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191.
采用Gaussian软件和HF方法, 通过从头计算(ab initio)法选取4-31G基组计算锂离子嵌入聚噻吩过程中结构与结合能的变化关系. 发现噻吩聚合时主要生成三或四聚合物. 聚合物在Li原子(或Li+离子)嵌入后, 聚噻吩间距离明显变小, 同时发生电荷转移, 形成稳定嵌合物; 并使噻吩环的C-α—C-β键级变小. 同时, 研究了锂离子(或原子)嵌入后体系的HOMO, LUMO能级. 聚噻吩在嵌入锂离子时LUMO轨道能级变为负值, 成为电池反应得电子的正极. 而金属Li2 释放Li+后的Li-的HOMO能级为+0.7427 eV, 则成为给电子的负极. 由此, 可以完成由锂/聚噻吩在高氯酸锂电解质中组成的放电过程, 并提出嵌合键级概念用来表征锂在聚噻吩间的结合程度. 相似文献
192.
Quasi-solid-state electrolytes were fabricated with mesoporous silica SBA-15 as a framework material. Ionic conductivity measurements revealed that SBA-15 can enhance the conductivity of the quasi-solid-state electrolyte. The diffusion coefficients of polyiodide ions such as Ⅰ3ˉ and Ⅰ5ˉ which were confirmed by Raman spectroscopic measurement, were about twice larger than that of I-. The optimized photoenergy conversion efficiency of dye-sensitized solar cells (DSSC) with the quasi-solid-state electrolyte was 4.3% under AM 1.5 irradiation at 75 mW·cm^-2 light intensity. 相似文献
193.
In response to the impact of the Covid-19 epidemic on organic chemistry laboratory teaching, this article analyzes and discusses the current limitation of traditional organic chemistry laboratory teaching. Taking the "preparation of n-bromobutane" as an example, a new "online-offline and virtual-actual combination" teaching mode with the combination of "Tencent Meeting, MLabs, laboratory and WeChat group" is introduced. The practice of the new mode of teaching includes the following steps: pre-class online guiding by teacher, student preview and practice based on the virtual simulation platform, students and teacher discussion and operation in laboratory, and post-classcomprehensive assessment and Q&A", and good teaching effects have been received. It is significant in cultivating and improving the independent innovation and practical ability, and provides reference for the organic chemistry laboratory teaching reform and also lays a foundation for the construction of "outstanding course" of organic chemistry. 相似文献
194.
M. Patri Varsha R. Hande Swati Phadnis B. Somaiah Suhasini Roychoudhury P. C. Deb 《先进技术聚合物》2004,15(5):270-274
A Novel solid polymer electrolyte (SPE) membrane containing both ? COOH and ? SO3H group has been prepared by simultaneous method of radiation grafting of acrylic acid onto FEP followed by sulfonation. The presence of weakly acidic acrylic acid controls the swelling in water while ? SO3H group provides conductivity due to its strongly ionic characteristic. FEP‐g‐acrylic acid and its sulfonated derivatives were characterized by their properties. While the mechanical properties decreased, other properties such as ion exchange capacity (IEC), water uptake and ionic conductivity increased with increase in graft content. These properties further changed on sulfonation. Acrylic acid being weakly acidic in nature, conductivity values of the grafted membrane were quite low. However, introduction of strong ? SO3H group resulted in conductivity closer to Nafion 117. Few sulfonated membranes have been tested with respect to H2/O2 fuel cell performance. Short‐term fuel cell test for 100 hr gave a stable performance. These membranes are less expensive compared to Nafion. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
195.
The rate of electron transfer from organic sulfides to [CrV(ehba)2]− (ehba-2-ethyl-2-hydroxy butyric acid) decreases with a decrease in the polarity of the medium. The anionic surfactant, SDS and the cationic surfactant, CTAB have different effects on the kinetics of this reaction. The micellar inhibition observed in the presence of SDS is probably due to the decrease in the polarity and the electrostatic repulsion faced by the anionic oxidant from the anionic micelle and the partition of the hydrophobic substrate between the aqueous and micellar phases. The micellar catalysis in the presence of CTAB is attributed to the increase in the concentration of both reactants in the micellar phase. This micellar catalysis is observed to offset the retarding effects of the less polar micellar medium and the unfavorable charge-charge interaction between the + charge developed on S center in the transition state and the cationic micelle. This catalysis is contrary to the enormous micellar inhibition observed with IO4−, HSO5− and HCO4− oxidation of organic sulfides. 相似文献
196.
Summary Two -cyclodextrin (-CD)-containing polymers have been prepared either by condensation of -CD molecules with a bifunctional reagent or by grafting a -CD derivative on to a linear polymer (polyvinylimidazole). HPLC stationary phases were obtained by adsorption of the -CD polymers on to silica. The ability of these chromatographic supports to resolve racemic mixtures of organic compounds such as amino acid derivatives, phenylhydantoins, barbiturates, and hydroxycoumarin derivatives has been investigated. Results were found to depend on the chemical structure of the -CD polymers 相似文献
197.
Miguel A. De La Rosa José A. Navarro Mercedes Roncel 《Applied biochemistry and biotechnology》1991,30(1):61-81
The production of chemicals and fuels, or energy-rich compounds, from water by sunlight is described as a particularly attractive
means for the conversion of solar energy to a valuable renewable resource. The redox properties of photoexcited molecules
and the operating mechanism of light-driven systems are first considered. The mechanism of water oxidation carried out by
higher plants and green algae-which is actually one of the most important biochemical reactions—as well as that of artificial
photosystems, up-to-now designed trying to simulate the natural process with higher efficiency and simplicity, are likewise
discussed. A number of biological and chemical light-driven systems are presented as practical ways to solar energy conversion. 相似文献
198.
绿色合成氧化剂高铁酸盐 总被引:13,自引:0,他引:13
高铁酸盐是绿色、无污染、高选择性和高活性的强氧化剂,其氧化性能比KMn04、O3和Cl还强,可以氧化醇类、含氮化合物、甚至烃类等有机化合物,高铁酸盐在有机物氧化合成中的应用具有很好的发展前景。本文介绍了有关高铁酸盐的制备方法、性质及有机物氧化合成方面的研究进展。 相似文献
199.
Liquid and solid cyclic peroxides derived from aliphatic ketones are explosive materials so their enthalpies of vaporization
and other thermodynamic or condensed-phase properties cannot be measured directly. In this work the enthalpies of vaporization
of peroxides at 298.15 K were estimated simply from gas chromatographic retention times measured at different temperatures.
The technique correlates changes in the retention times of compounds whose enthalpies of vaporization are known (called the
reference series), with those of the compounds of interest. If t
R′ is the adjusted retention time (retention time of each compound minus the retention time of unretained diethyl ether, used
as solvent) a plot of ln t
R′ against 1/T for each compound (reference compounds and cyclic peroxides) results in a straight line (r
2 > 0.99 for all compounds). The enthalpy of transfer from solution to the vapor state (Δsolg
H
m) can be obtained by multiplying the slope by the gas constant (R). A second plot correlates the enthalpies of transfer from
solution to the vapor state (Δsolg
H
m), as measured by gas–liquid chromatography (GLC), with enthalpies of vaporization of reference materials (Δvap
H
m at 298.15 K) available in the literature. C9–C15 fatty acid methyl esters and hydrocarbons were used as reference compounds. The enthalpies of vaporization of the cyclic
organic peroxides were calculated from the equation of the line obtained in this second correlation, the slope of which was
Δvap
H
m (at 298.15 K)/Δg
sol
H
m. The experiments were performed under isothermal conditions with a DB-5 capillary column, flame-ionization detection (FID),
and nitrogen as carrier gas. The column temperature was varied over a range of at least 30–70 K between 403 and 473 K, with
chromatograms being acquired at 10 K intervals. Enthalpies of vaporization of cyclic organic peroxides are not available in
the literature, and the values given in this paper, obtained by gas chromatography, are the first to be reported. 相似文献
200.
Bikshandarkoil R. Srinivasan Christian Näther Sunder N. Dhuri Wolfgang Bensch 《Monatshefte für Chemie / Chemical Monthly》2006,137(4):397-411
Summary. Four new organic ammonium tetrathiotungstates (N–Me–enH2)[WS4] (1), (N,N′-dm-1,3-pnH2)[WS4] (2), (1,4-bnH2)[WS4] (3), and (mipaH)2[WS4] (4), (N–Me–enH2 = N-methylethylenediammonium, N,N′-dm-1,3-pnH2 = N,N′-dimethyl-1,3-propanediammonium, 1,4-bnH2 = 1,4-butanediammonium, and mipaH = monoisopropylammonium) were synthesized by the base promoted cation exchange reaction and characterized by elemental analysis,
infrared, Raman, UV-Vis and 1H NMR spectroscopy as well as single crystal X-ray crystallography. The structures of 1–4 consist of [WS4]2− tetrahedra which are linked to the organic ammonium cations via N–H⋯S hydrogen bonding. The strength and number of the S⋯H
interactions affect the W–S bond lengths as evidenced by distinct short and long W–S bonds. The IR spectra exhibit splitting
of the W–S vibrations, which can be attributed to the distortion of the [WS4]2− tetrahedron. From a comparative study of several known tetrathiotungstates it is observed that a difference of more than
0.033 ? between the longest and shortest W–S bonds in a tetrathiotungstate will result in the splitting of the asymmetric
stretching vibration of the W–S bond. 相似文献