全文获取类型
收费全文 | 3178篇 |
免费 | 94篇 |
国内免费 | 11篇 |
专业分类
化学 | 2105篇 |
晶体学 | 18篇 |
力学 | 117篇 |
数学 | 418篇 |
物理学 | 625篇 |
出版年
2023年 | 25篇 |
2022年 | 72篇 |
2021年 | 114篇 |
2020年 | 99篇 |
2019年 | 69篇 |
2018年 | 56篇 |
2017年 | 48篇 |
2016年 | 135篇 |
2015年 | 107篇 |
2014年 | 91篇 |
2013年 | 169篇 |
2012年 | 209篇 |
2011年 | 247篇 |
2010年 | 151篇 |
2009年 | 105篇 |
2008年 | 195篇 |
2007年 | 210篇 |
2006年 | 189篇 |
2005年 | 158篇 |
2004年 | 166篇 |
2003年 | 118篇 |
2002年 | 96篇 |
2001年 | 45篇 |
2000年 | 21篇 |
1999年 | 16篇 |
1998年 | 16篇 |
1997年 | 26篇 |
1996年 | 28篇 |
1995年 | 19篇 |
1994年 | 22篇 |
1993年 | 14篇 |
1992年 | 18篇 |
1991年 | 5篇 |
1990年 | 10篇 |
1989年 | 10篇 |
1988年 | 13篇 |
1987年 | 9篇 |
1986年 | 9篇 |
1985年 | 16篇 |
1984年 | 23篇 |
1983年 | 16篇 |
1982年 | 16篇 |
1981年 | 13篇 |
1980年 | 11篇 |
1979年 | 13篇 |
1978年 | 5篇 |
1977年 | 11篇 |
1975年 | 7篇 |
1974年 | 4篇 |
1971年 | 4篇 |
排序方式: 共有3283条查询结果,搜索用时 15 毫秒
91.
Cholesterylbutyrate (Chol-but) was chosen as a prodrug of butyric acid. Butyrate is not often used in vivo because its half-life is very short and therefore too large amounts of the drug would be necessary for its efficacy. In the last few years butyric acid's anti-inflammatory properties and its inhibitory activity towards histone deacetylases have been widely studied, mainly in vitro. Solid Lipid Nanoparticles (SLNs), whose lipid matrix is Chol-but, were prepared to evaluate the delivery system of Chol-but as a prodrug and to test its efficacy in vitro and in vivo. Chol-but SLNs were prepared using the microemulsion method; their average diameter is on the order of 100-150 nm and their shape is spherical. The antineoplastic effects of Chol-but SLNs were assessed in vitro on different cancer cell lines and in vivo on a rat intracerebral glioma model. The anti-inflammatory activity was evaluated on adhesion of polymorphonuclear cells to vascular endothelial cells. In the review we will present data on Chol-but SLNs in vitro and in vivo experiments, discussing the possible utilisation of nanoparticles for the delivery of prodrugs for neoplastic and chronic inflammatory diseases. 相似文献
92.
Roberto Ballini Noelia Araújo Bazn Giovanna Bosica Alessandro Palmieri 《Tetrahedron letters》2008,49(24):3865-3867
A variety of primary and secondary amines give the conjugate reaction with β-nitroacrylates, via an anti-Michael addition, without any catalyst and/or solvent, allowing good yields of β-nitro-α-amino esters. 相似文献
93.
Molecular dynamics studies have been performed on the zwitterionic form of the dipeptide glycine-alanine in water, with focus on the solvation and electrostatic properties using a range of theoretical methods, from purely classical force fields, through mixed quantum mechanical/molecular mechanical simulations, to fully quantum mechanical Car-Parrinello calculations. The results of these studies show that the solvation pattern is similar for all methods used for most atoms in the dipeptide, but can differ substantially for some groups; namely the carboxy and aminoterminii, and the backbone amid NH group. This might have implications in other theoretical studies of peptides and proteins with charged -NH(3) (+) and -CO(2) (-) side chains solvated in water. Hybrid quantum mechanical/molecular mechanical simulations successfully reproduce the solvation patterns from the fully quantum mechanical simulations (PACS numbers: 87.14.Ee, 87.15.Aa, 87.15.He, 71.15.Pd). 相似文献
94.
Rigamonti L Rusconi M Forni A Pasini A 《Dalton transactions (Cambridge, England : 2003)》2011,40(39):10162-10173
One bond Pt-P coupling constants (1)J(PtP) of a series of cationic complexes [PtXL(PPh(3))(2)](+) (X = NO(3), Cl, Br, I; L = 4-Z-pyridines, Z = electron withdrawing or releasing groups, 4a-k; or X = Cl, L = NH(3), PhCH(2)NH(2) and (i)PrNH(2), 5a-c) have been used to establish the trans and cis influence sequences of X and pyridines. The crystal structure of compound 4f(BF(4)) with Z = (t)Bu has been resolved. In the pyridine complexes 4a-d (Z = H, variable X), both the trans and cis influence series of the anionic ligands X decrease along the same sequence I > Br > Cl > NO(3), as previously found for [PtX(PPh(3))(3)](+) (X = NO(3), Cl, Br, I, 3a-d), however in 4a-d the cis influence turns out to be more important than the trans. On the contrary, in [PtCl(4-Z-py)(PPh(3))(2)](+) (4b,e-k) the sequence of the trans influence of the 4-Z-pyridines is opposite to that of the cis, the latter being Z = CN > CHO > Br > PhCO > H > Me > (t)Bu > NH(2), i.e. the most basic pyridine gives rise to the lowest cis influence. This correlation was found to hold also for complexes 5a-c (L = amines). All the observed trends have been fully reproduced by B3LYP/def2-SVP DFT calculations, by looking at the relevant optimized bond lengths of selected complexes of type 3, 4 and 5. Subsequent evaluation of the atomic charges, by resorting to two independent methods, i.e., the Natural Bond Order analysis of the wavefunction and the Bader's Quantum Theory of Atoms in Molecules, allowed for rationalization of the origin of the cis and trans influences. The negative charge on the nitrogen atoms of free pyridines becomes more negative upon protonation and even more so when coordinated to the [PtCl(PPh(3))(2)](+) moiety. The least negatively charged nitrogen atom of coordinated pyridines is that of 4-CN-py (the highest cis influencing pyridine derivative), which gives rise to the lowest positive charge on Pt, confirming the relationship between the lowering of the charge on the metal ion and a high cis influence. The trans influence can be described in terms of competition between the charges on the two trans donor atoms. In contrast with the behaviour of pyridines, the positive charge on the phosphorous atom of free PPh(3) increases upon coordination to Pt(II), moreover the PPh(3) ligands acquire a substantial positive charge, thus efficiently delocalising the charge of the cationic complex. 相似文献
95.
A new family of optically pure tetrathiafulvalenium and tetraselenafulvalenium salts, D(3)[M(III)(S,S-EDDS)](2)·nH(2)O (where D = TTF, TSF; M = Co, Fe, Cr; EDDS = ethylenediaminedisuccinato), were synthesized electrochemically. These phases are semiconductors with conductivities between 6.9 × 10(-6) and 1.3 × 10(-5) S·cm(-1) (E(a)ca. 0.3 eV) for TTF and 2.8 × 10(-4) to 2.8 × 10(-5) S·cm(-1) (E(a)ca. 0.1 eV) for TSF compounds. While some crystals suffer from twinning, other well resolved structures consist of TTF/TSF stacks which, under the influence of the chiral anion, exhibit a periodic undulation described by an elliptical helix. The crystallographic data, along with computational work, indicate charge localization in the semiconducting motifs. 相似文献
96.
Livieri A Boiocchi M Desimoni G Faita G 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(2):516-520
Diels–Alder and 1,3‐dipolar cycloadditions involving (E)‐3‐aryl‐1‐(pyridin‐2‐yl‐N‐oxide)prop‐2‐en‐1‐ones as the 2π components are efficiently catalysed by bis(oxazoline)–CuII complexes. The cycloadducts are obtained in quantitative yields with up to 98 % ee; absolute configurations were determined by X‐ray analysis. The structure of the reactive complex, determined by X‐ray analysis, is fully consistent with the stereochemical outcome of the catalysed process (approach of the diene or nitrone to the less hindered face of the coordinated pyridine‐N‐oxide derivative). 相似文献
97.
Donoli A Marcuzzo V Moretto A Toniolo C Cardena R Bisello A Santi S 《Organic letters》2011,13(6):1282-1285
Two series of 3(10)-helical peptides of different lengths and rigidity, based on the strongly foldameric α-aminoisobutyric acid and containing a terminal ferrocenyl unit, have been synthesized. Oxidation-state sensitive spectroscopic tags of helical peptides, the N-H groups, allowed mapping of the charge delocalization triggered by oxidation of the terminal ferrocenyl moiety and were monitored by IR spectroelectrochemistry. 相似文献
98.
99.
100.
Ipomoea cairica cell cultures produced a tetrahydrofuran lignan, (+)-pinoresinol, identified by UV, IR, MS and NMR methods, not yet found in the intact plant, and new in the Convolvulaceae family. Pinoresinol was found to have antioxidant and Ca2+ antagonist properties. As it could be requested for its biological activity, we examined the possibility to raise the pinoresinol yield of I. cairica cultures, as well as we continued investigations on lignans' response to optimization. 相似文献