全文获取类型
收费全文 | 6176篇 |
免费 | 644篇 |
国内免费 | 594篇 |
专业分类
化学 | 3832篇 |
晶体学 | 36篇 |
力学 | 207篇 |
综合类 | 72篇 |
数学 | 2150篇 |
物理学 | 1117篇 |
出版年
2024年 | 7篇 |
2023年 | 43篇 |
2022年 | 64篇 |
2021年 | 93篇 |
2020年 | 156篇 |
2019年 | 161篇 |
2018年 | 160篇 |
2017年 | 214篇 |
2016年 | 181篇 |
2015年 | 199篇 |
2014年 | 279篇 |
2013年 | 951篇 |
2012年 | 266篇 |
2011年 | 297篇 |
2010年 | 254篇 |
2009年 | 315篇 |
2008年 | 335篇 |
2007年 | 352篇 |
2006年 | 343篇 |
2005年 | 287篇 |
2004年 | 272篇 |
2003年 | 249篇 |
2002年 | 849篇 |
2001年 | 174篇 |
2000年 | 180篇 |
1999年 | 115篇 |
1998年 | 140篇 |
1997年 | 76篇 |
1996年 | 85篇 |
1995年 | 74篇 |
1994年 | 58篇 |
1993年 | 36篇 |
1992年 | 28篇 |
1991年 | 16篇 |
1990年 | 17篇 |
1989年 | 15篇 |
1988年 | 16篇 |
1987年 | 12篇 |
1986年 | 7篇 |
1985年 | 4篇 |
1984年 | 9篇 |
1982年 | 3篇 |
1981年 | 3篇 |
1980年 | 2篇 |
1979年 | 5篇 |
1978年 | 3篇 |
1974年 | 1篇 |
1973年 | 2篇 |
1968年 | 1篇 |
1936年 | 1篇 |
排序方式: 共有7414条查询结果,搜索用时 15 毫秒
81.
Alcaide B Almendros P Alonso JM Aly MF 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(14):3415-3426
Imines derived from 4-oxoazetidine-2-carbaldehydes have been found to be versatile Diels-Alder reagents in that they exhibit two reactivity patterns. 2-Azetidinone-tethered imines undergo diastereoselective reaction with Danishefsky's diene in the presence of different Lewis acids. The effect of the amount of catalyst on the conversion rate as well as on the product ratio has been studied. Under standard reaction conditions, indium(III) chloride and zinc(II) iodide provided the best yields, and indium(III) triflate the highest diastereoselectivity in the Lewis acid promoted aza-Diels-Alder cycloaddition. Treatment of the aforementioned imines with cyclopentadiene, 2,3-dimethyl-1,3-butadiene or 3,4-dihydro-2 H-pyran led to cycloadducts arising from inverse electron-demand condensation involving the beta-lactam-tethered aryl imine as the heterodiene component. In addition, the first methodology for preparing indolizidines from beta-lactams has been developed. This process involves amide bond cleavage of the beta-lactam ring in the aza-Diels-Alder cycloadducts with concomitant cyclization. Full chirality transfer occurs when the reaction is performed with an enantiomerically pure substrate. 相似文献
82.
A new and efficient formal total synthesis of (3S,4S)-balanol, a potent protein kinase C inhibitor, was accomplished from tri-O-acetyl-d-glucal. Balanol and ophiocordin consists of a chiral hexahydro azepine-containing fragment and a benzophenone fragment. The azepine core was prepared in chiral form through intramolecular aza Wittig reaction. A triphenylphosphine mediated ring expansion process was employed to form the seven-membered nitrogen heterocycle. The aldehyde equivalent key intermediate was treated with triphenylphosphine to give the azepine core. To demonstrate the applicability of the new route, a synthesis of the balanol is described. 相似文献
83.
Drying dissipative structural patterns formed in the course of drying colloidal crystals of silica spheres (110 nm in diameter)
in water, methyl alcohol, ethyl alcohol, 1-propyl alcohol, diethyl ether, and in the mixtures of ethyl alcohol with the other
solvents above have been studied on a cover glass. The macroscopic broad rings were formed in the outside edges of the dried
film for all the solvents examined. Furthermore, much distinct broad rings appeared in the inner area when the solvents were
ethyl alcohol, methyl alcohol, and their mixtures. Profiles of the thickness of the dried films were sensitive to the organic
solvents and explained well with changes in the surface tensions, boiling points, and viscosities of the solvents. The macroscopic
and microscopic spoke-like crack patterns formed. The drying area (or the drying time) increased (or decreased) as the surface
tension of the solvent decreased. However, the absolute values of these drying parameters are determined also by the boiling
points of the solvents. Importance of the fundamental properties of the solvents is supported in addition to the characteristics
of colloidal particles in the drying dissipative pattern formation. 相似文献
84.
Stereoisomers of 1,5,6,7(H)- and 1,5,6,7(H)-guai-11(13)-en-6,12-olides are calculated using molecular mechanics. The possibility of forming various conformations in the 7-membered ring is examined as a function of the fusion to the 5-membered C-ring. The effect of the methyl orientation on the conformation of the 7-membered ring and the relative stability of the conformers are discussed.Insitute of Phytochemistry, Karaganda, fax (3212)-43-37-73. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 54–56, January–February, 2000. 相似文献
85.
本文研究了2,4-二氧代-1,3,2-苯并二氮磷杂环己烷的磷氢键对β-硝基苯乙烯、丙烯酸酯、丙烯腈及二硫化碳的加成反应,共合成了18个新的加成产物.发现通过选用不同的碱或控制碱的用量.可选择性的进行加成或开环反应.由X衍射证实:在加成产物的结构中,环外P-C键构象因受磷杂环船式构象影响,以邻位交叉式(A)为主. 相似文献
86.
C. André L. Ismaili M. Thomassin T. T. Truong B. Refouvelet Y. C. Guillaume 《Chromatographia》2003,58(3-4):165-170
Summary Lithium chloride (LiCl) effect on the retention process of a phenol derivative series was investigated on two types of fluorinated stationary phase (i.e. a silica grafted with fluorinated linear alkyl chain (L-FSP) and a silica grafted with fluorinated aromatic ring stationary phase (A-FSP)). The results showed that the solute retention is enhanced when the A-FSP was used instead of the L-FSP due to additional – interactions. For the two fluorinated stationary phases (FSPs), the phenol-FSP association process can be divided into two LiCl concentration domains demonstrated that it was important to take into account the adsorbtion of Cl– anion on the FSPs. As well, enthalpy-entropy compensation revealed that the solute retention mechanism was independent of the solute molecular structure and confirmed a change on the solute retention mechanism at a critical LiCl concentration value around 0.02M. 相似文献
87.
《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(1):324-330
A range of polynorbornenes (PNBs) with fused dipolar pendant groups at C‐5,6 positions was synthesized by ring‐opening metathesis polymerization catalyzed by a ruthenium carbene complex (Grubbs I). Photophysical studies, EFISH measurements, and atomic force microscopy images have been used to investigate the structures and morphology of these polymers. These results suggest that the polymers may adopt rigid rod‐like structures. The presence of the double bonds in PNBs appeared to be indispensable for the rigidity of the polymers. Interaction between unsaturated pendant groups may result in coherent alignment leading to a rod‐like structure. 相似文献
88.
The isolation and structure elucidation of xyloccensin L from the stem bark of Xylocarpus granatum is described. Xyloccensin L is a highly oxidized heptacyclic A, B, D-seco limonoid with an α-8, 30-epoxy ring and a rare 1, 29 oxygen bridge. 相似文献
89.
Schmidt EM Gleiter R Rominger F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(8):1814-1822
The synthesis of 1-alkyl and 1-aryl-1-azacyclotetradeca-3,5,10,12-tetraynes was achieved in a stepwise approach. The key intermediate was 1,13-dibromotrideca-2,4,9,11-tetrayne (18). Reaction with methyl- (19 a), ethyl- (19 b), isopropyl- (19 c), n-butyl- (19 d), and tert-butylamine (19 e) as well as aniline (19 f) and p-methoxyaniline (19 g) gave the corresponding 14-membered tetraynes 20 a-20 g. The ring inversion process of 20 b was studied by variable temperature (1)H NMR spectroscopy. From these measurements a value of 10.6 kcal mol(-1) was calculated for DeltaG(not equal). X-ray investigations on single crystals of 20 b, 20 c, and 20 f revealed the axial position for the substituent at each nitrogen atom. For 20 b we encountered the chair conformation, for 20 c both chair and boat conformations, and for 20 f the boat conformation in the solid state. The reaction of 20 c with concentrated HCl in ethanol yielded 2,10-dichloro-6-isopropyl-6-azatricyclo[9.3.0.0(4,8)]tetradeca-1(11),2,4(8),9-tetraene (25 c). Compound 25 c was oxidized by 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) to 27 c. The structure of the latter was confirmed by X-ray investigations. The reaction of 20 c in aqueous HCl lead to the formation of 10-chloro-2-isopropyl-1,3,4,6,7,8-hexahydro-2H-benzo[g]isoquinolin-9-one (37 c). The structure of 37 c was verified by X-ray studies on single crystals. 相似文献
90.
Synthesis,Structure, and Fluxionality of Strained Hypercoordinate Silicon‐Bridged [1]Ferrocenophanes
《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(13):3042-3054
The first hypercoordinate sila[1]ferrocenophanes [fcSiMe(2‐C6H4CH2NMe2)] ( 5 a ) and [fcSi(CH2Cl)(2‐C6H4CH2NMe2)] ( 5 b ) (fc=(η5‐C5H4)Fe(η5‐C5H4)) were synthesized by low‐temperature (?78 °C) reactions of Li[2‐C6H4CH2NMe2] with the appropriate chlorinated sila[1]ferrocenophanes ([fcSiMeCl] ( 1 a ) and [fcSi(CH2Cl)Cl] ( 1 d ), respectively). Single‐crystal Xray diffraction studies revealed pseudo‐trigonal bipyramidal structures for both 5 a and 5 b , with one of the shortest reported Si???N distances for an sp3‐hybridized nitrogen atom interacting with a tetraorganosilane detected for 5 a (2.776(2) Å). Elongated Si? Cipso bonds trans to the donating NMe2 arms (1.919(2) and 1.909(2) Å for 5 a and 5 b , respectively) were observed relative to both the non‐trans bonds ( 5 a : 1.891(2); 5 b : 1.879(2) Å) and the Si? Cipso bonds of the non‐hypercoordinate analogues ([fcSiMePh] ( 1 b ): 1.879(4), 1.880(4) Å; [fcSi(CH2Cl)Ph] ( 1 e ): 1.881(2), 1.884(2)). Solution‐state fluxionality of 5 a and 5 b , suggestive of reversible coordination of the NMe2 group to silicon, was demonstrated by means of variable‐temperature NMR studies. The ΔG≠ of the fluxional processes for 5 a and 5 b in CD2Cl2 were estimated to be 35.0 and 37.6 kJ mol?1, respectively (35.8 and 38.3 kJ mol?1 in [D8]toluene). The quaternization of 5 a and 5 b by MeOTf, to give [fcSiMe(2‐C6H4CH2NMe3)][OTf] ( 7 a‐ OTf) and [fcSi(CH2Cl)(2‐C6H4CH2NMe3)][OTf] ( 7 b‐ OTf), respectively, supported the reversibility of NMe2 coordination at the silicon center as the source of fluxionality for 5 a and 5 b . Surprisingly, low room‐temperature stability was detected for 5 b due to its tendency to intramolecularly cyclize and form the spirocyclic [fcSi(cyclo‐CH2NMe2CH2C6H4)]Cl ( 9 ‐Cl). This process was observed in both solution and the solid state, and isolation and Xray characterization of 9 ‐Cl was achieved. The model compound, [Fc2Si(2‐C6H4CH2NMe2)2] ( 8 ), synthesized through reaction of [Fc2SiCl2] with two equivalents of Li[2‐C6H4CH2NMe2] at ?78 °C, showed a lack of hypercoordination in both the solid state and in solution (down to ?80 °C). This suggests that either the reduced steric hindrance around Si or the unique electronics of the strained sila[1]ferrocenophanes is necessary for hypercoordination to occur. 相似文献