Arthur Greenberg | University of New Hampshire (original) (raw)
Papers by Arthur Greenberg
Acs Symposium Series, 2015
In honor of the fiftieth anniversary of the James Flack Norris Award in Physical Organic Chemistr... more In honor of the fiftieth anniversary of the James Flack Norris Award in Physical Organic Chemistry, a brief biographical sketch of Norris is presented along with discussion of his research accomplishments in the contexts of the influence of his doctoral mentor Dr. Ira Remsen and the early development of physical organic chemistry. Dr. Norris had two distinct academic careers, researcher and teacher at Massachusetts Institute of Technology (MIT) and administrator and teacher at Simmons College. A third career, scientific leader and statesman, co-existed with these dual careers. This chapter will briefly describe Norris's researches in molecular addition compounds, the triphenylmethyl system, Friedel-Crafts chemistry as well as his twenty paper series on "The reactivity of atoms and groups in organic compounds" (from 1920 through 1940). The Early Days of Physical Organic Chemistry and Some Modern Perspectives The origins of the field recognized as "physical organic chemistry" may be dated close to the start of the twentieth century. In 1895 Paul Walden demonstrated (1) the stereochemical inversion that now bears his name. The concept of steric hindrance had been introduced by Victor Meyer (2) one year earlier. In 1899, Julius Stieglitz made a solid proposal for the existence of carbocations (3). In 1900 Moses Gomberg published his groundbreaking discovery of the triphenylmethyl free radical (4). Explicit recognition of the field dates to the
Canadian Journal of Chemistry, Mar 1, 2017
Interest in the low carbonyl infrared frequency of 2-hydroxy-N,N-bis(2-hydroxyethyl)acetamide (2)... more Interest in the low carbonyl infrared frequency of 2-hydroxy-N,N-bis(2-hydroxyethyl)acetamide (2) initially prompted our interest in the amide rotational barrier of this molecule and four related amides which present a variety of hydrogen-bonding possibilities. In the course of this study, a previously incorrect structural assignment was established as N,N-bis[2-(acetyloxy)ethyl]-acetamide (6). In acetonitrile-d 3 , the carbonyl IR frequencies of the five amides were all essentially normal amide frequencies. Despite very different hydrogen-bonding possibilities in the five amides, no clear trends emerged in the comparison of the rotational barriers (ΔG ‡), and the rotational barriers were essentially normal for amides. The rotational barrier of 2 did not vary over one order of magnitude difference in concentration.
Toxic Air Pollution, 2018
Gas and Particle Phase Measurements of Atmospheric Organic Compounds, 2020
![Research paper thumbnail of Relative thermochemical stabilities and reactivities of benzo[a]pyrene and selected isomers](https://attachments.academia-assets.com/109459449/thumbnails/1.jpg)
](Science of The Total Environment, 1984
AESTRACT Gas-phase standard enthalpies of formation are calculated for benzo [a ] pyrene and thir... more AESTRACT Gas-phase standard enthalpies of formation are calculated for benzo [a ] pyrene and thirty-two isomeric polycyclic aromatic hydrocarbons including compounds having four-. five-and seven-membered rings. Additionally, reactivity data are summarized and include experimental ionization potentials, Huckcl itighest occupied molecular orbitals and selected reactivity indices. These data are compared with levels of those CzoHi2 hydrocarbons reported in the atmosphere. These thermodynamic and kinetic parameters are useful reference points for understanding the ataMities of airborne PAH. Additiunally, the data tabulations may be useful in predicting the existence of PAH nol, yet reported in environmental samples.
The amide linkage is one of the most fundamental and widespread chemical bonds in nature, underly... more The amide linkage is one of the most fundamental and widespread chemical bonds in nature, underlying the properties of a vast array of organic molecules, polymers, and materials, including peptides and proteins. Arthur Greenberg, Curt Breneman, and Joel Liebman's peerless text provides comprehensive coverage of the experimental, structural, and computational findings that shed light on the chemical and physical properties of the amide linkage, as well as its emerging applications in materials and biotechnology. Chapters in The Amide Linkage highlight how this chemical bond factors in the design of enzyme inhibitors, cyclic peptides, antibacterial agents, and emerging nanotechnology applications. This one-of-a-kind study also: • Discusses selected aspects of chemical reactions, structure, bonding, and energetics of the amide bond, including amide rotational barriers, stereochemistry, complexation, spectroscopy, and thermochemistry • Presents specific applications to supramolecular and stereospecific synthesis • Discusses ke y aspects of peptide and protein chemistry-such as molecular recognition, conformation, and folding-in terms of the amide linkage • Includes chapters contributed by numerous eminent chemists and biochemists Organic, medicinal, polymer, and physical chemists, as well as biochemists and materials scientists, will find The Amide Linkage to be an invaluable addition to their professional libraries.
ASTM International eBooks, Dec 4, 2008
Journal of the Air Pollution Control Association, Apr 1, 1983
Journal of the Air Pollution Control Association, Apr 1, 1986
While quality control has been defined and implemented for ambient criteria pollutant monitoring,... more While quality control has been defined and implemented for ambient criteria pollutant monitoring, such as for SO 2 , O 3 and total suspended particulates, most of the noncriteria air pollutants currently being measured have not been subject to similar levels of data assurance.. The New Jersey Project on Airborne Toxic Elements and Organic Substances (ATEOS) included the measurement of nearly 50 gaseous and particulate phase noncriteria pollutants, within the structure of a rigorous quality assurance/quality control (QA/QC) program. The following report details the QA/QC results for the particulate and vapor phase pollutants measured during the ATEOS project. Consideration is given to a number of basic differences between measuring inorganic and organic pollutants including method detection limits, number of valid samples, and precision and accuracy of the overall methods. Particular emphasis is placed on how the QA/QC data place limits on statistical analyses of noncriteria air pollutant data sets.
Tetrahedron Letters, 1974
![Research paper thumbnail of Analysis of 200 food items for benzo[a]pyrene and estimation of its intake in an epidemiologic study](https://attachments.academia-assets.com/106685946/thumbnails/1.jpg)
](Food and Chemical Toxicology, 2001
Analysis of 200 food items for benzo[a]pyrene and estimation of Analysis of 200 food items for be... more Analysis of 200 food items for benzo[a]pyrene and estimation of Analysis of 200 food items for benzo[a]pyrene and estimation of its intake ίη an epidemiologic study its intake an epidemiologic study
Atmospheric environment, 1985
The sites incfudcd three urban locations (Newark, Elizabeth and Camden) and one rural site (Ringw... more The sites incfudcd three urban locations (Newark, Elizabeth and Camden) and one rural site (Ringwood). The analytical methodology involved soxhlet extraction of preheated glassfiber filters with cyclohexane, thin-layer chromatography and ultimate analysis using reverse-phase highperformance liquid chromatography and ultraviolet and fluorescence detection. The quality assurance/quality control procedure is described. Discussions of differences in PAH levels between urban and rural sites as well as the summer/winter differences in concentrations rely upon consideration of sources as well as differences in PAH reactivities. Comparisons of PAH levels are also made between pollution episode and non-episode periods. In addition intra-and intersite correlations between PAHs as well as other pollutants are discussed. Profiles of PAH do not appear to differ significantly between the few sites during a given season.
Structural Chemistry, 2016
1-Methyl-4-silatranone could exhibit the structural aspects of a typical silatrane including a sh... more 1-Methyl-4-silatranone could exhibit the structural aspects of a typical silatrane including a short N-Si bond distance reflecting a dative bond. But given the significant amide resonance in a [3.3.3] bridgehead bicyclic lactam, the lone pair could be shared with the carbonyl group leading to a very long N-Si bond, essentially a Bnon-silatrane.^Ab initio calculations (MP2/6-311 + G*) predict that ground state conformations of this molecule are best regarded as lactams rather than silatranes, the most stable having a calculated N-Si bond length of 2.902 Å and an N-CO bond length of 1.387 Å. The calculated transition state for inversion of the amide ring retains very little amide resonance (N-CO, 1.440 Å). Some of this loss is compensated through tightening of the N-Si bond (2.422 Å), leading to a net energy of activation of ca 8 kcal/ mol. Attempts to synthesize 1-methyl-4-silatranone using conventional pathways successful for 1-methylsilatrane [condensations employing N,N-bis(2-hydroxyethyl)glycolamide in place of tris(2-hydroxyethyl)amine] were unsuccessful. This is due to the net loss in resonance energy of the amide reactant relative to that in the [3.3.3] system, the essential absence of the N-Si dative bond, and the rigidity introduced by the planar amide linkage in the starting material. A more likely pathway to successful synthesis should be formation of the amide linkage in the final step.
Greenberg/Alchemy to Chemistry, 2006
Greenberg/Alchemy to Chemistry, 2006
Greenberg/Alchemy to Chemistry, 2006
Greenberg/Alchemy to Chemistry, 2006
Substantia
When presented with a new multivolume series on the history of chemistry, one cannot help but com... more When presented with a new multivolume series on the history of chemistry, one cannot help but compare it to J. R. Partington's masterful four-volume A History of Chemistry. The new six-volume A Cultural History of Chemistry reviewed here, however, is really a different beast and should not be viewed as a simple attempt to update Partington's previous series. As highlighted by series editors Peter Morris and Alan Rocke in the Series Preface that begins each volume, "This is not a conventional history of chemistry, but a first attempt at creating a cultural history of the science." As such, this series brings together 50 contributors in an effort to present the first detailed and authoritative survey of the impact of chemistry on society, as well as how society has influenced and impacted chemical practice and thought. Spanning from the earliest applications of the chemical arts in antiquity up through the present, this cultural history is split into six volumes, eac...
Acs Symposium Series, 2015
In honor of the fiftieth anniversary of the James Flack Norris Award in Physical Organic Chemistr... more In honor of the fiftieth anniversary of the James Flack Norris Award in Physical Organic Chemistry, a brief biographical sketch of Norris is presented along with discussion of his research accomplishments in the contexts of the influence of his doctoral mentor Dr. Ira Remsen and the early development of physical organic chemistry. Dr. Norris had two distinct academic careers, researcher and teacher at Massachusetts Institute of Technology (MIT) and administrator and teacher at Simmons College. A third career, scientific leader and statesman, co-existed with these dual careers. This chapter will briefly describe Norris's researches in molecular addition compounds, the triphenylmethyl system, Friedel-Crafts chemistry as well as his twenty paper series on "The reactivity of atoms and groups in organic compounds" (from 1920 through 1940). The Early Days of Physical Organic Chemistry and Some Modern Perspectives The origins of the field recognized as "physical organic chemistry" may be dated close to the start of the twentieth century. In 1895 Paul Walden demonstrated (1) the stereochemical inversion that now bears his name. The concept of steric hindrance had been introduced by Victor Meyer (2) one year earlier. In 1899, Julius Stieglitz made a solid proposal for the existence of carbocations (3). In 1900 Moses Gomberg published his groundbreaking discovery of the triphenylmethyl free radical (4). Explicit recognition of the field dates to the
Canadian Journal of Chemistry, Mar 1, 2017
Interest in the low carbonyl infrared frequency of 2-hydroxy-N,N-bis(2-hydroxyethyl)acetamide (2)... more Interest in the low carbonyl infrared frequency of 2-hydroxy-N,N-bis(2-hydroxyethyl)acetamide (2) initially prompted our interest in the amide rotational barrier of this molecule and four related amides which present a variety of hydrogen-bonding possibilities. In the course of this study, a previously incorrect structural assignment was established as N,N-bis[2-(acetyloxy)ethyl]-acetamide (6). In acetonitrile-d 3 , the carbonyl IR frequencies of the five amides were all essentially normal amide frequencies. Despite very different hydrogen-bonding possibilities in the five amides, no clear trends emerged in the comparison of the rotational barriers (ΔG ‡), and the rotational barriers were essentially normal for amides. The rotational barrier of 2 did not vary over one order of magnitude difference in concentration.
Toxic Air Pollution, 2018
Gas and Particle Phase Measurements of Atmospheric Organic Compounds, 2020
Science of The Total Environment, 1984
AESTRACT Gas-phase standard enthalpies of formation are calculated for benzo [a ] pyrene and thir... more AESTRACT Gas-phase standard enthalpies of formation are calculated for benzo [a ] pyrene and thirty-two isomeric polycyclic aromatic hydrocarbons including compounds having four-. five-and seven-membered rings. Additionally, reactivity data are summarized and include experimental ionization potentials, Huckcl itighest occupied molecular orbitals and selected reactivity indices. These data are compared with levels of those CzoHi2 hydrocarbons reported in the atmosphere. These thermodynamic and kinetic parameters are useful reference points for understanding the ataMities of airborne PAH. Additiunally, the data tabulations may be useful in predicting the existence of PAH nol, yet reported in environmental samples.
The amide linkage is one of the most fundamental and widespread chemical bonds in nature, underly... more The amide linkage is one of the most fundamental and widespread chemical bonds in nature, underlying the properties of a vast array of organic molecules, polymers, and materials, including peptides and proteins. Arthur Greenberg, Curt Breneman, and Joel Liebman's peerless text provides comprehensive coverage of the experimental, structural, and computational findings that shed light on the chemical and physical properties of the amide linkage, as well as its emerging applications in materials and biotechnology. Chapters in The Amide Linkage highlight how this chemical bond factors in the design of enzyme inhibitors, cyclic peptides, antibacterial agents, and emerging nanotechnology applications. This one-of-a-kind study also: • Discusses selected aspects of chemical reactions, structure, bonding, and energetics of the amide bond, including amide rotational barriers, stereochemistry, complexation, spectroscopy, and thermochemistry • Presents specific applications to supramolecular and stereospecific synthesis • Discusses ke y aspects of peptide and protein chemistry-such as molecular recognition, conformation, and folding-in terms of the amide linkage • Includes chapters contributed by numerous eminent chemists and biochemists Organic, medicinal, polymer, and physical chemists, as well as biochemists and materials scientists, will find The Amide Linkage to be an invaluable addition to their professional libraries.
ASTM International eBooks, Dec 4, 2008
Journal of the Air Pollution Control Association, Apr 1, 1983
Journal of the Air Pollution Control Association, Apr 1, 1986
While quality control has been defined and implemented for ambient criteria pollutant monitoring,... more While quality control has been defined and implemented for ambient criteria pollutant monitoring, such as for SO 2 , O 3 and total suspended particulates, most of the noncriteria air pollutants currently being measured have not been subject to similar levels of data assurance.. The New Jersey Project on Airborne Toxic Elements and Organic Substances (ATEOS) included the measurement of nearly 50 gaseous and particulate phase noncriteria pollutants, within the structure of a rigorous quality assurance/quality control (QA/QC) program. The following report details the QA/QC results for the particulate and vapor phase pollutants measured during the ATEOS project. Consideration is given to a number of basic differences between measuring inorganic and organic pollutants including method detection limits, number of valid samples, and precision and accuracy of the overall methods. Particular emphasis is placed on how the QA/QC data place limits on statistical analyses of noncriteria air pollutant data sets.
Tetrahedron Letters, 1974
Food and Chemical Toxicology, 2001
Analysis of 200 food items for benzo[a]pyrene and estimation of Analysis of 200 food items for be... more Analysis of 200 food items for benzo[a]pyrene and estimation of Analysis of 200 food items for benzo[a]pyrene and estimation of its intake ίη an epidemiologic study its intake an epidemiologic study
Atmospheric environment, 1985
The sites incfudcd three urban locations (Newark, Elizabeth and Camden) and one rural site (Ringw... more The sites incfudcd three urban locations (Newark, Elizabeth and Camden) and one rural site (Ringwood). The analytical methodology involved soxhlet extraction of preheated glassfiber filters with cyclohexane, thin-layer chromatography and ultimate analysis using reverse-phase highperformance liquid chromatography and ultraviolet and fluorescence detection. The quality assurance/quality control procedure is described. Discussions of differences in PAH levels between urban and rural sites as well as the summer/winter differences in concentrations rely upon consideration of sources as well as differences in PAH reactivities. Comparisons of PAH levels are also made between pollution episode and non-episode periods. In addition intra-and intersite correlations between PAHs as well as other pollutants are discussed. Profiles of PAH do not appear to differ significantly between the few sites during a given season.
Structural Chemistry, 2016
1-Methyl-4-silatranone could exhibit the structural aspects of a typical silatrane including a sh... more 1-Methyl-4-silatranone could exhibit the structural aspects of a typical silatrane including a short N-Si bond distance reflecting a dative bond. But given the significant amide resonance in a [3.3.3] bridgehead bicyclic lactam, the lone pair could be shared with the carbonyl group leading to a very long N-Si bond, essentially a Bnon-silatrane.^Ab initio calculations (MP2/6-311 + G*) predict that ground state conformations of this molecule are best regarded as lactams rather than silatranes, the most stable having a calculated N-Si bond length of 2.902 Å and an N-CO bond length of 1.387 Å. The calculated transition state for inversion of the amide ring retains very little amide resonance (N-CO, 1.440 Å). Some of this loss is compensated through tightening of the N-Si bond (2.422 Å), leading to a net energy of activation of ca 8 kcal/ mol. Attempts to synthesize 1-methyl-4-silatranone using conventional pathways successful for 1-methylsilatrane [condensations employing N,N-bis(2-hydroxyethyl)glycolamide in place of tris(2-hydroxyethyl)amine] were unsuccessful. This is due to the net loss in resonance energy of the amide reactant relative to that in the [3.3.3] system, the essential absence of the N-Si dative bond, and the rigidity introduced by the planar amide linkage in the starting material. A more likely pathway to successful synthesis should be formation of the amide linkage in the final step.
Greenberg/Alchemy to Chemistry, 2006
Greenberg/Alchemy to Chemistry, 2006
Greenberg/Alchemy to Chemistry, 2006
Greenberg/Alchemy to Chemistry, 2006
Substantia
When presented with a new multivolume series on the history of chemistry, one cannot help but com... more When presented with a new multivolume series on the history of chemistry, one cannot help but compare it to J. R. Partington's masterful four-volume A History of Chemistry. The new six-volume A Cultural History of Chemistry reviewed here, however, is really a different beast and should not be viewed as a simple attempt to update Partington's previous series. As highlighted by series editors Peter Morris and Alan Rocke in the Series Preface that begins each volume, "This is not a conventional history of chemistry, but a first attempt at creating a cultural history of the science." As such, this series brings together 50 contributors in an effort to present the first detailed and authoritative survey of the impact of chemistry on society, as well as how society has influenced and impacted chemical practice and thought. Spanning from the earliest applications of the chemical arts in antiquity up through the present, this cultural history is split into six volumes, eac...