Fourier transform Raman spectroscopy of polymeric biomaterials and drug delivery systems

The characterization of drugs within polymer supports is an important prerequisite to our understanding of the chemical and/or physical mechanisms which control the release of drugs into the body from a biomedical polymer.The spectra of biomolecules obtained using a visible source are often accompanied by a strong persistent fluorescence background which is difficult to control. This has so far prevented the routine use of Raman spectroscopy in the analysis of biological compounds.FT Raman spectroscopy in the near infrared has proved on many occasions to be highly efficient in avoiding such problems. We have here reviewed the potential of FT Raman spectroscopy as an analytical technique for polymeric delivery systems by describing spectra of several significant drugs in clinically valuable polymeric supports.     

FT Raman investigation of sodium cellulose sulfate

FT Raman investigation of sodium cellulose sulfates (NaCS) was reported. Different NaCS were prepared by two diverse sulfation methods and their total degrees of substitution (DS) of sulfate groups were determined through either ¹³C-NMR spectroscopy or elemental analysis. Subsequently, these NaCS were characterized with FT Raman spectroscopy. The caused bands through the introduction of the sulfate groups in cellulose chain were explained and assigned. Additionally, a strong linear correlation between the areas under the bands ascribed to the stretching vibrations of C–O–S groups and the total DS of NaCS was presented. A rapid method of quantifying the total DS of NaCS was established. Finally, sodium sulfate (Na₂SO₄), a salt that is very often produced during the sulfation of cellulose, was found to be analyzable even with a weight content of 0.12% in NaCS. The method of quantifying the content of this salt in NaCS was investigated with Raman spectroscopy.     

Fourier transform Raman spectroscopy: Its value in the study of polymers

The advantages of FT Raman spectroscopy, using a near-infrared excitation source, are discussed. The details of the instrumentation are described and the many applications of FT Raman spectroscopy in polymer science are surveyed.     

拉曼光谱在分析化学中的应用进展

评述了各种拉曼技术在分析化学方面的应用进展,涉及到的拉曼光谱技术有常规拉曼光谱、常规共振拉曼光谱、表面增强拉曼光谱、表面增强共振拉曼光谱、傅里叶变换拉曼光谱、傅里叶变换表面增强拉曼光谱及其联用技术。共引用９１篇文献。     

Applications of FT Raman Spectroscopy and Micro Spectroscopy Characterizing Cellulose and Cellulosic Biomaterials

FT Raman spectroscopy and micro spectroscopy were used for the investigation of cellulose, cellulose derivatives and cellulosic plant fibres. Lattice structures of cellulose, polymorphic modifications I and II, as well as amorphous structure, were clearly identified by means of FT Raman vibrational spectra. Chemometric models were developed utilizing univariate calibration as well as methods of multivariate data analyses of FT Raman spectral data for the fast prediction of cellulose properties. Cellulose properties like the degree of crystallinity Xc_Raman, the degree of substitution DS_CMC, DS_AC and cellulose reactivity were determined. In situ/ in vivo FT Raman micro spectroscopy was used for the characterization of cellulose structures of flax and hemp fibres. Orientational and stress dependent FT Raman experiments were carried out.     

The destruction-free analysis of polymers by fourier transform infrared photoacoustic and fourier transform Raman spectroscopy: A comparison

With the introduction of rapid–scanning Fourier transform infrared (FTIR) and recently Raman (FT–Raman) spectroscopy, vibrational spectroscopy has been launched into a new era of applications in polymer chemistry and physics. Thus, the increase in sensitivity provided by multiple scanning has led to the breakthrough of new, destruction–free sampling techniques, such as photoacoustic and Raman spectroscopy. This paper provides a comparison between data produced by FTIR photoacoustic and FT–Raman analysis of a range of polymers, and structural information available from both techniques is discussed.     

NIR FT Raman Spectroscopy–a Rapid Analytical Tool for Detecting the Transformation of Cellulose Polymorphs

This is a report of the combined use of NIR FT Raman spectroscopy and X-ray diffraction measurements (WAXS) to investigate the polymorphic transformation of cellulose I into cellulose II. For this reason samples of cellulose I were swelled in different concentrations of NaOH and dissolved in different molten inorganic salts hydrates (LiCl·2ZnCl₂·6H₂O, LiClO₄·3H₂O, LiSCN·2,5H₂O and ZnCl₂·4H₂O). NIR FT Raman spectra of the alkali treated samples were recorded. They characterize the pure modifications cellulose I and II as well as mixtures of the two polymorphic phases. The results of the Raman measurements were confirmed by X-ray scattering. The paper demonstrates that FT Raman vibrational spectroscopy is a powerful, rapid analytical method which may be used to follow the polymorphic transformation of cellulose I into cellulose II.     

Effect of aggregation of p-phenylphenol on enzymatic polymer synthesis in dioxane/water mixture

The state of p-phenylphenol molecules in dioxane/water mixture, a commonly used reaction system for enzymatic polymerization of phenols and aromatic amines, was investigated by difference UV absorption spectroscopy and Fourier transform (FT) Raman spectroscopy. The aggregate of p-phenylphenols is found on the basis of the exciton peaks observed in difference UV absorption spectra. FT Raman spectroscopy demonstrates further that p-phenylphenol molecules aggregate together in “face to face” fashion. A simplified model is proposed for aggregation of p-phenylphenol molecules in dioxane/water mixture, which can elucidate the variation of the molecular weight of poly (p-phenylphenol) coupled in the reaction system. © 1995 John Wiley & Sons, Inc.     

Application of Fourier transform Raman spectroscopy to a range of compounds of pharmaceutical interest

Fourier transform (FT) Raman spectra have been obtained for a range of synthetic and semisynthetic samples to evaluate the utility of the technique for the characterization of compounds of pharmaceutical interest. These spectra are compared with the IR KBr disc spectra. Examples of the additional, important information which may be extracted from Raman data in comparison with IR spectroscopy are reported for the range of chemical structures studied. The superior ability of Raman to characterize the stretching modes of the CH bond compared with IR spectroscopy is demonstrated for several compounds.The characterization of highly symmetric vibrational modes is one of the most prominent and useful advantages of Raman spectroscopy and several examples of this primary application are also cited. These include the assignment of the ring breathing frequency of monosubstituted benzene rings, the CCC symmetric skeletal mode of a tricyclic fused ring system, the NO symmetric stretch of aromatic nitro groups and the stretching vibrations of various double bonds, several of which possess a high degree of local symmetry.     

Advances in surface-enhanced Raman spectroscopy for analysis of pharmaceuticals: A review

Recently, Raman spectroscopy become a popular and potential analytical technique for the analysis of pharmaceuticals as a result of its advancement. The innovation of laser technology, Fourier Transform-Raman spectrometers with charge coupled device (CCD) detectors, ease of sample preparation and handling, mitigation of sub-sampling problems using different geometric laser irradiance patterns and invention of different optical components of Raman spectrometers are contributors of the advancement of Raman spectroscopy. Transmission Raman Spectroscopy is a useful tool in pharmaceutical analysis to address the problems related with sub-sampling in conventional Raman back scattering. More importantly, the development of surface-enhanced Raman scattering (SERS) has been a prominent advancement for Raman spectroscopy to be applied for pharmaceuticals analysis as it avoids the inherent insensitivity and fluorescence problems. As the active pharmaceutical ingredients (APIs) contain aromatic or conjugated domains with strong Raman scattering activity, Raman spectroscopy is an attractive alternative conventional analytical method for pharmaceuticals. Coupling of Raman spectroscopy with separation techniques is also another advancement applied to reduce or avoid possible spectral interferences. Therefore, in this review, transmission Raman spectroscopy, SERS, and SERS coupled with various separation techniques for pharmaceutical analysis are presented.     

Applications of Fourier Transform Raman spectroscopy in the synthetic polymer field

The application of FT Raman spectroscopy in the study of a wide range of polymer systems is discussed. The following have been included to give the reader an insight into the variety of areas which can successfully be studied using this important technique: the problem of crystallinity; nylons; poly(aryl ether ketone) and poly(aryl ether ether ketone); poly(aryl ether ether sulphone) and poly(aryl ether sulphone); epoxy resin curing; copolymers; copolymers of tetrafluoroethylene and hexafluoropropylene; polythioethers; and gels.     

Characterisation and identification of bacteria using SERS

Within microbiology Raman spectroscopy is considered as a very important whole-organism fingerprinting technique, which is used to characterise, discriminate and identify microorganisms and assess how they respond to abiotic or biotic stress. Enhancing the sensitivity of Raman spectroscopy is very beneficial for the rapid analysis of bacteria (and indeed biological systems in general), where the ultimate goal is to achieve this without the need for lengthy cell culture. Bypassing this step would provide significant benefits in many areas such as medical, environmental and industrial microbiology, microbial systems biology, biological warfare countermeasures and bioprocess monitoring. In this tutorial review we will report on the advances made in bacterial studies, a relatively new and exciting application area for SERS.     

Ti-modified Mesoporous Molecular Sieves Containing both Selective Oxidation and Photocatalysis Centers

IntroductionIn recent years,titanium- containing meso-porous molecular sieves have attracted considerableattention of some scholars and scientists because oftheir remarkable catalytic properties in selectiveoxidation reactions by H2 O2 in aqueous solution asthe oxidant[1_ 3 ] .The high cost and low efficiencyof H2 O2 ,however,limits its application on an in-dustrial scale.In our previous work[4] ,we foundthat using Ti- substituted MCM- 41 as a catalystforthe hydroxylation ofbenzene with H2…     

New data for the characterization of Milos obsidians</p> </p>

Summary Newly produced fission track (FT), instrumental neutron activation analysis (INAA) and micro-Raman spectrometry data have been used to characterize the classical source areas of the Milos obsidians better and to check the provenance of obsidian artefacts. The Bombarda-Adhamas and Demenegaki obsidians yielded indistinguishable FT ages 1.57±0.12 and 1.60±0.06 My, respectively, in agreement with previous FT data. By INAA analyses it was possible to discriminate between the three obsidian sources on Milos: Bombarda-Adhamas, Demenegaki and A. Ioannes. Raman spectroscopy has been found to be a valuable technique to gain a chemico-structural characterization of a given obsidian population in terms of dissolved water content and microlite distribution/composition.</p> </p>     

Analyses of the surfaces of concrete by Raman and FT‐IR spectroscopies: comparative study of hardened samples after demoulding and after organic post‐treatment

Concrete surfaces were studied by two spectroscopic techniques, FT‐IR (in ATR mode) and Raman, to establish a nondestructive method to analyze the distribution of hydrated and organic phases. The surface composition of ordinary clinker, polished concrete, concrete after demoulding, and coated concrete as used in building construction was studied. The clinker's mineral phases and the polished concrete were first analyzed by Raman spectroscopy to determine a spectrum database of the specific phases located on the surface of the concrete. Then, both spectroscopic techniques were used to analyze, directly, the surface of hardened concrete after demoulding. No impact of roughness or porosity was highlighted using Raman spectroscopy; many cementitious, or hydrated phases (alite, belite, tricalcium aluminate, ferrite, portlandite and ettringite) were clearly identified. FT‐IR in ATR mode only identified some hydrated phases: portlandite and CaO? SiO₂? H₂O (C? S? H), but organic residues from the demoulding oil were characterized by this technique. Furthermore, the convenience of using these techniques together was tested by analyzing the composition of concrete surfaces coated by different organic post‐treatments. FT‐IR spectroscopy was useful to identify the main organic groups at the concrete surface, whereas Raman spectroscopy was especially able to characterize the mineral/hydrated phases under a thick post‐treatment layer (constituted of polyester varnish). Due to their own specificities, these complementary techniques should be used together to easily identify all the mineral phases and organic residues/coatings on concrete surfaces. Copyright © 2010 John Wiley & Sons, Ltd.     

Confined Raman Scattering – Easy Access to the Surface Phonons of Specific Crystalline Solids

An easily feasible method to measure surface phonons of specific crystalline solids is described. Special experimental conditions allow confining Raman scattering to the surface region of crystals, while the contribution of bulk scattering to the spectra is largely excluded. Such conditions exist for example in the case of hexaborides, using FT Raman spectroscopy with a commercial spectrometer with ND:YAG laser excitation. We show results obtained on LaB₆, SmB₆ and boron carbide. The surface phonon spectra of LaB₆ are analyzed by comparing them with bulk spectra and discussed in comparison with results of other experimental methods and theoretical calculations.     

Surface hydration of aqueous calcium minerals as studied by Fourier transform Raman and infrared spectroscopy

Rapid hydration reactions of several calcium minerals are studied using Fourier transform (FT) Raman and infrared (IR) spectroscopy. Oleate adsorption over aqueous synthetic fluorite, calcite and gypsum (pH 9) is investigated and adsorption mechanisms are discussed.     

Structure of polypropylene/polyethylene blends assessed by polarised PA-FTIR spectroscopy,polarised FT raman spectroscopy and confocal Raman microscopy

Physical structure and morphology of differently prepared and treated bulk specimens of isotactic polypropylene, linear polyethylene and their blend was studied by polarised FT Raman spectroscopy, polarised FTIR spectroscopy with photoacoustic detection, and by confocal Raman microscopy. The specimens differed in preparation technique, mechanical and thermal history. The orientation and reorientation of molecular chains of individual blend components, their crystallinity and the size and structure of the microdomains both in the skin and in the core of the specimens were correlated with the preparation conditions, mechanical treatment and thermal history. The possibilities and limitations of each method were discussed.     

Raman Spectroscopy—A Prospective Tool in the Life Sciences

Although the physics of Raman spectroscopy and its application to purely chemical problems is long established, it offers a noninvasive, nondestructive, and water‐insensitive probe to problems in the life sciences. Starting from the principles of Raman spectroscopy, its advantages, and methods for signal enhancement, the bulk of the review highlights recent applications. Structural investigations of a hormone receptor, testing the biocompatibility of dental implants, probing soil components and plant tissue alkaloids, and localization of single bacteria are just four problems in which Raman spectroscopy offers a solution or complements existing methods.