The objective of the article is to review biomedical applications which became possible after the development of sensitive and high throughput Raman and Fourier transform infrared spectrometers in the past decade. Technical aspects of the instrumentation are briefly described. Then the broad range of vibrational spectroscopic applications with the focus on imaging and fiber-optical methods are discussed to study mineralized tissue (bone, teeth), skin, brain, the gastrointestinal tract (mouth, pharynx, esophagus, colon), breast, arteries, cartilage, cervix uteri, the urinary tract (prostate, bladder), lung, ocular tissue, liver, heart and spleen. Experimental studies are summarized demonstrating the possibilities and prospects of these methods in various fields of biodiagnostics to detect and characterize diseases, tumors and other pathologies.

C. Krafft

V. Sergo

Biomedical applications of Raman and infrared spectroscopy to diagnose tissues

This paper reports the application of near-infrared Raman spectroscopy to detect ephedrine in biological medium. At present time, the doping control for ephedrine in athletes uses the urinalysis by the gas chromatography/mass spectrometry, with main disadvantage the need of collecting urine and the time delay to obtain results. This work aims to develop a noninvasive technique that will allow to evaluate the concentration of the ephedrine in a real time diagnosis. A Raman system composed by a Ti:Saphire laser pumped by an Argon laser was used, operating at the wavelength of 785 nm, with a laser power of 70 mW at sample position. Raman scattered photons were collected by a f/l.8 spectrometer and a N2-cooled CCD detector. Ephedrine Raman peaks at 1002 and 1603 cm−1 were studied, opening possibility for the identification and quantification of ephedrine. Raman spectra of ephedrine with different concentrations in human urine were taken, and the intensity of the ephedrine peak at 1002 cm−1 was measured as a function of its concentration. It was also studied the Raman spectrum of an urine sample from a Wistar rat, after a subcutaneous inoculation of an ephedrine solution in physiologic serum, at the concentration of 5 mg/ml. It was found that Raman spectroscopy could detect ephedrine in urine at concentrations lower than the doping limit legally permitted by the International Olympic Committee.

A. E. Guimarães

M. T. T. Pacheco

L. Silveira Jr.

D. Barsottini

J. Duarte

A. B. Villaverde

R. A. Zângaro

Near Infrared Raman Spectroscopy (NIRS): A technique for doping control

Macromolecular crowding is a general phenomenon of biological systems, and the evaluation of a correlation time for a specific molecule is difficult when the molecular crowding exists. The determination of an effective correlation time may therefore give useful insights into molecular dynamics of such systems. In this work, the relaxation rates in the mixture of D2O (80%) and cystic fluid (20%) were measured with a NMR operating at 400 MHz for three types of cysts (non-infected radicular, infected radicular and hemorrhagic). The effective correlation times (&#964; values) were then determined by using a formula derived from the observed relaxation rates. The &#964; value of the infected cyst was found to be longer than those of the others for the studied cases. The present data suggest that an effective correlation time for fluids with macromolecular crowding can be determined from NMR relaxation measurements.

Hatice Budak

M. Zafer K&#246;yl&#252;

U. Nezih Y&#105;lmaz

The effective correlation time &#964; in jaw cysts determined from 400 MHz NMR T1 and T2 measurements

In the light of the usefulness of amidines in medicinal chemistry, this paper considers the effects on biological properties and chemical reactivities of organic molecules affected by intramolecular interactions. The study of chemical shifts has been an important source of information on the electronic structure of amidine salts and their ability to form non-covalent bonds with nucleic acids. The NMR and IR results demonstrate that hydrogen bonds are a force for promoting chemical reactions. The thymine O2 carbonyl oxygen in a close proximity to the amidinium cation does interact with the appropriately spaced amidinium NH donor moieties. The 1H-15N 2D NMR (GHSQC and GHMBC) spectra with natural isotopic abundance of 15N fully confirm the intramolecular character of the bonds. A rule able to estimate the relative strength of the new multifurcated hydrogen bonds is given. The appearance of the &#916;&#948;NH chemical shift differences near zero is due to the strong intramolecular interactions. The strength of the H-bond donation by acetamidines is reflected in the N&#8211;H dissociation/recombination process (positive charge shift has been invoked to explain other effects on benzamidines). The temperature dependence of chemical shift for the amidine NH protons in dimethyl sulfoxide solutions is herein discussed.

Jaros&#x142;aw Spycha&#x142;a

Stabilization of N-, N,N-, N,N&#8242;-methylated and unsubstituted simple amidine salts by multifurcated hydrogen bonds

Simple modifications of the gradient enhanced version of the TROSY experiment allow to obtain four different spectra containing each one of the components of the H&#8211;N doublet in 15N labelled proteins. By measuring the difference in peak position among these four spectra, residual dipolar coupling values can be obtained for medium sized proteins. This experiment, which exploits the use of pulse field gradients to select the 15N coherence pathway, produces excellent results in terms of water suppression. Moreover, tuning of a single delay in the sequence reduces notably the presence of artifacts. The performance of this suite of experiments, that we called TEC (Trosy–E.Cosy) experiment, is tested against a J-modulation method, inherently more accurate but more time consuming, for the accuracy in the observed values of residual dipolar couplings. For larger proteins, the use of this strategy allows to select the most favourable combination of peaks giving the sharpest signals.

Tommaso Eliseo

Mariana Gallo

Riccardo Melis

Maurizio Paci

Renzo Bazzo

Daniel O. Cicero

Single scan TROSY and E.COSY suite of experiments for the measurement of residual dipolar couplings in proteins

In this review we discuss a range of spectroscopic techniques that are currently used for analysis of arsenic in human urine for understanding arsenic metabolism and toxicity, especially in relation to genetics/ethnicity, ingestion studies and exposure to arsenic through drinking water and diet. Spectroscopic techniques used for analysis of arsenic in human urine include inductively coupled plasma mass spectrometry (ICP-MS), hydride generation atomic absorption spectrometry (HG-AAS), hydride generation atomic fluorescence spectrometry (HG-AFS), graphite furnace atomic absorption spectrometry (GF-AAS) and liquid chromatography mass spectrometry (LC-MS). Advantages and disadvantages of each of these techniques are highlighted in relation to analysis of total arsenic and speciation of arsenic compounds in human urine which would be of particular benefit to those new to the field of arsenic speciation of urine samples. The review summarises our current understanding of arsenic metabolism through the analysis of urine samples and provides a list of arsenic species that have been identified in urine samples. This is done by focusing on recent published reports on arsenic metabolism and toxicity in relation to most investigated issues, i.e. genetics/ethnicity, ingestion and exposure.

Eid I. Brima

Richard O. Jenkins

Parvez I. Haris

Understanding arsenic metabolism through spectroscopic determination of arsenic in human urine

Gold-based drugs have been successfully used for the treatment of rheumatoid arthritis. When administered, they undergo ligand exchange reactions in the body with biofluids, cells and proteins. NMR spectroscopy is a very useful technique for probing these ligand exchange reactions under physiological conditions. The strength of the binding ligands can be estimated by studying the chemical shift changes in 13C and 31P NMR. It is also a powerful method for investigating the kinetics and thermodynamics of the exchange reactions of gold drugs with biomolecules. The purpose of this review report is to highlight the importance of NMR spectroscopy in the study of gold biochemistry and to bridge the fairly large gap in the progress of this interesting area of bioinorganic chemistry.

Anvarhusein A. Isab

Saeed Ahmad

Applications of NMR spectroscopy in understanding the gold biochemistry

Studies of the perturbing effect of chiral solvating agents (CSAs) namely the fluoroalcohols 5a and 5b upon the NMR spectra of chiral &#x394;2-thiazolines 1 presenting interesting insecticidal properties demonstrated the ability of these CSAs to afford diastereomeric solvates from these substrates providing their enantiomeric discrimination. Thus, for five of the six tested &#x394;2-thiazolines 1A and 1B there is at least one possibility to proceed to their enantiomeric discrimination either by 1H or 19F NMR using mostly 5b as CSA.

B&#xE9;rang&#xE8;re Merelli

Laurence Menguy

Estelle Soubeyrand-Lenoir

Jean-Claude Cherton

Determination of the enantiomeric composition of chiral delta-2-thiazolines-1,3 by 1H and 19F NMR spectroscopy using chiral solvating agents

Ultraviolet radiation is considered responsible for sunburning, premature skin aging, and cancerogenesis through the production of free radical species. Therefore, the favoured possibility for direct detection of unpaired electrons – electron paramagnetic resonance spectroscopy – is predestinated for detection and structural and dynamic analysis of this kind of molecules. However, many of UV induced radicals in skin have a short lifetime at ambient conditions and possibilities for stabilisation or transformation into definite para- or diamagnetic products have to be found. On the other hand, diamagnetic products, potentially also originated by reporter molecules, which are not detectable by EPR, are target molecules for mass spectrometric analysis. In this review, potentials and limitations of both spectroscopic methods are reviewed, and the effect of ultraviolet radiation on human skin is discussed in particular. Suitable combinations of both techniques result in detailed information about photoproducts and processes taking place within skin during and after irradiation. The literature is viewed from a recent perspective; historical aspects were not in the scope of this paper.

Ulrike Hochkirch

Werner Herrmann

Reinhard St&#0246;&#0223;er

Hans-Hubert Borchert

Michael W. Linscheid

Electron paramagnetic resonance and mass spectrometry: Useful tools to detect ultraviolet light induced skin lesions on a molecular basis – A short review

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Journal of Spectroscopy publishes research into the theory and application of spectroscopy across all disciplines, including biology, chemistry, engineering, earth sciences, medicine, materials science, physics, and space science.

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Chief Editor&nbsp;Dr Daniel Cozzolino&nbsp;is based at the University of Queensland, Australia. His research focuses on the developments of chemometric and spectroscopic methods for use in agriculture and food applications.

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Journal of Spectroscopy - Table of contents 2006

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Journal of Spectroscopy publishes research into the theory and application of spectroscopy across all disciplines, including biology, chemistry, engineering, earth sciences, medicine, materials science, physics, and space science.

Journal of Spectroscopy