全文获取类型
收费全文 | 2273篇 |
免费 | 91篇 |
国内免费 | 318篇 |
专业分类
化学 | 2137篇 |
晶体学 | 17篇 |
力学 | 5篇 |
综合类 | 16篇 |
数学 | 242篇 |
物理学 | 265篇 |
出版年
2024年 | 6篇 |
2023年 | 68篇 |
2022年 | 50篇 |
2021年 | 74篇 |
2020年 | 151篇 |
2019年 | 105篇 |
2018年 | 94篇 |
2017年 | 114篇 |
2016年 | 105篇 |
2015年 | 66篇 |
2014年 | 131篇 |
2013年 | 508篇 |
2012年 | 166篇 |
2011年 | 137篇 |
2010年 | 99篇 |
2009年 | 111篇 |
2008年 | 111篇 |
2007年 | 121篇 |
2006年 | 114篇 |
2005年 | 86篇 |
2004年 | 87篇 |
2003年 | 56篇 |
2002年 | 11篇 |
2001年 | 12篇 |
2000年 | 11篇 |
1999年 | 8篇 |
1998年 | 10篇 |
1997年 | 12篇 |
1996年 | 6篇 |
1995年 | 9篇 |
1994年 | 5篇 |
1993年 | 9篇 |
1992年 | 3篇 |
1991年 | 6篇 |
1990年 | 4篇 |
1989年 | 2篇 |
1988年 | 2篇 |
1987年 | 1篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1983年 | 2篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1979年 | 1篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1974年 | 1篇 |
排序方式: 共有2682条查询结果,搜索用时 421 毫秒
131.
Türsen Demir Frederick J. Raveney Robert A. Shaw 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3-4):155-163
Abstract The reactions of 4-methyl-2-[N-(p-toluidinyl)methyl]aniline with phosphorus oxychloride, thiophosphoryl chloride, and their derivatives yield 1,3,2-benzodiazaphosphorine 2-oxides and 2-sulphides. Their 1H NMR and infrared spectra are discussed. Related 1,3,2-benzodiazophosphorine and 1,3,2-dibenzodiazaphosphocine 2-oxides and 2-sulphides are compared. 相似文献
132.
P. V. Badadhe N. M. Chavan D. S. Ghotekar P. G. Mandhane R. S. Joshi C. H. Gill 《Phosphorus, sulfur, and silicon and the related elements》2013,188(10):2021-2032
Abstract Synthesis of some new functionalized thiazolidin-4-ones and α-amino phosphonate derivatives has been reported. The imines were synthesized from the reaction of various substituted anilines with 1-phenyl-3-(pyridine-4-yl)-1H-pyrazole-4-carbaldehyde in ethanol at reflux condition. The corresponding thiazolidin-4-ones and α-aminophosphonates were prepared by reaction of imines with mercaptoacetic acid and triethyl phosphite, respectively. The structures of the newly synthesized compounds were confirmed by IR, 1H NMR, and mass spectral data and were evaluated for their antimicrobial activities. GRAPHICAL ABSTRACT 相似文献
133.
The First Mitsunobu Protocol for Efficient Synthesis of α-Acyloxyphosphonates Using 4,4′-Azopyridine
Nasser Iranpoor Habib Firouzabadi Dariush Khalili 《Phosphorus, sulfur, and silicon and the related elements》2013,188(11):2166-2171
Abstract This is the first report on applying the Mitsunobu protocol for the synthesis of various α-acyloxyphosphonates using 4,4′-azopyridine and PPh3 with diverse aromatic and aliphatic carboxylic acids. Under these conditions, diethyl azodicarboxylate (DEAD) as the traditional reagent for Mitsunobu reaction is not efficient. The insoluble pyridine hydrazine byproduct can be simply isolated and recycled to its azopyridine by an oxidation reaction and reused again. [Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental resource: Characterization data of compounds 3a–3z2 and NMR spectra.] GRAPHICAL ABSTRACT 相似文献
134.
(S)-6-Acrylyl-2,2’-dimethoxy-1,1’-binaphthyl (ADBN) was synthesized and anionically polymerized using n-BuLi as an initiator. The absolute value of specific optical rotation [α]25589 of poly-ADBN is ?118.0 and that is about 8 times that of the starting monomer ADBN. Poly-ADBN was confirmed to exist in the form of one-handed helical structure in solution by means of comparing the specific optical rotation, the CD and UV-Vis spectra with that of ADBN and the model compounds such as (S)-6-propionyl-2,2’-dimethoxy-1,1’-binaphthyl (PDBN) and (S)-6-heptanoyl-2,2’-dimethoxy-1,1’-binaphthyl (HDBN). This conclusion was also confirmed by the fact that the g-value of poly-ADBN is about 13 times as high as that of its monomer and model compounds 相似文献
135.
AbstractIn this work, an effective method was developed to prepare novel PEO-b-PPO-b-PEO (EPE)/α-cyclodextrin (α-CD) supramolecular hydrogels containing exfoliated graphite nanoplates (xGNPs) by mixing an aqueous solution of α-CD with an aqueous dispersion of xGNPs at the presence of amphiphilic EPE copolymer. The EPE copolymer played three important roles in the preparation process: (1) as an exfoliating agent to break expanded graphites into xGNPs under ultrasonication, (2) as a dispersant to stabilize xGNPs in the aqueous solution, and (3)as a component to form the inclusion complexes with α-CD. The resultant xGNPs/EPE/α-CD hybridized hydrogels were characterized by scanning electron microscopy, wide-angle X-ray diffraction, differential scanning calorimetry, and Fourier transform infrared spectroscopy, which confirmed not only the formation of supramolecular hydrogel structure but also the homogenous dispersion of xGNPs in the hydrogel matrix. It was found that the existence of xGNPs can accelerate the speed of gel formation in comparison with that of the native EPE/α-CD hydrogel. Additionally, the water-retention ability and the release behavior of vancomycin hydrochloride for the xGNPs/EPE/α-CD hybridized hydrogels were investigated. 相似文献
136.
The emulsifier-free emulsion copolymerization of α-methylstyrene (AMS) and methyl methacrylate (MMA) in the presence of functional monomer acrylic acid (AA) was carried out in batch process, giving birth to sub-100 nm nanoparticles. The kinetics of polymerization was investigated. The morphology and size of particles were monitored by TEM. The influences of the functional monomer AA concentration, initiator ammonium persulfate (APS) concentration, and polymerization temperature were studied. It was found that AMS caused a drastic decrease in both the rate of polymerization and the average degree of polymerization. The activation energy calculated from Arrhenius plot turned out to be 83.6 kJ/mol. 相似文献
137.
Nino Zavradashvili Giuli Jokhadze Marekh Gverdtsiteli Giuli Otinashvili Nino Kupatadze Zaza Gomurashvili 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(5):449-465
A new class of biodegradable functional polymers – epoxy-poly(ester amide)s (EPEAs), was synthesized for the first time on the basis of naturally occurring α-amino acids, fatty diols and cis- and trans-epoxysuccinic acids. The syntheses were conducted via both solution Active Polycondensation and Interfacial Polycondensation using, accordingly, either activated di-p-nitrophenyl esters or dichlorides of cis- and trans-epoxysuccinic acids as bis-electrophilic monomers. Di-p-toluenesulfonic acid salts of bis-(L-phenylalanine)-1,6-hexylene and bis-(L-leucine)-1,6-hexylene diesters were used in both cases as bis-nucleophilic counter-partners. High-molecular-weight polymers (Mw up to 67.000) with desirable material properties were obtained via solution polycondensation using di-p-nitrophenyl-trans-epoxy succinate. The EPEAs were chemically modified further under mild conditions: oxirane groups along the backbone were reacted with both nucleophilic and electrophilic reagents, and also subjected to thermal and chemical curing. The macromolecular transformations of EPEAs substantially broaden material properties and, hence, the potential to apply amino acid-based biodegradable poly(ester amide)s as absorbable drug carriers and surgical devices. 相似文献
138.
Michal Achmatowicz Agnieszka Szczepańska Daniel T. Gryko Piotr Salański Janusz Jurczak 《Supramolecular chemistry》2013,25(1):93-95
Abstract Bisamidation of oxaloyl chloride using L-amino acid methyl ester hydrochlorides afforded chiral diesters. The following reactions of diesters with 2,2-(ethylene-dioxy)diethylamine, afforded tetramides possessing C2 symmetry. Coupling of N-hydroxysuccinimide ester of N-benzyloxycarbonyl-L-alanine with 1,5-diamino-3-oxapentane, followed by cleavage of protecting groups, afforded an optically active diamine, which was transformed consequently into tetramide via the reaction with diglycolic acid dimethyl ester under high pressure conditions. 相似文献
139.
Abstract With a 1:1 and a 2:1 host-guest stoichiometry, α-cyclodextrin (α-CD) forms inclusion complexes with 2-chloronaphthalene. From simulations concerning observed chemical-shift differences (Δδobs) of proton signals of 2-chloronaphthalene, intrinsic Δδ values are estimated for all the guest protons in the 1:1 and 2:1 inclusion complexes. The intrinsic Δδ values indicate that α-CD first binds to a part of a naphthalene ring bearing a C1 atom to form the 1:1 inclusion complex. In the 1:1 and 2:1 inclusion complexes, the symmetry axes of α-CD are tilted approximately 30° relative to a naphthalene longitudinal axis. In the 2:1 inclusion complex, the association through hydrogen bonding most likely occurs between two α-CD molecules whose symmetry axes are laterally shifted. 相似文献
140.