全文获取类型
收费全文 | 4475篇 |
免费 | 112篇 |
国内免费 | 33篇 |
专业分类
化学 | 3491篇 |
晶体学 | 42篇 |
力学 | 55篇 |
数学 | 230篇 |
物理学 | 802篇 |
出版年
2022年 | 29篇 |
2021年 | 42篇 |
2020年 | 57篇 |
2019年 | 62篇 |
2018年 | 45篇 |
2017年 | 29篇 |
2016年 | 67篇 |
2015年 | 47篇 |
2014年 | 77篇 |
2013年 | 169篇 |
2012年 | 206篇 |
2011年 | 251篇 |
2010年 | 132篇 |
2009年 | 155篇 |
2008年 | 245篇 |
2007年 | 249篇 |
2006年 | 259篇 |
2005年 | 263篇 |
2004年 | 227篇 |
2003年 | 187篇 |
2002年 | 167篇 |
2001年 | 94篇 |
2000年 | 68篇 |
1999年 | 75篇 |
1998年 | 60篇 |
1997年 | 55篇 |
1996年 | 83篇 |
1995年 | 56篇 |
1994年 | 36篇 |
1993年 | 44篇 |
1992年 | 59篇 |
1991年 | 42篇 |
1990年 | 37篇 |
1989年 | 50篇 |
1988年 | 56篇 |
1987年 | 48篇 |
1986年 | 34篇 |
1985年 | 80篇 |
1984年 | 61篇 |
1983年 | 39篇 |
1982年 | 57篇 |
1981年 | 55篇 |
1980年 | 43篇 |
1979年 | 60篇 |
1978年 | 51篇 |
1977年 | 51篇 |
1976年 | 36篇 |
1975年 | 38篇 |
1974年 | 40篇 |
1973年 | 39篇 |
排序方式: 共有4620条查询结果,搜索用时 15 毫秒
1.
2.
Dr. Takeshi Nanjo Natsuki Kato Xuan Zhang Prof. Yoshiji Takemoto 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(68):15504-15507
Strategies for the formation of amide bonds, that is, one of the most basic and important transformations in organic synthesis, have so far focused predominantly on dehydration reactions. Herein, we report and demonstrate the practical utility of a novel decarboxylative amidation of α-ketoacids by using inexpensive tert-butyl hydroperoxide (TBHP), which is characterized by high yields, a broad substrate scope, mild reaction conditions, and a unique chemoselectivity. These features enable the synthesis of peptides from amino acid derived α-ketoacids under preservation of the stereochemical information. 相似文献
3.
HPLC with fluorescence detection assay of perampanel,a novel AMPA receptor antagonist,in human plasma for clinical pharmacokinetic studies
下载免费PDF全文
![点击此处可从《Biomedical chromatography : BMC》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Perampanel (Fycompa®), a novel α‐amino‐3‐hydroxy‐5‐methyl‐4‐isoxazolepropionic acid (AMPA) receptor antagonist, is registered for the adjunctive treatment of patients (aged ≥12 years) with refractory partial‐onset seizures. To support therapeutic drug monitoring, a simple high‐performance liquid chromatography (HPLC) assay with fluorescence detection was developed to determine perampanel concentrations in human plasma and validated to support clinical trials. Human plasma samples (1.0 mL) were processed by liquid extraction using diethyl ether, followed by chromatographic separation on a YMC Pack Pro C18 column (150 × 4.6 mm i.d., 5 µm) with isocratic elution of acetonitrile–water–acetic acid–sodium acetate (840:560:3:1.8, v/v/v/w) at a flow rate of 1.0 mL/min. Column eluent was monitored at excitation and emission wavelengths of 290 and 430 nm, respectively. The assay was linear (range 1.0–500 ng/mL) and this could be extended to 25 µg/mL by 50‐fold dilution integrity. No endogenous peaks were detected in the elution of analytes in drug‐free blank human plasma from six individuals and no interference was observed with co‐medications tested. Intra‐ and inter‐batch reproducibility studies demonstrated accuracy and precision within the acceptance criteria of bioanalytical guidelines. Validation data demonstrated that our assay is simple, selective, reproducible and suitable for therapeutic drug monitoring of perampanel. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
4.
Surface texturing has been recognized as an effective means to improve the tribological performances of sliding surfaces. Usually, generation additional hydrodynamic pressure to increase the load carrying capacity is regarded as the most significant effect of surface texture. In the case of silicon carbide sliding against identical material in water, the experimental results indicate that surface texture is also helpful to improve the running-in progress to smooth the contact surfaces, showing another reason to result in low friction. Based on the consideration of enhancing the generation of hydrodynamic pressure and improving running-in progress, a surface texture pattern, which was combined with large (circle, 350 μm in diameter) and small (rectangular, 40 μm in length) dimples, was designed to maximize the texture effect on the load carrying capacity of SiC surfaces sliding in water. The friction coefficient of such textured surface was evaluated and compared with that of untextured and those only with large or small dimples only. The friction reduction mechanisms of the patterns with different dimples in size are discussed. 相似文献
5.
Katsunari Inoue Kazuaki Kato Norimitsu Tohnai Mikiji Miyata 《Journal of polymer science. Part A, Polymer chemistry》2004,42(18):4648-4655
We studied simulations by computer graphics to estimate the steric mechanism of the asymmetric polymerization of prochiral diene monomers in channels of inclusion compounds of steroidal bile acids, such as deoxycholic acid (DCA) and cholic acid. We applied a hierarchization method to interpret the crystal structures of bile acids, clarifying that the chiral host molecules associated to form characteristic 21-helical assemblies with uneven surfaces. A detailed analysis of the uneven channels in a close-packing state indicated that there were many possible arrangements of the monomers in the channels. The plausible arrangements in the channel could explain a previous study, which showed that the polymerization in the DCA channel yielded chiral polymers with a predominant configuration from prochiral diene monomers, such as 2-methyl-trans-1,3-pentadiene. On the basis of such simulation studies of the arrangements of guest monomers in the channel, we examined a plausible steric mechanism for asymmetric inclusion polymerization. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4648–4655, 2004 相似文献
6.
Seiichi Nishizawa Tomoyuki Kamaishi Tomoyuki Yokobori Ryo Kato Ying-Yu Cui Takeshi Shioya Norio Teramae 《Analytical sciences》2004,20(11):1559-1565
Facilitated SO4(2-) transfers by hydrogen bond-forming ionophores are investigated across the nitrobenzene (NB)-water interface by using polarography with a dropping electrolyte electrode. Bis-thiourea 1, alpha,alpha'-bis(N'-p-nitrophenylthioureylene)-m-xylene, is found to significantly facilitate the transfer of the highly hydrophilic SO4(2-) whereas its counterpart, N-(p-nitrophenyl)-N'-propylthiourea (ionophore 2), cannot. In contrast to the predominant formation of a 1:1 complex with SO4(2-) in the bulk NB phase, the SO4(2-) transfer assisted by 1 is indeed based on the formation of a 1:2 complex between SO4(2-) and ionophore, even under the condition of [SO4(2-)]aq > [1]org. Such an exclusive formation of the 1:2 (SO4(2-) to ionophore) complex at the NB-water interface is not observed with structurally similar bis-thiourea 3, alpha,alpha'-bis(N'-phenylthioureylene)-m-xylene, where p-nitrophenyl moietes of bis-thiourea 1 are simply replaced by phenyl groups. The facilitated transfer of SO4(2-) with bis-thiourea 1 is further compared to that of HPO4(2-) and H2PO4- across the NB-water interface, which was previously shown to be assisted by 1 through the formation of the 1:1 and 2:1 (anion to ionophore) complexes, respectively. On the basis of these examinations, unique binding behaviors of hydrogen bond-forming ionophores at the NB-water interface are discussed, with a view towards development of ionophore-based anion-selective chemical sensors. 相似文献
7.
Takashi Yoshitake Ryuji Iizuka Kaoru Fujino Osamu Inoue Kenji Yamagata Hitoshi Nohta Masatoshi Yamaguchi 《Analytical sciences》2004,20(12):1687-1690
An improved high-performance liquid-chromatographic (HPLC) assay for the simultaneous determination of serotonin (5-HT) and 5-hydroxyindole-3-acetic acid (5-HIAA) in human urine is reported. Following the automated precolumn derivatization of urinary 5-HT and 5-HIAA with benzylamine, the derivatives are separated by isocratic elution on a reversed-phase C18 semi-microbore column, and are fluorometrically detected at an excitation wavelength of 345 nm and an emission wavelength of 480 nm. The detection limits of 5-HT and 5-HIAA are 7 and 5 nmol/l in urine (0.7 and 0.5 fmol/20-microl injection). The proposed automatic method permits a highly selective and sensitive determination of 5-HT and 5-HIAA in human urine without any sample purification. 相似文献
8.
9.
The electronic states of the Cr overlayers on TiO2(0 0 1) surfaces have been investigated using angle-resolved and resonant photoemission spectroscopy with synchrotron radiation. At lower coverages, Cr deposition on TiO2(0 0 1) creates two well separated in-gap emissions due to the formation of surface Ti3+ (3d1) ions and Cr3+ (3d3) ions. At higher coverages, the in-gap emission is developed into the 2-peak-structure emission of Cr 3d character. The corresponding state is considered to be of metallic nature from the viewpoint of the high ability of oxygen adsorption, but has no Fermi edge, indicating a possibility of forming small Cr clusters on TiO2(0 0 1) at this stage. 相似文献
10.