全文获取类型
收费全文 | 1208篇 |
免费 | 29篇 |
国内免费 | 2篇 |
专业分类
化学 | 816篇 |
晶体学 | 15篇 |
力学 | 38篇 |
数学 | 165篇 |
物理学 | 205篇 |
出版年
2023年 | 8篇 |
2022年 | 50篇 |
2021年 | 41篇 |
2020年 | 26篇 |
2019年 | 38篇 |
2018年 | 21篇 |
2017年 | 26篇 |
2016年 | 51篇 |
2015年 | 38篇 |
2014年 | 44篇 |
2013年 | 96篇 |
2012年 | 87篇 |
2011年 | 92篇 |
2010年 | 62篇 |
2009年 | 63篇 |
2008年 | 73篇 |
2007年 | 79篇 |
2006年 | 44篇 |
2005年 | 34篇 |
2004年 | 35篇 |
2003年 | 27篇 |
2002年 | 28篇 |
2001年 | 11篇 |
2000年 | 12篇 |
1999年 | 12篇 |
1998年 | 6篇 |
1997年 | 11篇 |
1996年 | 9篇 |
1995年 | 6篇 |
1994年 | 10篇 |
1993年 | 4篇 |
1992年 | 7篇 |
1991年 | 3篇 |
1990年 | 5篇 |
1989年 | 6篇 |
1988年 | 3篇 |
1987年 | 5篇 |
1986年 | 6篇 |
1985年 | 4篇 |
1984年 | 3篇 |
1983年 | 4篇 |
1981年 | 4篇 |
1979年 | 6篇 |
1976年 | 7篇 |
1975年 | 4篇 |
1974年 | 4篇 |
1972年 | 6篇 |
1971年 | 6篇 |
1970年 | 2篇 |
1962年 | 2篇 |
排序方式: 共有1239条查询结果,搜索用时 15 毫秒
931.
da Silva CE Vandenabeele P Edwards HG de Oliveira LF 《Analytical and bioanalytical chemistry》2008,392(7-8):1489-1496
In this study nondestructive Raman spectroscopic analysis of rosehips has been conducted by laser excitation at 1064 nm, with the objective of direct measurement of different parts of the fruit, including the inside and outside of the seeds, while preserving the integrity of the more representative chemicals. Carotenoid substances are responsible for the major Raman features in the spectra of the fruit parts; analysis of the nu(1) mode (1520 cm(-1)) strongly indicates the presence of a C(9) carotene, and analysis of the main characteristic carotene band set (C=C, C-C, and C-CH(3) stretching modes at 1520, 1157, and 1007 cm(-1), respectively) suggests the presence of beta-carotene as the main constituent. Raman spectra of the seed parts show the presence of unsaturated fatty acids, which are predominant inside the seed; these spectra also reveal the fatty products content comprises cis isomers. Analysis of the CH-stretching region bands and comparison with those in the spectra obtained from linoleic acid and commercial rosehip oil indicate that the relative band intensity of the CH-stretching mode is strongly affected by the chemical environment of the fatty acid esters present in both parts (inside and outside) of rosehips seeds. 相似文献
932.
Luiz Renato Fontes Roberto H. Schonmann 《Probability Theory and Related Fields》2008,141(3-4):513-541
We study the threshold θ ≥ 2 contact process on a homogeneous tree of degree κ = b + 1, with infection parameter λ ≥ 0 and started from a product measure with density p. The corresponding mean-field model displays a discontinuous transition at a critical point and for it survives iff , where this critical density satisfies , . For large b, we show that the process on has a qualitatively similar behavior when λ is small, including the behavior at and close to the critical point . In contrast, for large λ the behavior of the process on is qualitatively distinct from that of the mean-field model in that the critical density has . We also show that , where 1 < Φ2 < Φ3 < ..., , and .
The work of L.R.F. was partially supported by the Brazilian CNPq through grants 307978/2004-4 and 475833/2003-1, and by FAPESP
through grant 04/07276-2. The work of R.H.S. was partially supported by the American N.S.F. through grant DMS-0300672. 相似文献
933.
Nikita V. Muravyev Giorgio Luciano Heitor Luiz Ornaghi Jr. Roman Svoboda Sergey Vyazovkin 《Molecules (Basel, Switzerland)》2021,26(12)
Artificial neural networks (ANNs) are a method of machine learning (ML) that is now widely used in physics, chemistry, and material science. ANN can learn from data to identify nonlinear trends and give accurate predictions. ML methods, and ANNs in particular, have already demonstrated their worth in solving various chemical engineering problems, but applications in pyrolysis, thermal analysis, and, especially, thermokinetic studies are still in an initiatory stage. The present article gives a critical overview and summary of the available literature on applying ANNs in the field of pyrolysis, thermal analysis, and thermokinetic studies. More than 100 papers from these research areas are surveyed. Some approaches from the broad field of chemical engineering are discussed as the venues for possible transfer to the field of pyrolysis and thermal analysis studies in general. It is stressed that the current thermokinetic applications of ANNs are yet to evolve significantly to reach the capabilities of the existing isoconversional and model-fitting methods. 相似文献
934.
Inflammatory bowel disease (IBD) is a non-communicable disease characterized by a chronic inflammatory process of the gut and categorized into Crohn’s disease and ulcerative colitis, both currently without definitive pharmacological treatment and cure. The unclear etiology of IBD is a limiting factor for the development of new drugs and explains the high frequency of refractory patients to current drugs, which are also related to various adverse effects, mainly after long-term use. Dissatisfaction with current therapies has promoted an increased interest in new pharmacological approaches using natural products. Coumarins comprise a large class of natural phenolic compounds found in fungi, bacteria, and plants. Coumarin and its derivatives have been reported as antioxidant and anti-inflammatory compounds, potentially useful as complementary therapy of the IBD. These compounds produce protective effects in intestinal inflammation through different mechanisms and signaling pathways, mainly modulating immune and inflammatory responses, and protecting against oxidative stress, a central factor for IBD development. In this review, we described the main coumarin derivatives reported as intestinal anti-inflammatory products and its available pharmacodynamic data that support the protective effects of these products in the acute and subchronic phase of intestinal inflammation. 相似文献
935.
Daniella M. de Faria Maria Irene Yoshida Carlos B. Pinheiro Kassílio José Guedes Klaus Krambrock Renata Diniz Luiz Fernando C. de Oliveira Flávia C. Machado 《Polyhedron》2007
The preparation, crystal structures and spectroscopic characterization of four oxalate copper(II) complexes containing the 4,4′-dimethyl-2,2′-bipyridine (Mebpy) or di(2-pyridyl)sulfide (DPS) nitrogen ligands namely [μ-(ox){Cu(Mebpy)(NO3)(H2O)}2] (1), [μ-(ox){Cu(Mebpy)(ClO4)(H2O)}2] (2), [μ-(ox){Cu(DPS)(H2O)}2](ClO4)2 (3) and [Cu(DPS)(ox)(H2O)] · 2H2O (4) are described. X-ray diffraction measurements have shown that complexes 1–3 are binuclear, in which the oxalate anion bridges two Cu(II) centers, while the complex (4) is mononuclear and the oxalate anion adopts the terminal bidentate chelating coordination mode. In 1 and 2 the Cu(II) sites display a distorted octahedral geometry (4+2 environment) and in compounds 3 and 4 the Cu(II) centers exhibit a slightly distorted square pyramidal geometry. In addition, complexes 1 and 2 present a 2D supramolecular arrangement through hydrogen bonds between coordination water molecules and nitrate or perchlorate anions and π-stacking interaction between the pyridyl rings of Mebpy nitrogen ligands. 相似文献
936.
The use of headspace adsorbent traps in combination with gas chromatography was evaluated for the determination of volatile constituents (i.e. higher alcohols and other congeners of alcoholic fermentation) in spirits. The headspace trap technology comprises an enhanced static headspace system that allows enrichment and focusing of analytes on adsorbent traps prior to gas chromatographic separation. Extraction yields 35-55 times higher than those seen with static headspace sampling were achieved. An excellent agreement of analysis results in comparison to the European reference procedure was found (R>0.98, p<0.0001). The fully automated headspace trap procedure requires only minimal sample preparation and is easy to apply. 相似文献
937.
Development of a fast capillary electrophoresis method for determination of creatinine in urine samples 总被引:2,自引:0,他引:2
Costa AC da Costa JL Tonin FG Tavares MF Micke GA 《Journal of chromatography. A》2007,1171(1-2):140-143
The aim of this work was to develop a fast method using capillary electrophoresis for the determination of creatinine in human urine samples. The pH and constituents of the background electrolyte were selected by inspection of effective mobility of creatinine and candidate urine interferents versus pH curves. The tendency of the analyte to undergo electromigration dispersion and the buffer capacity were evaluated by the Peakmaster software and considered in the optimization of the background electrolyte, composed by 10 mmol L(-1) tris(hydroxymethyl)aminomethane and 20 mmol L(-1) 2-hydroxyisobutyric acid (HIBA) at pH 3.93. Separation was conducted in a fused-silica capillary (32 cm total length and 8.5 cm effective length, 50 microm I.D.), with short-end injection configuration and direct UV detection at 215 nm. The migration time of creatinine was only 22s. A few figures of merit of the method are as follows: good linearity in the concentration interval of 5-70 mg L(-1) (R(2)>0.99), limit of detection of 0.5 mg L(-1), inter-day precision better than 2.7% (n=9) and recovery in the range 99.0-103.7% at three concentration levels (50, 100 and 150 mg L(-1)). Urine samples were prepared by deproteination with acetonitrile (1:3 sample:acetonitrile, v/v), centrifugation and dilution of a deproteinated aliquot with 12.5 mmol L(-1) HIBA (1:4, v/v). Creatinine concentrations between 489 and 1063 mg L(-1) were obtained in the urine of four healthy volunteers. 相似文献
938.
A total of 2400 samples of commercial Brazilian C gasoline were collected over a 6-month period from different gas stations in the S?o Paulo state, Brazil, and analysed with respect to 12 physicochemical parameters according to regulation 309 of the Brazilian Government Petroleum, Natural Gas and Biofuels Agency (ANP). The percentages (v/v) of hydrocarbons (olefins, aromatics and saturated) were also determined. Hierarchical cluster analysis (HCA) was employed to select 150 representative samples that exhibited least similarity on the basis of their physicochemical parameters and hydrocarbon compositions. The chromatographic profiles of the selected samples were measured by gas chromatography with flame ionisation detection and analysed using soft independent modelling of class analogy (SIMCA) method in order to create a classification scheme to identify conform gasolines according to ANP 309 regulation. Following the optimisation of the SIMCA algorithm, it was possible to classify correctly 96% of the commercial gasoline samples present in the training set of 100. In order to check the quality of the model, an external group of 50 gasoline samples (the prediction set) were analysed and the developed SIMCA model classified 94% of these correctly. The developed chemometric method is recommended for screening commercial gasoline quality and detection of potential adulteration. 相似文献
939.
Fischer LG Leitão R Etcheverry SR de Campos-Buzzi F Vãzquez AA Heinzen HA Cechinel Filho V 《Natural product research》2007,21(8):759-766
The present study describes the analgesic activity of extracts and some fractions obtained from Erythrina crista-galli leaves in different in vivo analgesic models, using mice as experimental animals. The results showed that extract E(2) was the most active, inhibiting 48% of the abdominal constrictions when evaluated against the writhing test at 10 mg kg(-1), intraperitoneal. It also caused dose-dependent inhibition in the same model, with a calculated ID(50) value and respective confidence interval of 10 (9-14) mg kg(-1), and was more potent than reference drugs. Administered orally, E(2) caused potent antinociceptive action, with a calculated ID(50) value of 35 (26-47) mg kg(-1). The fractions F(1) and F(2) obtained from E(2) were evaluated against the writhing test at 10 mg kg(-1), causing inhibitions of 41 and 88%, respectively. The most active fraction, F(2), presented ID(50) calculated value of 3 (2-4) mg kg(-1), being about 7-fold more active than the reference drugs (acetyl salicylic acid and acetaminophen). In the formalin test, F(2) inhibited both phases of pain (44%, first phase; 58%, second phase). However, in contrast to the results observed for E(2), it was not active against the hot-plate test. The phytochemical results showed that at least four main components are present in F(2), which show a positive reaction of terpenes with TLC spray reagents. 相似文献
940.
de Sousa JP Bueno PC Gregório LE da Silva Filho AA Furtado NA de Sousa ML Bastos JK 《Journal of separation science》2007,30(16):2656-2665
A sensitive and reliable RP-HPLC method was developed using a C18 CLC-ODS (M) - 4.6x250 mm(2)column and gradient elution for the analysis of phenolic compounds in propolis raw material and its products. A procedure for the extraction of phenolic compounds using aqueous ethanol (90%) with the addition of veratraldehyde as the internal standard (IS) was developed allowing to quantify ten compounds: caffeic acid, coumaric acid, ferulic acid, cinnamic acid, aromadendrin-4'-methyl ether (AME), isosakuranetin, drupanin, artepellin C, baccharin, and 2,2-dimethyl-6-carboxyethenyl-2H-1-benzopyran acid (DCBEN). The developed method gave good detection response and linearity in the range of 20.83-533.33 microg/mL. 相似文献