全文获取类型
收费全文 | 14988篇 |
免费 | 554篇 |
国内免费 | 42篇 |
专业分类
化学 | 10199篇 |
晶体学 | 233篇 |
力学 | 468篇 |
综合类 | 1篇 |
数学 | 1125篇 |
物理学 | 3558篇 |
出版年
2024年 | 65篇 |
2023年 | 176篇 |
2022年 | 450篇 |
2021年 | 432篇 |
2020年 | 472篇 |
2019年 | 532篇 |
2018年 | 493篇 |
2017年 | 476篇 |
2016年 | 677篇 |
2015年 | 486篇 |
2014年 | 763篇 |
2013年 | 1271篇 |
2012年 | 1122篇 |
2011年 | 1174篇 |
2010年 | 777篇 |
2009年 | 596篇 |
2008年 | 740篇 |
2007年 | 738篇 |
2006年 | 574篇 |
2005年 | 501篇 |
2004年 | 381篇 |
2003年 | 323篇 |
2002年 | 259篇 |
2001年 | 159篇 |
2000年 | 137篇 |
1999年 | 102篇 |
1998年 | 74篇 |
1997年 | 101篇 |
1996年 | 95篇 |
1995年 | 75篇 |
1994年 | 69篇 |
1993年 | 94篇 |
1992年 | 100篇 |
1991年 | 79篇 |
1990年 | 68篇 |
1989年 | 73篇 |
1988年 | 50篇 |
1987年 | 45篇 |
1986年 | 42篇 |
1985年 | 63篇 |
1984年 | 62篇 |
1983年 | 54篇 |
1982年 | 47篇 |
1981年 | 37篇 |
1980年 | 46篇 |
1979年 | 62篇 |
1978年 | 48篇 |
1977年 | 54篇 |
1976年 | 41篇 |
1975年 | 34篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
951.
Two diorganotin(IV) complexes of the general formula R2Sn[Ph(O)CCH-C(Me)N-NC(O)Ph] (R=Ph, 1; R=Me, 2) have been synthesised from the corresponding diorganotin(IV) dichloride and the ligand 4-phenyl-2,4-butanedionebenzoylhydrazone(2−) (H2L), derived from benzoyl acetone and benzoyl hydrazide in methanol at room temperature in presence of triethylamine. The syntheses were performed under very mild conditions, at room temperature and without exclusion of air or moisture from the reaction vessel. Previously, rigorous conditions have been considered necessary for these species. The two compounds have been characterised by elemental analysis, IR and 1H, 13C, 15N, 119Sn NMR spectra, and their structures have been confirmed single crystal X-ray structure analysis. The central tin atom of both complexes adopts a distorted trigonal bipyramidal coordination with two ligand oxygen atoms in axial positions, the nitrogen atom of the ligand and two organic groups on tin occupying equatorial sites. 2 has crystallised with two crystallographically independent molecules in the asymmetric unit. The δ(119Sn) values for the complexes 1 and 2 are −151.5 and −146.8 ppm, respectively, thus indicating penta-coordinated tin centres. 相似文献
952.
Mithlesh Kumar R. M. Kadam T. K. Seshagiri V. Natarajan A. G. Page 《Journal of Radioanalytical and Nuclear Chemistry》2004,262(3):633-637
Thermally stimulated luminescence (TSL) and electron paramagnetic resonance (EPR) investigations were carried out on gamma irradiated SrBPO5 samples doped with CeO2 and co-doped with CeO2 and Sm2O3. On gamma-irradiation at room temperature, BO3
2–, O2
– and O– radicals were produced. It was seen that the O– radical ion disappeared in the sample annealed at 500 K. It is proposed that the recombination between trapped electrons and O– radical ions results in transfer of recombination energy to the impurity centre Ce3+ resulting in TSL glow peak at 485 K. In the case of co-doped samples energy transfer occurs between Ce3+ to Sm3+ resulting in increase in the intensity of glow peak at 485 K.The authors are grateful to Dr. V. K. Manchanda, Head, Radiochemistry Division, BARC for his keen interest and encouragement during the course of this work. 相似文献
953.
An electrochemical method for the preparation of poly(pyronin B) film was proposed in this paper. A poly(pyronin B) (poly(PyB)) film modified glassy carbon electrode (GCE) has been fabricated via an electrochemical oxidation procedure and applied to the electrocatalytic oxidation of reduced form of nicotinamide adenine dinucleotide (NADH). The poly(PyB) film modified electrode surface has been characterized by atomic force microscope (AFM), scanning electron microscope (SEM), electrochemical impedance spectroscopy (EIS), UV‐visible absorption spectrophotometry (UV‐vis) and cyclic voltammetry (CV). These studies have been used to investigate the poly(PyB) film, which demonstrates the formation of the polymer film and the excellent electroactivity of poly(PyB) in neutral and even in alkaline media. Due to its potent catalytic effects towards the electrooxidation of NADH at lower potential (0.0 V), poly(PyB) film modified electrode can be used for the selective determination of NADH in real samples because of dopamine, ascorbic acid and uric acid oxidation can be avoided at this potential. The catalytic peak currents are linearly dependent on the concentrations of NADH in the range of 1.0×10?6 to 5.0×10?4 mol/L with correlation coefficients of 0.999. The detection limits for NADH is 0.5×10?6 mol/L. Poly(PyB) modified electrode also shows good stability and reproducibility due to the irreversible attachment of polymer film at GCE surface. 相似文献
954.
Altun M Kramer HB Willems LI McDermott JL Leach CA Goldenberg SJ Kumar KG Konietzny R Fischer R Kogan E Mackeen MM McGouran J Khoronenkova SV Parsons JL Dianov GL Nicholson B Kessler BM 《Chemistry & biology》2011,18(11):1401-1412
Converting lead compounds into drug candidates is a crucial step in drug development, requiring early assessment of potency, selectivity, and off-target effects. We have utilized activity-based chemical proteomics to determine the potency and selectivity of deubiquitylating enzyme (DUB) inhibitors in cell culture models. Importantly, we characterized the small molecule PR-619 as a broad-range DUB inhibitor, and P22077 as a USP7 inhibitor with potential for further development as a chemotherapeutic agent in cancer therapy. A striking accumulation of polyubiquitylated proteins was observed after both selective and general inhibition of cellular DUB activity without direct impairment of proteasomal proteolysis. The repertoire of ubiquitylated substrates was analyzed by tandem mass spectrometry, identifying distinct subsets for general or specific inhibition of DUBs. This enabled identification of previously unknown functional links between USP7 and enzymes involved in DNA repair. 相似文献
955.
Formation of protein-DNA complex is an important step in regulation of genes in living organisms. One important issue in this problem is the role played by water in mediating the protein-DNA interactions. In this work, we have carried out atomistic molecular dynamics simulations to explore the heterogeneous dynamics of water molecules present in different regions around a complex formed between the DNA binding domain of human TRF1 protein and a telomeric DNA. It is demonstrated that such heterogeneous water motions around the complex are correlated with the relaxation time scales of hydrogen bonds formed by those water molecules with the protein and DNA. The calculations reveal the existence of a fraction of extraordinarily restricted water molecules forming a highly rigid thin layer in between the binding motifs of the protein and DNA. It is further proved that higher rigidity of water layers around the complex originates from more frequent reformations of broken water-water hydrogen bonds. Importantly, it is found that the formation of the complex affects the transverse and longitudinal degrees of freedom of surrounding water molecules in a nonuniform manner. 相似文献
956.
Pandey S Das PP Singh AK Mukherjee R 《Dalton transactions (Cambridge, England : 2003)》2011,40(40):10758-10768
Using an acyclic hexadentate pyridine amide ligand, containing a -OCH(2)CH(2)O- spacer between two pyridine-2-carboxamide units (1,4-bis[o-(pyrydine-2-carboxamidophenyl)]-1,4-dioxabutane (H(2)L(9)), in its deprotonated form), four new complexes, [Co(II)(L(9))] (1) and its one-electron oxidized counterpart [Co(III)(L(9))][NO(3)]·2H(2)O (2), [Ni(II)(L(9))] (3) and [Cu(II)(L(9))] (4), have been synthesized. Structural analyses revealed that the Co(II) centre in 1 and the Ni(II) centre in 3 are six-coordinate, utilizing all the available donor sites and the Cu(II) centre in 4 is effectively five-coordinated (one of the ether O atoms does not participate in coordination). The structural parameters associated with the change in the metal coordination environment have been compared with corresponding complexes of thioether-containing hexadentate ligands. The μ(eff) values at 298 K of 1-4 correspond to S = 3/2, S = 0, S = 1 and S = 1/2, respectively. Absorption spectra for all the complexes have been investigated. EPR spectral properties of the copper(II) complex 4 have been investigated, simulated and analyzed. Cyclic voltammetric experiments in CH(2)Cl(2) reveal quasireversible Co(III)-Co(II), Ni(III)-Ni(II) and Cu(II)-Cu(I) redox processes. In going from ether O to thioether S coordination, the effect of the metal coordination environment on the redox potential values of Co(III)-Co(II) (here the effect of spin-state as well), Ni(III)-Ni(II) and Cu(II)-Cu(I) processes have been systematically analyzed. 相似文献
957.
Mohana Krishna Reddy Mudiam Rajeev Jain Virendra K. Dua Amit Kumar Singh V. P. Sharma R. C. Murthy 《Analytical and bioanalytical chemistry》2011,401(5):1699-1705
A simple and rapid analytical method based on in-matrix ethyl chloroformate (ECF) derivatization has been developed for the
quantitative determination of bisphenol-A (BPA) in milk and water samples. The samples containing BPA were derivatised with
ECF in the presence of pyridine for 20 s at room temperature, and the non-polar derivative thus formed was extracted using
polydimethylsiloxane solid-phase microextraction (SPME) fibres with thicknesses of 100 μm followed by analysis using gas chromatography–mass
spectrometry. Three alkyl chloroformates (methyl, ethyl and isobutyl chloroformate) were tested for optimum derivatisation
yields, and ECF has been found to be optimum for the derivatisation of BPA. Several parameters such as amount of ECF, pyridine
and reaction time as well as SPME parameters were studied and optimised in the present work. The limit of detection for BPA
in milk and water samples was found to be 0.1 and 0.01 μg L−1, respectively, with a signal-to-noise ratio of 3:1. The limit of quantitation for BPA in milk and water was found to be 0.38
and 0.052 μg L−1, respectively, with a signal-to-noise ratio of 10:1. In conclusion, the method developed was found to be rapid, reliable
and cost-effective in comparison to silylation and highly suitable for the routine analysis of BPA by various food and environmental
laboratories. 相似文献
958.
Chang GF Wang CH Lu HC Kan LS Chao I Chen WH Kumar A Lo L dela Rosa MA Hung CH 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(40):11332-11343
Group 12 and silver(I) tetramethyl‐m‐benziporphodimethene (TMBPDM) complexes with phenyl, methylbenzoate, or nitrophenyl groups as meso substituents were synthesized and fully characterized. The dimeric silver(I) complex displays an unusual η2,π coordination from the β‐pyrrolic C?C bond to the silver ion. All of the complexes displayed a close contact between the metal ion and the inner C(22)? H(22) on the m‐phenylene ring. The downfield chemical shifts of H(22) and large coupling constants between CdII and H(22) strongly support the presence of an agostic interaction between the metal ion and inner C(22)–H(22). Crystal structures revealed that the syn form is the predominant conformation for TMBPDM complexes. This is distinctively different from the exclusive anti conformation observed in m‐benziporphyrin and tetraphenyl‐m‐benziporphodimethene (TPBPDM) complexes. Evidently, intramolecular hydrogen‐bonding interactions between axial chloride and methyl groups stabilize syn conformations. Unlike the merely syn conformation observed in the solid‐state structures of TMBPDM complexes that contain an axial chloride, in solution these complexes display highly solvent‐ and temperature‐dependent syn/anti ratio changes. The observation of dynamic 1H NMR spectroscopic scrambling between syn and anti conformations from the titration of chloride ion into the solution of the TMBPDM complex suggests that axial ligand exchange is a likely pathway for the conversion between syn and anti forms. Theoretical calculations revealed that intermolecular hydrogen‐bonding interactions between the axial chloride and CHCl3 stabilizes the anti conformation, which explains the increased ratio for the anti form when dichloromethane or chloroform was used as the solvent. 相似文献
959.
Singh SK Tibrewal NK Rajaraman G 《Dalton transactions (Cambridge, England : 2003)》2011,40(41):10897-10906
Theoretical calculations using density functional methods have been performed on two dinuclear {Ni(II)-Gd(III)} and two trinuclear {Ni(II)-Gd(III)-Ni(II)} complexes having two and three μ-OR (R = alkyl or aromatic groups) bridging groups. The different magnetic behaviour, having moderately strong ferromagnetic coupling for complexes having two μ-OR groups and weak ferromagnetic coupling for complexes having three μ-OR groups, observed experimentally is very well reproduced by the calculations. Additionally, computation of overlap integrals MO and NBO analysis reveals a clear increase in antiferromagnetic contribution to the net exchange for three μ-OR bridged {Ni-Gd} dimers and also provides several important clues regarding the mechanism of magnetic coupling. Besides, MO and NBO analysis discloses the role of the empty 5d orbitals of the Gd(III) ion on the mechanism of magnetic coupling. Magneto-structural correlations for Ni-O-Gd bond angles, Ni-O and Gd-O bond distances, and the Ni-O-Gd-O dihedral angle have been developed and compared with the published experimental {Ni-Gd} structures and their J values indicate that the Ni-O-Gd bond angles play a prominent role in these types of complexes. The computation has then been extended to two trinuclear {Ni(II)-Gd(III)-Ni(II)} complexes and here both the {Ni-Gd} and the {Ni-Ni} interactions have been computed. Our calculations reveal that, for both structures studied, the two {NiGd} interactions are ferromagnetic and are similar in strength. The {Ni-Ni} interaction is antiferromagnetic in nature and our study reveals that its inclusion in fitting the magnetic data is necessary to obtain a reliable set of spin Hamiltonian parameters. Extensive magneto-structural correlations have been developed for the trinuclear complexes and the observed J trend for the trinuclear complex is similar to that of the dinuclear {Ni-Gd} complex. In addition to the structural parameters discussed above, for trinuclear complexes the twist angle between the two Ni-O-Gd planes is also an important parameter which influences the J values. 相似文献
960.