全文获取类型
收费全文 | 6469篇 |
免费 | 786篇 |
国内免费 | 174篇 |
专业分类
化学 | 6748篇 |
晶体学 | 55篇 |
力学 | 278篇 |
综合类 | 7篇 |
数学 | 164篇 |
物理学 | 177篇 |
出版年
2024年 | 4篇 |
2023年 | 82篇 |
2022年 | 93篇 |
2021年 | 156篇 |
2020年 | 266篇 |
2019年 | 194篇 |
2018年 | 111篇 |
2017年 | 113篇 |
2016年 | 258篇 |
2015年 | 280篇 |
2014年 | 293篇 |
2013年 | 392篇 |
2012年 | 386篇 |
2011年 | 396篇 |
2010年 | 360篇 |
2009年 | 392篇 |
2008年 | 480篇 |
2007年 | 506篇 |
2006年 | 394篇 |
2005年 | 405篇 |
2004年 | 428篇 |
2003年 | 350篇 |
2002年 | 116篇 |
2001年 | 110篇 |
2000年 | 95篇 |
1999年 | 131篇 |
1998年 | 119篇 |
1997年 | 108篇 |
1996年 | 93篇 |
1995年 | 103篇 |
1994年 | 45篇 |
1993年 | 32篇 |
1992年 | 28篇 |
1991年 | 20篇 |
1990年 | 8篇 |
1989年 | 11篇 |
1988年 | 12篇 |
1987年 | 11篇 |
1986年 | 3篇 |
1985年 | 6篇 |
1984年 | 3篇 |
1983年 | 3篇 |
1982年 | 6篇 |
1980年 | 2篇 |
1979年 | 4篇 |
1978年 | 2篇 |
1975年 | 4篇 |
1974年 | 2篇 |
1969年 | 2篇 |
1957年 | 2篇 |
排序方式: 共有7429条查询结果,搜索用时 156 毫秒
231.
Blanchard S Blain G Rivière E Nierlich M Blondin G 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(17):4260-4268
A new dinuclear manganese(II) complex was synthesised with the biscompartimental ligand 2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-nitrophenol (NO(2)BpmpH) and characterised by X-ray crystallography. Magnetic susceptibility measurements revealed that the two high-spin Mn(II) ions are antiferromagnetically coupled with a singlet-to-triplet separation of 7.2 cm(-1). The powder EPR spectra were recorded for both X- and Q-bands between 1.8 K and 35 K. A detailed analysis of these spectra led to the determination of three out of five individual spin-state zero-field splitting parameters. From the proposed simulations, the exchange coupling constant J and the intermetallic distance have been computed. 相似文献
232.
The synthesis and structures of nickel (II) complexes of chiral cyclams originating from l-proline are presented. Upon addition of nickel acteate, oxocyclams having amide groups underwent deprotonation forming distorted square-planar complexes. In the case of the all-amine analogue a six-coordinate octahedral complex is formed. 相似文献
233.
Malati Raghunath 《Tetrahedron letters》2005,46(47):8213-8216
Among the bisphosphine ligands, we have previously developed Cn-TunePhos (n = 1-6) as a family of ligands with tunable bite angles. The increase in spacer -CH2- groups in this family of ligands causes changes in ligand dihedral angle, which in turn causes P-Pd-P bite angle variation. Pd-catalyzed asymmetric alkylations and cycloadditions have been tested with Cn-TunePhos ligands. This study aims at a possible correlation between ligand bite angles with enantioselectivity of the Pd-catalyzed asymmetric products. 相似文献
234.
The interactions of [Pt(CNN)(4-dpt)]PF(6), (1; 4-dpt=2,4-diamino-6-(4-pyridyl)-1,3,5-triazine, HCNN=6-phenyl-2,2'-bipyridine) with double-stranded DNA, poly(dA-dT)(2), and poly(dG-dC)(2) were examined by spectroscopic, electrophoretic, and hydrodynamic methods. The spectroscopic data were analyzed with McGhee, van't Hoff, and Gibbs-Helmholtz equations. In a comparative study, [Pt(CNN)(py)]PF(6) (2; py=pyridine) was prepared and the nature of its binding towards DNA was investigated [preliminary results: ChemBioChem 2003, 4, 62-68]. For reactions with calf thymus DNA at 20 degrees C, the intrinsic binding constants for 1 and 2 are (4.6+/-0.2)x10(5) and (2.3+/-0.3)x10(4) mol(-1) dm(3), respectively. Results of DNA-binding reactions revealed that 1 and 2 preferentially bind to the AT sequence of duplex DNA. Intercalation is the preferred binding mode for 2, whereas both intercalation and minor-groove binding are observed for 1. Complex 1 is cytotoxic against a number of carcinoma cell lines, including KB-3-1, CNE-3, and HepG2, and remains potent against multidrug- or cisplatin-resistant KB-V-1 and CNE1 cell lines, for which the resistance ratios are 1.6 and 1.5, respectively. Importantly, 1 is almost an order of magnitude less toxic to the normal cell line CCD-19Lu (IC(50)=176+/-1.7 microM) and it selectively induced apoptosis leading to cancer cell death with less than 5 % detectable necrosis. 相似文献
235.
Samik Gupta Anil Kumar Barik Sachindranath Pal Arijit Hazra Somnath Roy Ray J. Butcher Susanta Kumar Kar 《Polyhedron》2007
Four cis-dioxomolybdenum complexes of general formula [MoO2(Ln)EtOH] (n = 1–4) and one oxomolybdenum(IV) complex [MoO(L4)EtOH], with potentially tridentate Schiff bases derived from 5-methyl pyrazole-3-carbohydrazide and salicylaldehyde/substituted salicylaldehyde/o-hydroxy acetophenone have been prepared. The Mo(IV) complex is derived from the Mo(VI) dioxo complex by oxotransfer reaction with PPh3. The complexes are characterized by elemental analysis, electronic spectra, IR, 1H NMR, and by cyclic voltammetry. All the Mo(VI) species are crystallographically characterized. The complexes have a distorted octahedral structure in which the ligand behaves as a binegative donor one, leaving the pyrazole –N uncoordinated towards the metal center. It is also revealed from the crystal structure that the Mo(VI) center enjoys an NO5 donor environment. 相似文献
236.
Vijay M. Krishnamurthy Dr. Brooks R. Bohall Chu‐Young Kim Dr. Demetri T. Moustakas Dr. David W. Christianson Prof. Dr. George M. Whitesides Prof. Dr. 《化学:亚洲杂志》2007,2(1):94-105
This paper describes a calorimetric study of the association of a series of seven fluorinated benzenesulfonamide ligands (C6HnF5?nSO2NH2) with bovine carbonic anhydrase II (BCA). Quantitative structure–activity relationships between the free energy, enthalpy, and entropy of binding and pKa and log P of the ligands allowed the evaluation of the thermodynamic parameters in terms of the two independent effects of fluorination on the ligand: its electrostatic potential and its hydrophobicity. The parameters were partitioned to the three different structural interactions between the ligand and BCA: the ZnII cofactor–sulfonamide bond (≈65 % of the free energy of binding), the hydrogen bonds between the ligand and BCA (≈10 %), and the contacts between the phenyl ring of the ligand and BCA (≈25 %). Calorimetry revealed that all of the ligands studied bind in a 1:1 stoichiometry with BCA; this result was confirmed by 19F NMR spectroscopy and X‐ray crystallography (for complexes with human carbonic anhydrase II). 相似文献
237.
Pierre Braunstein 《Journal of organometallic chemistry》2004,689(24):3953-3967
In this account, we focus on results from our laboratory to illustrate recent developments in various fields of organometallic chemistry. Studies on hemilabile P,N donor ligands and on the ion-pair behaviour of cationic Pd(II) complexes have led to the full characterization of complexes with η1-allyl ligands. This still rare bonding mode for the allyl ligand in palladium chemistry allows facile insertion of CO into the Pd-C σ-bond, in contrast to the situation in related η3-allyl Pd(II) complexes. In order to develop new homogeneous catalysts for the selective dimerization and oligomerization of ethylene, a range of Ni(II) complexes have been prepared with new chelating P,N ligands where P represents a phosphine, phosphinite or phosphonite donor group and N a pyridine or oxazoline moiety. Finally, we shall examine bottom-up approaches to the formation of new nanomaterials of magnetic or catalytic interest by covalent anchoring of metal complexes and clusters into mesoporous materials using functional phosphine or alkyne ligands containing an alkoxysilyl group. 相似文献
238.
Mund G Vidovic D Batchelor RJ Britten JF Sharma RD Jones CH Leznoff DB 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(19):4757-4763
Several iron(III) complexes incorporating diamidoether ligands are described. The reaction between [Li(2)[RN(SiMe(2))](2)O] and FeX(3) (X=Cl or Br; R=2,4,6-Me(3)Ph or 2,6-iPr(2)Ph) form unusual ate complexes, [FeX(2)Li[RN(SiMe(2))](2)O](2) (2, X=Cl, R=2,4,6-Me(3)Ph; 3, X=Br, R=2,4,6-Me(3)Ph; 4, X=Cl, R=2,6-iPr(2)Ph) which are stabilized by Li-pi interactions. These dimeric iron(III)-diamido complexes exhibit magnetic behaviour characteristic of uncoupled high spin (S= 5/2 ) iron(III) centres. They also undergo halide metathesis resulting in reduced iron(II) species. Thus, reaction of 2 with alkyllithium reagents leads to the formation of iron(II) dimer [Fe[Me(3)PhN(SiMe(2))](2)O](2) (6). Similarly, the previously reported iron(III)-diamido complex [FeCl[tBuN(SiMe(2))](2)O](2) (1) reacts with LiPPh(2) to yield the iron(II) dimer [Fe[tBuN(SiMe(2))](2)O](2) but reaction with LiNPh(2) gives the iron(II) product [Fe(2)(NPh(2))(2)[tBuN(SiMe(2))](2)O] (5). Some redox chemistry is also observed as side reactions in the syntheses of 2-4, yielding THF adducts of FeX(2): the one-dimensional chain [FeBr(2)(THF)(2)](n) (7) and the cluster [Fe(4)Cl(8)(THF)(6)]. The X-ray crystal structures of 3, 5 and 7 are described. 相似文献
239.
Wolfdieter A. Schenk Michael Stubbe Michael Hagel 《Journal of organometallic chemistry》1998,560(1-2):257-263
The P–Ph cleavage of phenyldibenzophosphole (1) with lithium in THF gives lithium dibenzophospholide (2). Reaction of 2 with ethyleneglycol ditosylate produces the known chelate ligand 1,2-bis(dibenzophospholyl)ethane (3) in good yield. Similarly, 2 and (2R,3R)-butanediol ditosylate give the new chiral chelate ligand (2S,3S)-bis(dibenzophospholyl)butane (4). Ligand exchange of [CpRu(PPh3)2Cl] with 3 or 4 yields the halfsandwich complexes [CpRu(C12H8PC2H4PC12H8)Cl] (5) and [CpRu((S,S)-C12H8PCHMeCHMePC12H8)Cl] (6). Complex 6 was characterized crystallographically (monoclinic, space group P21 (no. 4), a=820.6(4), b=1501.0(3), c=1172.8(6) pm, β=108.87(2)°, V=1.367(1)×109 pm3, Z=2). The most conspicuous feature of the structure of 6 is the perfect coplanarity of the two dibenzophosphole moieties imposed by their steric interaction with the Cp ligand. Complex 6 and the thiophene complex [CpRu((S,S)-C12H8PCHMeCHMePC12H8)(SC4H4)]BF4 (7) derived therefrom are remarkably unreactive with regard to ligand substitutions. A possible explanation is the lack of intramolecular –C stabilization en route to the transition state of ligand substitution. The enantiomeric purity of 6 and 7 could nevertheless be demonstrated by conversion to diastereomerically pure [CpRu((S,S)-C12H8PCHMeCHMePC12H8)((S)-CNCHMePh)]BF4 (8). 相似文献
240.
Fan J Gan L Kawaguchi H Sun WY Yu KB Tang WX 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(16):3965-3973
Six noninterpenetrating organic-inorganic hybridized coordination complexes, [Mn(3)(2)(H(2)O)(2)](ClO(4))(2).2 H(2)O (5), [Mn(3)(2)(H(2)O)(2)](NO(3))(2) (6), [Mn(3)(2)(N(3))(2)].2 H(2)O (7), [Cu(3)(2)(H(2)O)(2)](ClO(4))(2) (8), [Mn(4)(2)(H(2)O)(SO(4))].CH(3)OH.5 H(2)O (9) and [Mn(4)(2)](ClO(4))(2) (10) were obtained through self-assembly of novel tripodal ligands, 1,3,5-tris(1-imidazolyl)benzene (3) and 1,3-bis(1-imidazolyl)-5-(imidazol-1-ylmethyl)benzene (4) with the corresponding metal salts, respectively. Their structures were determined by X-ray crystallography. The results of structural analysis of complexes 5, 6, 7, and 8 with rigid ligand 3 indicate that their structures are mainly dependant on the nature of the organic ligand and geometric need of the metal ions, but not influenced greatly by the anions and metal ions. While in complexes 9 and 10, which contain the flexible ligand 4, the counteranion plays an important role in the formation of the frameworks. Entirely different structures of complexes 5 and 10 indicate that the organic ligands greatly affect the structures of assemblies. Furthermore, in complexes 5 and 6, the counteranions located between the cationic layers can be exchanged by other anions. Reversible anion exchanges between complexes 5 and 6 without destruction of the frameworks demonstrate that 5 and 6 can act as cationic layered materials for anion exchange, as determined by IR spectroscopy, elemental analyses, and X-ray powder diffraction. 相似文献