The use of optical spectroscopy in combinatorial chemistry

Infrared and Raman spectroscopy allow direct spectral analysis of the solid‐phase, thus avoiding the tedious cleavage of compounds from the solid support. With diagnostic bands in starting materials or products, infrared and Raman spectroscopy are efficient in monitoring each reaction step directly on the solid phase. Consequently, infrared and Raman spectroscopy have evolved as the premier analytical methodology for direct analysis on the solid support. While infrared transmission spectroscopy is a general analytical method for resin samples, internal reflection spectroscopy is especially suited for solid polymer substrates known as “pins” or “crowns.” Single bead analysis is done best by infrared microspectroscopy, whereas photoacoustic spectroscopy allows totally nondestructive analysis of resin samples. With an automated accessory, diffuse reflection spectroscopy provides a method for high throughput on‐bead monitoring of solid‐phase reactions. Providing identification based on molecular structure, HPLC‐FTIR is, therefore, complementary to LC‐MS. Additionally, Raman spectroscopy as a complement to infrared spectroscopy can be applied to resin samples and—using a Raman microscope—to single beads. Fluorometry as an extremely sensitive spectroscopic detection method allows rapid quantification of organic reactions directly on the resin. © 1999 John Wiley & Sons, Inc. Biotechnol Bioeng (Comb Chem) 61:179–187, 1998/1999.     

Spectroscopic investigation and in vitro cytotoxic activity toward HepG2 cells of a copper compound complexed with human serum albumin

The human serum albumin (HSA) interaction of a mixed‐ligand copper compound (1) with an imidazole and taurine Schiff base derived from salicylaldehyde and taurine was investigated using fluorescence spectroscopy, UV–vis spectroscopy, time‐resolved fluorescence spectroscopy, circular dichroism (CD) spectroscopy, Fourier transform infrared (FT‐IR) spectroscopy and a molecular docking technique. The results of fluorescence and time‐resolved fluorescence spectroscopy indicated that 1 can effectively quench the HSA fluorescence by a static mechanism. Binding constants (K) and the number of binding sites (n ≈ 1) were calculated using modified Stern–Volmer equations. The thermodynamic parameters were calculated. UV–vis, CD and FT‐IR spectroscopy measurements confirm the alterations in the HSA secondary structure induced by 1. The site marker competitive experiment confirms that 1 is located in subdomain IB of HSA. The combination of molecular docking results and fluorescence experimental results reveal that hydrophobic interaction and hydrogen bonds are the predominant intermolecular forces stabilizing the 1–HSA complex. The 1–HSA complex increases approximately three times its cytotoxicity in cancer cells but has no effect on normal cells in vitro. Compared with unbound 1, the 1–HSA complex promotes HepG2 cells apoptosis and also has a stronger capacity for cell cycle arrest at the S phase of HepG2 cells.     

Nuclear Magnetic Resonance Spectroscopy for the Study of B-Cell Epitopes

High-resolution nuclear magnetic resonance (NMR) spectroscopy is a structural technique that is finding increasing use in the study of antibody–antigen interactions. In this review we describe how the dynamic structural parameters obtained from NMR spectroscopy can further our understanding of B-cell epitopes and their function. Specific applications of NMR spectroscopy to examine the residues on peptides and proteins that contact the antibody combining site are also described. These include “footprinting” techniques using H–D exchange–COSY NMR spectroscopy, which are particularly useful for epitope mapping of protein antigens. For smaller systems, such as Fab–or Fv–peptide complexes, nuclear magnetization transfer difference NMR spectroscopy, transferred nuclear Overhauser effect spectroscopy, double-quantum-filtered NOE spectroscopy, and isotope editing techniques have been applied. The interpretation and limitations of the data obtained from these procedures and anticipated improvements in these applications in the future are discussed.     

激光拉曼光谱技术在生物分子DNA研究中的应用和进展

激光技术的兴起使拉曼光谱成为激光分析中最活跃的研究领域之一,已被广泛地用于物质成分的分析和分子结构的鉴定。本文综述了拉曼技术在DNA研究中近年来的最新进展,包括：DNA的常规拉曼光谱分析;DNA的激光共振拉曼光谱分析;DNA在金属表面或电极上吸附行为的表面增强拉曼光谱研究;DNA的傅立叶变换拉曼光谱研究等。并对拉曼光谱技术在DNA等生物大分子领域中的研究前景做了进一步的展望。     

功能红细胞研究的拉曼光谱技术与进展

红细胞在人体新陈代谢和物质运输方面起着非常重要的作用。作为一种无损、快速而灵敏的光谱学检测方法,拉曼光谱技术在生物医学领域的应用日渐广泛。本文综述了近年来拉曼光谱技术在红细胞及血红蛋白研究中的应用进展,详尽评述当前研究功能红细胞中较有优势的拉曼技术—显微拉曼光谱技术和光镊拉曼光谱技术,并对其技术的改进做出总结,以期为利用激光拉曼光谱研究红细胞提供较系统的参考。     

Comparative determination of polymorphs of indomethacin in powders and tablets by chemometrical near-infrared spectroscopy and X-ray powder diffractometry

The purpose of this research was to develop a rapid chemometrical method based on near-infrared (NIR) spectroscopy to determine indomethacin (IMC) polymorphic content in mixed pharmaceutical powder and tablets. Mixed powder samples with known polymorphic contents of forms α and γ were obtained from physical mixing of 50% of IMC standard polymorphic sample and 50% of excipient mixed powder sample consisting of lactose, corn starch, and hydroxypropyl-cellulose. The tablets were obtained by compressing the mixed powder at 245 MPa. X-ray powder diffraction profiles and NIR spectra were recorded for 6 kinds of standard materials with various polymorphic contents. The principal component regression analysis was performed based on normalized NIR spectra sets of mixed powder standard samples and tablets. The relationships between the actual and predicted polymorphic contents of form g in the mixed powder measured using x-ray powder diffraction and NIR spectroscopy show a straight line with a slope of 0.960 and 0.995, and correlation coefficient constants of 0.970 and 0.993, respectively. The predicted content values of unknown samples by x-ray powder diffraction and NIR spectroscopy were reproducible and in close agreement, but those by NIR spectroscopy had smaller SDs than those by x-ray powder diffraction. The results suggest that NIR spectroscopy provides a more accurate quantitative analysis of polymorphic content in pharmaceutical mixed powder and tablets than does conventional x-ray powder diffractometry.     

Isolation and structural characterization of a new crosslinking amino acid, cyclopentenosine, from the acid hydrolysate of elastin.

A novel polyfunctional crosslinking amino acid, which was developed slower than lysinonorleucine and faster than desmosine on thin layer chromatography, was isolated from the hydrolysate of bovine aorta elastin. Its proposed structure was verified by ultraviolet spectroscopy, fast atom bombardment mass spectroscopy, and nuclear magnetic resonance spectroscopy. The data indicated it to be a trifunctional amino acid with a cyclopentene structure. The mass spectral analysis indicated a parent compound with a mass of 381 (C18H27N3O6). The proposed structure is one derived from the condensation of three allysine residues. Based on the names of other crosslinking amino acids found in elastin, the trivial name of cyclopentenosine is given to this compound.     

Reaction of iron(III) with theaflavin: complexation and oxidative products

Theaflavins are a family of compounds, whose chemistry has been sparsely investigated. They can comprise up to 40% the dry weight of black tea. They are known to chelate metals, however very little knowledge exists on the mechanisms involved. There is some correlation between both of these areas in that following degradation of the iron theaflavin complex, subsequent redox reactions may lead to the formation of similar products on both occasions. The interaction of iron(III) with theaflavin at pH < 3.0 is investigated by means of liquid chromatography mass spectroscopy (LC-MS), stopped flow spectroscopy and multivariate data analysis. Iron theaflavin complexes are formed which subsequently decay to form a number of oxidative species. The difficulties involved in the elucidation of the structure of polymeric phenolic compounds from black tea has been highlighted by numerous authors. The intermediates and major low molecular weight oxidised theaflavin products from the reaction of excess iron with theaflavin have been detected and identified using multivariate data analysis of diode array spectroscopic data. It is not possible to characterise the extremely polar high molecular weight oxidation products obtained from polyphenol oxidation. High performance liquid chromatography (HPLC) and electrospray mass spectroscopy (ES-MS) detected the low molecular weight oxidised theaflavin species present in the system. Enzymatic oxidation of theaflavin using peroxidase (POD) resulted in the formation of one major low molecular weight species oxidative product, which was fully characterised using nuclear magnetic resonance spectroscopy (NMR), high performance liquid chromatography (HPLC), electrospray mass spectroscopy (ES-MS), UV-visible (UV-Vis) and Fourier transform infra-red spectroscopy (FT-IR). The major objective of this work is to investigate the reaction of iron(III) with theaflavin and to add some insight into the mechanistic interaction of iron(III) with this family of compounds.     

喇曼光谱技术在生物医学中的应用

喇曼光谱技术是一种非侵入、非弹性散射技术,能够在分子层次上探测物质的临床医学特征和结构特征。本文综述了近十年来喇曼光谱技术在生物医学中的最新发展,归纳出了四种目前在生物医学中最为活跃的喇曼光谱技术：近红外喇曼光谱、紫外共振喇曼光谱、表面增强喇曼光谱和多维喇曼成像技术。详细阐述了这四种技术的特点和适用范围,并且列举了丰富的成功范例。     

Chitosan pyrolysis and adsorption properties of chitosan and its carbonizate

Chitosan was characterized by Fourier transform infrared spectroscopy (FTIR), ¹³C-nuclear magnetic resonance (NMR), X-ray diffraction (XRD), and elemental analysis (EA). The thin chitosan films obtained by the casting method were heated in vacuum from room temperature to 600 °C. The progress of thermal degradation and carbonization process was monitored by FTIR spectroscopy in a vacuum cell, which allows the elimination of the influence of atmospheric humidity on the chitosan and carbonizate properties. The adsorption of water on the degassed chitosan and its carbonizate as well the oxidation process was also investigated by FTIR spectroscopy. The surface morphology of initial chitosan and obtained carbonaceous material was observed using atomic force microscopy (AFM). Detailed characterization of raw material and carbonization conditions is necessary for tailoring reproducible adsorbent properties.     

X-ray spectroscopy-based structure of the Mn cluster and mechanism of photosynthetic oxygen evolution

The mechanism by which the Mn-containing oxygen evolving complex (OEC) produces oxygen from water has been of great interest for over 40 years. This review focuses on how X-ray spectroscopy has provided important information about the structure of this Mn complex and its intermediates, or S-states, in the water oxidation cycle. X-ray absorption near-edge structure spectroscopy and high-resolution Mn Kbeta X-ray emission spectroscopy experiments have identified the oxidation states of the Mn in the OEC in each of the intermediate S-states, while extended X-ray absorption fine structure experiments have shown that 2.7 A Mn-Mn di-mu-oxo and 3.3 A Mn-Mn mono-mu-oxo motifs are present in the OEC. X-ray spectroscopy has also been used to probe the two essential cofactors in the OEC, Ca2+ and Cl-, and has shown that Ca2+ is an integral component of the OEC and is proximal to Mn. In addition, dichroism studies on oriented PS II membranes have provided angular information about the Mn-Mn and Mn-Ca vectors. Based on these X-ray spectroscopy data, refined models for the structure of the OEC and a mechanism for oxygen evolution by the OEC are presented.     

Characterization of mammalian cell culture raw materials by combining spectroscopy and chemometrics

Two of the primary issues with characterizing the variability of raw materials used in mammalian cell culture, such as wheat hydrolysate, is that the analyses of these materials can be time consuming, and the results of the analyses are not straightforward to interpret. To solve these issues, spectroscopy can be combined with chemometrics to provide a quick, robust and easy to understand methodology for the characterization of raw materials; which will improve cell culture performance by providing an assessment of the impact that a given raw material will have on final product quality. In this study, four spectroscopic technologies: near infrared spectroscopy, middle infrared spectroscopy, Raman spectroscopy, and fluorescence spectroscopy were used in conjunction with principal component analysis to characterize the variability of wheat hydrolysates, and to provide evidence that the classification of good and bad lots of raw material is possible. Then, the same spectroscopic platforms are combined with partial least squares regressions to quantitatively predict two cell culture critical quality attributes (CQA): integrated viable cell density and IgG titer. The results showed that near infrared (NIR) spectroscopy and fluorescence spectroscopy are capable of characterizing the wheat hydrolysate's chemical structure, with NIR performing slightly better; and that they can be used to estimate the raw materials’ impact on the CQAs. These results were justified by demonstrating that of all the components present in the wheat hydrolysates, six amino acids: arginine, glycine, phenylalanine, tyrosine, isoleucine and threonine; and five trace elements: copper, phosphorus, molybdenum, arsenic and aluminum, had a large, statistically significant effect on the CQAs, and that NIR and fluorescence spectroscopy performed the best for characterizing the important amino acids. It was also found that the trace elements of interest were not characterized well by any of the spectral technologies used; however, the trace elements were also shown to have a less significant effect on the CQAs than the amino acids. © 2017 The Authors Biotechnology Progress published by Wiley Periodicals, Inc. on behalf of American Institute of Chemical Engineers, 33:1127–1138, 2017     

Photoemission Spectroscopy Characterization of Halide Perovskites

Controlling the surface and interface properties of halide perovskites (HaPs) materials is key to improve performance and stability of HaP‐based optoelectronic devices such as solar cells. Here, an overview is given on the use of different photoemission spectroscopy (PES) techniques as a tool kit to investigate chemical and electronic properties of surfaces and interfaces in research on HaP compounds. The primary focus of the article is X‐ray photoelectron spectroscopy (XPS), hard X‐ray photoemission spectroscopy (HAXPES), ultraviolet photoemission spectroscopy (UPS), and inverse photoemission spectroscopy (IPES), highlighting the importance of good practices during PES measurements. Starting from the working principles of PES, critical measurement conditions are discussed. In particular, the exposure of the HaP surface to vacuum and high energy radiation can cause accelerated ageing, degradation, and also ionic migration in the sample. The impact of these changes on the electronic and chemical properties is discussed, followed by an analysis of the specific challenges encountered when performing PES measurements of HaPs. These include the deviation from pristine surface conditions, determination of “soft” band edges, and assessment of band bending. The review concludes by emphasizing good practices for PES measurements of HaP samples and outlining the scope of operando type measurements to capture the transient behavior of HaPs in the experiment.     

Spectroscopic investigation of the interaction of the toxicant, 2-naphthylamine, with bovine serum albumin

The mechanism of interaction between bovine serum albumin (BSA) and 2-naphthylamine (2-NA) in aqueous solution was investigated by fluorescence spectroscopy, circular dichroism (CD) spectra, and UV-vis spectroscopy. It was proved from fluorescence spectra that the fluorescence quenching of BSA by 2-NA was a result of the formation of complex between 2-NA and BSA, and the binding constants (K(a) ) as well as the numbers of binding sites for 2-NA in BSA were determined according to the modified Stern-Volmer equation. The results of synchronous fluorescence and CD spectra demonstrated 2-NA could decrease the amount of α-helix of BSA, leading to the loosening of protein skeleton. UV-vis spectroscopy and resonance light scattering spectra (RLS) results also suggested the conformation of BSA were changed and the BSA aggregation occured, which could induce toxic effects on the organism.     

The effect of the cellulose-binding domain from Clostridium cellulovorans on the supramolecular structure of cellulose fibers

The cellulose-binding domain (CBD) is the second important and the most wide-spread element of cellulase structure involved in cellulose transformation with a great structural diversity and a range of adsorption behavior toward different types of cellulosic materials. The effect of the CBD from Clostridium cellulovorans on the supramolecular structure of three different sources of cellulose (cotton cellulose, spruce dissolving pulp, and cellulose linters) was studied. Fourier-transform infrared spectroscopy (FTIR) was used to record amides I and II absorption bands of cotton cellulose treated with CBD. Structural changes as weakening and splitting of the hydrogen bonds within the cellulose chains after CBD adsorption were observed. The decrease of relative crystallinity index of the treated celluloses was confirmed by FTIR spectroscopy and X-ray diffraction (XRD). X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) were used to confirm the binding of the CBD on the cellulose surface and the changing of the cellulose morphology.     

Self-association of bis-(alpha,beta-D-glucopyranosyl)-polyisobutylene

In this paper, we report the structure and apparent molecular weights of bis-(alpha,beta-D-glucopyranosyl)-polyisobutylene (Gluc-PIB-Gluc) aggregates in CDCl(3) by NMR spectroscopy. Analysis of DOSY (diffusion-ordered NMR spectroscopy) experiments of a solution of Gluc-PIB-Gluc showed the presence of aggregates that were corroborated with dynamic light scattering. The structure of the aggregates was also studied by correlation spectroscopy (COSY) and nuclear Overhauser effect spectroscopy (NOESY) experiments.     

Fibrillation of human serum albumin shows nonspecific coordination on stoichiometric increment of Copper(II)

Protein aggregation is related to a series of pathological disorders the main cause of which are the fibrillar species generated during the process. Human serum albumin (HSA) undergoes rapid fibrillation in the presence of Cu(II) at pH 7.4 in 60% ethanol after 6-h incubation (～65?°C) followed by room temperature incubation. Here, we have investigated the effect of a stoichiometric variation of Cu(II) on the self-assembly of HSA using Congo red and thioflavin T dye-binding studies, circular dichroism spectroscopy, Fourier transform infrared spectroscopy, electron paramagnetic resonance spectroscopy, fluorescence microscopy and transmission electron microscopy. The simulation of EPR spectra suggests that with the increment in Cu(II) ion concentration, there is a change in ligand field coordination. Kinetic parameters indicate reduced cooperativity that may be related to the nonspecific coordination on increment of Cu(II) concentration. Cu(II) is also able to direct the accumulation of a large number of fibers along with a formation of dense fibrillar network which is evident from microscopic images.     

The application of spectroscopy techniques for diagnosis of malaria parasites and arboviruses and surveillance of mosquito vectors: A systematic review and critical appraisal of evidence

Spectroscopy-based techniques are emerging diagnostic and surveillance tools for mosquito-borne diseases. This review has consolidated and summarised recent research in the application of Raman and infrared spectroscopy techniques including near- and mid-infrared spectroscopy for malaria and arboviruses, identified knowledge gaps, and recommended future research directions. Full-length peer-reviewed journal articles related to the application of Raman and infrared (near- and mid-infrared) spectroscopy for malaria and arboviruses were systematically searched in PUBMED, MEDILINE, and Web of Science databases using the PRISMA guidelines. In text review of identified studies included the methodology of spectroscopy technique used, data analysis applied, wavelengths used, and key findings for diagnosis of malaria and arboviruses and surveillance of mosquito vectors. A total of 58 studies met the inclusion criteria for our systematic literature search. Although there was an increased application of Raman and infrared spectroscopy-based techniques in the last 10 years, our review indicates that Raman spectroscopy (RS) technique has been applied exclusively for the diagnosis of malaria and arboviruses. The mid-infrared spectroscopy (MIRS) technique has been assessed for the diagnosis of malaria parasites in human blood and as a surveillance tool for malaria vectors, whereas the near-infrared spectroscopy (NIRS) technique has almost exclusively been applied as a surveillance tool for malaria and arbovirus vectors.Conclusions/SignificanceThe potential of RS as a surveillance tool for malaria and arbovirus vectors and MIRS for the diagnosis and surveillance of arboviruses is yet to be assessed. NIRS capacity as a surveillance tool for malaria and arbovirus vectors should be validated under field conditions, and its potential as a diagnostic tool for malaria and arboviruses needs to be evaluated. It is recommended that all 3 techniques evaluated simultaneously using multiple machine learning techniques in multiple epidemiological settings to determine the most accurate technique for each application. Prior to their field application, a standardised protocol for spectra collection and data analysis should be developed. This will harmonise their application in multiple field settings allowing easy and faster integration into existing disease control platforms. Ultimately, development of rapid and cost-effective point-of-care diagnostic tools for malaria and arboviruses based on spectroscopy techniques may help combat current and future outbreaks of these infectious diseases.     

Growth of single-crystal diamonds in microwave plasma

A microwave plasma (2.45 GHz) was used for depositing single crystal diamond layers at the deposition rate up to 40 μm/h in hydrogen-methane mixtures on the substrates from natural and synthetic diamond with the (100) deposition surface and with the size up to 5 × 5 mm. The structure and the defect-impurity composition of the fabricated single crystals with the thickness up to 600 μm have been investigated using Raman spectroscopy, photoluminescence spectroscopy, cathode luminescence spectroscopy, and electron and optical microscopy. A high quality and purity of the diamond layers deposited from a plasma was confirmed.