全文获取类型
收费全文 | 9089篇 |
免费 | 1233篇 |
国内免费 | 1303篇 |
专业分类
化学 | 5553篇 |
晶体学 | 85篇 |
力学 | 1357篇 |
综合类 | 65篇 |
数学 | 539篇 |
物理学 | 4026篇 |
出版年
2024年 | 23篇 |
2023年 | 109篇 |
2022年 | 254篇 |
2021年 | 274篇 |
2020年 | 369篇 |
2019年 | 311篇 |
2018年 | 288篇 |
2017年 | 373篇 |
2016年 | 389篇 |
2015年 | 369篇 |
2014年 | 476篇 |
2013年 | 742篇 |
2012年 | 587篇 |
2011年 | 635篇 |
2010年 | 485篇 |
2009年 | 554篇 |
2008年 | 511篇 |
2007年 | 562篇 |
2006年 | 473篇 |
2005年 | 494篇 |
2004年 | 421篇 |
2003年 | 352篇 |
2002年 | 311篇 |
2001年 | 312篇 |
2000年 | 248篇 |
1999年 | 226篇 |
1998年 | 202篇 |
1997年 | 165篇 |
1996年 | 149篇 |
1995年 | 152篇 |
1994年 | 123篇 |
1993年 | 89篇 |
1992年 | 81篇 |
1991年 | 73篇 |
1990年 | 64篇 |
1989年 | 42篇 |
1988年 | 46篇 |
1987年 | 34篇 |
1986年 | 31篇 |
1985年 | 32篇 |
1984年 | 32篇 |
1983年 | 11篇 |
1982年 | 26篇 |
1981年 | 17篇 |
1980年 | 17篇 |
1979年 | 19篇 |
1978年 | 10篇 |
1977年 | 22篇 |
1976年 | 13篇 |
1973年 | 9篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
121.
K. V. Zaitsev S. S. Karlov M. V. Zabalov A. V. Churakov G. S. Zaitseva D. A. Lemenovskii 《Russian Chemical Bulletin》2005,54(12):2831-2840
Titanatrane CpTi(OCH(CH3)CH2)3N (3) was prepared by the reaction of CpTiCl3 with N(CH2CH(CH3)OH)3 in the presence of triethylamine. The reaction of CpTi(OMe)3 (8) with N(CH2CH2OH)2(CH2CHPhOH), erythro-N(CH2CH2OH)2(CHPhCHPhOH), and N(CH2CH2OH)2(CH2CPh2OH) gave cyclopentadienyltitanatranes 12–14. Compound 8 reacts with threo-N(CH2CH2OH)2(CHPhCHPhOH) to give a mixture of threo-CpTi(OCH2CH2)2(OCHPhCHPh)N and threo-MeOTi(OCH2CH2)2(OCHPhCHPh)N. Slow hydrolysis of the latter product gave threo-[Ti3O(OMe){(OCH2CH2)2− (OCHPhCHPh)N} 3]2, which was studied by X-ray diffraction analysis. The crystal structures of 3 and 12 were also determined by X-ray diffraction analysis. The titanium coordination polyhedron in these complexes is a distorted
trigonal bipyramid in which the equatorial positions are occupied by three oxygen atoms and the axial positions contain the
N atom and the Cp group. The titanium—nitrogen distances (2.313(2), 2.291(2) Å in two independent molecules of 3 and 2.271(2) Å in compound 12) confirm the presence of Ti←N transannular interaction.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2736–2744, December, 2005. 相似文献
122.
In order to study the influence of the side-chain orientation on the peptide backbone conformation we have synthesised the model dipeptides t-BuCO-l-Pro-(1S,2R)-c6Phe-NHMe and t-BuCO-l-Pro-(1R,2S)-c6Phe-NHMe, incorporating each enantiomer of the trans cyclohexane analogue of phenylalanine (trans-1-amino-2-phenylcyclohexanecarboxylic acid). The orientation of the aromatic side-chain determines the β-turn type accommodated by these peptides to the point that the (1S,2R)-c6Phe derivative retains the type I β-turn in the crystalline state, in contrast to the behaviour exhibited by the natural counterpart t-BuCO-l-Pro-l-Phe-NHMe. 相似文献
123.
Summary An extensive crystal survey of the Cambridge Structural Database has been carried out to provide hydrogen-bond data for use in drug-design strategies. Previous crystal surveys have generated 1D frequency distributions of hydrogen-bond distances and angles, which are not sufficient to model the hydrogen bond as a ligand-receptor interaction. For each hydrogen-bonding group of interest to the drug designer, geometric hydrogen-bond criteria have been derived. The 3D distribution of complementary atoms about each hydrogen-bonding group has been ascertained by dividing the space about each group into bins of equal volume and counting the number of observed hydrogen-bonding contacts in each bin. Finally, the propensity of each group to form a hydrogen bond has been calculated. Together, these data can be used to predict the potential site points with which a ligand could interact and there-fore could be used in molecular-similarity studies, pharmacophore query searching of databases, or de novo design algorithms. 相似文献
124.
Li-Ya Wang Xiao-Qiang Wang Kai Jiang Jiu-Li Chang Yu-Fang Wang 《Journal of Molecular Structure》2007,840(1-3):14-21
A new nitronyl nitroxide NIT2-bithph (1) and its manganese(II) compound [Mn(hfac)2(IMHBithph)]2·(NIT2-bithph)(C6H14) (2) (hfac = hexafluoroacetylacetonate; NIT2-bithph = 4,4,5,5-tetramethyl-2-(bithiophenal-2-yl)imidazoline-1-oxyl-3-oxide; IMHBithph = 1-hydroxy-2-bithiophenal-4,4,5,5-tetramethyl-4,5-dihydro- 1H-imidazole) have been synthesized and structurally characterized by X-ray diffraction methods. The units of compound 1 were connected as one-dimensional chain by the intermolecular hydrogen bonds which afford an intermolecular antiferromagnetic interaction between nitronyl nitroxide radicals within the chain (J = −1.89 cm−1). Compound 2 resulting from the reaction of Mn(hfac)2·2H2O and NIT2-bithph is dinuclear and includes the reduced amidino-oxide form of NIT2-bithph, it is made up of three parts: a [Mn(hfac)2(IMHBithph)]2 dimer unit, an uncoordinated NIT2-bithph radical and a noncoordinated solvent molecule of hexane, the molecule of radical is hydrogen bonded to its reduced form. Two reduced IMHBithph ligands bridge the two manganese(II) ions through their amidino-oxide oxygen atoms resulting in a small intramolecular antiferromagnetic interaction between the manganese ions (J = −1.55 cm−1). 相似文献
125.
The predictive accuracy for estimating infinite dilution activity coefficients by a modification of the UNIFAC method wherein the group interaction parameters were based on only data (referred to as -based UNIFAC) has been studied. Estimates and measured values were compared for six prototypical solutes in a series of homologous n-alkanes, l-alcohols and alkanenitrile solvents. Despite the fact that the interaction parameters were derived using only data, this approach still gave serious errors due to several inherent problems in the original UNIFAC model. Its performance is sometimes even poorer than that of the original UNIFAC method. For example for nitromethane in alcohols and p-dioxane in nitriles values predicted by the -based UNIFAC are essentially zero. The large errors for these systems are most likely due to inaccurate interaction parameters in the -based UNIFAC method. 相似文献
126.
C.?Buron C.?Filiatre F.?Membrey A.?FoissyEmail author J.?F.?Argillier 《Colloid and polymer science》2004,282(5):446-453
The interaction between sodium dodecyl sulphate (SDS) and gelatin was studied at pH 4.5 and 6.5 where the gelatin is positively charged (i.e.p. 8). At pH 4.5 a SDS/gelatin concentration range was found where gelatin precipitates. At pH 6.5 the SDS-gelatin complex remains soluble although three SDS concentration domains were distinguished where the SDS-gelatin complex had very different affinities for the solvent. Below C1 the complex was highly surface active but other measurements (viscosity, potentiometry, protons uptake) did not reveal any particular consequence of binding. Between C1 and C2 the molecular size decreased (viscosity lowering) upon charge neutralization and collapse about small SDS aggregates (17 SDS molecules per gelatin molecule). Above C2 a cooperative binding mechanism lead to the formation of SDS aggregates; the complex stretched out and turned strongly hydrophilic (the viscosity increases, low surface activity). At saturation one gelatin molecule bound about 200 SDS molecules. Above the overlap concentration (about 3 wt%) SDS aggregates formed between several gelatin molecules, the viscosity increased continuously with SDS concentration and the binding ratio was lower than in dilute gelatin solutions. A very good correspondence was found between the different analytical data including turbidity, viscosity, surface tension, protons uptake and direct potentiometric SDS binding measurements. 相似文献
127.
Yoshihiko Saito 《中国化学会会志》1991,38(5):405-424
A historical overview will be given on the structural studies on transition metal compounds and their interaction with other fields of coordination chemistry. About three decades have passed away since the structure and absolute configuration of tris(ethylenediamine)cobalt(III) complex ion were determined. At present accumulation of the structural data for isomers has enabled us to understand structural principles of chelate complexes in considerable detail. The energy minimization calculations can predict the detailed geometries of the complexes. Differences in thermodynamic properties between different conformers are well reproduced. Aspherical distribution of 3d electrons in transition metal complexes was detected for the first time in crystals of [Co(NH3)6][Co(CN)6] in 1973. Such an accurate electron density study provides important information on the d electrons placed in a ligand field. The high-spin and low-spin states can be distinguished unequivocally. In spite of a very small valence/total electron ratio, the asphericity of 4d and 5d electrons in a ligand field can be detected. The crystal structures of a series of dimeric copper(II) carboxylate adducts of the general formula [Cu(RCOO)2L]2 have been determined or redetermined as accurately as possible. The temperature dependent magnetic susceptibility of these crystals indicated that the isolated pairs of Cu(II) ions interact strongly through exchange forces. Molecular orbital calculations revealed that the electron population in the carbon atom of the bridging OCO group plays an important role in determining the strength of the spin superexchange interaction. In the crystals of some cobaloxime complexes, racemization of chiral groups bonded to Co proceeds on X-ray exposure without degradation of crystallinity. Several intermediate stages could be determined by X-ray analysis. Various reaction pathways were recognized and the reaction rate could be correlated with the atomic arrangement in the crystal. 相似文献
128.
Molecular structures of three emissive annular digold compounds [Au2(dmpm)(dtc)]Cl (dmpm = Me2PCH2PMe2,dtc = S2CNEt2), 1 , [Au2(dppm)(dtc)]PF6, (dppm = Ph2PCH2PPh2),2,and [Au2(dppe)(dtc)]-(PF2) (dppe = Ph2P(CH2)2PPh2), 3, were determined. All three compounds are dimetallacycles having two gold atoms bridged by a dithiolate ligand and a diphosphine ligand, the geometry around each gold atom being almost linear. All the dimetal lacy die rings are slightly distorted from planarity with intramolecular Au-Au distances shorter than 3.0 Å. Compound 1 forms a polymeric chain through intermolecular Au-Au contacts (3.061 ? 3.135 Å). Compound 2 forms a tetramer through intermolecular Au-Au interactions (Au-Au distances ranging from 3.086 to 3.222 ). Compound 3 is monomeric. All of the compounds luminesce at 77 K in the solid state. Emissions originating from 3LMCT from dtc ligand to Au excited states are assigned. The emission maxima of 1 ? 3 are at 541,535 and 520 nm respectively and are blue shifted as the number of Au-Au interactions is decreased. 相似文献
129.
The separation of diastereomeric esters derived from (±)-pyridylethanols and 3β-acetoxyetienic acid were achieved by an extraction technique using diethyl ether and aqueous hydrochloric acid. A formal total synthesis of PNU-142721 was effectively carried out to prepare the chiral, non-racemic synthon 1-furo[2,3-c]pyridin-5-yl-ethanol (1) by means of this technique. The structure optimized using MOPAC calculations on each diastereomer suggested the presence of intramolecular CH/π interaction in only the (S)-isomer of the diastereomers. 相似文献
130.
以作者开发的从蛋白质结合部位推导出其界面所具有的疏水性质和氢键性质的计算程序PP_SITE为基础,利用蛋白质结构数据库(PDB),对蛋白质-蛋白质相互作用界面进行了统计分析.从PDB中挑出非冗余的链间相互作用对,计算出这个数据集中所有链间界面的疏水和氢键相互作用特征.对得到的界面特征进行统计分析,寻找能够明显聚类的界面特征.结果表明,界面大小、氢键和疏水相互作用在界面所占比例以及疏水相互作用的集中程度可以作为分类的依据. 相似文献