全文获取类型
收费全文 | 14714篇 |
免费 | 1032篇 |
国内免费 | 875篇 |
专业分类
化学 | 10620篇 |
晶体学 | 117篇 |
力学 | 463篇 |
综合类 | 66篇 |
数学 | 2696篇 |
物理学 | 2659篇 |
出版年
2024年 | 12篇 |
2023年 | 129篇 |
2022年 | 230篇 |
2021年 | 402篇 |
2020年 | 442篇 |
2019年 | 389篇 |
2018年 | 343篇 |
2017年 | 319篇 |
2016年 | 642篇 |
2015年 | 581篇 |
2014年 | 692篇 |
2013年 | 1013篇 |
2012年 | 1241篇 |
2011年 | 1324篇 |
2010年 | 863篇 |
2009年 | 811篇 |
2008年 | 1043篇 |
2007年 | 1022篇 |
2006年 | 883篇 |
2005年 | 774篇 |
2004年 | 702篇 |
2003年 | 472篇 |
2002年 | 376篇 |
2001年 | 196篇 |
2000年 | 160篇 |
1999年 | 161篇 |
1998年 | 111篇 |
1997年 | 110篇 |
1996年 | 118篇 |
1995年 | 73篇 |
1994年 | 76篇 |
1993年 | 63篇 |
1992年 | 77篇 |
1991年 | 57篇 |
1990年 | 70篇 |
1989年 | 44篇 |
1988年 | 51篇 |
1987年 | 50篇 |
1986年 | 40篇 |
1985年 | 64篇 |
1984年 | 56篇 |
1983年 | 42篇 |
1982年 | 39篇 |
1981年 | 23篇 |
1980年 | 33篇 |
1979年 | 22篇 |
1978年 | 28篇 |
1977年 | 19篇 |
1976年 | 20篇 |
1974年 | 17篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
11.
Karen Beatriz Méndez-Rodríguez Nicté Figueroa-Vega César Arturo Ilizaliturri-Hernandez Mónica Cardona-Alvarado Jaime Antonio Borjas-García Carlos Kornhauser Juan Manuel Malacara Rogelio Flores-Ramírez Francisco Javier Pérez-Vázquez 《Biomedical chromatography : BMC》2020,34(12):e4956
Metabolomics is a potential tool for the discovery of new biomarkers in the early diagnosis of diseases. An ultra-fast gas chromatography system equipped to an electronic nose detector (FGC eNose) was used to identify the metabolomic profile of Volatile Organic Compounds (VOCs) in type 2 diabetes (T2D) urine from Mexican population. A cross-sectional, comparative, and clinical study with translational approach was performed. We recruited twenty T2D patients and twenty-one healthy subjects. Urine samples were taken and analyzed by FGC eNose. Eighty-eight compounds were identified through Kovats's indexes. A natural variation of 30% between the metabolites, expressed by study groups, was observed in Principal Component 1 and 2 with a significant difference (p < 0.001). The model, performed through a Canonical Analysis of Principal coordinated (CAP), allowed a correct classification of 84.6% between healthy and T2D patients, with a 15.4% error. The metabolites 2-propenal, 2-propanol, butane- 2,3-dione and 2-methylpropanal, were increased in patients with T2D, and they were strongly correlated with discrimination between clinically healthy people and T2D patients. This study identified metabolites in urine through FGC eNose that can be used as biomarkers in the identification of T2D patients. However, more studies are needed for its implementation in clinical practice. 相似文献
12.
AbstractRealistic stochastic modeling is increasingly requiring the use of bounded noises. In this work, properties and relationships of commonly employed bounded stochastic processes are investigated within a solid mathematical ground. Four families are object of investigation: the Sine-Wiener (SW), the Doering–Cai–Lin (DCL), the Tsallis–Stariolo–Borland (TSB), and the Kessler–Sørensen (KS) families. We address mathematical questions on existence and uniqueness of the processes defined through Stochastic Differential Equations, which often conceal non-obvious behavior, and we explore the behavior of the solutions near the boundaries of the state space. The expression of the time-dependent probability density of the Sine-Wiener noise is provided in closed form, and a close connection with the Doering–Cai–Lin noise is shown. Further relationships among the different families are explored, pathwise and in distribution. Finally, we illustrate an analogy between the Kessler–Sørensen family and Bessel processes, which allows to relate the respective local times at the boundaries. 相似文献
13.
14.
15.
Tatiana Monaretto Andre Souza Tiago Bueno Moraes Victor Bertucci-Neto Corinne Rondeau-Mouro Luiz Alberto Colnago 《Magnetic resonance in chemistry : MRC》2019,57(9):616-625
The traditional way to enhance signal-to-noise ratio (SNR) of nuclear magnetic resonance (NMR) signals is to increase the number of scans. However, this procedure increases the measuring time that can be prohibitive for some applications. Therefore, we have tested the use of several post-acquisition digital filters to enhance SNR up to one order of magnitude in time domain NMR (TD-NMR) relaxation measurements. The procedures were studied using continuous wave free precession (CWFP-T1) signals, acquired with very low flip angles that contain six times more noise than the Carr–Purcell–Meiboom–Gill (CPMG) signal of the same sample and experimental time. Linear (LI) and logarithmic (LO) data compression, low-pass infinity impulse response (LP), Savitzky–Golay (SG), and wavelet transform (WA) post-acquisition filters enhanced the SNR of the CWFP-T1 signals by at least six times. The best filters were LO, SG, and WA that have high enhancement in SNR without significant distortions in the ILT relaxation distribution data. Therefore, it was demonstrated that these post-acquisition digital filters could be a useful way to denoise CWFP-T1, as well as CPMG noisy signals, and consequently reducing the experimental time. It was also demonstrated that filtered CWFP-T1 method has the potential to be a rapid and nondestructive method to measure fat content in beef and certainly in other meat samples. 相似文献
16.
Highly Selective Copper‐Catalyzed Asymmetric [3+2] Cycloaddition of Azomethine Ylides with Acyclic 1,3‐Dienes 下载免费PDF全文
María González‐Esguevillas Ana Pascual‐Escudero Dr. Javier Adrio Prof. Dr. Juan C. Carretero 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(12):4561-4565
The first examples of the catalytic asymmetric 1,3‐dipolar cycloaddition of azomethine ylides with acyclic activated 1,3‐dienes (and 1,3‐enynes) are described. Under copper catalysis, a selective cycloaddition at the terminal γ,δ‐C?C bond is observed. In addition, depending on the ligand used, either the exo or the endo adduct can be obtained with high selectivity. Under appropriate reaction conditions, the acyclic 1,6‐addition product is detected, suggesting a stepwise mechanism. The resulting C4‐alkenyl‐substituted pyrrolidines are suitable substrates for further access to polycyclic systems, as highlighted by the preparation of hexahydrochromeno[4,3‐b]pyrrole and the tetracyclic core of the alkaloid gracilamine. 相似文献
17.
18.
Complementary regioselective esterification of non-reducing oligosaccharides catalyzed by different hydrolases 总被引:1,自引:0,他引:1
The enzymatic transesterification of several tri- and tetrasaccharides with vinyl laurate is described. The lipases from Candida antarctica B (Novozym 435) and Thermomyces lanuginosus (Lipozyme TL IM) and the alkaline protease from Bacillus licheniformis (subtilisin Carlsberg) have been used with each carbohydrate to obtain different regioisomers. By using the sugars in their amorphous form, complete solubility is achieved in the reaction media (tert-butanol/pyridine mixtures for the lipases and pyridine for the protease) and high isolated yields of the corresponding monoesters are obtained. Good to excellent regioselectivity is observed for all the enzymes, showing a final complementary picture respect to the primary hydroxyls of the oligosaccharides studied. 相似文献
19.
20.
Steven D. Bull Simon W. Epstein Nadeam Mujtaba Edward D. Savory Juan A. Tamayo 《Tetrahedron》2006,62(33):7911-7925
Enolates of (S)-N,N′-bis-(p-methoxybenzyl)-3-iso-propylpiperazine-2,5-dione exhibit high levels of enantiodiscrimination in alkylations with (RS)-1-aryl-1-bromoethanes and (RS)-2-bromoesters, affording substituted diketopiperazines containing two new stereogenic centres in high de. Deprotection and hydrolysis of the resultant substituted diketopiperazines provides a route to the asymmetric synthesis of homochiral methyl 2-amino-3-aryl-butanoates and 3-methyl-aspartates in high de and ee. 相似文献