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81.
提出了利用不同取代基烯类单体的电子亲和势来判断其负离子聚合反应活性的方法.采用密度泛函理论的B3LYP/6-31G(d)方法优化了不同取代基烯类单体几何构型,在B3LYP/6-311++G(3df,2p)水平上计算了其电子亲和势.通过电子亲和势计算值与文献报道实验数据比较,表明本文采用的计算方法是比较可靠的.结合不同取代基烯类单体的电子亲和势的计算结果,通过与Q-e关系及取代基常数σ数据进行比较表明,电子亲和势可以用来判断不同单体负离子聚合反应的活性高低. 相似文献
82.
Domenico Osella Mauro Ravera Carlo Floriani Euro Solari 《Journal of organometallic chemistry》1996,510(1-2):45-50
We describe the redox behaviour in non-aqueous solvents of some cyclopentadienyl(oxo)titanium derivatives. The derivative [Ti4{η5-C5H4(SiMe3)}4(μ-O)6] shows an electrochemically and chemically reversible le reduction process, followed by a multi-electron, chemically complicated reduction at a fairly cathodic potential. On the basis of the overall electrochemical features and the comparison with the redox behaviour of the quasi-planar compound [[Ti{η5-C5H4(SiMe3)}Cl(μ-O)]4] we propose an EECCEE mechanism for the first derivative, where the second electron-transfer induces a cascade of chemical reactions giving rise to irreversible cluster breakdown. The electrochemically induced fragmentation can be viewed as a retrosynthetic pathway. The heterometallic derivative [{Ti(η5-C5H4Me)2(μ2-MoO4)2}2] shows two consecutive reduction processes; the first is chemically reversible, and the second quasi-reversible. The molybdate bridges apparently increase the stability of the electrogenerated anions. However none of these poly-oxo clusters can be considered as good models of electron ‘sinks’. 相似文献
83.
84.
K. Bogdanowicz-Szwed M. Krasodomska 《Monatshefte für Chemie / Chemical Monthly》1996,127(12):1273-1281
Summary Reaction of 1,3-diaza-1,3-butadienes (1a–c) with various ketenes and chloroketenes results in the formation of substituted 4-oxo-pyrimido[2,1-b]benzothiazoles (4a–d) and 1,3,4-thiadiazolo[3,2-a]pyrimido-4-ones (4e,f). Reaction of 1,3-diaza-1,3-butadienes1d,e with ketenes and chloroketenes leads to the 2-morpholine-substituted compounds7 and15, respectively. All reactions proceedvia formation of [4+2] cycloadducts that eliminate methylthiol, methylsulfenyl chloride, or morpholine.
Hetero-Diels-Alder-Reaktion einiger 1,3-Diaza-1,3-butadiene mit Ketenen. Synthese funktionalisierter Pyrimido[1,2-b]benzothiazole und 1,3,4-Thiadiazolo[3,2-a]pyrimidine
Zusammenfassung Die Reaktion der 1,3-Diaza-1,3-butadiene1a–c mit verschiedenen Ketenen und Chlorketenen führt zu substituierten 4-Oxo-pyrimido[2,1-b]benzothiazolen (4a–d) und 1,3,4-Thiadiazolo[3,2-a]pyrimido-4-onen(4e,f). Die 1,3-Diaza-1,3-butadiene1d,e ergeben mit Ketenen und Chlorketenen die 2-Morpholin-substituierten Verbindungen7 und15. Alle Reaktionen verlaufen über [4+2]-Cycloaddukte, die Methylthiol, Methylsulfenylchlorid oder Morpholin eliminieren.相似文献
85.
采用密度泛函理论计算方法, 在B3LYP/6-311G*水平下, 计算并得到了SiHCl3与H2反应各反应通道上各驻点的构型、振动频率和能量. 结果表明, 在气相中SiHCl3分解的通道d和SiHCl3与H2反应的通道c为竞争反应, 但其均未还原出Si原子, 只有衬底Si参与SiHCl3-H2的反应, Si原子才淀积在Si衬底上. 相似文献
86.
钴(II)-联吡啶-α-氨基酸的热力学和动力学研究 总被引:3,自引:0,他引:3
关于联吡啶为第一配体的二元、三元配合物的热力学和动力学性质的研究,以铜(Ⅱ)作为中心离子最为多见,而以钴(Ⅱ)作为中心离子的报导较少.实验表明,过渡金属钻(Ⅱ)能与大多数的生物配体、大π共轭体系形成相当稳定的二元、三元配合物,是生物功能模拟的一个具有应用价值的中心离子·钴(Ⅱ)卟啉可以代替铁(Ⅱ)卟啉,模拟血红蛋白、肌红蛋白[1],在生物体内起到输送氧的作用.为了充分了解钴(Ⅱ)与生物配体的配伍能力、配位方式以及其配位过程的动态行为,为推动钴(Ⅱ)配合物及其生物功能的模拟研究,本文分别采用PH电位法… 相似文献
87.
The hydrogen peroxide-oxidation of o-phenylenediamine (OPD) catalyzed by horseradish peroxidase (HRP) at 37 °C in 50 mM phosphate buffer (pH 7.0) was studied by calorimetry. The apparent molar reaction enthalpy with respect to OPD and hydrogen peroxide were −447 ± 8 kJ mol−1 and −298 ± 9 kJ mol−1, respectively. Oxidation of OPD by H2O2 catalyzed by HRP (1.25 nM) at pH 7.0 and 37 °C follows a ping-pong mechanism. The maximum rate Vmax (0.91 ± 0.05 μM s−1), Michaelis constant for OPD Km,S (51 ± 3 μM), Michaelis constant for hydrogen peroxide Km,H2O2 (136 ± 8 μM), the catalytic constant kcat (364 ± 18 s−1) and the second-order rate constants k+1 = (2.7 ± 0.3) × 106 M−1 s−1 and k+5 = (7.1 ± 0.8) × 106 M−1 s−1 were obtained by the initial rate method. 相似文献
88.
Summary A general definition of reaction graphs is presented. For a pair of isomeric molecular graphs
and
, related by a chemical transformation
, the reaction graph
is determined using a maximal common subgraph defined for vertex mapping
. A binary operation defined for graphs constructed over the same vertex set enables us to decompose the reaction graph
into the sum of prototype reaction graphs. A decomposition of an overall reaction graph can be advantageously used for the construction of a reaction network. An oriented path in this network beginning at
and ending at
corresponds to a breakdown of the transformation
into a sequence of intermediates. 相似文献
89.
Istvan Bakk Dietrich Gudat Stefan Hp Martin Nieger Lszl Nyulaszi Lszl Szarvas 《无机化学与普通化学杂志》2005,631(1):47-54
Reactions of the phosphonio‐benzophospholide π‐complexes 3a, b[Cr] with [M(CO)5(olefin)] or of the σ‐complexes 2a, b[M] (M = Cr, Mo, W) with [M(CO)3(aren)] lead to the first binuclear complexes 4a, b[CrM] featuring phosphonoio‐benzophospholides as μ‐bridging 8e‐donor ligands to two group 6 metal atoms. The constitution of the products was determined by spectroscopic and X‐ray diffraction studies. Mixed complexes with both group 6 and 7 metals were not accessible. Mechanistic studies showed that the reactions follow a complicated mechanism whose single steps may involve transfer of either M(CO)n fragments or single CO ligands between complexes; the latter are associated with a σ/π‐coordination isomerization of the benzophospholide unit. Competition between both reaction channels can lead to the formation of product mixtures whose composition is controlled by the relative thermodynamic stabilities of the products. Computational studies suggest that in the more stable isomer of heterobimetallic complexes 4a, b[MM′] end‐on coordination to the heavier and side‐on coordination to the lighter metal atom is preferred. 相似文献
90.
LIU Peng-jun ZHANG Lian-hua SUN Hao CHANG Ying-fei WANG Rong-shun 《高等学校化学研究》2006,22(5):635-638
The reaction mechanisms of HNCS with NH(X^3∑ ) were theoretically investigated. The minimum energy paths (MEP) of the reaction were calculated by using the density functional theory(DFT) at the B3LYP/6-311 + + G^** level. The equilibrium structural parameters, the harmonic vibrational frequencies, the total energies, and the zeropoint energies(ZPE) of all the species were calculated. The single-point energies along the MEP were further refined at the QCISD(T)/6-311 + + G^* * level. It was found that the mechanisms of the HNCS + NH(X^3∑) reaction involve two channels producing the HNC + HNS and the N2H2 + CS products. Channel 1 plays a dominant role and the HNC + HNS are the main preduets. The reaction is exothermie. 相似文献