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71.
Le Guennic B Kirchner B Reiher M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(24):7448-7460
In several recent studies Schrock and collaborators demonstrated for the first time how molecular dinitrogen can be catalytically transformed under mild and ambient conditions to ammonia by a molybdenum triamidoamine complex. In this work, we investigate the geometrical and electronic structures involved in this process of dinitrogen activation with quantum chemical methods. Density functional theory (DFT) has been employed to calculate the coordination energies of ammonia and dinitrogen relevant for the dissociation/association step in which ammonia is substituted by dinitrogen. In the DFT calculations the triamidoamine chelate ligand has been modeled by a systematic hierarchy of increasingly complex substituents at the amide nitrogen atoms. The most complex ligand considered is an experimentally known ligand with an HMT = 3,5-(2,4,6-Me3C6H2)2C6H3 substituent. Several assumptions by Schrock and collaborators on key reaction steps are confirmed by our calculations. Additional information is provided on many species not yet observed experimentally. Particular attention is paid to the role of the charge of the complexes. The investigation demonstrates that dinitrogen coordination is enhanced for the negatively charged metal fragment, that is, coordination is more favorable for the anionic metal fragment than for the neutral species. Coordination of N2 is least favorable for the cationic metal fragment. Furthermore, ammonia abstraction from the cationic complex is energetically unfavorable, while NH3 abstraction is less difficult from the neutral and easily feasible from the anionic low-spin complex. 相似文献
72.
LU Zai-Sheng② NIU De-Zhong LI Xiu-Ling 《结构化学》2003,22(5)
1 INTRODUCTION 3-Hydroxy-2-methyl-4-pyranone (maltol) and 3-hydroxy-2-ethyl-4-pyranone (ethylmaltol) are nontoxic compounds that have been applied to bio- inorganic chemistry over several decades[1, 2]. Their iron(III) complexes are relevant to the control of iron levels in the human body. Such complexes have been assessed for the amelioration of anaemia[3] and their respective ligands have been tested for the removal of excess burdens of iron in diseases such as siderosis, haemochroma… 相似文献
73.
用红外光谱、X射线衍射(XRD)和热分析研究了饱和过渡金属锌的粘土矿物吸附半胱氨酸的机理;XRD结果显示吸附了半胱氨酸后的粘土矿物的d(001)方向的距离明显增大,说明被吸附的半胱氨酸进入了粘土的层状结构之中;饱和了锌的粘土矿物吸附半胱氨酸有两种方式,其一为弱相互作用,另一种强相互作用;后一种方式吸附的半胱氨酸与粘土的过渡金属之间形成了配合结构,结合力比较强,在热作用下,它们一直到395℃左右才分解;强相互作用吸附的半胱氨酸主要是以去质子的两性离子和阴离子形式存在于粘土矿物上,与过渡金属形成螯合的六元环结构。 相似文献
74.
Qiang Xu Prof. Dr. Nobuko Tsumori Prof. Dr. Ling Jiang Masanobu Kondo Ryuichi Arakawa Prof. Dr. 《化学:亚洲杂志》2007,2(5):599-608
Carbonyldinitrosyltris(fluorosulfato)tungstate(II) and ‐molybdate‐(II) anions, [fac‐M(CO)(NO)2(SO3F)3]? (M=W, Mo), which are novel weakly coordinating anions that contain a metal carbonyl/nitrosyl moiety, have been generated in fluorosulfonic acid and completely characterized by multinuclear NMR, IR, and Raman spectroscopy as well as ESI mass spectrometry. ESI MS measurements performed for the first time on a superacidic solution system unambiguously reveal the formation of the monoanionic, mononuclear W and Mo complexes formulated as [M(CO)(NO)2(SO3F)3]? (M=W, Mo). Multinuclear NMR spectroscopic studies at natural abundance and 13C and 15N enrichment clearly indicate the presence of one CO ligand, two equivalent NO ligands, and two types of nonequivalent SO3F? groups in a 2:1 ratio. The IR and Raman spectra reveal that the two equivalent NO ligands have a cis conformation, thus indicating a fac structure. Density functional calculations at the B3LYP level of theory predict that these anions have a singlet ground state (1A′) with a Cs symmetry along with C–O and N–O vibrational frequencies that are in agreement with the experimental observations. Mulliken population analysis shows that the monovalent negative charge is dispersed on the bulky sphere, the surface of which is covered by all the negatively charged O and F atoms with charge densities much lower than SO3F?, suggesting that [fac‐M(CO)(NO)2(SO3F)3]? (M=W, Mo) are weakly nucleophilic and poorly coordinating anions. 相似文献
75.
The structure of [(CF3N2NMe)Mo(CH2SiMe3)2] (in which (CF3N2NMe)2? is [(3‐CF3C6H4NCH2CH2)2NMe]2?) is approximately trigonal bipyramidal with one axial and one equatorial alkyl ligand. Heating of solutions of [(CF3N2NMe)Mo(CH2SiMe3)2] in [D6]benzene in the presence of five equivalents of 2‐butyne led to diamagnetic [(CF3N2NMe)Mo(CHSiMe3)(η2‐MeC?CMe)], whose structure is approximately square pyramidal with the alkyne occupying the axial site. Addition of one equivalent of cyclohexene sulfide to [(CF3N2NMe)Mo(CH2SiMe3)2] at room temperature produced the diamagnetic, dimeric molybdenum(IV) sulfido complex, [{(CF3N2NMe)MoS}2]. This complex is composed of two approximately trigonal bipyramidal centers, each containing one axial and one equatorial sulfur atom. Oxidation of [(CF3N2NMe)Mo(CH2SiMe3)2] with hexachloroethane resulted in formation of tetramethylsilane, HCl, and the sparingly soluble, red alkylidyne complex, [{(CF3N2NMe)Mo(CSiMe3)Cl}2]. This complex forms a dimer through bridging chlorides. The oxidation reactions of [(CF3N2NMe)Mo(CH2SiMe3)2] with 2‐butyne, cyclohexene sulfide, or C2Cl6 are all proposed to proceed by α‐hydrogen abstraction in the MoVI species to yield (initially) the Mo?CHSiMe3 species and tetramethylsilane. 相似文献
76.
A comparison of sequential extraction techniques for determining arsenic fractionation in synthetic mineral mixtures 总被引:6,自引:0,他引:6
The sequential extraction methods according to Tessier et al. [1], Borovec et al. [2], Zhang and Moore [3] and Hall et al. [4] have been tested for their suitability for arsenic fractionation in samples of artificially prepared mineral mixtures. Mixtures containing different amounts of As-containing phases were prepared so that their compositions corresponded to weathering products on As-bearing ore deposits. A comparison of different procedures on simple mineral mixtures containing calcium arsenate (CaHAsO4·H2O), As-bearing goethite (FeOOH) and arsenopyrite (FeAsS) showed that only the results of the Hall method satisfactorily correspond to the expected arsenic distribution. A detailed verification of the Hall method was subsequently carried out on most complex synthetic mineral mixtures with varying amounts of As-containing kaolinite and carbonate, calcium arsenate, As-bearing goethite and arsenopyrite. The results confirm that the Hall method cannot be fully employed for an accurate As speciation but may be applied for a route identification of As distribution between "labile", "medium-labile" and "residual" forms in heavily polluted soils. 相似文献
77.
78.
采用了研磨后超声和离心分离方法制备了二硫化钼纳米片,通过原子力显微镜(AFM)和扫描电子显微镜(SEM)对不同离心速度分离的二硫化钼纳米片进行了表征。使用循环伏安法(CV)和差分脉冲伏安法(DPV)在磺胺甲恶唑溶液中对二硫化钼纳米片修饰的玻碳电极进行了电化学行为研究。结果显示,磺胺甲恶唑在二硫化钼修饰电极的循环伏安图上有一对氧化还原峰。其峰电流值与扫描速度的平方根成正比,是扩散控制过程。DPV扫描结果显示,磺胺甲恶唑的峰电流与其浓度之间存在着明显的线性关系。研磨超声方法制备出的二硫化钼纳米片层材料在电极上能够加速电子的转移和传输,从而有效提高峰电流值,为进一步研制准确测定磺胺甲恶唑电化学传感器提供了一种可选择的材料和电化学分析方法。 相似文献
79.
分光光度法同时测定中草药中的钼和铜 总被引:2,自引:2,他引:2
本文建立了在混合显色剂(PF+PAN)的胶束体系中,利用分光光度法同时测定中草药中的钼和铜。实验表明:在混合体系中,钼量在0~10μg/25mL,铜量在0~50μg/25mL的范围内符合比尔定律,ε′Mo=9.2×104L·mol-1·cm-1;ε′Cn=1.5×104L·mol-1·cm-1。该法用于中草药样品的分析,结果满意,回收率可达92~111%。 相似文献
80.
研究新型无毒无机颜料,逐步取代如铅铬黄、镉黄等无机颜料,日益引人注意。我们以价廉易得的自云石凹凸棒、蒙脱石、凹凸棒石粘土矿为原料,制得黄色硅酸盐类无毒新型颜料。研究了该类颜料的骨架结构与成分,及其发色机理。工艺过程如下: 相似文献