200AGeV硫核及其重碎片与铜核作用的电荷改变总截面的测量

测量了200AGeV的^(32)S及其碎片P,si,Al,Mg,Na和Ne与Cu靶作用的电荷改变总截面。观察到次级碎片的电荷改变总截面比相同电荷的初级粒子的要高。导出的电磁散裂截面与弹丸电荷的平方成比例,与理论预言一致。

链状三核钼(钨)硫原子簇化合物[M_3O_2S_8]^(2-)的合成、光谱和晶体结构

本文以[NH_4]_2MO_nS_(4-n)(M=Mo、W,n=0-2)为原料,在酸性和中性条件下,合成出九个新的三核不对称钼硫和钨硫原子簇状化合物L_2[M_3O_2S_8][L=(n-Bu)_4N、Ph_4P、PyC_(16)H_(33)、(CH_3)_3NC_(16)H_(33)、Et_4N]。用元素分析、红外光谱、紫外光谱对簇合物进行了表征,并测定了其中 [(n-Bu)_4N]_2[Mo_3O_2S_8](1)和[(n-Bu)_4N]_2[W_3O_2S_8](5)两个簇合物的晶体结构,簇合物1和5均属单斜晶系,P2_1/c空间群,簇合物1的晶胞参数:a=15.910(2),b=15.411(1),c=20.407(5)A,β=103.40°(1),V=4867.5A^3,Z=4,最终偏离因子R=0.060。簇合物5的晶胞参数。a=15.896(4),b=15.674(2),c=20.409(9)A,β=103.43°(3),V=4946.5A^3,Z=4,最终偏离因子为R=0.051。本文又一次验证了钼(钨)硫成簇反应是分子内部电子转移反应,并提出了可能的成簇反应历程。

系列三核钼硫簇合物的合成、结构表征和性质研究

系统地报道了9个三核钼硫簇合物的合成和结构表征.晶体结构分析表明,其中化合物1和6具有[Mo3(μ3-S)(μ-S)3]簇芯,化合物2和3具有不对称的簇芯[Mo3(μ3-S)(μ-O)(μ-S)2],化合物4,5,7和8具有少见的[Mo3(μ3-O)(μ-S)3]簇芯,而化合物9则具有[Mo3(μ3-S)(μ-S2)3]簇芯.这一系列不同的簇芯以及桥配体和“松散”配位的端配体造成了不同的堆积结构.讨论了前三种簇芯的电子结构,并根据它们的立体构型和电子结构对某些重要的谱学表征结果做了合理的诠释.测定了化合物4的变温电导率,表明其具有半导体导电性能.

核/壳结构聚合物改性硬质聚氯乙烯的力学性能

采用种子乳液聚合制备了丙烯酸酯核/壳结构聚合物,总转化率超过95%,乳胶粒理论粒径与实测值基本一致,说明聚合体系没有明显的二次成核过程。将其用于硬质聚氯乙烯改性,当加入量为3phr时,就能产生显著的增韧效果,常温缺口冲击强度达到16.51 kJ/cm2,而拉伸强度基本保持不变。扫描电镜分析冲击断口表明,核/壳聚合物已经很好分散到聚氯乙烯基体中,呈网状结构,为明显的韧性断裂过程。该研究有望应用于工业生产。

新颖五核Mo/Cu/S簇合物[MoOS_3Cu_4(α-MePy)_6Br_2]的合成及晶体结构

Reaction of(NH 4) 2MoOS 3 with CuBr and AgBr(molar ratio=1∶4∶1) in α-MePy produced dark red crystals of [MoOS 3Cu 4(α-MePy) 6Br 2]. The product was characterized by elemental analysis, IR and X-ray diffraction. It crystallizes in a triclinic system with space group P1 and unit cell parameters a=0.950 9(3) nm, b=1.066 8(2) nm, c=2.153 6(3) nm, α=94.846(9)°, β=92.054(7)°, γ=99.299(8)°, V=2.145 5(8) nm 3, Z=2, D c=1.828 g·cm -3, F(000)=1 168, μ=42.79 cm -1, R=0.049 and R w=0.051. The compound consists of a nido-shaped MoS 3Cu 3 cluster unit and a four-membered CuBrCuS ring by sharing the same Cu3—S3 bond. The Mo atom and the four Cu atoms adopt a distorted tetrahedral geometry coordination. The Mo…Cu1, Mo…Cu2 and Mo…Cu3 distances are 0.271 1(3), 0 269 8(2), and 0.268 1(1) nm, respectively.

Kinetic model for calcium sulfate decomposition at high temperature

A modified shrinking unreacted-core model,based on thermogravimetric analysis,was developed to investigate CaSO4 decomposition in oxy-fuel combustion,especially under isothermal condition which is difficult to achieve in actual experiments due to high-temperature corrosion.A method was proposed to calculate the reaction rate constant for CaSO4 decomposition.Meanwhile,the diffusion of SO2 and O2,and the sintering of CaO were fully considered during the development of model.The results indicate that the model can precisely predict the decomposition of CaSO4 under high SO2 concentration（1100×10-6）.Concentrations of SO2 and O2 on the unreacted-core surface were found to increase first and then decrease with increasing temperature,and the average specific surface area and porosity of each CaO sintering layer decreased with increasing time.The increase of SO2 and/or O2 concentration inhibited CaSO4 decomposition.Moreover,the kinetics of CaSO4 decomposition had obvious dependence on temperature and the decomposition rate can be dramatically accelerated with increasing temperature.

Leaching kinetics of low-grade copper ore containing calcium-magnesium carbonate in ammonia-ammonium sulfate solution with persulfate

The leaching kinetics of copper from low-grade copper ore was investigated in ammonia-ammonium sulfate solution with sodium persulfate. The effect parameters of stirring speed, temperature, particle size, concentrations of ammonia, ammonium sulfate and sodium persulfate were determined. The results show that the leaching rate is nearly independent of agitation above 300 r/min and increases with the increase of temperature, concentrations of ammonia, ammonium sulfate and sodium persulfate. The EDS analysis and phase quantitative analysis of the residues indicate that bornite can be dissolved by persulfate oxidization. The leaching kinetics with activation energy of 22.91 kJ/mol was analyzed by using a new shrinking core model （SCM） in which both the interfacial transfer and diffusion across the product layer affect the leaching rate. A semi-empirical rate equation was obtained to describe the leaching process and the empirical reaction orders with respect to the concentrations of ammonia, ammonium sulfate and sodium persulfate are 0.5, 1.2 and 0.5, respectively.

Investigation of the binding behavior of human serum albumin and phosphorothioate oligodeoxynucleotide

Aim To study the binding behavior between human serum albumin （HSA） and phosphorothioate oligodeoxynucleotide （PS- ODN） and the effects of bivalent cations on the interaction. Methods Surface plasma resonance, circular dichroism and fluorescence experiments were conducted. Results （ 1 ） the binding ability was decreased along with the increase of pH; （2） Zn^2＋and Ni^2＋ enhanced the interaction between PS-ODN and HSA; （3） Upon PS-ODN binding, the conformation of HSA was changed with an increase of β - sheet. Conclusion The results provide experimental evidences to the hypothesis that PS-ODN binds with HSA in the positive potential region, and histidine residues located in the region play a crucial rule in the interaction.

Effect of temperature on copper corrosion in high-level nuclear waste environment

The effect of temperature on the corrosion behavior of copper in simulated high-level nuclear waste environment wassystematically studied.Electrochemical methods,including electrochemical impendence spectra,Mott–Schottky technology,cyclicpolarization,and potentiostatic polarization,were employed to characterize the corrosion behavior of copper at different temperatures.Stereoscopic microscopy and scanning electron microscopy were used to examine the surface morphology,and X-ray photoelectronspectroscopy analysis was used to identify the composition of the passive film.The experimental results show that corrosionresistance of the passive film does not blindly decrease with the increase of temperature but increases at60°C owing to a compactouter layer;there is a potential for pitting corrosion,which decreases as the temperature increases.The main product of copper in ananaerobic aqueous sulfide solution is Cu2S but the content of CuS increases at higher temperatures.The whole passivation rangeshows p-type semiconductor characteristics and the magnitude of the acceptor density is1023cm-3,which increases with increasingtemperature.

Isolation and characterization of organic-sulfur degradation bacterial strain

A bacterial strain that was capable of degrading organic sulfur (dibenzothiophene) was isolated by enrichment techniques from the petroleum-contaminated soil collected from Zhongyuan Oil Field. The strain is named ZYX and is gram-positive. This strain undergoes bacilus-coccus morphological change, and forms yellow-pigment glossy circular colonies with 1.5 mm in diameter on average after 2 d incubation on Luria-Bertani(LB) plates. The full-length of 16S rDNA sequence of strain ZYX was determined and analyzed. Strain ZYX is found most relative with the genus of Arthrobacter. The similarity values between ZYX and Arthrobacter sp. P2 is 99.53%. The main morphological, biochemical and physiological features of strain ZYX accord with those of Arthrobacter. It is found that the optimal initial pH for growth is about 7.0, and the optimal concentration of dibenzothiophene(DBT) for growth is 0. 10 gL. Additionally, the results show that the best carbon source and nitrogen source are glycerol and glutamine, respectively.

几种增感方式的光导对比

硫金增感核是强有力的电子陷阱;还原增感核起到加强原有电子陷阱的作用,具有产生光电子的能力;硫增感核是电子陷阱,但大的硫增感核具有一定空穴陷阱的效果。

Kinetics of Reductive Leaching of Low-grade Pyrolusite with Molasses Alcohol Wastewater in H_2SO_4

The kinetics of reductive leaching of manganese from low grade pyrolusite in dilute sulfuric acid in the presence of molasses alcohol wastewater was investigated. The shrinking core model was applied to quantify the effects of reaction parameters on leaching rate. The leaching rate increases with reaction temperature, concentrations of H 2 SO 4 and organic matter in molasses alcohol wastewater increase and ore particle size decreases. The leaching process follows the kinetics of a shrinking core model and the apparent activation energy is 57.5 kJ·mol –1 . The experimental results indicate a reaction order of 0.52 for H2SO4 concentration and 0.90 for chemical oxygen demand (COD) of molasses alcohol wastewater. It is concluded that the reductive leaching of pyrolusite with molasses alcohol wastewater is controlled by the diffusion through the ash/inert layer composed of the associated minerals.

Optimizing 6-mercaptopurine and azathioprine therapy in the management of inflammatory bowel disease

The thiopurine drugs,6-mercaptopurine(6-MP) and azathioprine,are efficacious in the arsenal of inflammatory bowel disease(IBD) therapy.Previous reports indicate that 6-thioguanine nucleotide(6-TGN) levels correlate with therapeutic efficacy,whereas high 6-methylmercaptopurine(6-MMP) levels are associated with hepatotoxicity and myelotoxicity.Due to their complex metabolism,there is wide individual variation in patient response therein,both in achieving therapeutic drug levels as well as in developing adverse reactions.Several strategies to optimize 6-TGN while minimizing 6-MMP levels have been adopted to administer the thiopurine class of drugs to patients who otherwise would not tolerate these drugs due to side-effects.In this report,we will review different approaches to administer the thiopurine medications,including the administration of 6-mercaptopurine in those unsuccessfully treated with azathioprine;coadministration of thiopurine with allopurinol;co-administration of thiopurine with anti-tumor necrosis factor α;6-TGN administration;desensitization trials;and split dosing of 6-MP.

MULTIPLE CENTER d-β ORBITALS AND CHARGE TRANSFER OF HETERONUCLEAR COUSTERS WITH CUBANE TYPE (Mo_3S_4)_xM^n+ (x=1, 2, M = Cu, W, Ni, Sb. Mo, Sn, Cu_2; n = 4,8)

In this work, with the analysis on MO and electronic structure for a series of heteronuclear cluster with cubane type (Mo4S1 )xMn1(x=1.2. M = Cu, W, Ni, Sb, Mo, Sn, Cu2) we found that it is with the multiple center d-pir orbitals that the ligand Mo3S44+ bonds to the M atom to form these class clusters. It is revealed that the charges transfer from the M atom to Mo atom of the ligand Mo3S44+ and its relationship with the MC (multiple center) d-pπ orbitals. Based on the charge transfer the electronic spectrum and the magnetic property of some cubane clusters have been discussed.

Selective alkylation and bioactivity of phosphorothioated nucleolin aptamer AS1411

An operationally simple and efficient method for the synthesis of a wide range of alkylated nucleotides under mild conditions was developed. This improved method furnishes alkylated nucleotides fi＇om both single nucleotides and oligonucleotides, and were prepared in high yields of 81% to 91%. Alkyl modified aptamer AS1411s were synthesized using this method and the biological activity screening results demonstrated that alkylation at the 1^st P-S site on yielded stronger target protein binding capacity, greater growth suppression effects against K562 and HL-60 cell lines, and improved serum stability, as compared with AS1411. This modified aptamer may be useful in tumor detection and treatment.

Synthesis and antiviral bioactivities of novel chiral bis-thiourea-type derivatives containing α-aminophosphonate moiety

Starting from 1-((1R,2R)-2-aminocyclohexyl)-3-substituted thioureas (3a–c) and substituted isothiocyanates (9a–d),chiral bis-thiourea derivatives containing α-aminophosphonate moiety 10a–l were prepared and completely characterized by elemental analysis,physical and spectral (IR,1H NMR,13C NMR,31P NMR) data.The results of bioassay revealed that compounds 10a and 10e possessed appreciable curative bioactivities on cucumber mosaic virus (CMV) at 0.5 mg/mL in vivo (inhibitory rate = 60.3%,64.8% respectively) and tobacco mosaic virus (TMV) at 0.5 mg/mL in vivo (inhibitory rate = 50.3%,50.8% respectively),which were comparable to the values shown by standard reference (58.7%) and commercial product Ningnanmycin (56.3%),respectively.Chiral compound 10e displayed more potent antiviral activity (EC50 = 0.149 mg/mL) than Ningnanmycin (EC50 = 0.201mg/mL) against CMV.

High-efficiency saturated red emission from binuclear cyclo-metalated platinum complex containing 5-(4-octyloxyphenyl)-1,3,4-oxadiazole-2-thiol ancillary ligand in PLEDs

A novel red-emitting binuclear platinum complex （dfppy）zPtz（C^OXT）z was synthesized and characterized, in which dfppy represents 2-（4＇,6＇-difluorophenyl）pyridinato unit and CsOXT is abbreviated for 5-（4-octyloxyphenyl）-1,3,4-oxadiazole-2-thiol as a bridging ancillary ligand. Its photophysical, electrochemical and electroluminescent characteristics were primarily studied. The made single-emissive-layer （SEL） polymer light-emitting devices using （dfppy）2Ptz（CsOXT）2 as emitter exhibited a satu- rated red emission peaked at 620 nm. The best device performances were obtained in the device at 8 wt% dopant concentration, with a maximum external quantum efficiency of 8.4%, a current efficiency of 4.2 cd/A and brightness of 3228 cd/m~. This work provides an effective approach to obtain high-efficiency red emission through construction of new binuclear platinum complex and its doped SEL devices.

Hydrogen sulfide from a NaHS source attenuates dextran sulfate sodium(DSS)-induced inflammation via inhibiting nuclear factor-κB

This study investigated the alleviating effects of hydrogen sulfide （H2S）, derived from sodium hydrosulfide （NariS）, on inflammation induced by dextran sulfate sodium （DSS） in both in vivo and in vitro models. We found that NariS injection markedly decreased rectal bleeding, diarrhea, and histological injury in DSS-challenged mice. NariS （20 pmol/L） reversed DSS-induced inhibition in cell viability in Caco-2 cells and alleviated pro-inflammation cytokine expression in vivo and in vitro, indicating an anti-inflammatory function for H2S. It was also found that H2S may regulate cytokine expression by inhibiting the nuclear factor-KB （NF-KB） signaling pathway. In conclusion, our results demon- strated that H2S alleviated DSS-induced inflammation in vivo and in vitro and that the signal mechanism might be associated with the NF-KB signaling pathway.

Magnetic particles and cadmium sulfide nanoparticles tagging for signal-amplifying detection of nucleic acids

A versatile DNA recognition system using cadmium sulfide nanoparticles (CdS NPs) as labels was proposed for ultrasensitive detection of specific sequence DNA based on target recycling. This strategy utilized the magnetic particles (MNPs) for the immobilization of linker DNA and CdS NPs and the subsequent target DNA hybridization. Using the unique characteristic of nicking endonuclease for cutting one specific strand of double strand DNA (ds DNA), the linker DNA could be transected and the target DNA could be liberated for re-hybridization and hence the amount of released CdS NPs was enhanced. Due to the advantage of the MNPs and signal amplification from the target recycling, the analyte DNA could be detected by the square-wave stripping voltammetry (SWV) in a wide linear range from 0.4 fM to 100 fM with the detection limit down to 0.08 fM. The proposed DNA detection strategy possesses high sensitivity, satisfactory reproducibility and excellent stability, which might have potential in other DNA biological assays.

Convenient synthesis of nucleoside 5'-(α-P-thio)triphosphates and phosphorothioate nucleic acids(DNA and RNA)

Modified deoxy-and ribo-nucleoside triphosphates are chemically synthesized in multiple steps due to the protection and deprotection of the nucleoside functionalities.To conveniently synthesize the S-modified triphosphates for enzymatically preparing phosphorothioate DNAs and RNAs(PS-DNA and PS-RNA) as potential therapeutics,herein we report a one-pot strategy to synthesize the deoxy-and ribo-nucleoside 5'-(α-P-thio)triphosphates(dNTPαS and NTPαS) without protecting any nucleoside functionalities.This facile synthesis is achieved by treating the nucleosides with a mild phosphitylating reagent,reacting selectively with the 5'-hydroxyl group of each unprotected nucleoside,followed by sulfurization and hydrolysis to afford the crude dNTPαS and NTPαS analogs(mixtures of Sp and Rp diastereomers).We also demonstrated that after just simple precipitation(without HPLC and ion-exchange purification),the quality of the synthesized dNTPαS and NTPαS analogs is excellent for direct DNA polymerization and RNA transcription,respectively.Since Klenow DNA polymerase and T7 RNA polymerase accept the Sp diastereomers of dNTPαS and NTPαS analogs,respectively,while the Rp diastereomers are neither substrates nor inhibitors,the diastereomerically-pure PS-DNAs and PS-RNAs can be conveniently synthesized enzymatically.