首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   1485篇
  免费   53篇
  国内免费   10篇
化学   1107篇
晶体学   25篇
力学   38篇
综合类   1篇
数学   133篇
物理学   244篇
  2023年   27篇
  2022年   63篇
  2021年   61篇
  2020年   58篇
  2019年   46篇
  2018年   36篇
  2017年   36篇
  2016年   59篇
  2015年   30篇
  2014年   61篇
  2013年   87篇
  2012年   117篇
  2011年   110篇
  2010年   68篇
  2009年   54篇
  2008年   73篇
  2007年   87篇
  2006年   63篇
  2005年   60篇
  2004年   30篇
  2003年   48篇
  2002年   39篇
  2001年   14篇
  2000年   11篇
  1999年   13篇
  1998年   18篇
  1997年   13篇
  1996年   8篇
  1995年   9篇
  1994年   8篇
  1993年   12篇
  1992年   10篇
  1991年   8篇
  1989年   5篇
  1988年   5篇
  1987年   9篇
  1986年   5篇
  1985年   11篇
  1984年   10篇
  1982年   4篇
  1981年   5篇
  1980年   4篇
  1979年   5篇
  1978年   5篇
  1976年   3篇
  1975年   6篇
  1974年   3篇
  1973年   4篇
  1972年   3篇
  1971年   4篇
排序方式: 共有1548条查询结果,搜索用时 15 毫秒
1.
A special family of partitions occurs in two apparently unrelated contexts: the evaluation of one-dimensional configuration sums of certain RSOS models, and the modular representation theory of symmetric groups or their Hecke algebras Hm. We provide an explanation of this coincidence by showing how the irreducible Hm-modules which remain irreducible under restriction to Hm_1 (Jantzen–Seitz modules) can be determined from the decomposition of a tensor product of representations sln.  相似文献   
2.
The reactions between rubidium carbonate and vanadium pentoxide were performed at different high temperatures. Four reaction products of the compositions: I. Rb2O · V2O5; II. 2 Rb2O · V2O5; III. 3 Rb2O · V2O5; and IV. Rb2O · 4 V2O5 were obtained. According to the determination of Rb and the X-ray powder photographs of the products the existence of rubidium metavanadate (RbVO3) and rubidium pyrovanadate (Rb4V2O7) was confirmed. On the other hand, the preparation of a pure rubidium orthovanadate (Rb3VO4) and rubidium tetravanadate (Rb2O · 4 V2O5) was not successful. The diffraction pattern of Rb2O · V2O5 obeys hexagonal indexing with lattice dimensions a = 7.347 and c = 13.608 Å.  相似文献   
3.
Reaction of Cr(CO)(6) with 2-(2'-pyridyl)benzimidazole (pbiH) under reduced pressure resulted in the formation of the dinuclear complex [Cr(2)(CO)(6)(pbiH)(2)]. Infra-red (IR) spectroscopy revealed the presence of terminal and bridge Cr-CO bonds. Interaction of M(CO)(6), M=Cr, Mo and W, with pbiH in the presence of 2,2'-bipyridine (bpy) gave the tetracarbonyl complexes [M(CO)(4)(pbiH)].bpy. Spectroscopic studies of the complexes indicated the presence of hydrogen bonding between the bpy nitrogen and the NH group of pbiH. Reactions of M(CO)(6) with pbiH in the presence of PPh(3) gave the tricarbonyl monosubstituted derivatives [M(CO)(3)(PPh(3))(pbiH)]. The spectroscopic studies of the complexes suggested the proposed structures.  相似文献   
4.
The interaction between poly(methymethacrylate) (PMMA) and poly(vinyl chloride) (PVC) has been studied indilute urea solutions of dimethylformamide (DMF) at 28℃ using a dilute solution viscometry method. The results show thatthe polymer mixtures are compatible in DMF solution in the absence of urea. The influence of urea addition on the degree ofcompatibility of the polymer mixtures has been studied in terms of the compatibility parameters (△b_m and △[η]_m). It wasfound that the compatibility of the polymer mixtures is decreased with increasing urea addition, passing through a minimumat 0.5 M urea.  相似文献   
5.
The preparation and characterization of MnII, FeIII and CuII complexes of three tridentate pyridyl hydrazones are reported. The ligands were prepared via Schiff base condensation of 6-chloro-2-hydrazopyridine with alpha-formyl-(L1), alpha-acetyl-(L2), or alpha-benzoyl-(L3) pyridine. The structural characterization of the compounds prepared was based on elemental analyses, electrical conductance and magnetic moment measurements, 1H-n.m.r., i.r., u.v.-vis. and e.s.r spectroscopic methods. The overall structure and reactivity of the metal chelates critically depend on the ligand substituents within the carbonyl moiety. Octahedral and tetrahedral monomeric species were proposed for MnII complexes, and an octahedral environment for the FeIII complexes. Regarding the copper(II) complexes, a monomeric square-planar and a dimeric structure with a chloride bridge in square-pyramidal geometry were suggested. In the presence of molecular oxygen, MnII and CuII complexes catalyse the oxidative transformation of catechol (benzene-1,2-diol) to the corresponding o-benzoquinone. Iron(III) complexes catalyse the aerobic oxidation of catechol to the intradiol cleavage product. The catalytic activity has been correlated with the Lewis acidity of the metal centres created according to the nature of the ligand substituents. The probable mechanistic implications of the catalysed oxidation reactions are discussed. This revised version was published online in June 2006 with corrections to the Cover Date.  相似文献   
6.
Summary Equilibrium betweenDCPHD,DC-4-Cl-PHD, andDC-4-Me-PHD and protons, transition, and lanthanide ions have been investigated at 30 °C by means of potentiometric titration in 75% (v/v) methanol-water mixture containing 0.10M KNO3 as a constant ionic medium. Thermodynamic parameters (G, H and S) referring to the formation of species HL ,L ––,ML +n–2 andML 2 +n–4 (L –– denotes the ligand anion) have been determined in solutions. The solvent effects on the thermodynamic parameters of the complex formation are discussed in terms of differences in the donor ability of methanol and water solvents. The plots of thermodynamic parameters versus ionic potential (Z 2/r) of the lanthanide elements is not linear as expected from ionic theory. The obtained curve can be resolved in an initial group (the lighter lanthanides), an intermediate group (Sm-Dy), and a final group (the heavier ones, Tb-Lu). This behavior was explained in terms of differences in the dehydration of lighter lanthanide(III) from that of heavier ones.
Thermodynamik der Komplexierung von Lanthaniden und einigen Übergangsmetall-Ionen mit 5,5-Dimethylcyclohexyl-2-(2-hydroxyphenyl)-hydrazono-1,3-dion (DCPHD) und seinen Derivaten
Zusammenfassung Die Gleichgewichte zwischenDCPHD,DC-4-Cl-PHD undDC-4-Me-PHD mit Protonen, Übergangsmetall- und Lanthaniden-Ionen wurden bei 30 °C mittels potentiometrischer Titration in 75% (v/v) Methanol-Wasser mit einem Gehalt an 0.10M KNO3 als konstantem ionischem Medium untersucht. Die thermodynamischen Parameter G, H und S zur Bildung der Spezies HL ,L ––,ML +n–2 undML 2 +n–4 (L –– steht für das Ligandenanion) wurden in Lösung bestimmt. Die Lösungsmitteleffekte auf diese Komplexbildungsparameter werden auf Basis der Differenz im Donorvermögen von Methanol und Wasser als Solventien diskutiert. Die Diagramme der thermodynamischen Parameter gegen die ionischen Potentiale (Z 2/r) der Lanthaniden sind, wie nach der Ionentheorie zu erwarten, nicht linear. Die erhaltene Kurve läßt eine Anfangsgruppe (die leichteren Lanthaniden), eine mittlere Gruppe (Sm-Dy) und eine Endgruppe (die schwereren Lanthaniden. Tb-Lu) erkennen. Dieses Verhalten kann aus dem Unterschied im Dehydratationsverhalten erklärt werden.
  相似文献   
7.
The enantiomers of 34 pharmaceutical weak-base analytes were separated by nonaqueous capillary electrophoresis in acidic methanol background electrolytes using the sodium salt of the new, single-isomer chiral resolving agent, octakis(2,3-O-dimethyl-6-O-sulfo)-gamma-cyclodextrin (ODMS). The effective mobilities, separation selectivities and peak resolution values of the weak-base analytes were determined as a function of the ODMS concentration in the 0-40 mM range and were found to follow the theoretical predictions of the charged resolving agent migration model (CHARM model) modified for ionic strength effects. Fast, efficient separations were achieved for both comparatively small and large enantiomers.  相似文献   
8.
H F Askal  G A Saleh  N M Omar 《The Analyst》1991,116(4):387-390
Two simple and sensitive spectrophotometric methods are described for the determination of six penicillin derivatives. The methods are based on the reaction of these drugs as n-electron donors with either 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) or 7,7,8,8-tetracyanoquinodimethane (TCNQ) as pi-acceptors, to give a highly coloured radical anion. The coloured products are quantified spectrophotometrically at 460 and 842 nm for DDQ and TCNQ, respectively. The optimization of the different experimental conditions is described. The interference from streptomycin sulphate and common degradation products was also studied. The proposed methods were applied successfully to the determination of the different penicillins investigated, either in pure or dosage forms, with good accuracy and precision. The results were compared with those given by the official United States Pharmacopeial XXI method.  相似文献   
9.
Assembling well-defined MOF superstructures remains challenging as it requires easily removable hard templates or readily available immiscible solutions for an emulsion-based soft-template approach. In this work, a single-step emulsion-free soft templating approach is reported to spontaneously prepare hollow ZIF-8 and ZIF-67 colloidosomes with no further purification. These superstructures can load different enzymes regardless of the size and charge with a high encapsulation efficiency of 99%. We envisage that this work will expand the repertoires of MOF superstructures by the judicious selection of precursors and the reaction medium.

An emulsion-free approach for the preparation of hollow ZIF-8 superstructures in a single step is established based on metal sulfate hydrates in methanol.  相似文献   
10.
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号