全文获取类型
收费全文 | 1175篇 |
免费 | 53篇 |
国内免费 | 13篇 |
专业分类
化学 | 948篇 |
晶体学 | 6篇 |
力学 | 16篇 |
数学 | 125篇 |
物理学 | 146篇 |
出版年
2023年 | 6篇 |
2022年 | 15篇 |
2021年 | 25篇 |
2020年 | 15篇 |
2019年 | 24篇 |
2018年 | 18篇 |
2017年 | 19篇 |
2016年 | 33篇 |
2015年 | 27篇 |
2014年 | 50篇 |
2013年 | 65篇 |
2012年 | 88篇 |
2011年 | 96篇 |
2010年 | 65篇 |
2009年 | 44篇 |
2008年 | 81篇 |
2007年 | 86篇 |
2006年 | 85篇 |
2005年 | 78篇 |
2004年 | 56篇 |
2003年 | 61篇 |
2002年 | 52篇 |
2001年 | 17篇 |
2000年 | 20篇 |
1999年 | 11篇 |
1998年 | 7篇 |
1997年 | 11篇 |
1996年 | 15篇 |
1995年 | 6篇 |
1994年 | 7篇 |
1993年 | 5篇 |
1992年 | 9篇 |
1991年 | 4篇 |
1990年 | 2篇 |
1988年 | 7篇 |
1987年 | 2篇 |
1986年 | 4篇 |
1985年 | 5篇 |
1984年 | 6篇 |
1983年 | 3篇 |
1982年 | 2篇 |
1981年 | 4篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1977年 | 1篇 |
1975年 | 2篇 |
排序方式: 共有1241条查询结果,搜索用时 46 毫秒
51.
Klaus Bieger Miguel Tomás José Barluenga Rafael Santiago Santiago García-Granda 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4)
Abstract The title compound is the main product of the 2:1 reaction of DMAD with diazaphosphinines. The supposed mechanisms with intermediates and related products will be presented. 相似文献
52.
53.
Comparison of the performance of three ion mobility spectrometers for measurement of biogenic amines
The performance of three different types of ion mobility spectrometer (IMS) devices: GDA2 with a radioactive ion source (Airsense, Germany), UV-IMS with a photo-ionization source (G.A.S. Germany) and VG-Test with a corona discharge source (3QBD, Israel) was studied. The gas-phase ion chemistry in the IMS devices affected the species formed and their measured reduced mobility values. The sensitivity and limit of detection for trimethylamine (TMA), putrescine and cadaverine were compared by continuous monitoring of a stream of air with a given concentration of the analyte and by measurement of headspace vapors of TMA in a sealed vial. Preprocessing of the mobility spectra and the effectiveness of multivariate curve resolution techniques (MCR-LASSO) improved the accuracy of the measurements by correcting baseline effects and adjusting for variations in drift time as well as enhancing the signal to noise ratio and deconvolution of the complex data matrix to their pure components. The limit of detection for measurement of the biogenic amines by the three IMS devices was between 0.1 and 1.2 ppm (for TMA with the VG-Test and GDA, respectively) and between 0.2 and 0.7 ppm for putrescine and cadaverine with all three devices. Considering the uncertainty in the LOD determination there is almost no statistically significant difference between the three devices although they differ in their operating temperature, ionization method, drift tube design and dopant chemistry. This finding may have general implications on the achievable performance of classic IMS devices. 相似文献
54.
55.
Patrícia Santiago de Oliveira Patricio Iaci Miranda Pereira Natália Cristina Ferreira da Silva Eliane Ayres Fabiano Vargas Pereira Rodrigo Lambert Oréfice 《European Polymer Journal》2013
Polyurethane waterborne synthesis was performed using a two-step method, commonly referred to as a prepolymer method. Nanocomposites based on waterborne polyurethane and cellulose nanocrystals were prepared by the prepolymer method by altering the mode and step in which the nanofillers were incorporated during the polyurethane formation. The morphology, structural, thermal, and mechanical properties of the resulting nanocomposite films were evaluated by Fourier transform infrared spectroscopy (FTIR), small angle X-ray scattering (SAXS), scanning electron microscopy (SEM), and tensile tests. FTIR results indicated that the degree of interaction between the nanofillers and the WPU through hydrogen bonds could be controlled by the method of cellulose nanocrystal incorporation. Data obtained from SAXS experiments showed that the cellulose nanocrystals as well as the step of the reaction in which they are added influenced the morphology of the polyurethane. The reinforcing effect of CNCs on the nanocomposites depends on their morphology. 相似文献
56.
This work describes the dielectric properties of piezoelectric poly(vinylidene fluoride) (PVDF) thin films in the frequency and temperature ranges relevant for usual applications. We measured the isothermal dielectric relaxation spectra of commercial piezoelectric PVDF thin films between 10 Hz to 10 MHz, at several temperatures from 278 K to 308 K. Measurements were made for samples in mechanically free and clamped conditions, in the direction of the poling field (perpendicular to the film). We found that the imaginary part of the dielectric relaxation spectra of free and clamped PVDF samples is dominated by a peak, above 100 kHz, that can be characterized by a Havriliak-Negami function. The characteristic time follows an Arrhenius dependence on temperature. Moreover, the spectra of the free PVDF samples show two additional peaks at low frequencies which are associated with mechanical relaxation processes. Our results are important for the characterization of piezoelectric PVDF, particularly after the stretching and poling processes in thin films, and for the design and characterization of a broad range of ultrasonic transducers. 相似文献
57.
Theolyta S. Araújo Claudener S. Teixeira Maria A. P. Falcão Vanir R. Pinto Junior Mayara Quiroz Santiago Raquel G. Benevides Plínio Delatorre Jorge L. Martins Magna S. Alexandre-Moreira Benildo S. Cavada Eliane A. Campesatto Bruno A. M. Rocha 《Applied biochemistry and biotechnology》2013,171(8):1944-1955
Lectins are a structurally heterogeneous group of proteins or glycoproteins with at least one noncatalytic domain binding reversibly to a specific mono- or oligosaccharide. Monocot mannose-binding lectins are an extended superfamily of structurally and evolutionarily related proteins. In this study, we evaluated anti-inflammatory and antinociceptive effects of monocot lectin from the Canna limbata seeds (CLL). To accomplish this, CLL was purified and subjected to pharmacological assays: abdominal writhing induced by acetic acid, formalin, hot plate and Zymosan A-induced peritonitis tests. The CLL was purified by chromatographic chitin column, and the relative mass of 21 kDa observed in electrophoresis was confirmed by electrospray mass spectrometry, which also revealed that purified CLL consists of a dimer having a weight of 49,676 Da. The CLL showed nociceptive activity in the acetic acid test as well as peripheral antinociceptive response. The CLL also showed anti-inflammatory effect with the reduction of inflammation in the formalin test and neutrophil migration into the peritoneal cavity. This is the first report of anti-inflammatory activity for a monocot lectin, and it suggests a new pharmacological tool to understand inflammatory and antinociceptive processes mediated through lectins. 相似文献
58.
59.
Ghasem Marandi Lotfali Saghatforoush Rafael Mendoza-Meroño Santiago García-Granda 《Tetrahedron letters》2014
The synthesis of a number of 3-(alkylamino)-2-arylimidazo[1,2-a]pyridine-8-carboxylic acids via a facile route involving the reaction between 2-amino-3-pyridinecarboxylic acid, benzaldehyde derivatives, and isonitriles is reported. The structures of the synthesized compounds are proved by X-ray crystallography. 相似文献
60.
Dr. Santiago Alonso-Gil Dr. Kamil Parkan Dr. Jakub Kaminský Dr. Radek Pohl Dr. Takatsugu Miyazaki 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(14):e202200148
The conformational changes in a sugar moiety along the hydrolytic pathway are key to understand the mechanism of glycoside hydrolases (GHs) and to design new inhibitors. The two predominant itineraries for mannosidases go via OS2→B2,5→1S5 and 3S1→3H4→1C4. For the CAZy family 92, the conformational itinerary was unknown. Published complexes of Bacteroides thetaiotaomicron GH92 catalyst with a S-glycoside and mannoimidazole indicate a 4C1→4H5/1S5→1S5 mechanism. However, as observed with the GH125 family, S-glycosides may not act always as good mimics of GH's natural substrate. Here we present a cooperative study between computations and experiments where our results predict the E5→B2,5/1S5→1S5 pathway for GH92 enzymes. Furthermore, we demonstrate the Michaelis complex mimicry of a new kind of C-disaccharides, whose biochemical applicability was still a chimera. 相似文献