全文获取类型
收费全文 | 5434篇 |
免费 | 290篇 |
国内免费 | 20篇 |
专业分类
化学 | 4097篇 |
晶体学 | 55篇 |
力学 | 92篇 |
数学 | 554篇 |
物理学 | 946篇 |
出版年
2022年 | 47篇 |
2021年 | 65篇 |
2020年 | 92篇 |
2019年 | 90篇 |
2018年 | 61篇 |
2017年 | 54篇 |
2016年 | 150篇 |
2015年 | 143篇 |
2014年 | 172篇 |
2013年 | 323篇 |
2012年 | 298篇 |
2011年 | 387篇 |
2010年 | 230篇 |
2009年 | 201篇 |
2008年 | 312篇 |
2007年 | 290篇 |
2006年 | 291篇 |
2005年 | 244篇 |
2004年 | 210篇 |
2003年 | 204篇 |
2002年 | 207篇 |
2001年 | 112篇 |
2000年 | 83篇 |
1999年 | 56篇 |
1998年 | 50篇 |
1997年 | 51篇 |
1996年 | 76篇 |
1995年 | 85篇 |
1994年 | 77篇 |
1993年 | 63篇 |
1992年 | 71篇 |
1991年 | 52篇 |
1990年 | 54篇 |
1989年 | 59篇 |
1988年 | 37篇 |
1987年 | 32篇 |
1986年 | 34篇 |
1985年 | 55篇 |
1984年 | 43篇 |
1983年 | 42篇 |
1982年 | 41篇 |
1981年 | 38篇 |
1980年 | 41篇 |
1979年 | 32篇 |
1978年 | 45篇 |
1977年 | 32篇 |
1976年 | 23篇 |
1975年 | 35篇 |
1974年 | 41篇 |
1973年 | 33篇 |
排序方式: 共有5744条查询结果,搜索用时 46 毫秒
91.
92.
Cooper TJ Talaty ER Van Stipdonk MJ 《Journal of the American Society for Mass Spectrometry》2005,16(8):1305-1310
We report a new fragmentation pathway for the CID of (b3 - 1 + Cat)+ product ions derived from the model peptide AXAG, where X = beta-alanine, gamma-aminobutyric acid, epsilon-amino-n-caproic acid, or 4-aminomethylbenzoic acid. By changing the amino acid to the C-terminal side of the amino acid X, and incorporating 15N and 13C labeled residues at the same position, we conclude that the dissociation pathway most likely leads to a metal cationized nitrile. With respect to the various amino acids at position X, the putative nitrile product becomes more prominent, relative to the conventional (a3 - 1 + Cat)+ species, in the order beta-alanine < gamma-aminobutyric acid < epsilon-aminocaproic acid < 4-aminomethylbenzoic acid. The pathway is not observed for peptides with alpha-amino acids at position X. The product ion is observed most prominently during the CID of Li+ and Na+ cationized peptides, only to a small extent for Ag+ cationized peptides, and not at all from protonated analogues. 相似文献
93.
94.
Long-lived metastable negative ions of CO2 have been observed in the gas phase as direct products of electron and cesium collisions with organic molecules which contain “bent” CO2 as a basic unit. The long autodetachment life-times are attributed to two related factors - first, the potential energy curve of CO−2(2A1) lies below that of CO2(1A1) at 134°, and, second, an unfavorable Franck-Condon overlap exists between the bent ion (134°) and the linear neutral parent. 相似文献
95.
The nitridorhenium(V) complexes ReNCl(2)(PCy3)(2) (1), ReNBr(2)(PCy3)(2) (2), ReNCl(2)(PPh3)(2) (3), and ReNBr(2)(PPh3)(2) (4) produce structured emission spectra upon excitation at low temperature. The origin, E(00), occurs at 15 775, 16 375, 15 875, and 16 300 cm(-1), respectively. The vibronic peaks are regularly spaced with an average energy separation corresponding to the Re triple bond N stretching frequency. The nitridorhenium stretching frequency ranges from 1095 to 1101 cm(-1), as determined by Raman and IR spectroscopy. The excited-state distortions are calculated by fitting the emission spectra. The excited state arises primarily from a d(xy) (ReN nonbonding) to d(yz) (ReN pi antibonding) transition. The rhenium-nitrogen bond length in the excited state is 0.08 A longer than in the ground electronic state, which is consistent with the difference in bond lengths of ReN bonds of bond order 3 and bond order 2.5 as determined from molecular structures. 相似文献
96.
Smaali M. Issam Gargouri Mohamed Legoy Marie Dominique Maugard Thierry Limam Farid Marzouki Nejib 《Applied biochemistry and biotechnology》2004,112(2):63-77
The filamentous fungus Sclerotinia sclerotiorum, grown on a xylose medium, was found to excrete one β-glucosidase (β-glu x). The enzyme was purified to apparent homogeneity
by ammonium sulfate precipitation, gel filtration, anion-exchange chromatography, and high-performance liquid chromatography
(HPLC) gel filtration chromatography. Its molecular mass was estimated to be 130 kDa by HPLC gel filtration and 60 kDa by
sodium dodecyl sulfate polyacrylamide gel electrophoresis, suggesting that β-glu x may be a homodimer. For p-nitrophenyl β-d-glucopyranoside hydrolysis, apparent K
m and V
max values were found to be 0.09 mM and 193 U/mg, respectively, while optimum temperature and pH were 55–60°C and pH 5.0, respectively. β-Glu x was strongly
inhibited by Fe2+ and activated about 35% by Ca2+. β-Glu x possesses strong transglucosylation activity in comparison with commercially available β-glucosidases. The production
rate of total glucooligosaccharides (GOSs) from 30% cellobiose at 50°C and pH 5.0 for 6 h with 0.6 U/mL of enzyme preparation
was 80 g/L. It reached 105 g/L under the same conditions when using cellobiose at 350 g/L (1.023 M). Finally, GOS structure was determined by mass spectrometry and 13C nuclear magnetic resonance spectroscopy. 相似文献
97.
The formation region of the various types of layered titanium hydrogen phosphate hydrates was investigated. The materials were prepared by hydrothermal methods, treating amorphous titanium phosphate with phosphoric acid (8 to 16M) in the temperature range 175 to 250°C. The materials obtained were:α-Ti(HPO4)2·H2O,γ-Ti(PO4)(H2PO4)·2H2O, and its anhydrous formβ-Ti(PO4)(H2PO4). The structure ofβ-Ti(PO4)(H2PO4) has been determined by Rietveld powder refinement of high resolution neutron diffraction data. The structure is refined in the monoclinic space groupP21/n(No. 14). The unit cell parameters are:a=18.9503(4) Å,b=6.3127(1) Å,c=5.1391(1) Å,β=105.366(2)°;Z=4. The final agreement factors were:Rp=2.9% andRwp=3.8%. The structure ofβ-Ti(PO4)(H2PO4) is built from TiO6octahedra linked together by tertiary phosphate (PO4) and dihydrogen phosphate ((OH)2PO2) tetrahedra. The layers are held together by hydrogen bonds. 相似文献
98.
Abachi S Abbott B Abolins M Acharya BS Adam I Adams DL Adams M Ahn S Aihara H Alitti J Álvarez G Alves GA Amidi E Amos N Anderson EW Aronson SH Astur R Avery RE Baden A Balamurali V Balderston J Baldin B Bantly J Bartlett JF Bazizi K Bendich J Beri SB Bertram I Bezzubov VA Bhat PC Bhatnagar V Bhattacharjee M Bischoff A Biswas N Blazey G Blessing S Boehnlein A Bojko NI Borcherding F Borders J Boswell C Brandt A Brock R Bross A Buchholz D Burtovoi VS Butler JM Casey D Castilla-Valdez H 《Physical review letters》1995,75(6):1023-1027
99.
100.
Abachi S Abbott B Abolins M Acharya BS Adam I Adams DL Adams M Ahn S Aihara H Alitti J Álvarez G Alves GA Amidi E Amos N Anderson EW Aronson SH Astur R Avery RE Baden A Balamurali V Balderston J Baldin B Bantly J Bartlett JF Bazizi K Bendich J Beri SB Bertram I Bezzubov VA Bhat PC Bhatnagar V Bhattacharjee M Bischoff A Biswas N Blazey G Blessing S Boehnlein A Bojko NI Borcherding F Borders J Boswell C Brandt A Brock R Bross A Buchholz D Burtovoi VS Butler JM Casey D Castilla-Valdez H 《Physical review letters》1995,75(4):618-623