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991.
Basallote MG Besora M Durán J Fernández-Trujillo MJ Lledós A Máñez MA Maseras F 《Journal of the American Chemical Society》2004,126(8):2320-2321
Kinetic studies indicate that trans-[FeH(H2)(dppe)2]+ reacts with an excess of NEt3 to form cis-[FeH2(dppe)2] in a single kinetic step. The second-order rate constant is strongly affected by the presence of added salts, an acceleration being observed with BF4- and PF6- salts and a deceleration with BPh4-. Theoretical calculations indicate that the role of the accelerating anions consists of the formation of ion pairs that provide a more effective reaction pathway for deprotonation. However, for the ion pair with the bulky BPh4- anion, steric crowding in the proximities of the dihydrogen ligand hinders the approach of the base, and the reaction is decelerated. 相似文献
992.
Antonio Doménech María Teresa Doménech-Carbó María Luisa Vázquez de Agredos Pascual 《Journal of Solid State Electrochemistry》2007,11(9):1335-1346
The preparation of indigo from Indigofera suffruticosa following the procedures attributed to ancient Mayas was electrochemically monitored using the voltammetry-of-microparticles
approach. The mechanism formation of indigotin and indirubin from its precursors, indican and isatan, is discussed. Comparison
of voltammetric profiles for differently prepared and commercial indigos and genuine Maya Blue samples suggests that the preparation
procedure of indigo changed during the Late Classical Maya period.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
993.
Garza-Ortiz A King-Díaz B Sosa-Torres ME Lotina-Hennsen B 《Journal of photochemistry and photobiology. B, Biology》2004,76(1-3):85-94
The effect of ruthenium red analogues on several thylakoid photosynthetic activities has been investigated. RR, RV, RRPh1, RRPh2 and Ph inhibit ATP synthesis and electron flow from water to MV (basal, phosphorylating and uncoupled) as their concentration increases, thus, they act as a Hill reaction inhibitor. They inhibit uncoupled electron transport through PSII from water to DCPIP and partially from DPC to DCPIP. However, these compounds do not affect uncoupled PSI electron transport from DCPIP to MV. Therefore, the target of interaction is at the level of OEC and the span P(680) to Q(A) for RR, RRPh1 and RRPh2. Chlorophyll a fluorescence studies corroborate the already found interference sites and may affect the disconnection between chlorophyll molecules within the LHCII and/or between antennae and RCs, or decreases the exciton to reach the RC and inhibition of PSII occurs. RRPh2 is six times more active than RR. Finally, Ph inhibits electron flow interacting at the level of Q(B). 相似文献
994.
Izquierdo S Rúa F Sbai A Parella T Alvarez-Larena A Branchadell V Ortuño RM 《The Journal of organic chemistry》2005,70(20):7963-7971
[Chemical reaction: See text] Several derivatives of (+)- and (-)-2-aminocyclobutane-1-carboxylic acid, 1, have been prepared through enantiodivergent synthetic sequences. The stereoselective synthesis of free amino acid (+)-1 has been achieved, and this product has been fully characterized for the first time. Stereocontrolled alternative synthetic methodologies have been developed for the preparation of bis(cyclobutane) beta-dipeptides in high yields. Among them, enantio and diastereomers have been synthesized. beta,beta- and beta,delta-Dimers resulting from the coupling of a cyclobutane residue and a linear amino acid have also been prepared. The ability of the cyclobutane ring as a structure-promoting unit both in the monomers and in the dimers has been manifested. The NMR structural study and DFT theoretical calculations evidence the formation of strong intramolecular hydrogen bonds giving rise to cis-fused [4.2.0]octane structural units that confer high rigidity on these molecules both in solution and in the gas phase. The contribution of a cis-trans conformational equilibrium derived from the rotation around the carbamate N-C(O) bond has also been observed, the trans form being the major conformer. In the solid state, this equilibrium does not exist, and moreover, intermolecular hydrogen bonds are present. 相似文献
995.
Cimas A Rayón VM Aschi M Barrientos C Sordo JA Largo A 《The Journal of chemical physics》2005,123(11):114312
The singlet potential-energy surface for the N(2D)+CH2F(2A') reaction has been studied employing both second-order M?ller-Plesset and density-functional theories. The energies of the involved species have been refined using the Gaussian-2, complete basis set, and coupled-cluster singles and doubles (triples) methods. The reaction proceeds through the formation of an initial intermediate, which does not involve any activation barrier. Based on the energy profile for the singlet potential-energy surface, the preferred product should be the most exothermic one, namely, HCN+HF, followed by HNC+HF and FCN+H2. This result seems in contradiction with a computational study of the kinetics of the title reaction in terms of the statistical theories, which leads to the prediction that the production of HNC+HF should be the dominant channel. Consequently, a limited molecular-dynamics study has been carried out, concluding that in fact the system behaves in a nonstatistical way. According to the molecular-dynamics study, the most exothermic channel, HCN+HF, should be the dominant one. An analysis of the possible role of the singlet surface in the reaction of N(4S) with CH2F(2A') has also been carried out. The computational study shows that the microcanonical coefficients for the nonadiabatic channels are much smaller than the competing adiabatic ones. Therefore, the reaction of N(4S) with CH2F(2A') should proceed on the triplet surface without spin change. 相似文献
996.
997.
[reaction: see text] The phosphoramidite 11 was prepared in three steps from methyl 2-mercaptoacetate and demonstrated efficiency in the synthesis of conventional 5'-/3'-phosphate/thiophosphate monoester derivatives of 2'-deoxyribonucleosides and DNA oligonucleotides. Moreover, the use of 11 has enabled the preparation of the dinucleoside phosphorothioate analogue 26 in high yields (>95%) with minimal cleavage (<2%) of the thermolytic thiophosphate protecting group. 相似文献
998.
Baeyer-Villiger oxidation with potassium peroxomonosulfate supported on acidic silica gel 总被引:1,自引:0,他引:1
González-Núñez ME Mello R Olmos A Asensio G 《The Journal of organic chemistry》2005,70(26):10879-10882
[reaction: see text] Potassium peroxomonosulfate deposited onto silica SiO2 x KHSO5 efficiently reacts with ketones in dichloromethane at room temperature to give the corresponding esters or lactones in quantitative yields. This method avoids hydrolysis of the reaction products. The Baeyer-Villiger reaction is catalyzed by potassium hydrogensulfate present in the supported reagent. 相似文献
999.
离子性指数、极化效应指数烷烃^13C NMR化学位移的 关系研究 总被引:5,自引:0,他引:5
定义了烷烃分子中碳原子的离子性指数(INI),用离子性指数(INI)、极化效应指数(PEI)及N^i~H(i=αβΥ)结构信息参数研究了烷烃的^13CNMR化学位移模型,结果表明,烷烃^13CNMR化学位移(CS)可用下式来定量描述:CS=194.6156-37.7394(INI)+98.6505(ΣPEI)+27.1630(INI/ΣPEI)-652.9106(ΣPEI/INI)+0.7735N^α~H+2.2468N^β~H-0.1742N^γ~H。用上式估算了304个碳原子的化学位移,平均绝对误差仅为0.77δ,标准差0.9860δ,预测值与实验值非常吻合。 相似文献
1000.
应用电喷雾(ESI)质谱及其多级串联质谱(MS~n)技术研究了三个氨基酸衍 生物N-(N-亚甲基-2-吡咯烷酮)-缬氨酸(PMV),N,N-二-(N-亚甲基-2-吡咯烷 酮)-亮氨酸(PML)和N,N-二-(N-亚甲基-2-吡咯烷酮)-β-丙氨酸(PMA)在电 喷雾条件下的质谱行为。在此条件下三个氨基酸衍生物PMV,PML和PMA可以质子化 形式PMVH~+,PMLH~+和PMAH~+存在,并且检测到它们的Na~+和K~+的加合物。在电 喷雾条件下PMV,PML和PMA优先采取C-N键的断裂,并且通过分子间的氢键作用形成 了许多二聚和三聚物种。 相似文献