全文获取类型
收费全文 | 444篇 |
免费 | 9篇 |
国内免费 | 9篇 |
专业分类
化学 | 281篇 |
晶体学 | 3篇 |
力学 | 6篇 |
数学 | 31篇 |
物理学 | 71篇 |
无线电 | 70篇 |
出版年
2022年 | 4篇 |
2020年 | 3篇 |
2019年 | 7篇 |
2018年 | 3篇 |
2016年 | 11篇 |
2015年 | 7篇 |
2014年 | 11篇 |
2013年 | 23篇 |
2012年 | 16篇 |
2011年 | 21篇 |
2010年 | 8篇 |
2009年 | 12篇 |
2008年 | 21篇 |
2007年 | 25篇 |
2006年 | 25篇 |
2005年 | 17篇 |
2004年 | 12篇 |
2003年 | 19篇 |
2002年 | 15篇 |
2001年 | 8篇 |
2000年 | 6篇 |
1999年 | 6篇 |
1998年 | 7篇 |
1997年 | 9篇 |
1996年 | 6篇 |
1995年 | 9篇 |
1994年 | 5篇 |
1993年 | 3篇 |
1992年 | 3篇 |
1990年 | 3篇 |
1989年 | 5篇 |
1988年 | 3篇 |
1986年 | 3篇 |
1985年 | 12篇 |
1984年 | 10篇 |
1983年 | 5篇 |
1982年 | 9篇 |
1981年 | 9篇 |
1980年 | 10篇 |
1979年 | 3篇 |
1977年 | 4篇 |
1975年 | 6篇 |
1974年 | 10篇 |
1973年 | 8篇 |
1971年 | 3篇 |
1970年 | 6篇 |
1968年 | 3篇 |
1961年 | 3篇 |
1933年 | 2篇 |
1927年 | 2篇 |
排序方式: 共有462条查询结果,搜索用时 6 毫秒
11.
The geometries of ten isomers of dimethyl cyclohexane were determined by ab initio gradient geometry refinement with the 4-21G basis set. It is found that many intramolecular interactions are clearly manifested by correlated structural trends, and that they are consistent with strain energies calculated by employing previously defined ab initio group equivalents. Specifically, non-bonded interactions are found between two adjacent methyl groups in some of the forms, and between axial methyl groups and adjacent axial C? H bonds in others. Unperturbed axial C? H and C? C bonds are consistently longer than equatorial bonds. In general, C? H bonds which are involved in non-bonded repulsive interactions are shortened, i.e., strengthened, and the corresponding H? C? C angles are large, compared to non-interacting parameters. 相似文献
12.
Van Hoof F Van Wiele P Bruchet A Schmitz I Bobeldiji I Sacher F Ventura F Marti I Morecos Do Monte MH Sa Da Costa M 《Journal of AOAC International》2001,84(5):1420-1429
As part of a project funded by the European Commission (EC) for the development and evaluation of multiresidue methods for analysis of drinking and related waters, 15 European laboratories evaluated a method using styrene-divinylbenzene co-polymer solid-phase extraction followed by gas chromatography/mass spectrometry. The main aim of the study was to evaluate whether the method meets the requirements of EC Directive 98/83 in terms of accuracy, precision, and detection limit for 22 pesticides according to the following requirements: limit of detection, < or = 0.025 microg/L; accuracy, expressed as recovery between 75 and 125%; and precision, expressed as repeatability relative standard deviation of the method of < 12.5% and as reproducibility relative standard deviation of the method of < 25%. Analyses for unknown concentrations were performed with fortified commercial bottled and tap waters. All laboratories were able to achieve detection limits of 0.01 microg/L for all pesticides except dimethoate and desisopropylatrazine (0.02 microg/L). The criteria for repeatability were met for all compounds except trifluralin, dimethoate, and lindane in bottled water and chlorpyrifos, dimethoate, and lindane in tap water. The criteria for reproducibility were met for all compounds except trifluralin, dimethoate, and lindane in bottled water and pendimethalin, chlorpyrifos, dimethoate, terbutryn, and lindane in tap water. In terms of accuracy, the method meets the requirements for all pesticides in both matrixes, except for lindane in bottled water and lindane and chlorpyrifos in tap water. 相似文献
13.
-A spectrophotometric method has been developed which is applicable to the determination of extremely small quantities of osmium. Osmium is oxidised to the octovalent state, then added to an acidic aqueous solution containing 1:5-diphenylcarbohydrazide (DPC). After heating the aqueous solution to 65°, the osmium-DPC complex is extracted with chloroform. A molar absorbancy index of about 150,000 is obtained. From 7 to 25 μg of osmium can be determined with a coefficient of variation of 6%. It was established that FeIII, CuII, RuIII and AuIII seriously interfere in the determination of osmium by this method, while CrVI, NiII, MoVI, IrIII and chloride interfere only when present in relatively high concentrations. 相似文献
14.
P. Caramella A. Coda Corsico A. Corsaro D. Del Monte F. Marinone Albini 《Tetrahedron》1982,38(1):173-182
Cycloadditions of benzonitrile oxide and mesitonitrile oxide to N-methylindole and indole yield the acid sensitive cycloadducts 1 a-d with high regioselectivity. With N-carbethoxyindole the stable cycloadducts 1 e,f and minor amounts of the regioisomeric 2 e,f are isolated. The electron withdrawing substituent reduces both the regioselectivity and the reactivity of the cycloadditions.Frontier orbital considerations, based on MINDO/3 calculations, allow elucidation of the observed changes in reactivity and regiochemistry. 相似文献
15.
D. Levy F. Del Monte X. Quintana J.M. Otón 《Journal of Sol-Gel Science and Technology》1997,8(1-3):1063-1066
Liquid crystal microdroplets trapped into silica gel-glasses by sol-gel processes may be used for display applications. Gel-glass
dispersed liquid crystals (GDLC) are switched between opaque and transparent states by applying external AC-voltage signals;
no polarizers are required. The feasibility of applying these materials to colored displays has been explored. A comparative
study of different dyes for GDLC color displays, which were either embedded in the sol-gel matrix or dissolved in the liquid
crystal microdroplets is presented. 相似文献
16.
Philip M. Carabateas R. Pauline Brundage Karl O. Gelotte Monte D. Gruett Roman R. Lorenz Chester J. Opalka Jr. Baldev Singh William H. Thielking Gordon L. Williams George Y. Lesher 《Journal of heterocyclic chemistry》1984,21(6):1849-1856
A series of substituted 3- and 4-(3-aminophenyl)pyridines has been prepared as intermediates for the synthesis of some 1-alkyl-1,4-dihydro-4-oxo-7-pyridinyl-3-quinolinecarboxylic acids. The Hantzsch, Hauser and other pyridine syntheses were used. 4-(3-Aminophenyl)pyridine was prepared via 3-(4-pyridinyl)-2-cyclohexen-1-one using the Semmler-Wolff reaction. 相似文献
17.
The reactions of [Co(η-C5H5)(L)I2] with Na[S2CNR2] (R = alkyl or phenyl) give [Co(η-C5H5)(I)(S2CNR2)] (I) when L = CO and [Co(η-C5H5)(L)(S2CNR2)]I (II) when L is a tertiary phosphine, phosphite or stibine, or organo-isocyanide ligand. In similar reactions [Co(η-C5H5)(CO)(C3F7)I] gives [Co(η-C5H5)(C3F7)(S2CNMe2)] and [Mn(η-MeC5H4)(CO)2(NO)]PF6 forms [Mn(η-MeC5H4)(NO)(S2CNR2)]. The iodide ligands in I may be displaced by L, to give II, or by other ligands such as [CN]?, [NCS]?, H2O or pyridine whilst SnCl2 converts it to SnCl2I. The iodide counter-anion in II may be replaced by others to give [BPh4]?, [Co(CO)4]? or [NO3]? salts. However [CN]? acts differently and displaces (PhO)3P from [Co(η-C5H5){P(OPh)3}(S2CNMe)]I to give [Co(η-C5H5)(CN)(S2CNMe2)] which may be alkylated reversibly by MeI and irreversibly by MeSO3F to [Co(η-C5H5)(CNMe)(S2CNMe2)]+ salts. Conductivity measurements suggest that solutions of I in donor solvents are partially ionized with the formation of [Co(η-C5H5)(solvent)(S2CNR2)]+ I? species. The IR and 1H NMR spectra of the various complexes are reported. They are consistent with pseudo-octahedral “pianostool” molecular structures in which the bidentate dithiocarbamate ligands are coordinated to the metal atoms through both sulphur atoms. 相似文献
18.
M.J. Boylan J. Bellerby Josephine Newman A.R. Manning 《Journal of organometallic chemistry》1973,47(2):C33-C35
Whereas Co2(CO)8 and RNC (R= Me, Et, and Cy) react to give mixtures of [(RNC)5Co] [Co(CO)4] and the covalent, carbonyl-bridged [(RNC)mCo2(CO)8?m] derivatives (m = 1–3), [(π-dienyl)Fe(CO)2]2 give only [(π-dienyl)2Fe2(CO)4?n(CNR)n] complexes (dienyl = C5H5, MeC5H4 and C9H7; n = 1–2) that exist in solution as mixtures of cis- and trans-CO- and RNC-bridged tautomers with the μ-RNC species decreasing in importance as the bulk of R increases. 相似文献
19.
Summary The dispersion of radioactive substances in the environment following nuclear weapon tests in atmosphere since 1954 and accidents to nuclear plants, like that in Chernobyl in 1986, have allowed us to study the migration processes of some radionuclides in complex ecosystems such as lakes are. In the present paper the behavior of 137Cs and 90Sr in different compartments of the Monterosi Lake (central Italy) was assessed. The 137Cs concentration was measured in lake water as well as sediment, stream water, aquatic plant and fish samples. 90Sr concentration in water and sediments was also determined. A total inventory of 4206±76 Bq . m-2 and 958±79 Bq . m-2 (on 27/6/01) has been found for 137Cs and 90Sr, respectively. The experimental data presented here allow to calibrate theoretical models predicting the temporal trend of radionuclide concentration in similar ecosystems. Moreover, information on cesium and strontium migration processes can be extended to other pollutants having similar environmental behavior. 相似文献
20.
Anthony Manning 《Bulletin of the Brazilian Mathematical Society》1992,22(2):157-177
The trouble with Newton's method for finding the roots of a complex polynomial is knowing where to start the iteration. In this paper we apply the theory of rational maps and some estimates based on distortion theorems for univalent functions to find lower bounds, depending only on the degreed, for the size of regions from which the iteration will certainly converge to a root. We can also bound the number of iterations required and we give a method that works for every polynomial and takes at most some constant timesd
2(logd)2 log(d
3/) iterations to find one root to within an accuracy of . 相似文献