全文获取类型
收费全文 | 1825篇 |
免费 | 64篇 |
国内免费 | 9篇 |
专业分类
化学 | 1209篇 |
晶体学 | 10篇 |
力学 | 65篇 |
数学 | 314篇 |
物理学 | 300篇 |
出版年
2023年 | 12篇 |
2022年 | 39篇 |
2021年 | 33篇 |
2020年 | 32篇 |
2019年 | 32篇 |
2018年 | 33篇 |
2017年 | 29篇 |
2016年 | 77篇 |
2015年 | 65篇 |
2014年 | 67篇 |
2013年 | 118篇 |
2012年 | 119篇 |
2011年 | 151篇 |
2010年 | 78篇 |
2009年 | 84篇 |
2008年 | 115篇 |
2007年 | 115篇 |
2006年 | 120篇 |
2005年 | 99篇 |
2004年 | 75篇 |
2003年 | 76篇 |
2002年 | 71篇 |
2001年 | 27篇 |
2000年 | 15篇 |
1999年 | 16篇 |
1998年 | 10篇 |
1997年 | 12篇 |
1996年 | 14篇 |
1995年 | 10篇 |
1994年 | 12篇 |
1993年 | 17篇 |
1992年 | 13篇 |
1991年 | 7篇 |
1990年 | 5篇 |
1989年 | 8篇 |
1988年 | 9篇 |
1987年 | 7篇 |
1986年 | 5篇 |
1985年 | 6篇 |
1984年 | 18篇 |
1983年 | 12篇 |
1982年 | 6篇 |
1981年 | 4篇 |
1980年 | 3篇 |
1979年 | 2篇 |
1978年 | 5篇 |
1977年 | 4篇 |
1976年 | 2篇 |
1975年 | 2篇 |
1935年 | 1篇 |
排序方式: 共有1898条查询结果,搜索用时 31 毫秒
91.
Supermolecular Columnar Liquid‐Crystalline Phosphorus Dendrimers Decorated with Sulfonamide Derivatives
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Cesar Augusto Hincapié Rosa María Sebastián Joaquín Barberá José Luis Serrano Teresa Sierra Jean‐Pierre Majoral Anne‐Marie Caminade 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(51):17047-17058
A series of supermolecular liquid crystals has been synthesized by combining phosphorus dendrimers of the zero, first, and fourth generations with sulfonamide derivatives, thus generating dendromesogens bearing 6, 12, and 96 mesogenic units on their surfaces. The relevant reactions could be monitored by 1H, 19F, and 31P{1H} NMR spectroscopies. The thermal and mesomorphic properties of the products have been studied by optical microscopy, differential scanning calorimetry, and X‐ray diffraction. All of the new macromolecules prepared in this work have been found to show mesomorphic properties over a wide temperature range; moreover, for all of the compounds, the columnar mesophases observed were maintained or vitrified at room temperature. On increasing the generation of these dendromesogens, mesophases appear at lower temperatures and remain stable over a wider temperature interval. In all cases, on the basis of X‐ray analysis, a cylindrical symmetry of the molecules can be proposed to promote the supramolecular columnar arrangement observed in the mesophases. In this type of model, the height of the dendrimer clearly increases with increasing dendrimer generation, whereas its cross‐ sectional area increases only slightly, probably due to compression of the highly hyperbranched structures as a consequence of their progressive steric constraints. The mesomorphic arrangement is governed by the peripheral sulfonamide units. 相似文献
92.
Suihan Feng Dr. Vibor Laketa Frank Stein Dr. Anna Rutkowska Dr. Aidan MacNamara Dr. Sofia Depner Prof. Ursula Klingmüller Dr. Julio Saez‐Rodriguez Priv.‐Doz. Dr. Carsten Schultz 《Angewandte Chemie (International ed. in English)》2014,53(26):6720-6723
Chemical dimerizers are powerful tools for non‐invasive manipulation of enzyme activities in intact cells. Here we introduce the first rapidly reversible small‐molecule‐based dimerization system and demonstrate a sufficiently fast switch‐off to determine kinetics of lipid metabolizing enzymes in living cells. We applied this new method to induce and stop phosphatidylinositol 3‐kinase (PI3K) activity, allowing us to quantitatively measure the turnover of phosphatidylinositol 3,4,5‐trisphosphate (PIP3) and its downstream effectors by confocal fluorescence microscopy as well as standard biochemical methods. 相似文献
93.
César R. García-Jacas Yovani Marrero-Ponce Ricardo Vivas-Reyes José Suárez-Lezcano Felix Martinez-Rios Julio E. Terán Longendri Aguilera-Mendoza 《Journal of computational chemistry》2020,41(12):1209-1227
Advances to the distributed, multi-core and fully cross-platform QuBiLS-MIDAS software v2.0 ( http://tomocomd.com/qubils-midas ) are reported in this article since the v1.0 release. The QuBiLS-MIDAS software is the only one that computes atom-pair and alignment-free geometrical MDs (3D-MDs) from several distance metrics other than the Euclidean distance, as well as alignment-free 3D-MDs that codify structural information regarding the relations among three and four atoms of a molecule. The most recent features added to the QuBiLS-MIDAS software v2.0 are related (a) to the calculation of atomic weightings from indices based on the vertex-degree invariant (e.g., Alikhanidi index); (b) to consider central chirality during the molecular encoding; (c) to use measures based on clustering methods and statistical functions to codify structural information among more than two atoms; (d) to the use of a novel method based on fuzzy membership functions to spherically truncate inter-atomic relations; and (e) to the use of weighted and fuzzy aggregation operators to compute global 3D-MDs according to the importance and/or interrelation of the atoms of a molecule during the molecular encoding. Moreover, a novel module to compute QuBiLS-MIDAS 3D-MDs from their headings was also developed. This module can be used either by the graphical user interface or by means of the software library. By using the library, both the predictive models built with the QuBiLS-MIDAS 3D-MDs and the QuBiLS-MIDAS 3D-MDs calculation can be embedded in other tools. A set of predefined QuBiLS-MIDAS 3D-MDs with high information content and low redundancy on a set comprised of 20,469 compounds is also provided to be employed in further cheminformatics tasks. This set of predefined 3D-MDs evidenced better performance than all the universe of Dragon (v5.5) and PaDEL 0D-to-3D MDs in variability studies, whereas a linear independence study proved that these QuBiLS-MIDAS 3D-MDs codify chemical information orthogonal to the Dragon 0D-to-3D MDs. This set of predefined 3D-MDs would be periodically updated as long as new results be achieved. In general, this report highlights our continued efforts to provide a better tool for a most suitable characterization of compounds, and in this way, to contribute to obtaining better outcomes in future applications. 相似文献
94.
Salvador G. Hernndez‐Vargas Carlos Alberto Cevallos‐Morillo Julio C. Aguilar‐Cordero 《Electroanalysis》2020,32(9):1938-1948
In this work 12 different ionic liquids (ILs) have been used added as co‐binders in the preparation of modified carbon paste electrodes (IL–CPEs) used for the voltammetric analysis of dopamine in Britton‐Robinson buffer. The ionic liquids studied were selected based on three main criteria: (1) increasing chain length of alkyl substituents (studying 1‐ethylimidazolium and ethyl, propyl, butyl, hexyl and decylmethylimidazolium bis(trifluoromethylsulfonyl)imide ionic liquids); (2) nature of the counter ion (dicyanamide, bis(trifluoromethylsulfonyl)imide and hexafluorophosphate) in 1‐butyl‐3‐methylimidazolium ionic liquids; and (3) cation ring structures (1‐butyl‐3‐methylimidazolium, 1‐butyl‐1‐methylpiperidinium, 1‐butyl‐1‐methylpyrrolidinium and 1‐butyl‐3‐methylpyridinium) in bis(trifluoromethylsulfonyl)imide or hexafluorophosphate (1‐butyl‐3‐methylimidazolium or 1‐butyl‐3‐methylpyridinium as cations) ionic liquids. The use of IL as co‐binders in IL–CPE results in a general enhancement of both the sensitivity and the reversibility of dopamine oxidation. In square wave voltammetry experiments, the peak current increased up to a 400 % when 1‐ethyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide was used as co‐binder, as compared to the response found with the unmodified CPE. Experimental data provide evidence that electrostatic and steric effects are the most important ones vis‐à‐vis these electrocatalytic effects on the anodic oxidation of dopamine on IL–CPE. The relative hydrophilicity of dicyanamide anions reduced the electrocatalytic effects of the corresponding ionic liquids, while the use of 1‐ethyl‐3‐methylimidazolium hexafluorophosphate or 1‐ethyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide (two relatively small and highly hydrophobic ionic liquids) as co‐binders in IL–CPE resulted in the highest electrocatalytic activity among all of the IL–CPE studied. 相似文献
95.
96.
Johannes Ihli Leonid Bloch Frank Krumeich Klaus Wakonig Mirko Holler Manuel Guizar‐Sicairos Thomas Weber Julio Cesar da Silva Jeroen Anton van Bokhoven 《Angewandte Chemie (International ed. in English)》2020,59(39):17266-17271
Hydrodesulphurization, the removal of sulphur from crude oils, is an essential catalytic process in the petroleum industry safeguarding the production of clean hydrocarbons. Sulphur removal is critical for the functionality of downstream processes and vital to the elimination of environmental pollutants. The effectiveness of such an endeavour is among other factors determined by the structural arrangement of the heterogeneous catalyst. Namely, the accessibility of the catalytically active molybdenum disulphide (MoS2) slabs located on the surfaces of a porous alumina carrier. Here, we examined a series of pristine sulfided Mo and NiMo hydrodesulphurization catalysts of increasing metal loading prepared on commercial alumina carriers using ptychographic X‐ray computed nanotomography. Structural analysis revealed a build consisting of two interwoven support matrix elements differing in nanoporosity. With increasing metal loading, approaching that of industrial catalysts, these matrix elements exhibit a progressively dissimilar MoS2 surface coverage as well as MoS2 cluster formation at the matrix element boundaries. This is suggestive of metal deposition limitations and/ or catalyst activation and following prohibitive of optimal catalytic utilization. These results will allow for diffusivity calculations, a better rationale of current generation catalyst performance as well as a better distribution of the active phase in next‐generation hydrodesulphurization catalysts. 相似文献
97.
Francisco Salgado Julio Caballero Reinaldo Vargas Alberto Cornejo 《Natural product research》2020,34(5):646-650
AbstractAlzheimer´s disease (AD) is the most common form of dementia involving Aβ and tau protein. So far, AD cure remains elusive, but considering that AD progresses throughout tau pathology, which turns tau protein an appropriate target, besides tau is also included in other neurodegenerative disorders named as tauopathies. Here, we have isolated seventeen compounds belonging to six lichens species. Due to scarce of spectroscopic data of the compound 5,7-dihydroxy-6-methylphthalide, we explained their structural elucidation based on NMR data. In this study, we show that only tenuiorin from Umbilicaria antarctica inhibited 50% of tau 4R at 100?µM. Then, we shown that molecular interactions of tenuiorin with the steric zipper model of the hexapeptide 306VQIVYK311 were studied by docking calculations and the results suggested that tenuiorin forms both hydrogen bonds with lysine and glutamine side chains and forms several hydrophobic interactions with valine and lysine from 306VQIVYK311 motif. 相似文献
98.
Eduardo Rosado Paloma Delgado-Fernndez Blanca de las Rivas Rosario Muoz Francisco Javier Moreno Nieves Corzo Cesar Mateo 《Molecules (Basel, Switzerland)》2022,27(4)
The synthesis of β-galactosyl xylitol derivatives using immobilized LacA β-galactosidase from Lactobacillus plantarum WCFS1 is presented. These compounds have the potential to replace traditional sugars by their properties as sweetener and taking the advantages of a low digestibility. The enzyme was immobilized on different supports, obtaining immobilized preparations with different activity and stability. The immobilization on agarose-IDA-Zn-CHO in the presence of galactose allowed for the conserving of 78% of the offered activity. This preparation was 3.8 times more stable than soluble. Since the enzyme has polyhistidine tags, this support allowed the immobilization, purification and stabilization in one step. The immobilized preparation was used in synthesis obtaining two main products and a total of around 68 g/L of β-galactosyl xylitol derivatives and improving the synthesis/hydrolysis ratio by around 30% compared to that of the soluble enzyme. The catalyst was recycled 10 times, preserving an activity higher than 50%. The in vitro intestinal digestibility of the main β-galactosyl xylitol derivatives was lower than that of lactose, being around 6 and 15% for the galacto-xylitol derivatives compared to 55% of lactose after 120 min of digestion. The optimal amount immobilized constitutes a very useful tool to synthetize β-galactosyl xylitol derivatives since it can be used as a catalyst with high yield and being recycled for at least 10 more cycles. 相似文献
99.
Paracyclophene based monomers can be polymerized in a living fashion using the alkylidene initiator Mo(NAr)(CHCMe2Ph)(OCMe(CF3)2)2. The cis-specific nature of the polymerization is critical, since small amounts of trans olefin in the backbone renders the material insoluble. These polymers have complex photophysical behavior, probably a consequence of the close proximity of chromophores along the polymer backbone. Polymerization of 9-(tert-butyldimethylsilyloxy)-[2.2]-paracyclophan-1-ene produces a new precursor material which furnishes PPV under remarkably mild conditions. 相似文献
100.
Least-squares support vector machines and near infrared spectroscopy for quantification of common adulterants in powdered milk 总被引:5,自引:0,他引:5
This paper proposes the use of the least-squares support vector machine (LS-SVM) as an alternative multivariate calibration method for the simultaneous quantification of some common adulterants (starch, whey or sucrose) found in powdered milk samples, using near-infrared spectroscopy with direct measurements by diffuse reflectance. Due to the spectral differences of the three adulterants a nonlinear behavior is present when all groups of adulterants are in the same data set, making the use of linear methods such as partial least squares regression (PLSR) difficult. Excellent models were built using LS-SVM, with low prediction errors and superior performance in relation to PLSR. These results show it possible to built robust models to quantify some common adulterants in powdered milk using near-infrared spectroscopy and LS-SVM as a nonlinear multivariate calibration procedure. 相似文献