全文获取类型
收费全文 | 2431篇 |
免费 | 47篇 |
国内免费 | 254篇 |
专业分类
化学 | 2527篇 |
晶体学 | 4篇 |
力学 | 3篇 |
综合类 | 3篇 |
数学 | 23篇 |
物理学 | 172篇 |
出版年
2024年 | 1篇 |
2023年 | 38篇 |
2022年 | 38篇 |
2021年 | 41篇 |
2020年 | 45篇 |
2019年 | 35篇 |
2018年 | 31篇 |
2017年 | 47篇 |
2016年 | 43篇 |
2015年 | 30篇 |
2014年 | 112篇 |
2013年 | 176篇 |
2012年 | 110篇 |
2011年 | 183篇 |
2010年 | 148篇 |
2009年 | 164篇 |
2008年 | 159篇 |
2007年 | 208篇 |
2006年 | 199篇 |
2005年 | 185篇 |
2004年 | 168篇 |
2003年 | 110篇 |
2002年 | 89篇 |
2001年 | 33篇 |
2000年 | 46篇 |
1999年 | 51篇 |
1998年 | 35篇 |
1997年 | 29篇 |
1996年 | 23篇 |
1995年 | 35篇 |
1994年 | 28篇 |
1993年 | 13篇 |
1992年 | 20篇 |
1991年 | 11篇 |
1990年 | 8篇 |
1989年 | 11篇 |
1988年 | 7篇 |
1987年 | 13篇 |
1986年 | 1篇 |
1985年 | 2篇 |
1984年 | 2篇 |
1981年 | 1篇 |
1979年 | 2篇 |
1973年 | 1篇 |
排序方式: 共有2732条查询结果,搜索用时 15 毫秒
1.
In this study, parenchyma cellulose, which was extracted from maize stalk pith as an abundant source of agricultural residues, was applied for preparing cellulose nanoparticles (CNPs) via an ultrasound-assisted etherification and a subsequent sonication process. The ultrasonic-assisted treatment greatly improved the modification of the pith cellulose with glycidyltrimethylammonium chloride, leading to a partial increase in the dissolubility of the as-obtained product and thus disintegration of sheet-like cellulose into nanoparticles. While the formation of CNPs by ultrasonication was largely dependent on the cellulose consistency in the cationic-modified system. Under the condition of 25% cellulose consistency, the longer sono-treated duration yielded a more stable and dispersible suspension of CNP due to its higher zeta potential. Degree of substitution and FT-IR analyses indicated that quaternary ammonium salts were grafted onto hydroxyl groups of cellulose chain. SEM and TEM images exhibited the CNP to have spherical morphology with an average dimeter from 15 to 55 nm. XRD investigation revealed that CNPs consisted mainly of a crystalline cellulose Ι structure, and they had a lower crystallinity than the starting cellulose. Moreover, thermogravimetric results illustrated the thermal resistance of the CNPs was lower than the pith cellulose. The optimal CNP with highly cationic charges, good stability and acceptable thermostability might be considered as one of the alternatively renewable reinforcement additives for nanocomposite production. 相似文献
2.
Intramolecular (2+2) photocycloaddition of β-stilbazoles tethered by silyl chains took place with high efficiency. Complexation with dicarboxylic acid or catechol further enhanced both the efficiency and stereoselectivity. 相似文献
3.
Summary The solubility parameters of cationic surfactants were obtained using the inverse gas chromatographic technique. The surfactants
didodecyl dimethyl ammonium bromide, dioctadecyl dimethyl ammonium bromide and dodecyl pyridinium chloride were used as stationary
phase and retention data of different probe solutes were measured at different temperatures. The results were analysed by
the combination of Flory-Huggins and Hildebrand theories, and the solubility parameters of the surfactants were obtained in
a range of temperatures between 80–120°C. 相似文献
4.
Xuyuan GuScott Cowell Jinfa YingXuejun Tang Victor J. Hruby 《Tetrahedron letters》2003,44(31):5863-5866
(2S,3S)- and (2R,3R)-2-amino-3-phenyl-5-hexenoic acids have been synthesized in large scale by using Ni(II)-complexes as a template. The amino acids were used in the synthesis of [4,3,0]-bicyclic β-turn mimetics by a convergent methodology. The unique advantage of this strategy is the convenience of introducing side chain groups with predetermined chiralities on both the five- and six-membered heterocyclic rings. 相似文献
5.
M. E. Carlotti S. Sapino R. Cavalli M. Trotta F. Trotta K. Martina 《Journal of inclusion phenomena and macrocyclic chemistry》2007,57(1-4):445-450
This work deals with the formation of inclusion complexes between cinnamaldehyde and two synthetic alkylcarbonates of γ-cyclodextrin, namely ethylcarbonate-γ-CD and octylcarbonate-γ-CD. Complexation was monitored by phase-solubility studies, by FT-IR spectroscopy and by DSC and TG analysis.
The diffusion of cinnamaldehyde through a cellulose membrane was investigated in the absence and in the presence of each of
the two γ-CD alkylcarbonates. Studies on photostability and stability over time were carried out on different cosmetic formulations
containing pure cinnamaldehyde or an equivalent amount of cinnamaldehyde complexed with the two alkylcarbonates.
Phase-solubility diagrams, DSC, FTIR and TGA analysis suggested the formation of inclusion complexes. The diffusion of cinnamaldehyde
through the cellulose membrane decreased in the presence of the two alkylcarbonates confirming the interaction of this molecule
with the inclusion agents.
Moreover the stability of cinnamaldehyde to light and heat resulted increased by complexing this fragrance material with the
two alkylcarbonates. 相似文献
6.
7.
Peptidosulfonamides are an emerging group of peptidomimetics with a variety of applications in medicinal chemistry. We present a novel approach to the synthesis of peptidosulfonamides, and apply it to a series of new potential inhibitors of the bacterial peptidoglycan biosynthesis enzymes MurD and MurE. The synthesis was conducted via N-phthalimido β-aminoethanesulfonyl chlorides, which are new building blocks for the synthesis of peptidosulfonamides. In the most crucial step, sulfonic acids or their sodium salts were converted into the corresponding sulfonyl chlorides using an excess of either SOCl2 or SOCl2/DMF, and then coupled to the C-protected amino acid. None of the compounds significantly inhibited MurD, however, some inhibited MurE; one had an IC50 below 200 μM, which constitutes a promising starting point for further development. Molecular modelling simulations were performed on two analogues to investigate the absence of inhibitory activity of the sulfonamide compounds on MurD. 相似文献
8.
T. Hayashita T. Kurosawa T. Miyata K. Tanaka M. Igawa 《Colloid and polymer science》1994,272(12):1611-1619
The cationic azo-surfactants possessing different spacers and tail alkyl chain lengths have been synthesized by azocoupling ofp-alkylaniline orop-ethoxyaniline with phenol, followed by alkylation and quaternalization with dibromoalkane and trimethylamine, respectively. These surfactants showed a good solubility in water. A reversibletrans-cis isomerization of the azosurfactants by photoirradiation was assessed by UV-Vis absorption spectra. Due to a difference in HLB between thetrans- andcis-surfactants, the observed critical micelle concentration (CMC) values and the electric conductivity of the surfactant solution at above the CMC were significantly affected by the photoinducedtrans-cis isomerization. The azo-surfactants bearing moderate alkyl chain lengths such as surfactants 6 (R2=C2H4, R3=C4H9) and 9 (R2=C4H8, R3=C2H5) were found to be effective to achieve large CMC changes (3.6 mmol/L for 6 and 5.9 mmol/L for 9) by UV-light irradiation. The replacement of the tail chain species also affected the photoresponsive function. The surfactant 12, possessingp-ethoxy group as the tail chain, was found to form a stable micelle aggregation as compared with the structurally related surfactant 10 having ethyl unit as its tail group, but it exhibited a large CMC change (5.3 mmol/L) by UV-light irradiation. 相似文献
9.
10.
Valérie Michaut Jean-Marc Paris Jean-Christophe Plaquevent 《Journal of fluorine chemistry》2007,128(8):889-895
Herein are studied new transformations of ethyl-4,4,4-trifluoroacetoacetate (ETFAA), giving access to a series of enantiopure chirons bearing both a trifluoromethyl group and an amino moiety. The key intermediate is obtained optically pure by a resolution procedure. 相似文献