全文获取类型
收费全文 | 2136篇 |
免费 | 75篇 |
国内免费 | 18篇 |
专业分类
化学 | 1350篇 |
晶体学 | 4篇 |
力学 | 69篇 |
数学 | 429篇 |
物理学 | 252篇 |
无线电 | 125篇 |
出版年
2022年 | 15篇 |
2021年 | 17篇 |
2020年 | 20篇 |
2019年 | 35篇 |
2018年 | 29篇 |
2017年 | 22篇 |
2016年 | 48篇 |
2015年 | 59篇 |
2014年 | 50篇 |
2013年 | 142篇 |
2012年 | 120篇 |
2011年 | 119篇 |
2010年 | 91篇 |
2009年 | 73篇 |
2008年 | 122篇 |
2007年 | 122篇 |
2006年 | 110篇 |
2005年 | 100篇 |
2004年 | 122篇 |
2003年 | 102篇 |
2002年 | 94篇 |
2001年 | 38篇 |
2000年 | 34篇 |
1999年 | 25篇 |
1998年 | 26篇 |
1997年 | 24篇 |
1996年 | 43篇 |
1995年 | 23篇 |
1994年 | 25篇 |
1993年 | 19篇 |
1992年 | 23篇 |
1991年 | 18篇 |
1990年 | 9篇 |
1989年 | 26篇 |
1988年 | 16篇 |
1987年 | 11篇 |
1986年 | 12篇 |
1985年 | 21篇 |
1984年 | 21篇 |
1983年 | 15篇 |
1982年 | 20篇 |
1981年 | 19篇 |
1980年 | 18篇 |
1979年 | 15篇 |
1978年 | 16篇 |
1977年 | 18篇 |
1976年 | 9篇 |
1975年 | 14篇 |
1974年 | 16篇 |
1973年 | 17篇 |
排序方式: 共有2229条查询结果,搜索用时 15 毫秒
91.
Lo C Le Blanc JC Yu CK Sze KH Ng DC Chu IK 《Rapid communications in mass spectrometry : RCM》2007,21(24):4101-4108
Transgenic Arabidopsis plants were analyzed by liquid chromatography/tandem mass spectrometry (LC/MS/MS) to investigate the glycosylation patterns of resveratrol derived from expression of a sorghum stilbene synthase gene. In negative ionization mode, the different resveratrol derivatives fragmented to yield the diagnostic deprotonated resveratrol ion at m/z 227.2. The use of precursor ion scanning led to the identification of precursor ions for different resveratrol glycosides through rapid differentiation from other phytochemical constituents. Structural information was generated simultaneously from the low-collision-energy product ion spectra using hybrid linear ion-trap mass spectrometry. Three additional resveratrol-related metabolites - a resveratrol diglucoside (M1) and trans- and cis-resveratrol acetylhexosides (M2 and M3) - were detected in the crude plant extracts. The identities of M1, M2, and M3 were confirmed by accurate mass analysis on a quadrupole time-of-flight mass spectrometer as well as beta-glucosidase digestion or UV-induced isomerization. Quantitative analyses by LC/MS in multiple reaction monitoring mode revealed that resveratrol diglucoside and cis-resveratrol acetyhexoside accumulated up to 2.79 and 10.38 microg/g, respectively, while trans-resveratrol acetylhexoside was barely detectable. This study demonstrated the power of the hybrid linear ion-trap technology for simultaneous profiling and structural characterization of stilbene-related metabolites, which would be useful to understand how resveratrol is modified in sorghum and other plants. 相似文献
92.
Pardo E Ruiz-García R Lloret F Julve M Cano J Pasán J Ruiz-Pérez C Filali Y Chamoreau LM Journaux Y 《Inorganic chemistry》2007,46(11):4504-4514
New homo- and heterometallic, hexa- and pentanuclear complexes of formula {[Cu2(mpba)2(H2O)F][Cu(Me5dien)]4}(PF6)(3).5H2O (1), {[Cu2(Me3mpba)2(H2O)2][Cu(Me5dien)]4}(ClO4)(4).12H2O (2), {[Cu2(ppba)2][Cu(Me5dien)]4}(ClO4)4 (3), and [Ni(cyclam)]{[Cu2(mpba)2][Ni(cyclam)]3}(ClO4)(4).6H2O (4) [mpba=1,3-phenylenebis(oxamate), Me3mpba=2,4,6-trimethyl-1,3-phenylenebis(oxamate), ppba=1,4-phenylenebis(oxamate), Me5dien=N,N,N'N' ',N' '-pentamethyldiethylenetriamine, and cyclam=1,4,8,11-tetraazacyclotetradecane] have been synthesized through the use of the "complex-as-ligand/complex-as-metal" strategy. The structures of 1-3 consist of cationic CuII6 entities with an overall [2x2] ladder-type architecture which is made up of two oxamato-bridged CuII3 linear units connected through two m- or p-phenylenediamidate bridges between the two central copper atoms to give a binuclear metallacyclic core of the cyclophane-type. Complex 4 consists of cationic CuII2NiII3 entities with an incomplete [2x2] ladder-type architecture which is made up of oxamato-bridged CuIINiII and CuIINiII2 linear units connected through two m-phenylenediamidate bridges between the two copper atoms to give a binuclear metallacyclophane core. The magnetic properties of 1-3 and 4 have been interpreted according to their distinct "dimer-of-trimers" and "dimer-plus-trimer" structures, respectively, (H=-J(S1A.S3A+S1A.S4A+S2B.S5B+S2B.S6B)-J'S1A.S2B). Complexes 1-4 exhibit moderate to strong antiferromagnetic coupling through the oxamate bridges (-JCu-Cu=81.3-105.9 cm-1; -JCu-Ni=111.6 cm-1) in the trinuclear and/or binuclear units. Within the binuclear metallacyclophane core, a weak to moderate ferromagnetic coupling (J'Cu-Cu=1.7-9.0 cm-1) operates through the double m-phenylenediamidate bridge, while a strong antiferromagnetic coupling (J'Cu-Cu=-120.6 cm-1) is mediated by the double p-phenylenediamidate bridge. 相似文献
93.
A convenient and selective TLC of 4-R-1,2,4-triazoles (Rtrz) and nitrogen containing aromatic rings is presented (molecules 1-11). This simple revelation method implies a complexation of heterocycles to Co(II) ions on a TLC plate, followed by a subsequent modification of the reduction potential which enables oxidation of Co(II) by permanganate. 相似文献
94.
Cador O Cattey H Halet JF Meier W Mugnier Y Wachter J Saillard JY Zouchoune B Zabel M 《Inorganic chemistry》2007,46(2):501-509
The novel cluster anion [Co(11)Te(5)(CO)15]- ([3]-) has been isolated and structurally characterized as part of the salt [Cp*(2)Nb(CO)2][3] (Cp* = C(5)Me(5)). The cobalt-centered Co10 pentagonal prism is surrounded by a shell of two mu5-Te, three mu4-Te ligands, and 15 CO groups in terminal, symmetrical, and sigma-semibridging bonding modes. The hybrid carbonyl-telluride character of the ligand shell is reflected in the solid state by a one-dimensional assembly of polyhedral prisms along a backbone of [Cp*(2)Nb(CO)2]+ cations. Electrochemical studies reveal the presence of four redox couples of [3]n (n = -1 to -5). The electronic structures of various metal-centered and empty pentagonal-prismatic (PP) M10 clusters (M = Co, Ni) are calculated and compared to those of pentagonal-antiprismatic (PA) M10 structures. Closed-shells of 152 and 156 metal valence electrons, respectively, are found to determine the electronic structures and chemical properties of these geometries. From these considerations, magnetic properties have been predicted. They have been verified for the [Co(11)Te(7)(CO)10]- cluster anion, which exhibits a singlet-triplet gap of 0.318 kcal/mol. 相似文献
95.
A series of 7-amino- and polyaminosterol analogues of squalamine and trodusquemine were synthesized involving a new stereoselective titanium reductive amination reaction in high chemical yields of up to 95% in numerous cases. These derivatives were evaluated for their in vitro antimicrobial properties against human pathogens. All the compounds present excellent activities against Gram-positive bacteria exhibiting similar results against Staphylococcus aureus and Streptococcus faecalis with minimum inhibitory concentrations (MICs) varying from 2.5 to 10 μg/mL. Numerous derivatives possess also MICs against Gram-negative Escherichia coli bacteria (MICs varying from 2.5 to 10 μg/mL) suggesting that nature of the amino group attached to the sterol moiety plays an important role on the activities of such products. 相似文献
96.
Marion Millot Marie Martin‐de‐Lassalle Marylne Chollet‐Krugler Yves Champavier Lengo Mambu Jos‐Albert Chulia Marie‐Aleth Lacaille‐Dubois 《Helvetica chimica acta》2016,99(2):169-173
Two new sesterterpenes, 1 and 2 , have been isolated from the lichen Leprocaulon microscopicum. In addition to classic chromatographic methods, a liquid‐liquid chromatography technique, namely centrifugal partition chromatography (CPC) was applied for the purification of compound 2 . The structures were determined by analyses of mass spectrometry and 1D‐ and 2D‐NMR data. The relative configuration of the isolated compounds was assigned on the basis of 2D‐NOESY experiments. The two compounds possess a rare pentacyclic carbon skeleton typical for lichen metabolism, and quite unusual in the vegetal kingdom. 相似文献
97.
Dominik Jacob Kathrin Thüring Aurellia Galliot Virginie Marchand Adeline Galvanin Akif Ciftci Karin Scharmann Michael Stock Jean‐Yves Roignant Sebastian A. Leidel Yuri Motorin Raffael Schaffrath Roland Klassen Mark Helm 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(28):9666-9670
98.
Thomas Marmin Prof. Yves L. Dory 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(27):6707-6711
Cyclohexane and cyclotri-β-alanyl have been used as scaffolds for the design of new C3-symmetric rings incorporating conjugated alkenes and dienes. All three C3-symmetric lactams share the same triangular shape and their crystal system is trigonal. They all belong to the R3 space group, R3m, R3 and R3c, for the increasingly large 12-, 18- and 24-membered rigid rings, respectively. All lactams stack on top of each other, through H-bonds and van der Waals noncovalent interactions, leading to endless supramolecular cylinders and tubes. The largest member of the family leads to tubes, the central pores of which is wide enough to let water in. A common feature of all the lactams is their very large dipole, of around 9 D, according to DFT calculations. Surprisingly, all the resulting cylinders and tubes pack side by side in the crystals, with all the dipoles pointing to the same direction. As a result, all three crystals are anisotropic and appear to be the first members of a new kind of highly polar crystals. 相似文献
99.
Conformational Mobility and Migration of the π Bonds of the [24]annulene. The configuration and the conformation of [24]annulene have been determined after a detailed analysis of its 1H-NMR spectrum recorded at −95°. At this temperature, molecular dynamics is practically frozen, and the spectrum can be correctly simulated considering eight magnetic sites with the relevant couplings. The [24]annulene exhibits alternation of the double and the single bonds with the CTTTCTTTCTTT sequence (C=cis, T=trans) expressing the connectivity of the double bonds. The signal of the 9 protons pointing inside the ring is 7.72 ppm at lower field than the signal of the 15 outer protons; this indicates a marked paramagnetic ring current. Molecular dynamics is revealed by the dependence of the spectrum upon the temperature; the simulation of the line shape of these spectra indicates that the [24]annulene in solution exists as an equilibrium of two conformers A and B ( B / A ≤0.05), both having the same configuration. Each of these conformers undergoes two isodynamic processes: a migration of the π bonds on the adjacent single bonds (bond shift) described by V and a conformational mobility described by K. The two conformers interconvert extremely rapidely. Conformer A complies with C3h symmetry, conformer B with C3 symmetry. The enthalpy, entropy, and free energy of activation for the processes described by V and K in the major conformer A have been determined: these processes are slower than those observed in [16]annulene. From their values, we could deduce that the resonance energy in the [24]-73annulene is negative and of the order of −9 to −10 kcal⋅mol−1. 相似文献
100.
The kinetics of peptide release during in vitro digestion of 4 protein sources (casein, cod protein, soy protein, and gluten) were investigated. Samples were sequentially hydrolyzed with pepsin (30 min) and pancreatin (2, 4, or 6 h) in a dialysis cell with continuous removal of digestion products. Nondialyzed digests were fractionated by ion-exchange chromatography and ultrafiltration. Animal proteins were digested at a greater rate than plant proteins. Target amino acids of specific enzymes appeared more rapidly in the dialyzed fractions when compared to other amino acids. Throughout the hydrolysis, nondialyzed digests contained a higher proportion of peptide mixtures with basic-neutral properties. Except for gluten, peptide fractions with molecular weights that exceeded 10 kDa (basic-neutral, BN > 10) were rapidly hydrolyzed during the first 2 h of pancreatin digestion. The kinetics of release and the composition of peptide fractions were different when the protein sources were compared. The analysis of amino acids revealed that threonine and proline proportions were relatively high in BN > 10 and in peptide fractions with molecular weight between 10-1 kDa (BN 10-1), while tyrosine, phenylalanine, lysine, and arginine predominated in the low molecular weight (<1 kDa) fractions. More resistant peptides were generally rich in proline and glutamic acid. The role of in vitro digestion assays in dietary protein quality evaluation is discussed. 相似文献