全文获取类型
收费全文 | 4505篇 |
免费 | 177篇 |
国内免费 | 50篇 |
专业分类
化学 | 2961篇 |
晶体学 | 21篇 |
力学 | 120篇 |
数学 | 959篇 |
物理学 | 671篇 |
出版年
2023年 | 47篇 |
2022年 | 87篇 |
2021年 | 99篇 |
2020年 | 112篇 |
2019年 | 93篇 |
2018年 | 66篇 |
2017年 | 64篇 |
2016年 | 153篇 |
2015年 | 162篇 |
2014年 | 174篇 |
2013年 | 251篇 |
2012年 | 277篇 |
2011年 | 318篇 |
2010年 | 196篇 |
2009年 | 208篇 |
2008年 | 296篇 |
2007年 | 258篇 |
2006年 | 260篇 |
2005年 | 212篇 |
2004年 | 200篇 |
2003年 | 125篇 |
2002年 | 150篇 |
2001年 | 50篇 |
2000年 | 55篇 |
1999年 | 43篇 |
1998年 | 48篇 |
1997年 | 36篇 |
1996年 | 35篇 |
1995年 | 24篇 |
1994年 | 20篇 |
1993年 | 33篇 |
1992年 | 27篇 |
1991年 | 29篇 |
1990年 | 19篇 |
1989年 | 14篇 |
1988年 | 18篇 |
1987年 | 31篇 |
1985年 | 20篇 |
1984年 | 31篇 |
1983年 | 29篇 |
1982年 | 21篇 |
1981年 | 39篇 |
1980年 | 25篇 |
1979年 | 23篇 |
1978年 | 21篇 |
1977年 | 23篇 |
1976年 | 16篇 |
1974年 | 12篇 |
1973年 | 13篇 |
1972年 | 12篇 |
排序方式: 共有4732条查询结果,搜索用时 15 毫秒
61.
Andersson LK Caspersson M Baltzer L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(16):3687-3697
Five 42-residue polypeptides have been designed to fold into hairpin helix-loop-helix motifs that dimerize to form four-helix bundles, and to serve as protein scaffolds for the elucidation at the molecular level of the principles that control and fine-tune lysine and ornithine reactivities in a protein context. Site-selective control of Lys and Orn reactivity provides a mechanism for addressing directly individual residues and is a prerequisite for the site-selective functionalization of folded proteins. Several lysine and one ornithine residues were introduced on the surface and in the hydrophobic core of the folded motif. The reactivity of each residue was determined by measuring the degree of acylation of the trypsin cleaved fragments by HPLC and mass spectrometry. The most reactive residues were Orn34 and Lys19, both of which were located in d positions in the heptad repeat, and therefore in hydrophobic environments. Upon reaction of the helix-loop-helix dimer KA-I with one equivalent of mono-p-nitrophenyl fumarate, Orn34 was acylated approximately three times more efficiently than Lys19, whereas Lys10 (b position), Lys15 (g position), and Lys33 (c position) remained unmodified. In the sequence KA-I-A(15) Lys15 was replaced by an alanine residue and the selectivity of Orn34 over Lys19 increased to approximately a factor of six, probably because Lys15 had the capacity to reduce the pK(a) value of Lys19 and 85 % of site-selectively monoacylated product was obtained. The pH dependence of the acylation reaction was determined and showed that the pK(a) of the reactive residues were 9.3, more than a pK(a) unit below the magnitude of the corresponding residue in a solvent exposed position. Introducing Lys and Orn residues into a or d positions of the heptad repeat therefore serves as a mechanism of depressing their pK(a) to increase their reactivity site selectively. Extensive NMR and CD spectroscopic analyses showed that the sequences fold according to prediction. 相似文献
62.
The partial hydrogenation of benzene to cyclohexene by nanoscale ruthenium catalysts in imidazolium ionic liquids 总被引:3,自引:0,他引:3
Silveira ET Umpierre AP Rossi LM Machado G Morais J Soares GV Baumvol IJ Teixeira SR Fichtner PF Dupont J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(15):3734-3740
The controlled decomposition of an Ru(0) organometallic precursor dispersed in 1-n-butyl-3-methylimidazolium hexafluorophosphate (BMI.PF(6)), tetrafluoroborate (BMI.BF(4)) or trifluoromethane sulfonate (BMI.CF(3)SO(3)) ionic liquids with H(2) represents a simple and efficient method for the generation of Ru(0) nanoparticles. TEM analysis of these nanoparticles shows the formation of superstructures with diameters of approximately 57 nm that contain dispersed Ru(0) nanoparticles with diameters of 2.6+/-0.4 nm. These nanoparticles dispersed in the ionic liquids are efficient multiphase catalysts for the hydrogenation of alkenes and benzene under mild reaction conditions (4 atm, 75 degrees C). The ternary diagram (benzene/cyclohexene/BMI.PF(6)) indicated a maximum of 1 % cyclohexene concentration in BMI.PF(6), which is attained with 4 % benzene in the ionic phase. This solubility difference in the ionic liquid can be used for the extraction of cyclohexene during benzene hydrogenation by Ru catalysts suspended in BMI.PF(6). Selectivities of up to 39 % in cyclohexene can be attained at very low benzene conversion. Although the maximum yield of 2 % in cyclohexene is too low for technical applications, it represents a rare example of partial hydrogenation of benzene by soluble transition-metal nanoparticles. 相似文献
63.
Bo?AndreassonEmail author Jennie?Forsstr?m Lars?W?gberg 《Cellulose (London, England)》2005,12(3):253-265
It has been shown, in the present investigation, that the two methods used to investigate the pore size distribution of unbleached
chemical pulps, i.e. inverse size exclusion chromatography (ISEC) and nuclear magnetic resonance (NMR), give different average
pore radius for the pores inside the fibre wall. This is due to the way in which these experiments are performed and the sensitivity
of the methods to different types of pores in the cell wall. It was also shown that the two methods gave different results
when changing the pH and the ionic strength of the pulp suspension. The pore radius, as detected with ISEC, decreased with
both increasing ionic strength and decreasing pH, indicating a loose structure of the exterior of the fibrillar network. However,
the pore radius as detected with NMR, was virtually unaffected when increasing the ionic strength, indicating a very rigid
structure of the interior of the fibre wall. Decreasing pH though, lead to a decrease in pore radius indicating that upon
protonation of the carboxylic groups in the fibre wall, the electrostatic repulsion is diminished and the average pore radius
decreases. The NMR technique was also used to study wet strength aid penetration into the fibre wall. It was shown that wet
strength aids with a small molecular weight, penetrated the fibre wall, as detected by a decrease in pore radius. It was also
shown that addition of different wet strength aids increased the tensile index of the sheet and decreased the fibre strength,
measured as zero span-strength of the sheets. 相似文献
64.
Lindén AA Hermanns N Ott S Krüger L Bäckvall JE 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,11(1):112-119
Eight different flavin derivatives have been synthesized and the electronic effects of substituents in various positions on the flavin redox chemistry were investigated. The redox potentials of the flavins, determined by cyclic voltammetry, correlated with their efficiency as catalysts in the H2O2 oxidation of methyl p-tolyl sulfide. Introduction of electron-withdrawing groups increased the stability of the reduced catalyst precursor. 相似文献
65.
Jacques Barrau Marsan Bouchaut Hlne Lavayssiere Gabriel Dousse Jacques Satg 《Helvetica chimica acta》1979,62(1):152-154
Complexed dialkylgermylenes R2GeNR3 or R2GePy react with oxiranes or thiirane and lead to dialkylgermanone and germathione via germaoxetanes or germathiacyclobutane. The formation of germadioxolanes or germadithiolane finally observed arises from condensation of dialkylgermanone (or germathione) on oxiranes (or thiirane). 相似文献
66.
Armando Navarro-Huerta Marcus J. Jellen Jessica Arcudia Simon J. Teat Rubn A. Toscano Gabriel Merino Braulio Rodríguez-Molina 《Chemical science》2021,12(6):2181
This work describes the use of C–H⋯F–C contacts in the solid-state from the stator towards the rotator to fine-tune their internal motion, by constructing a set of interactions that generate close-fitting cavities in three supramolecular rotors 1–3I. The crystal structures of these rotors, determined by synchrotron radiation experiments at different temperatures, show the presence of such C–H⋯F–C contacts between extended carbazole stators featuring fluorinated phenyl rings and the 1,4-diazabicyclo[2.2.2]octane (DABCO) rotator. According to the 2H NMR results, using deuterated samples, and periodic density functional theory computations, the rotators experience fast angular displacements (preferentially 120° jumps) due to their low rotational activation energies (Ea = 0.8–2.0 kcal mol−1). The higher rotational barrier for 1 (2.0 kcal mol−1) is associated with a larger number of weak C–H⋯F–C contacts generated by the stators. This strategy offers the possibility to explore the correlation among weak intermolecular forces, cavity shape, and internal dynamics, which has strong implications in the design of future fine-tuned amphidynamic crystals.This work describes the use of C–H⋯F–C contacts in the solid-state from the stator towards the rotator to fine-tune their internal motion, by constructing a set of interactions that generate close-fitting cavities in three supramolecular rotors 1–3I. 相似文献
67.
Jesús M. Ruiz Gonzalez Marcos Loroo Tania Crdova Gabriel Chuchani 《Journal of Molecular Structure》2005,732(1-3):55-61
Møller-Plesset MP2/6-31G method was used to examine the gas-phase elimination of 2-substituted alkyl ethyl N,N-dimethylcarbamates. The results of these calculations support a concerted non-synchronous six-membered cyclic transition state mechanism for carbamates containing a Cβ–H bond at the alkyl side of the ester. These substrates produce the N,N-dimethylcarbamic acid and the corresponding olefin. The unstable intermediate, N,N-dimethylcarbamic acid, rapidly decomposes through a four-membered cyclic transition state to dimethylamine and CO2 gas. Correlation of the logarithm of theoretical rate coefficients against original Taft's σ* values gave an approximate straight line (ρ*=−1.39, r=0.9558 at 360 °C). In addition to this fact, when log krel is plotted against the theoretical log krel for 2-substituted ethyl N,N-dimethylcarbamates a reasonable straight line (r=0.9919 at 360 °C) is obtained, suggesting similar mechanism. 相似文献
68.
Gregorio López María D. Santana Gabriel García Gregorio Sánchez Joaquín García 《Transition Metal Chemistry》1987,12(2):130-133
Summary The organopalladium(II) complexes: Pd(2,4,6-C6F3H2)2L2 [L=triphenylphosphine(PPh3), methyldiphenylphosphine(PPh2Me), dimethylphenylphosphine-(PPhMe2) or pyridine(py); L2=1,2-bis(diphenylphosphino)ethane(dpe), 2,2-bipyridine(bipy), 1, 10-phenanthroline(phen) or ethylenediamine(en)] have been prepared by addition of the appropriate compound to the THF-dioxane solution resulting from the arylation of potassium tetrachloropalladate(II) with (2,4,6-C6F3H2)MgBr. The i.r. data suggest that the py and PPhMe2 compounds are thecis-isomers, whereas the PPh3 and PPh2Me compounds have thetrans configuration.1H- and19F-n.m.r. data for the compounds are reported. 相似文献
69.
Carrier solutions for stripping voltammetry in flow systems are deoxygenated by reaction with glucose added to the carrier. The reaction was catalyzed by glocuse oxidase and catalase co-immobilized in an enzyme reactor which was inserted before the injector. The oxygenated was removed at least as efficiently as with nitrogen purging and the voltametric behaviour of cadmium(II), lead(II) and zinc(II) was unaffected by the glucose/gluconic acid system. A particular advantage is the rapid start-up compared to the lengthy purging of carrier solution when nitrogen degassing is used. The enzyme reactor made from porous glass was effective for several months. 相似文献
70.
Pescitelli G Gabriel S Wang Y Fleischhauer J Woody RW Berova N 《Journal of the American Chemical Society》2003,125(25):7613-7628
Chiral bis-porphyrins are currently the subject of intense interest as chiral receptors and as probes in the determination of structure and stereochemistry. To provide an improved framework for interpreting the circular dichroism (CD) spectra of bis-porphyrins, we have calculated the CD spectra of chiral bis-porphyrins from three classes: I, where porphyrins can adopt a relatively wide range of orientations relative to each other; II, porphyrins have a fixed relative orientation; III, porphyrins undergo pi-stacking. The calculations primarily utilized the classical polarizability theory of DeVoe, but were supplemented by the quantum mechanical matrix method. Class I was represented by three isomers of the diester of 5alpha-cholestane-3,17-diol with 5-(4'-carboxyphenyl)-10,15,20-triphenylporphin (2-alphabeta, 2-betaalpha, 2-betabeta). Careful analysis of the torsional degrees of freedom led to two to four minimum-energy conformers for each isomer, in each of which the phenyl-porphyrin bonds had torsional angles near 90 degrees. Libration about these bonds is relatively unrestricted over a range of +/-45 degrees. CD spectra in the Soret region were calculated as Boltzmann-weighted averages over the low-energy conformers for each isomer. Three models were used: the effective transition moment model, in which only one of the degenerate Soret components is considered, along the 5-15 direction; the circular oscillator model, in which both Soret components are given equal weight; and the hybrid model, in which the 10-20 oscillator is given half the weight of the 5-15 oscillator, to mimic the effect of extensive librational averaging about the 5-15 direction. All three models predict Soret exciton couplets with signs in agreement with experiment. Quantitatively, the best results are given by the hybrid and circular oscillator models. These results validate the widely used effective transition moment model for qualitative assignments of bis-porphyrin chirality and thus permit application of the exciton chirality model. However, for quantitative studies, the circular oscillator or hybrid models should be used. The simplified effective transition moment and hybrid models are justified by the librational averaging in the class I bis-porphyrins and should only be used with such systems. Two class II bis-porphyrins were also studied by DeVoe method calculations in the circular oscillator model, which yielded good agreement with experiment. Class III bis-porphyrins were represented by 2-alphaalpha, for which the calculations gave qualitative agreement. However, limitations in the conformational analysis with the close contacts and dynamic effects in these pi-stacked systems preclude quantitative results. 相似文献