全文获取类型
收费全文 | 1462篇 |
免费 | 44篇 |
国内免费 | 7篇 |
专业分类
化学 | 1207篇 |
晶体学 | 9篇 |
力学 | 10篇 |
数学 | 78篇 |
物理学 | 209篇 |
出版年
2022年 | 14篇 |
2021年 | 11篇 |
2020年 | 17篇 |
2019年 | 22篇 |
2018年 | 20篇 |
2017年 | 12篇 |
2016年 | 33篇 |
2015年 | 26篇 |
2014年 | 29篇 |
2013年 | 82篇 |
2012年 | 91篇 |
2011年 | 85篇 |
2010年 | 46篇 |
2009年 | 53篇 |
2008年 | 81篇 |
2007年 | 76篇 |
2006年 | 79篇 |
2005年 | 87篇 |
2004年 | 88篇 |
2003年 | 65篇 |
2002年 | 69篇 |
2001年 | 30篇 |
2000年 | 17篇 |
1999年 | 14篇 |
1998年 | 13篇 |
1997年 | 9篇 |
1996年 | 12篇 |
1995年 | 9篇 |
1994年 | 16篇 |
1993年 | 17篇 |
1992年 | 14篇 |
1991年 | 10篇 |
1990年 | 10篇 |
1989年 | 12篇 |
1987年 | 10篇 |
1985年 | 16篇 |
1984年 | 18篇 |
1983年 | 14篇 |
1982年 | 9篇 |
1981年 | 16篇 |
1980年 | 18篇 |
1979年 | 16篇 |
1978年 | 23篇 |
1977年 | 15篇 |
1976年 | 11篇 |
1975年 | 13篇 |
1969年 | 6篇 |
1968年 | 7篇 |
1967年 | 12篇 |
1965年 | 6篇 |
排序方式: 共有1513条查询结果,搜索用时 15 毫秒
1.
Direct Addition of Amides to Glycals Enabled by Solvation‐Insusceptible 2‐Haloazolium Salt Catalysis
Yuya Nakatsuji Yusuke Kobayashi Yoshiji Takemoto 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(40):14253-14257
The direct 2‐deoxyglycosylation of nucleophiles with glycals leads to biologically and pharmacologically important 2‐deoxysugar compounds. Although the direct addition of hydroxyl and sulfonamide groups have been well developed, the direct 2‐deoxyglycosylation of amide groups has not been reported to date. Herein, we show the first direct 2‐deoxyglycosylation of amide groups using a newly designed Brønsted acid catalyst under mild conditions. Through mechanistic investigations, we discovered that the amide group can inhibit acid catalysts, and the inhibition has made the 2‐deoxyglycosylation reaction difficult. Diffusion‐ordered two‐dimensional NMR spectroscopy analysis implied that the 2‐chloroazolium salt catalyst was less likely to form aggregates with amides in comparison to other acid catalysts. The chlorine atom and the extended π‐scaffold of the catalyst played a crucial role for this phenomenon. This relative insusceptibility to inhibition by amides is more responsible for the catalytic activity than the strength of the acidity. 相似文献
2.
Dr. Takeshi Nanjo Natsuki Kato Xuan Zhang Prof. Yoshiji Takemoto 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(68):15504-15507
Strategies for the formation of amide bonds, that is, one of the most basic and important transformations in organic synthesis, have so far focused predominantly on dehydration reactions. Herein, we report and demonstrate the practical utility of a novel decarboxylative amidation of α-ketoacids by using inexpensive tert-butyl hydroperoxide (TBHP), which is characterized by high yields, a broad substrate scope, mild reaction conditions, and a unique chemoselectivity. These features enable the synthesis of peptides from amino acid derived α-ketoacids under preservation of the stereochemical information. 相似文献
3.
Shinji Takesue 《Journal of statistical physics》1989,56(3-4):371-402
This is the first part of a series devoted to the study of thermodynamic behavior of large dynamical systems with the use of a family of fully-discrete and conservative models named elementary reversible cellular automata (ERCAs). In this paper, basic properties such as conservation laws and phase space structure are investigated in preparation for the later studies. ERCAs are a family of one-dimensional reversible cellular automata having two Boolean variables on each site. Reflection and Boolean conjugation symmetries divide them into 88 equivalence classes. For each rule, additive conserved quantities written in a certain form are regarded as a kind of energy, if they exist. By the aid of the discreteness of the variables, every ERCA satisfies the Liouville theorem or the preservation of phase space volume. Thus, if an energy exists in the above sense, statistical mechanics of the model can formally be constructed. If a locally defined quantity is conserved, however, it prevents the realization of statistical mechanics. The existence of such a quantity is examined for each class and a number of rules which have at least one energy but no local conservation laws are selected as hopeful candidates for the realization of thermodynamic behavior. In addition, the phase space structure of ERCAs is analyzed by enumerating cycles exactly in the phase space for systems of comparatively small sizes. As a result, it is revealed that a finite ERCA is not ergodic, that is, a large number of orbits coexist on an energy surface. It is argued that this fact does not necessarily mean the failure of thermodynamic behavior on the basis of an analogy with the ergodic nature of infinite systems. 相似文献
4.
The effect of oxygen isotope substitution on the transition temperature Tc of a superconducting (Nd1−xCex)2CuO4−δ system was studied, where the special synthetic method was taken to minimize ambiguous factors on the oxygen concentration and to guarantee the complete substitution of 16O by 18O. The isotope exponent in the relationship of Tc∝1/M was estimated to be less than 0.15 by magnetic susceptibility measurements. 相似文献
5.
6.
Takaaki Kakitsuka Shinji Matsuo Seok–Hwan Jeong Toru Segawa Hiroshi Okamoto Yoshihiro Kawaguchi Yasuhiro Kondo Yuzo Yoshikuni Hiroyuki Suzuki 《Optical and Quantum Electronics》2006,38(12-14):1053-1060
We theoretically investigated a digitally tunable laser with a chirped ladder filter and a ring resonator to obtain a wide wavelength tuning range covering the whole C- or L- band. The clear relation between the tuning range and laser structure, especially the ladder filter, is described analytically. The introduction of a chirped structure into a ladder filter is effective in achieving both wide tunability and a stable lasing mode. A numerical simulation based on multimode rate equations shows that a tuning range of over 40 nm and a mode suppression ratio over 40 dB can be achieved by introducing a chirped ladder filter. 相似文献
7.
A new 20-membered macrolide designated exiguolide has been isolated from the marine sponge Geodia exigua, and its structure determined by interpretation of spectroscopic data. Exiguolide specifically inhibited fertilization of sea urchin (Hemicentrotus pulcherrimus) gametes but not embryogenesis of the fertilized egg. 相似文献
8.
9.
10.