全文获取类型
收费全文 | 270篇 |
免费 | 6篇 |
专业分类
化学 | 246篇 |
力学 | 2篇 |
物理学 | 28篇 |
出版年
2023年 | 4篇 |
2022年 | 4篇 |
2021年 | 8篇 |
2020年 | 7篇 |
2019年 | 15篇 |
2018年 | 5篇 |
2017年 | 4篇 |
2016年 | 16篇 |
2015年 | 8篇 |
2014年 | 11篇 |
2013年 | 20篇 |
2012年 | 15篇 |
2011年 | 24篇 |
2010年 | 9篇 |
2009年 | 13篇 |
2008年 | 13篇 |
2007年 | 23篇 |
2006年 | 15篇 |
2005年 | 10篇 |
2004年 | 7篇 |
2003年 | 4篇 |
2002年 | 10篇 |
2001年 | 4篇 |
2000年 | 2篇 |
1999年 | 4篇 |
1998年 | 2篇 |
1997年 | 3篇 |
1996年 | 2篇 |
1995年 | 1篇 |
1994年 | 4篇 |
1992年 | 5篇 |
1984年 | 1篇 |
1981年 | 1篇 |
1979年 | 1篇 |
1974年 | 1篇 |
排序方式: 共有276条查询结果,搜索用时 31 毫秒
11.
A new AB type of monomer 4′-fluoro-3,5-dimethyl-3′-trifluoromethyl-biphenyl-4-ol has been synthesized that leads to a new poly(arylene ether) by self polycondensation reaction. The monomer and the polymer have been well characterized by elemental analyses, FT-IR and NMR spectroscopy. Both FT-IR and NMR spectra of the polymers did not show any terminal phenoxy group indicating high conversion. The polymer showed glass transition at 278°C and very good thermal stability in synthetic air. GPC results indicate high molar mass development; Mw = 53200 and MWD = 2.29. 相似文献
12.
Several new random and block copoly(imide siloxane)s have been prepared by the solution polycondensation of commercially available 4,4′-oxydianiline (ODA) and amino-propyl terminated polydimethylsiloxane (APPS) with 4,4′-(hexafluoro-isopropylidene)diphthalic anhydride (6FDA). The siloxane loading was kept to 10, 20, 30, 40 and 50 wt% in the copolymers. The random copolymers were prepared by a one pot solution imidization technique, and two pot solution imidization technique was adopted for the synthesis of the block copolymers. The diamine ODA and the dianhydride 6FDA composed the hard block segment, while APPS and 6FDA composed the soft block segment. The hard block length was kept constant while the soft block lengths were varied by varying the siloxane loading. Accordingly, block copoly(imide siloxane)s were prepared on increasing the soft block lengths (DP) from 3 to 6, 10, 18 and 36 for fixed hard block length of 22. The resulting polymers have been well characterized by IR, NMR and GPC techniques. Thermal and mechanical properties of the random and block copolymers were compared with the already reported homopolyimide without siloxane moiety. 相似文献
13.
Low dielectric constant apolar aprotic solvents, although employed on a limited scale for studying proton transfer reactions as compared with commonly used polar protic or dipolar aprotic ones, offer some particular advantages, namely, specific solute–solvent interactions are virtually eliminated and proton transfer occurs directly in an apolar aprotic solvent. An intriguing feature of these reactions is their general acid‐catalyzed/base‐catalyzed kinetics with a time scale over microseconds to minutes. In fact, the true or intrinsic relative strengths of acids/bases when measured in such solvents come to the fore much more clearly than those obtained in other classes of solvents. Recently, a review documenting the post‐1980 developments relating to proton transfer reactions in apolar aprotic solvents has been published. The present article is a commentary of the pre‐1980 developments in this area since the 1920s Brønsted–Lowry's “proton cult” of acid–base theory. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
14.
We demonstrate efficient frequency conversion with large frequency shifts of an anti-Stokes signal into a parametrically seeded Stokes idler, which is generated by a highly mismatched three-wave mixing interaction and subsequent Raman amplification in a normally dispersive single-mode fiber. The use of non-phase-matched waves in Raman-assisted three-wave mixing interactions overcomes the strict spectral limitations imposed by phase-matching conditions in parametric frequency-conversion processes. 相似文献
15.
Rauth Goutam Kumar Dinda Joydev Jasimuddin Sk. Sinha Chittaranjan 《Transition Metal Chemistry》2003,28(1):88-95
1-Alkyl-2-(naphthyl--azo)imidazoles [-NaiR; R = Me (a), Et (b), CH2Ph (c)] react with Pd(MeCN)2Cl2 to yield Pd(-NaiR)Cl2
(2), the i.r. spectra of which support the presence of a cis-PdCl2 configuration. The complexes react with catechols in the presence of Et3N to yield ternary complexes [Pd(-NaiR)(O,O)] [O,O = pyrocatecholato (cat) (3), 4-t-butylcatecholato (tbcat) (4), 3,5-di-t-butylcatecholato (dtbcat) (5), and tetrachlorocatecholato (tccat) (6)], which were characterized by elemental analysis, i.r. and 1H-n.m.r. spectral data. Redox studies by cyclic voltammetry suggest the existence of four successive redox couples wherein two responses, positive to s.c.e. are due to catechol to semiquinone and semiquinone to quinone oxidation, respectively; the couples at negative to s.c.e. are referred to azo reductions. The complexes exhibit ligand-ligand charge-transfer transitions in the near-i.r. region. The band position is largely dependent upon the substitutent on the catechol frame and exhibits negative solvatochromic effects. The transition is qualitatively assigned as the HOMO (cat) LUMO (-NaiR) transition. This fact is also supported by theoretical calculations using the PM3 method. 相似文献
16.
Apolar aprotic solvents are particularly advantageous for investigating the intrinsic metasubstituent effect free from complications of specific solvent effects. A kinetic study for toluene‐phase proton transfers between meta‐Me, F, Cl, Br, I, OMe, OPh, COPh, CF3, CN, NO2, H benzoic acids and Crystal Violet carbinol base has shown the forward rate constant (log k1) the most appropriate reactivity parameter in toluene. log k1 (toluene) as compared to other reported reactivity parameters in benzene or toluene have been found more sensitive to the metasubstituent effect. The regression results of the correlation of log k1 (toluene) of the acids according to the four dual substituent parameter models are statistically significant, and the best result has been obtained using Taft's model. The overall analysis reveals that metasubstituent's effect is exerted by a 65:35 pattern of its field and second‐order resonance effects. The results further demonstrate that a metasubstituent's resonance effect is virtually a relayed universal field/inductive effect. © 2011 Wiley Peiodicals, Inc. Int J Chem Kinet 43: 303–311, 2011 相似文献
17.
18.
Susanta Hazra Samit Majumder Michel Fleck Núria Aliaga-Alcalde Sasankasekhar Mohanta 《Polyhedron》2009,28(17):3707-3714
Synthesis, molecular and supramolecular structures, electrochemistry and magnetic properties of two diphenoxo-bridged dicopper(II) compounds [CuII2L(H2O)(ClO4)]·ClO4·2H2O (1) and [CuII2L(N3)2]·2H2O (2) derived from a tetraimino diphenolate macrocyclic ligand H2L, obtained on [2+2] condensation of 4-methyl-2,6-diformylphenol and 2,2′-dimethyl-1,3-diaminopropane, are presented. Supramolecular structure of both 1 and 2 are three-dimensional resulting from hydrogen bonding interactions. Interestingly, the 3-D self-assembly of 2 contains micropores having the dimension of 0.35 nm. Electrochemical analyses reveal that both of these compounds exhibit two-step couples in the reduction window. Variable-temperature (2–300 K) magnetic susceptibilities measurements of the two compounds reveal that the metal centers in both of the complexes are coupled by strong antiferromagnetic interactions with J values (H = ?JS1·S2) ?776 and ?836 cm?1 for 1 and 2, respectively. 相似文献
19.
Dinda E Rashid MH Biswas M Mandal TK 《Langmuir : the ACS journal of surfaces and colloids》2010,26(22):17568-17580
We describe a general one-step facile method for depositing gold nanoparticle (GNP) thin films onto any type of substrates by the in situ reduction of AuCl(3) using a newly designed redox-active ionic liquid (IL), tetrabutylphosphonium citrate ([TBP][Ci]). Various substrates such as positively charged glass, negatively charged glass/quartz, neutral hydrophobic glass, polypropylene, polystyrene, plain paper, and cellophane paper are successfully coated with a thin film of GNPs. This IL ([TBP][Ci]) is prepared by the simple neutralization of tetrabutylphosphonium hydroxide with citric acid. We also demonstrate that the [TBP][Ci] ionic liquid can be successfully used to generate GNPs in an aqueous colloidal suspension in situ. The deposited GNP thin films on various surfaces are made up of mostly discrete spherical GNPs that are well distributed throughout the film, as confirmed by field-emission scanning electron microscopy. However, it seems that some GNPs are arranged to form arrays depending on the nature of surface. We also characterize these GNP thin films via UV-vis spectroscopy and X-ray diffractometry. The as-formed GNP thin films show excellent stability toward solvent washing. We demonstrate that the thin film of GNPs on a glass/quartz surface can be successfully used as a refractive index (RI) sensor for different polar and nonpolar organic solvents. The as-formed GNP thin films on different surfaces show excellent catalytic activity in the borohydride reduction of p-nitrophenol. 相似文献
20.
Kinsuk Das Tarak Nath Mandal Somnath Roy Samik Gupta Anil Kumar Barik Partha Mitra Arnold L. Rheingold Susanta Kumar Kar 《Polyhedron》2010
The varying coordination modes of the title ligand, L [5-methyl-1-(pyridin-2-yl)-N′-[pyridin-2-ylmethylidene]pyrazole-3-carbohydrazide] towards the different metal centers is reported by preparation and characterization of Cu(II), Zn(II) and Cd(II) complexes, [Cu(L)NO3.H2O](NO3) (1) [Zn(L)2](ClO4)2·2DMF (2) and [Cd(L)(I)2] (3) respectively. In 1, the neutral ligand serves as tetradentate 4 N donor where both pyridine and pyrazole nitrogen atoms of pyridyl–pyrazole part are coordinatively active, leaving the carbonyl oxygen of the carbohydrazide part inactive. The same pyridine and pyrazole N atoms remain abstained from the coordination process towards the Zn(II) and Cd(II) metal centers. For 2 and 3 the ligand behaves as a tridentate NNO donor where the two nitrogen atoms come from azomethine, pyridine of pyridine-2-carbaldehyde parts and O from carbonyl oxygen atoms (carbohydrazide part). The complex 1 and 2 are distorted octahedral while complex 3 adopts distorted square pyramidal geometry. All the complexes are X-ray crystallographically characterized. 相似文献