Stereochemical effects in mass spectrometry - Determination of the optical purity of enantiomers by mass spectrometry

Due to the difference in reactivity of enantiomers with chiral reagents, it was found that in the Fast Atom Bombardment (FAB) mass spectra of enantiomer mixtures of R-alpha-phenylethylamine and S-alpha-phenylethylamine with a chiral reagent S-phosphorsaeure-(1,1'-bi-naphthyl-2,2'-diylester) (BNP acid), the relative abundance of the characteristic ion is linearly related to the composition of the mixture. We have, therefore, proposed a possible method for the determination of the optical purity of enantiomers by mass spectrometry.

Stereochemical effect in mass spectrometry .19. Determination of the optical purity of alpha-phenylethylamine by mass spectrometry

It is found that in the fast atom bombardment (FAB) mass spectra R-alpha-phenylethylamine and S-alpha-phenylethylamine can be clearly distinguished by S-1,1'-binaphthyl-2, 2'-diylhydrogenphosphate (S-BNP), Mixture of R-alpha-phenylethylamine and S-alpha-phenylethylamine also be tested and the relative abundance of the characteristic ion of mixture is related to the composition of the mixtute. We have therefore proposed a possible method to determine the optical purity of alpha-phenylethylamine.

Enrichment of the hydrogen-producing microbial community from marine intertidal sludge by different pretreatment methods

To determine the effects of pretreatment on hydrogen production and the hydrogen-producing microbial community, we treated the sludge from the intertidal zone of a bathing beach in Tianjin with four different pretreatment methods, including acid treatment, heat-shock, base treatment as well as freezing and thawing. The results showed that acid pretreatment significantly promoted the hydrogen production by sludge and provided the highest efficiency of hydrogen production among the four methods. The efficiency of the hydrogen production of the acid-pretreated sludge was 0.86 +/- 0.07 mol H-2/mol glucose (mean +/- S.E.), whereas that of the sludge treated with heat-shock, freezing and thawing, base method and control was 0.41 +/- 0.03 mol H-2/mol glucose, 0.17 +/- 0.01 mol H-2/mol glucose, 0.11 +/- 0.01 mol H-2/mol glucose and 0.20 +/- 0.04 mol H-2/mol glucose, respectively. The result of denaturing gradient gel electrophoresis (DGGE) showed that pretreatment methods altered the composition of the microbial community that accounts for hydrogen production. Acid and heat pretreatments were favorable to enrich the dominant hydrogen-producing bacterium, i.e. Clostridium sp., Enterococcus sp. and Bacillus sp., However, besides hydrogen-producing bacteria, much non-hydrogen-producing Lactobacillus sp. was also found in the sludge pretreated with base, freezing and thawing methods. Therefore, based on our results, we concluded that, among the four pretreatment methods using acid, heat-shock, base or freezing and thawing, acid pretreatment was the most effective method for promoting hydrogen production of microbial community. (C) 2009 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.

Diet-induced changes in lipid and fatty acid composition of Artemia salina

The influence of diet on lipid and fatty acid composition of the brine shrimp Artemia salina nauplii was investigated. Various diets with different lipid composition and fatty acid profiles were fed to nauplii for 2 weeks. The lipid composition of microalgal diets, Isochrysis galbana, Phaeodactylum tricornutum and Nannochloropsis oculata and baker's yeast was analyzed. Newly hatched nauplii were examined before the feeding experiment. It was shown that Artemia was able to incorporate and selectively concentrate some dietary lipids. Depot lipids were more sensitive to changes in the dietary lipid composition than the main structural lipids, polar lipids and sterols. Variations in the content of the lipid classes correlated with stage of development of the animal. The fatty acid composition of the animal varied with that of diet. The concentrations of saturated fatty acids were apparently supported in the nauplii by biosynthesis de novo. The acid 16:1(n-7) originated from the food. The concentration range of n-6 polyunsaturated fatty acids (PUFAs) remained constant through the accumulation from the diet. The proportion of n-3 PUFAs varied with their level in the diet. The dynamics of alteration of 20:5(n-3) content in Artemia fed on Isochrysis, which is poor in this acid, suggested a limited capacity for elongation and desaturation of 18:3(n-3) to 20:5(n-3). None of the diets provided dietary input of 22:6(n-3). (C) 1998 Elsevier Science Inc. All rights reserved.

印度与欧亚板块强烈相互作用区深部结构特征研究

The central-south Tibet is a part of the products of the continental plate collision between Eurasia and India. To study the deep structure of the study area is significant for understanding the dynamics of the continental-continental collision. A 3-D density model matched well with the observations in the central-south Tibet was proposed in this study. In addition, this study has also used numerical simulation method to prove that Quasi-Love (QL) wave is deduced by anisotropy variation but not by lateral heterogeneity. Meanwhile, anisotropy variation in the upper mantle of the Qiangtang terrane and Lhasa terrane is detected by the QL waves observed in recorded seismograms. Based on the gravity modeling, some results are summarized as follows: 1) Under the constrain of geometrical structure detected by seismic data, a 3-D density model and Moho interface are proposed by gravity inversion of the central-south Tibet. 2) The fact that the lower crustal densities are smaller than 3.2 g/cm3, suggests absence of eclogite or partial eclogitization due to delamination under the central-south Tibet. 3) Seismicity will be strong or weak in the most negative Bouguer gravity anomaly. So there is no a certain relationship between seismicity and Bouguer gravity anomaly. 4) Crustal composition are determined after temperature-pressure calibration of seismic P wave velocity. The composition of lower crust might be one or a mixture of: 1. amphibolite and greenschist facies basalt beneath the Qiangtang terrane; 2. gabbro-norite-troctolite and mafic granulite beneath the Lhasa terrane. Because the composition of the middle crust cannot be well constrained by the above data set, the data set published by Rudnick & Fountain (1995) is used for comparison. It indicated the composition of the middle crust is granulite facies and might be pelitic gneisses.Granulite facies used to be interpreted as residues of partial melting, which coincidences with the previous study on partial melting middle crust. Amphibolite facies are thought to be produced after delamination, when underplating works in the rebound of the lower crust and lithospheric mantle. From the seismology study, I have made several followed conclusions: 1) Through the numerical simulation experiment of surface wave propagating in heterogeneity media, we can find that amplitude and polarization of surface wave only change a little when considering heterogeneity. Furthermore, it is proved that QL waves, generated by surface wave scattering, are caused by lateral variation of anisotropy but not by heterogeneity. 2) QL waves are utilized to determine the variation of uppermost mantle anisotropy of the Tibetan plateau. QL waves are identified from the seismograms of the selected paths recorded by the CAD station. The location of azimuth anisotropy gradient is estimated from the group velocities of Rayleigh wave, Love wave and QL wave. It suggests that south-north lateral variation of azimuthal anisotropy locates in Tanggula mountain, and east-west lateral variation in the north of Gandese mountain with 85°E longitude and near the Jinsha river fault with 85°E longitude.

内蒙古东部喀喇沁地区早中生代底侵作用

Mafic granulite xenoliths have been extensively concerned over the recent years because they are critical not only to studies of composition and evolution of the deep parts of continental crust but to understanding of the crust-mantle interaction. Detailed petrology, geochemistry and isotope geochronology of the Early Mesozoic mafic-ultramafic cumulate xenoliths and mafic granulite xenoliths and their host diorites from Harqin area, eastern Inner-Mongolia have been studied here. Systematic Rb-Sr isochron, ~(40)Ar-~(39)Ar and K-Ar datings for mafic-ultramafic cumulate xenoliths give ages ranging from 237Ma to 221Ma. Geochemical research and forming temperature and pressure estimates suggest that cumulates are products of the Early Mesozoic mantle-derived magmatic underplating and they formed in the magmatic ponds at the lowermost of the continental crust and are later enclaved by the dioritic magma. Detailed study on the first-discovered mafic granulite xenoliths reveals that their modal composition, mineral chemistry and metamorphic P-T conditions are all different from those of the Precambrian granulite exposed on the earth surface of the North China craton. High-resolution zircon U-Pb dating suggests that the granulite facies metamorphism may take place in 253 ～ 236Ma. Hypersthene single mineral K-Ar dating gives an age of 229Ma, which is believed to represent a cooling age of the granulite. As the host rock of the cumulate and granulite xenoliths, diorites intruded into Archean metamorphic rocks and Permian granite. They are mainly composed of grandodiorite, tonalite and monzogranite and show metaluminous and calc-alkaline features. Whole rock and single mineral K-Ar dating yields age of 221 ～ 223Ma, suggesting a rapid uplift in the forming process of the diorites. Detailed field investigation and geochemical characteristics indicate that these diorites with different rock types are comagmatic rocks, and they have no genetic correlation with cumulate and granulite xenoliths. Geochemical model simulating demonstrates that these diorites in different lithologies are products of highly partial melting of Archean amphibolite. It is considered that the Early Mesozoic underplating induced the intrusion of diorites, and it reflects an extensional geotectonic setting. Compression wave velocity V_P have been measured on 10 representative rock samples from the Early Mesozoic granulite and mafic-ultramafic cumulate xenoliths population as an aid to interpret in-situ seismic velocity data and investigating velocity variation with depth in a mafic lower crust. The experiments have been carried out at constant confining pressures up to 1000MPa and temperatures ranging from 20 ℃ to around 1300 ℃, using the ultrasonic transmission technique. After corrections for estimated in situ crustal pressures and temperatures, elastic wave velocities range from 6.5 ～ 7.4 km s~(-1). On the basis of these experimental data, the Early-Mesozoic continental compression velocity profile has also been reestablished and compared with those of the present and of the different tectonic environments in the world. The result shows that it is similar to the velocity structure of the extensional tectonic area, providing new constraints on the Early Mesozoic continental structure and tectonic evolution of the North-China craton. Combining with some newly advancements about the regional geology, the thesis further proposes some constraints on the Mesozoic geotectonic evolution history, especially the features of deep geology of the North China craton.

北祁连与块状硫化物矿床有关的早古生代火山岩的地球化学研究

Different conclusions from previous work are made from the geochemical study for the early Paleozoic volcanic rocks hosting massive sulfide deposits in the north Qilian Orogen. The main points are: (1)The geochemical characteristics of the basalts and rhyolites from the Baiyin deposit are not consistent with that of the volcanic rocks in the continental rift setting, but show the relationship with subduction. The basalts and rhyolites from the Baiyin deposit are probably individual tectonic slice piled by subduction, and there is no bimodal volcanic rock suite occurred in the Baiyin deposit. Zircon U-Pb dating constrains the magmatic emplacement of basalts and rhyolites at 475±10Ma and 453±12Ma, respectively. The basalts are characterized by enriched Th and Sr, and depleted Nb, Ta and Ti. They have relatively high Th/Nb ratios between 0.9 and 1.3. Their εNd(T) values vary from -1.2 to +3.4. The chemical and isotopic compositions display a typical subduction-related signature, and they suggest that an enriched component with the isotopic composition of EMII might have contributed to the generation of the Baiyin basalts. The basalts were likely formed in a mature island-arc or a volcanic arc built on comparatively young or thin continental crust in an active continental margin. The rhyoIites have low concentrations of LILE compared to the basalts. They do not seen to have a relationship with the basalts, because of their significantly higher εNd(T) values (+4.3～+7.7). The high and positive εNd(T) values also rule out their derivation from anatexis of the continental crust. A modeling study suggests that the source.of the Zhe-Huo and Xiaotieshan rhyolites is similar to boninite and IAT (island-arc tholeiite), and hence indicating an intra-oceanic arc environment. (2) The formation of the Shangliugou volcanic rocks from .Qilian area is also related to subduction. The basaltic andesite have low TiO_2(0.45～0.63%) and P_2O_5(0.04～0.09) content, and high Th/Nb ratios (0.3～0.6). They show flat REE patterns. Their εNd(T) values vary in a narrow range from +4.8 to +6.4. The chemical and isotopic compositions indicate that they are derived from a slightly depleted mantle source and are fromed in intra-island arc setting. The rhyolites show calc-alkaline trend. They show enriched LREE and fiat HREE patterns with obvious negative Eu anomaly. They have high Th/Ta ratios (5.0 ～ 11.7) and large negative εNd(T) values (-2.6 ～ -8.4). The rhyolites are formed in active continental margin and result from a mixed process of two endmembers, or crust assimilation. (3) The metal elements of the volcanic-hosted massive sulfide deposit have two sources, the copper and zinc are derived from rhyolitic magmas whereas the lead are probably related to old sediments overlying the rhyolites. (4) It is suggested here that the volcanic rocks hosting massive sulfide deposit in the north Qilian orogen, which are previously considered as a bimodal suite of Neo-proterozoic to middle Cambrian age in a continental rift, are virtually related to subduction magmatism in Ordovician age, and there might have no continental rift magmatism of Neo-proterozoic to middle Cambrian in the north Qilian.

Molecular composition of biogenic secondary organic aerosols using ultrahigh resolution mass spectrometry: comparing laboratory and field studies

Numerous laboratory experiments have been performed in an attempt to mimic atmospheric secondary organic aerosol (SOA) formation. However, it is still unclear how close the aerosol particles generated in laboratory experiments resemble atmospheric SOA with respect to their detailed chemical composition. In this study, we generated SOA in a simulation chamber from the ozonolysis of α-pinene and a biogenic volatile organic compound (BVOC) mixture containing α- and β-pinene, Δ3-carene, and isoprene. The detailed molecular composition of laboratory-generated SOA was compared with that of background ambient aerosol collected at a boreal forest site (Hyytiälä, Finland) and an urban location (Cork, Ireland) using direct infusion nanoelectrospray ultrahigh resolution mass spectrometry. Kendrick Mass Defect and Van Krevelen approaches were used to identify and compare compound classes and distributions of the detected species. The laboratory-generated SOA contained a distinguishable group of dimers that was not observed in the ambient samples. The presence of dimers was found to be less pronounced in the SOA from the VOC mixtures when compared to the one component precursor system. The elemental composition of the compounds identified in the monomeric region from the ozonolysis of both α-pinene and VOC mixtures represented the ambient organic composition of particles collected at the boreal forest site reasonably well, with about 70% of common molecular formulae. In contrast, large differences were found between the laboratory-generated BVOC samples and the ambient urban sample. To our knowledge this is the first direct comparison of molecular composition of laboratory-generated SOA from BVOC mixtures and ambient samples.

Analysis of the peripheral T-cell compartment in the MHC class II deficiency syndrome.

To analyse the impact of lack of MHC class II expression on the composition of the peripheral T-cell compartment in man, the expression characteristics of several membrane antigens were examined on peripheral blood lymphocytes (PBL) and cultured T cells derived from an MHC-class-II-deficient patient. No MHC class II expression could be detected on either PBL or activated T cells. Moreover, the expression of MHC class I was reduced both on PBL and in vitro activated T cells compared to the healthy control. However, the reduced expression of CD26 observed on the PBL of the patient was restored after in vitro expansion. Despite the presumably class-II-deficient thymic environment, a distinct but reduced single CD4+ T-cell population was observed in the PBL of the patient. After in vitro expansion, the percentage of CD4+ cells dropped even further, most likely due to a proliferative disadvantage, compared to the single CD8+ T-cell population. However, proliferation analysis showed that T-cell activation via the TcR/CD3 pathway is not affected by the MHC class II deficiency.

Environmental impacts of the coal ash spill in Kingston, Tennessee: an 18-month survey.

An 18 month investigation of the environmental impacts of the Tennessee Valley Authority (TVA) coal ash spill in Kingston, Tennessee combined with leaching experiments on the spilled TVA coal ash have revealed that leachable coal ash contaminants (LCACs), particularly arsenic, selenium, boron, strontium, and barium, have different effects on the quality of impacted environments. While LCACs levels in the downstream river water are relatively low and below the EPA drinking water and ecological thresholds, elevated levels were found in surface water with restricted water exchange and in pore water extracted from the river sediments downstream from the spill. The high concentration of arsenic (up to 2000 μg/L) is associated with some degree of anoxic conditions and predominance of the reduced arsenic species (arsenite) in the pore waters. Laboratory leaching simulations show that the pH and ash/water ratio control the LCACs' abundance and geochemical composition of the impacted water. These results have important implications for the prediction of the fate and migration of LCACs in the environment, particularly for the storage of coal combustion residues (CCRs) in holding ponds and landfills, and any potential CCRs effluents leakage into lakes, rivers, and other aquatic systems.

A change in the zooplankton of the central North Sea (55 degree to 58 degree N): A possible consequence of changes in the benthos

The mesozooplankton taken in continuous plankton recorder samples from the Central North Sea has changed from being numerically dominated by holoplanktonic calanoid copepod species from 1958 to the late 1970s to a situation where pluteus larvae of echinoid and ophiuroid echinoderms have been more abundant than any single holoplanktonic species in the 1980s and early 1990s. The abundance of the echinoderm larvae as a proportion of the zooplankton taken in the samples has followed a continuous increasing trend over the Dogger Bank, but off the eastern coast of northern England and southern Scotland the increase did not become obvious until the 1980s. This trend is consistent with reported increases in abundance of the macrobenthos. It is proposed that changes in the benthos have influenced the composition of the plankton.

An Electron-Microscope X-Ray-Diffraction And Amino-Acid-Analysis Study Of The Opercular Filament Cuticle Calcareous Opercular Plate And Habitation Tube Of Pomatoceros Lamarckii Quatrefages (Polychaeta Serpulidae)

The structure, X-ray diffraction and amino acid compositions of the opercular filament cuticle, calcareous opercular plate and habitation tube of the polychaete serpulid, Pomatoceros lamarckii quatrefages, are reported. The opercular filament cuticle is made up of protein and chitin. The chitin is probably in the crystallographic α form. The structure and amino acid composition of the organic components of the opercular filament cuticle and calcareous opercular plate have similarities but are distinctly different from those of the calcareous habitation tube. The opercular plate and habitation tube are composed of different polymorphs of calcium carbonate, aragonite and calcite respectively. Comparisons are made with other chitin-protein systems, structural and calcified proteins.

Seasonality and interannual variability of the European Slope Current from 20 years of altimeter data compared with in situ measurements

The European Slope Current (SC) is a major section of the warm poleward flow from the Atlantic to the Arctic, which also moderates the exchange of heat, salt, nutrients and carbon between the deep ocean and the European shelf seas. The mean structure of the geostrophic flow, seasonality, interannual variability and long-term trend of SC are appraised with an unprecedented continuous 20-year satellite altimeter dataset. Comparisons with long term in situ data showed a maximum correlation of r2=0.51 between altimeter and Acoustic Doppler Current Profilers (ADCP), with similar results for drogued buoy data. Mean geostrophic currents were appraised more comprehensively than previous attempts, and the paths of 4 branches of the North Atlantic Current (NAC) and positions of 5 eddies in the region were derived quantitatively. A consistent seasonal cycle in the flow of the SC was found at all 8 sections along the European shelf slope, with maximum poleward flow in the winter and minimum in the summer. The seasonal difference in the altimetry current speed amounted to ~8-10 cm s-1 at the northern sections, but only ~5 cm s-1 on the Bay of Biscay slopes. This extended altimeter dataset indicates significant regional and seasonal variations, and has revealed new insights into the interannual variability of the SC. It is shown that there is a peak poleward flow at most positions along a ~2000 km stretch of the continental slope from Portugal to Scotland during 1995-1997, but this did not clearly relate to the extreme negative North Atlantic Oscillation (NAO) in the winter of 1995-1996. The speed of the SC exhibited a long term decreasing trend of ~1% per year. By contrast the NAC showed no significant trend over the 20-year period. Major changes in the NAC occurred three times, and these changes followed decreases in the NAO index.

Dynamic responses of the benthic bacterial community at the Western English Channel observatory site L4 are driven by deposition of fresh phytodetritus

The impact of the seasonal deposition of phytoplankton and phytodetritus on surface sediment bacterial abundance and community composition was investigated at the Western English Channel site L4. Sediment and water samples were collected from January to September in 2012, increasing in frequency during periods of high water column phytoplankton abundance. Compared to the past two decades, the spring bloom in 2012 was both unusually long in duration and contained higher than average biomass. Within spring months, the phytoplankton bloom was well mixed through the water column and showed accumulations near the sea bed, as evidenced by flow cytometry measurements of nanoeukaryotes, water column chlorophyll a and the appearance of pelagic phytoplankton at the sediment. Measurements of chlorophyll and chlorophyll degradation products indicated phytoplankton material was heavily degraded after it reached the sediment surface: the nature of the chlorophyll degradation products (predominantly pheophorbide, pyropheophorbide and hydroxychlorophyllone) was indicative of grazing activity. The abundance of bacterial 16S rRNA genes g−1 sediment (used as a proxy for bacterial biomass) increased markedly with the onset of the phytoplankton bloom, and correlated with measurements of chlorophyll at the surface sediment. Together, this suggests that bacteria may have responded to nutrients released via grazing activity. In depth sequencing of the 16S rRNA genes indicated that the composition of the bacterial community shifted rapidly through-out the prolonged spring bloom period. This was primarily due to an increase in the relative sequence abundance of Flavobacteria.

Effect of excitation wavelength on the Raman spectroscopy of the porcine photoreceptor layer from the area centralis.

Raman microscopy, based upon the inelastic scattering (Raman) of light by molecular species, has been applied as a specific structural probe in a wide range of biomedical samples. The purpose of the present investigation was to assess the potential of the technique for spectral characterization of the porcine outer retina derived from the area centralis, which contains the highest proportion of cone:rod cell ratio in the pig retina. METHODS: Retinal cross-sections, immersion-fixed in 4% (w/v) PFA and cryoprotected, were placed on salinized slides and air-dried prior to direct Raman microscopic analysis at three excitation wavelengths, 785 nm, 633 nm, and 514 nm. RESULTS: Raman spectra of each of the photoreceptor inner and outer segments (PIS, POS) and of the outer nuclear layer (ONL) of the retina acquired at 785 nm were dominated by vibrational features characteristic of proteins and lipids. There was a clear difference between the inner and outer domains in the spectroscopic regions, amide I and III, known to be sensitive to protein conformation. The spectra recorded with 633 nm excitation mirrored those observed at 785 nm excitation for the amide I region, but with an additional pattern of bands in the spectra of the PIS region, attributed to cytochrome c. The same features were even more enhanced in spectra recorded with 514 nm excitation. A significant nucleotide contribution was observed in the spectra recorded for the ONL at all three excitation wavelengths. A Raman map was constructed of the major spectral components found in the retinal outer segments, as predicted by principal component analysis of the data acquired using 633 nm excitation. Comparison of the Raman map with its histological counterpart revealed a strong correlation between the two images. CONCLUSIONS: It has been demonstrated that Raman spectroscopy offers a unique insight into the biochemical composition of the light-sensing cells of the retina following the application of standard histological protocols. The present study points to the considerable promise of Raman microscopy as a component-specific probe of retinal tissue.