全文获取类型
收费全文 | 66370篇 |
免费 | 10200篇 |
国内免费 | 1615篇 |
专业分类
化学 | 61062篇 |
晶体学 | 464篇 |
力学 | 1179篇 |
综合类 | 1篇 |
数学 | 8452篇 |
物理学 | 7027篇 |
出版年
2022年 | 181篇 |
2021年 | 438篇 |
2020年 | 1558篇 |
2019年 | 2884篇 |
2018年 | 1379篇 |
2017年 | 1027篇 |
2016年 | 4025篇 |
2015年 | 4141篇 |
2014年 | 4138篇 |
2013年 | 5733篇 |
2012年 | 4421篇 |
2011年 | 4045篇 |
2010年 | 3839篇 |
2009年 | 3649篇 |
2008年 | 3988篇 |
2007年 | 3371篇 |
2006年 | 3147篇 |
2005年 | 3098篇 |
2004年 | 2815篇 |
2003年 | 2441篇 |
2002年 | 3069篇 |
2001年 | 1834篇 |
2000年 | 1689篇 |
1999年 | 781篇 |
1998年 | 457篇 |
1997年 | 501篇 |
1996年 | 444篇 |
1995年 | 407篇 |
1994年 | 421篇 |
1993年 | 385篇 |
1992年 | 374篇 |
1991年 | 362篇 |
1990年 | 325篇 |
1989年 | 331篇 |
1988年 | 307篇 |
1987年 | 267篇 |
1986年 | 285篇 |
1985年 | 421篇 |
1984年 | 436篇 |
1983年 | 380篇 |
1982年 | 409篇 |
1981年 | 357篇 |
1980年 | 391篇 |
1979年 | 317篇 |
1978年 | 367篇 |
1977年 | 318篇 |
1976年 | 275篇 |
1975年 | 232篇 |
1974年 | 244篇 |
1973年 | 206篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
41.
Design and development of a two‐dimensional system based on hydrophilic and reversed‐phase liquid chromatography with on‐line sample treatment for the simultaneous separation of excreted xenobiotics and endogenous metabolites in urine
下载免费PDF全文
![点击此处可从《Biomedical chromatography : BMC》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Diego García‐Gómez Encarnación Rodríguez‐Gonzalo Rita Carabias‐Martínez 《Biomedical chromatography : BMC》2015,29(8):1190-1196
In the present work we describe a two‐dimensional liquid chromatographic system (2D‐LC) with detection by mass spectrometry (MS) for the simultaneous separation of endogenous metabolites of clinical interest and excreted xenobiotics deriving from exposure to toxic compounds. The 2D‐LC system involves two orthogonal chromatographic modes, hydrophilic interaction liquid chromatography (HILIC) to separate polar endogenous metabolites and reversed‐phase (RP) chromatography to separate excreted xenobiotics of low and intermediate polarity. Additionally, the present proposal has the novelty of incorporating an on‐line sample treatment based on the use of restricted access materials (RAMs), which permits the direct injection of urine samples into the system. The work is focused on the instrumental coupling, studying all possible options and attempting to circumvent the problems of solvent incompatibility between the RAM device and the two chromatographic columns, HILIC and RP. The instrumental configuration developed, RAM‐HILIC‐RPLC‐MS/MS, allows the simultaneous assessment of urinary metabolites of clinical interest and excreted compounds derived from exposure to toxic agents with minimal sample manipulation. Thus, it may be of interest in areas such as occupational and environmental toxicology in order to explore the possible relationship between the two types of compounds. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
42.
Tanja Vidaković-Koch Tamara Miličić Luka A. Živković Hoon Seng Chan Ulrike Krewer Menka Petkovska 《Current Opinion in Electrochemistry》2021
The nonlinear frequency response analysis (NFRA) can be seen as an extension of electrochemical impedance spectroscopy. NFRA gives a full and detailed representation of the system response and can establish a connection between model parameters and the experimentally observed phenomena. In this article, different theoretical NFRA approaches and the most recent application examples are discussed. A simple electrochemical example is used to showcase the benefits and disadvantages of analyzing the system response by using different approaches. In addition, it was shown how to extract experimental harmonic values and analyze them. 相似文献
43.
Quinones are electroactive species that have shown great promise for redox flow batteries due to the ability to tune their properties and to act as both negative and positive electrolytes. The following review outlines highlights of work in the last couple of years working to provide materials with higher stability, solubility, and performance. Developments toward stable negolytes have provided opportunities for potential commercial opportunities when paired with alternate chemistries. However, the stability of quinones in high potential electrolytes is still not sufficient and the number of potential quinones limited. 相似文献
44.
45.
DFT mechanistic study of the H2‐assisted chain transfer copolymerization of propylene and p‐methylstyrene catalyzed by zirconocene complex
下载免费PDF全文
![点击此处可从《Journal of polymer science. Part A, Polymer chemistry》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Cheng‐Gen Zhang Shu‐Yuan Yu Liaoyun Zhang Huayi Li Zhi‐Xiang Wang 《Journal of polymer science. Part A, Polymer chemistry》2015,53(4):576-585
DFT computations have been performed to investigate the mechanism of H2‐assisted chain transfer strategy to functionalize polypropylene via Zr‐catalyzed copolymerization of propylene and p‐methylstyrene (pMS). The study unveils the following: (i) propylene prefers 1,2‐insertion over 2,1‐insertion both kinetically and thermodynamically, explaining the observed 1,2‐insertion regioselectivity for propylene insertion. (ii) The 2,1‐inserion of pMS is kinetically less favorable but thermodynamically more favorable than 1,2‐insertion. The observation of 2,1‐insertion pMS at the end of polymer chain is due to thermodynamic control and that the barrier difference between the two insertion modes become smaller as the chain length becomes longer. (iii) The pMS insertion results in much higher barriers for subsequent either propylene or pMS insertion, which causes deactivation of the catalytic system. (iv) Small H2 can react with the deactivated [Zr]?pMS?PPn facilely, which displace functionalized pMS?PPn chain and regenerate [Zr]? H active catalyst to continue copolymerization. The effects of counterions are also discussed. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 576–585 相似文献
46.
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
47.
48.
Kai He Tsegaye TadesseTsega Xi Liu Jiantao Zai Xin‐Hao Li Xuejiao Liu Wenhao Li Nazakat Ali Xuefeng Qian 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(34):12029-12035
The modulation of electron density is an effective option for efficient alternative electrocatalysts. Here, p‐n junctions are constructed in 3D free‐standing FeNi‐LDH/CoP/carbon cloth (CC) electrode (LDH=layered double hydroxide). The positively charged FeNi‐LDH in the space‐charge region can significantly boost oxygen evolution reaction. Therefore, the j at 1.485 V (vs. RHE) of FeNi‐LDH/CoP/CC achieves ca. 10‐fold and ca. 100‐fold increases compared to those of FeNi‐LDH/CC and CoP/CC, respectively. Density functional theory calculation reveals OH? has a stronger trend to adsorb on the surface of FeNi‐LDH side in the p‐n junction compared to individual FeNi‐LDH further verifying the synergistic effect in the p‐n junction. Additionally, it represents excellent activity toward water splitting. The utilization of heterojunctions would open up an entirely new possibility to purposefully regulate the electronic structure of active sites and promote their catalytic activities. 相似文献
49.
Robin F. Weitkamp Beate Neumann Hans‐Georg Stammler Berthold Hoge 《Angewandte Chemie (International ed. in English)》2020,59(14):5494-5499
We report on the first examples of isolated silanol–silanolate anions, obtained by utilizing weakly coordinating phosphazenium counterions. The silanolate anions were synthesized from the recently published phosphazenium hydroxide hydrate salt with siloxanes. The silanol–silanolate anions are postulated intermediates in the hydroxide‐mediated polymerization of aryl and alkyl siloxanes. The silanolate anions are strong nucleophiles because of the weakly coordinating character of the phosphazenium cation, which is perceptible in their activity in polysiloxane depolymerization. 相似文献