全文获取类型
收费全文 | 13434篇 |
免费 | 2496篇 |
国内免费 | 1695篇 |
专业分类
化学 | 9690篇 |
晶体学 | 107篇 |
力学 | 1004篇 |
综合类 | 120篇 |
数学 | 1337篇 |
物理学 | 5367篇 |
出版年
2024年 | 23篇 |
2023年 | 141篇 |
2022年 | 283篇 |
2021年 | 314篇 |
2020年 | 425篇 |
2019年 | 465篇 |
2018年 | 501篇 |
2017年 | 491篇 |
2016年 | 556篇 |
2015年 | 619篇 |
2014年 | 872篇 |
2013年 | 1150篇 |
2012年 | 927篇 |
2011年 | 1001篇 |
2010年 | 776篇 |
2009年 | 943篇 |
2008年 | 918篇 |
2007年 | 873篇 |
2006年 | 825篇 |
2005年 | 762篇 |
2004年 | 677篇 |
2003年 | 630篇 |
2002年 | 435篇 |
2001年 | 346篇 |
2000年 | 345篇 |
1999年 | 289篇 |
1998年 | 263篇 |
1997年 | 248篇 |
1996年 | 207篇 |
1995年 | 219篇 |
1994年 | 173篇 |
1993年 | 122篇 |
1992年 | 132篇 |
1991年 | 82篇 |
1990年 | 96篇 |
1989年 | 77篇 |
1988年 | 61篇 |
1987年 | 57篇 |
1986年 | 47篇 |
1985年 | 36篇 |
1984年 | 40篇 |
1983年 | 14篇 |
1982年 | 33篇 |
1981年 | 26篇 |
1980年 | 17篇 |
1979年 | 21篇 |
1978年 | 10篇 |
1977年 | 13篇 |
1976年 | 12篇 |
1973年 | 10篇 |
排序方式: 共有10000条查询结果,搜索用时 765 毫秒
941.
Muhammet Uyanik Naoto Sahara Mayuko Tsukahara Yuhei Hattori Kazuaki Ishihara 《Angewandte Chemie (International ed. in English)》2020,59(39):17110-17117
We report high‐performance I+/H2O2 catalysis for the oxidative or decarboxylative oxidative α‐azidation of carbonyl compounds by using sodium azide under biphasic neutral phase‐transfer conditions. To induce higher reactivity especially for the α‐azidation of 1,3‐dicarbonyl compounds, we designed a structurally compact isoindoline‐derived quaternary ammonium iodide catalyst bearing electron‐withdrawing groups. The nonproductive decomposition pathways of I+/H2O2 catalysis could be suppressed by the use of a catalytic amount of a radical‐trapping agent. This oxidative coupling tolerates a variety of functional groups and could be readily applied to the late‐stage α‐azidation of structurally diverse complex molecules. Moreover, we achieved the enantioselective α‐azidation of 1,3‐dicarbonyl compounds as the first successful example of enantioselective intermolecular oxidative coupling with a chiral hypoiodite catalyst. 相似文献
942.
Dr. A. Shine J. Shenoy Parvathy Jayan Dr. A. C. Jiji Dr. Vinesh Vijayan 《Chemphyschem》2020,21(9):888-894
Although the conformation of the polymer chain of Ubiquitin (Ub) mainly depends on the type of isopeptide linkage connecting two Ub molecules, the non-covalent (noncovalent) interaction between two Ub molecules within the chain could also tune their conformational preference. Here, we studied the conformation of noncovalently formed Ub dimers in solution using residual dipolar couplings (RDCs). Comparing the RDC derived alignment tensor of the noncovalently formed dimer with the two most abundant (K11 and K48) covalent linked Ub dimers revealed that the conformation of K11 linked and noncovalent Ub dimers were similar. Between the various NMR and crystal structures of K11 linked Ub dimers, RDC tensor analysis showed that the structure of K11 linked dimer crystalized at neutral pH is similar to noncovalent dimer. Analogous to the experimental study, the comparison of predicted order matrix of various covalent Ub dimers with that of the experimentally determined order matrix of noncovalent Ub dimer also suggests that the conformation of K11 linked dimers crystalized at neutral pH is similar to the noncovalent dimer. 相似文献
943.
A rhodium(III)‐catalyzed redox‐neutral coupling of α‐trifluoromethylacrylic acid with bezamides proceeds smoothly accompanied by amide‐directed C?H bond cleavage to produce β‐[2‐(aminocarbonyl)phenyl]‐α‐trifluoromethylpropanoic acid derivatives. One of the products can be transformed to a trifluoromethyl substituted heterocyclic compound. In addition, the redox‐neutral coupling of α‐trifluoromethylacrylic acid with related aromatic substrates possessing a nitrogen‐containing directing group can also be conducted under similar conditions. 相似文献
944.
Nylon 6 and 6,6 literature data are collected over a wide range of water concentrations and temperatures (0 ≤ [W]0 ≤ 40.8 wt%, 200 ≤ T ≤300 °C) and used to fit parameters in an updated batch reactor model. The resulting copolymerization model uses side reactions to account for the complex influence of water on kinetics and reaction equilibria. The proposed parameter estimates result in a significant improvement in the fit to the data, corresponding to a 73% reduction in the weighted‐least‐squares objective function compared to when the parameters of Arai et al. are used. Copolymerization simulations are conducted at industrially relevant conditions, shedding light on the complex influence of water and on the potential to include waste nylon 6 cyclic dimer in the feedstock. The model and parameter estimates will be helpful in future models of nylon 6/6,6 copolymerization in continuous reactor systems. 相似文献
945.
为探究循环冲击损伤后大理岩的静态断裂力学特征,基于有限差分(finite difference method,FDM)-离散元(discrete element method,DEM)耦合的建模技术构建了三维分离式霍普金森压杆(split Hopkinson pressure bar,SHPB)数值模型,其中杆件系统和岩石试件分别采用FLAC3D和PFC3D程序建模。利用该模型对中心直切槽半圆盘(NSCB)试样进行了恒定子弹速度下的循环冲击,随后对受损试样进行静态三点弯曲断裂实验。通过编写Fish程序,提取试样断裂面数据,对断裂面进行重构并定量计算表面粗糙度。通过与相关室内实验结果的对比分析,验证了本文数值分析的合理性与可靠性。模拟结果表明,随着循环冲击次数的增加,试样内部微裂纹、破碎颗粒均增加。连接力场分布混乱,部分力链发生断裂。力链的变化是试样力学性能劣化的根本原因。在静态三点弯曲断裂实验中,冲击5次后试样的静态断裂韧度较天然试样产生一定程度的降低。试样在静载过程中产生的微裂纹和碎块的数量随循环冲击次数的增加而增加,断裂面粗糙度随循环冲击次数的增加而增加。 相似文献
946.
S. Spall A. A. Goodwin M. D. Zipper G. P. Simon 《Journal of Polymer Science.Polymer Physics》1996,34(14):2419-2431
The dynamic mechanical and dielectric spectra of a miscible polyester and polycarbonate blend are investigated with emphasis on the latter technique. It was found that relaxation spectra for the blends from both techniques are broader than those of the constituent homopolymers. This is ascribed to greater intermolecular coupling and concentration fluctuations within the blends. The composition at which the greatest coupling occurs is dependent on the relaxation technique used and is skewed towards the component which shows the highest degree of intermolecular coupling. A number of parameters, such as relaxation time of the polymer molecules in the blend and relaxation strength, are compared as a function of reduced temperature (experimental temperature scaled by the glass transition temperature). Whereas blend behavior is generally intermediate between that of the homopolymers, it appears as though mobility of compositions with low polyester content have a greater relaxation time and possess a higher activation energy when compared to a simple, weighted average of the corresponding homopolymer values. © 1996 John Wiley & Sons, Inc. 相似文献
947.
Akikazu Matsumoto Yoshinori Sano Masahiro Yoshioka Takayuki Otsu 《Journal of polymer science. Part A, Polymer chemistry》1996,34(2):291-299
The radical polymerization of dialkyl fumarates (DRF) bearing various ester alkyl groups was kinetically studied. The propagation and termination rate constants were determined using electron spin resonance (ESR) spectroscopy. The introduction of the bulky ester alkyl groups such as a tert-butyl group decreased the termination rate constant as expected. However, it has also been revealed that the bulky groups promote propagation despite the steric repulsion. The propagation rate and mechanism are discussed in relation to the propagation manner, i.e., tacticity of the polymer. © 1996 John Wiley & Sons, Inc. 相似文献
948.
949.
A modified loop-type interface is decribed which uses two 6-way valves and concurrent eluent evaporation to perform an on-line transfer and simultaneous gas chromatographic analysis of two different fractions pre-separated by liquid chromatography. The interface is used to simultaneously analyze aliphatic alcohols and sterols present in olive oil. LC pre-separation is carried out using a normal phase column (20 cm × 0.21 cm i.d.) and hexane-isopropanol (99:1) as a mobile phase at a flow of 0.2 ml/min; for the GC analysis a 5 % phenyl, 95 % dimethyl siloxane (25 m × 0.32 mm i.d., 0.4 μm film thickness) column is used. 相似文献
950.