全文获取类型
收费全文 | 1652篇 |
免费 | 45篇 |
国内免费 | 11篇 |
专业分类
化学 | 1204篇 |
晶体学 | 7篇 |
力学 | 29篇 |
数学 | 269篇 |
物理学 | 199篇 |
出版年
2021年 | 15篇 |
2020年 | 22篇 |
2019年 | 8篇 |
2018年 | 16篇 |
2017年 | 23篇 |
2016年 | 30篇 |
2015年 | 35篇 |
2014年 | 34篇 |
2013年 | 60篇 |
2012年 | 97篇 |
2011年 | 119篇 |
2010年 | 47篇 |
2009年 | 42篇 |
2008年 | 102篇 |
2007年 | 81篇 |
2006年 | 100篇 |
2005年 | 104篇 |
2004年 | 84篇 |
2003年 | 73篇 |
2002年 | 71篇 |
2001年 | 16篇 |
2000年 | 17篇 |
1999年 | 25篇 |
1998年 | 26篇 |
1997年 | 19篇 |
1996年 | 24篇 |
1995年 | 19篇 |
1994年 | 26篇 |
1993年 | 21篇 |
1992年 | 14篇 |
1991年 | 12篇 |
1990年 | 13篇 |
1989年 | 11篇 |
1988年 | 12篇 |
1987年 | 12篇 |
1986年 | 10篇 |
1985年 | 24篇 |
1984年 | 24篇 |
1983年 | 15篇 |
1982年 | 19篇 |
1981年 | 28篇 |
1980年 | 21篇 |
1979年 | 24篇 |
1978年 | 12篇 |
1977年 | 14篇 |
1976年 | 19篇 |
1975年 | 13篇 |
1974年 | 8篇 |
1973年 | 7篇 |
1971年 | 6篇 |
排序方式: 共有1708条查询结果,搜索用时 31 毫秒
841.
We describe here the isolation of three flavone 6-C-glycosides from the leaves of Anthurium andraeanum, The two new flavones were identified through detailed spectroscopic analysis as 4"'-(3,4-dimethoxycinnamoyl)-embinin (2) and 4"'-ferruloyl-embinin (3). 相似文献
842.
Unsaturated cyclic ethers can be mildly and selectively reduced with catalytic amounts of B(C(6)F(5))(3) in the presence of an alkylsilane. The allylic position is preferentially reduced with minimal or no scrambling of olefin geometry. For electronically equivalent substrates, steric factors guide the reducing agent to the least substituted site. 相似文献
843.
Decarboxylative benzylation of nitriles is achieved via coupling of metallated nitriles with Pd-π-benzyl complexes that are generated in situ from cyanoacetic benzyl esters. In addition, decarboxylative couplings of α,α-disubstituted 2-methylfuranyl cyanoacetates can lead to either decarboxylative arylation or benzylation depending on the reaction conditions. 相似文献
844.
845.
Bunt AJ Bailey CD Cons BD Edwards SJ Elsworth JD Pheko T Willis CL 《Angewandte Chemie (International ed. in English)》2012,51(16):3901-3904
trans-2,8-Dioxabicyclodecanes were prepared in high yield with the creation of up to three stereocenters in a single pot by the acid-mediated reaction of γ,δ-unsaturated alcohols with aldehydes (see scheme, Bn=benzyl). This versatile reaction enables the stereoselective introduction of substituents at the C3, C4, C7, and C9 positions of the bicyclic framework. 相似文献
846.
847.
Baxendale IR Deeley J Griffiths-Jones CM Ley SV Saaby S Tranmer GK 《Chemical communications (Cambridge, England)》2006,(24):2566-2568
A flow process for the multi-step synthesis of the alkaloid natural product (+/-)-oxomaritidine is described, mediated through the use of microfluidic pumping systems that progress material through various packed columns containing immobilized reagents, catalysts, scavengers or catch and release agents; our route involves the combination of seven separate synthetic steps linked into one continuous sequence utilizing flow chemistry. 相似文献
848.
Sinclair J Granfeldt D Pihl J Millingen M Lincoln P Farre C Peterson L Orwar O 《Journal of the American Chemical Society》2006,128(15):5109-5113
We report that GABA(A) receptors in a patch-clamped biological cell form a short-term memory circuit when integrated with a scanning-probe microfluidic device. Laminar patterns of receptor activators (agonists) provided by the microfluidic device define and periodically update the data input which is read and stored by the receptors as state distributions (based on intrinsic multistate kinetics). The memory is discharged over time and lasts for seconds to minutes depending on the input function. The function of the memory can be represented by an equivalent electronic circuit with striking similarity in function to a dynamic random access memory (DRAM) used in electronic computers. Multiplexed biohybrid memories may form the basis of large-scale integrated biocomputational/sensor devices with the curious ability to use chemical signals including odorants, neurotransmitters, chemical and biological warfare agents, and many more as input signals. 相似文献
849.
Patra AK Bill E Weyhermüller T Stobie K Bell Z Ward MD McCleverty JA Wieghardt K 《Inorganic chemistry》2006,45(16):6541-6548
The electronic structures of four members of the electron-transfer series [Fe2(1L)4]n (n = 2-, 1-, 0, 1+) have been elucidated in some detail by electronic absorption, IR, X-band electron paramagnetic resonance (EPR), and M?ssbauer spectroscopies where (1L)(2-) represents the ligand 1,2-bis(4-tert-butylphenyl)-1,2-ethylenedithiolate(2-) and (1L*)- is its pi-radical monoanion. It is conclusively shown that all redox processes are ligand-centered and that high-valent iron(IV) is not accessible. The following complexes have been synthesized: [FeIII2(1L*)2(1L)2]0 (1), [FeIII2(2L*)2(2L)2].2CH2Cl2 (1') where (2L)(2-) is 1,2-bis(p-tolyl)-1,2-ethylenedithiolate(2-) and (2L*)- represents its pi-radical monoanion, [Cp2Co][FeIII2(1L*))(1L)3].4(toluene).0.5Et2O (2), and [Cp2Co]2[FeIII2(1L)4].2(toluene) (3). The crystal structures of 1' and 2 have been determined by single-crystal X-ray crystallography at 100 K. The ground states of complexes have been determined by temperature-dependent magnetic susceptibility measurements and EPR spectroscopy: 1' and 1 are diamagnetic (S(t) = 0); 2 (S(t) = 1/2); 3 (S(t) = 0); the monocation [Fe(III)2(1L*)3(1L)]+ possesses an S(t) = 1/2 ground state (S(t) = total spin ground state of dinuclear species). All species contain pairs of intermediate-spin ferric ions (S(Fe) = 3/2), which are strongly antiferromagnetically coupled (H = -2JS(1).S(2), where S1 = S2 = 3/2 and J = approximately -250 cm(-1)). 相似文献
850.
The hydrothermal reactions of a vanadium source, an appropriate diphosphonate ligand, and water in the presence of HF provide a series of compounds with neutral V-P-O networks as the recurring structural motif. When the {O3P(CH2)(n)PO3}4- diphosphonate tether length n is 2-5, metal-oxide hybrids of type 1, [V2O2(H2O){O3P(CH2)(n)PO3}] x xH2O, are isolated. The type 1 oxides exhibit the prototypical three-dimensional (3-D) "pillared" layer architecture. When n is increased to 6-8, the two-dimensional (2-D) "pillared" slab structure of the type 2 oxides [V2O2(H2O)4{O3P(CH2)6PO3}] is encountered. Further lengthening of the spacer to n = 9 provides another 3-D structure, type 3, constructed from the condensation of pillared slabs to give V-P-O double layers as the network substructure. When organic cations are introduced to provide charge balance for anionic V-P-O networks, oxides of types 4-7 are observed. For spacer length n = 3, a range of organodiammonium cations are accommodated by the same 3-D "pillared" layer oxovanadium diphosphonate framework in the type 4 materials [H3N(CH2)(n)NH3][V4O4(OH)2 {O3P(CH)3PO3}2] x xH2O [n = 2, x = 6 (4a); n = 3, x = 3 (4b); n = 4, x = 2 (4c); n = 5, x = 1 (4d); n = 6, x = 0.5 (4e); n = 7, x = 0 (4f)] and [H3NR]y[V4O4(OH)2 {O3P(CH)3PO3}2] x xH2O [R = -CH2(NH3)CH2CH3, y = 1, x = 0 (4g); R = -CH3, n = 2, x = 3 (4h); R = -CH2CH3, y = 2, x = 1 (4i); R = -CH2CH2CH3, y = 2, x = 0 (4j); cation = [H2N(CH2CH3)2], y = 2, x = 0 (4k)]. These oxides exhibit two distinct interlamellar domains, one occupied by the cations and the second by water of crystallization. Furthermore, as the length of the cation increases, the organodiammonium component spills over into the hydrophilic domain to displace the water of crystallization. When the diphosphonate tether length is increased to n = 5, structure type 5, [H3N(CH2)2NH3][V4O4(OH)2(H2O){O3P(CH2)5PO3}2] x H2O, is obtained. This oxide possesses a 2-D "pillared" network or slab structure, similar in gross profile to that of type 2 oxides and with the cations occupying the interlamellar domain. In contrast, shortening the diphosphonate tether length to n = 2 results in the 3-D oxovanadium organophosphonate structure of the type 7 oxide [H3N(CH2)5NH3][V3O3{O3P(CH2)2PO3}2]. The ethylenediphosphonate ligand does not pillar V-P-O networks in this instance but rather chelates to a vanadium center in the construction of complex polyhedral connectivity of 7. Substitution of piperazinium cations for the simple alkyl chains of types 4, 5, and 7 provides the 2-D pillared layer structure of the type 6 oxides, [H2N(CH2CH2)NH2][V2O2{O3P(CH)(n)PO3H}2] [n = 2 (6a); n = 4 (6b); n = 6 (6c)]. The structural diversity of the system is reflected in the magnetic properties and thermal behavior of the oxides, which are also discussed. 相似文献