全文获取类型
收费全文 | 1250篇 |
免费 | 75篇 |
国内免费 | 5篇 |
专业分类
化学 | 1055篇 |
晶体学 | 22篇 |
力学 | 15篇 |
数学 | 72篇 |
物理学 | 166篇 |
出版年
2023年 | 16篇 |
2022年 | 21篇 |
2021年 | 27篇 |
2020年 | 30篇 |
2019年 | 25篇 |
2018年 | 34篇 |
2017年 | 20篇 |
2016年 | 53篇 |
2015年 | 43篇 |
2014年 | 67篇 |
2013年 | 75篇 |
2012年 | 110篇 |
2011年 | 150篇 |
2010年 | 73篇 |
2009年 | 68篇 |
2008年 | 94篇 |
2007年 | 70篇 |
2006年 | 68篇 |
2005年 | 57篇 |
2004年 | 52篇 |
2003年 | 47篇 |
2002年 | 32篇 |
2001年 | 14篇 |
2000年 | 11篇 |
1999年 | 6篇 |
1998年 | 9篇 |
1997年 | 5篇 |
1996年 | 6篇 |
1995年 | 6篇 |
1994年 | 5篇 |
1993年 | 6篇 |
1992年 | 3篇 |
1991年 | 2篇 |
1990年 | 2篇 |
1989年 | 2篇 |
1988年 | 2篇 |
1987年 | 1篇 |
1986年 | 3篇 |
1985年 | 2篇 |
1984年 | 2篇 |
1983年 | 1篇 |
1980年 | 3篇 |
1979年 | 2篇 |
1977年 | 1篇 |
1975年 | 1篇 |
1973年 | 1篇 |
1971年 | 1篇 |
1968年 | 1篇 |
排序方式: 共有1330条查询结果,搜索用时 0 毫秒
91.
Cylindrospermopsin determination using 2-[4-(2-hydroxyethyl)-1-piperazinyl]ethanesulfonic acid (HEPES) as the internal standard 总被引:1,自引:0,他引:1
Cylindrospermopsin (CYN) was determined by liquid chromatography/electrospray ionization-mass spectrometry (LC/ESI-MS) using 2-[4-(2-hydroxyethyl)-1-piperazinyl]ethanesulfonic acid (HEPES) as the internal standard. In the selected ion monitoring of LC/ESI-MS, m/z 414 for CYN and 237 for HEPES were monitored using the negative mode; the retention times of CYN and HEPES were 12.41 and 14.21 min, respectively. CYN was determined from peak area ratios of m/z 414/237. By the treatment of an anion exchange cartridge using a buffer at pH 10.5, CYN was isolated and condensed. No interfering peak was observed. Linearity of this method was observed at the range of 0.10-31.12 ng. Total coefficients of variation were 5.1 and 2.9% at 104 and 1038 μg CYN L−1. The quantitative limit at a signal-to-noise (S/N) ratio of 10 was 0.16 ng.CYN concentration in natural waters is low. CYN in waters should be condensed for determination. This method including the treatment for isolation and condensation of CYN is useful for determination of CYN in environmental and/or drinking waters. 相似文献
92.
An Efficient Method for the Conjugation of Hydrophilic and Hydrophobic Components by Solid‐Phase‐Assisted Disulfide Ligation 下载免费PDF全文
Kyohei Muguruma Takuya Shirasaka Daichi Akiyama Dr. Kentarou Fukumoto Dr. Akihiro Taguchi Dr. Kentaro Takayama Dr. Atsuhiko Taniguchi Prof. Yoshio Hayashi 《Angewandte Chemie (International ed. in English)》2018,57(8):2170-2173
Chemical conjugation between hydrophilic and hydrophobic components is difficult because of their extremely different solubility. Herein, we report a new versatile method with a solid‐phase‐assisted disulfide ligation to overcome the difficulty of conjugation attributed to solubility. The method involves two steps in a one‐pot process: 1) loading of a hydrophobic molecule onto a resin in an organic solvent, and 2) release of the solid‐supported hydrophobic molecule as a conjugate with a hydrophilic molecule into an aqueous solvent. This strategy allows the use of a suitable solvent system for the substrates in each step. Conjugates of a water‐insoluble drug, plinabulin, with hydrophilic carriers that could not be prepared by solution‐phase reactions were obtained in moderate yields (29–45 %). This strategy is widely applicable to the conjugation of compounds with solubility problems. 相似文献
93.
Inversion of Optical Activity in the Synthesis of Mercury Sulfide Nanoparticles: Role of Ligand Coordination 下载免费PDF全文
Jumpei Kuno Prof. Yutaka Imamura Dr. Michio Katouda Dr. Motomichi Tashiro Prof. Tsuyoshi Kawai Dr. Takuya Nakashima 《Angewandte Chemie (International ed. in English)》2018,57(37):12022-12026
Optical activity in inorganic colloidal materials was controlled through interactions of chiral molecules with the nanoparticle (NP) surface. An inversion of optical activity in the synthesis of mercury sulfide (HgS) NPs was demonstrated with an intrinsically chiral crystalline system in the presence of an identical chiral capping ligand. A continuous decrease in the positive first Cotton effect and an eventual reversal of CD profile were observed upon heating the aqueous solution of HgS NPs capped with N‐acetyl‐l ‐cysteine (Ac‐l ‐Cys) at 80 °C. Ac‐l ‐Cys afforded two bidentate coordination configurations with an almost mirror image of each other using the thiolate and either of carboxylate or acetyl–carbonyl groups on the HgS core. Experiment and calculation suggest that a shift in the distribution of the NP formation with energy in response to the combinations of ligand coordination structure and chiral crystalline surface is responsible for the inversion of optical activity. 相似文献
94.
95.
Wen Piao Satoru Tsuda Dr. Yuji Tanaka Dr. Satoshi Maeda Dr. Fengyi Liu Shodai Takahashi Yu Kushida Dr. Toru Komatsu Dr. Tasuku Ueno Dr. Takuya Terai Prof. Toru Nakazawa Prof. Masanobu Uchiyama Prof. Keiji Morokuma Prof. Tetsuo Nagano Dr. Kenjiro Hanaoka 《Angewandte Chemie (International ed. in English)》2013,52(49):13028-13032
96.
Takuya Hashimoto 《Tetrahedron letters》2010,51(4):761-8145
FeCl3/AgOTf-catalyzed hydroarylation of propiolic acid with electron-rich arenes such as mesitylene, tetramethylbenzene, and pentamethylbenzene in trifluoroacetic acid proceeded to give 3-arylpropenoic acids in moderate to high yields. The same reactions with anisole and 1,4-dimethoxybenzene afforded double hydroarylation products, 3,3-diarylpropionic acids. 相似文献
97.
Lembehsterols A and B,novel sulfated sterols inhibiting thymidine phosphorylase,from the marine sponge Petrosia strongylata 总被引:1,自引:0,他引:1
Aoki S Naka Y Itoh T Furukawa T Rachmat R Akiyama S Kobayashi M 《Chemical & pharmaceutical bulletin》2002,50(6):827-830
Lembehsterols A (1) and B (2), two novel sulfated sterols, were isolated from the marine sponge Petrosia strongylata. Both sterols showed inhibitory activity against thymidine phosphorylase, which is an enzyme related to angiogenesis in solid tumors. The structures of these sulfated sterols were established on the basis of chemical and physicochemical evidence. 相似文献
98.
Matsumoto T Kominami T Ueda K Sugimoto T Tada T Noguchi S Yoshino H Murata K Shiro M Negishi E Toyota N Endo S Takahashi K 《Inorganic chemistry》2002,41(18):4763-4769
The 2:1 charge-transfer (CT) salts (1(2).FeBr(4) and 1(2).GaBr(4)) of ethylenedithiotetrathiafulvalenoquinone-1,3-dithiolemethide (1) with FeBr(4)(-) and GaBr(4)(-) counteranions were obtained as needle crystals, whose structures are almost the same as each other. The 1 molecules form a one dimensionally stacked column with alternation of their molecular axis direction, while the counteranions are aligned in parallel with the 1-stacked columns with the direction of their distorted-tetrahedral geometry maintained. The room-temperature electrical conductivities measured on the single crystals of 1(2).FeBr(4) and 1(2).GaBr(4) were 4.6 and 2.1 S cm(-1), respectively. From the temperature dependences of their electrical conductivities in both cases the electrical conducting properties were metallic between ca. 170 and 300 K, but below ca. 170 K converted to be semiconducting and continued till 5 K, although the activation energies are very small (4-10 meV). For 1(2).FeBr(4) very weak and antiferromagnetic interaction occurred between the d spins of FeBr(4)(-) ions in the temperature range of ca. 1-300 K. However, below ca. 15 K the ferromagnetic interaction was reversely preferential possibly by participation of the pi spin of 1. 相似文献
99.
100.