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   1751篇
  免费   61篇
  国内免费   5篇
化学   1161篇
晶体学   11篇
力学   43篇
数学   180篇
物理学   422篇
  2023年   11篇
  2022年   12篇
  2021年   14篇
  2020年   23篇
  2019年   17篇
  2018年   25篇
  2017年   26篇
  2016年   51篇
  2015年   39篇
  2014年   50篇
  2013年   99篇
  2012年   101篇
  2011年   142篇
  2010年   63篇
  2009年   53篇
  2008年   99篇
  2007年   94篇
  2006年   73篇
  2005年   74篇
  2004年   86篇
  2003年   65篇
  2002年   43篇
  2001年   22篇
  2000年   28篇
  1999年   23篇
  1998年   26篇
  1997年   22篇
  1996年   29篇
  1995年   35篇
  1994年   19篇
  1993年   25篇
  1992年   20篇
  1991年   24篇
  1990年   21篇
  1989年   27篇
  1988年   12篇
  1987年   13篇
  1986年   12篇
  1985年   11篇
  1984年   18篇
  1983年   13篇
  1982年   10篇
  1981年   10篇
  1980年   14篇
  1979年   13篇
  1978年   14篇
  1977年   15篇
  1976年   12篇
  1975年   15篇
  1974年   9篇
排序方式: 共有1817条查询结果,搜索用时 15 毫秒
81.
The synthesis, mesomorphic and physical properties of 14 homologous series of laterally fluorinated 4?-alkyl-4-isothiocyanatoterphenyls were described. Influence of the number of fluorine atoms and their position in the terphenyl core on the phase transition temperatures, nematic range, dielectric and optic anisotropy as well as bulk viscosity were discussed. The compounds with the most optimal properties for formulation of nematic mixtures were selected, and mixture examples with low viscosity and medium or high birefringence were presented.  相似文献   
82.
The results of dielectric studies performed in a broad frequency range for two compounds, 4-cyanophenyl 4-n-heptylbenzoate (7BBCN) and 4-(4-cyanobutyloxy)phenyl 4- n-heptylbenzoate (7BB4CN), are compared. They have the same molecular core whereas the strongly polar CN group is attached to the benzene ring in 7BBCN or is separated from it by the butyloxy chain in 7BB4CN. 7BBCN has a nematic phase, whereas 7BB4CN exhibits a monotropic nematic and smectic A2 polymorphism. Large differences in the dielectric properties of the two substances were found. The analysis of the results led to the conclusion that the antiparallel dipole-dipole associations are considerably stronger in the substance with a decoupled CN group.  相似文献   
83.
Results of the dielectric studies of nine members of the nBT (4-n-alkyl-4'-thiocyanatobiphenyl, n= 2-10) homologous series in the crystal E (E) and isotropic (I) phases are presented. The dependence of the static permittivity ?s in the isotropic phase, the longitudinal relaxation times τis and τ, and the activation enthalpies ΔH is and ΔH on the number of carbon atoms in the alkyl chain n are analysed. A considerable increase in the retardation factor g= τis with decreasing n is observed. The results are compared with those obtained for similar two-ring homologous series. The parameters characterizing the molecular rotations around the short axis in the E phase (τ and ΔH ) indicate a hardening of this solid-like phase with shortening of the alkyl chain.  相似文献   
84.

Treatment of the 1,6‐anhydrosugar epoxide 5 with a cyano‐Gilman cuprate [(CuCN (6 eq.), MeLi (12 eq.)] surprisingly led to the open chain rearranged (2S,3R)‐1,2‐dihydroxy‐3,6‐dimethylheptan‐4‐one (7), structurally confirmed by conversion to the corresponding diacetate 8. Another unusual reaction was found by hydrogenation of the 2‐tosyl‐1‐bromosugar 11, leading in one operation to the twofold deoxygenated chiral pyran derivative 14. This procedure might prove to be useful in the rapid deoxygenation of sugar derivatives.  相似文献   
85.
In the course of our investigations on the synthesis of enantiomerically pure anthracycline antibiotics by incorporation of chiral building blocks we prepared the O-methyl 3-deoxy-2-C-ethylribopyranoside 1.1 The further synthetic plan required the conversion of 1 to the dithioacetal 2 followed by glycol cleavage to a partially protected 1,4-dialdehyde for coupling experiments to leucoquinizarine in a Marschalk reaction. However, the reaction sequence failed1 and optically active rhodomycinone had to be synthezised in a different way.2 A reinvestigation of the synthesis revealed that the thioacetalization of 1 using the acidic conditions recommended by Corey et al.3 did not yield the usual open chain dithioacetal 2 but rather three new unexpected products. The less polar fraction was identified by 1H and 13C NMR as tetrahydrofuran derivative 3a with the dithiane ring in a ß-orientation. The solid polar fraction (12%) consisted of a nonseparable 1:2.2 mixture of the epimeric deoxygenation products 4/5.  相似文献   
86.
The synthesis of the aliphatic subunit 9 of the macrolide LL‐Z1640‐2 (I), starting from a 4‐deoxy‐D‐mannose derivative 2a, is described. The procedure includes the first successful application of a Vasella ring opening reaction for a 4‐deoxypyranoside. Nucleophilic addition of an alkynyllithium reagent to the aldehyde 4 led to the propargylic alcohol 7, which was converted to the advanced building block 9 in two further steps.  相似文献   
87.
Versatile ruthenium(II) complexes allow for site‐selective C H oxygenations with weakly‐coordinating aldehydes. The challenging C H functionalizations proceed with high chemoselectivity by rate‐determining C H metalation. The new method features an ample substrate scope, which sets the stage for the step‐economical preparation of various bioactive heterocycles.  相似文献   
88.
The structures of 4‐chloro‐3‐nitroaniline, C6H5ClN2O2, (I), and 4‐iodo‐3‐nitroaniline, C6H5IN2O2, (II), are isomorphs and both undergo continuous (second order) phase transitions at 237 and 200 K, respectively. The structures, as well as their phase transitions, have been studied by single‐crystal X‐ray diffraction, Raman spectroscopy and difference scanning calorimetry experiments. Both high‐temperature phases (293 K) show disorder of the nitro substituents, which are inclined towards the benzene‐ring planes at two different orientations. In the low‐temperature phases (120 K), both inclination angles are well maintained, while the disorder is removed. Concomitantly, the b axis doubles with respect to the room‐temperature cell. Each of the low‐temperature phases of (I) and (II) contains two pairs of independent molecules, where the molecules in each pair are related by noncrystallographic inversion centres. The molecules within each pair have the same absolute value of the inclination angle. The Flack parameter of the low‐temperature phases is very close to 0.5, indicating inversion twinning. This can be envisaged as stacking faults in the low‐temperature phases. It seems that competition between the primary amine–nitro N—H...O hydrogen bonds which form three‐centred hydrogen bonds is the reason for the disorder of the nitro groups, as well as for the phase transition in both (I) and (II). The backbones of the structures are formed by N—H...N hydrogen bonding of moderate strength which results in the graph‐set motif C(3). This graph‐set motif forms a zigzag chain parallel to the monoclinic b axis and is maintained in both the high‐ and the low‐temperature structures. The primary amine groups are pyramidal, with similar geometric values in all four determinations. The high‐temperature phase of (II) has been described previously [Garden et al. (2004). Acta Cryst. C 60 , o328–o330].  相似文献   
89.
The contact physics of the wheel-rail contact of a railway vehicle under presence of water and ice at low temperatures is still not completely understood. For the investigation of the particular process in the contact zone a simulation is required, which is able to calculate the normal and tangential contact, the temperature field and the fluid-structural interaction between wheel and rail at low temperatures under presence of snow and ice. For that purpose the behaviour of ice under wheel-rail contact conditions is an important part. In this paper the thermal dynamic model of TSHIJOV [1], [3] for an adiabatic ice probe is updated by the new IAPWS equations of state for water [5] and ice phase Ih [4]. In a first approximation an ice specimen is loaded by specific wheel-rail contact pressure distributions calculated by the half-space formulation to clarify if phase transitions of ice can exist. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)  相似文献   
90.
Metal sulfides are among the most promising materials for a wide variety of technologically relevant applications ranging from energy to environment and beyond. Incidentally, ionic liquids (ILs) have been among the top research subjects for the same applications and also for inorganic materials synthesis. As a result, the exploitation of the peculiar properties of ILs for metal sulfide synthesis could provide attractive new avenues for the generation of new, highly specific metal sulfides for numerous applications. This article therefore describes current developments in metal sulfide nanoparticle synthesis as exemplified by a number of highlight examples. Moreover, the article demonstrates how ILs have been used in metal sulfide synthesis and discusses the benefits of using ILs over more traditional approaches. Finally, the article demonstrates some technological challenges and how ILs could be used to further advance the production and specific property engineering of metal sulfide nanomaterials, again based on a number of selected examples.  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