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.     

Estimate of carbonate production by scleractinian corals at Luhuitou fringing reef, Sanya, China

Carbonate production by scleractinian corals not only maintains coral reef growth, but also represents an important source of atmospheric carbon dioxide. In this paper the carbonate production by scler-actinian corals at Luhuitou fringing reef, Sanya, Hainan Island, China, is investigated with an ecological census-based method. Averaged carbonate production is 1.16 ± 0.55 kg·m-2·a-1 and 3.52 ± 1.32 kg·m-2·a-1 on the reef flat and reef slope, respectively, depending on the composition and distribution of cor...     

Hydrogen isotopic compositions and their environmental significance for individual n-alkanes in typical plants from land in China

Hydrogen isotopes of n-alkanes in grasses, tree leaves and reeds from six regions with latitudes of 20° to 39°N in China are measured by GC-TC-IRMS analytical technique in order to understand their hydrogen isotopic compositions and environmental significance. The results show that a difference in ° D values (from −42.1‰ to −66.6‰) of n-alkanes exists among the same kinds of plants from various regions. Hydrogen isotopic compositions of most even carbon numbered n-alkanes in every plant are slightly heavier than that of the odd homologues. A trend toward D-enrichment with increasing chain length of n-alkanes in most plant samples is observed. Mean ° D values of n-alkanes in the studied plants range from −202.6‰ to −130.7‰ and the reed from a salt marsh has the largest value. The mean ° D values of individual n-alkanes among the same kinds of plants from various regions have the characteristics of leaf > reed > grass. The hydrogen isotopic compositions of n-alkanes are apparently distinct among various kinds of plants from the same region and the mean ° D values exhibit a distribution of tree leaf > reed > grass. It is observed that the mean ° D values of n-alkanes and ° D values of C₂₇ and C₂₉ n-alkanes in the grasses and tree leaves from these studied regions correlate clearly negatively with latitude and positively with temperature, indicating that these values can be used as excellent indicators of environment and climate. These results provide important basic data for understanding the distributional law of hydrogen isotopes of individual n-alkanes and their applied research. Supported by National Natural Science Foundation of China (Grant Nos. 40642007 and 40772069), National Basic Research Program of China (Grant No. 2005CB422105) and Special Project for Winners of CAS President Award     

Interdecadal shift in the western North Pacific Summer SST anomaly in the late 1980s

An interdecadal shift in summer (June―August) sea surface temperature (SST) variations during the period of 1968―2002 was identified in the late 1980s, which is characterized by a phase alternating from negative to positive phases of the leading mode of the empirical orthogonal function (EOF) analysis of the summer monthly mean SST in the Pacific domain 100°―180°E and 0°―40°N, accounting for 30.5% of the total variance. During the period of 1968―1987, the leading mode with a mean negative phase state (mean standard deviation = ?0.586) controlled SST variability in the western North Pacific. Correspondingly, negative SST anomalies occupied the western North Pacific south of Japan and Chinese marginal seas. During the period of 1988―2002, the leading mode shifted to its strong positive polarity (mean standard deviation = 0.781), thus positive SST anomalies appeared in the western North Pacific. Accompanied by the interdecadal shift in summer mean SST, summer mean rainfall increased in southern and southeastern China during the late period, particularly in southeastern China where increase in summer mean rainfall exceeded 40 mm, at the 0.05 significance level.     

One-step and high-density protein immobilization on epoxysilane-modified silica nanoparticles

Silica nanoparticles are most commonly modified with amino-silanes, followed by post-modification activation for protein immobilization. In this work, epoxy-functionalized silica nanoparticles were prepared by modification with glycidyloxypropyl trimethoxysilane （GPTMS） for direct protein immobilization. Silica nanoparticles possessed an average size of 46 nm, but increased to 63 nm after GPTMS modification. Reaction time, reaction temperature and GPTMS content had no significant effect on par- ticle size. Zeta potential of SiO2 changed from -26mV to ＋38mV after modification. Fourier-transformed infrared spectroscopy revealed alkyl C--H bending and stretching bands at 2944 cm-1, 1343 cm-1 and 1465 cm-1, respectively, for the modified nanoparticles. Fluorescein cadaverine was found to bind to GPTMS-modified SiO2, but not to bare SiO2, indicating the chemical reactivity of epoxy groups on the modified nanoparticle with amines. Finally, fluorescenUy labeled bovine serum albumin （BSA） was used as a model protein to investigate the capacity of epoxy-SiO2 nanoparticles for protein immobilization. The results showed that more proteins were immobilized on the particle with longer reaction time, higher NaCI concentration, lower pH, and less GPTMS content. More importantly, proteins bound to epoxy-SiO2 nanoparticle were highly stable. Under optimized reaction conditions, as much as 25 mg BSA/g nanoparticle was covalentiy attached to the nanoparticle. The epoxy silane modification of silica nanoparticles offers a reactive surface for one-step and high-density protein immobilization.     

Estimation of soil respiration in a paddy ecosystem in the subtropical resion of China

Water vapor, energy exchange, and CO2 flux were measured continuously from 2003 to 2005 using the eddy covariance technique in a paddy ecosystem in the subtropical region of China. The CO2 fluxes at nighttime during fallow periods （from middle October to late April） were used to analyze the dynamics of soil respiration and its relationship with soil temperature, and to simulate the annual dynamics of soil respiration in paddy ecosystems. The variation of soil respiration showed a clear seasonal pattern. The soil respiration rates at night during the fallow periods were 52--398 mg· m^-2· h^-1, and exponentially correlated （P〈0.001） with soil temperatures at different depths of soil （5, 10, and 20 cm）, particularly the temperature measured at a depth of 5 cm. Based on the simulated exponential equations developed, annual average soil respiration rates and total soil respiration of paddy soil in the subtropical region of China were estimated to be 178.5--259.9 mg· m^-2· h^-1 and 1.56--2.28 kg· m^-2· a^-1, respectively. The simulation equations can be applied to evaluating soil respiration in paddy ecosystems during the rice-growing season.     

Photovoltaic properties of MEH-PPV/TiO2 nanocomposites

Photovoltaic properties of photodiodes based on nano-TiO2 and poly[2-methoxy,5-（2＇-ethlhexyloxy）-p-phenylenevinylene] （MEH-PPV） composites are investigated. By comparing composite devices with the same weight of TiO2 （nanoparticles and nanotubes）：MEH-PPV, it was found that the device with TiO2 nanotubes exhibited better performance. By further optimizing the weight radio of TiO2 nanotubes： MEH-PPV, we gained the device with a short circuit current density of 9.27μA/cm^2 with a light intensity of 16.7mW/cm^2 at the 500 nm wavelength, the highest open-circuit voltage of 1.1V, and a photosensitivity of 332 at reverse bias of -0.6V. The photosensitivity is improved by a factor of 33 compared with the undoped MEH-PPV device.     

Superconductivity in Ba1−xSmxFFeAs and Eu1−xSmxFFeAs systems

We synthesized the samples Ba1-xSmxFFeAs and Eu1-xSmxFFeAs with ZrCuSiAs-type structure. These samples were characterized by resistivity and susceptibility. It is found that the substitution of rare earth metal for alkaline earth metal in the two systems suppresses the anomaly in resistivity and induces superconductivity. Superconductivity at 54 K in nominal composition Ba0.5Sm0.5FFeAs and at 51 K for Eu0.5Sm0.5FFeAs is realized, indicating that the superconducting transition temperatures in the iron arsenide fluorides is the same as that in oxypnictides with the same structure.     

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.     

Crystal structures of catalytic and regulatory subunits of rat protein kinase CK2

Protein kinase CK2 consists of two catalytic subunits (CK2α) and two regulatory subunits (CK2β). Here, we report the crystal structures of rat CK2α mutant (rCK2α-△C, 1—335) and CK2β (rCK2β). The overall topology of rCK2α-△C and rCK2β are very similar to the human enzyme, although large structural differences could be observed in the N-terminal domain of rCK2α-△C. Our reported structure of rCK2α-△C is in the close conformation state while the counterpart hCK2α is in the open conformation state, indi- cating ...     

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.     

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.     

Carbonaceous particles in Muztagh Ata ice core,West Kunlun Mountains,China

Carbonaceous particles concentrations of OC and EC are determined using a two-step gas chroma- tography system in Muztagh Ata ice core covering the time period of 1955--2000. Over the period represented by the core, OC and EC concentrations appear to have changed significantly, varied in the range of 17.7--216.7 and 6.5--124.6, and averaged 61.8, 32.9 ng·g^-1, respectively. The average concentration of EC in Muztagh Ata ice core is much lower than that in an Alpine ice core record （100--300 ng·g^-1） during the same period, but it is a factor of 14 in Greenland ice core （2.3 ng·g^-1）, this may induce a strong impact on the snow albedo in the last 46 years in our study area. Observations indicate two periods with obviously high deposition concentrations （1955--1965 and 1974--1989） and two periods with low concentrations （1966--1973 and 1990--1995）, as well as a recent increasing trend. By comparing EC and SO4^2- concentration variations and deciphering OC/EC ratios recorded in the same ice core, we can judge roughly that the carbonaceous particles deposited in Muztagh Ata ice core were attributed to fossil fuel combustion sources.     

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.     

An experimental study of tin partition between melt and aqueous fluid in F/Cl-coexisting magma

In order to investigate the formation mechanism of tin ores associated with F-bearing granite, an ex-perimental study of tin partition between F-bearing granitic melt and coexisting HCl-bearing aqueous fluid was conducted at 850℃ and 100MPa with fo2 approaching NNO. Geochemical behavior of tin was traced by changes in starting solid materials with different alumina saturation index ASI, in F content and in starting fluids of various HCl concentrations. The results show that DSn increases with ASI of melt and peraluminous melt is favorable for tin partition into aqueous fluid in the F/Cl-coexisting sys-tem. Aqueous fluid of higher HCl concentrations is advantageous for enrichment of tin. Furthermore, chlorine contents in glass run products correlate positively with F and Cl contents in the magma. In the F/Cl-coexisting system, granitic melts with high F contents (> ~1 wt%) could extract and enrich tin in the melt which can serve as a reservoir for the formation of tin ores. However, the partition coefficient of tin would increase significantly when F contents in the melt were below 1 wt%. Therefore, the de-crease of F contents is favorable to the partition of tin into aqueous fluid with high HCl contents, thus promoting deposition of hydrothermal tin ores.     

Novel azobenzene-phthalocyanine dyads―― design of photo-modulated J-aggregation

Based on the J-aggregation mechanism of α-aryl/alkoxy-substituted zinc phthalocyanines(Pcs) in non-coordinating solvents, two novel azobenzene-phthalocyanine dyads (3-azo-ZnPc and 4-azo-ZnPc) were synthesized with the aim of developing Pc compounds whose ability to form J-aggregation could be photo-modulated. It was found that 3-azo-ZnPc in chloroform could be effectively photo-controlled in a wide range. This phenomenon could be explained by the changes in the geometry and dipole moment of azobenzene during the photo-isomerization process. 4-azo-ZnPc did not have this ability at all, with or without UV light illumination. The positions of the oxygen atoms to which the aryl/alkoxy substitution was attached relatively were found important in determining the aggregation ability. Supported by the National Natural Science Foundation of China (Grant Nos. 20572059, 20502013 and 20773077), National Key Fundamental Research Program (Grant No. 2007CB808000)     

Temperature-sensitive gold-nanotube array membranes modified with poly（N-isopropylacrylamide）

A kind of temperature-sensitive nanotube array membrane was developed by modifying gold-nanotube array membranes with poly（N-isopropylacrylamide） （PNIPAm）. The permeation ability of the mem-branes at different temperatures was investigated using sodium fluorescein and quantum dots as probes. The results showed that the pore diameter of nanotube was changed due to the reversible response of PNIPAm-modified membranes to temperature, and then the permeation ability of the mem-branes was changed. The permeation of fluorescence probes was slow and even almost blocked at 25℃ （below the lower critical solution temperature, LCST）, since PNIPAm formed expanded structures and decreased the pore size. While at 40℃ （above the LCST）, the permeation was increased, since PNIPAm became compact structures and the pore diameter was increased. Furthermore, the permeation ability of the temperature-sensitive nanotube array membranes could be adjusted reversibly and it is possible to use the membranes in nanofluidic devices, nanogates, etc.     

Recent temperature increase recorded in an ice core in the source region of Yangtze River

Interests on climate change in the source region of Yangtze River have been raised since it is a region with the greatest warming over the Tibetan Plateau (TP). A 70-year history of precipitation δ~(18)O has been recovered using an ice core record retrieved in a plat portion of the firn area in the Guoqu Glacier (33°34′37.8″N, 91°10′35.3″E, 5720 m a.s.l.), Mt. Geladaindong (the source region of Yangtze River), in November, 2005. By using a significant positive relationship between ice core δ~(18)O record and summer air temperature (July to September) from the nearby meteorological stations, a history of summer air temperature has been reconstructed for the last 70 years. Summer temperature was relatively low in 1940s and high in 1950s to the middle of 1960s. The lowest temperature occurred in the middle of 1970s. Temperature was low in 1980s and dramatically increased since 1990s, keeping the trend to the begin-ning of the 21st century. The warming rate recorded in the ice core with 0.5℃/10 a since 1970s is much higher that that in the central TP and the Northern Hemisphere (NH), and it becomes 1.1℃/10 a since 1990s which is also higher than these from the central TP and the NH, reflecting an accelerated warm-ing and a more sensitive response to global warming in the high elevation region.     

The program structure designing and optimizing tests of GRAPES physics

According to the modularization and standardization of program structure in Global/Regional Assimilation and Prediction System （GRAPES）, the plug-compatible and transplantable regional meso-scale and global middle-range physics software package is established. The package＇s component integrality is comparative with the other advanced models physics. A three-level structure of connecting GRAPES physics and dynamic frame has been constructed. The friendly interface is designed for users to plug in their own physics packages. Phenomenon of grid-point storm rainfall in numerical prediction is analyzed with the numerical tests. The scheme of air vertical velocity calculation is improved. Opti- mizing tests of physics schemes are performed with the correlative parameters adjusting. The results show that the false grid-point storm rainfall is removed by precipitation scheme improving. Then the score of precipitation forecast is enhanced.     

Micelles-template induced organic nanocrystals based on iodo…nitro interactions

The nanocrystals based on a polar organic compound INBP （4-iodo-4＇-nitrobiphenyl） have been fabricated by reprecipitation approach. For the formation of INBP based nanocrystals, the intermolecular iodo…nitro interaction is the dominant driving force and the micelles formed by the surfactant CTAB （cetyltrimethylammonium bromide） molecules are the efficient templates for controlling morphologies of nanocrystals. The field emission scanning electro microscope （FESEM） images demonstrated that prism-like and needle-like nanocrystals of INBP were formed in pure water and micell containing aqueous solution, respectively. XRD pattern and UV/vis absorption spectra were employed to characterize the nanocrystals.