Vibrational spectroscopic characterization of the phosphate mineral series eosphorite–childrenite–(Mn,Fe)Al(PO4)(OH)2·(H2O)

The phosphate mineral series eosphorite–childrenite–(Mn,Fe)Al(PO4)(OH)2·(H2O) has been studied using a combination of electron probe analysis and vibrational spectroscopy. Eosphorite is the manganese rich mineral with lower iron content in comparison with the childrenite which has higher iron and lower manganese content. The determined formulae of the two studied minerals are: (Mn0.72,Fe0.13,Ca0.01)(Al)1.04(PO4, OHPO3)1.07(OH1.89,F0.02)·0.94(H2O) for SAA-090 and (Fe0.49,Mn0.35,Mg0.06,Ca0.04)(Al)1.03(PO4, OHPO3)1.05(OH)1.90·0.95(H2O) for SAA-072. Raman spectroscopy enabled the observation of bands at 970 cm−1 and 1011 cm−1 assigned to monohydrogen phosphate, phosphate and dihydrogen phosphate units. Differences are observed in the area of the peaks between the two eosphorite minerals. Raman bands at 562 cm−1, 595 cm−1, and 608 cm−1 are assigned to the �4 bending modes of the PO4, HPO4 and H2PO4 units; Raman bands at 405 cm−1, 427 cm−1 and 466 cm−1 are attributed to the �2 modes of these units. Raman bands of the hydroxyl and water stretching modes are observed. Vibrational spectroscopy enabled details of the molecular structure of the eosphorite mineral series to be determined.

Vibrational spectroscopic characterization of the phosphate mineral kulanite Ba(Fe2+,Mn2+,Mg)2(Al,Fe3+)2(PO4)3(OH)3

The mineral kulanite BaFe2Al2(PO4)3(OH)3, a barium iron aluminum phosphate, has been studied by using a combination of electron microscopy and vibrational spectroscopy. Scanning electron microscopy with EDX shows the mineral is homogenous with no other phases present. The Raman spectrum is dominated by an intense band at 1022 cm−1 assigned to the PO43-ν1 symmetric stretching mode. Low intensity Raman bands at 1076, 1110, 1146, 1182 cm−1 are attributed to the PO43-ν3 antisymmetric stretching vibrations. The infrared spectrum shows a complex spectral profile with overlapping bands. Multiple phosphate bending vibrations supports the concept of a reduction in symmetry of the phosphate anion. Raman spectrum at 3211, 3513 and 3533 cm−1 are assigned to the stretching vibrations of the OH units. Vibrational spectroscopy enables aspects on the molecular structure of kulanite to be assessed.

Vibrational spectroscopic characterization of the phosphate mineral bermanite–Mn2+Mn23+(PO4)2(OH)2.4(H2O)

Bermanite Mn2þMn3þ2 ðPO4Þ2ðOHÞ2 � 4ðH2OÞ is a mixed valent hydrated hydroxy phosphate mineral. The mineral is reddish-brown and occurs in crystal aggregates and as lamellar masses. Bermanite is a common mineral in granitic pegmatites. The chemical composition of bermanite was obtained using EDS techniques. We have studied the molecular structure of bermanite using vibrational spectroscopy. The mineral is characterized by a Raman doublet at 991 and 999 cm-1 attributed to the phosphate stretching mode of two non-equivalent phosphate units. Raman bands at 1071, 1117 and 1142 cm-1 are assigned to the phosphate antisymmetric stretching modes. The hydroxyl stretching spectral region is complex with overlapping bands attributed to water and hydroxyl stretching vibrations. Vibrational spectroscopy proves most useful for the study of the mineral bermanite.

Infrared and Raman spectroscopic characterization of the borate mineral colemanite – CaB3O4(OH)3·H2O – implications for the molecular structure

Colemanite CaB3O4(OH)3 H2O is a secondary borate mineral formed from borax and ulexite in evaporate deposits of alkaline lacustrine sediments. The basic structure of colemanite contains endless chains of interlocking BO2(OH) triangles and BO3(OH) tetrahedrons with the calcium, water and extra hydroxide units interspersed between these chains. The Raman spectra of colemanite is characterized by an intense band at 3605 cm-1 assigned to the stretching vibration of OH units and a series of bands at 3182, 3300, 3389 and 3534 cm-1 assigned to water stretching vibrations. Infrared bands are observed in similar positions. The BO stretching vibrations of the trigonal and tetrahedral boron are characterized by Raman bands at 876, 1065 and 1084 cm-1. The OBO bending mode is defined by the Raman band at 611 cm-1. It is important to characterize the very wide range of borate minerals including colemanite because of the very wide range of applications of boron containing minerals.

Infrared and Raman spectroscopic characterization of the phosphate mineral fairfieldite – Ca2(Mn2+,Fe2+)2(PO4)2·2(H2O)

Raman spectroscopy complimented with infrared spectroscopy has been used to determine the molecular structure of the phosphate mineral fairfieldite. The Raman phosphate (PO4)3- stretching region shows strong differences between the fairfieldite phosphate minerals which is attributed to the cation substitution for calcium in the structure. In the infrared spectra complexity exists with multiple (PO4)2- antisymmetric stretching vibrations observed, indicating a reduction of the tetrahedral symmetry. This loss of degeneracy is also reflected in the bending modes. Strong Raman bands around 600 cm-1 are assigned to v4 phosphate bending modes. Multiple bands in the 400–450 cm-1 region assigned to m2 phosphate bending modes provide further evidence of symmetry reduction of the phosphate anion. Three broadbands for fairfieldite are found at 3040, 3139 and 3271 cm-1 and are assigned to OH stretching bands. By using a Libowitzky empirical equation hydrogen bond distances of 2.658 and 2.730 A are estimated. Vibrational spectroscopy enables aspects of the molecular structure of the fairfieldite to be ascertained.

Electrical property and characterization of nano-SnO2/wollastonite composite materials

Nano-tin oxide was deposited on the surface of wollastonite using the mixed solution including stannic chloride pentahydrate precursor and wollastonite by a hydrolysis precipitation process. The antistatic properties of the wollastonite materials under different calcined conditions and composite materials (nano-SnO2/wollastonite, SW) were measured by rubber sheeter and four-point probe (FPP) sheet resistance measurement. Effects of hydrolysis temperature and time, calcination temperature and time, pH value and nano-SnO2 coating amount on the resistivity of SW powders were studied, and the optimum experimental conditions were obtained. The microstructure and surface properties of wollastonite, precipitate and SW were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy-dispersive X-ray spectrometry (EDS), specific surface area analyzer (BET), thermogravimetry (TG), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and Fourier translation infrared spectroscopy (FTIR) respectively. The results showed that the nano-SnO2/wollastonite composite materials under optimum preparation conditions showed better antistatic properties, the resistivity of which was reduced from 1.068 × 104 Ω cm to 2.533 × 103 Ω cm. From TG and XRD analysis, the possible mechanism for coating of SnO2 nanoparticles on the surface of wollastonite was proposed. The infrared spectrum indicated that there were a large number of the hydroxyl groups on the surface of wollastonite. This is beneficial to the heterogeneous nucleation reaction. Through morphology, EDS and XPS analysis, the surface of wollastonite fiber was coated with a layer of 10–15 nm thickness of tin oxide grains the distribution of which was uniform.

Thermal analysis and vibrational spectroscopic characterization of the boro silicate mineral datolite – CaBSiO4(OH)

The objective of this work is to determine the thermal stability and vibrational spectra of datolite CaBSiO4(OH) and relate these properties to the structure of the mineral. The thermal analysis of datolite shows a mass loss of 5.83% over a 700–775 °C temperature range. This mass loss corresponds to 1 water (H2O) molecules pfu. A quantitative chemical analysis using electron probe was undertaken. The Raman spectrum of datolite is characterized by bands at 917 and 1077 cm−1 assigned to the symmetric stretching modes of BO and SiO tetrahedra. A very intense Raman band is observed at 3498 cm−1 assigned to the stretching vibration of the OH units in the structure of datolite. BOH out-of-plane vibrations are characterized by the infrared band at 782 cm−1. The vibrational spectra are based upon the structure of datolite based on sheets of four- and eight-membered rings of alternating SiO4 and BO3(OH) tetrahedra with the sheets bonded together by calcium atoms.

Vibrational spectroscopic characterization of the sulphate mineral khademite Al(SO4)F⋅5(H2O)

Vibrational spectroscopy has been used to characterize the sulphate mineral khademite Al(SO4)F∙5(H2O). Raman band at 991 cm-1 with a shoulder at 975 cm-1 is assigned to the ν1 (SO4)2- symmetric stretching mode. The observation of two symmetric stretching modes suggests that the sulphate units are not equivalent. Two low intensity Raman bands at 1104 and 1132 cm-1 are assigned to the ν3 (SO4)2- antisymmetric stretching mode. The broad Raman band at 618 cm-1 is assigned to the v4 (SO4)2- bending modes. Raman bands at 455, 505 and 534 cm-1 are attributable to the doubly degenerate v2 (SO4)2- bending modes. Raman bands at 2991, 3146 and 3380 cm-1 are assigned to the OH stretching bands of water. Five infrared bands are noted at 2458, 2896, 3203, 3348 and 3489 cm-1 are also due to water stretching bands. The observation of multiple water stretching vibrations gives credence to the non-equivalence of water units in the khademite structure. Vibrational spectroscopy enables an assessment of the structure of khademite.

Characterization of precursors to methanol synthesis catalysts Cu/ZnO system

The composition of a series of hydroxycarbonate precursors to copper/zinc oxide methanol synthesis catalysts prepared under conditions reported as optimum for catalytic activity has been studied. Techniques employed included thermogravimetry (TG), temperature-programmed decomposition (TPD), X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), and Raman and FTIR spectroscopies. Evidence was obtained for various structural phases including hydrozincite, copper hydrozincite, aurichalcite, zincian malachite and malachite (the concentrations of which depended upon the exact Cu/Zn ratio used). Significantly, previously reported phases such as gerhardite and rosasite were not identified when catalysts were synthesized at optimum solution pH and temperature values, and after appropriate aging periods. Calcination of the hydroxycarbonate precursors resulted in the formation of catalysts containing an intimate mixture of copper and zinc oxides. Temperature-programmed reduction (TPR) revealed that a number of discrete copper oxide species were present in the catalyst, the precise concentrations of which were determined to be related to the structure of the catalyst precursor. Copper hydrozincite decomposed to give zinc oxide particles decorated by highly dispersed, small copper oxide species. Aurichalcite appeared to result ultimately in the most intimately mixed catalyst structure whereas zincian malachite decomposed to produce larger copper oxide and zinc oxide grains. The reason for the stabilization of small copper oxide and zinc oxide clusters by aurichalcite was investigated by using carefully selected calcination temperatures. It was concluded that the unique formation of an 'anion-modified' oxide resulting from the initial decomposition stage of aurichalcite was responsible for the 'binding' of copper species to zinc moieties.

Advantages of tandem LC-MS for the rapid assessment of tissue-specific metabolic complexity using a pentafluorophenylpropyl stationary phase

In this study, a tandem LC-MS (Waters Xevo TQ) MRM-based MS method was developed for rapid, broad profiling of hydrophilic metabolites from biological samples, in either positive or negative ion modes without the need for an ion pairing reagent, using a reversed-phase pentafluorophenylpropyl (PFPP) column. The developed method was successfully applied to analyze various biological samples from C57BL/6 mice, including urine, duodenum, liver, plasma, kidney, heart, and skeletal muscle. As result, a total 112 of hydrophilic metabolites were detected within 8 min of running time to obtain a metabolite profile of the biological samples. The analysis of this number of hydrophilic metabolites is significantly faster than previous studies. Classification separation for metabolites from different tissues was globally analyzed by PCA, PLS-DA and HCA biostatistical methods. Overall, most of the hydrophilic metabolites were found to have a "fingerprint" characteristic of tissue dependency. In general, a higher level of most metabolites was found in urine, duodenum, and kidney. Altogether, these results suggest that this method has potential application for targeted metabolomic analyzes of hydrophilic metabolites in a wide ranges of biological samples.

Metabolic urinary profiling of alcohol hepatotoxicity and intervention effects of Yin Chen Hao Tang in rats using ultra-performance liquid chromatography/electrospray ionization quadruple time-of-flight mass spectrometry

This paper was designed to study metabonomic characters of the hepatotoxicity induced by alcohol and the intervention effects of Yin Chen Hao Tang (YCHT), a classic traditional Chinese medicine formula for treatment of jaundice and liver disorders in China. Urinary samples from control, alcohol- and YCHT-treated rats were analyzed by ultra-performance liquid chromatography/electrospray ionization quadruple time-of-flight mass spectrometry (UPLC/ESI-QTOF-MS) in positive ionization mode. The total ion chromatograms obtained from the control, alcohol- and YCHT-treated rats were easily distinguishable using a multivariate statistical analysis method such as the principal components analysis (PCA). The greatest difference in metabolic profiling was observed from alcohol-treated rats compared with the control and YCHT-treated rats. The positive ions m/z 664.3126 (9.00 min) was elevated in urine of alcohol-treated rats, whereas, ions m/z 155.3547 (10.96 min) and 708.2932 (9.01 min) were at a lower concentration compared with that in urine of control rats, however, these ions did not indicate a statistical difference between control rats and YCHT-treated rats. The ion m/z 664.3126 was found to correspond to ceramide (d18:1/25:0), providing further support for an involvement of the sphingomyelin signaling pathway in alcohol hepatotoxicity and the intervention effects of YCHT.

Development of a rapid and validated method for investigating the metabolism of scoparone in rat using ultra-performance liquid chromatography/electrospray ionization quadruple time-of-flight mass spectrometry

Scoparone (6,7-dimethoxycoumarin) is known to have a wide range of pharmacological properties. In this study, a rapid and validated ultra-performance liquid chromatography/electrospray ionization quadruple time-of-flight mass spectrometry (UPLC/ESI-QTof-MS) method was developed to investigate the metabolism of scoparone in rat for the first time. The new method reduced the sample handling and analytical time by three- to six-fold, and the detection limit by five- to 1000-fold, compared to published methods. Far more metabolites were detected and identified compared to published data, which were preliminarily identified as scopoletin, isoscopoletin, isofraxidin, and fraxidin, respectively, when subjected to tandem mass spectrometry analyses. It is found that the metabolic trajectory of scoparone in rat focused on phase I metabolism which is obviously different from published results, and revealed a wide range of pharmacological properties of scoparone partly attributed to the bioactivities of its metabolites.

Isolation and characterization of 21 polymorphic microsatellite loci in the iconic Australian lungfish, Neoceratodus forsteri, using the Ion Torrent next-generation sequencing platform

We isolated and characterized 21 microsatellite loci in the vulnerable and iconic Australian lungfish, Neoceratodus forsteri. Loci were screened across eight individuals from the Burnett River and 40 individuals from the Pine River. Genetic diversity was low with between one and six alleles per locus within populations and a maximum expected heterozygosity of 0.774. These loci will now be available to assess effective population sizes and genetic structure in N. forsteri across its natural range in South East Queensland, Australia.

Analysis of the constituents in the rat plasma after oral administration of Yin Chen Hao Tang by UPLC/Q-TOF-MS/MS

A UPLC/Q-TOF-MS/MS method for analyzing the constituents in rat plasma after oral administration of Yin Chen Hao Tang (YCHT), a traditional Chinese medical formula, has been established. The UPLC/MS fingerprints of the samples were established first in vitro and in vivo, with 45 compounds in YCHT and 21 compounds in rat plasma after oral administration of YCHT were detected. Of the 45 detected compounds in vitro, 30 were identified, and all of the 21 compounds detected in rat plasma were identified either by comparing the retention time and mass spectrometry data with that of reference compounds or by mass spectrometry analysis and retrieving the reference literatures. Of the identified 21 compounds in rat plasma, 19 were the original form of compounds absorbed from the 45 detected compounds in vitro, 2 were the metabolites of the compounds existed in YCHT. It is concluded that a rapid and validated method has been developed based on UPLC-MS/MS, which shows high sensitivity and resolution that is more suitable for identifying the bioactive constituents in plasma after oral administration of Chinese herbal medicines, and provides helpful chemical information for further pharmacology and active mechanism research on the Chinese medical formula.