全文获取类型
收费全文 | 5780篇 |
免费 | 426篇 |
国内免费 | 324篇 |
专业分类
化学 | 1702篇 |
晶体学 | 7篇 |
力学 | 677篇 |
综合类 | 45篇 |
数学 | 2313篇 |
物理学 | 1786篇 |
出版年
2023年 | 22篇 |
2022年 | 110篇 |
2021年 | 123篇 |
2020年 | 101篇 |
2019年 | 88篇 |
2018年 | 100篇 |
2017年 | 97篇 |
2016年 | 132篇 |
2015年 | 106篇 |
2014年 | 166篇 |
2013年 | 395篇 |
2012年 | 236篇 |
2011年 | 417篇 |
2010年 | 319篇 |
2009年 | 539篇 |
2008年 | 516篇 |
2007年 | 448篇 |
2006年 | 484篇 |
2005年 | 322篇 |
2004年 | 198篇 |
2003年 | 166篇 |
2002年 | 257篇 |
2001年 | 195篇 |
2000年 | 176篇 |
1999年 | 111篇 |
1998年 | 125篇 |
1997年 | 92篇 |
1996年 | 95篇 |
1995年 | 63篇 |
1994年 | 56篇 |
1993年 | 34篇 |
1992年 | 28篇 |
1991年 | 37篇 |
1990年 | 22篇 |
1989年 | 21篇 |
1988年 | 16篇 |
1987年 | 14篇 |
1986年 | 8篇 |
1985年 | 16篇 |
1984年 | 12篇 |
1983年 | 6篇 |
1981年 | 9篇 |
1980年 | 7篇 |
1979年 | 11篇 |
1978年 | 7篇 |
1977年 | 4篇 |
1976年 | 3篇 |
1975年 | 3篇 |
1974年 | 3篇 |
1973年 | 6篇 |
排序方式: 共有6530条查询结果,搜索用时 23 毫秒
991.
992.
Summary The imperfect mirror image relationship of the circular dichroism of (M) and (P) helical biliverdins bound to a homochiral entity (ICD) has been studied using the kinetically stable racemates (M+P)2 and (M+P)3. The phenomena associated with and eventual implications for the interpretation of ICD spectra of naturally occurring kinetically labile biliverdins in terms of chiral recognition are discussed.Dedicated to ProfessorKarl Schlögl on the occasion of his 70th birthday 相似文献
993.
Aki H. Niiya T. Iwase Y. Goto M. Kimura T. 《Journal of Thermal Analysis and Calorimetry》2004,77(2):423-435
The formation of inclusion complexes between amoxicillin (AMPC) and 2-hydroxypropyl-β-cyclodextrin (HPCD) was investigated
by isothermal microcalorimetry and molecular dynamics simulation to evaluate the inhibitory effects on the degradation of
AMPC in aqueous solutions at various pH. The process depended significantly on the ionic species of AMPC in the solution.
In a strong acid solution, cationic AMPC and HPCD formed two different types of inclusion complexes with a 1:1 stoichiometry:
the first-type had a high association constant K
1 of 4.0-8.0·103 M-1 and included the penam ring of AMPC in the HPCD cavity (Mode I), while the second-type with a K
2 of 1.0·103 M-1 contained the phenyl group of AMPC (Mode II). Furthermore, a complex with a 1:2 (AMPC:HPCD) stoichiometry was realized in
a two-step reaction and was characterized by a smaller K
1:2of 4.0·102 M-1 and larger negative enthalpy and entropy changes than the complexes with a 1:1 stoichiometry. Since the β-lactam ring of
AMPC could be protected by inclusion with HPCD in the 1:2 complex and Mode I of 1:1 complexes, the degradation of AMPC in
the presence of HPCD was approximately four times slower than in its absence at pH 1.2 and 37°C. In weak acid and neutral
solutions, zwitterionic AMPC and HPCD formed only one type of inclusion complex with a 1:1 stoichiometry, where the phenyl
group was included (Mode II). AMPC was very stable in these solutions (t
1/2=226 h at pH=6.0) and there is little significant difference in the degradation rate between complexed AMPC and uncomplexed
AMPC. Thus, the results indicated that the inclusion complex of AMPC with HPCD, effectively increasing the stability of AMPC
in a strong acidic solution like that the stomach, would be useful for eradicating Helicobacter pylori infection and as a drug delivery system.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
994.
The crystal structures of a pair isomers of [Co(3,3-tri)(amp)Cl][ZnCl4] (here 3,3-tri = N-(3-Aminoprop- yl)-1,3-propanediamine; amp=2-(Aminomethyl)pyridine) have been determined by single crystal X-ray diffrac-tion. They are the epimers with the only difference of the orientation of the Sec-NH proton in 3,3-tri ligand. The crystals with the anti-epimer (m1[ZnCl4]·CH3OH·H2O) are monoclinic, space group C2/c with eight molecules in a unit cell of dimensions a=30.401(5)?,b=8.0469(13)?,c=18.817(3)?,β=93.346(3)°,V=4595.3(12)?3,Dc=1.708g·cm-3,Z=8,F000=2416,R=0.0462,Rw=0.1304. The crystals of the syn-epimer (m2[ZnCl4]·H2O) are triclinic, space group P1 with two molecules in a unit cell of dimensions a=8.9752(12)?,b=9.8855(12)?,c=12.6886(16)?,α=89.228(3)°,β=76.447(2)°,γ=80.428(3)°,V=1078.8(2)nm3,Dc=1.721g·cm-3,Z=2,F000=568,R=0.0313,Rw=0.0929. The crystal parameters, such as bond lengths and angles, are well consistent with the data of an ab initio computational result (RHF/LANL2DZ opti-mised structure). The average error for bond length is about 1.6%, only two of them in the isomer m3 (Co-N2 and Co-N4) are over 3%, (3.09% and 4.28% respectively). The errormax for bond angle is 2.52%, the bond angles with an over 2% error are only 3.6% out of all bond angles. 相似文献
995.
Takeshi Shimomura Tatsuya Funaki Kohzo Ito Byoung-Ki Choi Tomihiro Hashizume 《Journal of inclusion phenomena and macrocyclic chemistry》2002,44(1-4):275-278
We have investigated the inclusion properties of molecular nanotubes composed ofcrosslinked -cyclodextrin. Induced circular dichroism was used to probe theformation and dissociation of complexes between the nanotubes and azobenzenemodified linear polymers. The polymer was poly(ethylene glycol) (PEG), either withor without a hydrophobic alkyl chain.It was found that the inclusion complex betweenthe nanotubes and polymers formed at room temperature, and that the polymers dissociated from the nanotubes with increasing temperature. Further, the polymer with hydrophobic alkyl chain was bound inside the nanotube more strongly and dissociated more abruptly with increasing temperature than its hydrophilic counterpart as expected theoretically. 相似文献
996.
L. G. Klapshina V. V. Semenov A. N. Kornev V. S. Rusakov O. I. Shchegolikhina A. A. Zhdanov G. A. Domrachev 《Russian Chemical Bulletin》1998,47(3):478-481
The photochemical interaction of polyphenylferrisiloxane with some oligoorganosilanes in benzene solutions has been studied by UV, IR, ESR, and Mössbauer spectroscopy. Silylene species formed during photolysis of oligoorganosilanes react with the high-spin iron(III) to reduce the latter to low-spin iron(II). The formation of the low-spin state of iron(II) was supported by measurements of the magnetic moments. The insertion of the silylene species into the polymer chain to form the Fe?Si bond occurs due to the photoreaction. 相似文献
997.
Six palladium(Ⅱ) complexes with isonitrosoethylacetoacetate imine Schiff base ligands, Pd(R-IEAI)2, were prepared and characterized by IR, Raman and electronic spectra. Complex tran Pd(p-CH3C6H4-IEAI)2 (2) cry- stallizes in the monoclinic system, space group P21/c,with a=1.2002(2),b=0.9972(2),c=1.1121(2)nm,β=90.43(3)°,Z=2,F(000)=616,μ=7.44cm-1. The final R and wR are 0.0244 and 0.0625 for 2620 ob-served reflections with I≥2σ(I), respectively. The geometry around the Pd(Ⅱ) ions in those complexes has a distorted PdN4 square plane, the Schiff base ligands R-IEAI- being coordinated through their oximino-nitrogen atoms and imino-nitrogen atoms. 相似文献
998.
The complex Cu2(μ-dppb)2(μ-Cl)2 has been synthesized from the reaction of CuCl, dppb and (n-Bu)4NCl. The crystal belongs to the triclinic with space group P1. The unit cell parameters are: a=9.939(4)?, b=10.083(6)?, c=14.104(5)?, α=76.46(3)°, β=71.02(2)°, γ=70.87(5)°. The single crystal X-ray diffraction analysis reveals that it has a bi-ring structure with a symmetry center at the middle of two Copper atoms. The outer ring is a 14-membered ring of Cu-dppb-Cu-dppb, and the inner ring is a 4-membered ring composed of two Cl- and two Cu(Ⅰ). Investigation of third-order optical nonlinearity shows that it exhibits considerable nonlinear absorptive and self-defocusing effect with α2=1.75×10-13m·W-1 and n2=3.19×10-18m2·W-1. CCDC: 193113. 相似文献
999.
A novel low-symmetry tetrabenzoporphine with D2h symmetry (1) and its zinc complex (2) were prepared via mixed condensation reaction of 5,6-dimethyl phthalimide and 4,5,6,7-tetraphenyl phthalimide with sodium acetate in the presence of zinc acetate. The zinc complex 2 exhibited a split Q band at 640 and 623 nm and a single Soret band at 435 nm. The absorption spectra of 1 and 2 were calculated and analyzed using Hartree-Fock theory based on INDO/S Hamiltonian. 相似文献
1000.
尖吻蝮蛇毒中抗血小板凝集素是凝血因子IX/凝血因子X结合蛋白,它具有抗凝血和抑制血小板凝集双重活性。用红外光谱、拉曼光谱和CD谱研究了抗血小板凝集素的二级结构以及pH值和钙离子对其二级结构的影响。用CD谱测得,在水溶液中,抗血小板凝集素的主要骨架构象为β-折叠(26.3%)和α-螺旋(19.6%)结构。拉曼光谱显示,在粉末状态,其α-螺旋含量显著降低。CD谱还表明,抗血小板凝集素在pH值3.0~11.0范围内保持稳定的天然结构,钙离子诱导的抗血小板凝集素结构变化是可逆的,钙离子在稳定抗血小板凝集素的天然结构中起重要作用。 相似文献