In electrospray ionization source hydrogen/deuterium exchange LC-MS and LC-MS/MS for characterization of metabolites

A new method is described for performing hydrogen/deuterium (H/D) exchange in an electrospray ionization (ESI) source. The use of liquid chromatography (LC)-mass spectrometer equipped with an ESI source and deuterium oxide (D2O) as the sheath liquid allows H/D exchange experiments to be performed on-line. This directly provides information for determining the number and position of exchangeable hydrogens, aiding in the elucidation of the structures of drug metabolites. To demonstrate the utility of this method, LC-mass spectrometry (MS) and LC-MS/MS experiments were performed using either H2O or D2O as sheath liquid on a matrix metalloprotease (MMP) inhibitor (PD 0200126) and its metabolites. Examination of the mass shift of the deuteriated molecule from that of the protonated molecule allowed the number of exchangeable protons to be determined. Interpretation of the production-spectra helped to determine the location of the exchanged protons and assisted in the assignment of the site(s) of modification for each metabolite.     

GC-MS characterization of proteinaceous and lipid binders in UV aged polychrome artifacts

This paper presents the most significant results obtained from the characterization of protein and lipid binders in a broad range of reference paint materials prepared and stored at Opificio delle Pietre Dure in Florence (Italian Ministry of the Cultural Heritage, Italy). The amino acid distribution for protein binders and the fatty acid distribution for lipid binders were determined by gas chromatography-mass spectrometry before and after being artificially aged through exposure to UV light at 254 nm or 366 nm for different time periods in a climatic chamber (20°C and 80% RH). The results were compared with those relevant to old paintings of different ages, and showed that UV light aging does not significantly affect the amino acid profile of protein binders. Consequently, protein binders in old paintings can be reliably identified by comparing the amino acid composition with that of reference paint materials which have not been aged. However, the composition of lipid binders is substantially affected by UV irradiation, leading to a lowering of oleic acid and the formation of azelaic acid and other dicarboxylic acids including oxalic acid. An oleic to stearic acid ratio of less than 0.5 was observed in all the samples of works of art, and this parameter can be used to evaluate the extent of the artificial aging process. The formation of oxalic acid was also observed starting with pure unsaturated fatty acids, thus supporting the chemical origin of oxalate patina.     

先锋褐煤热溶及热溶物红外光谱表征

利用高温热溶装置研究了不同溶剂中先锋褐煤热溶性能,并对热溶物和热溶残煤分别进行了红外光谱表征。结果表明,先锋褐煤以化学交联大分子结构为主,非共价键缔合低分子化合物含量较低;虽然高温热溶可以显著提高热溶效率,300℃甲苯和四氢萘溶剂中热溶率达到20.7%和21.3%,但是以热断裂煤结构中的非共价键作用,促进低分子化合物溶解为主;300℃热溶过程中不存在明显热解反应,供氢溶剂及氢键型溶剂作用不明显;先锋褐煤热溶物中含有丰富的脂肪结构和羧酸酯,羟基和芳香结构含量较低;热溶溶剂明显影响热溶物结构与组成。
     

Analytical methods to differentiate Romanian amber and Baltic amber for archaeological applications

The study aims to establish several definite criteria which will differentiate Romanian amber and Baltic amber to certify the local or Baltic origin of the materials found in archaeological sites on the Romanian territory, by using light microscopy and performing analytical methods, such as Fourier transform infrared spectroscopy-variable angle reflectance and liquid chromatography with mass spectrometry detection. Experiments especially by Fourier transformed infrared spectroscopy, were applied to a wide range of samples with controlled origin. The methods were optimised and resulted in premises to apply the techniques to analysis of the archaeological material.      

Identification and characterization of the degradation products of prasugrel hydrochloride tablets using LC-MS technique

New high-performance liquid chromatography method was developed for the determination of prasugrel HCl-related substances. Impurity profile of prasugrel HCl was established by studying the degradation profile of it as an active pharmaceutical ingredient, for the first time, in the tablet form. Two significant unknown degradation products (impurities) were detected and characterized, to the best of our knowledge; these impurities have not been previously reported in the literature. The first one resulted from acidic, basic, and neutral hydrolyses of prasugrel; it was nominated as impurity 1 (5-(2-cyclopropyl-1-(2-fluorophenyl)-2-oxoethyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridin-2(3H)-one), its structure was proposed using liquid chromatography/mass spectrometry technique. The second degradant was nominated as impurity 2 (5-(2-cyclopropyl-1-(2-fluorophenyl)-2-oxoethyl)-7a-hydroxy-5,6,7,7a-tetrahydrothieno[3,2-c]pyridin-2(4H)-one) that formed upon neutral hydrolysis of prasugrel with magnesium stearate; this impurity was identified using nuclear magnetic resonance and LC-MS techniques. Based on these findings, other lubricant materials should be used in prasugrel tablets instead of magnesium stearate to avoid formation of such impurity. Prasugrel HCl was susceptible to hydrolytic and oxidative degradation, whereas it was stable under these conditions.     

Developing qualitative LC-MS methods for characterization of Vaccinium berry Standard Reference Materials

Standard Reference Materials (SRMs) offer the scientific community a stable and homogenous source of material that holds countless application possibilities. Traditionally, the National Institute of Standards and Technology (NIST) has provided SRMs with associated quantitative information (certified values) for a select group of targeted analytes as measured in a solution or complex matrix. While the current needs of the SRM community are expanding to include non-quantitative data, NIST is attempting to broaden the scope of how and what information is offered to the SRM community by providing qualitative information about biomaterials, such as chromatographic fingerprints and profiles of untargeted identifications. In this work, metabolomic and proteomic profiling efforts were employed to characterize a suite of six Vaccinium berry SRMs. In the discovery phase, liquid chromatography-tandem mass spectrometry (LC-MS/MS) data was matched to mass spectral libraries; a subsequent validation phase based on multiple-reaction monitoring LC-MS/MS relied on both retention time matching of authentic standards along with fragmentation data for a qualitative overview of the most prominent organic compounds present. Definitive and putative identifications were determined for over 70 metabolites based on reporting guidelines set forth by the Metabolomics Standards Initiative (Metabolomics 3(3):211–221, 2007), and the capability of electrospray ionization mass spectrometry (ESI-MS) to profile untargeted metabolites within a complex matrix using mass spectral matching is demonstrated. Bottom-up proteomic analyses were possible using peptide databases translated from expressed sequence tags (ESTs). Homology searches provided identification of novel Vaccinium proteins based on homology to related genera. Chromatographic fingerprints of these berry materials were acquired for supplemental qualitative information to be provided to users of these SRMs. An unbounded set of qualitative data about a biomaterial is a valuable complement to quantitative information traditionally provided in NIST Certificates of Analysis.     

Structural characterization of steam-heat treated Tectona grandis wood analyzed by FT-IR and 2D-IR correlation spectroscopy

The properties of wood can be improved through steam-heat treatment.There are many studies about mechanical properties of steam-heat treated wood,but very few studies are on the aspects of chemical modifications.In this study,FT-IR spectra combined with SD-IR spectra,correlation coefficients and 2DIR spectra are employed to analyze the chemical modifications of teak[Tectona grandis L.F.) wood during steam-heat treatment under treatment temperatures from 120 ℃ to 220 ℃ at intervals of 20 ℃.Acetic acid,which is produced during steam-heat treatment,acts as a catalyst of condensation and degradation reactions of wood components.The changes of wood components are more and more intense with increasing the treatment temperature.The sensitivity of wood samples to thermal perturbation rises initially with increasing treatment temperature before falling back.The steam-heat treated wood under180℃ is the most sensitive.     

FT-IR/UATR and FT-IR transmission quantitative analysis of PBT/PC blends

Polymer blends are produced to achieve properties that pure polymers are unable to. The qualitative analysis of these blends is not always satisfactory to point out failures in the final product and, therefore, the determination of their content might be required. The aim of this study is to develop quantitative methodologies using Fourier transform infrared spectroscopy (FT-IR), reflection mode with the universal attenuated total reflectance accessory (UATR) and transmission techniques, for the determination of the content of each polymer present in the polymer blend poly (butylene terephthalate) (PBT) and polycarbonate (PC). FT-IR/UATR presented better results using the relative band (A₁₇₇₂/A₁₇₁₆). FT-IR/UATR presented error of 2.30%, which is a little higher than the accuracy limit of the spectrometer (≤2%), but still adequate for industrial applications.     

Vibrational characterization of L-leucine phosphonate analogues: FT-IR, FT-Raman, and SERS spectroscopy studies and DFT calculations

This study reports the Raman (FT-Raman) and absorption infrared (FT-IR) spectra, based on calculated wavenumbers and normal modes of vibrations, of the following compounds: L-Leu-D-NH-CH(Me)-PO(3)H(2) (LI), L-Leu-NH-C(Me)(2)-PO(3)H(2) (LII), L-Leu-D-NH-CH(Et)-PO(3)H(2) (LIII), L-Leu-L-NH-CH(Et)-PO(3)H(2) (LIV), L-Leu-L-NH-CH(EtOH)-PO(3)H(2) (LV), L-Leu-NH-C(Me)(Et)-PO(3)H(2) (LVI), L-Leu-L-NH-CH(PrA)-PO(3)H(2) (LVII), L-Leu-L-NH-CH(c-Pr)-PO(3)H(2) (LVIII), L-Leu-L-NH-CH(t-Bu)-PO(3)H(2) (LIX), L-Leu-L-NH-CH(BuA)-PO(3)H(2) (LX), L-Leu-L-NH-CH(c-Bu)-PO(3)H(2) (LXI), and L-Leu-L-NH-C(Adm)-PO(3)H(2) (LXII). The equilibrium geometries and vibrational wavenumbers were calculated using density functional theory (DFT) at the B3LYP, 6-311++G** level using Gaussian 03, Raint, GaussSum 0.8, and Gar2ped software. We briefly compare and analyze the experimental and calculated vibrational wavenumbers in the range 4000-400 cm(-1). In addition, the Raman wavenumbers are compared to those from the surface-enhanced Raman scattering (SERS) spectra for the phosphono analogues of l-leucine (l-Leu) adsorbed on a colloidal silver surface in an aqueous solution. The geometries of these molecules etched on the silver surface were deduced from observed changes in both the intensity and broadness of Raman bands in the spectra of the bound versus free species. For example, LVI appears to adsorb onto the colloidal silver particles mainly through the amine group and amide bond, which assists in the adsorption process, whereas LII shows strongly enhanced SERS bands due to the rocking, twisting, and stretching vibrations of the N(amid)C(sg)(Me)(2)P fragment, suggesting that this peptide's interaction with the silver surface occurs mainly via this fragment. On the other hand, the most dominant SERS bands of LIII and LIV due to the P═O bond stretches reflect P═O···Ag complex formation.     

FT-IR and FT-RAMAN investigations of nicotinaldehyde

The Fourier transform Raman and infrared spectra of nicotinaldehyde were recorded and the observed frequencies were assigned to various modes of vibration in terms of fundamentals by assuming Cs point group symmetry. A normal coordinate analysis was also carried out using a simple valence force field. A complete vibrational analysis is presented here for this molecule and the results are briefly discussed.     

LC-MS characterization of bioactive metabolites from two Yemeni Aloe spp. with antioxidant and antidiabetic properties

Two Yemeni Aloe(s) have been investigated; the resin from A. perry Baker (APR, Socotran Aloe), and the gel from A. vera (AVG, Saber Yamaniis). LC-MS for APR identified aloin B, aloinoside B/A, homonataloin B and microdontin B/A as the major components, constituting 67.7% w/w of the extract. AVG showed the same pattern of anthrones (19.5% w/w), in addition to the chromones aloesin, aloeresin A, aloeresin D and aloeresin E. Dihydro-isocoumarin glucoside was identified in both Aloe species. Aloe extracts showed high antioxidant activity: DPPH (0.09 & 0.05 mM/g TE), ABTS (0.06 & 0.03 mM/g TE), and FRAP (20.5 & 15.5 mM Fe⁺²E), for APR & AVG, respectively. The antidiabetic properties was evaluated through inhibition of α-glucosidase enzyme. APR showed inhibitory activity with IC₅₀ 0.76 μg/mL higher than AVG (IC₅₀ 0.76 mg/mL). Aloin A showed the highest inhibitory activity with IC₅₀ 0.34 mg/mL that was higher than acarbose (0.54 mg/mL) the positive control, indicating that the activity of Aloe extract is linked to the aloin and other anthrone compounds. These findings highlight the phytochemical profile, antioxidant and potential antidiabetic activity of the Yemeni Aloe species and draw attention to their potential application in food, medicine and cosmetic products.     

Synthesis, FT-Raman, FT-IR, NMR spectroscopic characterization and antimicrobial activity of new mixed aza-oxo-thia macrocyclic compounds

Series of new mixed aza-oxo-thia macrocyclic ligands {2,6,12,16-tetraaza-1,7,11,17-tetraoxo-9,19-dithia-[(4′-methyl-5′,4,3′)(14′-methyl-15′,14,13′)]ditriazine}cyclocosane (L ₁ ); {2,6,13,17-teraaza-1,7,12,18-tetraoxo-9,10,20,21-tetrathia-[(4′-methyl-5′,4,3′)(15′-methyl-14′,16′,15)]di-triazine}cyclodocosane (L ₂ ); {2,6,14,18-tetraaza-1,7,13,19-tetraoxo-10,22-dithia-[(4′-methyl-5′,3′,4)(16′-methyl-15′,17′,16)]ditriazine}cyclotetracosane (L ₃ ) and {2,6,15,19-tetraaza-1,7,14,12-tetraoxo-10,11,23,24-tetrathia-[(4′-methyl-5′,4,3′)(17′-methyl-8′,17,16′)]ditriazine}cyclohexa-cosane (L ₄ ) were synthesized. The structural features of the compounds have been studied by elemental analyses, Mass, FT-Raman, FT-IR, ¹H and ¹³C NMR spectroscopy. The antimicrobial activities of the ligands were evaluated using disk diffusion method in dimethyl sulfoxide as well as the minimal inhibitory concentration (MIC) dilution method, against 9 bacteria. The obtained results from disk diffusion method were assessed in side-by-side comparison with those of Penicillin-g, Ampicillin, Cefotaxime, Vancomycin, Oflaxacin, and Tetracyclin, well-known antibacterial agents. The results from dilution procedure were compared with Gentamycin as antibacterial and Nystatin as antifungal. The antifungal activities are reported on five yeast cultures namely Candida albicans, Kluyveromyces fragilis, Rhodotorula rubra, Debaryomyces hansenii, and Hanseniaspora guilliermondii, and the results are referenced with Nystatin, Ketaconazole, and Clotrimazole, commercial antifungal agents. In most cases, the compounds show strong antifungal activity in the comparison tests.     

计算机辅助确定LC-MS中的分子离子的初步研究

LC-MS联用技术灵敏度高、专属性好、样品处理简单、快速,而且多级质谱能够提供丰富的化合物结构信息.同时,电喷雾离子化(ESI)是一种软电离技术,特别适合热不稳定炸药及耐热炸药的分析,有关电喷雾电离质谱对炸药的分析已有若干报道.     

LC-MS characterization of efficacy substances in serum of experimental animals treated with Sophora flavescens extracts

Anti-DHBV (duck hepatitis B virus) activity was found in the aqueous extracts of Sophora flavescens Ait. in vivo. Liquid chromatography/electrospray ionization ion trap mass spectrometry was applied to characterize the components in duck serum after oral administration of S. flavescens extract. Oxymatrine (1), sophoranol (2), sophoridine (3) and matrine (4) were identified in the serum. Further research on the four compounds was evaluated for their antiviral activity against HBV (hepatitis B virus) in cell culture. The results suggested that oxymatrine, sophoranol and matrine were the efficacy substances for anti-HBV activity in aqueous extracts of S. flavescens Ait.     

Detailed FT-IR spectroscopy characterization and thermal analysis of synthesis of barium titanate nanoscale particles through a newly developed process

BaTiO₃ nanopowders were prepared at lower temperature and in shorter time span through a newly developed process. To reach an in-detail understanding of mechanism of the process, thermal analysis were performed using DTA/TGA and FT-IR techniques aided by in-depth discussions. The results indicated that thermal evolution of sol–gel-powder transformation consists of following steps: the vaporization of volatile organic solvents, the deformation of gel structure and pyrolysis of the Ba–Ti organic precursors, the decomposition of BaCO₃ into BaO and CO₂, reaction of resulted BaO with TiO₂ to form BaTiO₃. The results also elucidated the reaction pattern and formation mechanism of BaTiO₃ nanopowders from gel-derived precursor.     

Preparation and FT-IR spectra of calcium bilirubinate

In this investigation two calcium bilirubinates compounds, Ca(HBR)₂·H₂O and Ca(BR)·2H₂O, were prepared. Their Fourier transform infrared spectra were measured in KBr discs and in fluorolube and nujol mulls, respectively. The results suggest that it is better to identify the Ca(HBR)₂·H₂O and Ca(BR)·2H₂O with fluorolube and/or nujol mulls when examining mixtures (e.g. gallstone).     

FT-IR investigation of cordierite aerogel

Hypercritically dried cordierite aerogel and the different steps of transformation to highly ordered cordierite are analyzed by FT-IR spectrometry and X-ray diffraction. From IR spectra recorded at different temperature, either on the powder or on the gel forms, the bulk and the surface are discussed.