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Beschreibung

Applications of NMR Spectroscopy is a book series devoted to publishing the latest advances in the applications of nuclear magnetic resonance (NMR) spectroscopy in various fields of organic chemistry, biochemistry, health and agriculture.
The sixth volume of the series features reviews focusing on NMR spectroscopic techniques for studying tautomerism, applications in medical diagnosis, in food chemistry and identifying secondary metabolites.

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Seitenzahl: 418

Veröffentlichungsjahr: 2017

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Table of Contents
BENTHAM SCIENCE PUBLISHERS LTD.
End User License Agreement (for non-institutional, personal use)
Usage Rules:
Disclaimer:
Limitation of Liability:
General:
PREFACE
List of Contributors
NMR as a Tool for Studying Rapid Equilibria: Tautomerism
Abstract
INTRODUCTION
SUBSTITUENT EFFECTS
Tautomerism in β-ketonitriles
Tautomerism in β-ketoamides
Tautomerism in Schiff Bases
Hammett Substituent Constants
Temperature Effects
SOLVENT EFFECTS
CONCENTRATION EFFECTS
THORETICAL CALCULATIONS
CONCLUSION
CONFLICT OF INTEREST
ACKNOWLEDGEMENTS
REFERENCES
Identification & Characterization of Secondary Metabolites in the Biological Soup by NMR Spectroscopy
Abstract
INTRODUCTION
Metabolome, Metabolites and Metabolomics
Primary Metabolites
Secondary Metabolites
THE METABOLOMICS WORKFLOW
Sample Preparation
Metabolite Identification & Characterization
Mass Spectrometry
NMR Spectroscopy
Hyphenation of NMR Spectroscopy with Analytical techniques
NMR AS A TOOL IN METABOLOMICS
1H NMR Spectroscopy
1H-1H Correlation Spectroscopy (COSY)
1H-1H Total Correlation Spectroscopy (TOCSY)
2D J-resolved NMR Spectroscopy (J-RES)
1H-1H Rotating-frame Overhauser Spectroscopy (ROESY)
1H-13C Heteronuclear Correlations
13C NMR Spectroscopy
RECENT ADVANCES IN NMR SPECTROSCOPY
Non-uniform Sampling
Ultrafast NMR (UF-NMR)
NMR DATA PROCESSING AND STATISTICAL ANALYSIS
Statistical Pre-processing
Statistical Analysis
WORKED EXAMPLE
LIMITATIONS OF NMR IN METABOLOMICS
CONCLUSION
ABBREVIATIONS
CONFLICT OF INTEREST
ACKNOWLEDGEMENTS
REFERENCES
NMR Spectroscopy in Medical Diagnosis – Recent Developments
Abstract
INTRODUCTION
NMR Metabolomics
Sample Preparation
Types of NMR Studies
Limitations of NMR
NMR and Inborn Errors of Metabolism (IEM)
MR Spectroscopy in White Matter Disease
MRS and Other Neurological Conditions
MRI and MRS Studies of Cancer
MRS in Skeletal Muscle Disorders
Cardiac 31P MRS Studies
MRS and the Liver
MR Metabolomics and Bowel Disorders
Urinary Biomarkers
1H MRS in Neuropsychiatric Disorders
MRS in Clinical Microbiological Applications
MRS in Pediatric Disorders
MRS and Other Diseases
MRS Technology – Recent Developments
CONCLUSION
ABBREVIATIONS
CONFLICT OF INTEREST
ACKNOWLEDGEMENTS
REFERENCES
NMR Relaxometry Applied to Food Samples
Abstract
Introduction
Nuclear Magnetic Resonance
Relaxometry Experimental Measurements
Proton Spin-lattice Relaxation Time
Proton Spin-spin Relaxation Time
Application of NMR Techniques to Food Samples
a) Bauhinia forficata-complex Herb Evaluated Through T1 and T2 Parameters
Final Comments on Evaluation of the Bauhinia forficata Tea
b) The Evaluation of Hypolytrum Pungens with NMR Relaxometry
c) Evaluation of Baru Starch Seed through Low-field NMR Relaxometry
Final Comments on the Baru Results
d) Evaluation of Cassava Flour through Proton Spin-spin Relaxation Time
Final Comments on Cassava Studies
e) Evaluation of Fruit Seed from T1H
CONFLICT OF INTEREST
ACKNOWLEDGEMENTS
REFERENCES
Application of Nuclear Magnetic Resonance Spectroscopy in Molecular Structure Identification: A Microbial Biogeochemistry Perspective
Abstract
INTRODUCTION
NMR SPECTROSCOPY IN BIOGEOCHEMICAL RESEARCH
Scalability
NMR-Active Nuclei
HIGH RESOLUTION NMR SPECTROSCOPY
Solid-State NMR Spectroscopy
Sample Preparation
Data Analysis/Integration
Solution-State NMR Spectroscopy
Sample Preparation
Solvents
HR-MAS NMR Spectroscopy
Solvents
Sample Preparation
HR-MAS NMR AND SOIL MICROBIAL BIOGEOCHEMISTRY
Degradation of Microbial Biomass in Soil
Carbon Turnover in Microbial Biomass
Diffusion Editing NMR
Carbon Turnover in Microbial Leachate
Nitrogen Turnover in Microbial Biomass
Organo-mineral Interactions
CONCLUSIONS
CONFLICT OF INTEREST
ACKNOWLEDGEMENTS
REFERENCES

Applications of NMR 

Spectroscopy

(Volume 6)

Edited By

Atta-ur-Rahman, FRS

Kings College,University of Cambridge,Cambridge,UK
&

M. Iqbal Choudhary

H.E.J. Research Institute of Chemistry, International Center for Chemical and 
Biological Sciences,
University of Karachi,Karachi,Pakistan

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PREFACE

NMR Spectroscopy, over the years, has emerged as one of the most robust spectroscopic techniques for a variety of applications. Developed by physicists, and embraced initially by the chemists and later by biochemists, NMR spectroscopy is now owned by the communities of scientists in all major disciplines, including biology, medicine, chemistry, and agriculture and geological sciences.

The 6th volume of the book series entitled, “Application of NMR Spectroscopy”, is an attempt to update readers on some of the most important developments in the use of NMR. spectroscopy The broad fields covered in these chapters include NMR-based metabolomics for medical diagnosis, cellular studies and industrial applications, NMR techniques for structure determination and dynamic studies on chemicals obtained from different sources.

Allegretti et al. focussed their review on various NMR techniques used in the study of tautomerism. These NMR experiments can provide information about the causes of stabilization of different tautomeric forms, and help in predicting the reactivity, physical properties and biological behaviour of organic molecules. The authors have used examples of different classes of organic molecules, such as ketonitriles, ketoamides, salicylaldimines, etc., to demonstrate the power of NMR techniques in the study of rapid chemical equilibria.

Chugh et al. discussed the applications of NMR spectroscopy in the field of metabolomics, which deals with the understanding of the metabolic profile of a biological system. The authors, through examples of diverse metabolomes, have presented merits and demerits of various NMR methods, combined with high-throughput separation techniques in metabolomic studies. The authors have also commented on recent developments in NMR, relevant to metabolomics based measurement and analysis.

NMR spectroscopy has also emerged as a premier technique in medical diagnosis. Vaidyanathan has contributed an excellent review on the applications of NMR techniques in metabolomic based diagnosis of human diseases. Recent advances in NMR hardware, such as cryoprobe technology and high field magnets, have significantly enhanced the sensitivity of NMR experiments. NMR Spectroscopy now found wide application in the identification of biomarkers for various diseases such as cardiovascular and neurological diseases, metabolic disorders, cancer diagnosis and therapy, gastrointestinal disorders, etc.

The study of relaxation mechanisms of nuclear spins in NMR spectroscopy can provide insight into molecular mobility and structural features. Tavares has reviewed the importance of two key relaxation mechanisms (spin-lattice relaxation, and spin-spin relaxation) in the study of small and macromolecules in food samples. These relaxation values can help in the study of molecular changes during cooking, food storages process and shelf life studies of oils and other constituents, including anti-oxidants. This review provides yet another exciting application of NMR spectroscopy in industrial process and quality control of products.

Spence has contributed a comprehensive review on the molecular composition of soil biomass. Soil microorganisms are key indicators of environmental stresses, including climate change, land degradation, and agriculture footprint. Changes in the nature and chemistry of soil microorganisms, based on structural components, can be studied by using NMR spectroscopy. The author has provided examples of the use of NMR spectroscopy in the study of natural organic materials in microbial biogeochemistry using solid state NMR spectroscopy, isotopic enrichment techniques, etc.

We are grateful to the authors for their excellent contributions. We are also grateful to the entire team of Bentham Science Publishers who have efficiently processed and timely managed the publication of this much awaited volume of the book series. The commitment and hard work of Ms Fariya Zulfiqar (Assistant Manager Publications) and Mr. Shehzad Naqvi (Senior Manager Publications), and the leadership of Mr. Mahmood Alam (Director Publications) are duly acknowledged. We sincerely hope that like the previous volumes of this useful book series, the current compilation will contribute to the better understanding of the applications of NMR spectroscopy.

Prof. Atta-ur-Rahman, FRS Honorary Life Fellow Kings College University of Cambridge Cambridge UK &Prof. M. Iqbal Choudhary H.E.J. Research Institute of Chemistry International Center for Chemical and Biological Sciences University of Karachi

List of Contributors

Adrian SpenceInternational Centre for Environmental and Nuclear Sciences, University of the West Indies, Mona, Kingston 7, JamaicaDanila L. RuizLaboratorio de Estudio de Compuestos Orgánicos (LADECOR), Departamento de Química, Facultad de Ciencias Exactas Universidad Nacional de La Plata, ArgentinaDiego D. ColasurdoLaboratorio de Estudio de Compuestos Orgánicos (LADECOR), Departamento de Química, Facultad de Ciencias Exactas Universidad Nacional de La Plata, ArgentinaJeetender ChughDepartment of Chemistry, Department of Biology, Indian Institute of Science Education and Research (IISER), Dr Homi Bhabha Road, Pashan, Pune 411008, IndiaKannan VaidyanathanDepartment of Biochemistry & Scientist, Pushpagiri Research Centre, Pushpagiri Institute of Medical Science & Research Centre, Tiruvalla, Kerala, IndiaMaria Inês Bruno TavaresInstitute of Macromolecules, Federal University of Rio de Janeiro, Av. Horacio Macedo, 2030, Block J, CT, Fundão Island, Rio de Janeiro, RJ, BrazilNazia HussainDepartment of Biotechnology, Savitribai Phule Pune University (formerly University of Pune), Ganeshkhind, Pune 411007, IndiaPatricia E. AllegrettiLaboratorio de Estudio de Compuestos Orgánicos (LADECOR), Departamento de Química, Facultad de Ciencias Exactas Universidad Nacional de La Plata, ArgentinaSaleem YousfDepartment of Chemistry, Indian Institute of Science Education and Research (IISER), Dr Homi Bhabha Road, Pashan, Pune 411008, IndiaSergio L. LaurellaLaboratorio de Estudio de Compuestos Orgánicos (LADECOR), Departamento de Química, Facultad de Ciencias Exactas Universidad Nacional de La Plata, ArgentinaShilpy SharmaDepartment of Biotechnology, Savitribai Phule Pune University (formerly University of Pune), Ganeshkhind, Pune 411007, India

NMR as a Tool for Studying Rapid Equilibria: Tautomerism

Sergio L. Laurella,Diego D. Colasurdo,Danila L. Ruiz,Patricia E. Allegretti*
Laboratorio de Estudio de Compuestos Orgánicos (LADECOR), Departamento de Química, Facultad de Ciencias Exactas Universidad Nacional de La Plata, Argentina

Abstract

Tautomerism is a chemical equilibrium which involves rapid transference of a hydrogen atom. Its importance in biochemistry, medicinal chemistry, pharmacology and organic synthesis, as well as the wide variety of molecules in which it occurs, makes it an interesting chemical issue to be studied. NMR bears the advantage of allowing equilibrium observation without shifting it. The aim of this work is to sum up a variety of experiments that can be carried out on tautomeric equilibria in order to obtain structural and mechanistic information. In every case, the two (or more) major tautomeric forms must have relatively low conversion rates, i.e., they must exist long enough to survive (in average) the NMR experiment and then show different but overlapped NMR spectra. Assignation of the peaks to their corresponding tautomeric form has to be done with regarding signal integration, multiplicity and chemical shift of the signals. Theoretical calculations might be carried out in order to do this assignation. Once found two (or more) independent and non-overlapped peaks corresponding to each tautomer, their integration permits tautomeric contents and tautomerization constants calculation. Herein, equilibrium shifts caused by the presence of substituents (causing electronic and steric effects), solvents (interacting in different ways with the tautomers), internal chemical interactions (such as hydrogen bonds), tautomer-tautomer interactions (producing the formation of dimers) and temperature variation are discussed using a variety of compounds, such as ketonitriles, ketoamides and salicylaldimines, among others. All these facts give information about the causes of the stabilization or destabilization of different tautomeric forms.

Keywords: NMR, Solvent effect, Substituent effect, Tautomerism, Theoretical calculations.
*Corresponding author Patricia E. Allegretti: Laboratorio de Estudio de Compuestos Orgánicos (LADECOR), Departamento de Química, Facultad de Ciencias Exactas Universidad Nacional de La Plata, Argentina; Tel/Fax: 0054-221-424-3104; E-mail: [email protected]