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   6548篇
  免费   65篇
  国内免费   11篇
化学   3997篇
晶体学   59篇
力学   159篇
综合类   5篇
数学   723篇
物理学   1681篇
  2024年   34篇
  2023年   60篇
  2022年   211篇
  2021年   214篇
  2020年   180篇
  2019年   218篇
  2018年   207篇
  2017年   142篇
  2016年   260篇
  2015年   173篇
  2014年   234篇
  2013年   381篇
  2012年   392篇
  2011年   439篇
  2010年   336篇
  2009年   321篇
  2008年   380篇
  2007年   357篇
  2006年   297篇
  2005年   221篇
  2004年   197篇
  2003年   152篇
  2002年   146篇
  2001年   131篇
  2000年   103篇
  1999年   75篇
  1998年   67篇
  1997年   52篇
  1996年   51篇
  1995年   40篇
  1994年   60篇
  1993年   57篇
  1992年   56篇
  1991年   32篇
  1990年   24篇
  1989年   23篇
  1988年   21篇
  1987年   18篇
  1986年   17篇
  1985年   16篇
  1984年   19篇
  1983年   26篇
  1982年   19篇
  1981年   26篇
  1980年   20篇
  1979年   26篇
  1978年   18篇
  1977年   9篇
  1976年   9篇
  1975年   7篇
排序方式: 共有6624条查询结果,搜索用时 0 毫秒
991.
    
The complete assignment of the 1H and 13C NMR spectra of various 2‐acetamido‐3‐mercapto‐3‐methyl‐N‐aryl‐butanamides and 2‐acetamide‐3‐methyl‐3‐nitrososulfanyl‐N‐aryl‐butanamides with p‐methoxy, o‐chloro and m‐chloro substituents is reported. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   
992.
    
The widespread use of poly(3‐hexylthiophene) (P3HT) in the active layers of organic solar cells indicates that it possesses chemical stability and solubility suitable for such an application. However, it would be desirable to have a material that can maintain these properties but with a smaller bandgap, which would lead to more efficient energy harvesting of the solar spectrum. Fifteen P3HT derivatives were studied using the Density Functional Theory. The conclusion is that it is possible to obtain compounds with significantly smaller bandgaps and with solubility and stability similar to that of P3HT, mostly through the binding of oxygen atoms or conjugated organic groups to the thiophenic ring. © 2013 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys., 2013  相似文献   
993.
    
Xylella fastidiosa (X.f.) is a plant pathogen with high levels of genomic similarity to Xanthomonas campestris pv. campestris (X.c.c.). It has been shown that X. fastidiosa synthesizes a putative diffusible signal factor (X.f.-DSF) that activates regulation of pathogenicity factor (rpf) genes in a X.c.c. reporter system, which might be involved in the regulation of pathogenesis associated genes as in X.c.c., as well as in quorum-sensing. The nature of the X.f.-DSF is not known, whereas the X.c.c.-DSF has been identified as cis-11-methyl-2-dodecenoic acid. In this work, the chemical nature of a putative X.f.-DSF molecule, able to restore endoglucanase activity in a X.c.c. rpfF mutant, was investigated as if it was a fatty acid derivative. Bioassays with X.c.c. reporter bacterium and X.f. culture extracts, based on endoglucanase restoration activity, were also carried out in order to confirm the DSFs molecules similarities. For this reason, a gas chromatography-mass spectrometry method was developed with standard fatty acids methyl esters mixtures. The retention time, as well as the fragmentation patterns, of each standard was used to identify the DSF molecule synthesized by X.f. in the culture medium. Typical ester fragmentation patterns (the derivatized analyte) were observed, such as: McLafferty rearrangement and migration of the Hdelta followed by 1,4-hydrogen shift and cleavage of the bond Cbeta-Cgamma, confirming the nature of this molecule. This confirmation was corroborated by the common peaks in both spectra. Besides, the observed retention time reinforces our conclusion since it corresponds to a methyl ester with 15 carbons. Since the X.f.-DSF molecule was tentatively identified as 12-methyl-tetradecanoic acid (by mass spectra library comparison), this standard compound was also analyzed, strongly suggesting that this is the identification of such a molecule. To our knowledge, this is the first time a DSF produced by X.f. has been characterized.  相似文献   
994.
    
The energetics of the thermal dimerization of acenaphthylene to give Z- or E-heptacyclene was investigated. The standard molar enthalpy of the formation of monoclinic Z- and E-heptacyclene isomers at 298.15 K was determined as Delta(f)H(m)o (E-C24H16, cr) = 269.3 +/- 5.6 kJ x mol(-1) and Delta(f)H(m)o (Z-C24H16, cr) = 317.7 +/- 5.6 kJ x mol(-1), respectively, by microcombustion calorimetry. The corresponding enthalpies of sublimation, Delta(sub)H(m)o (E-C24H16) = (149.0 +/- 3.1) kJ x mol(-1) and Delta(sub)H(m)o (Z-C24H16) = (128.5 +/- 2.3) kJ x mol(-1) were also obtained by Knudsen effusion and Calvet-drop microcalorimetry methods, leading to Delta(f)H(m)o (E-C24H16, g) = (418.3 +/- 6.4) kJ x mol(-1) and Delta(f)H(m)o (Z-C24H16, g) = (446.2 +/- 6.1) kJ x mol(-1), respectively. These results, in conjunction with the reported enthalpies of formation of solid and gaseous acenaphthylene, and the entropies of acenaphthylene and both hepatcyclene isomers obtained by the B3LYP/6-31G(d,p) method led to the conclusion that at 298.15 K the thermal dimerization of acenaphthylene is considerably exothermic and exergonic in the solid and gaseous states (although more favorable when the E isomer is the product), suggesting that the nonobservation of the reaction under these conditions is of kinetic nature. A full determination of the molecular and crystal structure of the E dimer by X-ray diffraction is reported for the first time. Finally, molecular dynamics computer simulations on acenaphthylene and the heptacyclene solids were carried out and the results discussed in light of the corresponding structural and Delta(sub)H(m)o data experimentally obtained.  相似文献   
995.
    
An efficient and fast procedure for the synthesis of 2‐(2‐pyridyl)azoles is described using ionic liquids as catalysts under microwave irradiation. The X‐ray crystallographic analyses for three of the four synthesized compounds are presented. Potentiodynamic polarization studies were carried out to analyze the electrochemical behavior of the compounds in corrosive acidic media. Of the four derivatives, one compound was detected to be an effective corrosion inhibitor prototype for oil refinery environments.  相似文献   
996.
    
In our quest to find new ligands for highly stereoselective reactions, we tested a variety of chiral non-racemic pseudo-C2 symmetric bis-oxazolines derived from malonic acid containing an arylidene bridge unit (and appropriately termed Arylid-Box) in the catalytic asymmetric cyclopropanation (CAP) reaction of styrene and ethyl diazoacetate using between only 1-2 mol% of a Cu(I) pre-catalyst. Some very good e.e.s (up to 86%), were obtained. It was possible to isolate 10a′-[Cu(CH3CN)4]PF6 which existed as a bench stable solid that proved to be more efficient than the catalyst prepared in situ. Cu(I) pre-catalysts were used for the first time in the CAP reaction with the Isbut-Box ligands 13a and 13b and, although, the e.e.s were better for ligand 13a using these pre-catalysts, in the case of ligand 11b this was not the case. Spectroscopic studies (UV-Vis and 1H NMR) were carried out to gain an insight into the nature of the catalytic species at work so that the conditions could be optimised giving better results. Some theoretical studies were conducted to try to explain the better enantioselectivities obtained using Evans’ tert-Box-Cu(I) complex over our complex.  相似文献   
997.
In this work we propose the use of a targeting method applied to chaotic systems in order to reach special trajectories that encode arbitrary sources of messages. One advantage of this procedure is to overcome dynamical constraints which impose limits in the amount of information that the chaotic trajectories can encode. Another advantage is the message decoding, practically instantaneous and independent of any special technique or algorithm. Furthermore, with this procedure, information can be transmitted with no errors due to bounded noise.  相似文献   
998.
999.
We consider a cluster system in which each cluster is characterized by two parameters: an "order" i , following HortonStrahler rules, and a "mass" j following the usual additive rule. Denoting by c i,j ( t ) the concentration of clusters of order i and mass j at time t , we derive a coagulation-like ordinary differential system for the time dynamics of these clusters. Results about the existence and the behavior of solutions as   t   are obtained; in particular, we prove that   c i,j ( t ) 0  and   N i ( c ( t )) 0  as   t ,  where the functional   N i (·)  measures the total amount of clusters of a given fixed order i . Exact and approximate equations for the time evolution of these functionals are derived. We also present numerical results that suggest the existence of self-similar solutions to these approximate equations and discuss their possible relevance for an interpretation of Horton's law of river numbers.  相似文献   
1000.
We consider Farey series of rational numbers in terms of fractal sets labeled by the Hausdorff dimension with values defined in the interval 1<h<2 and associated with fractal curves. Our results come from the observation that the fractional quantum Hall effect-FQHE occurs in pairs of dual topological quantum numbers, the filling factors. These quantum numbers obey some properties of the Farey series and so we obtain that the universality classes of the quantum Hall transitions are classified in terms of h. The connection between Number Theory and Physics appears naturally in this context.  相似文献   
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