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181.
Jia-Le Xie Zheng Xu Han-Qi Zhou Yi-Xue Nie Jian Cao Guan-Wu Yin Jean-Philippe Bouillon Li-Wen Xu 《中国科学:化学(英文版)》2021,(5):761-769
Hydrosilylation is one of the most important reactions in synthetic chemistry and ranks as a fundamental method to access organosilicon compounds in industrial and academic processes. However, the enantioselective construction of chiral-at-silicon compounds via catalytic asymmetric hydrosilylation remained limited and difficult. Here we report a highly enantioselective hydrosilylation of ynones, a type of carbonyl-activated alkynes, using a palladium catalyst with a chiral binaphthyl phosphoramidite ligand. The stereospecific hydrosilylation of ynones affords a series of silicon-stereogenic silylenones with up to 94% yield, 20:1 regioselectivity and 98:2 enantioselectivity. The density functional theory(DFT) calculations were conducted to elucidate the reaction mechanism and origin of high degree of stereoselectivity, in which the powerful potential of aromatic interaction in this reaction is highlighted by the multiple C–H-π interaction and aromatic cavity-oriented enantioselectivitydetermining step during desymmetric functionalization of Si–H bond. 相似文献
182.
Mingzhu Du Shuanghong Yang Tong Jiang Tingting Liang Ying Li Shuzhen Cai Qingping Wu Jumei Zhang Wei Chen Xinqiang Xie 《Molecules (Basel, Switzerland)》2022,27(14)
Expression and purification of β-galactosidases derived from Bifidobacterium provide a new resource for efficient lactose hydrolysis and lactose intolerance alleviation. Here, we cloned and expressed two β-galactosidases derived from Bifidobacterium. The optimal pH for BLGLB1 was 5.5, and the optimal temperature was 45 °C, at which the enzyme activity of BLGLB1 was higher than that of commercial enzyme E (300 ± 3.6 U/mg) under its optimal conditions, reaching 2200 ± 15 U/mg. The optimal pH and temperature for BPGLB1 were 6.0 and 45 °C, respectively, and the enzyme activity (0.58 ± 0.03 U/mg) under optimum conditions was significantly lower than that of BLGLB1. The structures of the two β-galactosidase were similar, with all known key sites conserved. When o-nitrophenyl-β-D-galactoside (oNPG) was used as an enzyme reaction substrate, the maximum reaction velocity (Vmax) for BLGLB1 and BPGLB1 was 3700 ± 100 U/mg and 1.1 ± 0.1 U/mg, respectively. The kinetic constant (Km) of BLGLB1 and BPGLB1 was 1.9 ± 0.1 and 1.3 ± 0.3 mmol/L, respectively. The respective catalytic constant (kcat) of BLGLB1 and BPGLB1 was 1700 ± 40 s−1 and 0.5 ± 0.02 s−1, respectively; the respective kcat/Km value of BLGLB1 and BPGLB1 was 870 L/(mmol∙s) and 0.36 L/(mmol∙s), respectively. The Km, kcat and Vmax values of BLGLB1 were superior to those of earlier reported β-galactosidase derived from Bifidobacterium. Overall, BLGLB1 has potential application in the food industry. 相似文献
183.
FOURIER ANALYSIS OF TEMPORAL AND SPATIAL OSCILLATIONS OF TUNNELING CURRENT IN SCANNING TUNNELING MICROSCOPY 下载免费PDF全文
Partially oxidized Si(111) surfaces and surfaces of highly oriented pyrolytic graphite (HOPG) were studied by two different ultrahigh vacuum scanning tunneling microscope (UHV-STM) systems and by an STM system working under ambient conditions, respectively. The STM current images of partially oxidized Si(111) surfaces and HOPG surfaces were analyzed by one/two-dimensional fast Fourier transformation (1D-FFT/2D-FFT). The phenomenon of temporal oscillations of tunneling current on the partially oxidized Si(111) surfaces was detected with both UHV-STM systems. Temporal as well as spatial oscillations of tunneling current appeared in highly resolved STM current images of the Si(111) surfaces simultaneously, but both kinds of oscillations could be discriminated according to their different influence on the 2D-FFT spectra of the current images, while varying the scanning range and rate. On clean HOPG surfaces only spatial oscillations of tunneling current induced by the surface structure were observed. 相似文献
184.
本文利用红外光解离光谱研究了第三族金属氧化物离子对二氧化碳分子的转化机制. 研究表明,对于[ScO(CO2)n]+体系,在n≤4时,形成了溶剂化结构;在n=5时,形成了碳酸盐结构,实现了二氧化碳的转化. 对于[YO(CO2)n]+体系,需要4个二氧化碳分子就可以实现二氧化碳的转化. 而在[YO(CO2)n]+体系中,只发现了溶剂化结构,没有观察到碳酸盐结构. 理论计算表明,[YO(CO2)n]+体系拥有最小的溶剂化结构向碳酸盐结构转化能垒,[LaO(CO2)n]+体系拥有最大的溶剂化结构向碳酸盐结构转化能垒. 本文从分子水平揭示了不同金属氧化物离子对二氧化碳分子转化的影响规律. 相似文献
185.
Shengnan Xie Li Li Baihe Zhan Xue Shen Xuming Deng Wenxi Tan Tianqi Fang 《Molecules (Basel, Switzerland)》2022,27(9)
The emergence of the plasmid-mediated colistin resistance gene mcr-1 has resulted in the loss of available treatments for certain severe infections. Here we identified a potential inhibitor of MCR-1 for the treatment of infections caused by MCR-1-positive drug-resistant bacteria, especially MCR-1-positive carbapenem-resistant Enterobacteriaceae (CRE). A checkerboard minimum inhibitory concentration (MIC) test, a killing curve test, a growth curve test, bacterial live/dead assays, scanning electron microscope (SEM) analysis, cytotoxicity tests, molecular dynamics simulation analysis, and animal studies were used to confirm the in vivo/in vitro synergistic effects of pogostone and colistin. The results showed that pogostone could restore the bactericidal activity of colistin against all tested MCR-1-positive bacterial strains or MCR-1 mutant–positive bacterial strains (FIC < 0.5). Pogostone does not inhibit the expression of MCR-1. Rather, it inhibits the binding of MCR-1 to substrates by binding to amino acids in the active region of MCR-1, thus inhibiting the biological activity of MCR-1 and its mutants (such as MCR-3). An in vivo mouse systemic infection model, pogostone in combination with colistin resulted in 80.0% (the survival rates after monotherapy with colistin or pogostone alone were 33.3% and 40.0%) survival at 72 h after infection of MCR-1-positve Escherichia coli (E. coli) ZJ487 (blaNDM-1-carrying), and pogostone in combination with colistin led to one or more order of magnitude decreases in the bacterial burdens in the liver, spleen and kidney compared with pogostone or colistin alone. Our results confirm that pogostone is a potential inhibitor of MCR-1 for use in combination with polymyxin for the treatment of severe infections caused by MCR-1-positive Enterobacteriaceae. 相似文献
186.
Deep level transient spectroscopy investigation of deep levels in CdS/CdTe thin film solar cells with Te:Cu back contact 下载免费PDF全文
Deep levels in Cds/CdTe thin film solar cells have a
potent influence on the electrical property of these devices. As an
essential layer in the solar cell device structure, back contact is
believed to induce some deep defects in the CdTe thin film. With the
help of deep level transient spectroscopy (DLTS), we study the deep
levels in CdS/CdTe thin film solar cells with Te:Cu back contact.
One hole trap and one electron trap are observed. The hole trap H1,
localized at Ev+0.128~eV, originates from the vacancy of Cd
(VCd. The electron trap E1, found at Ec-0.178~eV,
is considered to be correlated with the interstitial Cui=
in CdTe. 相似文献
187.
为了实现装甲装备灭火系统故障的快速诊断,提出了一种故障树模块化分析方法;对灭火系统故障树进行深度优先最左遍历,并记录遍历过程,按照遍历顺序对故障树中的每个事件进行标定,并将灭火系统故障树划分为相互独立的模块,依据划分的模块可以通过故障现象对模块内的故障进行排查及修复;实验结果分析表明,该方法可以快速修复模块故障,恢复系统功能,简化了以往对灭火系统所有子事件遍历查错的繁琐过程。该方法同样可以计算故障模块的失效概率,并可以实现故障模块的整体更换,恢复系统性能;证明了故障树模块化方法在灭火系统故障诊断中具有较高的效率,简化了灭火系统诊断流程,在装甲车辆其他系统故障诊断中具有借鉴作用,符合现代作战对于装备保障的需求。 相似文献
188.
Effect of H impurity on misfit dislocation in Ni-based single-crystal superalloy: molecular dynamic simulations 下载免费PDF全文
The effect of H impurity on the misfit dislocation in Ni-based single-crystal superalloy is investigated using the molecular dynamic simulation.It includes the site preferences of H impurity in single crystals Ni and Ni 3 Al,the interaction between H impurity and the misfit dislocation and the effect of H impurity on the moving misfit dislocation.The calculated energies and simulation results show that the misfit dislocation attracts H impurity which is located at the γ/γˊinterface and Ni3 Al and H impurity on the glide plane can obstruct the glide of misfit dislocation,which is beneficial to improving the mechanical properties of Ni based superalloys. 相似文献
189.
190.