全文获取类型
收费全文 | 2190篇 |
免费 | 99篇 |
国内免费 | 697篇 |
专业分类
化学 | 2726篇 |
晶体学 | 9篇 |
力学 | 10篇 |
综合类 | 17篇 |
数学 | 10篇 |
物理学 | 214篇 |
出版年
2024年 | 1篇 |
2023年 | 26篇 |
2022年 | 38篇 |
2021年 | 68篇 |
2020年 | 78篇 |
2019年 | 84篇 |
2018年 | 65篇 |
2017年 | 85篇 |
2016年 | 82篇 |
2015年 | 76篇 |
2014年 | 105篇 |
2013年 | 230篇 |
2012年 | 155篇 |
2011年 | 127篇 |
2010年 | 125篇 |
2009年 | 132篇 |
2008年 | 148篇 |
2007年 | 146篇 |
2006年 | 137篇 |
2005年 | 112篇 |
2004年 | 125篇 |
2003年 | 108篇 |
2002年 | 104篇 |
2001年 | 74篇 |
2000年 | 66篇 |
1999年 | 72篇 |
1998年 | 44篇 |
1997年 | 39篇 |
1996年 | 43篇 |
1995年 | 48篇 |
1994年 | 45篇 |
1993年 | 42篇 |
1992年 | 30篇 |
1991年 | 25篇 |
1990年 | 16篇 |
1989年 | 14篇 |
1988年 | 12篇 |
1987年 | 10篇 |
1986年 | 13篇 |
1985年 | 2篇 |
1984年 | 7篇 |
1983年 | 6篇 |
1982年 | 4篇 |
1981年 | 5篇 |
1980年 | 4篇 |
1979年 | 1篇 |
1978年 | 2篇 |
1977年 | 2篇 |
1976年 | 2篇 |
1974年 | 1篇 |
排序方式: 共有2986条查询结果,搜索用时 15 毫秒
1.
Herein, we successfully construct the 3D biocompatible graphene through crosslinking 2D graphene nanosheet onto carbon fiber paper with poly(diallyldimethylammonium chloride) (PDDA) as anode of the alcohol biofuel cell. Compared with the bioanode without 3D graphene, the current density and output power of PDDA-graphene-ADH bioanode is increased by 23 % and 41 % at a high concentration of ethanol at pH 8.9, suggesting the stabilization role of graphene in enzyme loading. The study provides us a deep analysis on structures and performances of the bioanode incl. electrochemistry, X-ray photoelectron spectra, and atomic force microscopy images, which is significant to develop the new methods to construct 3D porous electrodes in energy conversion device. 相似文献
2.
3.
Nabil N. AL‐Hashimi Rand O. Shahin Aqeel N. AL‐Hashimi Ajeal M. Al Ajeal Lubna H. Tahtamouni Chanbasha Basheer 《Biomedical chromatography : BMC》2019,33(2)
A new cetyl‐alcohol‐reinforced hollow fiber solid/liquid‐phase microextraction (CA–HF–SLPME) followed by high‐performance liquid chromatography–diode array detection (HPLC–DAD) method was developed for simultaneous determination of ezetimibe and simvastatin in human plasma and urine samples. To prepare the CA–HF–SLPME device, the cetyl‐alcohol was immobilized into the pores of a 2.5 cm hollow fiber micro‐tube and the lumen of the micro‐tube was filled with 1‐octanol with the two ends sealed. Afterwards, the prepared device was introduced into 10 mL of the sample solution containing the analytes with agitation. Under optimized conditions, calibration curves plotted in spiked plasma and urine samples were linear in the ranges of 0.363–25/0.49–25 μg L?1 for ezetimibe/simvastatin and 0.193–25/0.312–25 μg L?1 for ezetimibe/simvastatin in plasma and urine samples, respectively. The limit of detection was 0.109/0.174 μg L?1 for ezetimibe/simvastatin in plasma and 0.058/0.093 μg L?1 for ezetimibe/simvastatin in urine. As a potential application, the proposed method was applied to determine the concentration of selected analytes in patient plasma and urine samples after medication and satisfactory results were achieved. In comparison with reference methods, the CA–HF–SLPME–HPLC–DAD method demonstrates considerable potential in the biopharmaceutical analysis of selected drugs. 相似文献
4.
In this study, we present a versatile and easy procedure for modifying a cobalt ferrite nanoparticle step by step. A new nanocatalyst was prepared via CuII immobilized onto CoFe2O4@HT@Imine. The catalyst was fully characterized by Fourier‐transform infrared (FT‐IR), energy‐dispersive X‐ray spectroscopy (EDX), field emission scanning electron microscopy (FE‐SEM), X‐ray diffraction (XRD), and vibrating sample magnetometer (VSM) analyses. The current procedure as a green protocol offers benefits including a simple operational method, an excellent yield of products, mild reaction conditions, minimum chemical wastes, and short reaction times. Without any significant reduction in the catalytic performance, up to five recyclability cycles of the catalyst were obtained. The optimization results suggest that the best condition in the oxidation of benzyl alcohol derivatives is 0.003 g of the CoFe2O4@HT@Imine‐CuII catalyst, TEMPO, at 70°C under solvent‐free condition and air. 相似文献
5.
Anthony Blanchard Flavien Melis Fabrice Gouanvé Jean-Matthieu Brouillat Eliane Espuche 《Journal of polymer science. Part A, Polymer chemistry》2021,59(1):70-83
The influences of the molar mass (low, medium, and high) and content of poly(vinyl alcohol) (PVOH) dispersed by melt-blending in an ethylene vinyl alcohol (EVOH) copolymer on the morphology, microstructure, thermal, mechanical, and oxygen barrier properties were investigated. Multilayer films with external low-density polyethylene layers and inner EVOH/PVOH blend layer and respective monolayer films were elaborated and characterized. EVOH/PVOH blends exhibited a good compatibility because of the initial presence of PVOH segments in EVOH. The detailed quantitative analysis of the morphology performed for all blends showed that the finest dispersion was obtained with the PVOH with the lowest molar mass. The properties of the films as a function of the PVOH content and its molar mass were determined herein. Significant improvement of barrier properties was obtained at moderated water activities (up to aw = 0.6) by using the PVOH with the lowest molar mass. Compared to the neat EVOH material, the oxygen permeability coefficients decreased by a factor 2 by adding 15 vol% PVOH while the thermal and mechanical properties remained similar. 相似文献
6.
Farid Farajollahi Othmar Marti Masoud Amirkhani 《Journal of Polymer Science.Polymer Physics》2015,53(10):709-718
The condensation of water vapor on a volatile polymeric solution leads to a porous surface after evaporation of both solvent and water. However, the stabilization of the water microdroplet is of great importance, which can be achieved using specific polymer or adding a third substance to the polymer solution. Short chain alcohols (methanol, ethanol, and n‐propanol) are utilized to fabricate a self‐assembled porous honeycomb film of linear, low molecular weight polystyrene using the breath figure technique. A combination of breath figure processing and the effect of alcohol on a water droplet can stabilize the pattern and make pores on the surface of the polymer film. The quality of the porous honeycomb film is strongly dependent on the type of alcohols and the concentration of polymer. In a specific range of polymer and alcohol concentration, pores cover all the surface of the polymer film. This method offers the possibility of producing a honeycomb structure with no trace of additive residual after the fabrication process and avoiding polymer modification. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 709–718 相似文献
7.
Miscible blends of poly(ethylene oxide) with brush copolymers of poly(vinyl alcohol)‐graft‐poly(l‐lactide) 下载免费PDF全文
Ainhoa Lejardi Jose‐Ramon Sarasua Agustin Etxeberria Emilio Meaurio 《Journal of Polymer Science.Polymer Physics》2016,54(13):1217-1226
Even though poly(ethylene oxide) (PEO) is immiscible with both poly(l ‐lactide) (PLLA) and poly(vinyl alcohol) (PVA), this article shows a working route to obtain miscible blends based on these polymers. The miscibility of these polymers has been analyzed using the solubility parameter approach to choose the proper ratios of the constituents of the blend. Then, PVA has been grafted with l ‐lactide (LLA) through ring‐opening polymerization to obtain a poly(vinyl alcohol)‐graft‐poly(l ‐lactide) (PVA‐g‐PLLA) brush copolymer with 82 mol % LLA according to 1H and 13C NMR spectroscopies. PEO has been blended with the PVA‐g‐PLLA brush copolymer and the miscibility of the system has been analyzed by DSC, FTIR, OM, and SEM. The particular architecture of the blends results in DSC traces lacking clearly distinguishable glass transitions that have been explained considering self‐concentration effects (Lodge and McLeish) and the associated concentration fluctuations. Fortunately, the FTIR analysis is conclusive regarding the miscibility and the specific interactions in these systems. Melting point depression analysis suggests that interactions of intermediate strength and PLOM and SEM reveal homogeneous morphologies for the PEO/PVA‐g‐PLLA blends. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1217–1226 相似文献
8.
As the enantiomers of 1-phenylethanol are valuable intermediates in several industries, the lipase catalyzed kinetic resolution of (R,S) -1-phenylethanol is a relevant research topic. In this study, the goal was to determine the optimum reaction parameters to produce enantiomerically pure 1-phenylethanol by lipase (Novozyme 435) catalyzed kinetic resolution using response surface methodology (RSM). Reactions were performed with 40–400 mM (R,S)-1-phenylethanol, 120–1200 mM vinyl acetate and 2–22 mg/mL biocatalyst concentrations (BC L ), at 20–60 °C and with a stirring rate of 50–400 rpm for 5–120 min. The samples were analyzed using high performance liquid chromatography (HPLC) with a Chiralcel OB column. Optimum reaction parameters to reach 100% enantiomeric excess for the substrate ( ee s ) were determined as follows: substrate concentration (C s ): 240 mM, BC L : 11 mg/mL, at 42 °C with a reaction time of 75 min. Model validation was performed using these conditions and ee s was calculated as 100%, which indicates the predicted model was efficient and accurate. When compared to the literature, it was observed that the reaction time decreased significantly. This is an important result considering the industrial scale perspective. 相似文献
9.
Xiao-Guang Yang Feng-Huan Du Jun-Jie Li Prof. Dr. Chi Zhang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(27):e202200272
The development of convenient new methods for the synthesis of organic azides is highly desirable. Herein, we report a practical method for dehydroxyazidation of alcohols via an SN2 pathway involving PPh3 and trifunctional benziodazolone-based hypervalent azido-iodine(III) reagents, which function as an electrophilic center, an azido source, and a base. This mild, chemoselective method was used for late-stage azidation of structurally complex alcohols, as well as for a new synthetic route to the antiepileptic drug rufinamide. The reaction mechanism was also investigated both experimentally and computationally. 相似文献
10.
Haruki Inoue Dr. Shin-ichi Naya Atsunobu Akita Dr. Hisashi Sugime Prof. Dr. Hiroaki Tada 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(46):e202201653
Gold nanoparticles with different mean sizes were formed on antimony-doped tin oxide nanocrystals by the temperature-varied deposition-precipitation method (Au/ATO NCs). Au/ATO NCs possess strong absorption in the near-infrared region due to Drude excitation in addition to the localized surface plasmon resonance (LSPR) of AuNPs around 530 nm. Au/ATO NCs show thermally activated catalytic activity for the oxidation of cinnamyl alcohol to cinnamaldehyde by hydrogen peroxide. The catalytic activity increases with a decrease in the mean Au particle size (dAu) at 5.3 nm≤dAu≤8.2 nm. Light irradiation (λex >660 nm, ∼0.5 sun) of Au/ATO NCs increases the rate of reaction by more than twice with ∼95 % selectivity. Kinetic analyses indicated that the striking enhancement of the reaction stems from the rise in the temperature near the catalyst surface of ∼30 K due to the photothermal effect of the ATO NCs. 相似文献