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51.
From reactions between different Cu(II) salts and the Schiff base 6-amino-5-formyl-1,3-dimethyluracil-benzoylhydrazone (H2BEZDO) in alcohol, six new copper complexes with simplified formulas [Cu(HBEZDO)(H2O)(MeOH)]NO3 (1), [CuCl(HBEZDO)(DMF)] (2), [CuBr(HBEZDO)]·2H2O (3), CuBr(HBEZDO) (4), Cu(ClO4)(HBEZDO)·H2O (5), and Cu(SO4)1/2(HBEZDO)·1H2O (6) were isolated. The structures of compounds 1, 2 and 3 have been established by means of XRD diffraction methods. In the three compounds, the Schiff base acts as a tridentate monodeprotonated ligand through the N(6), N(51) and O(52) atoms, making two five- and six-membered chelate rings. In the structure of 1 and 2, the solvent molecules are coordinated giving square-based pyramidal environments, with the basal plane completed by a MeOH (1) or Cl (2) and the apical positions occupied by the oxygen atom of a water (1) or a DMF molecule (2). The molecular unit of the complex [CuBr(HBEZDO)]·2H2O (3) is defined by a square-plane containing the three donor atoms of the organic ligand and a bromide ligand (Cu–Br 2.384 Å), but there is a stronger tetragonally elongated pyramidal geometry around the metal, the apical position of the polyhedron being occupied by a weakly bound-to-copper bromine atom (3.086 Å) of a neighbouring molecule. This fact gives the appearance of an apparent dimer with very asymmetric bromine bridges, in which there are no exchange interactions between metal centres. Also, infrared, magnetic and EPR data of the isolated complexes are reported.  相似文献   
52.
研究了水/ 甲苯乳化液中二苯并噻吩( 硫芴) 在分散型钼酸、磷钼酸和四硫钼酸铵催化剂存在下的加氢脱硫反应. 反应在高压釜中于340 ℃及三种不同的气氛即H2 ,H2/H2 O和CO/H2O(CO 和H2O 经水煤气转换反应( WGSR) 产生原位氢) 的存在下进行. 用GC和GCMS鉴定、分析了气体和液体产物的组成. 结果表明: 对硫芴的加氢脱硫反应,在分散型四硫钼酸铵催化剂存在下,原位产生的氢的效果仅比加入的氢气稍好,而在分散型钼酸和磷钼酸催化剂存在下,原位产生的氢远比加入的氢气有效. 实验结果还表明: 硫化氢能显著提高分散型钼酸和磷钼酸催化剂的加氢脱硫活性,但在分散型四硫钼酸铵催化剂存在下,硫化氢能促进加氢反应而抑制氢解反应. 一氧化碳和水均选择性地抑制氢解反应.  相似文献   
53.
A simple semi-empirical approximation for the exchange energy (Ex), coupled with a tractable representation of the Coulomb energy (EC), has been found to yield very accurate results for the isotropic part of the interaction energy (Eint = Ex + EC) between two closed shell systems. The expression for Eint is based on the knowledge of the first order Coulomb energy and the first three terms in the asymptotic long range expansion of the second order Coulomb energy for the interaction and contains but one adjustable parameter which occurs in Ex. The usefulness of this approach for evaluating Eint is tested critically by using the non-bonded H(1s)H(1s) (3Σu+) interaction as a model (accurate values of the total interaction energy, the exchange energy, and various orders of Coulomb energies, are available for a wide range of R for this system). The results obtained for both Eint and (dEint/dR) are inremarkable agreement with the exact results of Kotos and Wolniewicz for R > 3 ao. Since the law of corresponding states for inert gas pairs holds equally well for the HH(3Σu+) interaction, our analysis of this simple system yields valuable information on the reliability of the approach for other van der Waals dimers.  相似文献   
54.
The formation and behavior of photo-and mechanoinduced free radicals in cellulose were studied by ESR spectroscopy and the capability of these free radicals to initiate graft copolymerization reactions was demonstrated. Although an 11-line ESR signal was detected from cellulose irradiated with ultraviolet (UV) light, a higher-intensity ESR signal with a five-line pattern was detected from a sample mechanically milled at 77 K. The decay of photoinduced free radicals when heated took place monotonously, whereas mechanoradicals exhibited an anomalous behavior with an increased signal intensity at 150 K before decaying at a higher temperature. Mechanoradicals have been found to react more efficiently and rapidly with oxygen and methyl methacrylate (MMA) than photoinduced free radicals. The peroxy mechanoradicals, however, were mobile and decayed more rapidly than the peroxy photoinduced radicals. Simultaneous graft copolymerizations of MMA to cellulose demonstrated that mechano-and photoinduced free radicals are capable of initiating grafting reactions, but a higher degree of grafting efficiency was obtained from cellulose treated mechanically.  相似文献   
55.
56.
Various free radicals formed during UV.-irradiation of aliphatic dicarboxylic acids in aqueous and methanolic solution are identified by ESR.-spectroscopy. Their structures point to α-cleavage and photoreduction as the dominant primary photochemical decay processes. The relative contributions of these reactions to the overall photodecomposition depend on solvent and degree of α-alkylation of the acid. Emission ESR.-spectra are found for radicals formed by C, CO-bond cleavage of α-dimethyl substituted acids. The polarization is referred to the triplet mechanism of CIDEP. and indicates this cleavage reaction occurs from a triplet molecular state.  相似文献   
57.
A rapid, selective and sensitive assay has been developed for the determination of the anti-anginal drug, bepridil, in biological samples. The lowest concentration of bepridil which can be measured accurately and precisely in a 2-ml plasma or urine sample is 10 ng/ml. The standard curve is linear in the concentration range 10-2000 ng/ml. Accuracy and precision of the assay, expressed as relative deviation and coefficient of variation (inter-run) are less than 6.5% at all concentrations in the linear range. No interfering peaks are observed. Using an automatic injector and a laboratory computer system, 48 samples are analyzed routinely in an 8-h day.  相似文献   
58.
Three ternary copper(II) complexes, [Cu(phen)(L-phe)Cl]·2H2O, [Cu(phen)(L-leu)Cl]·4½H2O, and [Cu(phen)(L-tyr)Cl]·3H2O, and four binary copper(II) complexes, [Cu(phen)Cl2], Cu(L-phe)2·½H2O, Cu(L-leu)2·½H2O, and Cu(L-tyr)2·H2O (where phen = 110-phenanthroline, L-phe = L-phenylalanine, L-tyr = L-tyrosine, L-leu = L-leucine and Cl- = chloride), were synthesized and characterized by elemental analysis, spectroscopic techniques (FTIR, UV–visible, fluorescence spectroscopy), magnetic susceptibility, molar conductivity, and lipophilicity measurement. X-ray diffraction determination of a single crystal of [Cu(phen)(L-tyr)Cl] showed two independent molecules in the asymmetric unit, each with the same distorted square pyramidal geometry about copper(II). p-Nitrosodimethylaniline assay revealed that the three ternary complexes were better inducers of reactive oxygen species over time than binary complexes, CuCl2, and free ligands. All the copper(II) complexes in this series inhibited the three proteolytic activities in the order Trypsin-like > Caspase-like > Chymotrypsin-like. In terms of anticancer properties, the copper(II)-phen complexes had GI50 values of less than 4 μM against MCF-7, HepG2, CNE1 and A549 cancer cell lines, more potent than cisplatin.  相似文献   
59.
Bis(dicyclohexylammonium) bis(2,6-pyridinedicarboxylato)dibutylstannate is assigned seven-fold coordination at tin on the basis of its 119Sn CP/MAS NMR chemical shift (δ=−424.9 ppm). The assignment has been corroborated by a crystal structure determination of its monohydrate, whose tin atom has the trans -C2SnNO4 pentagonal bipyramidal [Sn–C=2.040(9), 2.067(8) Å; C–Sn–C =168.9(5)°] geometry. One 2,6-pyridine- dicarboxylato group chelates to the tin atom (Sn–O=2.234(4), 2.260(4); Sn–N =2.279(5) Å) whereas the other binds through only one carboxyl –CO2 end (Sn–O=2.416(5), 2.441(5) Å). Hydrogen bonds link the cation and the stannate into a linear chain parallel to the b -axis. The lattice water molecule is hydrogen-bonded to the free carboxyl end. The anhydrous compound showed higher in vitro antitumor activity than those of carboplatin and cisplatin when screened against breast (MCF-7, EVSAT), colonic (WiDr), ovarian (IGROV) and renal (A498) carcinoma, and melanoma (M19 MEL) cell lines. © 1997 by John Wiley & Sons, Ltd.  相似文献   
60.
    
Reaction-based fluorescent-probes have proven successful for the visualisation of biological species in various cellular processes. Unfortunately, in order to tailor the design of a fluorescent probe to a specific application (i.e. organelle targeting, material and theranostic applications) often requires extensive synthetic efforts and the synthetic screening of a range of fluorophores to match the required synthetic needs. In this work, we have identified Pinkment-OH as a unique “plug-and-play” synthetic platform that can be used to develop a range of ONOO responsive fluorescent probes for a variety of applications. These include theranostic-based applications and potential material-based/bioconjugation applications. The as prepared probes displayed an excellent sensitivity and selectivity for ONOO over other ROS. In vitro studies using HeLa cells and RAW 264.7 macrophages demonstrated their ability to detect exogenously and endogenously produced ONOO. Evaluation in an LPS-induced inflammation mouse model illustrated the ability to monitor ONOO production in acute inflammation. Lastly, theranostic-based probes enabled the simultaneous evaluation of indomethacin-based therapeutic effects combined with the visualisation of an inflammation biomarker in RAW 264.7 cells.

Pinkment, a resorufin based ONOO selective and sensitive ‘plug and play’ fluorescence-based platform for in vitro and in vivo use, enables facile functionalisation for various imaging and theranostic applications.  相似文献   
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