William Lipscomb
Encyclopedia
William Nunn Lipscomb, Jr. (December 9, 1919 April 14, 2011) was a Nobel Prize-winning American
inorganic
and organic
chemist working in nuclear magnetic resonance
, theoretical chemistry
, boron chemistry
, and biochemistry
.
. His family moved to Lexington, Kentucky
in 1920, and he lived there until he received his Bachelor of Science
degree
in Chemistry at the University of Kentucky
in 1941. He went on to earn his Doctor of Philosophy
degree in Chemistry from the California Institute of Technology (Caltech)
in 1946.
From 1946 to 1959 he taught at the University of Minnesota
. From 1959 to 1990 he was a professor of chemistry
at Harvard University
, where he was a professor emeritus since 1990.
Lipscomb was married to the former Mary Adele Sargent from 1944 to 1983.http://boards.ancestry.com/surnames.sargent/1429/mb.ashx
They had three children, one of whom lived only a few hours.
He married Jean Evans in 1983.http://articles.latimes.com/2011/apr/16/local/la-me-william-lipscomb-20110416
They had one adopted daughter.
Lipscomb resided in Cambridge, Massachusetts
until his death in 2011 from pneumonia
.
Interest in astronomy led him to visitor nights at the Observatory of the University of Kentucky, where Prof. H. H. Downing gave him a copy of Baker's Astronomy.
Lipscomb credits gaining many intuitive physics concepts from this book and from his conversations with Downing, who became Lipscomb's life long friend.
The young Lipscomb participated in other projects, such as Morse-coded
messages over wires and crystal radio sets, with five nearby friends who became physicists, physicians, and an engineer.
At age of 12, Lipscomb was given a small Gilbert chemistry set
,
He expanded it by ordering apparatus and chemicals from suppliers and by using
his father's privilege as a physician to purchase chemicals at the local drugstore at a discount.
Lipscomb made his own fireworks and entertained visitors with color changes, odors, and explosions.
His mother questioned his home chemistry hobby only once, when he attempted to isolate a large amount of urea
from urine
.
Lipscomb credits perusing the large medical texts in his physician father's library and the influence of Linus Pauling
years later to his undertaking biochemical studies in his later years. Had Lipscomb become a physician like his father, he would have been the fourth physician in a row along the Lipscomb male line.
The source for this subsection, except as noted, is Lipscomb's autobiographical sketch.
, analytical
, and general chemistry
, and asked only that Lipscomb take the examinations.
During the class lectures, Lipscomb in the back of the classroom did research that he thought was original (but he later found was not): the preparation of hydrogen
from sodium formate
(or sodium oxalate) and sodium hydroxide.
He took care to include gas analyses and to search for probable side reactions.
Lipscomb later had a high-school physics course and took first prize in the state contest on that subject. He also become very interested in special relativity
.
In college at the University of Kentucky Lipscomb had a music scholarship.
He pursued independent study there, reading Dushman' s Elements of Quantum Mechanics, the University of Pittsburgh
Physics Staff's An Outline of Atomic Physics, and Pauling's The Nature of the Chemical Bond and the Structure of Molecules and Crystals.
Prof. Robert H. Baker suggested that Lipscomb research the direct preparation of derivatives of alcohol
s from dilute aqueous solution
without first separating the alcohol and water, which led to Lipscomb's first publication.
For graduate school Lipscomb chose Caltech, which offered him a teaching assistantship in Physics at $20/month. He turned down more money from Northwestern University
, which offered a research assistantship at $150/month. Columbia University
rejected Lipscomb's application in a letter written by Nobel prizewinner Prof. Harold Urey
.
At Caltech Lipscomb intended to study theoretical quantum mechanics
with Prof. W. V. Houston
in the Physics Department, but after one semester switched to the Chemistry Department under the
influence of Prof. Linus Pauling. World War II work divided Lipscomb's time in graduate school beyond his other thesis work, as he partly analyzed smoke particle size, but mostly worked with nitroglycerin-nitrocellulose
propellants, which involved handling vials of pure nitroglycerin on many occasions.
Brief audio clips by Lipscomb about his war work may be found from the External Links section at the bottom of this page, past the References.
The source for this subsection, except as noted, is Lipscomb's autobiographical sketch.
Some years later in 1973 Lipscomb was made a member of the Honorable Order of Kentucky Colonels
.
Lipscomb, along with several other Nobel laureates, was a regular presenter at the annual Ig Nobel
Awards Ceremony, last doing so on September 30, 2010.http://improbable.com/airchives/paperair/volume17/v17i4/v17i4.htmlhttp://improbable.com/ig/2010/#webcastinfo
In at least the first two of these areas Lipscomb gave himself a big challenge likely to fail,
and then plotted a course of intermediate goals.
"... progress in structure determination, for new polyborane species and for substituted borane
s and carborane
s, would be greatly accelerated if the [boron-11] nuclear magnetic resonance
spectra, rather than X-ray diffraction, could be used."
This goal was partially achieved, although X-ray diffraction is still necessary to determine many such atomic structures. The diagram at left shows a typical nuclear magnetic resonance (NMR) spectrum of a borane molecule.
Lipscomb investigated, "... the carboranes, C2B10H12, and the sites of electrophilic attack on these compounds using nuclear magnetic resonance (NMR) spectroscopy. This work led to [Lipscomb's publication of a comprehensive] theory of chemical shifts. The calculations provided the first accurate values for the constants that describe the behavior of several types of molecules in magnetic or electric fields."
Much of this work is summarized in a book by Gareth Eaton and William Lipscomb, NMR Studies of Boron Hydrides and Related Compounds, one of Lipscomb's two books.
s, and then to discover a systematic valence
description of the vast numbers of electron deficient intermetallic
compounds. I have made little progress toward this latter objective. Instead, the field of boron
chemistry has grown enormously, and a systematic understanding of some of its complexities has now begun."
Examples of these intermetallic compounds are KHg13 and Cu5Zn7. Of perhaps 24,000 of such compounds the structures of only 4,000 are known (in 2005) and we cannot predict structures for the others, because we do not sufficiently understand the nature of the chemical bond.
This study was not successful, in part because the calculation time required for intermetallic compounds was out of reach in the 1960s, but intermediate goals involving boron bonding were achieved, sufficient to be awarded a Nobel Prize.
Lipscomb deduced the molecular structure
of borane
s (compounds of boron and hydrogen) using X-ray crystallography
in the 1950s and developed theories to explain their bond
s. Later he applied the same methods to related problems, including the structure of carborane
s (compounds of carbon, boron, and hydrogen).
Diborane
is a simple molecule (diagrams at right) that illustrates some of Lipscomb's contributions to understanding the nature of the chemical bond.
Over several decades the structure and bonding arrangement was gradually discovered by
Dilthey,
Price, and others.
In an ordinary covalent bond a pair of electrons bonds two atoms together, one at either end of the bond.
Longuet-Higgins
and Roberts
employed a three-center two-electron bond
, in which a pair of electrons bonds three atoms (a boron atom at either end and a hydrogen atom in the middle), as the correct way to understand bonding in diborane using a molecular orbital description similar to what the Lipscomb group found.
Eberhardt, Crawford, and Lipscomb proposed the mechanism of the three-center two-electron bond, and Lipscomb's group achieved an understanding of it through electron orbital calculations using formulas by Edmiston and Ruedenberg and by Boys.
The Eberhardt, Crawford, and Lipscomb paper also devised the "styx number" method to catalog certain kinds of boron-hydride bonding configurations.
Compounds of boron and hydrogen tend to form closed cage structures. Sometimes the vertices of these cages move substantial distances with respect to each other. The diamond-square-diamond mechanism (diagram at left) was suggested by Lipscomb to explain the rearrangement of BH and CH vertices in polyhedral closo-boranes and closo-carboranes
. The DSD diagram at left shows the first two steps of rearrangement shown in this link. Lipscomb proposed that conversion of the ortho-carborane involves six simultaneous DSD processes that give rise typically to a cuboctahedron
,
which can then collapse.
The B10H16 structure (diagram at right) determined by Grimes, Wang, Lewin, and Lipscomb found a bond directly between two boron atoms without terminal hydrogens, a feature not previously seen in other boron hydrides.
Lipscomb's group developed calculation methods, both empirical and from quantum mechanical theory.
Calculations by these methods produced accurate Hartree–Fock self-consistent field (SCF) molecular orbital
s and were used to study boranes and carboranes.
The ethane
barrier to rotation (diagram at left) was first calculated accurately by Pitzer
and Lipscomb using the Hartree-Fock (SCF) method.
Lipscomb's calculations continued to a detailed examination of partial bonding through "... theoretical studies of multicentered chemical bonds including both delocalized and localized molecular orbitals
."
This included "... proposed molecular orbital descriptions in which the bonding electrons are delocalized over the whole molecule."http://accessscience.proxy.mpcc.edu/content.aspx?searchStr=Carborane&id=M0090688
"Lipscomb and his coworkers developed the idea of transferability of atomic properties, by which approximate theories for complex molecules are developed from more exact calculations for simpler but chemically related molecules, ...."http://accessscience.proxy.mpcc.edu/content.aspx?searchStr=Carborane&id=M0090688
Subsequent Nobel Prize
winner Roald Hoffmann
was a doctoral student
in Lipscomb's laboratory.
Under Lipscomb's direction the Extended Huckel method
of molecular orbital calculation was developed by Lawrence Lohr and by Roald Hoffmann. This method was later extended by Hoffman.
In Lipscomb's laboratory this method was reconciled with self-consistent field (SCF) theory by Newton and by Boer.
Noted boron chemist M. Frederick Hawthorne
conducted early and continuing research with Lipscomb.
Much of this work is summarized in a book by Lipscomb, Boron Hydrides, one of Lipscomb's two books.
The 1976 Nobel Prize in Chemistry
was awarded to Lipscomb "for his studies on the structure of boranes illuminating problems of chemical bonding".http://nobelprize.org/nobel_prizes/chemistry/laureates/1976/
In a way this continued work on the nature of the chemical bond by his Doctoral Advisor at the California Institute of Technology, Linus Pauling
, who was awarded the 1954 Nobel Prize in Chemistry "for his research into the nature of the chemical bond and its application to the elucidation of the structure of complex substances."http://nobelprize.org/nobel_prizes/chemistry/laureates/1954/
The source for about half of this section is Lipscomb's Nobel Lecture.
s, particularly how enzymes work.
His group used x-ray diffraction to solve the three-dimensional structure of these proteins to atomic resolution, and then to analyze the atomic detail of how the molecules work.
The images below are of Lipscomb's structures from the Protein Data Bank http://www.rcsb.org/ displayed in simplified form with atomic detail suppressed. Proteins are chains of amino acids, and the continuous ribbon shows the trace of the chain with, for example, several amino acids for each turn of a helix.
Carboxypeptidase A
(left) was the first protein structure from Lipscomb's group. Carboxypeptidase A is a digestive enzyme, a protein that digests other proteins. It is made in the pancreas and transported in inactive form to the intestines where it is activated. Carboxypeptidase A digests by chopping off certain amino acids one-by-one from one end of a protein.
The size of this structure was ambitious. Carboxypeptidase A was a much larger molecule than anything solved previously.
Aspartate carbamoyltransferase
. (right) was the second protein structure from Lipscomb's group.
For a copy of DNA
to be made, a duplicate set of its nucleotide
s is required. Aspartate carbamoyltransferase performs a step in building the pyrimidine
nucleotides (cytosine
and thymidine
). Aspartate carbamoyltransferase also ensures that just the right amount of pyrimidine nucleotides is available, as activator and inhibitor molecules attach to aspartate carbamoyltransferase to speed it up and to slow it down.
Aspartate carbamoyltransferase is a complex of twelve molecules.
Six large catalytic molecules in the interior do the work, and six small regulatory molecules on the outside control how fast the catalytic units work.
The size of this structure was ambitious. Aspartate carbamoyltransferase was a much larger molecule than anything solved previously.
Leucine aminopeptidase
, (left) a little like carboxypeptidase A, chops off certain amino acids one-by-one from one end of a protein or peptide
.
HaeIII methyltransferase
(right)
binds to DNA where it methylates
(adds a methy group to)
it.
Human interferon
beta (left)
is released by lymphocyte
s in response to pathogen
s to trigger the immune system
.
Chorismate mutase
(right)
catalyzes
(speeds up) the production of the amino acids phenylalanine
and tyrosine
.
Fructose-1,6-bisphosphatase (left)
and its inhibitor MB06322 (CS-917)
were studied by Lipscomb's group in a collaboration, which included Metabasis Therapeutics, Inc., acquired by Ligand Pharmaceuticals in 2010, exploring the possibility of finding a treatment for type 2 diabetes
, as the MB06322 inhibitor slows the production of sugar by fructose-1,6-bisphosphatase.
Lipscomb's group also contributed to an understanding of
concanavalin A
(low resolution structure),
glucagon
, and
carbonic anhydrase
(theoretical studies).
Subsequent Nobel Prize
winner Thomas A. Steitz
was a doctoral student in Lipscomb's laboratory.
Under Lipscomb's direction, after the training task of determining the structure of the small molecule methyl ethylene phosphate, Steitz made contributions to determining the atomic structures of carboxypeptidase A
and aspartate carbamoyltransferase
.
Steitz was awarded the 2009 Nobel Prize in Chemistry
for determining the even larger structure of the large 50S
ribosomal subunit, leading to an understanding of possible medical treatments.
Subsequent Nobel Prize
winner Ada Yonath
, who shared the 2009 Nobel Prize in Chemistry with Thomas A. Steitz
and Venkatraman Ramakrishnan, spent some time in Lipscomb's lab where both she and Steitz were inspired to pursue later their own very large structures. This was while she was a postdoctoral student at MIT in 1970.
(picture at right) was named after Professor Lipscomb by the mineralogist John Gruner who first made it artificially.
Low-temperature x-ray diffraction was pioneered in Lipscomb's laboratory at about the same time as parallel work in Isadore Fankuchen’s laboratory at the then Polytechnic Institute of Brooklyn.
Lipscomb began by studying compounds of nitrogen, oxygen, fluorine, and other substances that are solid only below liquid nitrogen temperatures, but other advantages eventually made low-temperatures a normal procedure.
Keeping the crystal cold during data collection produces a less-blurry 3-D electron-density map because the atoms have less thermal motion. Crystals may yield good data in the x-ray beam longer because x-ray damage may be reduced during data collection and because the solvent may evaporate more slowly, which for example may be important for large biochemical molecules whose crystals often have a high percentage of water.
Other important compounds were studied by Lipscomb and his students.
Among these are
hydrazine
,
nitric oxide
,
metal-dithiolene complexes,
methyl ethylene phosphate,
mercury amide
s,
(NO)2,
crystalline hydrogen fluoride
,
Roussin's black salt
,
(PCF3)5,
complexes of cyclo-octatetraene
with iron tricarbonyl
,
and leurocristine (Vincristine)
, which is used in several cancer therapies.
Five books and published symposia are dedicated to Lipscomb.
A complete list of Lipscomb's awards and honors is in his Curriculum Vitae.http://wlipscomb.tripod.com/publications_biog_cv.html
People of the United States
The people of the United States, also known as simply Americans or American people, are the inhabitants or citizens of the United States. The United States is a multi-ethnic nation, home to people of different ethnic and national backgrounds...
inorganic
Inorganic chemistry
Inorganic chemistry is the branch of chemistry concerned with the properties and behavior of inorganic compounds. This field covers all chemical compounds except the myriad organic compounds , which are the subjects of organic chemistry...
and organic
Organic chemistry
Organic chemistry is a subdiscipline within chemistry involving the scientific study of the structure, properties, composition, reactions, and preparation of carbon-based compounds, hydrocarbons, and their derivatives...
chemist working in nuclear magnetic resonance
Nuclear magnetic resonance
Nuclear magnetic resonance is a physical phenomenon in which magnetic nuclei in a magnetic field absorb and re-emit electromagnetic radiation...
, theoretical chemistry
Theoretical chemistry
Theoretical chemistry seeks to provide theories that explain chemical observations. Often, it uses mathematical and computational methods that, at times, require advanced knowledge. Quantum chemistry, the application of quantum mechanics to the understanding of valency, is a major component of...
, boron chemistry
Boron
Boron is the chemical element with atomic number 5 and the chemical symbol B. Boron is a metalloid. Because boron is not produced by stellar nucleosynthesis, it is a low-abundance element in both the solar system and the Earth's crust. However, boron is concentrated on Earth by the...
, and biochemistry
Biochemistry
Biochemistry, sometimes called biological chemistry, is the study of chemical processes in living organisms, including, but not limited to, living matter. Biochemistry governs all living organisms and living processes...
.
Overview
Lipscomb was born in Cleveland, OhioCleveland, Ohio
Cleveland is a city in the U.S. state of Ohio and is the county seat of Cuyahoga County, the most populous county in the state. The city is located in northeastern Ohio on the southern shore of Lake Erie, approximately west of the Pennsylvania border...
. His family moved to Lexington, Kentucky
Lexington, Kentucky
Lexington is the second-largest city in Kentucky and the 63rd largest in the US. Known as the "Thoroughbred City" and the "Horse Capital of the World", it is located in the heart of Kentucky's Bluegrass region...
in 1920, and he lived there until he received his Bachelor of Science
Bachelor of Science
A Bachelor of Science is an undergraduate academic degree awarded for completed courses that generally last three to five years .-Australia:In Australia, the BSc is a 3 year degree, offered from 1st year on...
degree
Academic degree
An academic degree is a position and title within a college or university that is usually awarded in recognition of the recipient having either satisfactorily completed a prescribed course of study or having conducted a scholarly endeavour deemed worthy of his or her admission to the degree...
in Chemistry at the University of Kentucky
University of Kentucky
The University of Kentucky, also known as UK, is a public co-educational university and is one of the state's two land-grant universities, located in Lexington, Kentucky...
in 1941. He went on to earn his Doctor of Philosophy
Doctor of Philosophy
Doctor of Philosophy, abbreviated as Ph.D., PhD, D.Phil., or DPhil , in English-speaking countries, is a postgraduate academic degree awarded by universities...
degree in Chemistry from the California Institute of Technology (Caltech)
California Institute of Technology
The California Institute of Technology is a private research university located in Pasadena, California, United States. Caltech has six academic divisions with strong emphases on science and engineering...
in 1946.
From 1946 to 1959 he taught at the University of Minnesota
University of Minnesota
The University of Minnesota, Twin Cities is a public research university located in Minneapolis and St. Paul, Minnesota, United States. It is the oldest and largest part of the University of Minnesota system and has the fourth-largest main campus student body in the United States, with 52,557...
. From 1959 to 1990 he was a professor of chemistry
Chemistry
Chemistry is the science of matter, especially its chemical reactions, but also its composition, structure and properties. Chemistry is concerned with atoms and their interactions with other atoms, and particularly with the properties of chemical bonds....
at Harvard University
Harvard University
Harvard University is a private Ivy League university located in Cambridge, Massachusetts, United States, established in 1636 by the Massachusetts legislature. Harvard is the oldest institution of higher learning in the United States and the first corporation chartered in the country...
, where he was a professor emeritus since 1990.
Lipscomb was married to the former Mary Adele Sargent from 1944 to 1983.http://boards.ancestry.com/surnames.sargent/1429/mb.ashx
They had three children, one of whom lived only a few hours.
He married Jean Evans in 1983.http://articles.latimes.com/2011/apr/16/local/la-me-william-lipscomb-20110416
They had one adopted daughter.
Lipscomb resided in Cambridge, Massachusetts
Cambridge, Massachusetts
Cambridge is a city in Middlesex County, Massachusetts, United States, in the Greater Boston area. It was named in honor of the University of Cambridge in England, an important center of the Puritan theology embraced by the town's founders. Cambridge is home to two of the world's most prominent...
until his death in 2011 from pneumonia
Pneumonia
Pneumonia is an inflammatory condition of the lung—especially affecting the microscopic air sacs —associated with fever, chest symptoms, and a lack of air space on a chest X-ray. Pneumonia is typically caused by an infection but there are a number of other causes...
.
Early Years
In grade school Lipscomb collected animals, insects, pets, rocks, and minerals.Interest in astronomy led him to visitor nights at the Observatory of the University of Kentucky, where Prof. H. H. Downing gave him a copy of Baker's Astronomy.
Lipscomb credits gaining many intuitive physics concepts from this book and from his conversations with Downing, who became Lipscomb's life long friend.
The young Lipscomb participated in other projects, such as Morse-coded
Morse code
Morse code is a method of transmitting textual information as a series of on-off tones, lights, or clicks that can be directly understood by a skilled listener or observer without special equipment...
messages over wires and crystal radio sets, with five nearby friends who became physicists, physicians, and an engineer.
At age of 12, Lipscomb was given a small Gilbert chemistry set
Chemistry set
A chemistry set is an educational toy allowing the user to perform simple chemistry experiments. The best known such sets were produced by the A. C. Gilbert Company, an early and middle 20th century American manufacturer of educational toys...
,
He expanded it by ordering apparatus and chemicals from suppliers and by using
his father's privilege as a physician to purchase chemicals at the local drugstore at a discount.
Lipscomb made his own fireworks and entertained visitors with color changes, odors, and explosions.
His mother questioned his home chemistry hobby only once, when he attempted to isolate a large amount of urea
Urea
Urea or carbamide is an organic compound with the chemical formula CO2. The molecule has two —NH2 groups joined by a carbonyl functional group....
from urine
Urine
Urine is a typically sterile liquid by-product of the body that is secreted by the kidneys through a process called urination and excreted through the urethra. Cellular metabolism generates numerous by-products, many rich in nitrogen, that require elimination from the bloodstream...
.
Lipscomb credits perusing the large medical texts in his physician father's library and the influence of Linus Pauling
Linus Pauling
Linus Carl Pauling was an American chemist, biochemist, peace activist, author, and educator. He was one of the most influential chemists in history and ranks among the most important scientists of the 20th century...
years later to his undertaking biochemical studies in his later years. Had Lipscomb become a physician like his father, he would have been the fourth physician in a row along the Lipscomb male line.
The source for this subsection, except as noted, is Lipscomb's autobiographical sketch.
Education
Lipscomb's high-school chemistry teacher, Frederick Jones, gave Lipscomb his college books on organicOrganic chemistry
Organic chemistry is a subdiscipline within chemistry involving the scientific study of the structure, properties, composition, reactions, and preparation of carbon-based compounds, hydrocarbons, and their derivatives...
, analytical
Analytical chemistry
Analytical chemistry is the study of the separation, identification, and quantification of the chemical components of natural and artificial materials. Qualitative analysis gives an indication of the identity of the chemical species in the sample and quantitative analysis determines the amount of...
, and general chemistry
General chemistry
General chemistry is a course often taught at the high school and introductory university level. It is intended to serve as a broad introduction to a variety of concepts in chemistry and is widely taught...
, and asked only that Lipscomb take the examinations.
During the class lectures, Lipscomb in the back of the classroom did research that he thought was original (but he later found was not): the preparation of hydrogen
Hydrogen
Hydrogen is the chemical element with atomic number 1. It is represented by the symbol H. With an average atomic weight of , hydrogen is the lightest and most abundant chemical element, constituting roughly 75% of the Universe's chemical elemental mass. Stars in the main sequence are mainly...
from sodium formate
Sodium formate
Sodium formate, HCOONa, is the sodium salt of formic acid, HCOOH. It usually appears as a white deliquescent powder.-Uses:Sodium formate is used in several fabric dyeing and printing processes...
(or sodium oxalate) and sodium hydroxide.
He took care to include gas analyses and to search for probable side reactions.
Lipscomb later had a high-school physics course and took first prize in the state contest on that subject. He also become very interested in special relativity
Special relativity
Special relativity is the physical theory of measurement in an inertial frame of reference proposed in 1905 by Albert Einstein in the paper "On the Electrodynamics of Moving Bodies".It generalizes Galileo's...
.
In college at the University of Kentucky Lipscomb had a music scholarship.
He pursued independent study there, reading Dushman' s Elements of Quantum Mechanics, the University of Pittsburgh
University of Pittsburgh
The University of Pittsburgh, commonly referred to as Pitt, is a state-related research university located in Pittsburgh, Pennsylvania, United States. Founded as Pittsburgh Academy in 1787 on what was then the American frontier, Pitt is one of the oldest continuously chartered institutions of...
Physics Staff's An Outline of Atomic Physics, and Pauling's The Nature of the Chemical Bond and the Structure of Molecules and Crystals.
Prof. Robert H. Baker suggested that Lipscomb research the direct preparation of derivatives of alcohol
Alcohol
In chemistry, an alcohol is an organic compound in which the hydroxy functional group is bound to a carbon atom. In particular, this carbon center should be saturated, having single bonds to three other atoms....
s from dilute aqueous solution
Aqueous solution
An aqueous solution is a solution in which the solvent is water. It is usually shown in chemical equations by appending aq to the relevant formula, such as NaCl. The word aqueous means pertaining to, related to, similar to, or dissolved in water...
without first separating the alcohol and water, which led to Lipscomb's first publication.
For graduate school Lipscomb chose Caltech, which offered him a teaching assistantship in Physics at $20/month. He turned down more money from Northwestern University
Northwestern University
Northwestern University is a private research university in Evanston and Chicago, Illinois, USA. Northwestern has eleven undergraduate, graduate, and professional schools offering 124 undergraduate degrees and 145 graduate and professional degrees....
, which offered a research assistantship at $150/month. Columbia University
Columbia University
Columbia University in the City of New York is a private, Ivy League university in Manhattan, New York City. Columbia is the oldest institution of higher learning in the state of New York, the fifth oldest in the United States, and one of the country's nine Colonial Colleges founded before the...
rejected Lipscomb's application in a letter written by Nobel prizewinner Prof. Harold Urey
Harold Urey
Harold Clayton Urey was an American physical chemist whose pioneering work on isotopes earned him the Nobel Prize in Chemistry in 1934...
.
At Caltech Lipscomb intended to study theoretical quantum mechanics
Quantum mechanics
Quantum mechanics, also known as quantum physics or quantum theory, is a branch of physics providing a mathematical description of much of the dual particle-like and wave-like behavior and interactions of energy and matter. It departs from classical mechanics primarily at the atomic and subatomic...
with Prof. W. V. Houston
William Vermillion Houston
William Vermillion Houston was an American physicist who made contributions to spectroscopy, quantum mechanics, and solid-state physics as well as being a teacher and administrator.His family name is pronounced HOW-stun, in contrast to the pronunciation of the city of Houston in which he lived...
in the Physics Department, but after one semester switched to the Chemistry Department under the
influence of Prof. Linus Pauling. World War II work divided Lipscomb's time in graduate school beyond his other thesis work, as he partly analyzed smoke particle size, but mostly worked with nitroglycerin-nitrocellulose
Nitrocellulose
Nitrocellulose is a highly flammable compound formed by nitrating cellulose through exposure to nitric acid or another powerful nitrating agent. When used as a propellant or low-order explosive, it is also known as guncotton...
propellants, which involved handling vials of pure nitroglycerin on many occasions.
Brief audio clips by Lipscomb about his war work may be found from the External Links section at the bottom of this page, past the References.
The source for this subsection, except as noted, is Lipscomb's autobiographical sketch.
Later Years
The Colonel is how Lipscomb's students referred to him, directly addressing him as Colonel. "His first doctoral student, Murray Vernon King, pinned the label on him, and it was quickly adopted by other students, who wanted to use an appellation that showed informal respect. ... Lipscomb's Kentucky origins as the rationale for the designation."Some years later in 1973 Lipscomb was made a member of the Honorable Order of Kentucky Colonels
Kentucky colonel
Kentucky colonel is the highest title of honor bestowed by the Commonwealth of Kentucky. Commissions for Kentucky colonels are given by the Governor and the Secretary of State to individuals in recognition of noteworthy accomplishments and outstanding service to a community, state or the nation...
.
Lipscomb, along with several other Nobel laureates, was a regular presenter at the annual Ig Nobel
Ig Nobel Prize
The Ig Nobel Prizes are an American parody of the Nobel Prizes and are given each year in early October for ten unusual or trivial achievements in scientific research. The stated aim of the prizes is to "first make people laugh, and then make them think"...
Awards Ceremony, last doing so on September 30, 2010.http://improbable.com/airchives/paperair/volume17/v17i4/v17i4.htmlhttp://improbable.com/ig/2010/#webcastinfo
Scientific Studies
Lipscomb has worked in three main areas, nuclear magnetic resonance and the chemical shift, boron chemistry and the nature of the chemical bond, and large biochemical molecules. These areas overlap in time and share some scientific techniques.In at least the first two of these areas Lipscomb gave himself a big challenge likely to fail,
and then plotted a course of intermediate goals.
Nuclear Magnetic Resonance and the Chemical Shift
In this area Lipscomb proposed that:"... progress in structure determination, for new polyborane species and for substituted borane
Borane
In chemistry, a borane is a chemical compound of boron and hydrogen. The boranes comprise a large group of compounds with the generic formulae of BxHy. These compounds do not occur in nature. Many of the boranes readily oxidise on contact with air, some violently. The parent member BH3 is called...
s and carborane
Carborane
A carborane is a cluster composed of boron and carbon atoms. Like many of the related boranes, these clusters are polyhedra and are similarly classified as closo-, nido-, arachno-, hypho-, etc...
s, would be greatly accelerated if the [boron-11] nuclear magnetic resonance
Nuclear magnetic resonance
Nuclear magnetic resonance is a physical phenomenon in which magnetic nuclei in a magnetic field absorb and re-emit electromagnetic radiation...
spectra, rather than X-ray diffraction, could be used."
This goal was partially achieved, although X-ray diffraction is still necessary to determine many such atomic structures. The diagram at left shows a typical nuclear magnetic resonance (NMR) spectrum of a borane molecule.
Lipscomb investigated, "... the carboranes, C2B10H12, and the sites of electrophilic attack on these compounds using nuclear magnetic resonance (NMR) spectroscopy. This work led to [Lipscomb's publication of a comprehensive] theory of chemical shifts. The calculations provided the first accurate values for the constants that describe the behavior of several types of molecules in magnetic or electric fields."
Much of this work is summarized in a book by Gareth Eaton and William Lipscomb, NMR Studies of Boron Hydrides and Related Compounds, one of Lipscomb's two books.
Boron Chemistry and the Nature of the Chemical Bond
In this area Lipscomb originally intended a more ambitious project: "My original intention in the late 1940’s was to spend a few years understanding the boraneBorane
In chemistry, a borane is a chemical compound of boron and hydrogen. The boranes comprise a large group of compounds with the generic formulae of BxHy. These compounds do not occur in nature. Many of the boranes readily oxidise on contact with air, some violently. The parent member BH3 is called...
s, and then to discover a systematic valence
Valence (chemistry)
In chemistry, valence, also known as valency or valence number, is a measure of the number of bonds formed by an atom of a given element. "Valence" can be defined as the number of valence bonds...
description of the vast numbers of electron deficient intermetallic
Intermetallics
Intermetallics or intermetallic compounds is a term that is used in a number of different ways. Most commonly it refers to solid-state phases involving metals. There is a "research definition" adhered to generally in scientific publications, and a wider "common use" term...
compounds. I have made little progress toward this latter objective. Instead, the field of boron
Boron
Boron is the chemical element with atomic number 5 and the chemical symbol B. Boron is a metalloid. Because boron is not produced by stellar nucleosynthesis, it is a low-abundance element in both the solar system and the Earth's crust. However, boron is concentrated on Earth by the...
chemistry has grown enormously, and a systematic understanding of some of its complexities has now begun."
Examples of these intermetallic compounds are KHg13 and Cu5Zn7. Of perhaps 24,000 of such compounds the structures of only 4,000 are known (in 2005) and we cannot predict structures for the others, because we do not sufficiently understand the nature of the chemical bond.
This study was not successful, in part because the calculation time required for intermetallic compounds was out of reach in the 1960s, but intermediate goals involving boron bonding were achieved, sufficient to be awarded a Nobel Prize.
Lipscomb deduced the molecular structure
Molecular structure
The molecular structure of a substance is described by the combination of nuclei and electrons that comprise its constitute molecules. This includes the molecular geometry , the electronic properties of the...
of borane
Borane
In chemistry, a borane is a chemical compound of boron and hydrogen. The boranes comprise a large group of compounds with the generic formulae of BxHy. These compounds do not occur in nature. Many of the boranes readily oxidise on contact with air, some violently. The parent member BH3 is called...
s (compounds of boron and hydrogen) using X-ray crystallography
X-ray crystallography
X-ray crystallography is a method of determining the arrangement of atoms within a crystal, in which a beam of X-rays strikes a crystal and causes the beam of light to spread into many specific directions. From the angles and intensities of these diffracted beams, a crystallographer can produce a...
in the 1950s and developed theories to explain their bond
Chemical bond
A chemical bond is an attraction between atoms that allows the formation of chemical substances that contain two or more atoms. The bond is caused by the electromagnetic force attraction between opposite charges, either between electrons and nuclei, or as the result of a dipole attraction...
s. Later he applied the same methods to related problems, including the structure of carborane
Carborane
A carborane is a cluster composed of boron and carbon atoms. Like many of the related boranes, these clusters are polyhedra and are similarly classified as closo-, nido-, arachno-, hypho-, etc...
s (compounds of carbon, boron, and hydrogen).
Diborane
Diborane
Diborane is the chemical compound consisting of boron and hydrogen with the formula B2H6. It is a colorless gas at room temperature with a repulsively sweet odor. Diborane mixes well with air, easily forming explosive mixtures. Diborane will ignite spontaneously in moist air at room temperature...
is a simple molecule (diagrams at right) that illustrates some of Lipscomb's contributions to understanding the nature of the chemical bond.
Over several decades the structure and bonding arrangement was gradually discovered by
Dilthey,
Price, and others.
In an ordinary covalent bond a pair of electrons bonds two atoms together, one at either end of the bond.
Longuet-Higgins
H. Christopher Longuet-Higgins
Hugh Christopher Longuet-Higgins FRS was both a theoretical chemist and a cognitive scientist. He was born on April 11, 1923 in Kent, England and died on March 27, 2004....
and Roberts
employed a three-center two-electron bond
Three-center two-electron bond
A three-center two-electron bond is an electron-deficient chemical bond where three atoms share two electrons. The combination of three atomic orbitals form three molecular orbitals: one bonding, one non-bonding, and one anti-bonding. The two electrons go into the bonding orbital, resulting in a...
, in which a pair of electrons bonds three atoms (a boron atom at either end and a hydrogen atom in the middle), as the correct way to understand bonding in diborane using a molecular orbital description similar to what the Lipscomb group found.
Eberhardt, Crawford, and Lipscomb proposed the mechanism of the three-center two-electron bond, and Lipscomb's group achieved an understanding of it through electron orbital calculations using formulas by Edmiston and Ruedenberg and by Boys.
The Eberhardt, Crawford, and Lipscomb paper also devised the "styx number" method to catalog certain kinds of boron-hydride bonding configurations.
Compounds of boron and hydrogen tend to form closed cage structures. Sometimes the vertices of these cages move substantial distances with respect to each other. The diamond-square-diamond mechanism (diagram at left) was suggested by Lipscomb to explain the rearrangement of BH and CH vertices in polyhedral closo-boranes and closo-carboranes
Polyhedral skeletal electron pair theory
In chemistry the polyhedral skeletal electron pair theory provides electron counting rules useful for predicting the structures of clusters such as borane and carborane clusters. The electron counting rules were originally formulated by Kenneth Wade and were further developed by D. M. P. Mingos and...
. The DSD diagram at left shows the first two steps of rearrangement shown in this link. Lipscomb proposed that conversion of the ortho-carborane involves six simultaneous DSD processes that give rise typically to a cuboctahedron
Cuboctahedron
In geometry, a cuboctahedron is a polyhedron with eight triangular faces and six square faces. A cuboctahedron has 12 identical vertices, with two triangles and two squares meeting at each, and 24 identical edges, each separating a triangle from a square. As such it is a quasiregular polyhedron,...
,
which can then collapse.
The B10H16 structure (diagram at right) determined by Grimes, Wang, Lewin, and Lipscomb found a bond directly between two boron atoms without terminal hydrogens, a feature not previously seen in other boron hydrides.
Lipscomb's group developed calculation methods, both empirical and from quantum mechanical theory.
Calculations by these methods produced accurate Hartree–Fock self-consistent field (SCF) molecular orbital
Molecular orbital
In chemistry, a molecular orbital is a mathematical function describing the wave-like behavior of an electron in a molecule. This function can be used to calculate chemical and physical properties such as the probability of finding an electron in any specific region. The term "orbital" was first...
s and were used to study boranes and carboranes.
The ethane
Ethane
Ethane is a chemical compound with chemical formula C2H6. It is the only two-carbon alkane that is an aliphatic hydrocarbon. At standard temperature and pressure, ethane is a colorless, odorless gas....
barrier to rotation (diagram at left) was first calculated accurately by Pitzer
Russell M. Pitzer
Russell Mosher Pitzer is an American theoretical chemist and educator.He was born on May 10, 1938, in Berkeley, California and attended public schools in this and the Washington, DC area....
and Lipscomb using the Hartree-Fock (SCF) method.
Lipscomb's calculations continued to a detailed examination of partial bonding through "... theoretical studies of multicentered chemical bonds including both delocalized and localized molecular orbitals
Localized molecular orbitals
Localized molecular orbitals are molecular orbitals which are concentrated in a limited spatial region of a molecule, for example a specific bond or a lone pair on a specific atom...
."
This included "... proposed molecular orbital descriptions in which the bonding electrons are delocalized over the whole molecule."http://accessscience.proxy.mpcc.edu/content.aspx?searchStr=Carborane&id=M0090688
"Lipscomb and his coworkers developed the idea of transferability of atomic properties, by which approximate theories for complex molecules are developed from more exact calculations for simpler but chemically related molecules, ...."http://accessscience.proxy.mpcc.edu/content.aspx?searchStr=Carborane&id=M0090688
Subsequent Nobel Prize
Nobel Prize in Chemistry
The Nobel Prize in Chemistry is awarded annually by the Royal Swedish Academy of Sciences to scientists in the various fields of chemistry. It is one of the five Nobel Prizes established by the will of Alfred Nobel in 1895, awarded for outstanding contributions in chemistry, physics, literature,...
winner Roald Hoffmann
Roald Hoffmann
Roald Hoffmann is an American theoretical chemist who won the 1981 Nobel Prize in Chemistry. He currently teaches at Cornell University in Ithaca, New York.-Escape from the Holocaust:...
was a doctoral student
in Lipscomb's laboratory.
Under Lipscomb's direction the Extended Huckel method
Extended Huckel method
The extended Hückel method is a semiempirical quantum chemistry method, developed by Roald Hoffmann since 1963. It is based on the Hückel method but, while the original Hückel method only considers pi orbitals, the extended method also includes the sigma orbitals.The extended Hückel method can be...
of molecular orbital calculation was developed by Lawrence Lohr and by Roald Hoffmann. This method was later extended by Hoffman.
In Lipscomb's laboratory this method was reconciled with self-consistent field (SCF) theory by Newton and by Boer.
Noted boron chemist M. Frederick Hawthorne
M. Frederick Hawthorne
Professor M. Frederick Hawthorne was born in 1928 in Fort Scott, Kansas and he received his elementary and secondary education in Kansas and Missouri. Prior to high school graduation, through examination he entered the Missouri School of Mines and Metallurgy, Rolla, Missouri as a chemical...
conducted early and continuing research with Lipscomb.
Much of this work is summarized in a book by Lipscomb, Boron Hydrides, one of Lipscomb's two books.
The 1976 Nobel Prize in Chemistry
Nobel Prize in Chemistry
The Nobel Prize in Chemistry is awarded annually by the Royal Swedish Academy of Sciences to scientists in the various fields of chemistry. It is one of the five Nobel Prizes established by the will of Alfred Nobel in 1895, awarded for outstanding contributions in chemistry, physics, literature,...
was awarded to Lipscomb "for his studies on the structure of boranes illuminating problems of chemical bonding".http://nobelprize.org/nobel_prizes/chemistry/laureates/1976/
In a way this continued work on the nature of the chemical bond by his Doctoral Advisor at the California Institute of Technology, Linus Pauling
Linus Pauling
Linus Carl Pauling was an American chemist, biochemist, peace activist, author, and educator. He was one of the most influential chemists in history and ranks among the most important scientists of the 20th century...
, who was awarded the 1954 Nobel Prize in Chemistry "for his research into the nature of the chemical bond and its application to the elucidation of the structure of complex substances."http://nobelprize.org/nobel_prizes/chemistry/laureates/1954/
The source for about half of this section is Lipscomb's Nobel Lecture.
Large Biological Molecule Structure and Function
Lipscomb's later research focused on the atomic structure of proteinProtein
Proteins are biochemical compounds consisting of one or more polypeptides typically folded into a globular or fibrous form, facilitating a biological function. A polypeptide is a single linear polymer chain of amino acids bonded together by peptide bonds between the carboxyl and amino groups of...
s, particularly how enzymes work.
His group used x-ray diffraction to solve the three-dimensional structure of these proteins to atomic resolution, and then to analyze the atomic detail of how the molecules work.
The images below are of Lipscomb's structures from the Protein Data Bank http://www.rcsb.org/ displayed in simplified form with atomic detail suppressed. Proteins are chains of amino acids, and the continuous ribbon shows the trace of the chain with, for example, several amino acids for each turn of a helix.
Carboxypeptidase A
Carboxypeptidase A
Carboxypeptidase A usually refers to the pancreatic exopeptidase which hydrolyzes peptide bonds of C-terminal residues with aromatic or aliphatic side chains...
(left) was the first protein structure from Lipscomb's group. Carboxypeptidase A is a digestive enzyme, a protein that digests other proteins. It is made in the pancreas and transported in inactive form to the intestines where it is activated. Carboxypeptidase A digests by chopping off certain amino acids one-by-one from one end of a protein.
The size of this structure was ambitious. Carboxypeptidase A was a much larger molecule than anything solved previously.
Aspartate carbamoyltransferase
Aspartate carbamoyltransferase
Aspartate carbamoyltransferase catalyzes the first step in the pyrimidine biosynthetic pathway .In E. coli, the enzyme is a multi-subunit protein complex composed of 12 subunits...
. (right) was the second protein structure from Lipscomb's group.
For a copy of DNA
DNA
Deoxyribonucleic acid is a nucleic acid that contains the genetic instructions used in the development and functioning of all known living organisms . The DNA segments that carry this genetic information are called genes, but other DNA sequences have structural purposes, or are involved in...
to be made, a duplicate set of its nucleotide
Nucleotide
Nucleotides are molecules that, when joined together, make up the structural units of RNA and DNA. In addition, nucleotides participate in cellular signaling , and are incorporated into important cofactors of enzymatic reactions...
s is required. Aspartate carbamoyltransferase performs a step in building the pyrimidine
Pyrimidine
Pyrimidine is a heterocyclic aromatic organic compound similar to benzene and pyridine, containing two nitrogen atoms at positions 1 and 3 of the six-member ring...
nucleotides (cytosine
Cytosine
Cytosine is one of the four main bases found in DNA and RNA, along with adenine, guanine, and thymine . It is a pyrimidine derivative, with a heterocyclic aromatic ring and two substituents attached . The nucleoside of cytosine is cytidine...
and thymidine
Thymidine
Thymidine is a chemical compound, more precisely a pyrimidine deoxynucleoside. Deoxythymidine is the DNA nucleoside T, which pairs with deoxyadenosine in double-stranded DNA...
). Aspartate carbamoyltransferase also ensures that just the right amount of pyrimidine nucleotides is available, as activator and inhibitor molecules attach to aspartate carbamoyltransferase to speed it up and to slow it down.
Aspartate carbamoyltransferase is a complex of twelve molecules.
Six large catalytic molecules in the interior do the work, and six small regulatory molecules on the outside control how fast the catalytic units work.
The size of this structure was ambitious. Aspartate carbamoyltransferase was a much larger molecule than anything solved previously.
Leucine aminopeptidase
Leucyl aminopeptidase
Leucyl aminopeptidases are enzymes that preferentially catalyze the hydrolysis of leucine residues at the N-terminus of peptides and proteins. Other N-terminal residues can also be cleaved, however. LAPs have been found across superkingdoms. Identified LAPs include human LAP, bovine lens LAP,...
, (left) a little like carboxypeptidase A, chops off certain amino acids one-by-one from one end of a protein or peptide
Peptide
Peptides are short polymers of amino acid monomers linked by peptide bonds. They are distinguished from proteins on the basis of size, typically containing less than 50 monomer units. The shortest peptides are dipeptides, consisting of two amino acids joined by a single peptide bond...
.
HaeIII methyltransferase
Methyltransferase
A methyltransferase is a type of transferase enzyme that transfers a methyl group from a donor to an acceptor.Methylation often occurs on nucleic bases in DNA or amino acids in protein structures...
(right)
binds to DNA where it methylates
Methylation
In the chemical sciences, methylation denotes the addition of a methyl group to a substrate or the substitution of an atom or group by a methyl group. Methylation is a form of alkylation with, to be specific, a methyl group, rather than a larger carbon chain, replacing a hydrogen atom...
(adds a methy group to)
it.
Human interferon
Interferon
Interferons are proteins made and released by host cells in response to the presence of pathogens—such as viruses, bacteria, or parasites—or tumor cells. They allow communication between cells to trigger the protective defenses of the immune system that eradicate pathogens or tumors.IFNs belong to...
beta (left)
is released by lymphocyte
Lymphocyte
A lymphocyte is a type of white blood cell in the vertebrate immune system.Under the microscope, lymphocytes can be divided into large lymphocytes and small lymphocytes. Large granular lymphocytes include natural killer cells...
s in response to pathogen
Pathogen
A pathogen gignomai "I give birth to") or infectious agent — colloquially, a germ — is a microbe or microorganism such as a virus, bacterium, prion, or fungus that causes disease in its animal or plant host...
s to trigger the immune system
Immune system
An immune system is a system of biological structures and processes within an organism that protects against disease by identifying and killing pathogens and tumor cells. It detects a wide variety of agents, from viruses to parasitic worms, and needs to distinguish them from the organism's own...
.
Chorismate mutase
Chorismate mutase
In enzymology, a chorismate mutase is an enzyme that catalyzes the chemical reaction for the conversion of chorismate to prephenate in the pathway to the production of phenylalanine and tyrosine, also known as the shikimate pathway....
(right)
catalyzes
Catalysis
Catalysis is the change in rate of a chemical reaction due to the participation of a substance called a catalyst. Unlike other reagents that participate in the chemical reaction, a catalyst is not consumed by the reaction itself. A catalyst may participate in multiple chemical transformations....
(speeds up) the production of the amino acids phenylalanine
Phenylalanine
Phenylalanine is an α-amino acid with the formula C6H5CH2CHCOOH. This essential amino acid is classified as nonpolar because of the hydrophobic nature of the benzyl side chain. L-Phenylalanine is an electrically neutral amino acid, one of the twenty common amino acids used to biochemically form...
and tyrosine
Tyrosine
Tyrosine or 4-hydroxyphenylalanine, is one of the 22 amino acids that are used by cells to synthesize proteins. Its codons are UAC and UAU. It is a non-essential amino acid with a polar side group...
.
Fructose-1,6-bisphosphatase (left)
and its inhibitor MB06322 (CS-917)
were studied by Lipscomb's group in a collaboration, which included Metabasis Therapeutics, Inc., acquired by Ligand Pharmaceuticals in 2010, exploring the possibility of finding a treatment for type 2 diabetes
Diabetes mellitus type 2
Diabetes mellitus type 2formerly non-insulin-dependent diabetes mellitus or adult-onset diabetesis a metabolic disorder that is characterized by high blood glucose in the context of insulin resistance and relative insulin deficiency. Diabetes is often initially managed by increasing exercise and...
, as the MB06322 inhibitor slows the production of sugar by fructose-1,6-bisphosphatase.
Lipscomb's group also contributed to an understanding of
concanavalin A
Concanavalin A
Concanavalin A is a lectin originally extracted from the jack-bean, Canavalia ensiformis. It binds specifically to certain structures found in various sugars, glycoproteins, and glycolipids, mainly internal and nonreducing terminal α-D-mannosyl and α-D-glucosyl groups...
(low resolution structure),
glucagon
Glucagon
Glucagon, a hormone secreted by the pancreas, raises blood glucose levels. Its effect is opposite that of insulin, which lowers blood glucose levels. The pancreas releases glucagon when blood sugar levels fall too low. Glucagon causes the liver to convert stored glycogen into glucose, which is...
, and
carbonic anhydrase
Carbonic anhydrase
The carbonic anhydrases form a family of enzymes that catalyze the rapid interconversion of carbon dioxide and water to bicarbonate and protons , a reversible reaction that occurs rather slowly in the absence of a catalyst...
(theoretical studies).
Subsequent Nobel Prize
Nobel Prize in Chemistry
The Nobel Prize in Chemistry is awarded annually by the Royal Swedish Academy of Sciences to scientists in the various fields of chemistry. It is one of the five Nobel Prizes established by the will of Alfred Nobel in 1895, awarded for outstanding contributions in chemistry, physics, literature,...
winner Thomas A. Steitz
Thomas A. Steitz
-Publications:* Steitz, T. A., et al. , nsls newsletter, .* Steitz, T. A., et al. , NSLS Activity Report .-External links:* , from the Office of Scientific and Technical Information, United States Department of Energy...
was a doctoral student in Lipscomb's laboratory.
Under Lipscomb's direction, after the training task of determining the structure of the small molecule methyl ethylene phosphate, Steitz made contributions to determining the atomic structures of carboxypeptidase A
Carboxypeptidase A
Carboxypeptidase A usually refers to the pancreatic exopeptidase which hydrolyzes peptide bonds of C-terminal residues with aromatic or aliphatic side chains...
and aspartate carbamoyltransferase
Aspartate carbamoyltransferase
Aspartate carbamoyltransferase catalyzes the first step in the pyrimidine biosynthetic pathway .In E. coli, the enzyme is a multi-subunit protein complex composed of 12 subunits...
.
Steitz was awarded the 2009 Nobel Prize in Chemistry
Nobel Prize in Chemistry
The Nobel Prize in Chemistry is awarded annually by the Royal Swedish Academy of Sciences to scientists in the various fields of chemistry. It is one of the five Nobel Prizes established by the will of Alfred Nobel in 1895, awarded for outstanding contributions in chemistry, physics, literature,...
for determining the even larger structure of the large 50S
50S
50S is the larger subunit of the 70S ribosome of prokaryotes. It is the site of inhibition for antibiotics such as macrolides, chloramphenicol, clindamycin, and the pleuromutilins. It includes the subunits 5S and 23S.-Structure:...
ribosomal subunit, leading to an understanding of possible medical treatments.
Subsequent Nobel Prize
Nobel Prize in Chemistry
The Nobel Prize in Chemistry is awarded annually by the Royal Swedish Academy of Sciences to scientists in the various fields of chemistry. It is one of the five Nobel Prizes established by the will of Alfred Nobel in 1895, awarded for outstanding contributions in chemistry, physics, literature,...
winner Ada Yonath
Ada Yonath
Ada E. Yonath is an Israeli crystallographer best known for her pioneering work on the structure of the ribosome. She is the current director of the Helen and Milton A. Kimmelman Center for Biomolecular Structure and Assembly of the Weizmann Institute of Science. In 2009, she received the Nobel...
, who shared the 2009 Nobel Prize in Chemistry with Thomas A. Steitz
Thomas A. Steitz
-Publications:* Steitz, T. A., et al. , nsls newsletter, .* Steitz, T. A., et al. , NSLS Activity Report .-External links:* , from the Office of Scientific and Technical Information, United States Department of Energy...
and Venkatraman Ramakrishnan, spent some time in Lipscomb's lab where both she and Steitz were inspired to pursue later their own very large structures. This was while she was a postdoctoral student at MIT in 1970.
Other Results
The mineral lipscombiteLipscombite
Lipscombite 222 is a green gray, olive green, or black. phosphate-based mineral containing iron, magnesium, and iron phosphate....
(picture at right) was named after Professor Lipscomb by the mineralogist John Gruner who first made it artificially.
Low-temperature x-ray diffraction was pioneered in Lipscomb's laboratory at about the same time as parallel work in Isadore Fankuchen’s laboratory at the then Polytechnic Institute of Brooklyn.
Lipscomb began by studying compounds of nitrogen, oxygen, fluorine, and other substances that are solid only below liquid nitrogen temperatures, but other advantages eventually made low-temperatures a normal procedure.
Keeping the crystal cold during data collection produces a less-blurry 3-D electron-density map because the atoms have less thermal motion. Crystals may yield good data in the x-ray beam longer because x-ray damage may be reduced during data collection and because the solvent may evaporate more slowly, which for example may be important for large biochemical molecules whose crystals often have a high percentage of water.
Other important compounds were studied by Lipscomb and his students.
Among these are
hydrazine
Hydrazine
Hydrazine is an inorganic compound with the formula N2H4. It is a colourless flammable liquid with an ammonia-like odor. Hydrazine is highly toxic and dangerously unstable unless handled in solution. Approximately 260,000 tons are manufactured annually...
,
nitric oxide
Nitric oxide
Nitric oxide, also known as nitrogen monoxide, is a diatomic molecule with chemical formula NO. It is a free radical and is an important intermediate in the chemical industry...
,
metal-dithiolene complexes,
methyl ethylene phosphate,
mercury amide
Amide
In chemistry, an amide is an organic compound that contains the functional group consisting of a carbonyl group linked to a nitrogen atom . The term refers both to a class of compounds and a functional group within those compounds. The term amide also refers to deprotonated form of ammonia or an...
s,
(NO)2,
crystalline hydrogen fluoride
Hydrogen fluoride
Hydrogen fluoride is a chemical compound with the formula HF. This colorless gas is the principal industrial source of fluorine, often in the aqueous form as hydrofluoric acid, and thus is the precursor to many important compounds including pharmaceuticals and polymers . HF is widely used in the...
,
Roussin's black salt
Roussin's black salt
Roussin's Black Salt is a chemical compound with the formula NaFe4S37. It is classified as metal nitrosyl compound. It consists of the sodium salt of the [Fe4S37]− anion. The geometry of the anion cluster is that of an incomplete cubane...
,
(PCF3)5,
complexes of cyclo-octatetraene
Cyclooctatetraene
1,3,5,7-Cyclooctatetraene is an unsaturated derivative of cyclooctane, with the formula C8H8. It is also known as [8]annulene. This polyunsaturated hydrocarbon is a colorless to light yellow flammable liquid at room temperature...
with iron tricarbonyl
(Benzylideneacetone)iron tricarbonyl
The organometallic compound iron tricarbonyl is a widely employed reagent for transferring the Fe3 unit to other organic molecules. This red-colored compound is commonly abbreviated Fe3. It is prepared by the reaction of Fe29 with benzylideneacetone, typically in refluxing diethyl ether...
,
and leurocristine (Vincristine)
Vincristine
Vincristine , formally known as leurocristine, sometimes abbreviated "VCR", is a vinca alkaloid from the Catharanthus roseus , formerly Vinca rosea and hence its name. It is a mitotic inhibitor, and is used in cancer chemotherapy.-Mechanism:Tubulin is a structural protein that polymerizes to...
, which is used in several cancer therapies.
Awards and Honors
- Guggenheim Fellow, 1954
- Fellow of the American Academy of Arts and SciencesAmerican Academy of Arts and SciencesThe American Academy of Arts and Sciences is an independent policy research center that conducts multidisciplinary studies of complex and emerging problems. The Academy’s elected members are leaders in the academic disciplines, the arts, business, and public affairs.James Bowdoin, John Adams, and...
in 1960. - Member of National Academy of SciencesUnited States National Academy of SciencesThe National Academy of Sciences is a corporation in the United States whose members serve pro bono as "advisers to the nation on science, engineering, and medicine." As a national academy, new members of the organization are elected annually by current members, based on their distinguished and...
, (1961) - Foreign Member of the Royal Netherlands Academy of Arts and SciencesRoyal Netherlands Academy of Arts and SciencesThe Royal Netherlands Academy of Arts and Sciences is an organisation dedicated to the advancement of science and literature in the Netherlands...
, (1976) - Nobel Prize in ChemistryNobel Prize in ChemistryThe Nobel Prize in Chemistry is awarded annually by the Royal Swedish Academy of Sciences to scientists in the various fields of chemistry. It is one of the five Nobel Prizes established by the will of Alfred Nobel in 1895, awarded for outstanding contributions in chemistry, physics, literature,...
, (1976)
Five books and published symposia are dedicated to Lipscomb.
A complete list of Lipscomb's awards and honors is in his Curriculum Vitae.http://wlipscomb.tripod.com/publications_biog_cv.html
External links
- Research page at Harvard.
- "Reflections" on Linus Pauling: Video of a talk by Lipscomb. See especially the "Linus and Me" section.
- World War 2 research in brief audio clips by Lipscomb, which include his attempt to save the life of Elizabeth Swingle. Technical description of the Swingle accident.
- Scientific Character of W. Lipscomb Curriculum Vitae, publication list, science humor, Nobel Prize scrapbook, scientific aggression, family stories, portraits, eulogy.