 2012, 1:16:15 PM11/20/12
to
dlzc wrote:

> Dear Timothy Sutter:

> Timothy Sutter wrote:

> > dlzc wrote:

> > > Timothy Sutter wrote:
> ...
> > > > calling my posts "abusive" is a libel

> > > Calling your posts off topic spam in this
> > > newsgroup is truth.

> > no, this would be your opinion.

> Your off topic posts are spam according to posting guidelines.

posting guidelines that you won't show
and quite likely are peculiar to your own
personal opinion of what constitutes topicallity,.

for instance, you seem to feel that posts -about-
topicallity are "on topic" when some people may
feel that such posts -about- "topicallity"
are not "on topic"

so, you can already see that your
opinion of "topicallity" is questuionable.

of course, in -your- mind, -anything- you post
is automatically "on topic"

fine.


> No opinion required,

except your opinon has weaseled its way
in to your ow personal "guidelines"

guidelines which you allude to but are, apparently,
unable to produce for inspection by anyone else.


> however apparently others agree with me.


a consensus of opinion is still a stack of opinions

maybe this is why you feel that my posts are not ontopic

because you have failed to distinguish the differentce
bewteen fact and opinion, a thing they teach elementary
school children and a thing adults should not have
such difficulty with.

this problem of yours is seeping its way in to your
opinions about what constuitutes "good science" no doubt.


> Either you stick to one thread title,

so, -you'd- be comfortable with me posting all of my posts
as "Timothy Sutter post" jut so -you- could manage to ignore them,
when you -could- simply see my name attached to a post
and manage to ignore based on this criterion alone.

i'll not title all of my posts as "Timothy Sutter post" to plase anyone.


> so I can easily ignore your off-topic musings, or reporting continues.


you can easily ignore all of my postings with out
such constrictions on my posting titles.


and you can "report" things to your little heart's content

and, as i see fit, i shall continue to repost any post
that i see disappear from the google archive that i
saw fit to post as topical in the foirst place.


you may do well to flag your own posts in this thread

except of course, if you grant yourself the allowance
of posting -about- what constitutes topicallity into an open forum.

=some= people will likely feel that posts -about-
topicallity are better dealt with via e-mail.

but, of course, you have your very own criterion for
topicallity and you demand that everyone else adhere
to your personal and peculiar criteria which you
have not yet made public.

enjoy your exercise in futility...

Timothy Sutter

unread,
Nov 20, 2012, 1:47:34 PM11/20/12
to
> > Your off topic posts are spam according to posting guidelines.

> posting guidelines that you won't show
> and quite likely are peculiar to your own
> personal opinion of what constitutes topicallity,.

at least it's been made obvious someone is flagging
my posts at gurgle and says so in public not
affiliated with gurglegroups.

i'm quite aware that what gurgle does with
its "archive" is irrelevant to other usenet outlets.

fine, but, if and when i see fit to repost
posts that have been hidden at this "archive"

i shall do so.

i must give those idle minds and their idle hands something to do.

they can thank me later...

Timothy Sutter

unread,
Nov 20, 2012, 1:50:12 PM11/20/12
to
> i must give those idle minds and their idle hands something to do.

that, and the outside chance that someone may
actually read them and get something out of them.

Timothy Sutter

unread,
Nov 20, 2012, 2:41:10 PM11/20/12
to
this is quite olde, 1999, but, as you can see,
sci.chem is unmoderated and covers the discussion
of all scientific aspects of chemistry and that
there is no Charter that would define topics for
discussion in the group.

like i have said, my posts are chemically related
as i consider that chemsitry, also called
"the central science" is related to a mountaion
of information and not just what John Smith or
the writers of this particular FAQ may suggest.

one point being;

I do not consider my posts "off topic"

if I considered my posts to be "off topic"

someone may have a -reason- to call them "abusive"

but I am telling you that i do not consider them

"off topic" and, likewise, I feel justified

in reposting my posts when i see fit.

this is what "common sense" -should- tell you.


===
http://www.faqs.org/faqs/sci/chem-faq/part1/
Archive-name: sci/chem-faq/part1
Posting-Frequency: monthly
Last-modified: 22 October 1999
Version: 1.17

5.1 What topics does sci.chem cover?.

Sci.chem is an unmoderated discussion group, and it covers the
discussion
of all scientific aspects of chemistry. It is not intended to be an
educational resource that replaces your local library - which should
still
be your first port of call when seeking information. Because sci.chem
was
created in the 1980s, there is no Charter that would define topics for
discussion in the group, however common sense suggests that posts should
be
focused on aspects of chemistry not discussed elsewhere on Usenet. Newer
groups in the hierarchy do have Charters.

<..>

Please do not post messages complaining about what you perceive as noise
in
the group, as such posts usually just generate additional noise. If you
wish,
you can email posters asking them to desist from posting the material
that
offends you, but don't be surprised if you are also offended by their
responses.

Some news-reading software can not display, or post, long articles (
like
this FAQ ), and you may have to ask your system administrator or ISP for
alternative software. A consistent inability to display large posts is
usually a problem with your reading software, not a mistake by the
posters.
===

Timothy Sutter

unread,
Nov 20, 2012, 2:44:11 PM11/20/12
to

Timothy Sutter

unread,
Nov 20, 2012, 2:45:02 PM11/20/12
to

Timothy Sutter

unread,
Nov 20, 2012, 2:46:27 PM11/20/12
to
http://www.faqs.org/faqs/sci/chem-faq/part1/

nothing in here gives me an impression
that what i post is "abusive" or "off topic"

that's as simple as that.

i shall repost some of my posts.

enjoy...

Timothy Sutter

unread,
Nov 20, 2012, 2:56:47 PM11/20/12
to
> http://www.faqs.org/faqs/sci/chem-faq/part1/

and, if you gurgle this URL or just sci.chem FAQ

you get nothing of note

a reference from 2008 that doesn't

even seem to be in sci.chem

and, with the deterioration of usenet in general

it is probably that FAQs have been

more often than not, abandoned outright.

but, you go ahead and continue

your exercise in futility.


not that usenet was ever a "successful" enterprise

inasmuch as some people consider "success"

having everyone run lockstep with their dictates.

thank you, no.

my posts are "topical" because i say so.

i don't -need- nor am i asking for anyone's

=permission= to post them

abnd, as far as i can see,

i need no such permission.

exercize in futility.

enjoy...

dlzc

unread,
Nov 20, 2012, 3:06:06 PM11/20/12
to
Dear Timothy Sutter:

On Tuesday, November 20, 2012 11:16:03 AM UTC-7, Timothy Sutter wrote:
...
> posting guidelines that you won't show
> and quite likely are peculiar to your own
> personal opinion of what constitutes topicallity,.

Because *you* just discovered usenet, does not mean it is not as old as the hills.

Here I did an internet search for you:
http://www.faqs.org/faqs/usenet/spam-faq/
http://www.faqs.org/faqs/usenet/posting-rules/part1/

Choose a newsgroup on topic for evoluton, and post there. Never hear from me again, if you only post there.

Please note that usenet postings are government property, are admissible in court, and can be used against you in a court of law. Not sure, but I think an applicant's postings have been used to squash a job offer as well.

David A. Smith

Timothy Sutter

unread,
Nov 20, 2012, 3:14:03 PM11/20/12
to
dlzc wrote:

> Dear Timothy Sutter:

> On Tuesday, November 20, 2012 11:16:03 AM UTC-7, Timothy Sutter wrote:
> ...
> > posting guidelines that you won't show
> > and quite likely are peculiar to your own
> > personal opinion of what constitutes topicallity,.

> Because *you* just discovered usenet, does not mean it is not as old as the hills.

> Here I did an internet search for you:
> http://www.faqs.org/faqs/usenet/spam-faq/
> http://www.faqs.org/faqs/usenet/posting-rules/part1/

too late, i already posted this;

https://groups.google.com/d/msg/sci.chem/IsAOmxO38dU/4gbgu8aQySEJ
========
this is quite olde, 1999, but, as you can see,
sci.chem is unmoderated and covers the discussion
of all scientific aspects of chemistry and that
there is no Charter that would define topics for
discussion in the group.

like i have said, my posts are chemically related
as i consider that chemsitry, also called
"the central science" is related to a mountaion
of information and not just what John Smith or
the writers of this particular FAQ may suggest.

one point being;

I do not consider my posts "off topic"

if I considered my posts to be "off topic"

someone may have a -reason- to call them "abusive"

but I am telling you that i do not consider them

"off topic" and, likewise, I feel justified

in reposting my posts when i see fit.

======


> Choose a newsgroup on topic for evoluton, and post there.

i don't need to do such a thing, my posts are already
topical here where i ampostingthem -now-


> Never hear from me again, if you only post there.

not worried about hearing from you again


> Please note that usenet postings are government property,
> are admissible in court, and can be used against you in a court of law.


well, now you have a career ahead of you

seeking to have me prosecuted for my posts.



> Not sure, but I think an applicant's postings
> have been used to squash a job offer as well.


i'm not asking you for a job.

Timothy Sutter

unread,
Nov 20, 2012, 3:15:32 PM11/20/12
to

Timothy Sutter

unread,
Nov 20, 2012, 3:20:20 PM11/20/12
to
T
> > http://www.faqs.org/faqs/sci/chem-faq/part1/
>
> and, if you gurgle this URL or just sci.chem FAQ

but, i was already willing to keep my topics

confined to a thread or two

but that wasn't good enough for the mad post flaggr,

so, i expanded to more threads.

i'm still willing to postin fewer threads,

but if that thread gets flagged, i shall likely

resume my multiple thread posting.

Timothy Sutter

unread,
Nov 20, 2012, 3:25:07 PM11/20/12
to
> T
> > > http://www.faqs.org/faqs/sci/chem-faq/part1/

> > and, if you gurgle this URL or just sci.chem FAQ

> but, i was already willing to keep my topics

> confined to a thread or two

this because the relevance of some of my posts in this area,

are assisted the others to show a contiguous line of reasoning

but, they are still all perfectly well "topical" as stand alone items.

but, as i have said, i am still willing to confine

myself to a smallernumber of threads,

but, if all of my posts are automatically flagged,

which they were for a while,

i shall continue the exercise in futillity.

exercises in futility, in themselves,

being "topical" in a chemistry forum.

you -should- become acquainted with exercises in futility,

they happen.

Timothy Sutter

unread,
Nov 20, 2012, 3:39:10 PM11/20/12
to
===
http://www.faqs.org/faqs/sci/chem-faq/part1/

"""Because sci.chem was created in the 1980s, there
is no Charter that would define topics for
discussion in the group"""
===

sci.chem has no Charter...period

one would do well to not try to enforce

a Charter that does not exist.


eggscellant

Timothy Sutter

unread,
Nov 20, 2012, 3:41:59 PM11/20/12
to
=obviously= the mad post flagger can continue

flagging posts according to personal whimsy

but it is -this- behavior which is abusive and incorrect.


knock yourself out...

Bruce Sinclair

unread,
Nov 20, 2012, 7:22:19 PM11/20/12
to
In article <72Hqs.20663$_c1....@newsfe16.iad>, Martin Brown <|||newspam|||@nezumi.demon.co.uk> wrote:
(snip)
>> all of my posts are being anonymously
>> hidden in the gurgle archive.
>
>Good for them. You post complete garbage.
>
>Unfortunately what you say is *NOT* true your garbage is cluttering up
>Google archives along with the many copy watch, handbag spammers dross.
>Now stop morphing to escape my kill file you demented fuckwit.

Suggestion - filter on ...

Timothy Sutter

He always feels the need to identify himself even when nymshifting. :)

Timothy Sutter

unread,
Nov 25, 2012, 6:40:04 AM11/25/12
to
==
Many important biomolecules are thermally unstable in aqueous media;
for instance, functionalized sugars (both aminated and phosphorylated),
peptides, polyphosphates, or thioesters will not survive long in water
under hot hydrothermal conditions (e.g., Larralde et al. 1995; Shapiro
1995). Nitriles, such as cyanoacetylene and cyanoacetaldeyde � proposed
as possible prebiotic precursors for pyrimidines (Robertson & Miller
1995)
� will be rapidly hydrolyzed to carboxylic acids in hot water (Siskin et
al. 1990). Therefore, if the synthesis of nucleotides and their
subsequent
oligomerization to promote an "RNA" world is requisite to the emergence
of life, then such chemistry would be extremely improbable
(and likely impossible) in high-temperature water
(e.g., Miller & Lazcano 1995).
===


===
The discovery of hydrothermal vents at the oceanic ridge crests and
the appreciation of their significance in the element balance of the
hydrosphere represents a major development in oceanography [126].
Since the process of hydrothermal circulation probably began early in
the Earth�s history, it is likely that vents were present in the Archean
oceans. Large amounts of ocean water now pass through the vents,
with the whole ocean going through them every 10 million years [127].
This flow was probably greater during the early history of the Earth,
since the heat flow from the planet�s interior was greater during
that period. The topic has received a great deal of attention, partly
because of doubts regarding the oxidization state of the early
atmosphere. Following the first report of the vents� existence,
a detailed hypothesis suggesting a hydrothermal emergence of life
was published [128], in which it was suggested that amino acids and
other organic compounds are produced during passage through the
temperature gradient of the 350 �C vent waters to the 0 �C ocean waters.
Polymerization of the organic compounds thus formed, followed by their
self-organization, was also proposed to take place in this environment,
leading to the first forms of life.

At first glance, submarine hydrothermal springs would appear
to be ideally suited for creating life, given the geological
plausibility of a hot early Earth. More than a hundred vents
are known to exist along the active tectonic areas of the Earth,
and at least in some of them catalytic clays and minerals interact
with an aqueous reducing environment rich in H2, H2S, CO, CO2,
and perhaps HCN, CH4, and NH3.

Unfortunately it is difficult to corroborate these speculations with
the findings of the effluents of modern vents, as a great deal of the
organic material released from modern sources is diagenized biological
material, and it is difficult to separate the biotic from the abiotic
components of these reactions. Much of the organic component of
hydrothermal
fluids may be formed from diagenetically altered microbial matter.
So far, the most articulate autotrophic hypothesis stems from
the work of W�chtersh�user [129,130], who has argued that life
begun with the appearance of an autocatalytic, two-dimensional
chemolithtrophic metabolic system based on the formation of the
highly insoluble mineral pyrite (FeS2).
The reaction FeS + H2S -> FeS2+ H2 is very favorable.
It is irreversible and highly exergonic with a standard
free energy change ?G� = -9.23 kcal/mol, which corresponds
to a reduction potential E� = -620 mV. Thus, the FeS/H2S
combination is a strong reducing agent, and has been shown
to provide an efficient source of electrons for the reduction
of organic compounds under mild conditions. The scenario proposed
by W�chtersh�user [129,130] fits well with the environmental
conditions found at deep-sea hydrothermal vents, where H2S, CO2,
and CO are quite abundant. The FeS/H2S system does not reduce CO2
to amino acids, purines, or pyrimidines, although there is more
than adequate free energy to do so [131]. However, pyrite formation
can produce molecular hydrogen, and reduce nitrate to ammonia,
and acetylene to ethylene [132]. More recent experiments have shown
that the activation of amino acids with carbon monoxide and (Ni,Fe)S
can lead to peptide-bond formation [133]. In these experiments,
however, the reactions take place in an aqueous environment to which
powdered pyrite has been added; they do not form a dense monolayer
of ionically bound molecules or take place on the surface of pyrite.
None of the experiments using the FeS/H2S system reported so far
suggests that enzymes and nucleic acids are the evolutionary outcome
of surface-bounded metabolism. The results are also compatible with
a more general model of the primitive soup in which pyrite formation
is an important source of electrons for the reduction of organic com-
pounds. It is possible that under certain geological conditions the
FeS/H2S combination could have reduced not only CO but also CO2
released from molten magna in deep-sea vents, leading to biochemical
monomers [134]. Peptide synthesis could have taken place in an iron
and nickel sulfide system [133] involving amino acids formed by elec-
tric discharges via a Strecker-type synthesis,

although this scenario requires the transportation of compounds formed
at the surface to the deep-sea vents [135]. It seems likely that
concentrations of reactants would be prohibitively low
based on second-order reaction kinetics.

If the compounds synthesized by this process did not remain bound
to the pyrite surface, but drifted away into the surrounding aqueous
environment, then they would become part of the prebiotic soup, not
of a two-dimensional organism.

=================================
In general, organic compounds are decomposed rather than created
at hydrothermal vent temperatures, although of course temperature
gradients exist. As has been shown by Sowerby and coworkers [136],
concentration on mineral surfaces would tend to concentrate any
organics created at hydrothermal vents in cooler zones, where other
reaction schemes would need to be appealed to.
=================================

The presence of reduced metals and the high temperatures of
hydrothermal vents have also led to suggestions that reactions
similar to those in Fischer�Trospch-type (FTT) syntheses may be
common under such regimes. It is unclear to what extent this is
valid, as typical FTT catalysts are easily poisoned by water and
sulfide. It has been argued that some of the likely environmental
catalysts such as magnetite may be immune to such poisoning [137].

Stability of Biomolecules at High Temperatures
A thermophilic origin of life is not a new idea. It was first suggested
by Harvey [138], who argued that the first life forms were het-
erotrophic thermophiles that had originated in hot springs such as
those found in Yellowstone Park. As underlined by Harvey, the one
advantage of high temperatures is that the chemical reactions could
go faster and the primitive enzymes could have been less efficient.
However, high temperatures are destructive to organic compounds.
Hence, the price paid is loss of biochemical compounds to decomposition.
Although some progress has been made in synthesizing small
molecules under hydrothermal vent type conditions, the larger trend
for biomolecules at high-temperature conditions is decomposition. As
has been demonstrated by various authors, most biological molecules
have half-lives to hydrolysis on the order of minutes to seconds at
the high temperatures associated with hydrothermal vents. As noted
above, ribose and other sugars are very thermolabile compounds [79].
The stability of ribose and other sugars is problematic, but pyrimidines
and purines, and many amino acids, are nearly as labile. At 100 �C
the half-life for deamination of cytosine is 21 days, and 204 days for
adenine [139,140]. Some amino acids are stable, for example, alanine
with a half-life for decarboxylation of approximately 19,000 years
at 100 �C, but serine decarboxylates to ethanolamine with a half-life of
320 days [141]. White [142] measured the decomposition of various com-
pounds at 250 �C and pH 7 and found half-lives of amino acids from 7.5 s
to 278 min, half-lives for peptide bonds from <1min to 11.8 min,
half-lives for glycoside cleavage in nucleosides from <1s to 1.3 min,
decomposition of nucleobases from 15 to 57min, and half-lives for
phosphate esters from 2.3 to 420 min. It should be borne in mind
that the half-lives for polymers would be even shorter as there
are so many potential breakage points in a polymer. Thus, while
the vents may serve as synthesis sites for simpler compounds such
as acetate or more refractory organic compounds such as fatty acids,
it is unlikely they played a major role in synthesizing most
biochemicals or their polymers.

350�C submarine vents do not seem to presently synthesize organic
compounds, more likely they decompose them in a time span ranging
from seconds to a few hours. Thus, the origin of life in the vents is
improbable. This does not imply that the hydrothermal springs were a
negligible factor on the primitive Earth. If the mineral assemblages
were sufficiently reducing, the rocks near the vents may have been
a source of atmospheric CH4 or H2. As stated earlier, the concentra-
tions of biomolecules which could have accumulated on the primitive
Earth is governed largely by the rates of production and the rates
of destruction. Submarine hydrothermal vents would have also been
important in the destruction rather than in the synthesis of organic
compounds, thus fixing the upper limit for the organic compound
concentration in the primitive oceans. Although it is presently not
possible to state which compounds were essential for the origin of life,
it does seem possible to preclude certain environments if even fairly
simple organic compounds were involved [143].


79. Larralde, R., M. Robertson and S. Miller.
Rates of decomposition of ribose and other sugars:
implications for chemical evolution. Proceedings of
the National Academy of Sciences USA, 92:8158�60, 1995.
126. Corliss, J., J. Dymond, L. Gordon, J. Edmond,
R. von Herzen, R. Ballard, K. Green, D. Williams,
A. Bainbridge, K. Crane and T. van Andel. Submarine
thermal springs on the Galapagos Rift. Science, 203:1073�83, 1979.
127. Edmond, J., K. Von Damn, R. McDuff and C. Measures. Chemistry of
hot springs on the east Pacific Rise and their effluent dispersal.
Nature, 297:187�91, 1982.
128. Corliss, J., J. Baross and S. Hoffman.
An hypothesis concerning the relationship between
submarine hot springs and the origin of life on Earth.
Oceanologica Acta, 4 Suppl, 59�69, 1981.
129. W�chtersh�user, G. Before enzymes and templates:
theory of surface metabolism. Microbiological Reviews,
52:452�84, 1988.
130. W�chtersh�user, G. Groundworks for an
evolutionary biochemistry: the iron-sulphur world.
Progress in Biophysical Molecular Biology
58:85�201,1992.
131. Keefe, A., S. Miller, G. McDonald and J. Bada.
Investigation of the prebiotic synthesis of amino acids
and RNA bases from CO2 using FeS/H2S as a reducing agent.
Proceedings of the National Academy of Sciences USA,
92:11904�6, 1995.
132. Maden, B. No soup for starters? Autotrophy and
origins of metabolism. Trends in Biochemical Sciences,
20:337�41, 1995.
133. Huber, C. and G. W�chtersh�user. Peptides by
activation of amino acids with CO on (Ni, Fe)S surfaces
and implications for the origin of life.
Science, 281:670�2, 1998.
134. Orgel, L. The origin of life�a review of facts
and speculations. Trends in Biochemical Sciences,
23:491�5, 1998.
135. Rode, B. Peptides and the origin of life.
Peptides, 20:773�86, 1999.
136. Sowerby, S., C. Morth and N. Holm. Effect
of temperature on the adsorption of adenine.
Astrobiology, 1(4):481�7, 2001.
137. Holm, N. and E. Andersson. Hydrothermal systems.
In Brack, A. (Ed.), The Molecular Origins of Life:
Assembling the Pieces of the Puzzle (pp.86�99).
Cambridge University Press, Cambridge, 1998.
138. Harvey, R. Enzymes of thermal algae. Science, 60:481�2, 1924.
139. Garrett, E. and J. Tsau. Solvolyses of cytosine and cytidine.
Journal of Pharmaceutical Sciences, 61(7):1052�61, 1972.
140. Shapiro, R. The prebiotic role of adenine:
a critical analysis. Origins of Life and Evolution
of the Biosphere, 25:83�98, 1995.
141. Vallentyne, J. Biogeochemistry of organic matter.
II. Thermal reaction kinetics and transformation products
of amino compounds. Geochimica et Cosmochimica Acta, 28:157�88, 1964.
142. White, R. Hydrolytic stability of biomolecules
at high temperatures and its implication for life at 250�
C. Nature, 310(5976):430�2, 1984.
143. Cleaves, H. and J. Chalmers. Extremophiles may
be irrelevant to the origin of life. Astrobiology, 4(1):1�9, 2004.
144. Or�, J. Comets and the formation of biochemical
compounds on the primitive Earth. Nature, 190:442�3, 1961.

Timothy Sutter

unread,
Nov 25, 2012, 6:40:28 AM11/25/12
to
"Unless the molecule can literally copy itself,"
Joyce and Orgel note, "that is, act simultaneously
as both template and catalyst, it must encounter
another copy of itself that it can use as a template."
Copying any given RNA in its vicinity will lead to
an error catastrophe, as the population of RNAs
will decay into a collection of random sequences.
But to find another copy of itself, the self-replicating
RNA would need (Joyce and Orgel calculate)
a library of RNA that "far exceeds
the mass of the earth."

Joyce G.F. & Orgel L.E., "Prospects for Understanding
the Origin of the RNA World," in "The RNA World,"
Gesteland R.F. & Atkins J.F., eds.



Joyce and Orgel suggest that one must reject
the myth of a self-replicating RNA molecule that arose de novo
from a soup of random polynucleotides. Not only is such a notion
unrealistic in light of our current understanding of prebiotic
chemistry, but it should strain the credulity of even an optimist's
view of RNA's catalytic potential. If you doubt this, ask yourself
whether you believe that a replicase ribozyme would arise in a
solution containing nucleoside 5'-diphosphates and
polynucleotide phosphorylase!

Joyce G.F. & Orgel L.E.,
"Prospects for Understanding the Origin
of the RNA World," in "The RNA World,"
Gesteland R.F. & Atkins J.F., eds.

==
you may wish to peruse this
review [abridged by me for space]


Self-organizing biochemical cycles
Leslie E. Orgel*
Salk Institute for Biological Studies,
10010 North Torrey Pines Road,
La Jolla, CA 92037-1099
*E-mail: or...@salk.edu.
Contributed by Leslie E. Orgel
Accepted August 24, 2000.


Abstract
I examine the plausibility of theories that postulate the development
of complex chemical organization without requiring the replication
of genetic polymers such as RNA. One conclusion is that theories
that involve the organization of complex, small-molecule metabolic
cycles such as the reductive citric acid cycle on mineral surfaces
make unreasonable assumptions about the catalytic properties of
minerals and the ability of minerals to organize sequences of
disparate reactions. Another conclusion is that data in the Beilstein
Handbook of Organic Chemistry that have been claimed to support
the hypothesis that the reductive citric acid cycle originated as a
self-organized cycle can more plausibly be interpreted
in a different way.

<...>

One possible saving hypothesis is that the molecules that
are the carriers of the cycle are also catalysts for the difficult
reactions of the cycle. Unfortunately, catalytic reactions of
the required kind in aqueous solution are virtually unknown;
there is no reason to believe, for example, that any intermediate
of the citric acid cycle would specifically catalyze any reaction
of the citric acid cycle. The explanation of this is simple:
noncovalent interactions between small molecules in
aqueous solution are generally too weak to permit large
and regiospecific catalytic accelerations. To postulate
one fortuitously catalyzed reaction, perhaps catalyzed
by a metal ion, might be reasonable, but to postulate
a suite of them is to appeal to magic.

<...>


The idea that a complex polymerization reaction such as the
formose reaction or the polymerization of hydrogen cyanide
is likely to simplify to a specific cycle under the influence of
autocatalysis in aqueous solution is implausible. It is not
logically impossible that such an autocatalytic cycle exists,
but because it seems very unlikely from what we already
know about the chemistry of aqueous solutions,
the burden of proof lies with the proposers of such cycles.

W�ソスchtersh�ソスuser has put forward a very specific hypothesis that,
if correct, would overcome all of the difficulties discussed above.
In a scenario that he describes as �ソスTwo-Dimensional Chemi-Autotrophic
Surface Metabolism in an Iron-Sulfur World�ソス (9), he proposes that
the reductive citric acid cycle and much other organized, nonenzymatic
chemistry occurred on the primitive earth, but on the surface of
iron sulfide minerals rather than in aqueous solution. W�ソスchtersh�ソスuser
points out that the conversion of ferrous sulfide (FeS) to pyrites
(FeS2)
in the presence of hydrogen sulfide makes available reducing power
equivalent to molecular hydrogen. This reducing power could be used
to convert carbon dioxide to carbon-containing metabolites.
W�ソスchtersh�ソスuser also claims that the surface of iron sulfide would
constrain the spatial distribution and orientation of the newly
formed products of reduction in such a way as to support
complex sequences of metabolic reactions.

<...>

In summary, it seems very likely that minerals played an important part
in prebiotic chemistry, both as simple adsorbents and as catalysts.
A single mineral is unlikely to have functioned as a specific catalyst
for several unrelated reactions. Even if the members of a suite of
minerals could each catalyze one step in a complex cycle, it does not
seem likely that the cycle would self-organize on their surfaces.
Any suite of minerals that included catalysts for each step of the cycle
would be likely to include, in addition, catalysts for reactions that
disrupt the cycle. Efficient transport of the intermediates from one
catalytic mineral to another would also present severe problems.
There is at present no reason to expect that multistep cycles
such as the reductive citric acid cycle will self-organize
on the surface of FeS/FeS2 or some other mineral.


While it seems almost impossible that a cycle of reactions as
complicated as the reductive citric acid cycle could self-organize
on a mineral surface, W�ソスchterh�ソスuser's suggestion does raise an
interesting and important question. How much self-organization
is it reasonable to expect on a mineral surface in the absence
of evolved, informational catalysts? Clearly, a simple surface
could reasonably be expected to carry out a series of reactions of
essentially the same type, say a series of aldol and reverse
aldol reactions of the type involved in the formose reaction [.],
or a series of reductions of the type involved in the reductive
citric acid cycle. It is not clear that any surface is likely
to catalyze two or more unrelated chemical reactions, but it
would be interesting to try to discover multifunctional surfaces.

The problem of stereospecificity of a sequence of similar reactions
in aqueous solution or on a mineral surface is equally difficult.
Repetition of some basic reaction with constant stereospecificity
does not seem unlikely, because it is routinely achieved by
polymer chemists. Catalysis of a sequence of reactions, each
with a different defined stereospecificity, seems much less plausible.
Just how far one can go in the direction of self-organization
on mineral surfaces is a question for the future. One can be sure
that the complete reverse citric acid cycle is out of range, but
it is not obvious that some much simpler cycle relevant to the
origin of life is impossible. Huber and W�ソスchtersh�ソスuser have
noted the possibility of such a cycle in a footnote added in
proof to ref. 23, but it is not clear whether this cycle is
intended to augment the citric acid cycle or replace it.

The demonstration of a simple specific version of the
formose reaction, for example, would be important, but
studies of the specificity of the formose reaction when
catalyzed by minerals have been disappointing (23).

23. Schwartz A W, de Graaf R M. J Mol Evol. 1993;36:101�ソス106.

<...>

The novel, potentially replicating polymers that have been described
up to now, like the nucleic acids, are formed by joining together
relatively complex monomeric units. It is hard to see how any could
have accumulated on the early earth. A plausible scenario for the
origin of life must, therefore, await the discovery of a genetic polymer
simpler than RNA and an efficient, potentially prebiotic, synthetic
route to the component monomers. The suggestion that relatively
pure, complex organic molecules might be made available in large
amounts via a self-organizing, autocatalytic cycle might, in principle,
help to explain the origin of the component monomers. I have
emphasized the implausibility of the suggestion that complicated
cycles could self-organize, and the importance of learning more
about the potential of surfaces to help organize simpler cycles.



===

==
Postulate 2: Beta-D ribonucleotides spontaneously form polymers
linked together by 3', 5'-phosphodiester linkages (i.e., they link to
form molecules of RNA).

Joyce and Orgel discuss candidly the problems with this postulate.
They note that nucleotides do not link unless there is some type of
activation of the phosphate group. The only effective activating groups
for the nucleotide phosphate group (imidazolides, etc.), however, are
those that are totally implausible in any prebiotic scenario. In living
organisms today, adenosine-5'-triphosphate (ATP) is used for activation
of nucleoside phosphate groups, but ATP would not be available
for prebiotic syntheses. Joyce and Orgel note the possible use
of minerals for polymerization reactions, but then express
their doubts about this possibility:

=================================================
Whenever a problem in prebiotic synthesis seems intractable,
it is possible to postulate the existence of a mineral that
catalyzes the reaction...such claims cannot easily be refuted.
=================================================

-
G.F. Joyce and L.E. Orgel,
"Prospects for understanding the origin of the RNA World,"
in The RNA World, eds. R.F. Gesteland and J.F. Atkins
(Cold Spring Harbor, NY:
Cold Spring Harbor Laboratory Press, 1993), pp. 1-25.
===




Gerald Joyce and Leslie Orgel-two scientists who
have worked on the origin of life problem-call RNA
`the prebiotic chemist's nightmare.

`Scientists interested in the origins of life seem to divide
neatly into two classes. The first, usually but not always
molecular biologists, believe that RNA must have been the
first replicating molecule and that chemists are exaggerating
the difficulties of nucleotide synthesis.... The second
group of scientists are much more pessimistic. They believe
that the de novo appearance of oligonucleotides on the
primitive earth would have been a near miracle.
(The authors subscribe to this latter view).
Time will tell which is correct.
[Joyce G.F. & Orgel L.E., "Prospects for Understanding the Origin
of the RNA World," in "The RNA World," Gesteland R.F. & Atkins J.F.,
eds. Cold Spring Harbor Laboratory Press,
Cold Spring Harbor NY, 1993, p.19]


Even if the miracle-like coincidence should occur and RNA be produced,
however, Joyce and Orgel see nothing but obstacles ahead. In an article
section entitled "Another Chicken-and-Egg Paradox" they write the
following:


This discussion ... has, in a sense, focused on a straw man:
the myth of a self-replicating RNA molecule that arose de novo
from a soup of random polynucleotides. Not only is such a notion
unrealistic in light of our current understanding of prebiotic
chemistry, but it should strain the credulity of even an optimist's
view of RNA s catalytic potential.... Without evolution it appears
unlikely that a self-replicating ribozyme could arise, but without
some form of self-replication there is no way to conduct an
evolutionary search for the first, primitive self-replicating
ribozyme.' [Joyce & Orgel, 1993, p.13]


===
Incubation of the pool RNA...led to rapid and extensive aggregation;
more than half of the pool RNA precipitated when incubated for 90
minutes at 37�ソス C in high concentrations of Mg2+ and monovalent
ions...and
precipitation was even more rapid at higher temperatures. It appears
that conditions that favor RNA intramolecular structure also stabilize
intermolecular interactions; as molecules find regions of
complementarity with more than one other molecule, RNA networks
form and eventually become too large to remain in solution.

David P. Bartel and Jack W. Szostak,
"Isolation of New Ribozymes from a
Large Pool of Random Sequences,
" Science 261 (1993): 1411-1418; p. 1412.
===
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