全文获取类型
收费全文 | 12389篇 |
免费 | 2088篇 |
国内免费 | 2439篇 |
专业分类
化学 | 10230篇 |
晶体学 | 254篇 |
力学 | 637篇 |
综合类 | 144篇 |
数学 | 1162篇 |
物理学 | 4489篇 |
出版年
2024年 | 56篇 |
2023年 | 286篇 |
2022年 | 541篇 |
2021年 | 566篇 |
2020年 | 594篇 |
2019年 | 659篇 |
2018年 | 538篇 |
2017年 | 538篇 |
2016年 | 632篇 |
2015年 | 664篇 |
2014年 | 796篇 |
2013年 | 987篇 |
2012年 | 1069篇 |
2011年 | 1064篇 |
2010年 | 874篇 |
2009年 | 791篇 |
2008年 | 817篇 |
2007年 | 675篇 |
2006年 | 686篇 |
2005年 | 643篇 |
2004年 | 541篇 |
2003年 | 458篇 |
2002年 | 489篇 |
2001年 | 455篇 |
2000年 | 305篇 |
1999年 | 241篇 |
1998年 | 156篇 |
1997年 | 97篇 |
1996年 | 123篇 |
1995年 | 85篇 |
1994年 | 95篇 |
1993年 | 86篇 |
1992年 | 59篇 |
1991年 | 70篇 |
1990年 | 41篇 |
1989年 | 31篇 |
1988年 | 22篇 |
1987年 | 18篇 |
1986年 | 21篇 |
1985年 | 16篇 |
1984年 | 7篇 |
1983年 | 10篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1980年 | 2篇 |
1979年 | 2篇 |
1971年 | 1篇 |
1959年 | 3篇 |
1957年 | 1篇 |
1936年 | 3篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
992.
993.
994.
995.
用两种相似多糖类手性固定相拆分阿托品外消旋对映体的比较 总被引:1,自引:0,他引:1
分别涂敷纤维素-三(3,5-二甲基苯基氨基甲酸酯)(CDMPC)与直链淀粉-三(3,5-二甲基苯基氰基甲酸酯)(ADMPC)于自制的球形氨丙基硅胶上,制备了两种多糖类手性崮定相。用高效液相色谱法(HPLC)在正相条件下,用两种固定相直接拆分了阿托品(atmpine)外消旋体、在正己烷中加入了不同的醇类改性剂对阿托品进行拆分,并优化了流动相中醇类改性剂的比例:结果发现,阿托品在CDMPC固定相上可以得到基线拆分,而在ADMPC固定相上只能得到部分拆分。 相似文献
996.
Jing‐Zheng Song Lok Man Cheung Xin Liu Chun‐Feng Qiao Yan Zhou Song‐Lin Li Shi‐Lin Chen Hong‐Xi Xu 《Journal of separation science》2010,33(13):1909-1915
(+)‐Pinoresinol 4,4′‐di‐O‐β‐D ‐glucopyranoside ((+)‐PDG) is one of the major lignans with various pharmacological activities which could be isolated from Duzhong and other plant species. In this study, a diastereomeric impurity, (?)‐pinoresinol 4,4′‐di‐O‐β‐D ‐glucopyranoside ((?)‐PDG), the main impurity was identified in (+)‐PDG chemical reference substance (CRS) and a reliable chromatographic method for rapid purity determination of (+)‐PDG CRS was firstly developed. The optimal chromatographic condition was found to be using ACN/1,4‐dioxane–water (2.5:6:91.5, v/v/v) as mobile phase on a Waters Acquity UPLC HSS T3 column (2.1 mm×100 mm, 1.8 μm) with column temperature of 37°C. The method was validated and applied to determine the chromatographic purity of five (+)‐PDG CRS samples. The content of (?)‐PDG in four commercial (+)‐PDG CRS was 8.47–20.30%, whereas no (?)‐PDG was detected in our in‐house prepared (+)‐PDG CRS in which purity was confirmed to be 99.80%. The above results confirmed that this method is fast and highly efficient for purity determination of the (+)‐PDG CRS. 相似文献
997.
Xiao‐Chi Ma Xiulan Xin Bao‐jing Zhang Sha Deng Ji‐hong Yao Chang‐yuan Wang Jian Cui Yan Tian Ke‐xin Liu 《Journal of separation science》2010,33(15):2272-2277
An efficient separation method of using high‐speed counter‐current chromatography was successfully established to directly purify cytotoxic transformed products of cinobufagin by Cordyceps militaris. The two‐phase solvent system composed of n‐hexane–ethyl acetate–methanol–water (4:6:3:4, v/v) was used in high‐speed counter‐current chromatography. A total of 9 mg of 4β,12α‐dihydroxyl‐cinobufagin ( 1 ), 15 mg of 12β‐hydroxyl‐cinobufagin ( 2 ), 8 mg of 5β‐hydroxyl‐cinobufagin ( 3 ), 12 mg of deacetylcinobufagin ( 4 ) and 6 mg of 3‐keto‐cinobufagin ( 5 ) were obtained in a one‐step separation from 400 mg of the crude extract with purity of 98.7, 97.2, 90.6, 99.1 and 99.4%, respectively, as determined by HPLC. Their chemical structures were identified on the basis of 1H‐NMR and 13C‐NMR technology. All products ( 1 – 5 ) showed the potent activities against human carcinoma cervicis (Hela) and malignant melanoma (A375) cells in vitro. 相似文献
998.
Yan Li Peng Wang Xin Wang Ming Cao YunSheng Xia Chun Cao MeiGui Liu ChangQing Zhu 《Mikrochimica acta》2010,169(1-2):65-71
A method for determination of vitamin B1 has been developed that is based on the enhancement effect of vitamin B1 on the luminescence of water-soluble CdTe nanorods modified with thioglycolic acid and cysteine. The effect of variables including the size of the nanorods on the enhancement of luminescence have been investigated. A preliminary mechanistic study showed that the passivating action of vitamin B1 on the surface of the CdTe nanorods is likely to be responsible for the enhancement. Interferences by shortwave fluorescence are effectively eliminated because measurements are performed in the near-infrared. Due to the near-infrared measurement character, the fluorescence interference of vitamin B2 can be effectively eliminated. Under the optimum conditions, the extent of luminescence enhancement is proportional to the concentration of vitamin B1 in the range from 0.1 to 3.0 μmol L?1 and the detection limit is 0.03 μmol L?1. The relative standard deviation for 2.0 μmol L?1 vitamin B1 is 1.3% (n?=?6). The method is highly sensitive and selective, avoids the sample treatment needed in other procedures, and can be applied to the determination of vitamin B1 in real samples with satisfactory results. 相似文献
999.
Xin‐Gang Xie Dr. Xun‐Wei Wu Dr. Hing‐Ken Lee Dr. Xiao‐Shui Peng Prof. Dr. Henry N. C. Wong Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(23):6933-6941
Plakortone B is a naturally occurring bicyclic[3.3.0]furanolactone compound with attractive bioactivities. Although the relative configuration of plakortone B’s central core had been established by NMR spectroscopic methods, the absolute configuration of its four stereocenters remained unknown. In the present paper, all four possible isomers of plakortone B were synthesized and one of these molecules was found to be identical with the natural plakortone B on the basis of 1H, 13C NMR spectra and specific rotation comparisons. Thus, the absolute configuration of the natural plakortone B was determined to be (3S,4S,6R,10R). 相似文献
1000.
Facile strategy for synthesis of silica/polymer hybrid hollow nanoparticles with channels 总被引:1,自引:0,他引:1
Wu C Wang X Zhao L Gao Y Ma R An Y Shi L 《Langmuir : the ACS journal of surfaces and colloids》2010,26(23):18503-18507
The silica/polymer hybrid hollow nanoparticles with channels and gatekeepers were successfully fabricated with a facile strategy by using thermoresponsive complex micelles of poly(ethylene glycol)-b-poly(N-isopropylacrylamide) (PEG-b-PNIPAM) and poly(N-isopropylacrylamide)-b-poly(4-vinylpyridine) (PNIPAM-b-P4VP) as the template. In aqueous solution, the complex micelles (PEG-b-PNIPAM/PNIPAM-b-P4VP) formed with the PNIPAM block as the core and the PEG/P4VP blocks as the mixed shell at 45 °C and pH 4.0. After shell cross-linking by 1,2-bis(2-iodoethoxyl)ethane (BIEE), tetraethylorthosilicate (TEOS) selectively well-deposited on the P4VP block and processed the sol-gel reaction. When the temperature was decreased to 4 °C, the PNIPAM block became swollen and further soluble, and the PEG-b-PNIPAM block copolymer escaped from the hybrid nanoparticles as a result of swelled PNIPAM and weak interaction between PEG and silica at pH 4.0. Therefore, the hybrid hollow silica nanoparticles with inner thermoresponsive PNIPAM as gatekeepers and channels in the silica shell were successfully obtained, which could be used for switchable controlled drug release. In the system, the complex micelles, as a template, could avoid the formation of larger aggregates during the preparation of the hybrid hollow silica nanoparticles. The thermoresponsive core (PNIPAM) could conveniently control the hollow space through the stimuli-responsive phase transition instead of calcination or chemical etching. In the meantime, the channel in the hybrid silica shell could be achieved because of the escape of PEG chains from the hybrid nanoparticles. 相似文献