全文获取类型
收费全文 | 7369篇 |
免费 | 190篇 |
国内免费 | 57篇 |
专业分类
化学 | 4261篇 |
晶体学 | 32篇 |
力学 | 257篇 |
数学 | 1478篇 |
物理学 | 1588篇 |
出版年
2023年 | 40篇 |
2022年 | 51篇 |
2021年 | 76篇 |
2020年 | 85篇 |
2019年 | 86篇 |
2018年 | 133篇 |
2017年 | 98篇 |
2016年 | 176篇 |
2015年 | 177篇 |
2014年 | 178篇 |
2013年 | 405篇 |
2012年 | 449篇 |
2011年 | 1065篇 |
2010年 | 310篇 |
2009年 | 280篇 |
2008年 | 339篇 |
2007年 | 374篇 |
2006年 | 323篇 |
2005年 | 316篇 |
2004年 | 261篇 |
2003年 | 217篇 |
2002年 | 185篇 |
2001年 | 109篇 |
2000年 | 77篇 |
1999年 | 54篇 |
1998年 | 40篇 |
1997年 | 55篇 |
1996年 | 49篇 |
1995年 | 45篇 |
1994年 | 46篇 |
1993年 | 41篇 |
1992年 | 36篇 |
1991年 | 32篇 |
1990年 | 34篇 |
1989年 | 26篇 |
1985年 | 35篇 |
1984年 | 34篇 |
1983年 | 31篇 |
1982年 | 34篇 |
1981年 | 38篇 |
1980年 | 34篇 |
1979年 | 25篇 |
1978年 | 24篇 |
1974年 | 24篇 |
1973年 | 31篇 |
1936年 | 27篇 |
1934年 | 27篇 |
1932年 | 29篇 |
1929年 | 25篇 |
1927年 | 30篇 |
排序方式: 共有7616条查询结果,搜索用时 0 毫秒
81.
Trifluoromethoxy-substituted anilines undergo hydrogen/lithium permutation ("metalation") with optional site selectivity depending on the N-protective group employed. N-tert-Butoxycarbonyl-2- and -4-(trifluoromethoxy)aniline react with tert-butyllithium at the nitrogen-adjacent 6- and 2-position affording, after electrophilic trapping, products 1-6. In contrast, deprotonation of the para isomer occurs at the oxygen-neighboring 3-position, giving rise to the acid 12, when the amino group is carrying two trimethylsilyl groups. sec-Butyllithium attacks 3-trifluoromethoxy-N-mono(trimethylsilyl)aniline at the 2-position, but 3-trifluoromethoxy-N,N-bis(trimethylsilyl)aniline at the 4-position to provide respectively the acids 10 and 11 after carboxylation. The synthesis of two new benzodiazepines illustrates (19 and 22) the preparative potential of the aniline functionalization mediated by organometallic reagents. 相似文献
82.
F. Sauter J. Fröhlich A. Z. M. S. Chowdhury C. Hametner 《Monatshefte für Chemie / Chemical Monthly》1997,128(5):503-508
Summary A variety of partly novel tri- and tetracyclic hetero systems were obtained by reaction of heteroaromatic 2-aminoesters with 2-(methylthio)-2-thiazoline, yielding double-annelation of a thiazolo[2,3-b]pyrimido moiety in a one-pot process.On leave from University of Chittagong, Bangladesh 相似文献
83.
A brief treatment of 2-thiopyrimidine nucleosides (s2U∗) with trans-2-phenylsulfonyl-3-phenyloxaziridine (PSO) results in efficient substrate desulfurization leading to the corresponding 4-pyrimidinone analogues (H2U∗). The key transformation proceeds through oxidation of the 2-thiocarbonyl group to a sulfur oxyacid derivative and subsequent elimination of sulfur dioxide. 4-Pyrimidinone 1-β-d-riboside (H2U) has been transformed into the respective phosphoramidite, a ready-to-use monomer for the introduction of a modified nucleoside into an oligonucleotide chain. Moreover, the effective desulfurization of the 2-thiouridine nucleotide could be achieved directly at the oligonucleotide level, by treatment of the TdA(s2U)dGdC oligonucleotide with PSO, as verified by MALDI-TOF mass spectrometry. 相似文献
84.
Karancsi T Gödörházy L Szalay D Papp B Németh L Darvas F 《Journal of chromatography. A》2005,1079(1-2):349-353
In order to support high-throughput library purification, a novel UV triggered fraction collection method was developed in which a maximum-seeking-algorithm-driven, six-port valve collects the largest chromatographic peak. This straightforward strategy achieves the one sample-one fraction approach, thus resulting in a simpler and less error prone workup procedure. The effectiveness of this main component fraction collection method will be illustrated here by the results of the purification of compound libraries (altogether 6086 compounds, having an averaged success rate of 79.4%). Advanced applications, where the desired component differs from the main component, will also be discussed. 相似文献
85.
Kazimierz Frąckiewicz 《General Relativity and Gravitation》1985,17(10):953-970
It is shown that in the ECSK theory (coupled to an arbitrary tensor matter field) the degeneration distribution of the symplectic 2-form is closely connected with the action of the gauge groupG in the space of solutions to the field equations. 相似文献
86.
J. Lédé 《Journal of Thermal Analysis and Calorimetry》1996,46(1):67-84
This paper deals with models describing the thermal and chemical behaviour of solid particles undergoing fast endothermic reactions under the influence of an external heat flux. The heat source temperature is supposed to be constant, to increase with time, or to deliver a simple thermal flash. It is shown that the pyrolysis conditions (reaction temperature, conversion, etc.) depend on the chemical characteristics of the reaction and also to a large extent on the external heating conditions. Relationships are proposed to take into account these parameters. The results are applied to the thermal decomposition of NaHCO3. The pyrolysis of cellulose is finally chosen in order to show how these operating parameters can also affect the selectivity of a more complex reaction. 相似文献
87.
Electrochromatography (EC) in microfluidic chips is emerging as an attractive alternative to capillary electrophoresis (CE) for on-chip separations. This review summarizes recent developments in the rapidly growing area of chip electrochromatography with a focus on "column" technologies. Relevant achievements are summarized according to the types of stationary phase used for the separations including open channels, microfabricated structures, and channels packed with beads or containing a porous monolith. The advantages and disadvantages of each, as well as practical aspects of their application, are discussed. The analytical performance of these devices is demonstrated with separations involving various families of compounds mostly in the reversed-phase chromatographic mode. 相似文献
88.
Frère P Allain M Elandaloussi el H Levillain E Sauvage FX Riou A Roncali J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(4):784-792
The electrochemical and chemical oxidation of extended TTF 4 and 5 are analysed by cyclic voltammetry, Visible/NIR and ESR spectroscopies, and the X-ray structures of the new salts 5 x BF(4)(CH(2)Cl(2)) and 4 x ClO(4)(THF)(1/2) are presented. The effects of structural factors on the pi-dimerization or the disproportionation reaction of the cation radical are shown. The oxidation of compound 4 presents the successive formation of stable cation radical and dication species both in dichloromethane (DCM) and in a CH(3)CN/THF mixture. In contrast, for compound 5, the stability of the oxidation states strongly depends on the nature of the solvent. In DCM, the oxidation of 5 proceeds by two close one-electron transfers while in CH(3)CN/THF the dication is directly formed via a two-electron process. The X-ray structures of the two salts reveal the formation of pi-dimers of cation radical. While the dimer (5(2))(2+) is due mainly to pi-pi interactions between the conjugating spacer, the multiplication of the sulfur atoms in compound 4 contributes to stabilize the dimer by the combined effects of S-S and pi-pi interactions. Visible/NIR and ESR experiments confirm the higher tendency of 4(+)(.) to dimerize with the occurrence of dimer and monomer in solution, while for 5(+)(.) only the monomer is detected in DCM. On the other hand, by dissolution of 5 x BF(4)(CH(2)Cl(2)) in CH(3)CN, only the neutral and the dicationic states of compounds 5 are observed owing to the disproportionation reaction. 相似文献
89.
Axially disymmetric tertiary amines or quaternary ammonium salts are synthesized by double alkylation of primary or secondary amines with racemic or optically pure 2,2′-bis (bromomethyl)-1,1′-binaphthyl. Their reductive cleavage by lithium aluminium hydride in refluxing THF leads to chiral secondary or tertiary amines , substituted by a binaphthyl unit, with high yields and absence of racemization. 相似文献
90.
Polyethylene encased porous poly(chloromethylstyrene-co-divinylbenzene) disks have been prepared by polymerization in a cylindrical glass mold and cut to a disk format. Following attachment of a free radical azo initiator 4,4'-azobis(4-cyanovaleric acid) to available functionalities at the surface of the pores, the polymerization of 2-vinyl-4,4-dimethylazlactone was initiated from the surface. To avoid an undesirable increase in flow resistance and to improve the yield of grafting, divinylbenzene was added to the polymerization mixture in order to form a layer of swellable reactive polymer gel within the pores. The use of these disks as scavenging filters to remove various amines from solutions in flow-through operations was demonstrated by effective removal of amines in a very short period of time from their solutions in a variety of solvents, even including alcohols and water. 相似文献