全文获取类型
收费全文 | 21841篇 |
免费 | 2926篇 |
国内免费 | 2630篇 |
专业分类
化学 | 16105篇 |
晶体学 | 263篇 |
力学 | 1027篇 |
综合类 | 204篇 |
数学 | 2622篇 |
物理学 | 7176篇 |
出版年
2023年 | 264篇 |
2022年 | 327篇 |
2021年 | 471篇 |
2020年 | 636篇 |
2019年 | 691篇 |
2018年 | 551篇 |
2017年 | 528篇 |
2016年 | 918篇 |
2015年 | 908篇 |
2014年 | 1110篇 |
2013年 | 1467篇 |
2012年 | 1715篇 |
2011年 | 1936篇 |
2010年 | 1372篇 |
2009年 | 1419篇 |
2008年 | 1641篇 |
2007年 | 1474篇 |
2006年 | 1319篇 |
2005年 | 1110篇 |
2004年 | 1032篇 |
2003年 | 853篇 |
2002年 | 957篇 |
2001年 | 728篇 |
2000年 | 555篇 |
1999年 | 387篇 |
1998年 | 292篇 |
1997年 | 217篇 |
1996年 | 260篇 |
1995年 | 218篇 |
1994年 | 227篇 |
1993年 | 207篇 |
1992年 | 161篇 |
1991年 | 139篇 |
1990年 | 129篇 |
1989年 | 100篇 |
1988年 | 110篇 |
1987年 | 78篇 |
1986年 | 82篇 |
1985年 | 107篇 |
1984年 | 76篇 |
1983年 | 78篇 |
1982年 | 52篇 |
1981年 | 52篇 |
1980年 | 50篇 |
1979年 | 43篇 |
1978年 | 38篇 |
1977年 | 39篇 |
1976年 | 38篇 |
1974年 | 51篇 |
1973年 | 45篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
91.
Dr. Sanil E. Sivan Minhui Lee Su-Kyung Lee Dr. Ji Woong Yoon Dr. Kiwoong Kim Dr. Do-Young Hong Kyung-Ho Cho Dr. U-Hwang Lee Prof. Jong-San Chang Dr. Jaehoon Jung Prof. Young Kyu Hwang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(56):12889-12894
Oxo-bridged trimeric chromium acetate clusters [Cr3O(OOCCH3)6(H2O)3]NO3 have been encapsulated for the first time in the mesoporous cages of the chromium terephthalate MIL-101(Cr). The isolated clusters in MIL-101(Cr) have increased affinity towards propylene compared to propane, due to generation of a new kind of pocket-based propylene-binding site, as supported by DFT calculations. 相似文献
92.
针对Ni单原子催化剂表面的CO2电还原反应(CO2RR), 提出了以Ni为活性位点的“单中心”机理以及同时借助Ni位点还原和碳氮锚定位水解的“双功能”机理. 依据稳态极化的实验结果, 开展了CO2RR的动力学解析与模型参数的敏感性分析; 借助暂态模型方程, 分别获取可表达CO2RR线性与非线性频响特征的电化学阻抗谱(EIS)与总谐波失真(THD)谱. 研究结果表明, CO2的溶解分压对CO2RR活性影响最显著. 若CO2RR遵循“单中心”机理, Ni位点COOHads的形成为速率控制步骤; 但若为“双功能”机理, 碳氮锚定位的水解与Ni位点的CO2,ads还原同为速率控制步骤. EIS理论上可用于区分CO2RR的“单中心”机理与“双功能”机理; 与之相比, THD谱在CO2RR的机理识别中并无优势. 相似文献
93.
Dr. On Ying Yuen Dr. Chau Ming So 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(52):23644-23650
This study describes the first palladium-catalyzed, site-selective α- and γ-arylation of α,β-unsaturated ketones with (hetero)aryl halides. A wide range of hetero(aryl)halides coupled with α,β-unsaturated ketones, and transformation into the arylated products proceeded with excellent to good yields. The site selectivity of the reaction is switchable by simply changing the phosphine ligand to access either α-arylated or γ-arylated products in good to excellent yields by using a low catalyst loading, and the method demonstrates good functional-group compatibility. 相似文献
94.
Yan Gao Saimeng Zhang Xiaoguang Li Shuyao Jiang Yajing Yang Xiaohong Chang 《应用有机金属化学》2020,34(2):e5330
Salicylaldimine-bridged dinuclear cyclopalladated complexes were synthesized by the reactions of cyclopalladated chloro dimers [Pd{(4-R)C6H3CH=N-C6H3–2,6-i-Pr2}(μ-Cl)]2 (R = H; OMe) with salen-based bridging ligands. The complexes were characterized by FTIR, NMR spectroscopy, elemental analysis and X-ray crystallography. The binding interaction of cyclopalladated complexes to bovine serum albumin (BSA) was investigated by UV–vis, fluorescence and synchronous fluorescence spectroscopy. The experimental results showed that these Pd (II) complexes could bind to BSA with high affinity and quench its intrinsic fluorescence by a static or combined process. Also the interaction of Pd complexes with BSA affected the conformation of the tryptophan and tyrosine residues. 相似文献
95.
A novel metal–organic framework material {[N(C2H5)3][Zn2(ptmda)2(μ2-H2O)]·(H2O)0.5}n { GUT-3 ; H2ptmda is 4,4′-([p-tolylazanediyl]bis [methylene])dibenzoic acid} was successfully synthesized using the hydrothermal method and characterized by X-ray diffraction, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. GUT-3 has a two-dimensional network based on dinuclear [Zn2(ptmda)2(μ2-H2O)]− building units which formed an eightfold interpenetration network in GUT-3 molecules. Hirshfeld surface analysis revealed that H–H, C–H, and O–H bonds accounted for the majority of intermolecular interactions. Moreover, the interactions between GUT-3 and As(V) – the form of As(V) is AsO43− – were analyzed in aqueous solutions in a batch system to study the effect of pH, concentration, adsorbent dose, adsorption time, adsorption temperature, and shaking speed. The kinetic and isotherm data of arsenic adsorption on GUT-3 were accurately modeled by pseudo-second-order, Langmuir (qm = 33.91 mg/g), and Freundlich models. The Box–Behnken response surface method was used to optimize the adsorption conditions of As(V) from the simulated arsenic-contaminated wastewater. The effect of various experimental parameters and optimal experimental conditions was ascertained using the quadratic model. 相似文献
96.
97.
Dr. Yuan Liu Dr. Jin-Cheng Liu Teng-Hao Li Zeng-Hui Duan Dr. Tian-Yu Zhang Ming Yan Dr. Wan-Lu Li Prof. Dr. Hai Xiao Prof. Dr. Yang-Gang Wang Prof. Dr. Chun-Ran Chang Prof. Dr. Jun Li 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(42):18745-18749
The direct, nonoxidative conversion of methane on a silica-confined single-atom iron catalyst is a landmark discovery in catalysis, but the proposed gas-phase reaction mechanism is still open to discussion. Here, we report a surface reaction mechanism by computational modeling and simulations. The activation of methane occurs at the single iron site, whereas the dissociated methyl disfavors desorption into gas phase under the reactive conditions. In contrast, the dissociated methyl prefers transferring to adjacent carbon sites of the active center (Fe1©SiC2), followed by C−C coupling and hydrogen transfer to produce the main product (ethylene) via a key −CH−CH2 intermediate. We find a quasi Mars–van Krevelen (quasi-MvK) surface reaction mechanism involving extracting and refilling the surface carbon atoms for the nonoxidative conversion of methane on Fe1©SiO2 and this surface process is identified to be more plausible than the alternative gas-phase reaction mechanism. 相似文献
98.
Wei Chang Dandan Zheng Chaosheng Zhao Yanping Du 《Monatshefte für Chemie / Chemical Monthly》2020,151(3):319-324
The adsorption behavior of congo red from aqueous solution on Cu-BTC/SiO2 was investigated. Cu-BTC/SiO2 with mesoporous structure and large surface area was prepared by loading Cu-BTC into the mesoporous silica using in-situ synthesis method. The X-ray diffraction, scanning electron microscopy, and nitrogen adsorption–desorption analysis were used to characterize the structure and morphology of the prepared materials. The adsorption studies showed that the adsorption isotherm of congo red on Cu-BTC/SiO2 fitted well with Freundlich adsorption model and congo red is easy to be adsorbed by Cu-BTC/SiO2. The thermodynamic study showed that the adsorption behavior of congo red on Cu-BTC/SiO2 is an exothermic process at temperature under investigation. 相似文献
99.
以黄磷炉渣和铜渣为原料,添加一定比例的焦炭,熔融法制备了黄磷炉渣-铜渣微晶玻璃.借助Kissinger方程分析黄磷炉渣-铜渣基础玻璃的析晶能力,借助X射线衍射仪(XRD)进行物相分析.结果表明:随着黄磷炉渣与铜渣的质量添加比的增大,黄磷炉渣-铜渣基础玻璃的析晶峰峰温值Tp和析晶活化能E逐渐减小;当黄磷炉渣:铜渣=6:1时,黄磷炉渣-铜渣基础玻璃的析晶活化能最小,析晶能力最强;黄磷炉渣与铜渣添加比并不对黄磷炉渣-铜渣微晶玻璃晶相类型产生影响,其晶相均为钙长石Ca2 Al2 SiO7和镁黄长石Ca2 MgSiO7. 相似文献
100.
Rongzhen Wu Hongyu Chen Dr. Ninghui Chang Yuzhi Xu Prof. Dr. Jiao Jiao Prof. Dr. Hailong Zhang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(6):1166-1195
Bryostatins are a class of naturally occurring macrocyclic lactones with a unique fast developing portfolio of clinical applications, including treatment of AIDS, Alzheimer's disease, and cancer. This comprehensive account summarizes the recent progress (2014–present) in the development of bryostatins, including their total synthesis and biomedical applications. An emphasis is placed on the discussion of bryostatin 1 , the most-studied analogue to date. This review highlights the synthetic and biological challenges of bryostatins and provides an outlook on their future development. 相似文献