全文获取类型
收费全文 | 8504篇 |
免费 | 1390篇 |
国内免费 | 671篇 |
专业分类
化学 | 5763篇 |
晶体学 | 88篇 |
力学 | 504篇 |
综合类 | 36篇 |
数学 | 999篇 |
物理学 | 3175篇 |
出版年
2024年 | 22篇 |
2023年 | 165篇 |
2022年 | 288篇 |
2021年 | 294篇 |
2020年 | 372篇 |
2019年 | 310篇 |
2018年 | 275篇 |
2017年 | 260篇 |
2016年 | 426篇 |
2015年 | 429篇 |
2014年 | 472篇 |
2013年 | 596篇 |
2012年 | 787篇 |
2011年 | 751篇 |
2010年 | 529篇 |
2009年 | 488篇 |
2008年 | 551篇 |
2007年 | 419篇 |
2006年 | 456篇 |
2005年 | 330篇 |
2004年 | 263篇 |
2003年 | 218篇 |
2002年 | 172篇 |
2001年 | 142篇 |
2000年 | 148篇 |
1999年 | 175篇 |
1998年 | 155篇 |
1997年 | 127篇 |
1996年 | 131篇 |
1995年 | 112篇 |
1994年 | 97篇 |
1993年 | 81篇 |
1992年 | 79篇 |
1991年 | 76篇 |
1990年 | 45篇 |
1989年 | 38篇 |
1988年 | 39篇 |
1987年 | 35篇 |
1986年 | 28篇 |
1985年 | 21篇 |
1984年 | 20篇 |
1983年 | 21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 |
排序方式: 共有10000条查询结果,搜索用时 9 毫秒
311.
Dusan Miljković Nada Vukojević DuŜAn Minie Pavle Hadzcircć Gordana Hajduković 《Journal of carbohydrate chemistry》2013,32(3):501-508
Abstract 1,2-O-Cyclohexylidene-α-d-xylofuranuronic acid (2) has been converted into its 3-O-acetyl derivative and consecutively to the corresponding acid chloride and ethyl ester. Direct reaction of 2 with ethanol in the presence of p-to-luene sulphonic acid gave the ethyl ester. Reaction of 2 with phosphorus pentachloride in dry ether gave the acid chloride of 1,2-O-cyclohexylidene-3-O-dichlorophosphoryl–α-d-xylofuranuronic acid. Conformational data have been obtained from 1H and 13C NMR measurements. 相似文献
312.
Abstract The glycosidic coupling reaction of 1,2-anhydro-3,4,6-tri-O-benzyl-β-d-mannopyranose (7), 1,2-anhydro-3,4,6-tri-O-benzyl-α-d-galactopyranose (21), and 1,2-anhydro-3,4-di-O-benzyl-α-d-xylopyranose (18) with N-tosyl- (10) or N-benzyloxycarbonyl- (11) L-serine methyl ester provides a new stereocontrolled synthesis of 1,2-trans linked glycopeptides. The 1,2-anhydro sugars are shown to react smoothyl with 10 or 11 in the presence of Lewis acid (ZnCl2 or AgOTf) as well as powdered 4A molecular sieves in CH2Cl2 at room temperature to afford glycosyl serine derivatives with high stereoselectivity and high yield in less than 30 min. An improved method using 2-O-acetyl-3,4,6-tri-O-benzyl-α-d-mannopyranosyl chloride (6) as the key intermediate for ring closure was applied for the synthesis of 1,2-anhydro-3,4,6-tri-O-benzyl-β-d-mannopyranose. 相似文献
313.
Wei-Bin Huang Cai-Yan Du Jian-An Jiang Ya-Fei Ji 《Research on Chemical Intermediates》2013,39(6):2849-2856
A method for concurrent synthesis of vanillin and isovanillin has been developed by a nonregioselective Vilsmeier–Haack reaction of O-alkyl guaiacols. O-Alkylation of guaiacol provided the corresponding O-alkyl guaiacol (1), which was then formylated with N-methylformanilide/phosphorus oxychloride to give a mixture of 4-alkoxy-3-methoxy-benzaldehyde (2) and 3-alkoxy-4-methoxybenzaldehyde (3). Finally, the obtained mixture underwent a selective dealkylation by anhydrous aluminium trichloride, while leaving methyl groups intact to simultaneously achieve the significant fine chemicals vanillin and isovanillin. 相似文献
314.
Dr. Libo Du Siqingaowa Suo Guangqing Wang Dr. Hongying Jia Prof. Dr. Ke Jian Liu Prof. Dr. Baolu Zhao Prof. Dr. Yang Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(4):1281-1287
The enhanced antioxidant activity of surface‐functionalized gold nanoparticles (AuNPs) synthesized by self‐assembly has attracted great attention, but little is known about the mechanism behind the enhanced activity. To address this challenge, the antioxidant activity of Au@PEG3SA (i.e., surface‐functionalization of spherical AuNPs with the antioxidant salvianic acid A) was used as an example to illustrate the mechanism of the enhanced activity. Evaluation of the antioxidant activity was performed in a radical‐scavenging reaction between Au@PEG3SA and 2,2‐diphenyl‐1‐picrylhydrazyl (DPPH) radical. As expected, the rate constant for the reaction of Au@PEG3SA with DPPH was about nine times greater than that for the salvianic acid A monomer. A comparative analysis of the spectral characteristics of Au@PEG3SA and the salvianic acid A monomer further imply that the enhancement of the antioxidative reaction kinetics may be ascribed to the variation in the transition state for the DPPH‐radical scavenging reaction through π–π stacking interactions between and among adjacent groups on the surface of Au@PEG3SA. On the other hand, the kinetic enhancement of Au@PEG3SA on reactive‐oxygen‐species (ROS) scavenging can be observed in living cells and in vivo, which possibly provides new insight for the bioapplication of self‐assembly of surface‐functionalized AuNPs. 相似文献
315.
采用原位聚合法,制备了聚氨酯(PU)/聚甲基丙烯酸甲酯(PMMA)/层状双金属氢氧化物(LDH)纳米复合体系(PU/PMMA/LDH).通过广角X射线衍射(WXRD)、透射电子显微镜(TEM)对其结构和形貌进行了表征,并通过热失重(TGA)、动态力学分析(DMA)和宽频介电谱(BDRS)研究了LDH含量(φ)对PU/PMMA体系热稳定性和弛豫行为的影响.结果表明,当φ<1 wt%时,LDH在聚合物基体中以剥离结构为主,PU/PMMA/LDH体系的玻璃化温度(Tg)降低,最大损耗因子(tanδmax)增大;而当φ>1 wt%时,LDH在聚合物基体中以插层结构为主,插层结构对聚合物分子链的限制使复合体系的Tg升高、tanδmax降低.LDH表面与PU硬段间的氢键作用,使复合体系的α介电弛豫转变随φ增加而向高温方向移动,弛豫过程激活参数增大. 相似文献
316.
The power supply for IEF based on features of the Cockcroft‐Walton voltage multiplier (CW VM) is described in this work. The article describes a design of the IEF power supply, its electric characteristics, and testing by IEF analysis. A circuit diagram of the power supply included two opposite charged branches (each consisting of four voltage doublers). The designed CW VM was powered by 230 V/50 Hz alternate current and it generated up to 5 kV and 90 mW at the output. Voltage and current characteristics of the power supply were measured by known load resistances in the range from 10 kΩ to 1 GΩ, which is a common resistance range for IEF strip geometry. Further, the power supply was tested by a separation of a model mixture of colored pI markers using a 175 × 3 × 0.5 mm focusing bed. Automatically limited power load enabled analysis of samples without previous optimization of the focusing voltage or electric current time courses according to sample composition. Moreover, the developed power supply did not produce any intrinsic heat and was easy to set up with cheap and commonly available parts. 相似文献
317.
318.
Substituent effects on the redox potentials of dihydroxybenzenes: theoretical and experimental study
Tao Liu Meng-Meng Liu Xiao-Wen Zheng Chong-Yang Du Xiang-Yang Cui Lu Wang Ling-Li Han Zhang-Yu Yu 《Tetrahedron》2014
The redox reactions of p-hydroquinone and pyrocatechol undergo a two-proton-two-electron process in aqueous solution. We calculated their redox potentials at the B3LYP/6-311+G(d,p) level, and verified the values by employing cyclic voltammetry experiments. Then we selected seven substituent groups (–F, –Cl, –OH, –COOH, –CN, –NH2, and –NO2 groups) to systematically investigate the substituent effect, including the sort, position, and number of the substituent, on the redox potentials of p-hydroquinone and pyrocatechol. The calculated results show that –NH2 and –OH groups can decrease the redox potentials, while –F, –Cl, –COOH, –CN, and –NO2 groups increase the potential values of p-hydroquinone and pyrocatechol. The calculations can accurately predict the substituent effects on the redox potentials of pyrocatechol and p-hydroquinone. We would expect that the accurate calculation results for the model systems could be applied in the prediction of electrode potentials of other molecules. 相似文献
319.
Xiu-Jiang Du Zhi-Peng WangYan-Ling Hou Cheng ZhangZheng-Ming Li Wei-Guang Zhao 《Tetrahedron letters》2014
A new method has been developed for the Michael addition of nitrogen- and carbon-containing nucleophiles to cyclic enones. Using this conjugate addition reaction, a variety of different nucleophiles can react with a range of cyclic enones in the presence of p-toluenesulfonic acid under solvent-free ultrasound irradiation conditions affording the corresponding C–N or C–C adducts in good to excellent yields. Comparatively, performing the reaction under ultrasound irradiation gives higher yields, is more efficient and environmentally benign than performing it at high pressure. 相似文献
320.
Qi Zhang Yingxiang Du Jiaquan Chen Guangfu Xu Tao Yu Xiaoyi Hua Jinjing Zhang 《Analytical and bioanalytical chemistry》2014,406(5):1557-1566
Various chiral selectors have been utilized successfully in capillary electrophoresis (CE); however, the number of polysaccharides used as chiral selectors is still small and the mechanism of enantiorecognition has not been fully elucidated. Chondroitin sulfate D (CSD) and chondroitin sulfate E (CSE), belonging to the group of glycosaminoglycans, are linear, sulfated polysaccharides with large mass. In this paper, they were investigated for the first time for their potential as chiral selectors by CE. The effect of buffer composition and pH, chiral selector concentration, and applied voltage were systematically examined and optimized. A variety of drug enantiomers were resolved in the buffer pH range of 2.8–3.4 using 20 mM Tris/H3PO4 buffer with 5.0 % CSD or CSE and 20 kV applied voltage. A central composite design was used to validate the optimized separation parameters and satisfactory uniformity was obtained. As observed, CSE allowed satisfactory separation of the enantiomers of amlodipine, laudanosine, nefopam, sulconazole, and tryptophan methyl ester, as well as partial resolution of citalopram, duloxetine, and propranolol under the optimized conditions. CSD allowed partial or nearly baseline separation of amlodipine, laudanosine, nefopam, and sulconazole. The results indicated that CSE has a better enantiorecognition capability than CSD toward the tested drugs. Figure
Chiral separation of various drug enantiomers in CE with CSE (A) and CSD (B) as chiral selectors 相似文献