Large selenium isotopic variations and its implication in the Yutangba Se deposit, Hubei Province, China

The selenium isotopic ratios have been measured in the Yutangba Se deposit, Hubei Province, China. The results show that the δ 82/76SeNIST values vary from -12.77‰ to 4.93‰, which is the largest Se iso- topic variation found so far in natural terrestrial samples. The sample Ytb-5 of high-selenium carbona-ceous shale has the lightest Se isotopic composition with a δ 82/76SeNIST value of -12.77‰. On the basis of variations of Se isotope in the deposit along with other geological and geochemical evidence, the "redox model" is suggested to favor the explanation of the occurrence of native Se in the deposit. The application to the Yutangba Se deposit with the discovery of large Se isotopic fractionation for natural samples indicates the potential of Se isotope as a new geochemical tracer.     

Pure CO2 fluids in the Sarekoubu gold deposit at southern margin of Altai Mountains in Xinjiang, West China

Sarekoubu gold deposit occurs in metamorphosed acid volcanic rocks and volcaniclastic rocks of Devonian Kangbutiebao Formation along the southern margin of Altai Mountains in Xinjiang, West China. Pyritization, silicification and carbonatization are developed in wallrocks, and main gold mineralization stages are pyrite-quartz stage (Ⅱ)and polymetallic sulfide stage (Ⅲ). Primary fluid inclusions are often seen in main gold mineralization stages, which are almost pure CO2 liquid inclusions (Lco2) under room temperature with high densities of 0.85--1.07 g/cm^3. CO2-rich inclusions (Lco2-LH2O) and H2O-rich inclusions (LH2O-LCo2)are subordinate. Fluid inclusions in stage Ⅰ (polymetallic sulfide stage) are more complex than in stage Ⅱ, containing CO2-CH4 system with -78.1-61.9℃ of solid CO2 melting temperatures and -33.7-17.7℃ of partial homogenization temperatures. The trapping pressures of high densities are estimated to be 150-350 MPa. Laser Raman microprobe was used to confirm the composition of pure CO2 liquid inclusions. δ^13C values of CO2 inclusions range from -10.73‰ to -21.15‰, which are similar to some of fluids in the mantle-derived minerals that contain surface organic carbon by subduction recycling. These characteristics differ from many hydrothermal gold deposits. CO2 fluids have a regional source related to post-collisional orogeny.     

Effects of inorganic arsenic on growth and microcystin production of a <Emphasis Type="Italic">Microcystis</Emphasis> strain isolated from an algal bloom in Dianchi Lake,China

Our previous data have shown that inorganic arsenic concentrations were high in Dianchi Lake, China, where Microcystis blooms often occur. To explore the relationship between arsenic and the growth of Microcystis, the effects of arsenite [As(III)] and arsenate [As(V)] on the growth and toxin production of M. aeruginosa strain FACHB 905 were tested. Results showed that M. aeruginosa FACHB 905 was tolerant to inorganic arsenic and its growth was not inhibited when the concentration of As(III) was below 10⁻⁵ mol L⁻¹ or that of As(V) below 10⁻³ mol L⁻¹. Total microcystin production was stimulated in the presence of 10⁻⁷ mol L⁻¹ As(III) and the response of this M. aeruginosa strain to As(III) seemed to be a typical inverted U-shaped hormesis. The content increase of microcystin-LR per cell indicated that the toxicity was enhanced as M. aeruginosa FACHB 905 was exposed to As(V). Considering the relatively high concentration of inorganic arsenic in Dianchi Lake (139 μg L⁻¹ in epilimnetic water), the origin of the M. aeruginosa strain, inorganic arsenic favors survival of M. aeruginosa FACHB 905 and may stimulate its microcystin production and cellular toxicity.     

A theoretical study of the proton transfer process in the spin-forbidden reaction ^1HNO（^1A＇） ＋ OH^-→^ 3NO^-（^3∑^-） ＋ H2O

The spin-forbidden reaction 1HNO（^1A＋OH^-→3NO^-（^3∑^-）＋H2O has been extensively explored using vari- ous CASSCF active spaces with MP2 corrections in several basis sets. Natural bond orbital （NBO） analysis, together with the NBO energetic （deletion） analysis, indicates that the two isomers have nearly equal total energy and could compete with each other in the title reaction. More significantly, the singlet/triplet surface crossing regions have been examined and the spin-orbit coupling （SOC） and energetics have been computed. The computational results indicate that the SOC is very large at the crossing point T1/S0 trans （ca. 40.9 cm^-1）. Moreover, the T1/S0 trans has a low energy of 10.67 kcal/mol relative to that of trans-So. Therefore, the surface crossing to the triplet state seems much more efficient at the T1/S0 trans region along the minimum energy path （MEP）, However, The values of single （P1^ISC） and double （P2^ISC） passes estimated at T1/S0 trans show that the ISC occurs with a little probability.     

Compression behavior and equation of state of Ni77P23 amorphous alloy

The compression behavior of Ni77P23 amorphous alloy is investigated at room temperature in a diamond-anvil cell instrument using insitu high pressure energy dispersive X-ray diffraction with a syn- chrotron radiation source. The equation of state is determined by fitting the experimental data accord- ing to Birch-Murnaghan equation: -ΔV/V0=0.08606P-3.2×10-4P2 5.7×10-6P3. It is found that the structure of Ni77P23 amorphous alloy is stable under pressures up to 30.5 GPa.     

An acetylcholinesterase inhibitor, 3-benzidino-5-methyl-6-phenylpyridazine, blocking outward potassium currents in acutely isolated rat hippocampal pyramidal neurons

3-benzidino-5-methyl-6-phenylpyridazine (BMP) inhibited electric eel acetylcholinesterase (AChE), with IC50 being 0.58 μmol·L-1. As an AChE inhibitor, the effects of BMP on delayed rectifier potassium current (IK(DR)) and transient outward potassium current (IK(A)) in acutely isolated rat hippocampal pyramidal neurons were studied using the whole cell patch-clamp technique. BMP (0.1―50 μmol·L-1) inhibited IK(DR) and IK(A) in a concentration-dependent and voltage-independent manner. The IC50 value for the bl...     

The comparative investigation on redox property and second-order nonlinear response of Keggin-type α-[PM12O39NPh]3− (M = W and Mo) and Mo6NPh

Keggin-type phenylimido-polyoxometalates α-[PM₁₂O₃₉NPh]³⁻ (M = W and Mo) have been systematically investigated on the electronic structures, redox as well as nonlinear optical (NLO) properties by density functional theory (DFT). The strong M≡N bond confirmed by natural bond orbital (NBO) analysis comprises one s bond and two π bonds, the same as Mo≡N in [Mo₆O₁₈NPh]²⁻. Furthermore, phenylimido segment effectively modifies the electronic properties of α-[PM₁₂O₃₉NPh]³⁻. On one hand, when enlarging the inorganic cluster from {Mo₆O₁₈} to {PMo₁₂O₃₉}, the energy gap between HOMO and LUMO in α-[PMo₁₂O₃₉NPh]³⁻ decreased, resulting in enormously anodic shift for the reduction potential, while the excitation energy is less and the total second-order polarizability β ₀ is up to 438-3×10⁻³⁰ esu, which is nearly 10 times larger than that of [Mo₆O₁₈NPh]²⁻. On the other hand, when metal W in α-[PM₁₂O₃₉NPh]³⁻ is substituted by Mo, the interaction between Mo and N is enhanced and the redox ability becomes stronger. The β ₀ value for α-[PMo₁₂O₃₉NPh]³⁻ is more than 5 times higher than that of α-[PW₁₂O₃₉NPh]³⁻. It indicates that changing appropriate metal or enlarging the inorganic cluster will improve the redox properties and second-order nonlinear response. Moreover, the electron transition for three compounds mentioned above occurred mainly from organoimido segment (as the electron donor) to polyanion cluster (as the acceptor). As a result, α-[PMo₁₂O₃₉NPh]³⁻ may be a promising candidate for oxidant and nonlinear optical material. Electronic Supplementary Material  Supplementary material is available for this article at and is accessible for authorized users. Supported by National Natural Science Foundation of China (Grant No. 20573016), Training Fund of NENU’s Scientific Innovation Project (Grant No. NENUSTC07017), Science Foundation for Young Teachers of Northeast Normal University (Grant No. 20070304) and Program for Changjiang Scholars and Innovative Research Team in University (PCSIRT)     

Rate constants for the reaction of ozone with <Emphasis Type="Italic">n</Emphasis>-butyl, <Emphasis Type="Italic">s</Emphasis>-butyl and <Emphasis Type="Italic">t</Emphasis>-butyl methyl sulfides

The rate constants for the ozone reactions with n-butyl methyl sulfide （n-BMS, CHaCH2CH2CH2SCH3）, sec-butyl methyl sulfide （s-BMS, CH3CH2（CH3）CHSCHa） and tert-butyl methyl sulfide （t-BMS, （CH3）3CSCH3） were measured using our smog chamber under supposedly pseudo-first-order conditions at 30002 K and 760 Torr. The experimental determined rate constants for n-butyl, s-butyl and t-butyl methyl sulfide are （1.23 ± 0.06）×10-19, （5.08 ± 0.19）×10-20 and （2.26 ± 0.14）×10-20 cm3 molecule-1· s-1, respectively. The reactivity-structure relationship of the reactions was discussed and used to illustrate the mechanism of the ozone reaction with thioethers. The results enrich the kinetics data of atmospheric chemistry.     

Transmission of oxygen isotope signals of precipitation-soil water-drip water and its implications in Liangfeng Cave of Guizhou,China

According to systemically monitoring results of oxygen （hydrogen） isotope compositions of precipitation, soil waters, soil CO2, cave drip waters and their corresponding speleothems in Liangfeng Cave （LFC） in Guizhou Province, Southwest China, it is found that local precipitation is the main source of soil waters and drip waters, and that the amplitudes of those δ18O values of three waters （precipitation, soil water and drip water） decrease in turn in the observed year, which are 0‰ to -10‰, -2‰ to -9‰ and -6‰ to -8‰, respectively. Moreover, the δ18O values for three waters show a roughly simultaneous variation, namely, that those values are lighter in the rainy seasons, weightier in the dry seasons, and that the average δ18O value of drip waters is about 0.3‰ weightier than that of precipitation, which is modified by surface evaporation processes. We also find that oxygen isotope equilibrium is reached or neared in the formation processes of speleothems in LFC system, and that it is feasible to reconstruct paleotemperature and paleoprecipitation by using δ18O values of speleothems. However, it should be noted that surface evaporation would affect the oxygen isotope values in the study area.     

Direct electrochemistry and electrocatalysis of horseradish peroxidase in MnO2 nanosheet film

A novel material MnO2 nanosheet has been used as the support matrix for the immobilization of horseradish peroxidase （HRP）. HRP entrapped in MnO2 nanosheet film exhibits facile direct electron transfer with the electron transfer rate constant of 6.86 s^-1. The HRP/MnO2 nanosheet film gives a reversible redox couple with the apparent formal peak potential （E^0＇） of -0.315 V （vs. Ag/AgCl） in pH 6.5 phosphate buffer solution （PBS）. The formal potential E^0＇ of HRP shifts linearly with pH with a slope of -53.75 mV.pH^-1, denoting that an electron transfer accompanies single-proton transportation. The immobilized HRP shows an electrocatslytic activity to the reduction of H2O2. The response time of the biosensor for H2O2 is less than 3 s, and the detection limit is 0.21 μmol · L^-1 based on signal/noise = 3.     

Preparation of Ln3-xEuxS4 （Ln=Ce,Pr, and Nd） ceramics by pressureless sintering

The preparation of ternary rare earth sulfides of Ln3-xEuxS4 （Ln = Ce, Pr, and Nd） ceramics was investigated, and the effect of Eu substitution on Ln3-xEuxS4 ceramics was also studied. Ln3-xEuxS4 powders were synthesized by the sulfurization of their oxide powders using carbon disulfide gas. Ln3-xEuxS4 ceramics were sintered by pressure-less sintering method. All pressureless sintered Ln3-xEuxS4 ceramics crystallized in y-phase. It was found that Eu substitution could improve the density of Ln3-xEuxS4 ceramics. Furthermore, Eu substitution might narrow the optical band gaps of Ln3-xEuxS4 ceramics.     

Effect of Cl- on photosynthetic bicarbonate uptake in two cyanobacteria Microcystis aeruginosa and Synechocystis PCC6803

Photosynthetic inorganic carbon utilization was investigated in two cyanobacteria Microcystis aeruginosa and Synechocystis PCC6803 grown in standing culture. Photosynthetic rates for the two algae reached about 10 times the theoretical CO₂ supply rate at low dissolved inorganic carbon (DIC) of 100 μmol/L, and the rates were unaffected by the addition of 20 mmol/L Na⁺, indicating that the two algae possessed Na+-independent HCO^-₃ utilization for photosynthesis under low DIC. Their photo- synthetic rates at low DIC were inhibited by higher Cl^- and the degrees of inhibition were increased with the rise of CI^- concentration, and in the presence of Diphenylamine-2-carboxylate (DPC), a reported Cl^- channel inhibitor, the rates decreased by 74%－82%, implying that putative DPC-sensitive Cl^- channels participate in Na+-independent HCO₃^- uptake for photosynthesis. The experiment of intracellular 14C-DIC accumulation for photosynthesis showed that internal DIC pools decreased by about 80% with 200 μmol/L DPC and by 64%－70% with 100 mmol/L Cl^-. The experiment of chlorophyll a fluorescence quenching showed that initial rates and extents of fluorescence quenching obviously decreased with 200 μmol/L DPC or 100 mmol/L Cl^-. The two experiments gave further evidence that putative DPC-sen- sitive Cl^- channels participate in Na+-independent HCO^-₃ uptake for photosynthesis in the two algae grown in standing culture.     

Magnetoelectric and converse magnetoelectric res ponses in TbxDy1-xFe2-y alloy ＆ Pb（Mg1/3Nb2/3）（1-x）TixO3 crystal laminated composites

Measured results of magnetoelectric （ME） and converse magnetoelectric （CME） effects of TbxDy1-xFe2-y/ Pb（Mg1/3Nb2/3）（1-x）TixO3/TbxDy1-xFe2-y （TD/PMNT/TD） and PMNT/TD/PMNT laminated composites are presented. ME effect was determined by measuring laminate voltage output under a Helmholtz-generated AC field biased by a DC field （0-1 kOe） （1Oe = 79.58 A/m）. The CME effect was measured by recording the voltage induced in a solenoid encompassing the ME sample while exposed to a DC bias field and PMNT layer driven by a 10 V AC source. The ME and CME responses in the two laminated structure are linear. The highest values of ME coefficients in TD/PMNT/TD and PMNT/TD/PMNT composites are 384 mV/Oe and 158 mV/Oe, respectively, while the highest values of CME coefficients in the two composites are 118 mG/V and 162 mG/V （1 G=10^-4 T）, respectively.     

Diet control on carbon isotopic composition of land snail shell carbonate

Carbon isotope compositions for both the carbonate shells and soft bodies (organic tissue) of living land snails collected mostly from the Loess Plateau, China have been measured. The result shows that δ 13C values range from -13.1‰ to -4.3‰ for the aragonite shell samples and from -26.8‰ to -18.0‰ for the soft body samples. Although the shells are enriched in 13C relative to the bodies averagely by 14.2(±0.8)‰, the shell δ 13Ca values are closely correlated to the body δ 13Corg values, expressed as δ 13Ca = 1.021 δ 13Corg 14.38 (R = 0.965; N = 31). This relationship indicates that δ 13Ca is primarily a function of the isotopic composition of the snail diets since previous studies have proved that the snail body is the same as their food in carbon isotope composition. In other words, carbon isotope compo-sition of the carbonate shell can be used as a proxy to estimate the dietary 13C abundance of the land snails. The data also support that the 13C enrichment of the carbonate shells results mainly from the equilibrium fractionations between the metabolic CO2, HCO3-in the hemolymph and shell aragonite, and partially from kinetic fractionations when snail shells form during their activity.     

Preliminary Mo isotope data of Phanerozoic clastic sediments from the northern margin of the Yangtze block and its implication for paleoenvironmental conditions

Mo isotopes along with Nd isotopes and other geochemical characteristics of the Phanerozoic clastic sediments from the northern margin of the Yangtze block were analyzed by MC-ICP-MS and some other techniques, spanning the period from Cambrian to Jurassic. The δ 98Mo values and εNd(t ) in these sedimets were observed to exhibit a large range of variation (?0.65‰―+1.87‰, ?1.46―?10.90, respec-tively). Specifically, the sample from Late Permian Maokou Formation has relatively positive values in both δ 98Mo and...     

Icariin suppresses bone resorption activity of rabbit osteoclasts in vitro

The effect of icariin on the bone resorption activity of rabbit osteoclasts is assessed in vitro. Osteoclasts were isolated from Japanese white rabbits and cultured on plates with a sterilized bone slice in each well. After treatment with icariin at various concentrations, the bone resorption activity of osteoclasts was evaluated by examining pit areas, superoxide anion (·O2-) generation, size and number of actin rings and intracellular calcium concentration [Ca2 ]i. As revealed by these data, icariin elicited continuous decline of [Ca2 ]i, making actin ring constricted and ·O2- generation decreased. These events resulted in smaller and fewer pits which indicate suppressed bone resorption activity of rabbit osteoclasts by icariin.     

Characterization of Fe-S minerals influenced by buried ancient woods in the intertidal zone, East China Sea

An ancient wood layer dated at about 5600 cal. a BP by AMS14C dating was discovered in the intertidal zone, East China Sea. Samples affected by ancient woods, including fresh coast bedrock, weathering bedrock, seepage water from coast, seepage water from ancient wood layer, intertidal seawater, fresh water, beach mud, ancient wood barks and ancient peat, were collected for geochemical analysis. The beach mud and the bacteriogenic iron oxides （BIOS） in coastal seepage water were analyzed by min- eralogical and high-resolution transmission electron microscopy （HRTEM）-selected area electron dif- fraction （SAED） analysis. Inorganic sulfur compositions and b＇34S of the ancient peat and the beach mud were determined. The results showed that Fe, Mn, S （SO~-） were enriched in the intertidal area at different levels, very likely caused by fermentation of ancient woods. The presence of abundant iron- oxidizing bacteria （FeOB） and sulfate-reducing bacteria （SRB） in this intertidal zone was confirmed by HRTEM-SAED observation, and these bacteria were involved in Fe-S cycle to induce extracellular biomineralization. The negative ~4Sv.cDT （--2.9%o） likely indicated the biogenic origin of iron-sulfide minerals in the beach mud at high sulfate reduction rate （SRR）. These findings are helpful for under- standing the biogeochemical Fe-S cycle and biomineralization process at high organic matter deposition rate and high SRR in the intertidal zone, estuary, or near shoreline.     

Photodegradation of <Emphasis Type="Italic">N</Emphasis>-nitrosodiethylamine in water with UV irradiation

The direct photolysis of N-nitrosodiethylamine （NDEA） in water with ultraviolet （UV） irradiation was investigated. Results showed that NDEA could be completely degraded under the direct UV irradiation. The effects of the experimental conditions, including the initial concentration of NDEA, humic acid and solution pH, were studied. The degradation products of NDEA were identified and quantified with gas chromatography-mass spectrometry （GC-MS） and high performance liquid chromatography （HPLC）. It was confirmed that methylamine （MA）, dimethylamine （DMA）, ethylamine （EA）, diethylamine （DEA）, NO2^- and NO3^- were the main degradation products. The photolysis degradation mechanism of NDEA was also discussed. As a result of N-N bond fission, NDEA was degraded by direct UV irradiation.     

Interaction of aloe-emodin with human serum albumin

The presence of several high affinity binding sites on human serum albumin (HSA) makes it a possible target for many drugs. This study is designed to examine the effect of aloe-emodin on HSA by fluo-rescence, CD spectroscopy and molecular modeling. The results of fluorescence measurements sug-gested that the hydrophobic interaction was the predominant intermolecular force stabilizing the AE-HSA complex, which was in good agreement with the result of molecular modeling study. And the enthalpy change ΔH0 and the entropy change ΔS0 were calculated to be -7.041 kJ·mol-1 and 76.619 J·mol-1·K-1 according to the Van't Hoff equation. The alterations of protein secondary structure in the presence of AE in aqueous solution were quantitatively calculated from CD spectra, and the content of α-helices obviously increased.     

Foliar δ^13C and δ^15N values of C3 plants in the Ethiopia Rift Valley and their environmental controls

The foliar C and N stable isotopic compositions （δ^13C and δ^15N） and the relationships between these compositions and environmental factors of C3 plants in the Ethiopia Rift Valley were investigated. There were three distribution patterns for foliar δ^13C with mean values of -26.7‰±0.4‰, -29.7‰ ±0.6‰ , and -26.9‰± 1.2‰ in cold-moist, temperate-moist, and arid-hot environments, respectively. The δ^15N values ranged from -1.4‰ ±1.7‰ to 14.3‰ ± 0.1‰, with higher values under arid-hot conditions and the lowest values in plants growing at higher altitudes under cold-moist conditions. A strong negative relationship between mean annual precipitation and δ^15N explained more than half of the observed variation in the δ^15N values （r2= 0.54, P 〈 0.001）; a modest positive relationship was also found between δ^15N and temperature （r2 = 0.32, P 〈 0.01）. A weakly positive relationship existed between δ^13C and temperature, and changes in δ^13C values with precipitation and altitude followed quadratic curves. This suggests a shift in the effects of water and heat conditions caused by altitude on carbon isotopic discrimination.