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   726篇
  免费   11篇
  国内免费   3篇
化学   461篇
晶体学   3篇
力学   65篇
数学   89篇
物理学   122篇
  2022年   8篇
  2021年   6篇
  2020年   5篇
  2019年   9篇
  2018年   6篇
  2017年   7篇
  2016年   12篇
  2014年   14篇
  2013年   29篇
  2012年   36篇
  2011年   35篇
  2010年   13篇
  2009年   21篇
  2008年   35篇
  2007年   40篇
  2006年   32篇
  2005年   48篇
  2004年   33篇
  2003年   25篇
  2002年   31篇
  2001年   12篇
  2000年   21篇
  1999年   6篇
  1996年   13篇
  1995年   7篇
  1993年   7篇
  1992年   17篇
  1991年   6篇
  1990年   7篇
  1989年   6篇
  1988年   9篇
  1987年   15篇
  1986年   7篇
  1985年   10篇
  1984年   11篇
  1983年   7篇
  1982年   5篇
  1981年   12篇
  1980年   7篇
  1979年   11篇
  1978年   15篇
  1977年   7篇
  1976年   14篇
  1975年   8篇
  1974年   5篇
  1973年   4篇
  1971年   5篇
  1970年   4篇
  1968年   5篇
  1967年   3篇
排序方式: 共有740条查询结果,搜索用时 15 毫秒
1.
This article sets forth a way of connecting the classroom instructional environment with individual students' generalizations. To do so, we advance the notion of focusing phenomena, that is, regularities in the ways in which teachers, students, artifacts, and curricular materials act together to direct attention toward certain mathematical properties over others. The construct of focusing phenomena emerged from an empirical study conducted during a 5-week unit on slope and linear functions in a high school classroom using a reform curriculum. Qualitative evidence from interviews with 7 students revealed that students interpreted the m value in y = b + mx as a difference rather than a ratio as a result of counterproductive generalization afforded by focusing phenomena. Classroom analysis revealed 4 focusing phenomena, which regularly directed students' attention to various sets of differences rather than to the coordination of quantities.  相似文献   
2.
The performance of two external plastic scintillator detectors has been tested in an off-line mode using a source of106RuFe at UNISOR/NOF. The measurement of beta asymmetries at various temperatures has resulted in the reproduction of the previously-determined magnetic dipole moment for the 1+ ground state of106Rh and in addition the conclusion that the sign of this moment is positive.  相似文献   
3.
4.
A sensitive and specific method for the determination of bencyclane in human plasma is presented. Bencyclane was extracted from human plasma with two 3-ml volumes of isooctane and was shaken for 10 min. The organic phase was separated and evaporated to dryness at 40 degrees C under a nitrogen stream. The residue was dissolved and an aliquot was injected into the gas chromatograph. The separation was performed with a DB-17 column with helium as the carrier gas. Nitrogen-selective detection was performed. The quantification was performed with the signal output. The limit of detection was 1 ng/ml.  相似文献   
5.
The protonation scheme of L-cysteine has been investigated by nuclear magnetic resonance. Chemical shift data as a function of pH are given for L-cysteine, L-cysteine methyl ester and S-methyl-L-cysteine. Use of derivatives of L-cysteine permits determination of the effect of protonation of the amino, sulfhydryl and carboxylic sites on the chemical shift of the -CH and -CH2 protons. On the basis of these results, a set of simultaneous equations was written whose solution yielded the fraction of protonation of each site upon the addition of n equivalents of acid to the initially completely deprotonated molecule.  相似文献   
6.
The reactions of sodium ethoxide in ethanol with various fluoroaromatics, C6F6?nHn, C6F5?nHnNO2, C6F5X (X = CF3, C6F5, COCH3, CH2Br), C6Cl6 and mH2C6Cl4 have been studied. Partial substitution of the aromatic halogen was observed. The new products have been characterized by elemental analysis, NMR (H?1 and F?19), infrared and mass spectroscopy.  相似文献   
7.
A series of sterically demanding diporphyrins H2(por)-X-(por)H2 ligands that contain spacers (X) with different degrees of flexibility were synthesized from the trimesitylporphyrin derivatives 5-(4-hydroxyphenyl)-10,15,20-trimesitylporphyrin (TMP-OH)H2 (1a) and 5-(2,6-dimethyl-4-hydroxyphenyl)-10,15,20-trimesityl-porphyrin, (DMTMP-OH)H2 (1b). The monomeric porphyrins 1a,b, which have steric demands similar to that of tetramesitylporphyrin, (TMP)H2, and carry a hydroxyl functional group at the para position of one of the mesophenyl substituents, were constructed from reaction of pyrrole with two aromatic aldehydes by a mixed aldehyde condensation approach. The diporphyrins with alkyl diether tethers were obtained stepwise from reactions of the hydroxy functionalized porphyrins 1a,b with dibromides Br(CH2)nBr. The diporphyrin which contains a more rigid m-xylylene spacer, was made directly from reaction of 1b with alpha,alpha'-dibromo-m-xylene. Rhodium was inserted into the porphyrins using Rh2(CO)2Cl2 and converted to dimethyl complexes Me-Rh(Por)-X-(Por)Rh-Me. The dirhodium(II) derivatives .Rh(por)-X-(por)Rh.) were generated by photolysis of the dimethyl complexes and observed to occur as stable bimetalloradicals because the ligand steric demands prohibit Rh(II)-Rh(II) bonding. EPR spectra of the dirhodium(II) derivatives, triphenyl phospine adducts, and dioxygen complexes are reported. The kinetic advantage of bimetalloradical complexes for substrate reactions that have two metal-centered radicals in the transition state is demonstrated by reactions of dihydrogen with dirhodium(II) bimetalloradical complexes.  相似文献   
8.
fac-[RuII(Cl)(dpp)(L3)]+ (L3 = tris(pyrid-2-yl)methoxymethane (tpmm) = [1A]+ and tris(pyrid-2-yl)pentoxymethane (tppm) = [1B]+ and dpp = di(pyrazol-1-yl)propane) rapidly undergo ligand substitution with water to form fac-[RuII(H2O)(dpp)(L3)]2+ (L3 = tpmm = [2A]2+ and tppm = [2B]2+). In the structure of [2A]2+, the distorted octahedral arrangement of ligands around Ru is evident by a long Ru(1)-O(40) of 2.172(3) A and a large angle O(40)-Ru(1)-N(51) of 96.95(14) degrees . The remarkably short distance between O(40) of H2O and H(45a) of dpp confirms the heteroscorpionate ligand effect of dpp on H2O. [2B]2+ aerobically catalyzes methyl p-tolyl sulfide to methyl p-tolyl sulfoxide in 1,2-dichlorobenzene at 25.0 +/- 0.1 degrees C under 11.4 psi of O2. Experimental facts in support of this aerobic sulfide oxidation are the absence of H2O2 and the oxidative reactivity of the putative Ru(IV)-oxo intermediate toward methyl p-tolyl sulfide, 2-propanol, and allyl alcohol. This study provides the first documented example of aerobic-sulfide oxidation catalyzed by the remarkably labile heteroscorpionate Ru(II)-aqua complex without the formation of a highly reactive peroxide as an intermediate.  相似文献   
9.
Mupirocin, a polyketide-derived antibiotic from Pseudomonas fluorescens NCIMB10586, is a mixture of pseudomonic acids (PA) that target isoleucyl-tRNA synthase. The mup gene cluster encodes both type I polyketide synthases and monofunctional enzymes that should play a role during the conversion of the product of the polyketide synthase into the active antibiotic (tailoring). By in-frame deletion analysis of selected tailoring open-reading frames we show that mupQ, mupS, mupT, and mupW are essential for mupirocin production, whereas mupO, mupU, mupV, and macpE are essential for production of PA-A but not PA-B. Therefore, PA-B is not simply produced by hydroxylation of PA-A but is either a precursor of PA-A or a shunt product. In the mupW mutant, a new metabolite lacking the tetrahydropyran ring is produced, implicating mupW in oxidation of the 16-methyl group.  相似文献   
10.
O-Methyl-α-ketophenylacetohydroximoyl chloride ( 1 ) was prepared by the reaction of O-methyl-α-methoxyphenylacetohydroximoyl chloride ( 5 ) with N-bromosuccinimide and concentrated hydrobromic acid. Reaction of 1 with ethylenediamine gave 3-phenyl-5,6-dihydro-2(1H)-pyrazinone-O-methyloxime ( 6 ). 3-Phenyl-5,6-cyclohexano-5,6-dihydro-2(1H)-pyrazininone-O-methyloxime ( 7 ) was prepared by reaction of 1 with trans-1,2-diaminocyclohexane. The X-ray structure of 6 has been determined. The crystals are orthorhombic, space group Pbca with a = 10.264(3), b = 18.262(4), c = 23.530(4)Å, V = 4411(2)Å3, and Z = 16. The structure, which was refined to R = 0.038 using 1652 observed reflections, shows the amidoxime moiety to be the Z configuration. Reaction of benzohydroximoyl chloride with aziridine gave (Z)-aziridinylbenzaldoxime ( 16a ). Ultraviolet irradiation of a benzene solution of 16a gave a mixture of the Z and E isomers 16a and 16b . The E isomer 16b underwent thermal isomerization to 16a at 100°. Reaction of 16a with dimethyl sulfate in sodium hydroxide solution gave (Z)-O-methylaziridinylbenzaldoxime ( 17a ). Photoisomerization of a hexane solution of 17a gave a mixture of the Z and E isomers 17a and 17b which were separated by preparative glc. The isomers 17a and 17b are resistant to thermal Z = E isomerization. The mechanisms of thermal isomerization of benzamidoximes are discussed.  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