David Kiemle - Academia.edu (original) (raw)

Papers by David Kiemle

Research paper thumbnail of Spectrometric Identification of Organic Compounds. VonR. M. Silverstein undG. C. Bassler. Verlag John Wiley & Sons, Inc., New York-London 1963. 1. Aufl., 177 S., geb. £ 3.4.0

Research paper thumbnail of Using 13 C nuclear magnetic resonance spectroscopy for the study of northern hardwood tissues

Canadian Journal of Forest Research, 2005

Nuclear magnetic resonance (NMR) spectroscopy is a useful tool for examining the structural chemi... more Nuclear magnetic resonance (NMR) spectroscopy is a useful tool for examining the structural chemistry of natural organic matter. The use of cross-polarization and magic-angle spinning to study 13C functionality (CPMAS 13C NMR) is convenient, but not always quantitative. We used various 13C NMR techniques to examine the structural chemistry of bark and wood of sugar maple (Acer saccharum Marsh.), American beech (Fagus grandifolia Ehrh.), and yellow birch (Betula alleghaniensis Britt.). Spin counting experiments showed that 87%–97% of the 13C in the samples was observable by CPMAS 13C NMR. A comparison of CPMAS and Bloch decay experiments revealed few differences in spectral properties. Together, these results suggest that CPMAS 13C NMR is quantitative for these tissues. We observed little variation in the structural chemistry of wood, either among samples of the same species or among species. Within-species variations in bark chemistry were greater than in wood, probably because of v...

Research paper thumbnail of Structural identities of four glycosylated lipids in the oral bacterium Streptococcus mutans UA159

Biochimica et Biophysica Acta (BBA) - Molecular and Cell Biology of Lipids, 2013

Research paper thumbnail of Unusual macrocyclic lactone sex pheromone of Parcoblatta lata, a primary food source of the endangered red-cockaded woodpecker

Proceedings of the National Academy of Sciences, 2011

Wood cockroaches in the genus Parcoblatta , comprising 12 species endemic to North America, are h... more Wood cockroaches in the genus Parcoblatta , comprising 12 species endemic to North America, are highly abundant in southeastern pine forests and represent an important prey of the endangered red-cockaded woodpecker, Picoides borealis . The broad wood cockroach, Parcoblatta lata , is among the largest and most abundant of the wood cockroaches, constituting >50% of the biomass of the woodpecker's diet. Because reproduction in red-cockaded woodpeckers is affected dramatically by seasonal and spatial changes in arthropod availability, monitoring P. lata populations could serve as a useful index of habitat suitability for woodpecker conservation and forest management efforts. Female P. lata emit a volatile, long-distance sex pheromone, which, once identified and synthesized, could be deployed for monitoring cockroach populations. We describe here the identification, synthesis, and confirmation of the chemical structure of this pheromone as (4 Z ,11 Z )-oxacyclotrideca-4,11-dien-2-...

Research paper thumbnail of 2-Methyl-1,4,4a,9a-tetrahydroanthracene-9,10-dione (Me-THAD) as a catalyst in alkaline chemical pulping

Journal of Wood Chemistry and Technology

Research paper thumbnail of C-4 sterol demethylation enzymes distinguish bacterial and eukaryotic sterol synthesis

Proceedings of the National Academy of Sciences of the United States of America, Jun 5, 2018

Sterols are essential eukaryotic lipids that are required for a variety of physiological roles. T... more Sterols are essential eukaryotic lipids that are required for a variety of physiological roles. The diagenetic products of sterol lipids, sterane hydrocarbons, are preserved in ancient sedimentary rocks and are utilized as geological biomarkers, indicating the presence of both eukaryotes and oxic environments throughout Earth's history. However, a few bacterial species are also known to produce sterols, bringing into question the significance of bacterial sterol synthesis for our interpretation of sterane biomarkers. Recent studies suggest that bacterial sterol synthesis may be distinct from what is observed in eukaryotes. In particular, phylogenomic analyses of sterol-producing bacteria have failed to identify homologs of several key eukaryotic sterol synthesis enzymes, most notably those required for demethylation at the C-4 position. In this study, we identified two genes of previously unknown function in the aerobic methanotrophic γ-Proteobacterium that encode sterol demethy...

Research paper thumbnail of Adsorption equilibrium and mechanisms of tris(2-chloroethyl)phosphate (TCEP) on zeolite- β under environmentally relevant and competitive conditions with methyl tert-butyl ether (MTBE)

Environmental Technology & Innovation

Research paper thumbnail of Experimental and Computational Modeling of H-Bonded Arginine–Tyrosine Groupings in Aprotic Environments

Research paper thumbnail of NMR Tube Degradation Method for Sugar Analysis of Glycosides

Journal of Natural Products, 2016

Research paper thumbnail of Spetrometric identification of organic compounds

Research paper thumbnail of Examining the low temperature fluidity of lubricant base oils using 600 mhz HR-MAS NMR spectroscopy

Preprints American Chemical Society Division of Petroleum Chemistry, 1999

Research paper thumbnail of Proton NMR Methods in the Compositional Characterization of Polysaccharides

ACS Symposium Series, 2003

Research paper thumbnail of Structure Elucidation by NMR

Methods in Chemical Ecology Volume 1, 1998

Research paper thumbnail of Mass Spectrometry

Methods in Chemical Ecology Volume 1, 1998

Research paper thumbnail of Spectrometric identification of organic compounds

Journal of Chemical Education, 1962

Consider the plight of the chemist confronted mit,ha few milligrams of a completely un-known orga... more Consider the plight of the chemist confronted mit,ha few milligrams of a completely un-known organic liquid which he has isolated by means of gas chromatography from a complex mixture. Gas chromatography, though fantastically successful as a tool for isolation, ...

Research paper thumbnail of Spectrometric identification of organic compounds

Journal of Chemical Education, 1962

Consider the plight of the chemist confronted mit,ha few milligrams of a completely un- known org... more Consider the plight of the chemist confronted mit,ha few milligrams of a completely un- known organic liquid which he has isolated by means of gas chromatography from a complex mixture. Gas chromatography, though fantastically successful as a tool for isolation, ...

Research paper thumbnail of Nanogram-Scale Preparation and NMR Analysis for Mass-Limited Small Volatile Compounds

Research paper thumbnail of Review of Spectrometric Identification of Organic Compounds , 8th EditionSpectrometric Identification of Organic Compounds, 7th edition by Robert M. Silverstein, Francis X. Webster, David J. Kiemle, and Robert L.Bryce. John Wiley and Sons: Hoboken, NJ, 2015. viii + 455 pp. ISBN 978-0-470-61637-6 ...

Journal of Chemical Education, 2015

Research paper thumbnail of Quantitative 2D HSQC NMR Analysis of Mixed Wood Sugars in Hemicellulosic Hydrolysate Fermentation Broth

Journal of Bioprocess Engineering and Biorefinery, 2012

ABSTRACT Due to the complex composition of lignocellulosic feedstocks accurate quantification of ... more ABSTRACT Due to the complex composition of lignocellulosic feedstocks accurate quantification of the fermentable sugars can be challenging. These types of samples generally contain a mixture of 5- and 6-carbon sugars and while high performance liquid chromatography (HPLC) and nuclear magnetic resonance (NMR) spectroscopy have been used to quantify concentrations of sugars in hemicellulosic extracts and hydrolysates both of these methods had problems. In the case of HPLC the carbohydrate column had a relatively short lifespan when running these types of samples. In the case of proton NMR (1H-NMR) the close proximity of the various peaks corresponding to the anomeric protons for the different sugars caused complications. Even more problematic was when the samples were not completely hydrolyzed as the oligosaccharides generate peaks with very similar resonance frequencies to those of the monosaccharides making integration difficult. In order to quantify the sugar concentrations of samples taken during the fermentation of dilute acid hydrolyzed hemicellulosic extracts a two dimensional heteronuclear single quantum coherence (2D-HSQC) technique was used. The addition of the 13C axis resulted in almost no overlapping of the peaks between the various carbohydrates. This makes integrating these peaks less problematic and improves the accuracy of the carbohydrate analysis in the fermentation samples. In addition to being able to quantify the sugars, the ethanol concentrations which were previously determined using a separate gas chromatography method can be also be determined from the same NMR sample which reduced the number of samples that needed to be prepared.

Research paper thumbnail of 2D HSQC NMR Analysis and Application to Hot-Water Wood Extract Hydrolysate Characterization

Hot-water extraction has been evolved into a necessary biorefinery step that enables the incremen... more Hot-water extraction has been evolved into a necessary biorefinery step that enables the incremental conversion of lignocellulosic materials to chemicals, materials and energy. The extraction liquor and subsequent hydrolysate are a complex mixture of organic and inorganic substances. 5-carbon and 6-carbon sugars and their derivatives make up the bulk of the mixture. Developing a reliable technique to quantify the mixture has become the bottleneck of the hot-water extraction process development. In this study, we present the development of the 2D HSQC NMR characterization of the complex mixture. It can economically produce quantifications for the monomoeric and some of the oligomeric sugars.

Research paper thumbnail of Spectrometric Identification of Organic Compounds. VonR. M. Silverstein undG. C. Bassler. Verlag John Wiley & Sons, Inc., New York-London 1963. 1. Aufl., 177 S., geb. £ 3.4.0

Research paper thumbnail of Using 13 C nuclear magnetic resonance spectroscopy for the study of northern hardwood tissues

Canadian Journal of Forest Research, 2005

Nuclear magnetic resonance (NMR) spectroscopy is a useful tool for examining the structural chemi... more Nuclear magnetic resonance (NMR) spectroscopy is a useful tool for examining the structural chemistry of natural organic matter. The use of cross-polarization and magic-angle spinning to study 13C functionality (CPMAS 13C NMR) is convenient, but not always quantitative. We used various 13C NMR techniques to examine the structural chemistry of bark and wood of sugar maple (Acer saccharum Marsh.), American beech (Fagus grandifolia Ehrh.), and yellow birch (Betula alleghaniensis Britt.). Spin counting experiments showed that 87%–97% of the 13C in the samples was observable by CPMAS 13C NMR. A comparison of CPMAS and Bloch decay experiments revealed few differences in spectral properties. Together, these results suggest that CPMAS 13C NMR is quantitative for these tissues. We observed little variation in the structural chemistry of wood, either among samples of the same species or among species. Within-species variations in bark chemistry were greater than in wood, probably because of v...

Research paper thumbnail of Structural identities of four glycosylated lipids in the oral bacterium Streptococcus mutans UA159

Biochimica et Biophysica Acta (BBA) - Molecular and Cell Biology of Lipids, 2013

Research paper thumbnail of Unusual macrocyclic lactone sex pheromone of Parcoblatta lata, a primary food source of the endangered red-cockaded woodpecker

Proceedings of the National Academy of Sciences, 2011

Wood cockroaches in the genus Parcoblatta , comprising 12 species endemic to North America, are h... more Wood cockroaches in the genus Parcoblatta , comprising 12 species endemic to North America, are highly abundant in southeastern pine forests and represent an important prey of the endangered red-cockaded woodpecker, Picoides borealis . The broad wood cockroach, Parcoblatta lata , is among the largest and most abundant of the wood cockroaches, constituting >50% of the biomass of the woodpecker's diet. Because reproduction in red-cockaded woodpeckers is affected dramatically by seasonal and spatial changes in arthropod availability, monitoring P. lata populations could serve as a useful index of habitat suitability for woodpecker conservation and forest management efforts. Female P. lata emit a volatile, long-distance sex pheromone, which, once identified and synthesized, could be deployed for monitoring cockroach populations. We describe here the identification, synthesis, and confirmation of the chemical structure of this pheromone as (4 Z ,11 Z )-oxacyclotrideca-4,11-dien-2-...

Research paper thumbnail of 2-Methyl-1,4,4a,9a-tetrahydroanthracene-9,10-dione (Me-THAD) as a catalyst in alkaline chemical pulping

Journal of Wood Chemistry and Technology

Research paper thumbnail of C-4 sterol demethylation enzymes distinguish bacterial and eukaryotic sterol synthesis

Proceedings of the National Academy of Sciences of the United States of America, Jun 5, 2018

Sterols are essential eukaryotic lipids that are required for a variety of physiological roles. T... more Sterols are essential eukaryotic lipids that are required for a variety of physiological roles. The diagenetic products of sterol lipids, sterane hydrocarbons, are preserved in ancient sedimentary rocks and are utilized as geological biomarkers, indicating the presence of both eukaryotes and oxic environments throughout Earth's history. However, a few bacterial species are also known to produce sterols, bringing into question the significance of bacterial sterol synthesis for our interpretation of sterane biomarkers. Recent studies suggest that bacterial sterol synthesis may be distinct from what is observed in eukaryotes. In particular, phylogenomic analyses of sterol-producing bacteria have failed to identify homologs of several key eukaryotic sterol synthesis enzymes, most notably those required for demethylation at the C-4 position. In this study, we identified two genes of previously unknown function in the aerobic methanotrophic γ-Proteobacterium that encode sterol demethy...

Research paper thumbnail of Adsorption equilibrium and mechanisms of tris(2-chloroethyl)phosphate (TCEP) on zeolite- β under environmentally relevant and competitive conditions with methyl tert-butyl ether (MTBE)

Environmental Technology & Innovation

Research paper thumbnail of Experimental and Computational Modeling of H-Bonded Arginine–Tyrosine Groupings in Aprotic Environments

Research paper thumbnail of NMR Tube Degradation Method for Sugar Analysis of Glycosides

Journal of Natural Products, 2016

Research paper thumbnail of Spetrometric identification of organic compounds

Research paper thumbnail of Examining the low temperature fluidity of lubricant base oils using 600 mhz HR-MAS NMR spectroscopy

Preprints American Chemical Society Division of Petroleum Chemistry, 1999

Research paper thumbnail of Proton NMR Methods in the Compositional Characterization of Polysaccharides

ACS Symposium Series, 2003

Research paper thumbnail of Structure Elucidation by NMR

Methods in Chemical Ecology Volume 1, 1998

Research paper thumbnail of Mass Spectrometry

Methods in Chemical Ecology Volume 1, 1998

Research paper thumbnail of Spectrometric identification of organic compounds

Journal of Chemical Education, 1962

Consider the plight of the chemist confronted mit,ha few milligrams of a completely un-known orga... more Consider the plight of the chemist confronted mit,ha few milligrams of a completely un-known organic liquid which he has isolated by means of gas chromatography from a complex mixture. Gas chromatography, though fantastically successful as a tool for isolation, ...

Research paper thumbnail of Spectrometric identification of organic compounds

Journal of Chemical Education, 1962

Consider the plight of the chemist confronted mit,ha few milligrams of a completely un- known org... more Consider the plight of the chemist confronted mit,ha few milligrams of a completely un- known organic liquid which he has isolated by means of gas chromatography from a complex mixture. Gas chromatography, though fantastically successful as a tool for isolation, ...

Research paper thumbnail of Nanogram-Scale Preparation and NMR Analysis for Mass-Limited Small Volatile Compounds

Research paper thumbnail of Review of Spectrometric Identification of Organic Compounds , 8th EditionSpectrometric Identification of Organic Compounds, 7th edition by Robert M. Silverstein, Francis X. Webster, David J. Kiemle, and Robert L.Bryce. John Wiley and Sons: Hoboken, NJ, 2015. viii + 455 pp. ISBN 978-0-470-61637-6 ...

Journal of Chemical Education, 2015

Research paper thumbnail of Quantitative 2D HSQC NMR Analysis of Mixed Wood Sugars in Hemicellulosic Hydrolysate Fermentation Broth

Journal of Bioprocess Engineering and Biorefinery, 2012

ABSTRACT Due to the complex composition of lignocellulosic feedstocks accurate quantification of ... more ABSTRACT Due to the complex composition of lignocellulosic feedstocks accurate quantification of the fermentable sugars can be challenging. These types of samples generally contain a mixture of 5- and 6-carbon sugars and while high performance liquid chromatography (HPLC) and nuclear magnetic resonance (NMR) spectroscopy have been used to quantify concentrations of sugars in hemicellulosic extracts and hydrolysates both of these methods had problems. In the case of HPLC the carbohydrate column had a relatively short lifespan when running these types of samples. In the case of proton NMR (1H-NMR) the close proximity of the various peaks corresponding to the anomeric protons for the different sugars caused complications. Even more problematic was when the samples were not completely hydrolyzed as the oligosaccharides generate peaks with very similar resonance frequencies to those of the monosaccharides making integration difficult. In order to quantify the sugar concentrations of samples taken during the fermentation of dilute acid hydrolyzed hemicellulosic extracts a two dimensional heteronuclear single quantum coherence (2D-HSQC) technique was used. The addition of the 13C axis resulted in almost no overlapping of the peaks between the various carbohydrates. This makes integrating these peaks less problematic and improves the accuracy of the carbohydrate analysis in the fermentation samples. In addition to being able to quantify the sugars, the ethanol concentrations which were previously determined using a separate gas chromatography method can be also be determined from the same NMR sample which reduced the number of samples that needed to be prepared.

Research paper thumbnail of 2D HSQC NMR Analysis and Application to Hot-Water Wood Extract Hydrolysate Characterization

Hot-water extraction has been evolved into a necessary biorefinery step that enables the incremen... more Hot-water extraction has been evolved into a necessary biorefinery step that enables the incremental conversion of lignocellulosic materials to chemicals, materials and energy. The extraction liquor and subsequent hydrolysate are a complex mixture of organic and inorganic substances. 5-carbon and 6-carbon sugars and their derivatives make up the bulk of the mixture. Developing a reliable technique to quantify the mixture has become the bottleneck of the hot-water extraction process development. In this study, we present the development of the 2D HSQC NMR characterization of the complex mixture. It can economically produce quantifications for the monomoeric and some of the oligomeric sugars.