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   925篇
  免费   59篇
  国内免费   22篇
化学   592篇
晶体学   3篇
力学   82篇
数学   136篇
物理学   193篇
  2024年   2篇
  2023年   5篇
  2022年   9篇
  2021年   42篇
  2020年   46篇
  2019年   46篇
  2018年   50篇
  2017年   55篇
  2016年   74篇
  2015年   45篇
  2014年   68篇
  2013年   121篇
  2012年   103篇
  2011年   83篇
  2010年   58篇
  2009年   36篇
  2008年   28篇
  2007年   34篇
  2006年   20篇
  2005年   15篇
  2004年   3篇
  2003年   5篇
  2002年   4篇
  2001年   5篇
  2000年   3篇
  1999年   2篇
  1998年   1篇
  1997年   2篇
  1996年   1篇
  1995年   2篇
  1994年   2篇
  1993年   2篇
  1991年   2篇
  1990年   2篇
  1989年   2篇
  1988年   1篇
  1987年   3篇
  1985年   2篇
  1984年   1篇
  1983年   1篇
  1982年   1篇
  1980年   4篇
  1979年   2篇
  1977年   5篇
  1976年   2篇
  1975年   3篇
  1974年   2篇
  1972年   1篇
排序方式: 共有1006条查询结果,搜索用时 31 毫秒
1.
Journal of Analytical Chemistry - In this article, a new spectrofluorometric method was developed for the determination of methamphetamine based on a turn-on luminescence response of captopril...  相似文献   
2.
A new ammonia optical sensor was designed using bis(acetylacetoneethylendiamine)tributylphosphin cobalt(III) tetraphenylborate complex, coated on transparent triacetylcellulose film as membrane. The change in the absorbance of the optode at the maximum wavelength of 408 nm was related to ammonia concentration in aqueous samples. A buffer solution with a pH of 9 (sodium borate-HCl) was used. The optode was fully regenerated in pH 2. The linear dynamic range for determination of ammonia was 3.3 x 10(-4) to 6.9 x 10(-3) mol l(-1) with a detection limit of 5.0 x 10(-5) mol l(-1) and a response time range of 4 - 6 min. This membrane was successfully applied for determination of ammonia in drinking water.  相似文献   
3.
Quantum de Rham complexes on the quantum plane and the quantum group itself are constructed for the nonstandard deformation of Fun(SL(2)). It is shown that in contrast to the standardq-deformation of SL(2), the above complexes are unique for SL h (2). Also, as a byproduct, a new deformation of the two-dimensional Heisenberg algebra is obtained which can be used to construct models ofh-deformed quantum mechanics.  相似文献   
4.
Based on the stress transport model, a rate-dependent algebraic expression for the Reynolds stress tensor is developed. It is shown that the new model includes the normal stress effects and exhibits viscoelastic behavior. Furthermore, it is compatible with recently developed improved models of turbulence. The model is also consistent with the limiting behavior of turbulence in the inertial sublayer and is capable of predicting secondary flows in noncircular ducts. The TEACH code is modified according to the requirements of the rate-dependent model and is used to predict turbulent flow fields in a channel and behind a backward-facing step. The predicted results are compared with the available experimental data and those obtained from the standard k-ε and algebraic stress models. It is shown that the predictions of the new model are in better agreements with the experimental data.  相似文献   
5.
In this work a modified form of the Ghotbi–Vera Mean Spherical Approximation model (MGV-MSA) has been used to correlate the mean ionic activity coefficients (MIAC) for a number of symmetric and asymmetric aqueous electrolyte solutions at 25 °C. In the proposed model the hard sphere as well as the electrostatic contributions to the MIAC and the osmotic coefficient of the previously GV-MSA model has been modified. The results of the proposed model for the MIAC of the electrolyte solutions studied in this work are used to directly calculate the values of the osmotic coefficients without introducing any new adjustable parameter. In the MGV-MSA model the cation diameter as well as the relative permittivity of water depends on the electrolyte concentration. Having considered such dependency for both cation and relative permittivity for water in an electrolyte solution the modification of the GV-MSA has been made. It should be stated that in the MGV-MSA model the anion diameter in the solution similar to that in the GV-MSA model remains constant and independent of the electrolyte concentration. The results obtained from the proposed model have been favorably compared with those of the GV-MSA model. The results showed that the MGV-MSA model can more accurately correlate the MIAC of the single electrolyte solutions than those of the GV-MSA model. The same comparison has been observed in case of the osmotic coefficients for the electrolyte solutions studied in this work. It should be noted that in order to do an unequivocal comparison between the results obtained from the models used in this work the same minimization procedure and the same experimental data for the MIAC and the osmotic coefficients have been used. Also it should be mentioned that in the MGV-MSA model the conversion from the McMillan–Mayer (MM) framework to that of the Lewis–Randall (LR) has been performed. It has been concluded that such transformation can affect the results in particular at higher electrolyte concentrations.  相似文献   
6.
Oxidations of 2,2-disubstituted-1,4-butanediols by the combination of nickel(II) bromide and benzoyl peroxide and by trityl tetrafluoroborate produce β,β-disubstituted-γ-butyrolactones with exceptional selectivity.  相似文献   
7.
The reaction of an ethanolic solution 2,6‐pyridinedicarboxylic acid ( 1 , LH2) with TlNO3 in the presence of triethylamine led to the coordination polymer [Tl(LH)]n ( 2 ). The complex was characterized by elemental analysis, IR spectroscopy and single‐crystal X‐ray diffraction. Crystal data for 2 at –80 °C: monoclinic, space group I2/a, a = 696.1(1), b = 1190.6(2), c = 931.0(2) pm, β = 103.28(1)°, Z = 4, R1 = 0.0256.  相似文献   
8.
The thermocatalytic rearrangements of cyclopropenes 1-4 have been investigated in the presence of Rh(IT) perfiuorobutyrate. 1, 2, 3-Triphenylcyclopropene ( 1a ) undergoes rearrangement lo diphenylindene 5a or, with alkoxycyclopropene derivatives, to α, β-unsaturated ketone 6. Furan formation occurs with 2, 3-diphenylcyclo-propenecarboxylate 2, but the diethyl counterpart 3 rearranges to dienoate 8. 2-Alkylcyclopropenecarboxylates 4 afforded (E)-methylidenecyclopentane derivatives 9 as the only isolable product in yields of ca. 35 %. A mechanism involving regio- and stereospecific cyclopropene ring opening to a Rh-complexed vinylcarbene and insertion of the latter into the C? H bond to give 9 is proposed. An analogous mechanism should account for the rearrangement products of 1 to 3 .  相似文献   
9.
The reaction of 2,6‐pyridinedicarboxylic acid ( 1 , LH2) with CeCl3·7H2O and Sm(NO3)3·6H2O in the presence of triethylamine led to the coordination polymer complexes [M(L)(LH)(H2O)2]·4H2O [M = Ce ( 2 ) and Sm ( 3 )]. Both complexes were characterized by elemental analyses, IR spectroscopy and the crystal structures of 2 and 3 . Crystal data for 2 at ?80 °C: monoclinic, space group P21/c, a = 1404.6(1), b = 1122.1(1), c = 1296.1(1) pm, β = 102.09(1)°, Z = 4, R1 = 0.0217 and for 3 at ?80 °C: monoclinic, space group P21/c, a = 1395.1(1), b = 1120.1(1), c = 1282.8(1) pm, β = 102.71(1)°, Z = 4, R1 = 0.019.  相似文献   
10.
In the present work, the cathodic stripping voltammetric methodology using a hanging mercury drop electrode was described for simultaneous determination of lead and zinc in different real samples. The method is based on adsorption of metal ions on mercury electrode using carbidopa as a suitable complexing agent. The potential was scanned to the negative direction and the differential pulse stripping voltammograms were recorded. Optimal conditions were found to be: accumulation time; 70 s, accumulation potential; 50 mV versus Ag/AgCl, scan rate; 40 mV s?1, supporting electrolyte; 0.01 M ammonia buffer at pH 8.5, and concentration of carbidopa; 8.0 μM. The relationship between the peak current versus concentration was linear over the range of 0.1–210 and 0.2–170 nM for lead and zinc, respectively. The detection limits are 0.09 and 0.15 nM for lead and zinc ions respectively. The relative standard deviations at a concentration level of 70 nM of both metal ions are found 1.08 and 1.24% for lead and zinc ions respectively.  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