全文获取类型
收费全文 | 372篇 |
免费 | 17篇 |
国内免费 | 2篇 |
专业分类
化学 | 226篇 |
晶体学 | 2篇 |
力学 | 5篇 |
数学 | 72篇 |
物理学 | 86篇 |
出版年
2022年 | 2篇 |
2020年 | 2篇 |
2019年 | 2篇 |
2017年 | 7篇 |
2016年 | 8篇 |
2015年 | 7篇 |
2014年 | 10篇 |
2013年 | 18篇 |
2012年 | 22篇 |
2011年 | 23篇 |
2010年 | 22篇 |
2009年 | 7篇 |
2008年 | 20篇 |
2007年 | 23篇 |
2006年 | 29篇 |
2005年 | 23篇 |
2004年 | 16篇 |
2003年 | 19篇 |
2002年 | 8篇 |
2001年 | 5篇 |
2000年 | 16篇 |
1999年 | 3篇 |
1998年 | 4篇 |
1997年 | 7篇 |
1996年 | 6篇 |
1995年 | 3篇 |
1994年 | 4篇 |
1993年 | 4篇 |
1992年 | 4篇 |
1990年 | 2篇 |
1989年 | 2篇 |
1988年 | 1篇 |
1986年 | 6篇 |
1985年 | 7篇 |
1984年 | 1篇 |
1983年 | 3篇 |
1982年 | 3篇 |
1981年 | 8篇 |
1980年 | 6篇 |
1979年 | 3篇 |
1978年 | 5篇 |
1977年 | 1篇 |
1976年 | 5篇 |
1975年 | 2篇 |
1974年 | 2篇 |
1973年 | 1篇 |
1972年 | 1篇 |
1969年 | 2篇 |
1967年 | 1篇 |
1923年 | 1篇 |
排序方式: 共有391条查询结果,搜索用时 15 毫秒
101.
So‐Lin Hsu Chia‐Min Chen Kung‐Hwa Wei 《Journal of polymer science. Part A, Polymer chemistry》2010,48(22):5126-5134
We have synthesized and characterized two new carbazole‐based conjugated polymers, PCDCN and PCDTA , incorporating two strong light‐absorbing organic dyes. These polymers exhibit relatively low band gaps (~1.5 eV) and broad absorption ranges (from 300 to 700 nm). We fabricated polymer solar cells incorporating these polymers as donors and [6,6]‐phenyl‐C71‐butyric acid methyl ester (PC71BM) as the acceptor. At a blending ratio of 1:4, we obtained power conversion efficiencies, under simulated AM 1.5 (100 mW/cm2) conditions, of 2.31% and 2.47% for the PCDCN ‐ and PCDTA ‐based devices, respectively. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010 相似文献
102.
Sheng‐Huei Hsiao Guey‐Sheng Liou Yi‐Chun Kung Tzu‐Jung Hsiung 《Journal of polymer science. Part A, Polymer chemistry》2010,48(15):3392-3401
A new triphenylamine‐based diamine monomer, 4,4′‐diamino‐2″,4″‐dimethoxytriphenylamine ( 2 ), was synthesized from readily available reagents and was reacted with various aromatic dicarboxylic acids to produce a series of aromatic polyamides ( 4a–h ) containing the redox‐active 2,4‐dimethoxy‐substituted triphenylamine (dimethoxyTPA) unit. All the resulting polyamides were readily soluble in polar organic solvents and could be solution cast into tough and flexible films. These polymers exhibited good thermal stability with glass transition temperatures of 243–289 °C and softening temperatures of 238–280 °C, 10% weight loss temperatures in excess of 470 °C in nitrogen, and char yields higher than 60% at 800 °C in nitrogen. The redox behaviors of the polymers were examined using cyclic voltammetry (CV). All these polyamides showed two reversible oxidation processes in the first CV scan. The polymers also displayed low ionization potentials as a result of their dimethoxyTPA moieties. In addition, the polymers displayed excellent stability of electrochromic characteristics with coloration change from a colorless neutral state to green and blue‐purple oxidized states. These anodically coloring polyamides showed high green coloration efficiency (CE = 329 cm2/C), high contrast of optical transmittance change (ΔT% = 84% at 829 nm), and long‐term redox reversibility. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3392–3401, 2010 相似文献
103.
We show that homogeneous polymer blend microparticles can be prepared in situ from droplets of dilute solution of codissolved polymers. Provided that the droplet of solution is small enough (<10 mum), solvent evaporation is rapid enough to inhibit phase separation. Thus the polymers that are being mixed need not be miscible, which greatly enhances the applicability of the technique. From analysis of two-dimensional Fraunhofer diffraction (angular scattering) patterns, we show that both the real and the imaginary parts of the refractive index can be tuned by adjustment of the relative weight fractions of polymers in solution. 相似文献
104.
A new synthetic sequence involving the use of Ireland-Claisen rearrangement of propargylic acetates to form the corresponding benzannulated enyne-allenes followed by Schmittel cyclization to generate benzofulvene biradicals for radical cyclizations leading to polycyclic aromatic compounds was established. Treatment of 9-fluorenone (8) with the lithium acetylide 9 followed by acetic anhydride produced the propargylic acetate 10. A sequence of reactions occurred after 10 was converted to the corresponding silyl ketene acetal 11. An initial Ireland-Claisen rearrangement produced the benzannulated enyne-allene 12, which then underwent a Schmittel cyclization reaction to generate the benzofulvene biradical 13. A subsequent intramolecular radical-radical coupling then produced the formal Diels-Alder adduct 14, which in turn underwent a prototropic rearrangement to give the silyl ester 15 and, after hydrolysis, the carboxylic acid 16 in 57% overall yield from 10 in a single operation. An intramolecular acylation reaction of 16 produced the ketone 17. The carboxylic acids 24-26 were likewise prepared from the diaryl ketones 18-20, respectively. However, the intramolecular [2 + 2] cycloaddition reaction of the benzannulated enyne-allene 33 having a tert-butyl group at the allenic terminus occurred preferentially, producing the 1H-cyclobut[a]indenyl acetic acid 35 as the predominant product. 相似文献
105.
106.
Microwave synthesis of polymer-embedded Pt-Ru catalyst for direct methanol fuel cell 总被引:2,自引:0,他引:2
Bensebaa F Farah AA Wang D Bock C Du X Kung J Le Page Y 《The journal of physical chemistry. B》2005,109(32):15339-15344
Platinum-ruthenium nanoparticles stabilized within a conductive polymer matrix are prepared using microwave heating. Polypyrrole di(2-ethylhexyl) sulfosuccinate, or PPyDEHS, has been chosen for its known electrical conductivity, thermal stability, and solubility in polar organic solvents. A scalable and quick two-step process is proposed to fabricate alloyed nanoparticles dispersed in PPyDEHS. First a mixture of PPyDEHS and metallic precursors is heated in a microwave under reflux conditions. Then the nanoparticles are extracted by centrifugation. Physical characterization by TEM shows that crystalline and monodisperse alloyed nanoparticles with an average size of 2.8 nm are obtained. Diffraction data show that crystallite size is around 2.0 nm. Methanol electro-oxidation data allow us to propose these novel materials as potential candidates for direct methanol fuel cells (DMFC) application. The observed decrease in sulfur content in the polymer upon incorporation of PtRu nanoparticles may have adversely affected the measured catalytic activity by decreasing the conductivity of PPyDEHS. Higher concentration of polymer leads to lower catalyst activity. Design and synthesis of novel conductive polymers is needed at this point to enhance the catalytic properties of these hybrid materials. 相似文献
107.
Activation of Au/TiO2 catalyst for CO oxidation 总被引:2,自引:0,他引:2
Yang JH Henao JD Raphulu MC Wang Y Caputo T Groszek AJ Kung MC Scurrell MS Miller JT Kung HH 《The journal of physical chemistry. B》2005,109(20):10319-10326
Changes in a Au/TiO(2) catalyst during the activation process from an as-prepared state, consisting of supported AuO(x)(OH)(4-2x)(-) species, were monitored with X-ray absorption spectroscopy and FTIR spectroscopy, complemented with XPS, microcalorimetry, and TEM characterization. When the catalyst was activated with H(2) pulses at 298 K, there was an induction period when little changes were detected. This was followed by a period of increasing rate of reduction of Au(3+) to Au(0), before the reduction rate decreased until the sample was fully reduced. A similar trend in the activation process was observed if CO pulses at 273 K or a steady flow of CO at about 240 K was used to activate the sample. With both activation procedures, the CO oxidation activity of the catalyst at 195 K increased with the degree of reduction up to 70% reduction, and decreased slightly beyond 80% reduction. The results were consistent with metallic Au being necessary for catalytic activity. 相似文献
108.
Several derivatives of the pyrido[1',2':1,2]pyrimido[4,5-b]indoles 4 and the pyrazino[1',2':1,2]pyrimido[4,5-b]indoles 14 were synthesized by treatment of the benzannulated enyne-isocyanates 8 with the iminophosphoranes 9 and 13, respectively, for the aza-Wittig reaction followed by thermolysis. The reaction presumably proceeds through an initial formation of the corresponding benzannulated enyne-carbodiimides, such as 10, followed by a formal intramolecular hetero Diels-Alder reaction. Surprisingly, when the iminophosphorane 17 was used for condensation with 8, the expected pyrimido[1',6':1,2]pyrimido[4,5-b]indoles 16 were not obtained. Instead, the isomeric pyrimido[6',1':2,3]pyrimido[4,5-b]indoles 21 were isolated. Presumably, an alternative reaction pathway involving an initial [2 + 2] cycloaddition reaction to form 19 followed by ring opening could lead to 20 and, after an intramolecular radical-radical coupling, 21. Treatment of the urea derivatives 24 with dibromotriphenylphosphorane also produced in situ the benzannulated enyne-carbodiimides 25, which on thermolysis gave the isoquinolino[2',1':1,2]pyrimido[4,5-b]indoles 26. Methylation of 4a, 14a, and 26a with methyl iodide occurred exclusively at the site of the indolo nitrogen. The planar geometry of those novel heteroaromatic compounds, resembling many DNA-binding agents, makes them potential candidates as DNA intercalators. 相似文献
109.
Additivity and the physical basis of multivalency effects: a thermodynamic investigation of the calcium EDTA interaction 总被引:1,自引:0,他引:1
Christensen T Gooden DM Kung JE Toone EJ 《Journal of the American Chemical Society》2003,125(24):7357-7366
To better understand the origin of multivalency effects in ligand binding, the binding of a series of mono-, bi-, tri- and tetravalent carboxylate ligands to Ca(II) was examined by isothermal titration calorimetry (ITC). The data are inconsistent with an entropic origin of enhanced affinity, but rather show that at least in this instance the multivalency effect is enthalpic in origin. Analysis of binding data using the Jencks model shows the addition of incremental carboxylate "ligands" produces an unfavorable interaction entropy that is more than offset by a strongly favorable interaction enthalpy. The most likely source of this interaction enthalpy is the relief of repulsive Coulombic interactions in the unbound state. The conformational entropy penalty arising from the restriction of flexible dihedrals is negligible, within experimental error. On the other hand, an enthalpic contribution from linker restriction contributes strongly to the overall thermodynamics of ligand binding. Together, these data suggest that enthalpic effects dominate ligand binding, and design strategies should seek to optimize these interactions. The incorporation of unfavorable interactions in the unbound ligand that are relieved during binding provides an important mechanism by which to enhance ligand affinities. 相似文献
110.
M. S. Jovanović J. Brborić S. Vladimirov B. Zmbova LJ. Vuksanović D. Živanov-Stakić V. Obradović 《Journal of Radioanalytical and Nuclear Chemistry》1999,240(1):321-324
A new diiodine substituted IDA derivative, 2,4-diiodine-6-methyl IDA (DIIODIDA) was synthesized and labeled with99mTc. It was established that99mTc-DIIODIDA had high radiochemical purity. Biodistribution and influence of bilirubin on99mTc-DIIODIDA biokinetics has been studied in rats and compared to the corresponding results for99mTc-SOLCOIODIDA. Related to99mTc-SOLCOIODIDA,99mTc-DIIODIDA has much better biliary exretion (55.18 versus 43.63%). No change of99mTc-DIIODIDA biokinetics, under influence of bilirubin was noticed. Biliary excretion of99mTc-SOLCOIODIDA has been reduced for about 60%. The protein binding of99mTc-DIIODIDA and99mTc-SOLCOIODIDA were also determined, using in vitro method of precipitation. These results showed that99mTc-DIIODIDA hepatobiliary imaging agent is superior to the presently used99mTc-monoiodine IDA derivatives. 相似文献