Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry with a matrix of carbon nanotubes for the analysis of low-mass compounds in environmental samples

The use of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) for environmental analysis has been mainly focused on qualitative analysis of high-mass molecules, such as toxins, humic acid, and microorganisms. Herein,we describe a novel MALDI-TOF-MS method with a matrix of oxidized carbon nanotubes for analysis of low-mass compounds in environmental samples. A number of chemicals in the environment were qualitatively analyzed by the present method, and it was found that most of them, especially the highly polar chemicals, were measurable with high sensitivity. With the intrinsic ability to measure high-mass chemicals, this method can compensate for the current shortage of methods for environmental analysis for the measurement of highly polar or high-mass chemicals. For sample analysis, arsenic speciation in Chinese traditional medicines was qualified and diphenylolpropane in water samples was quantified. With the relatively high tolerance of the method to interfering molecules, a simple pretreatment or even no pretreatment could be employed before MS detection. Furthermore, this method can be employed in a high-throughput format.

A novel approach to Co/CNTs catalyst via chemical vapor deposition of organometallic compounds

A novel approach for attaching well-dispersed cobalt nanoparticles homogeneously onto carbon nanotubes via metal organic chemical vapor deposition technique is reported. The obtained Co/CNTs catalysts feature a narrow size distribution of Co particles centering around 7.5 nm, and show high activity and regioselectivity for hydroformylation of 1-octene.

Integration of ion-exchange chromatography fractionation with reversed-phase liquid chromatography-atmospheric pressure chemical ionization mass spectrometer and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry for isolation and identification of compounds in Psoralea corylifolia

An approach for the separation and identification of components in a traditional Chinese medicine Psoralea corylifolia was developed. Ion-exchange chromatography (IEC) was applied for the fractionation of P corylifolia extract, and then followed by concentration of all the fractions with rotary vacuum evaporator. Each of the enriched fractions was then further separated on an ODS column with detection of UV absorbance and atmospheric pressure chemical ionization mass spectrometer (APCI/MS), respectively, and also analyzed by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF/MS) with matrix of oxidized carbon nanotubes. Totally more than 188 components in P. corylifolia extract were detected with this integrated approach, and 12 of them were preliminary identified according to their UV spectra and mass spectra performed by APCI/MS and MALDI-TOF/MS. The obtained analytical results not only demonstrated the powerful resolution of integration IEC fractionation with reversed-phase liquid chromatography (RPLC)-APCI/MS and MALDI-TOF/MS for analysis of compounds in a complex sample, but also exhibited the superiority of APCI/MS and MALDI-TOF/MS for identification of low-mass compounds, such as for study of traditional Chinese medicines (TCMs) and metabolome. (c) 2005 Published by Elsevier B.V.

Separation of compounds interacting with liposome membrane in combined prescription of traditional Chinese medicines with immobilized liposome chromatography

Immobilized liposome chromatography (ILC), the stationary phase of which has been regarded as a mimic biomembranes system was used to separate and analyze compounds interacting with liposome membrane in Danggui Buxue decoction, a combined prescription of traditional Chinese medicines (CPTCMs), and its compositions Radix Astragli and Radix Angelica Sinensis. More than 10 main peaks in the extract of Danggui Buxue decoction were resolved on the ILC column, suggesting that more than 10 components in the prescription have significant retention on ILC column. Ligustilide, astragaloside, TV and formononetin, three main bioactive ingredients in Danggui Buxue decoction, were found to have relatively significant, while ferulic acid, another bioactive ingredient in the prescription, relatively weak retention on ILC column. Effects of the eluent pH and amount of immobilized phosphatidylcholine (PC) on separation of interactional compounds in the extract of Danggui Buxue decoction were also investigated. It was found that these two factors strongly affected the retention of some interactional compounds. In addition, the fractions partitioned with different solvents from water extract of this combined prescription were evaluated with this ILC column system. (c) 2005 Elsevier B.V. All rights reserved.

Separation and detection of compounds in Honeysuckle by integration of ion-exchange chromatography fractionation with reversed-phase liquid chromatography-atmospheric pressure chemical ionization mass spectrometer and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry analysis

A hyphenated method for the isolation and identification of components in a traditional Chinese medicine of Honeysuckle was developed. Ion-exchange chromatography (IEC) was chosen for the fractionation of Honeysuckle extract, and then followed by concentration of all the fractions with rotary vacuum evaporator. Each of the enriched fractions was then further analyzed by reversed-phase liquid chromatography-atmospheric pressure chemical ionization mass spectrometer (RPLC-APCI/MS) and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF/MS) with matrix of oxidized carbon nanotubes, respectively. It can be noted totally more than 117 components were detected by UV detector, APCI/MS and MALDI-TOF/MS in Honeysuckle extract except the, 145 components identified by MALDI-TOF/MS alone with this integrated approach, and 7 of them were preliminary identified according to their UV spectra and mass spectra performed by APCI/MS and MALDI-TOF/MS, respectively. The obtained analytical results not only indicated the approach of integration IEC fractionation with RPLC-APCI/MS and MALDI-TOF/MS is capable of analyzing complex samples, but also exhibited the potential power of the mass spectrometer in detection of low-mass compounds, such as traditional Chinese medicines (TCMs) and complex biological samples. (c) 2005 Elsevier B.V. All rights reserved.

Analyses of patterns of copper and lead mineralisation in human skeletons excavated from an ancient mining and smelting centre in the Jordanian desert

Grattan, J.P., Al-Saad, Z., Gilbertson, D.D., Karaki, L.O., Pyatt, F.B 2005 Analyses of patterns of copper and lead mineralisation in human skeletons excavated from an ancient mining and smelting centre in the Jordanian desert Mineralogical Magazine. 69(5) 653-666.

Investigating the removal of some pharmaceutical compounds in hospital wastewater treatment plants operating in Saudi Arabia

The concentrations of 12 pharmaceutical compounds (atenolol, erythromycin, cyclophosphamide, paracetamol, bezafibrate, carbamazepine, ciprofloxacin, caffeine, clarithromycin, lidocaine, sulfamethoxazole and Nacetylsulfamethoxazol (NACS)) were investigated in the influents and effluents of two hospital wastewater treatment plants (HWWTPs) in Saudi Arabia. The majority of the target analytes were detected in the influent samples apart from bezafibrate, cyclophosphamide, and erythromycin. Caffeine and paracetamol were detected in the influent at particularly high concentrations up to 75 and 12 ug/L, respectively. High removal efficiencies of the pharmaceutical compounds were observed in both HWWTPs, with greater than 90 % removal on average. Paracetamol, sulfamethoxazole, NACS, ciprofloxacin, and caffeine were eliminated by between >95 and >99 % on average. Atenolol, carbamazepine, and clarithromycin were eliminated by >86 % on average. Of particular interest were the high removal efficiencies of carbamazepine and antibiotics that were achieved by the HWWTPs; these compounds have been reported to be relatively recalcitrant to biological treatment and are generally only partially removed. Elevated temperatures and high levels of sunlight were considered to be the main factors that enhanced the removal of these compounds.

Application of gold complexes in the development of sensors for volatile organic compounds

Two different kinds of sensors have been developed by using the same kind of vapochromic complexes. The vapochromic materials [Au2Ag2(C6F5)(4)L-2](n) have different colours depending on the ligand L. These materials change, reversibly, their optical properties, colour and fluorescence, in the presence of the vapours of volatile organic compounds (VOCs). For practical applications, two different ways of fixing the vapochromic material to the optical fibre have been used: the sol-gel technique and the electrostatic self-assembly method (ESA). With the first technique the sensors can even be used to detect VOCs in aqueous solutions, and using the second method it has been possible to develop nanosensors.

Occupational lead neurotoxicity: A behavioural and electrophysiological evaluation. study design and year one results.

To evaluate the effects of chronic lead exposure on the nervous system in adults, a set of neurobehavioural and electrophysiological tests was administered to 99 lead exposed foundry employees and 61 unexposed workers. Current and past blood lead concentrations were used to estimate the degree of lead absorption; all previous blood lead concentrations had been less than or equal to 90 micrograms/100 ml. Characteristic signs (such as wrist extensor weakness) or symptoms (such as colic) of lead poisoning were not seen. Sensory conduction in the sural nerve was not affected. By contrast, various neurobehavioural functions deteriorated with increasing lead burden. Workers with blood lead concentrations between 40 and 60 micrograms/100 ml showed impaired performance on tests of verbal concept formation, visual/motor performance, memory, and mood. Thus impairment in central nervous system function in lead exposed adults occurred in the absence of peripheral nervous system derangement and increased in severity with increasing lead dose.

Occupational lead neurotoxicity: Improvement in behavioural effects after reduction of exposure.

To evaluate critical exposure levels and the reversibility of lead neurotoxicity a group of lead exposed foundry workers and an unexposed reference population were followed up for three years. During this period, tests designed to monitor neurobehavioural function and lead dose were administered. Evaluations of 160 workers during the first year showed dose dependent decrements in mood, visual/motor performance, memory, and verbal concept formation. Subsequently, an improvement in the hygienic conditions at the plant resulted in striking reductions in blood lead concentrations over the following two years. Attendant improvement in indices of tension (20% reduction), anger (18%), depression (26%), fatigue (27%), and confusion (13%) was observed. Performance on neurobehavioural testing generally correlated best with integrated dose estimates derived from blood lead concentrations measured periodically over the study period; zinc protoporphyrin levels were less well correlated with function. This investigation confirms the importance of compliance with workplace standards designed to lower exposures to ensure that individual blood lead concentrations remain below 50 micrograms/dl.

Investigation of catalyst effects in enantioselective copper- and rhodium-mediated transformations of α-diazocarbonyl compounds

This thesis describes the synthesis and reactivity of a series of α-diazocarbonyl compounds with particular emphasis on the use of copper-bis(oxazoline)-mediated enantioselective C–H insertion reactions leading to enantioenriched cyclopentanone derivatives. Through the use of additives, the enantioselectivity achieved with the copper catalysts for the first time reaches synthetically useful levels (up to 91% ee). Chapter one provides a comprehensive overview of enantioselective C–H insertions with α-diazocarbonyl compounds from the literature. The majority of reports in this section involve rhodium-catalysed systems with limited reports to date of asymmetric C–H insertion reactions in the presence of copper catalysts. Chapter two focuses on the synthesis and C–H insertion reactions of α-diazo-β-keto sulfones leading to α-sulfonyl cyclopentanones as the major product. Detailed investigation of the impact of substrate structure (both the sulfonyl substitutent and the substituent at the site of insertion), the copper source, ligand, counterion, additive and solvent was undertaken to provide an insight into the mechanistic basis for enantiocontrol in the synthetically powerful C–H insertion process and to enable optimisation of enantiocontrol and ligand design. Perhaps the most significant outcome of this work is the enhanced enantioselection achieved through use of additives, substantially improving the synthetic utility of the asymmetric C–H insertion process. In addition to the C–H insertion reaction, mechanistically interesting competing reaction pathways involving hydride transfer are observed. Chapter three reports the extension of the catalyst-additive systems, developed for C–H insertions with α-diazo-β-keto sulfones in chapter two, to C–H insertion in analogous α-diazo-β-keto phosphonate and α-diazo-β-keto ester systems. While similar patterns were seen in terms of ligand effects, the enantiopurities achieved for these reactions were lower than those in the cyclisations with analogous α-diazo-β-keto sulfones. Extension of this methodology to cyclopropanation and oxium ylide formation/[2,3]-sigmatropic rearrangement was also explored. Chapter four contains the full experimental details and spectral characterisation of all novel compounds synthesised in this project, while details of chiral stationary phase HPLC analysis and X-ray crystallography are included in the appendix.

Studies of ferrite, borosilicate and intercalation materials

This thesis is concerned with several aspects of the chemistry of iron compounds. The preparation (with particular emphasis on coprecipitation and sol-gel techniques) and processing of ferrites are discussed. Chapter 2 describes the synthesis of Ni-Zn ferrites with various compositions by three methods. These methods include coprecipitation and sol-gel techniques. The Ni-Zn ferrites were characterised by powder X-ray diffactometry (PXRD), scanning electron microscopy (SEM), vibrating sample magnetometry (VSM), Mössbauer spectroscopy and resistivity measurements. The results for the corresponding ferrites prepared by each method are compared. Chapter 3 reports the sol-gel preparation of a lead borosilicate glass and its addition to Ni-Zn ferrites prepared by the sol-gel method in Chapter 2. The glass-ferrites formed were analysed by the same techniques employed in Chapter 2. Alterations in the microstructure, magnetic and electronic properties of the ferrites due to glass addition are described. Chapter 4 introduces compounds containing Fe-O-B, Fe-O-Si or B-O-Si linkages. The synthesis and characterisation of compounds containing Fe-O-B units are described. The structure of [Fe(SALEN)]2O.CH2Cl2 (17), used in attempts to prepare compounds with Fe-O-Si bonds, was determined by X-ray crystallography. Chapter 4 also details the synthesis of three new borosilicate compounds containing ferrocenyl groups, i.e. [FcBO)2(OSiBut2)2] (19), [(FcBO)2(OSiPh2)2] (20) and [FcBOSiPh3] (21). The structure of (19) was determined by X-ray Crystallographic analysis. Chapter 5 reviews the intercalation properties of the layered host compound iron oxychloride (FeOCI). Intercalation compounds prepared with the microwave dielectric heating technique are also discussed. The syntheses of intercalation compounds by the microwave method with FeOCI as host and ferrocene, ferrocenylboronic acid and 4-aminopyridine as guest species are described. Characterisation of these compounds by powder X-ray diffractometry (PXRD) and M{ssbauer spectroscopy is reported. The attempted synthesis of an intercalation compound with the borosilicate compound (19) as guest species is discussed. Appendices A-E describe the theory and instrumentation involved in powder X-ray diffractometry (PXRD), scanning electron microscopy (SEM0, vibrating sample magnetometry (VSM), Mössbauer spectroscopy and electrical resistivity measurements, respectively. Appendix F details the attempted syntheses of compounds with Fe-O-B and Fe-O-Si linkages.

Copper-catalysed asymmetric sulfide oxidation

The focus of this thesis is the preparation of enantiopure sulfoxides by means of copper-catalysed asymmetric sulfoxidation, with particular emphasis on the synthesis of aryl benzyl and aryl alkyl sulfoxides. Chapter 1 contains a review of the methods employed for the asymmetric synthesis of sulfoxides, compounds with many applications in stereoselective synthesis and in some cases with pharmaceutical application. Chapter 1 describes asymmetric oxidation, including metal-catalysed, non metal-catalysed and enzyme-catalysed, in addition to synthetic approaches via nucleophilic substitution of appropriately substituted precursors. Kinetic resolution in oxidation of sulfoxides to the analogous sulfones is also discussed; in certain cases, access to enantioenriched sulfoxides can be achieved via a combination of asymmetric sulfoxidation and complementary kinetic resolution. The design and synthesis of a series of sulfides to enable exploration of the substituent effects of the copper-mediated oxidation was undertaken, and oxidation to the racemic sulfoxides and sulfones to provide reference samples was conducted. Oxidation of the sulfides using copper-Schiff base catalysis was undertaken leading to enantioenriched sulfoxides. The procedure employed is clean, inexpensive, not air-sensitive and utilises aqueous hydrogen peroxide as oxidant. Extensive investigation of the influence of the reaction conditions such as solvent, temperature, copper salt and ligand was undertaken to lead to the optimised conditions. While the direct attachment of one aryl substituent to the sulfide is essential for efficient enantiocontrol, in the case of the second substituent the enantiocontol is dependent on the steric rather than electronic features of the substituent. Significantly, use of naphthyl-substituted sulfides results in excellent enantiocontrol; notably 97% ee, obtained in the oxidation of 2-naphthyl benzyl sulfide, represents the highest enantioselectivity reported to date for a copper-mediated sulfur oxidation. Some insight into the mechanistic features of the copper-mediated sulfur oxidation has been developed based on this work, although further investigation is required to establish the precise nature of the catalytic species responsible for asymmetric sulfur oxidation. Full experimental details, describing the synthesis and structural characterisation, and determination of enantiopurity are included in chapter 3.