全文获取类型
收费全文 | 366篇 |
免费 | 30篇 |
国内免费 | 1篇 |
专业分类
化学 | 345篇 |
晶体学 | 1篇 |
力学 | 1篇 |
数学 | 17篇 |
物理学 | 33篇 |
出版年
2023年 | 3篇 |
2022年 | 1篇 |
2021年 | 2篇 |
2020年 | 6篇 |
2019年 | 3篇 |
2018年 | 5篇 |
2017年 | 4篇 |
2016年 | 11篇 |
2015年 | 27篇 |
2014年 | 15篇 |
2013年 | 22篇 |
2012年 | 31篇 |
2011年 | 34篇 |
2010年 | 12篇 |
2009年 | 22篇 |
2008年 | 18篇 |
2007年 | 21篇 |
2006年 | 26篇 |
2005年 | 24篇 |
2004年 | 23篇 |
2003年 | 15篇 |
2002年 | 18篇 |
2001年 | 3篇 |
2000年 | 1篇 |
1999年 | 2篇 |
1998年 | 4篇 |
1997年 | 4篇 |
1996年 | 1篇 |
1995年 | 2篇 |
1994年 | 1篇 |
1993年 | 1篇 |
1990年 | 1篇 |
1989年 | 2篇 |
1988年 | 3篇 |
1987年 | 3篇 |
1986年 | 5篇 |
1985年 | 3篇 |
1984年 | 5篇 |
1983年 | 2篇 |
1981年 | 3篇 |
1980年 | 1篇 |
1979年 | 2篇 |
1978年 | 1篇 |
1976年 | 1篇 |
1975年 | 2篇 |
1966年 | 1篇 |
排序方式: 共有397条查询结果,搜索用时 15 毫秒
91.
Kansuinine A, isolated from the plant Euphorbia kansui Liou, is one of a series of jatrophane diterpenes that have novel structural features, which include contiguous stereocenters, a highly oxygenated carbon framework, and a tricyclic ring system. We describe here a short and concise synthesis of the cyclopentane segment of kansuinine A via SmI2-mediated cyclization of δ-iodoester as a key construction method. 相似文献
92.
Katsuhiko Saido Takeshi Kuroki Tadashi Ikemura Makoto Kirisawa 《Journal of Analytical and Applied Pyrolysis》1984,6(2):171-181
A flow apparatus equipped with a spray nozzle was developed for investigating the thermal decomposition of esters with high boiling points and viscosities. The thermal decomposition of bis(2-ethylhexyl) phthalate (BEHP), which is a typical plasticizer for poly(vinyl chloride) with a high boiling point and viscosity, was carried out by the use of the flow apparatus. The thermal decomposition products were analysed by gas chromatography and the kinetic parameters were calculated. The kinetic parameter of bis(2-ethylhexyl) phthalate was kBEHP (s?1)=4.59·1011 exp(?40600/RT). From a comparison with the values for phthalic esters, it is proposed that a cis-elimination reaction takes place with a two-step mechanism in which the rate-determining step is α-carbon cleavage. 相似文献
93.
We have extended the van der Waals and Platteeuw theory to treat multiple occupancy of a single cage of clathrate hydrates, which has not been taken into account in the original theory but has been experimentally confirmed as a real entity. We propose a simple way to calculate the free energy of multiple cage occupancy and apply it to argon clathrate structure II in which a larger cage can be occupied by two argon atoms. The chemical potential of argon is calculated treating it as an imperfect gas, which is crucial to predict accurate pressure dependence of double occupancy expected at high pressure. It is found that double occupancy dominates over single occupancy when the guest pressure in equilibrium with the clathrate hydrate exceeds 270 MPa. 相似文献
94.
Kenichiro Todoroki Yasuhiro Ishii Koji Toyoda Takashi Ikawa Jun Zhe Min Koichi Inoue Shuji Akai Toshimasa Toyo’oka 《Analytical and bioanalytical chemistry》2013,405(25):8121-8129
In this paper, we report a new type of chiral high-performance liquid chromatography (HPLC) column—a so-called dress-up chiral column—featuring a chiral stationary phase adsorbed reversibly in a commercial fluorous HPLC column through fluorous interactions. We synthesized perfluroalkylated proline derivatives as chiral stationary phase compounds and then adsorbed them reversibly in the fluorous HPLC column through the pumping of their solutions. By using this dress-up chiral column and fluorophobic elution of an aqueous copper(II) sulfate/MeOH mixture, we could enantioseparate seven racemic amino acids within 40 min. When we washed the dress-up chiral column with fluorophilic tetrahydrofuran or MeOH, the adsorbed chiral stationary phase compounds desorbed from the column, completely destroying its enantioseparation ability. The relative standard deviation of the retention times, the number of theoretical plates, and the resolution for each of four preparations of the dress-up columns were all less than or equal to 9.53 % in 20-times repeated analysis, and were all less than or equal to 18.7 % in four different preparations, respectively. 相似文献
95.
96.
Saori Ichinose Mayumi Nakamura Mayu Maeda Rie Ikeda Mitsuhiro Wada Mio Nakazato Yoshihito Ohba Noboru Takamura Takahiro Maeda Kiyoshi Aoyagi Kenichiro Nakashima 《Biomedical chromatography : BMC》2009,23(9):935-939
A semi‐micro column HPLC‐fluorescence method for routine determination of thiol derivatives such as homocysteine (Hcy), cysteine (Cys) and cysteamine (CA) is described. The thiol derivatives labeled with ammonium‐7‐fluorobenzo‐2‐oxa‐1,3‐diazole‐4‐sulfonate (SBD‐F) were isocratically separated within 12 min on a semi‐micro ODS column (Daisopak‐SP‐120‐5‐ODS‐BP) with a mixture of 25 mm acetate buffer (pH 2.00) and CH3CN as a mobile phase. The purity and similarity of SBD‐thiols by a multi‐wavelength fluorescence detector were more than 92.3 and 96.7%. The detection limits of Hcy, Cys and CA at a signal‐to‐noise ratio of 3 were 0.16, 0.47 and 0.03 µm , respectively. Furthermore validation parameters such as accuracy, precision and robustness of the proposed method showed satisfactory results. Almost 850 plasma sample injections (range 572–1076, n = 3) for a column could be performed without differences in retention time and peak heights of labels. As an application of the proposed method, the determination of thiol derivatives in normal human plasma (n = 103) was demonstrated. The correlation coefficients between Hcy vs Cys and Hcy vs CA were 0.38 and −0.35, respectively. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
97.
Ohyama Kaname Oyamada Kana Kishikawa Naoya Arakawa Miyuki Ohba Yoshihito Kamino Masahiro Wada Mitsuhiro Nakashima Kenichiro Kuroda Naotaka 《Chromatographia》2009,70(9-10):1501-1504
A new class of chiral stationary phases (CSP) with peptide chiral selectors was prepared by solid-phase synthesis with a tert-butoxycarbonyl-L-amino acid on silica. The type of amino acid that is favorable for this class of CSP is discussed. Using the CSP with the phenylalanine peptide selector, the effect of peptide length on the enantioselectivity was investigated in normal-phase mode. The applicability of the CSP with a phenylalanine peptide to chiral ligand-exchange chromatography was also examined.
相似文献98.
99.
100.
Mitsuhiro Wada Rie Ikeda Naotaka Kuroda Kenichiro Nakashima 《Analytical and bioanalytical chemistry》2010,397(3):1039-1067
Hair has been focused on for its usability as an alternative biological specimen to blood and urine for determining drugs
of abuse in fields such as forensic and toxicological sciences because hair can be used to elucidate the long intake history
of abused drugs compared with blood and urine. Hair analysis consists of several pretreatment steps, such as washing out contaminates
from hair, extraction of target compounds from hair, and cleanup for instrumental analysis. Each step includes characteristic
and independent features for the class of drugs, e.g., stimulants, narcotics, cannabis, and other medicaments. In this review,
recently developed methods to determine drugs of abuse are summarized, and the pretreatment steps as well as the sensitivity
and applicability are critically discussed. 相似文献