全文获取类型
收费全文 | 2558篇 |
免费 | 80篇 |
国内免费 | 5篇 |
专业分类
化学 | 2088篇 |
晶体学 | 14篇 |
力学 | 22篇 |
数学 | 264篇 |
物理学 | 255篇 |
出版年
2024年 | 3篇 |
2023年 | 25篇 |
2022年 | 75篇 |
2021年 | 80篇 |
2020年 | 60篇 |
2019年 | 54篇 |
2018年 | 29篇 |
2017年 | 33篇 |
2016年 | 82篇 |
2015年 | 88篇 |
2014年 | 92篇 |
2013年 | 150篇 |
2012年 | 177篇 |
2011年 | 203篇 |
2010年 | 118篇 |
2009年 | 117篇 |
2008年 | 194篇 |
2007年 | 200篇 |
2006年 | 159篇 |
2005年 | 150篇 |
2004年 | 106篇 |
2003年 | 104篇 |
2002年 | 68篇 |
2001年 | 20篇 |
2000年 | 34篇 |
1999年 | 19篇 |
1998年 | 11篇 |
1997年 | 18篇 |
1996年 | 16篇 |
1995年 | 12篇 |
1994年 | 9篇 |
1993年 | 13篇 |
1992年 | 8篇 |
1991年 | 7篇 |
1990年 | 9篇 |
1988年 | 7篇 |
1987年 | 10篇 |
1986年 | 10篇 |
1985年 | 16篇 |
1984年 | 10篇 |
1983年 | 6篇 |
1982年 | 5篇 |
1981年 | 7篇 |
1980年 | 5篇 |
1979年 | 7篇 |
1978年 | 6篇 |
1975年 | 2篇 |
1938年 | 1篇 |
1933年 | 1篇 |
1931年 | 1篇 |
排序方式: 共有2643条查询结果,搜索用时 15 毫秒
181.
Duquesnoy E Marongiu B Castola V Piras A Porcedda S Casanova J 《Natural product communications》2010,5(12):1995-1998
Two samples (leaves and twigs) of Abies alba Miller from Corsica were extracted using supercritical CO2 and their chemical compositions were compared with those of the essential oils obtained from the same batch of plant material. In total 45 components were identified using combined analysis by GC (RI), GC-MS and 13C NMR. It was observed that the contents of monoterpenes (mainly represented by limonene, alpha-pinene and camphene) were significantly lower in the supercritical fluid extract (SFE) than in the essential oil (EO). Conversely, the proportions of sesquiterpenes were much higher in CO2 extracts than in essential oils (around 30% vs 4%). Cis-abienol, a diterpene alcohol, was identified only in SFE, and the proportions of this constituent (7.5% and 17.3%) were determined using quantitative 13C NMR since it was under estimated using the standard conditions of GC. 相似文献
182.
In this article, the miscibility of poly(ε‐caprolactone) (PCL) with poly(styrene‐co‐acrylonitrile) (SAN) containing 25 wt % of acrylonitrile is studied from both a qualitative and a quantitative point of view. The evidences coming from thermal analysis (differential scanning calorimetry) demonstrate that PCL and SAN are miscible in the whole range of composition. The Flory interaction parameter χ1,2 was calculated by the Patterson approximation and the melting point depression of the crystalline phase in the blends; in both cases, negative values of χ1,2 were found, confirming that the system is miscible. The interaction parameter evaluated within the framework of the mean field theory demonstrates that the miscibility of PCL/SAN blends is due to the repulsive interaction between the styrene and acrylonitrile segments in SAN. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010 相似文献
183.
Fabio Fenili Clara Rigamonti Alberto Bossi Paolo Ferruti Amedea Manfredi Stefano Maiorana Clara Baldoli Silvia Cauteruccio Emanuela Licandro Elisabetta Ranucci 《Journal of polymer science. Part A, Polymer chemistry》2010,48(21):4704-4710
A tetrathia‐[7]‐helicene bearing in the 2 and 13 positions cyanovinyl groups was used as comonomer in the Michael‐type polyaddition reaction with N,N′‐bis(β‐mercaptoethyl)piperazine. This led to a new polymer bearing tetrathia‐[7]‐helicene units regularly distributed along the polymer backbone, which may be regarded as the first example of a new family of potentially useful nonlinear optical materials. All products were structurally characterized by 1H and 13C NMR spectroscopy. Differential scanning calorimetry characterizations revealed the presence, in both monomeric and polymeric helicenes, of glass‐transition like temperatures, associated to some conformational variation of the helicene units. The optical properties, the film formation and the morphology of the polymer‐containing tetratia‐[7]‐helicenes were also investigated. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010 相似文献
184.
Diogo P. Rivelli Carlos A. H. Filho Rebeca L. Almeida Cristina D. Ropke Tânia C. H. Sawada Silvia B. M. Barros 《Photochemistry and photobiology》2010,86(5):1005-1007
Chlorogenic acid is a natural potent antioxidant. It can be used in cosmetics formulations, but for this purpose its photochemical stability should be determined to ensure that the compound will not be degraded after UV radiation exposure. To evaluate this possibility, the concentration of a chlorogenic acid solution was determined by HPLC before and after UVA and UVB irradiation. The results indicate that chlorogenic acid is not degraded under UVA or UVB irradiation. 相似文献
185.
The title compound crystallizes in the monoclinic P2(1)/c space group with a = 11.2470(3) ?, b = 5.9034(2) ?, c = 12.0886(3) ?, β = 115.143(1)°, and V = 726.58(4) ?(3) and consists of discrete monomeric NiCl(2)(o-phenylendiamine)(2) molecules. Each o-phen ligand coordinates in a bidentate mode with the chloride ions occupying trans positions in the resulting tetragonally distorted octahedral coordination sphere. Two discrete sets of N-H···Cl hydrogen bonds link the octahedral molecules into a two-dimensional network, with type 1 interactions linking adjacent monomers along the c axis and type 2 interactions linking monomers along the diagonals in the bc plane. Analysis of the magnetic data reveals the existence of weak antiferromagnetic coupling within the layers via these hydrogen bonds, in addition to the presence of zero field splitting, with the best fit obtained for a 1d antiferromagnetic model with g = 2.0917(7), J/k = -2.11(4) K [J = -1.47(3) cm(-1)], and D = 1.05(3) cm(-1) [β = D/|J| = 0.72(6)] for the model with D > 0 and g = 2.0911(6), J/k = -2.26(1) K [J = -1.57(1) cm(-1)], and D = -0.86(1) cm(-1) [β = D/|J| = 0.55(6)] for the model with D < 0. Theoretical calculations of the exchange coupling confirm the experimental results, yielding values of J(1) = -1.39 cm(-1) for the type 1 hydrogen bonds and J(2)/k = -0.56 cm(-1) for the type 2 hydrogen bonds. 相似文献
186.
The effect of different alternative techniques to the traditional aging on lees on the low molecular weight phenolic compounds of red wines was study as well as their evolution during the aging in oak wood barrels for six months. The study was carried out with Tempranillo red grapes from two consecutive vintages. The techniques assayed were the traditional aging on lees with or without the addition of exogenous β-glucanase enzymes, the use of yeast derivative preparations also with or without the addition of exogenous β-glucanase enzymes, the micro-oxygenation applied together with the aging on lees, and the use of non-toasted oak wood chips. 相似文献
187.
Silvia Reboredo Prof. Efraím Reyes Prof. Jose L. Vicario Prof. Dr. Dolores Badía Prof. Luisa Carrillo Dr. Abel de Cózar Prof. Dr. Fernando P. Cossío 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(23):7179-7188
The catalytic enantioselective [3+2] cycloaddition between azomethine ylides and α,β‐unsaturated aldehydes catalyzed by α,α‐diphenylprolinol has been studied in detail. In particular, the reaction has been extended to the use of 2‐alkenylidene aminomalonates generated in situ as azomethine ylide precursors. These reactions lead to the formation of pyrrolidines containing a 5‐alkenyl side chain with potential for chemical manipulation. Moreover, a detailed and concise computational study has been carried out to understand the exact nature of the mechanism of this reaction and especially the consequences derived from the incorporation of the chiral secondary amine catalyst on the reaction pathway. 相似文献
188.
189.
Silvia Medina-Casanellas Fernando BenaventeJosé Barbosa Victoria Sanz-Nebot 《Analytica chimica acta》2012
In this study, we explored a procedure for the preparation of an immunoaffinity (IA) sorbent for the analysis of opioid peptides by on-line immunoaffinity solid-phase extraction capillary electrophoresis–mass spectrometry (IA-SPE-CE–MS). We followed a site-specific antibody immobilization approach based on the covalent attachment of the oxidized antibodies through their carbohydrate moieties to hydrazide silica particles, using a polyclonal antibody against Endomorphin 1 and 2 (End1 and End2). The main features of the IA sorbent were studied, such as the amount of hydrazide groups and antibodies attached onto oxidized diol silica particles. Once the procedure was optimized, standard solutions of End1 and End2 were used in order to establish the IA-SPE-CE–MS methodology. Acceptable repeatability, reproducibility and linearity range values were obtained for the proposed methodology. The limits of detection (LODs) of 1 ng mL−1 were approximately 100-fold better than those obtained by CE–MS. Selectivity of the IA sorbent was good but some cross-reactivity against Dynorphin A (1–7) was observed when a mixture of several opioid peptides was analyzed. Human plasma samples spiked with End1 and End2 were also analyzed and both peptides could be detected down to 100 ng mL−1. 相似文献
190.
Rapid determination of minority organic acids in honey by high-performance liquid chromatography 总被引:8,自引:0,他引:8
Suárez-Luque S Mato I Huidobro JF Simal-Lozano J Sancho MT 《Journal of chromatography. A》2002,955(2):207-214
A rapid high-performance liquid chromatographic method for the determination of organic acids in honey is reported. Malic, maleic, citric, succinic and fumaric acids were identified and quantified in 15 min. First time repeatibility, reproducibility and recoveries were determined out for these acids in honey samples. Maleic acid was also quantified for first time by a chromatographic method. The organic acids were removed from honey by using a solid-phase extraction procedure with anion-exchange cartridges. Previously, the solution of honey was adjusted to pH 10.50 with 0.1 M NaOH and stirred for 15 min at room temperature. Then, this solution was adjusted to pH 5.00 with 0.1 M H2SO4. This procedure was carried out to avoid interferences in the baseline. The chromatographic separation was achieved with only one Spherisorb ODS-2 S5 column thermostated at 25 degrees C. Metaphosphoric acid (pH 2.20) was used as mobile phase at a flow-rate of 0.7 ml/min. Organic acids were detected with a UV-vis detector (215 nm). The precision results showed that the relative standard deviations of the repeatability and reproducibility were < or =3.20% and < or =4.86%, respectively. The recoveries of the organic acids ranged from 62.9 to 99.4%. Under optimum conditions the detection limits ranged from 0.0064 to 7.57 mg/kg and the quantification limits ranged from 0.025 to 10.93 mg/kg. 相似文献