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   428篇
  免费   4篇
  国内免费   5篇
化学   252篇
晶体学   1篇
力学   14篇
数学   82篇
物理学   88篇
  2022年   8篇
  2021年   12篇
  2020年   3篇
  2019年   4篇
  2018年   4篇
  2017年   4篇
  2016年   10篇
  2015年   8篇
  2014年   11篇
  2013年   31篇
  2012年   20篇
  2011年   27篇
  2010年   11篇
  2009年   16篇
  2008年   15篇
  2007年   27篇
  2006年   16篇
  2005年   18篇
  2004年   21篇
  2003年   18篇
  2002年   19篇
  2001年   4篇
  2000年   10篇
  1999年   9篇
  1998年   7篇
  1997年   3篇
  1996年   8篇
  1992年   9篇
  1991年   6篇
  1990年   3篇
  1989年   3篇
  1988年   6篇
  1987年   3篇
  1986年   3篇
  1985年   8篇
  1984年   5篇
  1983年   3篇
  1982年   2篇
  1981年   2篇
  1980年   2篇
  1979年   4篇
  1978年   2篇
  1977年   2篇
  1976年   2篇
  1975年   3篇
  1973年   3篇
  1970年   2篇
  1967年   2篇
  1966年   2篇
  1960年   2篇
排序方式: 共有437条查询结果,搜索用时 15 毫秒
1.
Ferroelectric composite two-dimensional ferroelectric/aluminum oxide nanostructures were studied. A porous aluminum oxide matrix was used as a template into which a ferroelectric precursor was introduced, followed by annealing. The prepared nanostructures were studied using optical second harmonic generation and micro-Raman scattering.  相似文献   
2.
We apply previous results on the pathwise exponential loss of memory of the initial condition for stochastic differential equations with small diffusion to the problem of the asymptotic distribution of the first exit times from an attracted domain. We show under general hypotheses that the suitably rescaled exit time converges in the zero-noise limit to an exponential random variable. Then we extend the results to an infinite-dimensional case obtained by adding a small random perturbation to a nonlinear heat equation.  相似文献   
3.
Head-space sampling (HS) has been combined with enantioselective gas chromatography (GC) for the analysis of chiral and non-chiral monoterpenes present in the cortical tissues of five different Norway spruce clones. (1S)-(-)-alpha-Pinene, (1S,5S)-(-)sabinene, (1S)-(-)-beta-pinene, and (4S)-(-)limonene dominated over (1R)-(+)-alpha-pinene, (1R,5R)-(+)-sabinene, (1R)-(+)-beta-pinene, and (4R)-(+)-limonene. Results showed a large variation in the enantiomeric composition of cortical tissues between different clones. The development of HS-GC greatly increased the speed of precise analyses of chiral monoterpenes in small samples and therefore offer excellent opportunities in studies on the ecophysiological and chemotaxomic roles of these chiral components.  相似文献   
4.
The present work deals with the spatially extended oscillatory Belousov Zhabotinsky reaction-diffusion system carried out in an anisotropic environment of phosphatidylcholines/water binary system, which presents layered aqueous domains separated by lipid bilayers. We report the occurrence of stable Turing patterns, spiral waves, and other exotic structures in phospholipids bilayers that are generally used as a models for cell plasma membranes.  相似文献   
5.
Intrinsic bond dissociation energies (BDEs) of selected fluorinated polymers are critically evaluated. Two distinctive approaches were followed. In the first one, according to Wu and Rodgers [E.-C. Wu, A.S. Rodgers, J. Am. Chem. Soc. 98 (1976) 6112-6115], starting from the gas-phase enthalpy of polymerization we obtained the polymer backbone BDE through appropriate thermodynamic cycles. Revised experimental results indicate that the CC BDEs of all the polymers taken into account fall within a limited energy interval, comparable to the average experimental uncertainty. Central to the second methodology adopted, is a model compound approach. Thanks to the large number of reliable thermodynamic data available in the scientific literature and to simple end-capping rules, C2 molecules were chosen as suitable models for infinite linear polymers and alternating copolymers between ethylene and fluorinated olefins. For partially fluorinated polymers, like polyvinylidene fluoride (PVDF), alternating ethylene-tertrafluoroethylene (ETFE) and alternating ethylene-chlorotrifluoroethylene (ECTFE), the weight loss due to HF and HCl evolution during heating experiments was successfully related to the threshold energy Eo(HX) for 1,2-elimination from chemically activated hydrofluoro and hydrofluorochlorocarbons according to the modified Rice-Rampsberger-Kassel (RRKM) unimolecular theory.  相似文献   
6.
Polyethylene glycols (PEG) are fair solvents for inorganic salts and organic substrates; their use in some organic reactions is described.  相似文献   
7.
Derrida's random energy model is considered. Almost sure andL P convergence of the free energy at any inverse temperature are proven. Rigorous upper and lower bounds to the finite size corrections to the free energy are given.  相似文献   
8.
Multielement determinations by high-flux absolute n.a.a. require careful methodology to avoid systematic error. The ORNL high-flux facility with a thermal flux of 5 ·1014 cm-2 s-1 and a thermal-to-resonance flux ratio of
T004. Analysis of Knoxville tree-core samplesa
ElementIncrement no.20 (1832–1838)Increment no.8 (1932–1838)Increment no.3 (1858–1863)Increment no.1 (1868–1872)
Core NumberCore NumberCore NumberCore Number
13131313
Na12.9(1.1)2.67(3.3)33.8(1.0)11.2(1.6)15.6(1.5)31.4(1.2)22.4(0.93)9.9(1.8)
Mgcc160(12)b80(27)b100(21)b100(30)bcc
Al15.2(5.4)5.6(6.1)12.5(3.8)11.0(4.4)7.8(6.6)8.4(7.4)6.5(14)6.6(6.2)
Cl15.4(9.1)ND66(5.4)NDND55(6.1)26(5.5)22(5.1)
K205(2.6)223(3.3)493(1.8)b457(1.9)b478(1.9)b439(2.1)b449(1.8)570(1.7)
Ca1600(11)NDNDNDNDNDNDND
CrNDNDNDbNDb0.3(>30)b0.6(>30)b0.6(>30)bND
Mn109(0.30)107(0.23)64.1(042)108(0.32)46.7(051)66.8(0.44)38.9(0.39)45.0(0.34)
FeNDNDNDNDND19(19)25(18)ND
CoND0.02(>30)NDNDNDND0.30(>30)ND
Zn7.2(7)7.4(4.2)13.0(2.4)9.2(3.3)5.6(4.0)4.5(4.7)ND2.4(8.8)
Br0.10(20)ND0.07(12)ND0.024(13)ND0.04(>30)ND
RbNDND0.9(13)0.8(18)0.8(15)0.7(17)ND1.1(18)
AgNDND1.06(3.0)15.3(0.71)0.15(15)0.69(4.8)0.11(28)ND
Ba11(7.3)10(13)3.2(16)ND3.0(15)2.9(18)ND3(32)
WNDNDNDNDNDND0.06(29)ND
a
Results in p.p.m followed by (per cent counting statistical error).
b
Computer forced result.Also V,Se,Sr,Sb,Cs and au (forced) were not detected.
c
Element possibly present but missed by peak-finding routine.7 35–45, was used in developing an instrumental absolute multielement method. The detector was calibrated for absolute counting with two independent sets of radioactivity standards for four detector- -source distances; the absolute activities of the standards were reproducible within accuracies of 9%. Five sources of systematic error were investigated: (a) correction for counting of cylindrical sources for 26 γ-ray energies reached 14–17% for photon energies below 500 keV; (b) flux variation during bombardment and within the irradiation capsule volume was not significant; (c) samples were sufficiently stable during high-flux bombardment; (d) multi-element impurities in accessory materials (polyethylene and “Nucleopore” filters) were not significant; (e) correction for sample activation during rabbit transfer was necessary for short bombardments, e.g., 8.6 % for 6 s and 19.6 % for 4 s. This methodology resulted in accuracies of 10–15 % for most elements, as determined by analysis of N.B.S. orchard leaves and coal and of Bowen's kale standards. The method was applied to a preliminary chronological study of environmental baselines and contamination levels, based on tree ring samples, covering a period of 100 years.
  相似文献   
9.
Some cis,cis,cis-RuX(2)(Me(2)SO)(2)(1,2-Me(2)Im)L complexes [L = 1,2-Me(2)Im (1,2-dimethylimidazole) or Me(3)Bzm (1,5,6-trimethylbenzimidazole), X = Cl or Br, and Me(2)SO = S-bonded DMSO] have been synthesized and their rotamers studied in CDCl(3). From 2D NMR data, cis,cis,cis-RuCl(2)(Me(2)SO)(2)(1,2-Me(2)Im)(Me(3)Bzm) has 1,2-Me(2)Im in position "a" (cis to both Me(2)SO's and cis to "b") and Me(3)Bzm in position "b" (trans to one Me(2)SO and cis to the other). There are two stable atropisomers [head-to-tail (HT, 84%) and head-to-head (HH, 16%), defining the aromatic H of Ru-N-C-H as head for both ligands]. Me(3)Bzm has the same orientation in both atropisomers. In this orientation, the unfavorable interligand steric interactions of Me(3)Bzm with the Me(2)SO and 1,2-Me(2)Im ligands appear to be countered by favorable electrostatic attraction between the delta+ N(2)CH moiety of Me(3)Bzm and the delta- cis Cl ligands. The 1,2-Me(2)Im lacks a delta+ N(2)CH group, and its orientation is dominated by steric effects of the 2-Me group. The NMR spectrum of cis,cis,cis-RuCl(2)(Me(2)SO)(2)(1,2-Me(2)Im)(2) is consistent with four rotamers in restricted rotation about both Ru-N bonds: two HH and two HT. 2D NMR techniques (NOESY and ROESY) afforded complete proton signal assignments. The ligand disposition could be assessed from the large chemical shift dispersion of some 1,2-Me(2)Im ligand signals (Delta 0.86-1.52 ppm) arising from cis-1,2-Me(2)Im shielding modulated by deshielding influences of the cis halides. The relative stability of the four rotamers correlates best with steric interactions between the 2-Me groups and the Me(2)SO ligands. The most favorable conformer (46%) is the HH rotamer with both 2-Me groups pointing away from the Me(2)SO ligands. The least favorable conformer (14%) was also HH, but the methyl groups in this case point toward the Me(2)SO ligands. In the HT conformers of intermediate stability ( approximately 20%), one 2-Me group is toward and the other is away from the Me(2)SO ligands. The exchange cross-peaks in the 2D spectra are unusually informative about the dynamic processes in solution; the spectra provide evidence that the rotamers interchange in a definite pattern of succession. Thus, all conceivable exchange pathways are not available. 1,2-Me(2)Im "b" can rotate regardless of the orientation of 1,2-Me(2)Im "a". 1,2-Me(2)Im "a" can rotate only when "b" has the orientation with its 2-Me group directed away from "a". Thus, 1,2-Me(2)Im "b" can switch 1,2-Me(2)Im "a" rotation on or off.  相似文献   
10.
Electron spin resonance (ESR) and quasielastic laser scattering (QELS) measurements have been carried out on sodium taurodeoxycholate (NaTDC) micellar aqueous solutions. Computer simulation of the ESR line shape has been used to quantitatively analyze the rotational dynamics of the cholestan-spin label (CSL) dissolved by the NaTDC micellar aggregates as a function of temperature and NaCl concentration. The local reorientation of CSL has been accounted for motionally-averaged g- and A-tensors assuming fast oscillation around the spin-probe long molecular axis. The overall Brownian tumbling of CSL-micelle complexes has been modeled by an axially symmetric rotational tensor. Good agreement with experimental spectra is obtained. Best-fit rotational parameters and QELS data suggest that, in the circumstance of large aggregation, NaTDC micelles have cylindrical shape and micellar growth occurs along the cylinder axis.  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