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991.
Armstrong DR Clegg W García-Álvarez P Kennedy AR McCall MD Russo L Hevia E 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(30):8333-8341
Numerous organic transformations rely on organozinc compounds made through salt-metathesis (exchange) reactions from organolithium or Grignard reagents with a suitable zinc precursor. By combining X-ray crystallography, NMR spectroscopy and DFT calculations, this study sheds new light on the constitution of the organometallic species involved in this important synthetic tool. Investigations into the metathesis reactions of equimolar amounts of Grignard reagents (RMgX) and ZnCl(2) in THF led to the isolation of novel magnesium-zinc hybrids, [{(thf)(2)Mg(μ-Cl)(3)ZnR}(2)] (R=Et, tBu, nBu or o-OMe-C(6)H(4)), which exhibit an unprecedented structural motif in mixed magnesium-zinc chemistry. Furthermore, theoretical modelling of the reaction of EtMgCl with ZnCl(2) reveals that formation of the mixed-metal compound is thermodynamically preferred to that of the expected homometallic products, RZnCl and MgCl(2). This study also assesses the alkylating ability of hybrid 3 towards the sensitive ketone trifluoroacetophenone, revealing a dramatic increase in the chemoselectivity of the reaction when LiCl is introduced as an additive. This observation, combined with recent related breakthroughs in synthesis, points towards the existence of a trilateral Li/Mg/Zn synergistic effect. 相似文献
992.
测定了5种平均相对分子质量和相对分子质量(以下简称分子量)分布不同的烷基芳基磺酸盐复配体系的吸附等温线,分别考察了分子量、分子量分布、温度和无机盐对复配体系在油砂/石英砂表面的吸附量的影响。 结果表明,对5种分子量分布复配体系吸附量依次降低的顺序为递增分布、正态分布、反正态分布、递减分布和均匀分布;复配体系在油砂表面的吸附量随着磺酸盐的平均分子量的增大而增大,随温度的升高而降低,随NaCl浓度的增加而增加。另外,在低浓度时,MgCl2、CaCl2和Na2SO4比NaCl对吸附的影响显著。 NaCl对复配体系在油砂表面的吸附影响比对石英砂表面吸附的影响略大。 相似文献
993.
994.
通过加速碳化试验方法, 研究了碳化与氯盐复合作用下水泥浆体的微观结构, 分析了氯盐掺量对水泥基材料的抗碳化性能的影响. 同时, 利用X射线衍射分析了碳化前后样品的物相组成、水化产物类型和微观结构特征. 结果表明, 碳化养护更有利于浆体裂缝的愈合, 但碳化后大孔占比增加; 碳化作用下掺加氯盐会减缓水泥浆碳化速度; 碳化后产生单硫型水化硫铝酸钙和碳酸盐类物质, 钙矾石消失, 浆体的孔隙总体积减少, 孔隙结构得到了细化. 相似文献
995.
《化学学报》2012,70(4)
利用LiPF6和三氟乙酰胺为前驱物,制备了低共熔温度约为-62℃的室温熔盐,并测试了该熔盐作为碳-碳电化学电容器(EDLCs)电解液时的性能。其中,使用差示扫描量热法(DSC)和红外光谱法(FTIR)分析了不同LiPF6和三氟乙酰胺配比熔盐的热稳定性,拟制了该二元组分的共熔相图,认为LiPF6和三氟乙酰胺极性基团间的氢键作用促成了室温熔盐的形成。循环伏安(CV)、交流阻抗(EIS)和电导等测定结果表明,所制备的LiPF6/三氟乙酰胺电解液的室温电导率为1.30mS/cm,电化学窗口大于5.6V,大于60℃的使用温度,作为电解液可满足碳-碳EDLCs的使用要求。 相似文献
996.
以市售普通活性炭为碳源,先对其进行强碱活化处理制得多孔碳材料,再经硝酸氧化后,通过水热溶剂法将季鏻阳离子负载于多孔碳上,得到功能化的多孔碳材料。通过比表面积(BET)、热重分析(TGA)、X射线衍射(XRD)、高分辨透射电镜(HRTEM)以及ζ电位对其形貌和结构进行分析,并对其抗菌活性进行表征。结果表明,该方法成功合成了功能化多孔碳材料,该碳材料在水溶液中具有较好的分散性、稳定性和荷电性,并对大肠杆菌(E.coli)和金黄色葡萄球菌(S.aureus)具有良好的抗菌活性。 相似文献
997.
998.
A novel, simple and versatile protocol for covalent immobilization of horseradish peroxidase (HRP) on screen‐printed carbon electrode (SPCE) based on the combination of diazonium salt electrografting and click chemistry has been successfully developed. The ethynyl‐terminated monolayers are obtained by diazonium salt electrografting, then, in the presence of copper (I) catalyst, the ethynyl modified surfaces reacted efficiently and rapidly with horseradish peroxidase bearing an azide function (azido‐HRP), thus forming a covalent 1,2,3‐triazole linkage by means of click chemistry. All the experimental results suggested that HRP was immobilized onto the electrode surface successfully without denaturation. Furthermore, the immobilized HRP showed a fast electrocatalytic reduction for H2O2. A linear range from 5.0 to 50.0 µM in a phosphate buffer (pH 5.5) with detection limit of 0.50 µM and sensitivity of 0.23 nA/µM were obtained. The heterogeneous electron transfer rate constant Kct was 1.52±0.22 s?1 and the apparent Michaelis? Menten constant was calculated to be 0.028 mM. The HRP‐functionalized electrode demonstrated a good reproducibility and long‐term stability. 相似文献
999.
《Journal of Coordination Chemistry》2012,65(7):1005-1018
Solid compounds of Cd(II), Hg(II) and Pb(II) with the sodium salt of morin-5′-sulfonic acid (NaMSA) were obtained. The molecular formula of the complexes are: Cd(C15H8O10SNa)2?·?6H2O, CdOH(C15H8O10SNa)?·?4H2O, Hg(C15H8O10S)?·?4H2O and Pb(C15H8O10S)?·?3H2O. Some of their physicochemical properties such as UV-Vis, infrared, 13C NMR and mass spectra, thermogravimetric analysis, and solubility were studied. On the basis of spectroscopic data NaMSA was bound to Cd2+ via 4C=O and 3C?–?oxygen and the Hg2+ and Pb2+ ions by 5C–OH, 4C=O and 3C–OH. 相似文献
1000.
《Journal of Coordination Chemistry》2012,65(16-18):2584-2603
AbstractThe syntheses of bis(trifluoromethane) sulfonimide N-(ferrocenylmethyl) N,N,N-trimethyl ammonium salt 1 and bis(trifluoromethane) sulfonimide N′,N-bis(ferrocenylmethyl) inmidazolium salt 2 are reported. The compounds show low melting points, 76° and 125?°C, respectively, and were characterized by spectroscopic techniques 1H-NMR, mass spectrometry, FT-IR spectroscopy, cyclic voltammetry, and XRD crystallographic analysis. Cyclic voltammetry results demonstrate that both salts have a quasi-reversible electrochemical behavior, similar to the reversible one shown by ferrocene under the same conditions. In the case of 1, a coupled chemical reaction was detected at slow scan rates after the oxidation. Transient species in the redox processes were investigated using flash photolysis and pulse radiolysis. In both cases, transient spectra of the products were similar to transient spectra observed for ferrocene. The decay kinetics of the oxidized and reduced transients were examined and mechanistic information was obtained. The experimental results show the potential uses of the two complexes as catalytic materials for electrochemical applications. 相似文献