全文获取类型
收费全文 | 140210篇 |
免费 | 15898篇 |
国内免费 | 7735篇 |
学科分类
数理化 | 163843篇 |
出版年
2023年 | 868篇 |
2022年 | 1487篇 |
2021年 | 2347篇 |
2020年 | 3668篇 |
2019年 | 5048篇 |
2018年 | 4054篇 |
2017年 | 3758篇 |
2016年 | 6919篇 |
2015年 | 6025篇 |
2014年 | 7135篇 |
2013年 | 9295篇 |
2012年 | 8698篇 |
2011年 | 8369篇 |
2010年 | 7622篇 |
2009年 | 7584篇 |
2008年 | 7382篇 |
2007年 | 6496篇 |
2006年 | 5796篇 |
2005年 | 5443篇 |
2004年 | 4831篇 |
2003年 | 4265篇 |
2002年 | 5107篇 |
2001年 | 4169篇 |
2000年 | 3505篇 |
1999年 | 2197篇 |
1998年 | 1797篇 |
1997年 | 1551篇 |
1996年 | 1473篇 |
1995年 | 1207篇 |
1994年 | 1308篇 |
1993年 | 1201篇 |
1992年 | 1161篇 |
1991年 | 1211篇 |
1990年 | 1190篇 |
1989年 | 1101篇 |
1988年 | 970篇 |
1987年 | 956篇 |
1986年 | 902篇 |
1985年 | 936篇 |
1984年 | 920篇 |
1983年 | 828篇 |
1982年 | 803篇 |
1979年 | 799篇 |
1978年 | 810篇 |
1977年 | 808篇 |
1976年 | 918篇 |
1975年 | 812篇 |
1974年 | 839篇 |
1973年 | 843篇 |
1972年 | 751篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
101.
介绍了D*-度量空间中的相关知识, 并基于D*-度量空间, 将度量空间中与两种距离控制函数(ψ,?)有关的广义弱压缩映射推广到D*-度量空间, 通过构造迭代序列,讨论了广义弱压缩条件下映射不动点的存在性和唯一性, 给出了几个不动点定理, 所得结果丰富了D*-度量空间的不动点理论。 相似文献
102.
静止轨道卫星差分吸收光谱仪采用摆扫成像方式对大气进行探测,针对其工作时CCD成像系统信噪比大于1 000、高速探测模式下探测周期小于10min、高分辨率模式下探测周期小于1h的要求,进行CCD成像系统设计.选取CCD47-20作为探测器,设计成像电路实现光谱图像信号的采集和上传.分析了帧叠加和像元合并对时间、空间分辨率的影响.结合帧转移CCD的特点设计了每个位置最后一帧读出时摆镜转动的成像方式,并合理设置了帧叠加数和像元合并数,达到优化成像周期的目的.1s曝光时间条件下,该CCD成像系统的高速、高分辨率模式探测周期分别为515s和3 315s,图像信噪比均大于1 000,污染物观测实验中未出现失帧或重复的现象.该CCD成像系统方案满足静止轨道星载差分吸收光谱仪的探测需求,为静止轨道环境监测仪器设计提供参考. 相似文献
103.
104.
Metabolic profiles of dioscin in rats revealed by ultra‐performance liquid chromatography quadrupole time‐of‐flight mass spectrometry 下载免费PDF全文
He Zhu Jin‐Di Xu Qian Mao Hong Shen Ming Kong Jian‐Ping Chen Song‐Lin Li 《Biomedical chromatography : BMC》2015,29(9):1415-1421
Dioscin (DIS), one of the most abundant bioactive steroidal saponins in Dioscorea sp., is used as a complementary medicine to treat coronary disease and angina pectoris in China. Although the pharmacological activities and pharmacokinetics of DIS have been well demonstrated, information regarding the final metabolic fates is very limited. This study investigated the in vivo metabolic profiles of DIS after oral administration by ultra‐performance liquid chromatography quadrupole time‐of‐flight mass spectrometry method. The structures of the metabolites were identified and tentatively characterized by means of comparing the molecular mass, retention time and fragmentation pattern of the analytes with those of the parent compound. A total of eight metabolites, including seven phase I and one phase II metabolites, were detected and tentatively identified for the first time. Oxidation, deglycosylation and glucuronidation were found to be the major metabolic processes of the compound in rats. In addition, a possible metabolic pathway on the biotransformation of DIS in vivo was proposed. This study provides valuable and new information on the metabolism of DIS, which will be helpful for further understanding its mechanism of action. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
105.
以典型的双稳态系统——屈曲梁结构为例,基于等效模型,结合解析、数值和实验手段,研究了双稳态结构中的1/2次谐波共振特性、演化过程、参数调节规律及其对隔振特性的影响.研究发现,当非线性刚度系数或激励幅值增加到一定程度时,系统会在一定带宽下产生显著的1/2次谐波共振;随着激励幅值增加,阻尼系统的1/2次谐波遵循“产生-增强-衰退-消失”的过程,该过程对峰值频率和峰值传递率有重要影响;适当提高非线性强度能有效改善双稳态结构隔振特性.针对双稳态屈曲梁结构开展的实验验证了1/2次谐波特性和隔振特性变化规律. 相似文献
106.
107.
Photoisomerisation in Aminoazobenzene‐Substituted Ruthenium(II) Tris(bipyridine) Complexes: Influence of the Conjugation Pathway 下载免费PDF全文
Dr. Anissa Amar Dr. Paul Savel Dr. Huriye Akdas‐Kilig Dr. Claudine Katan Prof. Hacène Meghezzi Prof. Abdou Boucekkine Dr. Jean‐Pierre Malval Dr. Jean‐Luc Fillaut 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(22):8262-8270
Transition‐metal complexes containing stimuli‐responsive systems are attractive for applications in optical devices, photonic memory, photosensing, as well as luminescence imaging. Amongst them, photochromic metal complexes offer the possibility of combining the specific properties of the metal centre and the optical response of the photochromic group. The synthesis, the electrochemical properties and the photophysical characterisation of a series of donor–acceptor azobenzene derivatives that possess bipyridine groups connected to a 4‐dialkylaminoazobenzene moiety through various linkers are presented. DFT and TD‐DFT calculations were performed to complement the experimental findings and contribute to their interpretation. The position and nature of the linker (ethynyl, triazolyl, none) were engineered and shown to induce different electronic coupling between donor and acceptor in ligands and complexes. This in turn led to strong modulations in terms of photoisomerisation of the ligands and complexes. 相似文献
108.
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
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
109.
110.
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
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