Influence of O2/Ar ratio on the properties of transparent conductive niobium-doped ZnO films

Niobium-doped ZnO transparent conductive films are deposited on glass substrates by radio frequency sputtering at 300℃. The influence of O2/Ar ratio on the structural, electrical and optical properties of the as-deposited films is investigated by X-ray diffraction, Hall measurement and optical transmission spectroscopy. The lowest resistivity of 4.0×10^-4Ω· cm is obtained from the film deposited at the O2/Ar ratio of 1/12. The average optical transmittance of the films is over 90%.     

Structural dependences of the <Emphasis Type="Italic">η</Emphasis><Superscript>6</Superscript> complexes of 3-amino-9-ethylcarbazole with chromium tricarbonyl fragment on third-order optical nonlinearities

Degenerate four-wave mixing measurements, using the 35 ps pulses at 532 nm, have been employed to investigate the third-order nonlinear optical parameters of two chromium tricarbonyl complexes η6-bonded to 3-amino-9-ethylcarbazole at either the NH2-substituted aryl ring （1） or the unsubstituted ring （2） and their precursor 3-amino-9-ethylcarbazole （AECz）. The second-order hyperpolarizability y of the compounds 1 and 2 were found to be 42.9×10^-31 and 35.9×10^-31 esu, respectively, approximately one order of magnitude greater than AECz. The relation between the molecular structure and second-order hyperpolarizability of the compounds I and 2 was explored in detail based on the three-level model and the density functional theory （DFT） calculation. The theoretical results indicate that the spatial distribution of electron density has the profound role in the third-order nonlinear optical properties.     

Fabrication of the 19-filament Fe/Cu clad MgB2 wire via in situ powder-in-tube method

Using commercial amorphous B powder (92% in purity) and Mg powder (99% in purity) as starting materials, 19-filament Fe/Cu clad MgB2 wires were fabricated by an in situ powder-in-tube method. Heat treatment was performed at 700℃ for 1 h under an argon gas atmosphere. The influence of Mg/B ratio on the microstructure and superconducting properties of the wires was investigated. It was found that the major phases of MgB2 wires were MgB2 accompanied with relatively small amounts of MgO and Fe2B impurities. With 5% excess Mg addition, the onset TC slightly decreased. However, the transport JC at 4.2 K and 4 T reached 1.07×104 A·cm-2, increasing by a factor of 1.4 compared to the stoichiometric sample. Moreover, the Mg1.05B2 sample showed an improved field dependence of JC, suggesting that less voids and smaller grain size of the Mg1.05B2 core lead to better grain connectivity and stronger flux pinning.     

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.     

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.     

Effect of the contact distance on transport properties of an orsanic molecular device

Using a spatially symmetric phenyldithiolate molecule sandwiched between two gold electrodes as model system and through shifting one electrode from symmetric contact site to form asymmetric contact, we investigated the properties of electronic transport in such a device by the first-principles. It was found that the/（G ）-V characteristics of a device show significant asymmetry and the magnitudes of current and conductance depend remarkably on the variation of molecule-metal distance at one of the two contacts. Namely, an asymmetric contact would lead to the weak rectifying effects on the current-voltage characteristics of a molecular device. The analysis shows that the HOMO is responsible for the resonant tunneling and its shift due to the charging of the device while the bias voltage is the intrinsic origin of asymmetric/（G）- Vcharacteristics.     

Experimental investigation of incremental reactivity of di-tert-butyl peroxide

Large quantities of di-tert-butyl peroxide (DTBP) have been emitted into the troposphere due to human activities. Its role in the atmospheric photochemical reaction has not been understood. This study presents the results of the photochemical reactions of DTBP and NOx, which have been simulated in a self-made smog chamber under the temperature of (29±1)℃. Both the wall decays of ozone and NO2 could be neglected, compared to the results in simulative experiments. The effective intensity of UV light used in the experiments was 1.28×10-3 s-1, which was expressed by the rate constant of NO2 photolysis in purified air. The reaction mechanism was proposed according to our results and reports of other researchers. The maximum values of incremental reactivity (IR) in the three simulative ex- periments were 9.53×10-2, 5.23×10-2 and 3.78×10-2, respectively. The incremental reactivity decreased with the increase of initial concentrations of DTBP. The IR value of DTBP obtained in this study was comparable to that of acetylene reported in our previous research.     

Comparison of the carbon isotope composition of total organic carbon and long-chain <Emphasis Type="Italic">n</Emphasis>-alkanes from surface soils in eastern China and their significance

Surface soil samples collected over a high spatial resolution in eastern China were analyzed for carbon isotope composition （δ^13C） of total organic carbon （TOC） and higher plant-derived long-chain n-alkanes, with the latter reported as weighted mean values. The two sets of δ^13C values are significantly correlated and show similar trends in spatial variation. The spatial distribution of δ^13C shows less negative values in the mid-latitudes between 31°N and 40°N and more negative ones at higher and lower latitudes. This is consistent with previously reported carbon isotope data from surface soil phytoliths in the same region and suggests that the mid-latitude area provides relatively favorable growing condi- tions for C4 plants. Furthermore, δ^13C values of both TOC and long-chain n-alkanes from 12 surface soil samples collected from a small grassland in north China displayed similar carbon isotope values and the difference between paired δ^13C of a soil samples remains relatively constant. Our data demonstrate that in eastern China, soil δ^13C composition of both TOC and long-chain n-alkanes is effective indicators of C3/C4 ratios of the prevailing vegetation. This work suggests that -22‰ and -32‰ are good es- timated end members for the weighted mean δ^13C values of long-chain n-alkanes （C27, C29 and C31 n-alkanes） from soils under dominant C4 or C3 vegetation, allowing us to reconstruct paleovegetation trends.     

Styrene polymerization catalyzed by nickel complexes bearing hydroxyindanone-iminate ligands

Activated by methylaluminoxane, mononuclear bis（hydroxyindanone-iminate）nickel complexes Ni[ArN=CC2H3（CH3）C6H2（R）O]2 （Ar = 2,6-i-Pr2C6H3, R=Me（1）, R=CI（2）, and R=H（3）） showed good activity for the styrene polymerization. The effect of many reaction parameters including the AI/Ni ratio, temperature, and reaction time on catalytic activities of catalytic systems and the molecular weights of the obrained polystyrene was ascertained. The highest activity of 1.34×10^5g（PS）·mol^-1（Ni）·h^-1 was obtained under the optimum reaction condition. The ^13C NMR spectra of the polymers revealed that the polymer was isotactic-rich atactic polystyrene. And the coordination mechanism was confirmed by the analyses of the polymer chain end-groups.     

The uptake of ethyl iodide on black carbon surface

The importance of the iodine chemistry in the atmosphere has been demonstrated by recent obserations. The uptake of ethyl iodine on black carbon surface was inestigated at 298 K for the first time. Degussa FW2 （an amorphous black carbon comprising medium oxides） was used as black carbon sample. Black carbon surface was found to be deactiated in reaction with C2H51, and the uptake coefficient （r） was dependent on the time of exposure. The alue of （2.3±0.9）×10^-2 was determined for the initial uptake coefficient （No）. The result suggests that the heterogeneous loss of C2H51 on carbonaceous aerosols may be important under the atmospheric conditions.     

Fluorescence and sensitization performance of phenylene-vinylene-substituted polythiophene

A new kind of polythiophene derivative, Poly(3-{2-[4-(2-ethylhexyloxy)-phenyl]-vinyl}-2,2′-bithiophene) (PTh), was applied in dye-sensitized solar cell to extend the light response of nanocrystalline TiO2 electrode. UV-vis absorption and fluorescence spectra were employed to investigate the interaction of PTh with nanocrystalline TiO2. The absorption coefficient of the PTh was high in visible part of spec- trum, and the fluorescence emission of the PTh can be efficiently quenched by TiO2 nanoparticles ow- i...     

Combining docking and comparative molecular similarity indices analysis （COMSIA） to predict estrogen activity and probe molecular mechanisms of estrogen activity for estrogen compounds

Estrogen compounds are suspected of disrupting endocrine functions by mimicking natural hormones, and such compounds may pose a serious threat to the health of humans and wildlife. Close attention has been paid to the prediction and molecular mechanisms of estrogen activity for estrogen com- pounds. In this article, estrogen receptor a subtype （ERa） -based comparative molecular similarity indices analysis （COMSIA） was performed on 44 estrogen compounds with structural diversity to find out the structural relationship with the activity and to predict the activity. The model with the significant correlation and the best predictive power （R^2= 0.965, Q^2 LOO： 0.599, R^2 pred ： 0.825） was achieved. The COMSIA and docking results revealed the structural features for estrogen activity and key amino acid residues in binding pocket, and provided an insight into the interaction between the ligands and these amino acid residues.     

Vp of muscovite-biotite gneiss up to 950℃ at 400 MPa: Constraints on the origin of abnormal seismic layers in continental crust

Here we present experimental results of compressional wave velocity (Vp) of muscovite-biotite gneiss from Higher Himalayan Crystallines (HHC) at the temperature up to 950℃ and the pressure of 0.1―400 MPa. At 400 MPa, when the temperature is lower than 600℃, Vp decreases linearly with increasing temperature at the rate of (Vp/T)p -4.43×10-4 km/s ℃. In the temperature range of 600―800℃, Vp drops significantly and the signal is degraded gradually due to the dehydration of muscovite and α-quartz softening. When the temperature rises from 800℃ to 875℃, Vp increases and the signals become clear again as a result of the temperature going through the β-quartz range. The experiments indicate that the duration has great influence on the experimental results when temperature is above the dehydration point of biotite. During the first 30 h at 950℃, the Vp decreases substantially from 5.9 to 5.4 km/s and the signal amplitude is attenuated by more than 80%. After the 30-h transition, the Vp and the amplitude of ultrasonic wave signals become steady. The decrease of Vp and attenuation of the signals at 950℃ are associated with the breakdown reactions of biotite. The experiments suggest that the breakdown of muscovite and/or quartz softening can contribute to the low seismic wave velocity in thickened quartz-rich felsic-crust such as what is beneath southern Tibet. Additionally, α-β quartz transition generates a measurable high seismic velocity zone, which provides a possibility of precisely constraining the temperature in the upper-middle continental crust. Our study also demonstrates that duration is a key factor to obtain credible experimental results.     

Investigation on the key factors in the hydrothermal synthesis of BN： The way of introducing sodium azide

The way of introducing sodium azide (NaN_3) into the reaction solution played an important role in the preparation of cBN by hydrothermal synthesis method. The results showed that both cBN content and crystalline perfection of the samples improved with increasing R_N value, and pure cBN could be obtained at 300℃ and 10 MPa when R_N increased to 3:1. Here R_N is defined as R_N =NaN_3(I)/NaN_3(II), wherNaN_3(I) denotes the amount of NaN_3 (in molar) that is added into the autoclave at the beginning of threaction process, and NaN_3(II) is the amount of NaN_3 (also in molar) introduced into the autoclave ahigh temperature and high pressure (i.e. 300℃ and 10 MPa). In order to explain the experimental results, a preliminary model was proposed in this paper.     

Microplate chemiluminescence enzyme immunoassay for the quantitative evaluation of carbohydrate antigen 72-4 in human serum

A highly sensitive and specific microplate chemiluminescence enzyme immunoassay （CLEIA） was developed for the quantitative evaluation of carbohydrate antigen 72-4 （CA72-4） in human serum, using luminol-H2O2 catalyzed by horseradish peroxidase （HRP） as the chemiluminescence system. The simple and quick determination was accomplished through a sandwich reaction mode. Several physicochemical parameters of the immunoreaction, including incubation conditions, antibody coating conditions, dilution ratio of anti-CA72-4-HRP conjugate, and chemiluminescence reaction time, were studied and optimized. The proposed method exhibited a linear range of 0-200 U/mL with correlation coefficient and detection limit of 0.9995 and 0.18 U/mL, respectively. The inter-assay and intra-assay coefficients of variation （CV） were both less than 10%. The average recovery of two clinical sera with low and high concentration CA72-4 was 99.3% and 98.7%, respectively. Normal tumor markers, including AFP, CEA, CA24-2, CA19-9 and CA15-3, did not cross-react with each other. The method＇s stability was evaluated by assessing its analytical performance after storing the immunoreagents at 4℃ and 37℃ for 7 days. Little difference was found, indicating satisfactory stability of the method. The present method has been successfully applied to the detection of CA72-4 human serum, and showed a good correlation with the commercially available ELISA kit （r^2=0.9383）. This method showed great potential in the fabrication of diagnostic kit for CA72-4, and could be well used in diagnosis of cancer in clinical practice.     

Synthesis and pervaporation performance of high-reproducibility silicalite-1 membranes

High-reproducibility silicalite-1 membranes were synthesized on silica tubes by in-situ hydrothermal synthesis, and the relative standard deviation （R.S.D.） of average separation factor for eight membranes was only 7.5%. By using an effective method called ＂solution-filling （SF）＂, the average flux of membranes prepared with SF method was improved by about 49% compared to membranes prepared without SF method, and the highest flux of membrane prepared with SF method towards ethanol/H2O mixture at 80℃ was 1.49 kg/（m^2·h）. Pervaporation experiments showed that the fluxes of silicalite-1 membranes at 60℃ were 2.63, 0.87, 0.24, and 0.20 kg/（m^2·h） towards methanol/H2O, ethanol/H=O, 2-propanol/H2O, and 1-propanol/H2O mixtures, respectively, and the corresponding separation factors were 22, 69, 81, and 159, respectively.     

He-Ar isotopic system of fluid inclusions in pyrite from the molybdenum deposits in south margin of North China Block and its trace to metallogenetic and geodynamic background

The helium and argon isotopic compositions of the ore-forming fluids from the molybdenum deposits such as Jinduicheng, Donggou, Shijiawan, and Sandaozhuang, which are located in the East Qinling molybdenum belt in south margin of North China Block （SMCNB）, are reported in this paper. The origin and the evolution of the ore-forming fluids and their coupled-relationships with the intra-continental collision and orogenic process of Qinling Orogen in Mesozoic-Cenozoic have been discussed. The 3He/4He and 40Ar/36Ar values （3He/4He=1.38-3.64 Ra, and 40Ar/36Ar=295.68-346.39, respectively） of the fluid inclusions in pyrite from the molybdenum deposits in East Qinling suggest that, the ore-forming fluid system is mixed by two end members. One is the high temperature deep-derived fluid congenetic with the porphyries generated by crust-mantle mixing, and the other is the low-temperature meteoric water which is rich in crustal radiogenic He with the component of atmospheric Ar. From the Pb isotopic composition, and ore-bearing potential of the porphyry and the regional stratum, we can conclude that the ore-forming materials of the deposits in the East Qinling molybdenum belt are derived from the deep source by the mixing of lower crust and upper mantle. Therefore, the formation of the molybdenum deposits in SMNCB can be related to the crust-mantle interaction, which is accompanied by the intra-continental orogenic and extension process in the post-collision period of Qinling Orogen. The granitic porphyries which are related to Mo mineralization are not simple crust-remelting type granites or S type granites, but belong to syntexis-type or mantle-derived granites, hence their formation has a profound and regional geodynamic background.     

Pollen assemblage characteristics of lakes in the monsoon fringe area of China

This paper presents the pollen assemblages from 108 surface sediment samples from 4 lakes （the Lake Daihai, Lake Hongjiannao, Lake Hulunnao and Lake Duikounao） in the monsoon fringe area of China. The herb pollen taxa Artemisia, Chenopodiaceae, Poaceae and Compositae are the major components of pollen assemblages of the 4 lakes and Pinus, Betula, Quercus, Ulmus, Populus, Ostryopsis and Elaeagnaceae are frequently presented, which reflect regional and local vegetation well. The mean similarity coefficients for samples from the Lake Daihai, Lake Hongjiannao, Lake Hulunnao and Lake Duikounao are 0.66±0.17, 0.71±0.11,0.73±0.12 and 0.67±0.12 respectively, so pollen assemblages are relatively consistent in each lake, which shows that focusing and mixing effects have occurred before and after pollen deposition. However, pollen assemblages do differ between sampling sites in each lake. The largest difference is seen in the Lake Daihai, followed by the Lake Duikounao, Lake Hulunnao and Lake Hongjiannao （The mean Euclidean distance is 20.09 ± 11.11, 11.22 ± 3.64, 10.67 ± 4.03 and 8.44 ± 4.51 respectively）. These differences are possibly caused by the differences of focusing and mixing effects, pollen source areas, drainage areas and regional vegetation compositions. The Lake Daihai and Lake Hongjiannao have water deeper than 5 m and strong re-suspension, focusing and mixing effects occur in the lakeshore and shallow water areas, where pollen concentrations are lower than in deeper lake areas. In the Lake Hulunnao and Lake Duikounao, with depths less than 5 m, re-suspension and mixing effects are obvious across the whole lake area, so pollen assemblages and pollen concentrations are more consistent among sampling sites in each lake. Comparison between the lake samples and samples from the inflowing river reveals that wind is primary pollen transportation force in the Lake Hongjiannao, where the consistency of pollen assemblage is conspicuous, while there is greater variation in lakes where pollen input is do     

Pollen flux and vertical dispersion in coniferous and deciduous broadleaved mixed forest in the Changbai Mountains

The pollen flux in coniferous and deciduous broadleaved mixed forest in the Changbai Mountains is presented in one year's experiments. The results indicate that arboreal pollen percentages are more than 65% and pollen flux is higher than 5000 grain·cm-2·a-1,while less than 2% and lower than 1000 grain·cm-2·a-1 for shrubby pollen,and less than 20% and lower than 3000 grain·cm-1·a-1 for herbaceous pollen for most samples at different heights. The pollen assemblages are similar to those in the samples under 8 m height where Pinus and Ouercus are dominant and followed by the few non-local pollen types,and Fraxinus percentages are high with a few non-local pollen types at 16 m to 32 m height as well as non-local pollen clearly increased at 40 m height. Comparisons between pollen assemblages and vegetation composition suggest that similarities are higher for pollen trap samples than for surface moss samples.     

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.