全文获取类型
收费全文 | 8263篇 |
免费 | 1343篇 |
国内免费 | 660篇 |
专业分类
化学 | 5580篇 |
晶体学 | 85篇 |
力学 | 501篇 |
综合类 | 43篇 |
数学 | 995篇 |
物理学 | 3062篇 |
出版年
2023年 | 159篇 |
2022年 | 179篇 |
2021年 | 241篇 |
2020年 | 359篇 |
2019年 | 303篇 |
2018年 | 269篇 |
2017年 | 253篇 |
2016年 | 414篇 |
2015年 | 406篇 |
2014年 | 456篇 |
2013年 | 580篇 |
2012年 | 785篇 |
2011年 | 763篇 |
2010年 | 533篇 |
2009年 | 490篇 |
2008年 | 550篇 |
2007年 | 421篇 |
2006年 | 457篇 |
2005年 | 335篇 |
2004年 | 265篇 |
2003年 | 222篇 |
2002年 | 175篇 |
2001年 | 133篇 |
2000年 | 139篇 |
1999年 | 171篇 |
1998年 | 150篇 |
1997年 | 126篇 |
1996年 | 127篇 |
1995年 | 111篇 |
1994年 | 94篇 |
1993年 | 78篇 |
1992年 | 77篇 |
1991年 | 76篇 |
1990年 | 43篇 |
1989年 | 38篇 |
1988年 | 39篇 |
1987年 | 34篇 |
1986年 | 28篇 |
1985年 | 20篇 |
1984年 | 20篇 |
1983年 | 20篇 |
1982年 | 9篇 |
1981年 | 14篇 |
1980年 | 9篇 |
1977年 | 6篇 |
1976年 | 10篇 |
1975年 | 9篇 |
1973年 | 8篇 |
1972年 | 6篇 |
1970年 | 5篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
101.
Frontispiece: A Step‐by‐Step Assembly of a 3D Coordination Polymer in the Solid‐State by Desolvation and [2+2] Cycloaddition Reactions 下载免费PDF全文
102.
Nicholle G. A. Bell Adam A. L. Michalchuk John W. T. Blackburn Dr. Margaret C. Graham Dr. Dušan Uhrín 《Angewandte Chemie (International ed. in English)》2015,54(29):8382-8385
Humic substances, the main component of soil organic matter, could form an integral part of green and sustainable solutions to the soil fertility problem. However, their global‐scale application is hindered from both scientific and regulatory perspectives by the lack of understanding of the molecular make‐up of these chromatographically inseparable mixtures containing thousands of molecules. Here we show how multidimensional NMR spectroscopy of isotopically tagged molecules enables structure characterization of humic compounds. We illustrate this approach by identifying major substitution patterns of phenolic aromatic moieties of a peat soil fulvic acid, an operational fraction of humic substances. Our methodology represents a paradigm shift in the use of NMR active tags in structure determination of small molecules in complex mixtures. Unlike previous tagging methodologies that focused on the signals of the tags, we utilize tags to directly probe the identity of the molecules they are attached to. 相似文献
103.
Corrigendum: Crowdsourcing Natural Products Discovery to Access Uncharted Dimensions of Fungal Metabolite Diversity 下载免费PDF全文
104.
Enantioselective Synthesis of Quaternary Carbon Stereocenters: Addition of 3‐Substituted Oxindoles to Vinyl Sulfone Catalyzed by Pentanidiums 下载免费PDF全文
Dr. Lili Zong Shubo Du Kek Foo Chin Dr. Chao Wang Prof. Dr. Choon‐Hong Tan 《Angewandte Chemie (International ed. in English)》2015,54(32):9390-9393
A pentanidium‐catalyzed highly enantioselective conjugate addition of 3‐alkyloxindoles to phenyl vinyl sulfone has been demonstrated. This approach allows the construction of 3,3‐dialkyl‐substituted oxindole frameworks with high yield and excellent enantioselectivity (up to 99 %) under simple phase‐transfer conditions. A variety of oxindoles bearing all‐carbon quaternary stereogenic centers were obtained in the presence of 0.25 mol % pentanidium. Meanwhile, practicality was illustrated by a gram‐scale asymmetric synthesis of two 3,3‐dialkyl‐substituted oxindoles. The resulting adduct can be smoothly transformed to the natural product analogue in a short synthetic route. 相似文献
105.
A Two‐Coordinate Cobalt(II) Imido Complex with NHC Ligation: Synthesis,Structure, and Reactivity 下载免费PDF全文
Jingzhen Du Linbo Wang Prof. Dr. Meihua Xie Prof. Dr. Liang Deng 《Angewandte Chemie (International ed. in English)》2015,54(43):12640-12644
The synthesis, structural characterization, and reactivity of the first two‐coordinate cobalt complex featuring a metal–element multiple bond [(IPr)Co(NDmp)] ( 4 ; IPr=1,3‐bis(2′,6′‐diisopropylphenyl)imidazole‐2‐ylidene; Dmp=2,6‐dimesitylphenyl) is reported. Complex 4 was prepared from the reaction of [(IPr)Co(η2‐vtms)2] (vtms=vinyltrimethylsilane) with DmpN3. An X‐ray diffraction study revealed its linear C? Co? N core and a short Co? N distance (1.691(6) Å). Spectroscopic characterization and calculation studies indicated the high‐spin nature of 4 and the multiple‐bond character of the Co? N bond. Complex 4 effected group‐transfer reactions to CO and ethylene to form isocyanide and imine, respectively. It also facilitated E? H (E=C, Si) σ‐bond activation of terminal alkyne and hydrosilanes to produce the corresponding cobalt(II) alkynyl and cobalt(II) hydride complexes as 1,2‐addition products. 相似文献
106.
Zhen Long Dongping Yu Yanfang Liu Nana Du Yanduo Tao Lijuan Mei Zhimou Guo Xinmiao Liang 《Analytica chimica acta》2015
This study investigated the influence of organic sample solvents on separation efficiency of basic compounds under strong cation exchange (SCX) mode. The mixtures of acidic aqueous solution and organic solvent such as acetonitrile, ethanol, methanol and dimethyl sulfoxide (DMSO) were tested as sample solvents. For later-eluting analytes, the increase of sample solvent elution strength was responsible for the decrease of separation efficiency. Thus, sample solvents with weak elution strength could provide high separation efficiencies. For earlier-eluting analytes, the retention of organic sample solvents was the main factor affecting separation efficiency. Weakly retained solvents could provide high separation efficiency. In addition, an optimized approach was proposed to reduce the effect of organic sample solvent, in which low ionic solvent was employed as initial mobile phase in the gradient. At last, the analysis of impurities in hydrophobic drug berberine was performed. The results showed that using acidic aqueous methanol as sample solvents could provide high separation efficiency and good resolution (R > 1.5). 相似文献
107.
A novel cedar-like Au nanoparticles (AuNPs) coating was fabricated on an etched stainless steel (SS) wire by direct chemical deposition and used as an efficient and unbreakable solid phase microextraction (SPME) fiber. The etched SS wire offers a rough surface structure for subsequent growth of AuNPs in chloroauric acid solution. As a result, the uniform cedar-like AuNPs coating with larger surface area was tightly attached to the etched SS wire substrate. The AuNPs coated etched SS fiber (AuNPs/SS) was examined for SPME of ultraviolet (UV) filters, phthalate esters and aromatic hydrocarbons coupled to high-performance liquid chromatography with UV detection. The fabricated fiber exclusively exhibited excellent extraction efficiency and selectivity for some aromatic hydrocarbons. Influential parameters of extraction and desorption time, temperature, stirring rate and ionic strength were investigated and optimized. The limits of detection ranged from 0.008 μg L−1 to 0.037 μg L−1. The single fiber repeatability varied from 3.90% to 4.50% and the fiber-to-fiber reproducibility ranged from 5.15% to 6.87%. The recovery of aromatic hydrocarbons in real water samples spiked at 2.0 μg L−1 and 20 μg L−1 ranged from 94.38% to 106.2% with the relative standard deviations below 6.44%. Furthermore the growth of the cedar-like AuNPs coating can be performed in a highly reproducible manner. This fabricated fiber exhibits good stability and withstands at least 200 extraction and desorption replicates. 相似文献
108.
A novel ratiometric electrochemical sensor for sensitive and selective determination of deoxyribonucleic acid (DNA) had been developed based on signal-on and signal-off strategy. The target DNA hybridized with the loop portion of ferrocene (Fc) labeled hairpin probe immobilized on the gold electrode (GE), the Fc away from the surface of GE and the methylene blue (MB) was attached to an electrode surface by hybridization between hairpin probe and MB labeled primer. Such conformational changes resulted in the oxidation peak current of Fc decreased and that of MB increased, and the changes of dual signals are linear with the concentration of DNA. Furthermore, with the help of strand-displacement polymerization, polymerase catalyzed the extension of the primer and the sequential displacement of the target DNA, which led to the release of target and another polymerization cycle. Thus the circular strand displacement produced the multiplication of the MB confined near the GE surface and Fc got away from the GE surface. Therefore, the recognition of target DNA resulted in both the “signal-off” of Fc and the “signal-on” of MB for dual-signal electrochemical ratiometric readout. The dual signal strategy offered a dramatic enhancement of the stripping response. The dynamic range of the target DNA detection was from 10−13 to 10−8 mol L−1 with a detection limit down to 28 fM level. Compared with the single signaling electrochemical sensor, the dual-signaling electrochemical sensing strategy developed in this paper was more selective. It would have important applications in the sensitive and selective electrochemical determination of other small molecules and proteins. 相似文献
109.
Xi Dai Tao Zhang Zhi-Fang Du Xiang-Jian Cao Ming-Yu Chen Sheng-Wen Hu Jun-Ying Miao Bao-Xiang Zhao 《Analytica chimica acta》2015
We have developed the first two-photon colorimetric and ratiometric fluorescent probe, BICO, for the detection of bisulfite (HSO3−) in aqueous solution. The probe contains coumarin and benzimidazole moieties and can detect HSO3− based on the Michael addition reaction with a limit of detection 5.3 × 10−8 M in phosphate-buffered saline solution. The probe was used to detect bisulfite in tap water, sugar and dry white wine. Moreover, test strips were made and used easily. We successfully applied the probe to image living cells, using one-photon fluorescence imaging. BICO overcomes the limitations in sensitivity of previously reported probes and the solvation effect of bisulfite, which demonstrates its excellent value in practical application. 相似文献
110.
Chiral Separations in Normal‐phase Liquid Chromatography: Updating a Screening Strategy with a Chlorine‐containing Polysaccharide‐based Selector 下载免费PDF全文
Jie Zhou Shanshan Chen Pei Luo Chong Sun Lingchang Meng Qiuzheng Du Fang Sun 《中国化学会会志》2015,62(12):1059-1067
The screening conditions of an existing column and mobile phase selection strategy for chiral compounds in normal‐phase high performance liquid chromatography (NP‐HPLC) were tested for their applicability on Chiralpak IC, which is a chiral stationary phase (CSP) made by immobilising cellulosic tris (3,5‐dichlorophenyl‐carbamate) on silica gel. In this study, the applicability of the optimization steps of the existing separation strategy was examined using 36 compounds representing the three possible resolution situations that occur after screening. The cumulative number of separated compounds is 27 (75.0 %), and the cumulative number of baseline separated compounds is 19 (52.8 %). 相似文献