全文获取类型
收费全文 | 1385篇 |
免费 | 41篇 |
国内免费 | 8篇 |
专业分类
化学 | 788篇 |
晶体学 | 8篇 |
力学 | 64篇 |
数学 | 86篇 |
物理学 | 488篇 |
出版年
2023年 | 24篇 |
2022年 | 33篇 |
2021年 | 48篇 |
2020年 | 36篇 |
2019年 | 39篇 |
2018年 | 39篇 |
2017年 | 36篇 |
2016年 | 50篇 |
2015年 | 36篇 |
2014年 | 49篇 |
2013年 | 108篇 |
2012年 | 92篇 |
2011年 | 123篇 |
2010年 | 57篇 |
2009年 | 46篇 |
2008年 | 68篇 |
2007年 | 70篇 |
2006年 | 70篇 |
2005年 | 52篇 |
2004年 | 38篇 |
2003年 | 33篇 |
2002年 | 29篇 |
2001年 | 17篇 |
2000年 | 14篇 |
1999年 | 9篇 |
1998年 | 13篇 |
1997年 | 14篇 |
1996年 | 21篇 |
1995年 | 17篇 |
1994年 | 16篇 |
1993年 | 9篇 |
1992年 | 14篇 |
1991年 | 5篇 |
1990年 | 8篇 |
1989年 | 8篇 |
1988年 | 6篇 |
1987年 | 2篇 |
1986年 | 7篇 |
1985年 | 11篇 |
1984年 | 10篇 |
1983年 | 7篇 |
1982年 | 7篇 |
1981年 | 4篇 |
1980年 | 6篇 |
1979年 | 9篇 |
1978年 | 7篇 |
1976年 | 4篇 |
1975年 | 4篇 |
1974年 | 3篇 |
1969年 | 2篇 |
排序方式: 共有1434条查询结果,搜索用时 15 毫秒
31.
32.
33.
34.
Attempts have been made to determine the enthalpy and entropy of transfer of H+ ion from water to mixed solvents using the calorimetric data of earlier experiments. The results are in qualitative agreement with the facts that ΔH t 0 (H+) passes through an exothermic maximum andTΔS t 0 passes through a minimum at about 20 to 30 wt% of organic solvent indicating the initial structure formation and the ultimate breakdown of the solvent structure with the addition of organic solvent. 相似文献
35.
Chakraborty T Holm AI Hvelplund P Nielsen SB Poully JC Worm ES Williams ER 《Journal of the American Society for Mass Spectrometry》2006,17(12):1675-1680
Electron capture by both bare and microsolvated small peptide dications was investigated by colliding these ions with sodium vapor in an accelerator mass spectrometer to provide insight into processes that occur on the microsecond time frame. Survival of the intact peptide monocation after electron capture depends strongly on molecular size. For dipeptides, no intact reduced species were observed; the predominant ions correspond to loss of hydrogen and ammonia. In contrast, the intact reduced species was observed for larger peptides. Calculated structures indicate that the diprotonated dipeptide ions form largely extended structures with low probability of internal ionic hydrogen bonding (i.e., charge solvation) whereas internal ionic H-bonding occurs extensively for larger peptide dications. Solvation of the peptide ions with between one to seven methanol molecules reduces the total extent of H loss even for dipeptides where intact reduced species can survive more than a microsecond after electron capture. The yield of ions corresponding to cleavage of NCalpha bonds (c+ and z+* ions) does not depend strongly on peptide size but decreases with the extent of microsolvation for the dipeptide dications. H-bonding appears to play an important role for the survival of the intact reduced ions but less so for the formation of c+ and z+* ions. Our results indicate that electron capture predominantly occurs at the ammonium groups (at least 70 to 80%), and provides important new insights into the electron capture dissociation process. 相似文献
36.
Kinetic speciation of uranium in model solutions containing uranium and humic acid (HA) and in natural waters has been investigated by Competitive Ligand Exchange Method (CLEM). In alkaline freshwaters, most of uranium species were uranium-carbonate species, which were labile in the CLEM experiment. The uranium speciation of every sample was characterized either as “labile” or “non-labile” uranium complexes depending on the dissociation rate coefficients of the complexes. The results showed that as the U(VI)/HA ratio was decreased, the dissociation rate coefficients decreased and the labile fraction decreased as well. When the U(VI)/HA ratio was 0.1, the labile fraction of the U(VI)-HA increased with increasing pH; however, there was no pH effect on the dissociation of U(VI)-HA complexes at lower U(VI)/HA ratios. Chelex-100 had some limitations in its use for the study of dissociation of U(VI)-HA complex at very low U(VI)/HA ratios. By developing an analytical method and procedure for quantitative determination of kinetic parameters for the dissociation of uranium-HA complexes in model solutions and natural waters, this work has made a substantial contribution to analytical chemistry. 相似文献
37.
Joy Chakraborty Brajagopal Samanta Andrei S. Batsanov Joan Ribas M. Salah El Fallah Samiran Mitra 《Structural chemistry》2006,17(4):401-407
A ligand–metal–ligand type co-ordination polymer [Ni (C6H12N4)(NCS)2(H2O)2]
n
has been synthesised under controlled hydrothermal conditions. Here 1,3,5,7-tetraazatricyclo[3.3.1]decane [or hexamethylenetetramine (hmt)] has been used as a μ-(N,N′) bidentate spacer molecule. The prepared polymeric complex has been characterised by elemental and spectral analyses. The structure has been confirmed by a single crystal X-ray diffraction study. Magneto-structural correlation has been drawn from cryomagnetic susceptibility measurements (2–300 K) which unequivocally reflects very weak magnetic spin interactions among the long distant octahedral Ni(II) metal centres mediated by hmt and weak hydrogen bonding interactions between the adjacent zigzag one-dimensional polymeric chains carrying into a two-dimensional infinite polymeric framework. 相似文献
38.
Y. D. Kolekar S. B. Kulkarni Keka Chakraborty A. Das S. K. Paranjpe P. B. Joshi 《Pramana》2004,63(2):189-197
Nd2Sn2O7 pyrochlores with the substitution of Zr4+ were prepared by conventional ceramic double sintering technique. The single-phase formation was confirmed by X-ray diffraction
and neutron diffraction techniques. Relative intensity calculations for X-ray diffraction analysis were performed for oxygen
positional parametersx = 0.331 and 0.375, while Rietveld refinements were employed for neutron diffraction data. The neutron diffraction study revealed
that there are only two anion sites with 48f and 8b positions. This indicates that the 8a site, i.e. O(3) sublattice, is completely
vacant and the structure is a perfect cubic pyrochlore with space group Fd3m (O
h
7
). From the conductivity measurements, it is observed that the electronic conductivity dominates from room temperature up
to about 525 K and forT > 525 K, the oxygen ion conduction dominates the charge transport in these compositions. Complex impedance spectroscopy indicates
the existence of grain and grain boundary as two separate elements. 相似文献
39.
Bo-Hwa Choi Goutam Chakraborty Kwanghee Baek Ho Sup Yoon 《Experimental & molecular medicine》2013,45(10):e47
Here, we report that B-cell lymphoma 2 (Bcl-2) is a novel target molecule of aspirin in breast cancer cells. Aspirin influenced the formation of a complex by Bcl-2 and FKBP38 and induced the nuclear translocation of Bcl-2 and its phosphorylation. These events inhibited cancer cell proliferation and subsequently enhanced MCF-7 breast cancer cell apoptosis. Bcl-2 knockdown using small interfering RNA (siRNA) delayed apoptotic cell death, which correlated with increased proliferation following aspirin exposure. In contrast, Bcl-2 overexpression enhanced the onset of aspirin-induced apoptosis, which was also associated with a significant increase in Bcl-2 phosphorylation in the nucleus. Therefore, this study may provide novel insight into the molecular mechanism of aspirin, particularly its anticancer effects in Bcl-2- and estrogen receptor-positive breast cancer cells. 相似文献
40.
Regioselective opening of the aziridine ring in the carbohydrate-based precursor led to the stereoselective synthesis of N-Boc-O-benzyl-(4S,5S)-5-amino-4-hydroxy-6-phenylhexanoic acid methyl ester, the hydroxyethylene dipeptide isostere moiety of potent HIV-1 protease inhibitor. 相似文献