全文获取类型
收费全文 | 24929篇 |
免费 | 455篇 |
国内免费 | 101篇 |
专业分类
化学 | 13838篇 |
晶体学 | 152篇 |
力学 | 758篇 |
综合类 | 9篇 |
数学 | 3480篇 |
物理学 | 7248篇 |
出版年
2022年 | 315篇 |
2021年 | 391篇 |
2020年 | 359篇 |
2019年 | 314篇 |
2018年 | 407篇 |
2017年 | 363篇 |
2016年 | 622篇 |
2015年 | 514篇 |
2014年 | 597篇 |
2013年 | 967篇 |
2012年 | 1248篇 |
2011年 | 1420篇 |
2010年 | 792篇 |
2009年 | 753篇 |
2008年 | 1195篇 |
2007年 | 1175篇 |
2006年 | 1061篇 |
2005年 | 1491篇 |
2004年 | 1525篇 |
2003年 | 1073篇 |
2002年 | 716篇 |
2001年 | 598篇 |
2000年 | 554篇 |
1999年 | 346篇 |
1998年 | 289篇 |
1997年 | 290篇 |
1996年 | 355篇 |
1995年 | 314篇 |
1994年 | 306篇 |
1993年 | 326篇 |
1992年 | 320篇 |
1991年 | 264篇 |
1990年 | 216篇 |
1989年 | 203篇 |
1988年 | 180篇 |
1987年 | 175篇 |
1986年 | 173篇 |
1985年 | 225篇 |
1984年 | 213篇 |
1983年 | 185篇 |
1982年 | 186篇 |
1981年 | 185篇 |
1980年 | 168篇 |
1979年 | 154篇 |
1978年 | 176篇 |
1977年 | 138篇 |
1976年 | 134篇 |
1975年 | 113篇 |
1974年 | 133篇 |
1973年 | 123篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
951.
Braga D Maini L de Sanctis G Rubini K Grepioni F Chierotti MR Gobetto R 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(22):5538-5548
Mechanical mixing of solid dicarboxylic acids of variable chain length HOOC(CH(2))(n)COOH (n = 1-7) with solid 1,4-diazabicyclo[2.2.2]octane generates the corresponding salts or co-crystals of the formula [N(CH(2)CH(2))(3)N]-H-[OOC(CH(2))(n)COOH] (n=1-7). Preparation of the same systems from solution has been instrumental for a full characterization of the mechanochemical products by means of single-crystal and powder-diffraction X-ray analyses, as well as by solid-state NMR. The acid-base adducts, whether involving proton transfer from the COOH group to the N-acceptor, that is having ((-))O...H-N((+)) interactions, or the formation of neutral O-H...N hydrogen bonds, show a melting point alternation phenomenon analogous to that shown by the neutral carboxylic acids. The carbon chemical shift tensors of the COOH group obtained from the sideband intensity of low speed spinning NMR spectra provide a reliable criterion for assigning the protonation state of the adducts. 相似文献
952.
Vugts DJ Jansen H Schmitz RF de Kanter FJ Orru RV 《Chemical communications (Cambridge, England)》2003,(20):2594-2595
In a multi-component reaction (MCR) of a phosphonate, nitriles, aldehydes and isocyanates, N3-functionalised dihydropyrimidines can be synthesised efficiently via a Horner-Emmons/aza Diels-Alder pathway. 相似文献
953.
1-Deoxy-D-xylulose-5-phosphate (DXP) is a key intermediate in the non-mevalonate pathway to terpenoids in bacteria, and it is the substrate for the enzyme 1-deoxy-D-xylulose-5-phosphate reductoisomerase (DXP-R). In order to study the mechanism of DXP-R, we required a flexible synthesis of the substrate which would allow the incorporation of isotopic labels, and the variation of the two stereocentres. Thus 1,4-dihydroxypent-2-yne was selectively reduced to give the E-olefin, and selective phosphorylation of the primary alcohol followed by oxidation of the secondary alcohol gave a substrate suitable for dihydroxylation. Dihydroxylation using stoichiometric OsO4 in the presence of chiral ligands gave protected DXP in high ee. Final hydrogenolysis gave DXP in quantitative yield and high purity. DXP-R was produced by rapid cloning of the dxr gene from Escherichia coli through controlled expression and ion exchange chromatography. The synthetic DXP was fully active in enzyme assays catalysed by recombinant DXP-R. 相似文献
954.
Patrick Gredin Gwenaël Corbel Jonathan P. Wright Nathalie Dupont Ariel de Kozak 《无机化学与普通化学杂志》2003,629(11):1960-1964
Ba3Cu2Al2F16 is monoclinic: a = 7.334(1)Å, b = 5.320(2)Å, c = 16.022(1)Å, β = 96.34(1)°, Z = 2. Its crystal structure was solved in the space group P21 (No. 4) from synchrotron X‐ray single crystal data using 2685 unique reflections (2639 with Fo/σ(Fo) > 4). The final R factor is 0.044. The structure consists of a succession along the c‐axis of the cell of three layers of two different kinds of sheets developing in the (a, b) plane. The first one, formulated [(AlF5)2]∞4— and hereafter named A, is built up from infinite cis‐chains of aluminium‐fluorine octahedra [AlF6], linked by two vertices and distanced by a. The second one, formulated [Cu2AlF11]∞4— and named B, is bidimensional. It is constituted of distorted copper‐fluorine octahedra [CuF6], linked by edges, which form infinite chains interconnected by three vertices of isolated [AlF6] octahedra. The stacking sequence of the sheets is (A, B, B)∞. The barium ions, 12‐coordinated, are inserted between the sheets. The crystal structure of Ba3Cu2Al2F16 is closely related to that of Ba4Cu2Al3F21. Only the proportion and the stacking sequence of the two kinds of sheets in the c‐direction differ, according to two different compositions and two different symmetries. 相似文献
955.
Elisabete Curti Douglas de Britto Srgio Paulo Campana‐Filho 《Macromolecular bioscience》2003,3(10):571-576
N,N,N‐trimethylchitosan (TMC) was prepared by reacting purified chitosan with iodomethane, in the presence of sodium hydroxide, water and sodium iodide, at room temperature. The reaction medium was N‐methyl‐2‐pyrrolidone. Different samples of TMC were obtained by adding to the reaction medium a fixed volume (5.5 mL) of aqueous NaOH solutions at different concentrations (15, 20, 30 and 40 wt.‐%) and carrying out the reactions for 9 or 24 h. The features observed in the 1H and 13C NMR spectra of these chitosan derivatives, in respect of the chemical shift, number and relative intensity of the signals, depended strongly on the excess of NaOH and H3CI added to the reaction medium, but when the lowest excess was employed, the characteristics of the derivative were not affected by the reaction time to the same extent. The average degree of quaternization of these N‐methylated derivatives of chitosan ranged from 10.5% to 44.8%, according to the reaction conditions. Increasing the excess of NaOH, in reactions carried out for 9 h, resulted in TMC samples with progressively higher content of trimethylated sites however, the reaction yields were correspondingly lower and O‐alkylation was favored in these cases.
956.
Sheyla Santa Isabel Marques Iracema Andrade Nascimento Paulo Fernando de Almeida Fábio Alexandre Chinalia 《Applied biochemistry and biotechnology》2013,171(8):1933-1943
Microalgae farming has been identified as the most eco-sustainable solution for producing biodiesel. However, the operation of full-scale plants is still limited by costs and the utilization of industrial and/or domestic wastes can significantly improve economic profits. Several waste effluents are valuable sources of nutrients for the cultivation of microalgae. Ethanol production from sugarcane, for instance, generates significant amounts of organically rich effluent, the vinasse. After anaerobic digestion treatment, nutrient remaining in such an effluent can be used to grow microalgae. This research aimed to testing the potential of the anaerobic treated vinasse as an alternative source of nutrients for culturing microalgae with the goal of supplying the biodiesel industrial chain with algal biomass and oil. The anaerobic process treating vinasse reached a steady state at about 17 batch cycles of 24 h producing about 0.116 m3CH4 kgCODvinasse ?1. The highest productivity of Chlorella vulgaris biomass (70 mg l?1 day?1) was observed when using medium prepared with the anaerobic digester effluent. Lipid productivity varied from 0.5 to 17 mg l?1 day?1. Thus, the results show that it is possible to integrate the culturing of microalgae with the sugarcane industry by means of anaerobic digestion of the vinasse. There is also the advantageous possibility of using by-products of the anaerobic digestion such as methane and CO2 for sustaining the system with energy and carbon source, respectively. 相似文献
957.
Carlos Victor Montefusco-Pereira Maria José de Carvalho Ana Paula de Araújo Boleti Lorisa Simas Teixeira Humberto Reis Matos Emerson Silva Lima 《Applied biochemistry and biotechnology》2013,170(6):1367-1378
Diabetes mellitus is a metabolic disease characterized by abnormally high plasma glucose levels, leading to major complications, such as insulin resistance, obesity, hyperlipidemia, and hypertension, also with alterations in the immune and neuronal systems. Brazilian plants have been studied as important sources for new molecules with medicinal properties. The genus Passiflora known as “Maracujá” has been used as a traditional folk medicine for a long time, so an investigation was performed regarding an endemic kind of passion fruit (Passiflora nitida Kunth) from Amazonas, Brazil. Here, we aimed to determine its potential biological activity against metabolic syndrome, oxidative stress, pain, and inflammation. The hydroethanol leaf extract revealed an in vitro α-glucosidase inhibitory activity of 50 % inhibitory concentration (IC50)?=?6.78?±?0.31 μg/mL and an α-amylase inhibition of IC50?=?93.36?±?4.37. In vivo, experiments of different saccharide tolerance resulted in significant glycemia control and, with alloxan-diabetic mice, resulted in a decrease of total cholesterol, a hypoglycemic effect, and an antioxidant activity by thiobarbituric acid-reactive substances measurement. Also, it decreased the carrageenan-induced edema volume and the rate of writhing as a nociceptive response. These results indicate positive effects of P. nitida extract and its potential to inhibit metabolic syndrome. 相似文献
958.
Fernanda Cortez Lopes Deise Michele Tichota Jamile Queiroz Pereira Jéferson Segalin Alessandro de Oliveira Rios Adriano Brandelli 《Applied biochemistry and biotechnology》2013,171(3):616-625
The search for new sources of natural pigments has increased, mainly because of the toxic effects caused by synthetic dyes used in food, pharmaceutical, textile, and cosmetic industries. Fungi provide a readily available alternative source of natural pigments. In this context, the fungi Penicillium chrysogenum IFL1 and IFL2, Fusarium graminearum IFL3, Monascus purpureus NRRL 1992, and Penicillium vasconiae IFL4 were selected as pigments producers. The fungal identification was performed using ITS and part of the β-tubulin gene sequencing. Almost all fungi were able to grow and produce water-soluble pigments on agro-industrial residues, with the exception of P. vasconiae that produced pigments only on potato dextrose broth. The production of yellow pigments was predominant and the two strains of P. chrysogenum were the largest producers. In addition, the production of pigments and mycotoxins were evaluated in potato dextrose agar using TOF-MS and TOF-MS/MS. Metabolites as roquefortine C, chrysogine were found in both extracts of P. chrysogenum, as well fusarenone X, diacetoxyscirpenol, and neosolaniol in F. graminearum extract. In the M. purpureus extract, the pigments monascorubrin, rubropunctatin, and the mycotoxin citrinin were found. The crude filtrates have potential to be used in the textile industry; nevertheless, additional pigment purification is required for food and pharmaceutical applications. 相似文献
959.
Ch. Jesús F. Socorro M. Rodríguez de Rivera 《Journal of Thermal Analysis and Calorimetry》2013,113(3):1003-1007
A calorimetric sensor has been developed for local and direct measurement of calorific dissipations in different parts of the human body. The constructed prototype has a detection surface of 36 cm2. The calibration of the sensor is based on a semi-empirical model that permits to simulate the operation of the device, making easier an operational functioning method. The device is modeled as a system with two inputs and two outputs. The inputs are the calorific power (W) that is intended to be measured and the power (W pid) that dissipates a resistance, keeping constant the thermostat temperature through the use of a PID controller. The outputs are the thermostat temperature (T pid) and the calorimetric signal (y) that provides the thermopile that is in contact with the body. 相似文献
960.
A methodology for kinetic modeling of conversion processes is presented.The proposed approach allows to overcome the lack of molecular detail of the petroleum fractions and to simulate the reactions of the process by means of a two-step procedure.In the first step,a synthetic mixture of molecules representing the feedstock is generated via a molecular reconstruction method,termed SR-REM molecular reconstruction.In the second step,a kinetic Monte Carlo method,termed stochastic simulation algorithm(SSA),is used to simulate the effect of the conversion reactions on the mixture of molecules.The resulting methodology is applied to the Athabasca vacuum residue hydrocracking.An adequate molecular representation of the vacuum residue is obtained using the SR-REM algorithm.The reaction simulations present a good agreement with the laboratory data for Athabasca vacuum residue conversion.In addition,the proposed methodology provides the molecular detail of the vacuum residue conversion throughout the reactions simulations. 相似文献