全文获取类型
收费全文 | 32407篇 |
免费 | 2268篇 |
国内免费 | 5027篇 |
专业分类
化学 | 26913篇 |
晶体学 | 549篇 |
力学 | 199篇 |
综合类 | 289篇 |
数学 | 6962篇 |
物理学 | 4790篇 |
出版年
2024年 | 65篇 |
2023年 | 339篇 |
2022年 | 722篇 |
2021年 | 652篇 |
2020年 | 806篇 |
2019年 | 1776篇 |
2018年 | 928篇 |
2017年 | 1722篇 |
2016年 | 1071篇 |
2015年 | 947篇 |
2014年 | 1258篇 |
2013年 | 2747篇 |
2012年 | 1842篇 |
2011年 | 2060篇 |
2010年 | 1558篇 |
2009年 | 1961篇 |
2008年 | 2147篇 |
2007年 | 2094篇 |
2006年 | 2032篇 |
2005年 | 1756篇 |
2004年 | 1714篇 |
2003年 | 1386篇 |
2002年 | 1203篇 |
2001年 | 1021篇 |
2000年 | 984篇 |
1999年 | 769篇 |
1998年 | 711篇 |
1997年 | 586篇 |
1996年 | 472篇 |
1995年 | 452篇 |
1994年 | 322篇 |
1993年 | 287篇 |
1992年 | 279篇 |
1991年 | 198篇 |
1990年 | 125篇 |
1989年 | 115篇 |
1988年 | 96篇 |
1987年 | 56篇 |
1986年 | 49篇 |
1985年 | 62篇 |
1984年 | 49篇 |
1983年 | 23篇 |
1982年 | 51篇 |
1981年 | 45篇 |
1980年 | 26篇 |
1979年 | 45篇 |
1978年 | 19篇 |
1977年 | 20篇 |
1976年 | 16篇 |
1975年 | 11篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
11.
12.
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
13.
《Discrete Mathematics》2020,343(12):112117
Let be an edge-colored graph of order . The minimum color degree of , denoted by , is the largest integer such that for every vertex , there are at least distinct colors on edges incident to . We say that an edge-colored graph is rainbow if all its edges have different colors. In this paper, we consider vertex-disjoint rainbow triangles in edge-colored graphs. Li (2013) showed that if , then contains a rainbow triangle and the lower bound is tight. Motivated by this result, we prove that if and , then contains two vertex-disjoint rainbow triangles. In particular, we conjecture that if , then contains vertex-disjoint rainbow triangles. For any integer , we show that if and , then contains vertex-disjoint rainbow triangles. Moreover, we provide sufficient conditions for the existence of edge-disjoint rainbow triangles. 相似文献
14.
Pu Duan Bo Zhi Luke Coburn Christy L. Haynes Klaus Schmidt-Rohr 《Magnetic resonance in chemistry : MRC》2020,58(11):1130-1138
The composition of fluorescent polymer nanoparticles, commonly referred to as carbon dots, synthesized by microwave-assisted reaction of citric acid and ethylenediamine was investigated by 13C, 13C{1H}, 1H─13C, 13C{14N}, and 15N solid-state nuclear magnetic resonance (NMR) experiments. 13C NMR with spectral editing provided no evidence for significant condensed aromatic or diamondoid carbon phases. 15N NMR showed that the nanoparticle matrix has been polymerized by amide and some imide formation. Five small, resolved 13C NMR peaks, including an unusual ═CH signal at 84 ppm (1H chemical shift of 5.8 ppm) and ═CN2 at 155 ppm, and two distinctive 15N NMR resonances near 80 and 160 ppm proved the presence of 5-oxo-1,2,3,5-tetrahydroimidazo[1,2-a]pyridine-7-carboxylic acid (IPCA) or its derivatives. This molecular fluorophore with conjugated double bonds, formed by a double cyclization reaction of citric acid and ethylenediamine as first shown by Y. Song, B. Yang, and coworkers in 2015, accounts for the fluorescence of the carbon dots. Cross-peaks in a 1H─13C HETCOR spectrum with brief 1H spin diffusion proved that IPCA is finely dispersed in the polyamide matrix. From quantitative 13C and 15N NMR spectra, a high concentration (18 ± 2 wt%) of IPCA in the carbon dots was determined. A pronounced gradient in 13C chemical-shift perturbations and peak widths, with the broadest lines near the COO group of IPCA, indicated at least partial transformation of the carboxylic acid of IPCA by amide or ester formation. 相似文献
15.
16.
17.
Ieva
Dauickait Amos S. Lawless Jennifer A. Scott Peter Jan van Leeuwen 《Numerical Linear Algebra with Applications》2020,27(5)
We consider the large sparse symmetric linear systems of equations that arise in the solution of weak constraint four‐dimensional variational data assimilation, a method of high interest for numerical weather prediction. These systems can be written as saddle point systems with a 3 × 3 block structure but block eliminations can be performed to reduce them to saddle point systems with a 2 × 2 block structure, or further to symmetric positive definite systems. In this article, we analyse how sensitive the spectra of these matrices are to the number of observations of the underlying dynamical system. We also obtain bounds on the eigenvalues of the matrices. Numerical experiments are used to confirm the theoretical analysis and bounds. 相似文献
18.
《Journal of Saudi Chemical Society》2020,24(10):754-764
A kinetic study of the reactions of potentially bioactive 2-amino-4-arylthiazoles with highly reactive 4,6-dinitrobenzofuroxan (DNBF) is reported herein in acetonitrile solution. The complexation reaction was followed by recording the UV–vis spectra with time at λmax = 482 nm. Electronic effects of substituents influencing the rate of reaction have been studied using structure-reactivity relationships. It is shown that the Hammett plot relative to the reaction of DNBF with 2-amino-4-(4-chlorophenyl)thiazole exhibit positive deviation from the log k1 versus σ correlation, while it showed excellent linear correlation in terms of Yukawa–Tsuno equation. It has be noticed that the nonlinear Hammett plot observed for 2-amino-4-(4-chlorophenyl) thiazole is not attributed to a change in rate-determining step but is due to nature of electronic effect of substituent caused by the resonance of stabilization of substrates. The second-order rate constant (k1) relating to the bond C–C and C-N forming step of the complexation processes of DNBF with 4-substituted-aminothiazoles and 2-amino-5-methyl-4-phenylthiazole, respectively, is fit into the linear relationship log k = sN (N + E), thereby permitting the assessment of the nucleophilicity parameter (N) of the 2-amino-4-arylthiazoles of the range (4.90 < N < 6.85). 2-amino-4-arylthiazoles is subsequently ranked by positioning its reactivity on the general nucleophilicity scale developed recently by Mayr and coworkers (2003) leading an interesting and a direct comparison over a large domain of π-, σ -, and n-nucleophiles. The global electrophilicity/nucleophilicity reactivity indexes of the 2-amino-4-arylthiazoles have been investigated by means of a density functional theory (DFT) method. . 相似文献
19.
《Discrete Mathematics》2019,342(3):623-627
Wang and Lih (2002) conjectured that every planar graph without adjacent triangles is 4-choosable. In this paper, we prove that every planar graph without any 4-cycle adjacent to two triangles is DP-4-colorable, which improves the results of Lam et al. (1999), Cheng et al. (2016) and Kim and Yu [ arXiv:1709.09809v1]. 相似文献
20.
《Discrete Mathematics》2019,342(2):339-343
A strong edge-coloring of a graph is a partition of its edge set into induced matchings. Let be a connected planar graph with girth and maximum degree . We show that either is isomorphic to a subgraph of a very special -regular graph with girth , or has a strong edge-coloring using at most colors. 相似文献