全文获取类型
收费全文 | 3209篇 |
免费 | 36篇 |
国内免费 | 6篇 |
专业分类
化学 | 2141篇 |
晶体学 | 22篇 |
力学 | 26篇 |
数学 | 506篇 |
物理学 | 556篇 |
出版年
2016年 | 37篇 |
2015年 | 31篇 |
2014年 | 35篇 |
2013年 | 82篇 |
2012年 | 74篇 |
2011年 | 100篇 |
2010年 | 70篇 |
2009年 | 53篇 |
2008年 | 74篇 |
2007年 | 81篇 |
2006年 | 80篇 |
2005年 | 80篇 |
2004年 | 79篇 |
2003年 | 80篇 |
2002年 | 63篇 |
2001年 | 47篇 |
2000年 | 57篇 |
1999年 | 35篇 |
1998年 | 33篇 |
1996年 | 36篇 |
1995年 | 50篇 |
1994年 | 45篇 |
1993年 | 52篇 |
1992年 | 37篇 |
1991年 | 37篇 |
1990年 | 25篇 |
1989年 | 40篇 |
1988年 | 36篇 |
1987年 | 42篇 |
1986年 | 31篇 |
1985年 | 52篇 |
1984年 | 59篇 |
1983年 | 55篇 |
1982年 | 55篇 |
1981年 | 44篇 |
1980年 | 46篇 |
1979年 | 52篇 |
1978年 | 57篇 |
1977年 | 41篇 |
1976年 | 61篇 |
1975年 | 48篇 |
1974年 | 37篇 |
1973年 | 43篇 |
1972年 | 31篇 |
1971年 | 40篇 |
1970年 | 21篇 |
1966年 | 22篇 |
1932年 | 25篇 |
1929年 | 19篇 |
1913年 | 22篇 |
排序方式: 共有3251条查询结果,搜索用时 296 毫秒
21.
Ernst Ruch 《Angewandte Chemie (International ed. in English)》1977,16(2):65-72
Chemistry judging by its applications, physics according to its methods, and heavily reliant upon the tools of mathematics—that is what makes theoretical chemistry. And yet that is where its strength lies—in the variety of these sciences. It is quite natural that, in answer to specific problems, results and methods can sometimes be developed whose scope extends far beyond the original application. Rather it is a mark of quality if consequences can be found in chemistry and physics and the pathway leads via new mathematical procedures and concepts. Regrettably, any publication aiming to present such aspects will usually encounter little resonance since the linguistic confusion in science, its disciplines, and subdisciplines, lies like a veil over our understanding. The author nevertheless wishes to attempt to present, in a series of articles, results of research into chemical themes in a manner designed to appeal to the interest of chemists, without neglecting interdisciplinary aspects. All that is required to understand the argumentation is a lively interest. The first two articles are concerned with the chirality of molecules, and in particular with questions relating to the chirality phenomenon of molecules in the framework of molecular classes. In view of the algebraic nature of the mathematical methods adopted, it is not surprising that precise statements result. It appears of primary interest to establish the degree to which such statements can be considered valid for molecular models or molecules themselves. 相似文献
22.
23.
Polymers containing intact lactone groups are a new class of macromolecules with reactive groups, which are relatively easy to obtain by polymerization, polycondensation and polyaddition, as well as by reactions on existing macromolecules. Polymers with β-lactone Groups in particular can enter into numerous addition reactions, which can be used, for example, to obtain macromolecules containing hydroxy acid or amino acid groupings. The reactions proceed under mild conditions, and can even be carried out in aqueous media, frequently giving water-soluble polymers. The polymers can be cross-linked at low temperatures, even from the aqueous phase, by the addition of bifunctional or oligofunctional reagents. Polymers containing β-lactone groups can also be used as a basis for graft co-polymers; polyester or polyether branches can be grafted on, depending on whether monomeric lactones or monomeric epoxides are used. 相似文献
24.
Nabeshima T Yoshihira Y Saiki T Akine S Horn E 《Journal of the American Chemical Society》2003,125(1):28-29
In supramolecular chemistry, a great deal of attention has focused on regulating guest binding via an external stimulus. To utilize the same effector for both highly guest-selective positive and negative allosteric effects, however, stricter and more precise regulation of the host structure is required. A novel allosteric host 1 binds Fe(II) to afford the pseudocryptand, 1.Fe(II), which bears a cavity that is surrounded by three polyether chains in a helical fashion. The binding selectivity of 1 (Na+ > K+ > Rb+ > Cs+) is the opposite of 1.Fe(II) (Cs+ > Rb+ > K+ > Na+). Single-ion transport through a liquid membrane shows ion selectivity similar to the equilibrium constants. To the best of our knowledge, this is the first example of an allosteric recognition system, in which the same effector, that is, Fe(II), exhibits both large positive and negative allosteric effects on equilibrium and dynamic recognition events. The X-ray analysis and 1H NMR examination indicate that the combination of the macrobicyclic effect and the intramolecular interchain interactions (CH-pi interaction and steric hindrance) finely controls the positive and negative allosteric effects, which depend on the size of the guest. The helical framework opens a new general method for constructing more sophisticated, controllable receptors for helical biomolecules, for example, DNA and proteins, and helical molecular devices such as a molecular coil or spring responding to a stimulus. 相似文献
25.
Heinz Falk Ernst Haslinger Thomas Schlederer 《Monatshefte für Chemie / Chemical Monthly》1979,110(6):1287-1294
The1H-NMR spin lattice relaxation times of aetiobiliverdin-IV- and biliverdindimethylester were determined using the inversion recovery technique. The relaxation times of protons attached to the terminal rings A and D are longer than those situated at the rings B and C which points to a higher mobility of rings A and D. Moreover these measurements allowed an independent assignment of the1H-NMR-signals of the methyl groups of biliverdindimethylester.
30. Mitt.:H. Falk undT. Schlederer, Ann. Chem., im Druck. 相似文献
26.
Pressure-supported packed capillary electrochromatography (CEC) and packed capillary high-performance liquid chromatography (pHPLC) have been coupled on-line to electrospray ionization-mass spectrometry (ESI-MS) and coordination ion spray-mass spectrometry (CIS-MS). Separation of enantiomers of barbiturates and chlorinated alkyl phenoxypropanoates were performed on a permethylated beta-cyclodextrin stationary phase by pressure-supported CEC. For on-line detection with ESI- and CIS-MS, a modified sheath-liquid interface was used. CIS-MS is a universal, novel ionization technique which improves the selectivity as well as the sensitivity. Charged complexes were formed through the addition of central complexing ions such as silver(I), cobalt(II), copper(II), and lithium(I) to the sheath flow. Advantages of CIS-MS detection compared to the ESI-MS mode are discussed. In the CIS-MS mode, increased sensitivity and high selectivity was attained through different possibilities of complexation. The superiority of pressure-supported CEC compared to pHPLC in the hyphenation with CIS-MS is demonstrated. 相似文献
27.
For the assignment of the configuration at C(8) and C(15) of the natural oviposition-deterring pheromone 1 in Rhagoletis cerasi L., the four possible stereoisomers of 1 are synthesized. By condensing the C6 building blocks (5R)- 4 and (5S)- 4 with the boron enolates of the C10 building blocks (4S)- 13 and (4R)- 13 , followed by decarboxylative dehydration, all stereoisomers of 16 are available (Scheme 5). Glucosylation of 16 followed by formation of the taurin amide gives, after deprotection, the four stereoisomers (8R,15S)- 1 , (8R,15R)- 1 , (8R,15S) -1 , and (8S,15S)- 1 (Scheme 6). 相似文献
28.
Pucci V Bugamelli F Mandrioli R Ferranti A Kenndler E Raggi MA 《Biomedical chromatography : BMC》2004,18(1):37-44
An accurate and precise high-performance liquid chromatographic method using diode array detection for the determination of the novel antiepileptic, Levetiracetam, has been developed. Three clean-up procedures for the analysis of Levetiracetam in human plasma were implemented and evaluated, namely solid-phase extraction, deproteinization by addition of organic solvents and formation of insoluble salts. Adenosine was used as the internal standard for all three sample pretreatment procedures. Among the several cartridges used for solid-phase extraction, the hydrophilic-lypophilic balance (Oasis) HLB) phase provides the best extraction yield of Levetiracetam, together with high precision. With the two other clean-up procedures involving plasma deproteinization by addition of methanol or zinc sulphate, lower sensitivity and precision of the assays were obtained. However, they are cheaper and faster when compared with the solid-phase extraction procedure. 相似文献
29.
Isothiosemicarbazides 2 react with acyl isothiocyanates under addition-cyclization to yield 1,3,4-thiadiazoline-2-imines 3 as well as the isomeric 2-amino-substituted 1,3,4-thiadiazolium-5-acylaminides 3′ . In a similar manner the 2-hydrazino-substituted 1,3-thiazoline 4 adds ethoxycarbonyl isothiocyanate to give the thiosemicarbazide 5 , which undergoes a rearrangement to the 1,3,4-thiadiazoline-2-imine 5′. The [2+2] cycloreversion of 3d involving ethoxycarbonyl iso(thio)cyanate and the thermal induced Dimroth rearrangement of 3′f and h are also discussed. 相似文献
30.
Treatment of transition-metal—ammonia complexes with ketones yields complexes with RR′CNH ligands. Of particular interest is the stabilization of dialkylketimines such as e.g. (CH3)2CNH and C6H10NH in [M(CO)5{NHC(CH3)2}] or [M(CO)5 {NHC6H10}] (M = Cr, Mo, W). The principle of synthesis may be applied to a wide range of different metals and types of complexes, as can be shown by the synthesis of [C5H5Mn(CO)2 {NHC(CH3)2}], [C5H5Fe(CO)2{NHC(CH3)2}]PF6, [M(CO)4L2] (M = Cr, Mo, W; L = (CH3)2CNH, C6H10NH) and [W(CO)3(diphos){NHC(CH3)}2]. Treatment of [Cr(CO)5NH3] with urotropine gives [Cr(CO)5 {N4(CH2)6}] which is also obtained from [Cr(CO)5THF] and urotropine. The methods of preparation, reactions and spectroscopic properties of the complexes are reported. 相似文献