全文获取类型
收费全文 | 229篇 |
免费 | 3篇 |
国内免费 | 36篇 |
专业分类
化学 | 248篇 |
晶体学 | 3篇 |
物理学 | 17篇 |
出版年
2023年 | 9篇 |
2022年 | 4篇 |
2021年 | 3篇 |
2020年 | 2篇 |
2019年 | 6篇 |
2018年 | 11篇 |
2017年 | 9篇 |
2016年 | 5篇 |
2015年 | 4篇 |
2014年 | 5篇 |
2013年 | 19篇 |
2012年 | 15篇 |
2011年 | 6篇 |
2010年 | 15篇 |
2009年 | 18篇 |
2008年 | 8篇 |
2007年 | 19篇 |
2006年 | 18篇 |
2005年 | 19篇 |
2004年 | 13篇 |
2003年 | 9篇 |
2002年 | 3篇 |
2001年 | 1篇 |
2000年 | 8篇 |
1999年 | 7篇 |
1998年 | 3篇 |
1997年 | 1篇 |
1996年 | 6篇 |
1995年 | 2篇 |
1994年 | 4篇 |
1993年 | 2篇 |
1989年 | 3篇 |
1987年 | 1篇 |
1986年 | 2篇 |
1984年 | 3篇 |
1982年 | 3篇 |
1980年 | 1篇 |
1977年 | 1篇 |
排序方式: 共有268条查询结果,搜索用时 406 毫秒
41.
The alkylation of ethyl 1H-pyrazole-3-carboxylate with a variety of alkylating agents in the presence of K2CO3 was found to largely favor the formation of ethyl 1-substituted pyrazole-3-carboxylates. The alkylation could be sterically redirected by the use of a triphenylsilyl group (ethyl 3-(triphenylsilyl)-1H-pyrazole-5-carboxylate) to provide synthetically useful yields of ethyl 1-substituted-3-(triphenylsilyl)-1H-pyrazole-5-carboxylates. The triphenylsilyl group could be removed with Bu4NF. Other triorganosilyl groups (TMS, TES, TBDMS) failed to provide significant redirection, while TIPS proved refractory to protodesilylation. 相似文献
42.
Hongxin Li Peng Tao Yanan Xu Xinwen Zhang Shujuan Liu Qiang Zhao 《Tetrahedron letters》2018,59(18):1748-1751
A novel and highly efficient bis(trifluoromethyl)phenyl functionalized iridium(III) complex is designed and synthesized. The complex shows intensive greenish yellow phosphorescence (525?nm with 563?nm as shoulder), high photoluminescence efficiency (0.90) and moderate full width at half maximum (72?nm). The bulky bis(trifluoromethyl)phenyl moiety introduced into the complex provides the excellent solubility and effective steric hindrance for solution-processed organic light-emitting diodes. The maximum power efficiency and current efficiency of electroluminescence are 4.13?lm/W and 9.54?cd/A, respectively. 相似文献
43.
Masaki Matsui Yuya Tsuzuki Yasuhiro Kubota Kazumasa Funabiki Toshiyasu Inuzuka Kazuhiro Manseki Shinji Higashijima Hidetoshi Miura Hiroyasu Sato Tsukasa Yoshida 《Tetrahedron》2018,74(40):5867-5878
(2R,3aR,8bR)- and (2S,3aS,8bS)-2-Methyl indoline dye tetrabutylammonium carboxylates exhibited the highest conversion efficiency among four regio and stereo isomers. These indoline dyes also showed higher conversion efficiency than DN350. 相似文献
44.
Shaopeng Li Jing Du Bin Zhang Yanzhen Liu Qingqing Mei Qinglei Meng Minghua Dong Juan Du Zhijuan Zhao Lirong Zheng Buxing Han Meiting Zhao Huizhen Liu 《物理化学学报》2023,38(10):2206019
Selective hydrogenation is a vital class of reaction. Various unsaturated functional groups in organic compounds, such as aromatic rings, alkynyl (C≡C), carbonyl (C=O), nitro (-NO2), and alkenyl (C=C) groups, are typical targets in selective hydrogenation. Therefore, selectivity is a key indicator of the efficiency of a designed hydrogenation reaction. 5-(Hydroxymethyl)furfural (HMF) is an important platform compound in the context of biomass conversion, and recently, the hydrogenation of HMF to produce fuels and other valuable chemicals has received significant attention. Controlling the selectivity of HMF hydrogenation is paramount because of the different reducible functional groups (C=O, C-OH, and C=C) in HMF. Moreover, the exploration of new routes for hydrogenating HMF to valuable chemicals is becoming attractive. 5-Methylfurfural (MF) is also an important organic compound; thus, the selective hydrogenation of HMF to MF is an essential synthetic route. However, this reaction has challenging thermodynamic and kinetic aspects, making it difficult to realize. Herein, we propose a strategy to design a highly efficient catalytic system for selective hydrogenation by exploiting the synergy between steric hindrance and hydrogen spillover. The design and preparation of the Pt@PVP/Nb2O5 catalyst (PVP = polyvinyl pyrrolidone; Nb2O5 = niobium(V) oxide) were also conducted. Surprisingly, HMF could be converted to MF with 92% selectivity at 100% HMF conversion. The reaction pathway was revealed through the combination of control experiments and density functional theory calculations. Although PVP blocked HMF from accessing the surface of Pt, hydrogen (H2) could be activated on the surface of Pt due to its small molecular size, and the activated H2 could migrate to the surface of Nb2O5 through a phenomenon called H2 spillover. The Lewis acidic surface of Nb2O5 could not adsorb the C=O group but could adsorb and activate the C-OH group of HMF; therefore, when HMF was adsorbed on Nb2O5, the C-OH groups were hydrogenated by the spilled over H2 to form MF. The high selectivity of this reaction was realized because of the unique combination of steric effects, hydrogen spillover, and tuning of the electronic states of the Pt and Nb2O5 surfaces. This new route for producing MF has great potential for practical application owing to its discovered advantages. We believe that this novel strategy can be used to design catalysts for other selective hydrogenation reactions. Furthermore, this study demonstrates a significant breakthrough in selective hydrogenation, which will be of interest to researchers working on the utilization of biomass, organic synthesis, catalysis, and other related fields.
相似文献
45.
Yunshan Liu Haojie Zhang Wanqing Zhang Prof. Bernard P. Binks Prof. Zhenggang Cui Prof. Jianzhong Jiang 《Angewandte Chemie (International ed. in English)》2023,62(5):e202210050
A ferrocene surfactant can be switched between single and double head form (FcN+C12/Fc+N+C12) triggered by redox reaction. FcN+C12 can neither stabilize an O/W emulsion alone nor an oil-in-dispersion emulsion in combination with alumina nanoparticles due to the steric hindrance of the ferrocene group. However, such steric hindrance can be overcome by increasing the charge density in Fc+N+C12, so that oil-in-dispersion emulsions can be co-stabilized by Fc+N+C12 and alumina nanoparticles at very low concentrations (1×10−7 M (≈50 ppb) and 0.001 wt %, respectively). Not only can reversible formation/destabilization of oil-in-dispersion emulsions be achieved by redox reaction, but also reversible transformation between oil-in-dispersion emulsions and Pickering emulsions can be obtained through reversing the charge of alumina particles by adjusting the pH. The results provide a new protocol for the design of surfactants for stabilization of smart oil-in-dispersion emulsions. 相似文献
46.
Somaiyeh Charoughchi Jiang Tian Liu Melissa Berteau-Rainville Hannes Hase Mohammad S. Askari Shubham Bhagat Pat Forgione Ingo Salzmann 《Angewandte Chemie (International ed. in English)》2023,62(31):e202304964
Molecular p-dopants designed to undergo electron transfer with organic semiconductors are typically planar molecules with high electron affinity. However, their planarity can promote the formation of ground-state charge transfer complexes with the semiconductor host and results in fractional instead of integer charge transfer, which is highly detrimental to doping efficiency. Here, we show this process can be readily overcome by targeted dopant design exploiting steric hindrance. To this end, we synthesize and characterize the remarkably stable p-dopant 2,2′,2′′-(cyclopropane-1,2,3-triylidene)tris(2-(perfluorophenyl)acetonitrile) comprising pendant functional groups that sterically shield its central core while retaining high electron affinity. Finally, we demonstrate it outperforms a planar dopant of identical electron affinity and increases the thin film conductivity by up to an order of magnitude. We believe exploiting steric hindrance represents a promising design strategy towards molecular dopants of enhanced doping efficiency. 相似文献
47.
Mahmut Ulusoy Hasan Karabıyık Rafet Kılınçarslan Muhittin Aygün Bekir Çetinkaya Santiago García-Granda 《Structural chemistry》2008,19(5):749-755
Copper(II) and cobalt(II) complexes of salicylaldimine obtained by the condensation of N,N-diethyl-2-methyl-1,4-phenylenediamine with 3,5-di-tert-butyl-2-hydroxybenzaldehyde have been synthesized and characterized by elemental analyses, magnetic susceptibility measurements,
cyclic voltammetry, and FT-IR and UV–Vis spectroscopy. The molecular structure of the title copper(II) complex was determined
by the single crystal X-ray diffraction technique. The Cu(II) center is coordinated by four atoms of the donor set in a compressed
tetrahedral trans-[N2O2] environment, which can be essentially ascribed to the presence of bulky fragments of the ligand. The computed bond valences
of the copper verify +2 oxidation state and indicate that the copper bonds, in particular Cu–N bonds, are elongated due to
steric effects from bulky substituents in the ligands, N-(4-diethylamino-2-methylphenyl). Intermolecular C–H···π interactions leading to centrosymmetric synthons serve to stabilize
periodic organization of the molecules. 相似文献
48.
Rasitha Manha Veedu Niklas Niemeyer Dr. Nils Bäumer Dr. Krishnan Kartha Kalathil Prof. Dr. Johannes Neugebauer Prof. Dr. Gustavo Fernández 《Angewandte Chemie (International ed. in English)》2023,62(49):e202314211
The functionalization of π-conjugated scaffolds with sterically demanding substituents is a widely used tactic to suppress cofacial (H-type) stacking interactions, which may even inhibit self-assembly. Contrary to expectations, we demonstrate herein that increasing steric effects can result in an enhanced thermodynamic stability of H-type supramolecular polymers. In our approach, we have investigated two boron dipyrromethene (BODIPY) dyes with bulky phenyl ( 2 ) and mesityl ( 3 ) meso-substituents and compared their self-assembly in nonpolar media with that of a parent meso-methyl BODIPY 1 lacking bulky groups. While the enhanced steric demand induces pathway complexity, the superior thermodynamic stability of the H-type pathways can be rationalized in terms of additional enthalpic gain arising from intermolecular C−H⋅⋅⋅F−B interactions of the orthogonally arranged aromatic substituents, which overrule their inherent steric demand. Our findings underline the importance of balancing competing non-covalent interactions in self-assembly. 相似文献
49.
设计并合成了7种新型甲壳型液晶高分子,研究了液晶基元的化学结构和立体效应对单体及其聚合物液晶性的影响.发现在液晶基元的末端引入极性或可极化的原子基团提高了单体的熔点和液晶相的热稳定性;液晶基元的长径比越大,单体的熔点和清亮点越高;聚合使单体的液晶稳定性增加、液晶相温度范围变宽;侧链液晶基元的极性、刚性和空阻越大,聚合物的玻璃化温度越高;酰胺基团无论是在分子的末端还是在连接部位,都使单体的熔点和聚合物的玻璃化温度提高,但在分子末端时液晶相较稳定,作为中心桥键时不利于液晶相的稳定形成. 相似文献
50.
采用分子力学方法计算了与AlPO4-5分子筛相关的64种设计结构的空间能。计算得到的空间能与其骨架拓扑结构间密切相关。正交AlPO4-500的空间能最低(-3447kJ/mol),意味着该结构是最稳定的。它的结构与六方AlPO4-5具有相同的骨架结构,另有两个设计的正交结构分子筛AlPO4-562和AlPO4-557的空间能较低,分别为-3419和-3418kJ/mol,表明这两种结构是稳定的,并有可能被合成出来。发现空间能与结构中的层间氧桥"向上"或"向下"连接的有序性有关。因此,空间能可以作为设计的分子筛骨架存在的可能性大小的判据。 相似文献