Synthesis and characterization of newberyite

Phosphates belong to the extensive group of inorganic pigments that are very often used in industry of plastics and anticorrosive paints. Also, the powders of newberyite MgHPO₄·3H₂O and α-pyrophosphate Mg₂P₂O₇ can find the usage in this field. Thus, these compounds were the centre of our attention. Newberyite and α-pyrophosphate were synthesized by the method of gelling. Impact of various ways of synthesis, especially reaction conditions, on the structural, thermal, physical and optical properties was investigated. α-pyrophosphate was synthesized by the thermal decomposition of newberyite at temperature around 500°C. Both powders are white color, but the newberyite is the whitest one. The reaction pH particularly affected the particle size distribution and optical properties.     

Interaction of hypericin with serum albumins: surface-enhanced Raman spectroscopy, resonance Raman spectroscopy and molecular modeling study

Surface-enhanced Raman spectroscopy, resonance Raman spectroscopy and molecular modeling were employed to study the interaction of hypericin (Hyp) with human (HSA), rat (RSA) and bovine (BSA) serum albumins. The identification of the binding site of Hyp in serum albumins as well as the structural model for Hyp/HSA complex are presented. The interactions mainly reflect: (1) a change of the strength of H bonding at the N1-H site of Trp; (2) a change of the Trp side-chain conformation; (3) a change of the hydrophobicity of the Trp environment; and (4) a formation of an H-bond between the carbonyl group of Hyp and a proton donor in HSA and RSA which leads to a protonated-like carbonyl in Hyp. Our results indicate that Hyp is rigidly bound in IIA subdomain of HSA close to Trp214 (distance 5.12 A between the centers of masses). In the model presented the carbonyl group of Hyp is hydrogen bonded to Asn458. Two other candidates for hydrogen bonds have been identified between the bay-region hydroxyl group of Hyp and the carbonyl group of the Trp214 peptidic link and between the peri-region hydroxyl group of Hyp and the Asn458 carbonyl group. It is shown that the structures of the Hyp/HSA and Hyp/RSA complexes are similar to, and in some aspects different from, those found for the Hyp/BSA complex. The role of aminoacid sequence in the IIA subdomains of HSA, RSA and BSA is discussed to explain the observed differences.     

Raman and surface Raman spectroscopy with ultraviolet excitation

We record the accurate and reliable Raman spectra of benzoic acid (BA), p-nitrobenzoic acid (PNBA) and o-nitrobenzoic (ONBA) in aqueous solution with ultraviolet excitation. And we find that the ultraviolet (UV) Raman spectrum of aqueous BA solution has one-to-one correspondence to that of BA solid whereas the others are less resemble to the solid counterparts. We also report surface Raman spectroscopy of them in silver colloid without any enhancement in UV region and call it surface-unenhanced Raman spectroscopy (SUERS) while the surface-enhanced Raman scattering (SERS) effects are perfect in near infrared or visible regions. It demonstrates the SERS effects are strongly dependent on the excitation wavelength. On the basis of the experiments, we discuss the mechanism of SERS excited in different regions.     

Raman spectroscopy of halotrichite from Jaroso, Spain

Raman spectroscopy complimented with infrared ATR spectroscopy has been used to characterise a halotrichite FeSO(4) x Al(2)(SO(4))(3) x 22 H(2)O from The Jaroso Ravine, Aquilas, Spain. Halotrichites form a continuous solid solution series with pickingerite and chemical analysis shows that the jarosite contains 6% Mg(2+). Halotrichite is characterised by four infrared bands at 3569.5, 3485.7, 3371.4 and 3239.0 cm(-1). Using Libowitsky type relationships, hydrogen bond distances of 3.08, 2.876, 2.780 and 2.718 Angstrom were determined. Two intense Raman bands are observed at 987.7 and 984.4 cm(-1) and are assigned to the nu(1) symmetric stretching vibrations of the sulphate bonded to the Fe(2+) and the water units in the structure. Three sulphate bands are observed at 77K at 1000.0, 991.3 and 985.0 cm(-1) suggesting further differentiation of the sulphate units. Raman spectrum of the nu(2) and nu(4) region of halotrichite at 298 K shows two bands at 445.1 and 466.9 cm(-1), and 624.2 and 605.5 cm(-1), respectively, confirming the reduction of symmetry of the sulphate in halotrichite.     

Raman spectroscopy of thiosulphates

The narrow line-width of Fourier transform Raman spectroscopy has been utilized to produce spectra of various simple thiosulphates. The accuracy of the technique has enabled us to show wide frequency shifts and splitting from counter ion to counter ion, and has thrown doubt on the use of vibrational spectra to indicate ion interactions.     

Raman spectroscopy of diamondoids

A selection of diamondoid hydrocarbons, from adamantane to [121321] heptamantane, have been analysed by multi-wavelength laser Raman spectroscopy. Spectra were assigned using vibrational frequencies and Raman intensities were calculated by employing the B3LYP functional and the split valence basis set of Schafer, Horn and Ahlrichs with polarisation functions on carbon atoms. The variation of the spectra and associated vibrational modes with the structure and symmetry of the molecules are discussed. Each diamondoid was found to produce a unique Raman spectrum, allowing for easy differentiation between molecules. Using the peak assignments derived from the calculations we find that the low frequency region of the spectra, corresponding to CCC-bending/CC-stretching modes, is particularly characteristic of the geometric shape of the diamondoid molecules.     

Raman under nitrogen. The high-resolution Raman spectroscopy of crystalline uranocene, thorocene, and ferrocene

The utility of recording Raman spectroscopy under liquid nitrogen, a technique we call Raman under nitrogen (RUN), is demonstrated for ferrocene, uranocene, and thorocene. Using RUN, low-temperature (liquid nitrogen cooled) Raman spectra for these compounds exhibit higher resolution than previous studies, and new vibrational features are reported. The first Raman spectra of crystalline uranocene at 77 K are reported using excitation from argon (5145 A) and krypton (6764 A) ion lasers. The spectra obtained showed bands corresponding to vibrational transitions at 212, 236, 259, 379, 753, 897, 1500, and 3042 cm(-1), assigned to ring-metal-ring stretching, ring-metal tilting, out-of-plane CCC bending, in-plane CCC bending, ring-breathing, C-H bending, CC stretching and CH stretching, respectively. The assigned vibrational bands are compared to those of uranocene in THF, (COT)2-, and thorocene. All vibrational frequencies of the ligands, except the 259 cm(-1) out-of-plane CCC bending mode, were found to increase upon coordination. A broad, polarizable band centered about approximately 460 cm(-1) was also observed. The 460 cm(-1) band is greatly enhanced relative to the vibrational Raman transitions with excitations from the krypton ion laser, which is indicative of an electronic resonance Raman process as has been shown previously. The electronic resonance Raman band is observed to split into three distinct bands at 450, 461, and 474 cm(-1) with 6764 A excitation. Relativistic density functional theory is used to provide theoretical interpretations of the measured spectra.     

Raman spectroscopy: Recent advancements,techniques and applications

Vibrational spectroscopy has proven itself to be a valuable contributor in the study of various fields of science, primarily due to the extraordinary versatility of sampling methods. Raman measurement gives the vibrational spectrum of the analyte, which can be treated as its “fingerprint,” allows easy interpretation and identification. Over the last years, there has been tremendous technical improvement in Raman spectroscopy, as overcome by the problems like fluorescence, poor sensitivity or reproducibility. This article reviews the recent advances in Raman spectroscopy and its new trend of applications ranging from ancient archaeology to advanced nanotechnology. It includes the aspects of Raman spectroscopic measurements to the analysis of various substances categorized into distinct application areas such as biotechnology, mineralogy, environmental monitoring, food and beverages, forensic science, medical and clinical chemistry, diagnostics, pharmaceutical, material science, surface analysis, etc. Advances in the instrumental design of Raman spectrometers coupled with newly developed sampling methodologies have also been described which enable trace level detection and satisfactory analysis.     

Quantitative surface-enhanced Raman spectroscopy

The purpose of this tutorial review is to show how surface-enhanced Raman (SERS) and resonance Raman (SERRS) spectroscopy have evolved to the stage where they can be used as a quantitative analytical technique. SER(R)S has enormous potential for a range of applications where high sensitivity needs to be combined with good discrimination between molecular targets, particularly since low cost, compact spectrometers can read the high signal levels that SER(R)S typically provides. These advantages over conventional Raman measurements come at the cost of increased complexity and this review discusses the factors that need to be controlled to generate stable and reproducible SER(R)S calibrations.     

Raman spectroscopy in astrobiology

Raman spectroscopy is proposed as a valuable analytical technique for planetary exploration because it is sensitive to organic and inorganic compounds and able to unambiguously identify key spectral markers in a mixture of biological and geological components; furthermore, sample manipulation is not required and any size of sample can be studied without chemical or mechanical pretreatment. NASA and ESA are considering the adoption of miniaturised Raman spectrometers for inclusion in suites of analytical instrumentation to be placed on robotic landers on Mars in the near future to search for extinct or extant life signals. In this paper we review the advantages and limitations of Raman spectroscopy for the analysis of complex specimens with relevance to the detection of bio- and geomarkers in extremophilic organisms which are considered to be terrestrial analogues of possible extraterrestial life that could have developed on planetary surfaces.     

Filament-driven impulsive Raman spectroscopy

Vibrational Raman spectroscopy is performed in the gas phase using a femtosecond laser pulse undergoing filamentation as an impulsive excitation source. The molecular coherence induced by the filamentary pulse is subsequently probed using a narrowband, sub-picosecond laser pulse to produce Raman spectra of gas phase species in a few tens of milliseconds (~10 laser shots). Pulse shortening with concomitant spectral broadening during filamentation results in a pulse that is both sufficiently short and of sufficient spectral power density to impulsively excite the highest energy ground state vibrations (up to 4158 cm(-1) corresponding to H(2)). Gas phase detection of chloroform, methylene chloride, cyclohexane, toluene, pentane, triethylamine, ammonia, nitromethane, and gasoline is performed.     

Raman spectroscopy on zeolites

The zeolite Raman literature is reviewed, with an emphasis on zeolite structure and synthesis, adsorption and metal complex formation in zeolites     

Non-linear coherent Raman spectroscopy

A general introduction to several coherent Raman methods, which are based on the third-order non-linear susceptibility is given. These methods are described basically under a common point of view, which is the excitation of coherent molecular vibrations in the field of two strong laser beams operating at different frequencies. Most of these methods can be applied successfully also under electronic resonance conditions. As a particular example, studies of coherent anti-Stokes continuum resonance Raman scattering in iodine vapour will be presented and discussed in detail.     

Ionization-detected stimulated Raman spectroscopy

We report a new spectroscopic technique which we call “ionization-detected stimulated Raman spectroscopy” that combines the high sensitivity of resonant laser ionization methods with the high spectral resolution of stimulated Raman spectroscopy. A Q-branch spectrum of NO at 10 mTorr pressure illustrates an improvement in sensitivity of over 1000-fold compared to previous stimulated Raman methods.     

Fourier transform Raman spectroscopy

The basic experimental aspects of Fourier transform Raman Spectroscopy are reviewed with an emphasis on detector technology. The sensitivity is comparable to dispersive Raman Spectroscopy using visible lasers. The ease of spectral subtraction is demonstrated and examples are given showing the elimination of fluorescence.     

Frequency modulation Raman spectroscopy

A frequency modulation (FM) technique is described for elimination of the fluorescence background from Raman spectra of surfaces. The experimental apparatus is described, and theoretical considerations regarding the detection limits are presented and compared with experimental results.     

Raman spectroscopy in bioanalysis

Recent advances in instrument design have allowed researchers to use smaller, more efficient components in designing Raman spectrometers. Advances in instrumentation have increased the performance of Raman instruments and increased their usage in bioanalysis. This paper reviews recent improvements in instrument design and discusses several applications of Raman spectroscopy to diagnosis in biology, chemistry and medicine.