全文获取类型
收费全文 | 997篇 |
免费 | 36篇 |
国内免费 | 2篇 |
专业分类
化学 | 712篇 |
晶体学 | 5篇 |
力学 | 21篇 |
数学 | 107篇 |
物理学 | 190篇 |
出版年
2023年 | 2篇 |
2022年 | 6篇 |
2021年 | 28篇 |
2020年 | 21篇 |
2019年 | 21篇 |
2018年 | 17篇 |
2017年 | 18篇 |
2016年 | 41篇 |
2015年 | 22篇 |
2014年 | 44篇 |
2013年 | 89篇 |
2012年 | 66篇 |
2011年 | 82篇 |
2010年 | 49篇 |
2009年 | 40篇 |
2008年 | 70篇 |
2007年 | 68篇 |
2006年 | 50篇 |
2005年 | 40篇 |
2004年 | 28篇 |
2003年 | 25篇 |
2002年 | 43篇 |
2001年 | 21篇 |
2000年 | 24篇 |
1999年 | 10篇 |
1998年 | 11篇 |
1997年 | 6篇 |
1996年 | 6篇 |
1995年 | 8篇 |
1994年 | 15篇 |
1993年 | 14篇 |
1992年 | 8篇 |
1991年 | 5篇 |
1989年 | 1篇 |
1988年 | 1篇 |
1987年 | 2篇 |
1985年 | 3篇 |
1984年 | 3篇 |
1983年 | 3篇 |
1982年 | 3篇 |
1981年 | 4篇 |
1980年 | 2篇 |
1979年 | 3篇 |
1978年 | 2篇 |
1977年 | 1篇 |
1975年 | 2篇 |
1974年 | 2篇 |
1970年 | 1篇 |
1965年 | 1篇 |
1894年 | 1篇 |
排序方式: 共有1035条查询结果,搜索用时 15 毫秒
981.
982.
It has been determined, using neutron diffraction, that hydrogen dissolved in the α (h.c.p.) phase of titanium is distributed randomly among the tetrahedral sites. 相似文献
983.
B. Mario Pinto Walter A. Szarek T. Bruce Grindley 《Magnetic resonance in chemistry : MRC》1984,22(11):676-692
Analogs of N-acetyl- and N-benzoyl-azacyclohex-2-enes having an oxygen atom, a methylene-d2 group or a carbonyl group in place of the C-4 methylene group have been synthesized. The amide rotational barriers in these compounds have been measured by the total line-shape analysis of variable-temperature 1H NMR spectra. The free energies of activation for both the N-acetyl and N-benzoyl series decrease in the sequence O?CD2 > C?O. The barriers for the first two compounds in each series are similar to those of the corresponding saturated analogs, a result which confirms recent reports that the long accepted barrier-decreasing effect of an α-olefinic substituent on nitrogen is counteracted. Evidence is presented that resonance stabilization of the rotational transition state in the unsaturated compounds still obtains. It is suggested that the introduction of an α-olefinic substituent on nitrogen has a negligible effect on the amide rotational barriers in the cases of the oxygen and methylene-d2 analogs, since any increase in the stabilization of the transition state by resonance is offset by the accompanying decrease in the sp3 character of the nitrogen atom. In cases in which a substituent on the olefinic group can interact directly with the lone pair on nitrogen, for example in the carbonyl analogs, then the resonance stabilization of the transition state is dominant. 相似文献
984.
Cláudio C. Lopes Rosangela S. C. Lopes Antonio V. Pinto Paulo R. R. Costa 《Journal of heterocyclic chemistry》1984,21(2):621-622
From the ethanol extract of the stem bark of Tabebuia cassinoides (Lam.) DC (Bignoniaceae), Kingston and Rao [1] isolated two new furonaphthoquinones 6 and 7 that showed activity in KB cell culture assay (ED50 1.0 and 2.0 μg/ml, respectively). These values may be significant since lapachol, which has an ED50 value of 4.4 μg/ml in the same assay, showed sufficient in vivo activity to reach clinical trial at the National Cancer Institute of the United States. The syntheses of these compounds ( 6 and 7 ) were realized in 36% overall yield starting from furan and phthalic anhydride. 相似文献
985.
Robert T. Gampe Gary E. Martin Angelo C. Pinto Richard A. Hollins 《Journal of heterocyclic chemistry》1981,18(1):155-161
Total assignment of the 13C-nmr spectrum of the novel tetracyclic phenothiazine, pyrrolo[3,2,1-kl]phenothiazine is described. Assignments were determined from model systems, 1H-13C spin-coupling behavior in conjunction with selective excitation techniques and spin-lattice (T1) relaxation measurements. The anisotropic reorientation of this ring system via a principal axis passing through the center of the molecule, which provides a qualitative basis for signal discrimination, is also discussed. 相似文献
986.
Proteomics on a chip: promising developments 总被引:8,自引:0,他引:8
The field of proteomics is expanding rapidly due to the completion of the human genome and the realization that genomic information is often insufficient to comprehend cellular mechanisms. This considerable expansion of proteomics towards high-throughput platforms is stressing its current technical capabilities. In recent years, technologies in microfluidic and array technologies have appeared for proteomics. These novel approaches might help solve current technical challenges in proteomics. This review presents a general survey of the recent development in microfluidic and array technologies from a proteomics perspective. 相似文献
987.
988.
Near infrared spectroscopy (NIRS) is an analytical technique that can be very useful for stability studies in particular because of its non destructive analytical capability. However, the spectral interpretation and treatment of this kind of multivariate data remains difficult without the use of chemometrics. In this article, a recent chemometrics method, analysis of variance - principal component analysis (ANOVA-PCA), was used for NIRS stability studies of sunflower and bread wheat external reference materials (ERM). It provided a practical tool for the study of the significance of various storage conditions according to an experimental design. Thus, the effect of the temperature, the nature of the atmosphere in the packaging and the storage duration were tested. ANOVA-PCA highlighted the influence of temperature and storage duration on the stability of the sunflower materials. For the bread wheat materials, the storage conditions did not have a significant effect on stability. Consequently, by applying ANOVA-PCA to near infrared spectral data, the sunflower materials were found to be considered stable for the time length of the study, i.e. 18 months stored in a cold room, while the bread wheat materials were found to be considered stable for the time length of the study, i.e. 12 months under the same conditions. 相似文献
989.
Practical reversed-phase high-performance liquid chromatography method for laboratory-scale purification of recombinant human thyrotropin 总被引:1,自引:0,他引:1
A small, semi-preparative C(4) RP-HPLC column was used to set up the conclusive laboratory-scale purification of Chinese hamster ovary-derived human thyrotropin (hTSH), after a preliminary concentration-purification of an extremely dilute and poorly ( approximately 0.6 microg hTSH/mL; mass fraction=0.35%) conditioned medium on a cation exchanger. Several fractions of this eluate were repeatedly injected on the semi-preparative column, obtaining, in a single run (<1h chromatographic time), a concentrated pool ( approximately 1.2 mg/mL) of highly purified hTSH that could be further concentrated to >3 mg/mL and then efficiently lyophilized. The overall recovery in the rapid RP-HPLC purification step, including concentration and lyophilization, was of the order of 80%. The final product, when tested via a precise, single-dose in vivo bioassay, confirmed that it did not suffer any loss of bioactivity. This same methodology can be easily adapted to the small-scale purification of other recombinant products, even when obtained from genetically modified organisms at extremely low concentrations and mass fractions. 相似文献
990.
Applications of counter-current chromatography in organic synthesis purification of heterocyclic derivatives of lapachol 总被引:1,自引:0,他引:1
Silva RS Leitão GG Brum TB Lobato AP Pinto Mdo C Pinto AV 《Journal of chromatography. A》2007,1151(1-2):197-202
This work describes the application of counter-current chromatography (CCC) as a useful, fast and economic alternative for the isolation and purification of heterocyclic derivatives from lapachol and beta-lapachone, two naturally occurring compounds from Tabebuia species, and nor-beta-lapachone, a synthetic congener of lapachol. The discussed data comprise four examples of purification of synthetic reactions with different solvent systems - the mixture of the oxazole and the imidazole from beta-lapachone; the quinoxaline from nor-beta-lapachone; and the purification of the N-oxides from the quinoxaline and the phenazine from nor-beta-lapachone from their respective not fully reacted substrates by means of aqueous reversed- and normal-phase elution modes and non-aqueous solvent systems. Traditional purification of these reaction products by silica gel column chromatography demanded a large amount of solvent and time and, in some cases, serious degradation of the products occurred, leading to low yield of the reaction. High-speed counter-current chromatography (HSCCC) was used as an alternative to optimize the process and raise the yield of the reactions. 相似文献