Development and validation of the quantitative analysis of ampicillin sodium in powder for injection by Fourier-transform infrared spectroscopy (FT-IR)

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Isolation and characterization of sodium 2-fluoroacetate from Mascagnia rigida using chromatography and infrared spectroscopy

Sodium monofluoroacetate was first identified in Dichapetalum cymosum, a South African plant that can cause livestock poisoning and death. After, several other plants also showed to contain this toxin, which leads to the "sudden death". Mascagnia rigida, a well identified poisonous plant, commonly found in northeast of Brazil also cause sudden death in cattle, which shows clinical signs similar to those produced by the ingestion of plants that contain monofluoroacetate. Our aim was to identify the toxic compound present in the aqueous extract of M. rigida. For this purpose, the dried and milled plant was extracted; the extract was lyophilized and submitted to successive chromatographic process, until the desired purity of the active compound was achieved. The study of this material by planar chromatography and by infrared spectrometry indicated that the toxin can be a mixture of mono, di and trifluoroacetate. (C) 2012 Elsevier Ltd. All rights reserved.

Effect of dental tissue conditioners and matrix metalloproteinase inhibitors on type I collagen microstructure analyzed by Fourier transform infrared spectroscopy

This study aimed to evaluate the chemical interaction of collagen with some substances usually applied in dental treatments to increase the durability of adhesive restorations to dentin. Initially, the similarity between human dentin collagen and type I collagen obtained from commercial bovine membranes of Achilles deep tendon was compared by the Attenuated Total Reflectance technique of Fourier Transform Infrared (ATR-FTIR) spectroscopy. Finally, the effects of application of 35% phosphoric acid, 0.1M ethylenediaminetetraacetic acid (EDTA), 2% chlorhexidine, and 6.5% proanthocyanidin solution on microstructure of collagen and in the integrity of its triple helix were also evaluated by ATR-FTIR. It was observed that the commercial type I collagen can be used as an efficient substitute for demineralized human dentin in studies that use spectroscopy analysis. The 35% phosphoric acid significantly altered the organic content of amides, proline and hydroxyproline of type I collagen. The surface treatment with 0.1M EDTA, 2% chlorhexidine, or 6.5% proanthocyanidin did not promote deleterious structural changes to the collagen triple helix. The application of 6.5% proanthocyanidin on collagen promoted hydrogen bond formation. (c) 2012 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 2012.

Trasmission and Reflection (ATR)Far-Infrared Spectroscopy Applied in the Analysis of Cultural Heritage Materials

FIR spectroscopy is an alternative way of collecting spectra of many inorganic pigments and corrosion products found on art objects, which is not normally observed in the MIR region. Most FIR spectra are traditionally collected in transmission mode but as a real novelty it is now also possible to record FIR spectra in ATR (Attenuated Total Reflectance) mode. In FIR transmission we employ polyethylene (PE) for preparation of pellets by embedding the sample in PE. Unfortunately, the preparation requires heating of the PE in order to produces at transparent pellet. This will affect compounds with low melting points, especially those with structurally incorporated water. Another option in FIR transmission is the use of thin films. We test the use of polyethylene thin film (PETF), both commercial and laboratory-made PETF. ATR collection of samples is possible in both the MIR and FIR region on solid, powdery or liquid samples. Changing from the MIR to the FIR region is easy as it simply requires the change of detector and beamsplitter (which can be performed within a few minutes). No preparation of the sample is necessary, which is a huge advantage over the PE transmission method. The most obvious difference, when comparing transmission with ATR, is the distortion of band shape (which appears asymmetrical in the lower wavenumber region) and intensity differences. However, the biggest difference can be the shift of strong absorbing bands moving to lower wavenumbers in ATR mode. The sometimes huge band shift necessitates the collection of standard library spectra in both FIR transmission and ATR modes, provided these two methods of collecting are to be employed for analyses of unknown samples. Standard samples of 150 pigment and corrosion compounds are thus collected in both FIR transmission and ATR mode in order to build up a digital library of spectra for comparison with unknown samples. XRD, XRF and Raman spectroscopy assists us in confirming the purity or impurity of our standard samples. 24 didactic test tables, with known pigment and binder painted on the surface of a limestone tablet, are used for testing the established library and different ways of collecting in ATR and transmission mode. In ATR, micro samples are scratched from the surface and examined in both the MIR and FIR region. Additionally, direct surface contact of the didactic tablets with the ATR crystal are tested together with water enhanced surface contact. In FIR transmission we compare the powder from our test tablet on the laboratory PETF and embedded in PE. We also compare the PE pellets collected using a 4x beam condenser, focusing the IR beam area from 8 mm to 2 mm. A few samples collected from a mural painting in a Nepalese temple, corrosion products collected from archaeological Chinese bronze objects and samples from a mural paintings in an Italian abbey, are examined by ATR or transmission spectroscopy.

Study of molecules of astrochemical, astrophysical and atmospheric interest by means of High - Resolution Infrared Spectroscopy

The spectroscopic investigation of the gas-phase molecules relevant for the chemistry of the atmosphere and of the interstellar medium has been performed. Two types of molecules have been studied, linear and symmetric top. Several experimental high-resolution techniques have been adopted, exploiting the spectrometers available in Bologna, Venezia, Brussels and Wuppertal: Fourier-Transform-Infrared Spectroscopy, Cavity-Ring-Down Spectroscopy, Cavity-Enhanced-Absorption Spectroscopy, Tunable-Diode-Laser Spectroscopy. Concerning linear molecules, the spectra of a number of isotopologues of acetylene, 12C2D2, H12C13CD, H13C12CD, 13C12CD2, of DCCF and monodeuterodiacetylene DC4H, have been studied, from 320 to 6800 cm-1. This interval covers bending, stretching, overtone and combination bands, the focus on specific ranges depending on the molecule. In particular, the analysis of the bending modes has been performed for 12C2D2 (450-2200 cm-1), 13C12CD2 (450-1700 cm-1), DCCF (320-850cm-1) and DC4H (450-1100 cm-1), of the stretching-bending system for 12C2D2 (450-5500 cm-1) and of the 2nu1 and combination bands up to four quanta of excitation for H12C13CD, H13C12CD and 13C12CD2 (6130-6800 cm-1). In case of symmetric top molecules, CH3CCH has been investigated in the 2nu1 region (6200-6700 cm-1), which is particularly congested due to the huge network of states affected by Coriolis and anharmonic interactions. The bending fundamentals of 15ND3 (450-2700 cm-1) have been studied for the first time, characterizing completely the bending states, v2 = 1 and v4 = 1, whereas the analysis of the stretching modes, which evidenced the presence of several perturbations, has been started. Finally, the fundamental band nu4 of CF3Br in the 1190-1220 cm-1 region has been investigated. Transitions belonging to the CF379Br and CF381Br molecules have been identified since the spectra were recorded using a sample containing the two isotopologues in natural abundance. This allowed the characterization of the v4 = 1 state for both isotopologues and the evaluation of the bromine isotopic splitting.

Fourier transform infrared spectroscopy, a new method for rapid determination of total organic and inorganic carbon and biogenic silica concentration in lake sediments

Abstract We demonstrate the use of Fourier transform infrared spectroscopy (FTIRS) to make quantitative measures of total organic carbon (TOC), total inorganic carbon (TIC) and biogenic silica (BSi) concentrations in sediment. FTIRS is a fast and costeffective technique and only small sediment samples are needed (0.01 g). Statistically significant models were developed using sediment samples from northern Sweden and were applied to sediment records from Sweden, northeast Siberia and Macedonia. The correlation between FTIRS-inferred values and amounts of biogeochemical constituents assessed conventionally varied between r = 0.84–0.99 for TOC, r = 0.85– 0.99 for TIC, and r = 0.68–0.94 for BSi. Because FTIR spectra contain information on a large number of both inorganic and organic components, there is great potential for FTIRS to become an important tool in paleolimnology.

Quantification of hydroxycinnamic acids and lignin in perennial forage and energy grasses by Fourier-transform infrared spectroscopy and partial least squares regression

Levels of lignin and hydroxycinnamic acid wall components in three genera of forage grasses (Lolium,Festuca and Dactylis) have been accurately predicted by Fourier-transform infrared spectroscopy using partial least squares models correlated to analytical measurements. Different models were derived that predicted the concentrations of acid detergent lignin, total hydroxycinnamic acids, total ferulate monomers plus dimers, p-coumarate and ferulate dimers in independent spectral test data from methanol extracted samples of perennial forage grass with accuracies of 92.8%, 86.5%, 86.1%, 59.7% and 84.7% respectively, and analysis of model projection scores showed that the models relied generally on spectral features that are known absorptions of these compounds. Acid detergent lignin was predicted in samples of two species of energy grass, (Phalaris arundinacea and Pancium virgatum) with an accuracy of 84.5%.

Observation of a 331 K (58 °C) spin transition for bis[hydrotris(1,2,4-triazol-1-yl)borate]iron(II) by variable temperature infrared spectroscopy and magnetic susceptibility measurements

Fe{HB(CHN)} is observed by variable temperature infrared and magnetic studies to have a spin transition between the low spin S = 0 and high spin S = 2 states at 331 K (58 °C) with thermal hysteresis of ~1.5 K. Changes in the triazole ligand IR absorptions demonstrate that distant non-metal-ligand vibrations are altered upon the change in electronic structure associated with the spin-crossover can be used to monitor the the spin-crossover transition.

Identification and relative quantification of tyrosine nitration in a model peptide using two-dimensional infrared spectroscopy

Nitration of tyrosine in proteins and peptides is a post-translational modification that occurs under conditions of oxidative stress. It is implicated in a variety of medical conditions, including neurodegenerative and cardiovascular diseases. However, monitoring tyrosine nitration and understanding its role in modifying biological function remains a major challenge. In this work, we investigate the use of electron-vibration-vibration (EVV) two-dimensional infrared (2DIR) spectroscopy for the study of tyrosine nitration in model peptides. We demonstrate the ability of EVV 2DIR spectroscopy to differentiate between the neutral and deprotonated states of 3-nitrotyrosine, and we characterize their spectral signatures using information obtained from quantum chemistry calculations and simulated EVV 2DIR spectra. To test the sensitivity of the technique, we use mixed-peptide samples containing various levels of tyrosine nitration, and we use mass spectrometry to independently verify the level of nitration. We conclude that EVV 2DIR spectroscopy is able to provide detailed spectroscopic information on peptide side-chain modifications and to detect nitration levels down to 1%. We further propose that lower nitration levels could be detected by introducing a resonant Raman probe step to increase the detection sensitivity of EVV 2DIR spectroscopy. (Graph Presented).

Optical immersion of mid-infrared LEDs and photodiodes for gas-sensing applications

The high gains in performance predicted for optical immersion are difficult to achieve in practice due to total internal reflection at the lens/detector interface. By reducing the air gap at this interface optical tunneling becomes possible and the predicted gains can be realized in practical devices. Using this technique we have demonstrated large performance gains by optically immersing mid-infrared heterostructure InA1Sb LEDs and photodiodes using hypershperical germanium lenses. The development of an effective method of optical immersion that gives excellent optical coupling has produced a photodiode with a peak room temperature detectivity (D*) of 5.3 x 109 cmHz½W-1 at λpeak=5.4μm and a 40° field of view. A hyperspherically immersed LED showed a f-fold improvement in the external efficiency, and a 3-fold improvement in the directionality compared with a conventional planar LED for f/2 optical systems. The incorporation of these uncooled devices in a White cell produced a NO2 gas sensing system with 2 part-per-million sensitivity, with an LED drive current of <5mA. These results represent a significant advance in the use of solid state devices for portable gas sensing systems.

Mid-infrared passively switched pulsed dual wavelength Ho3+ -doped fluoride fiber laser at 3 μm and 2 μm

Cascade transitions of rare earth ions involved in infrared host fiber provide the potential to generate dual or multiple wavelength lasing at mid-infrared region. In addition, the fast development of saturable absorber (SA) towards the long wavelengths motivates the realization of passively switched mid-infrared pulsed lasers. In this work, by combing the above two techniques, a new phenomenon of passively Q-switched ~3 μm and gain-switched ~2 μm pulses in a shared cavity was demonstrated with a Ho3+-doped fluoride fiber and a specifically designed semiconductor saturable absorber (SESAM) as the SA. The repetition rate of ~2 μm pulses can be tuned between half and same as that of ~3 μm pulses by changing the pump power. The proposed method here will add new capabilities and more flexibility for generating mid-infrared multiple wavelength pulses simultaneously that has important potential applications for laser surgery, material processing, laser radar, and free-space communications, and other areas.