全文获取类型
收费全文 | 892篇 |
免费 | 29篇 |
国内免费 | 1篇 |
专业分类
化学 | 701篇 |
晶体学 | 11篇 |
力学 | 4篇 |
数学 | 85篇 |
物理学 | 121篇 |
出版年
2024年 | 1篇 |
2023年 | 6篇 |
2022年 | 15篇 |
2021年 | 29篇 |
2020年 | 16篇 |
2019年 | 20篇 |
2018年 | 26篇 |
2017年 | 19篇 |
2016年 | 38篇 |
2015年 | 22篇 |
2014年 | 33篇 |
2013年 | 74篇 |
2012年 | 61篇 |
2011年 | 75篇 |
2010年 | 44篇 |
2009年 | 43篇 |
2008年 | 54篇 |
2007年 | 55篇 |
2006年 | 47篇 |
2005年 | 35篇 |
2004年 | 45篇 |
2003年 | 28篇 |
2002年 | 26篇 |
2001年 | 16篇 |
2000年 | 16篇 |
1999年 | 8篇 |
1998年 | 1篇 |
1997年 | 4篇 |
1996年 | 16篇 |
1995年 | 4篇 |
1994年 | 7篇 |
1993年 | 5篇 |
1992年 | 1篇 |
1991年 | 1篇 |
1990年 | 1篇 |
1988年 | 1篇 |
1986年 | 1篇 |
1985年 | 7篇 |
1984年 | 3篇 |
1983年 | 1篇 |
1982年 | 3篇 |
1981年 | 4篇 |
1980年 | 4篇 |
1979年 | 1篇 |
1978年 | 3篇 |
1977年 | 2篇 |
排序方式: 共有922条查询结果,搜索用时 31 毫秒
41.
M. Parra Corresponding author J. Vergara C. Zúñiga E. Soto T. Sierra J. L. Serrano 《Liquid crystals》2013,40(4):457-462
Two new homologous series of chiral esters derived from Schiff's bases containing a 1,3,4‐thiadiazole unit (series 6 and 7) were synthesized and their liquid crystalline and ferroelectric properties investigated. All the compounds of series 6 exhibit SmC*–SmA dimorphism and the compounds of series 7 exhibit a SmC* phase. All the compounds of these series are ferroelectric liquid crystals. 相似文献
42.
Novel liquid crystal materials base on amino-thiadiazoles, specifically 5-(3,4-di-, and/or 3,4,5-tri-n-alkoxy)phenyl-2-amino-1,3,4-thiadiazoles (3a–f, n?=?10, 12, 14) and 5-(3,4-di- and/or 3,4,5-tri-n-alkoxy)phenyl-2-(4-amino)phenyl-1,3,4-thiadiazoles (6a–f, n?=?10, 12, 14) were synthesised. The mesomorphic properties of these compounds were studied by differential scanning calorimetry and polarising optical microscopy. All the compounds in series 3a–f and series 6a–f display an enantiotropic columnar phase. The mesomorphic properties were found to be dependent on the number of the side alkoxy chains, and on the length of the rigid core, and on the position of the thiadiazole ring. The best results were obtained with compounds of series 3a–f. 相似文献
43.
44.
Crispín Cristóbal Dr. Yohar A. Hernández Dr. Joaquín López‐Serrano Prof. Dr. Margarita Paneque Dr. Ana Petronilho Prof. Dr. Manuel L. Poveda Dr. Verónica Salazar Florencia Vattier Dr. Eleuterio Álvarez Dr. Celia Maya Prof. Dr. Ernesto Carmona 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(12):4003-4020
The reactivity of a series of iridium? pyridylidene complexes with the formula [TpMe2Ir(C6H5)2(C(CH)3C(R)N H] ( 1 a – 1 c ) towards a variety of substrates, from small molecules, such as H2, O2, carbon oxides, and formaldehyde, to alkenes and alkynes, is described. Most of the observed reactivity is best explained by invoking 16 e? unsaturated [TpMe2Ir(phenyl)(pyridyl)] intermediates, which behave as internal frustrated Lewis pairs (FLPs). H2 is heterolytically split to give hydride? pyridylidene complexes, whilst CO, CO2, and H2C?O provide carbonyl, carbonate, and alkoxide species, respectively. Ethylene and propene form five‐membered metallacycles with an IrCH2CH(R)N (R=H, Me) motif, whereas, in contrast, acetylene affords four‐membered iridacycles with the IrC(?CH2)N moiety. C6H5(C?O)H and C6H5C?CH react with formation of Ir? C6H5 and Ir? C?CPh bonds and the concomitant elimination of a molecule of pyridine and benzene, respectively. Finally the reactivity of compounds 1 a – 1 c against O2 is described. Density functional theory calculations that provide theoretical support for these experimental observations are also reported. 相似文献
45.
Stereoselective hydrogenation of methylcyclohex-2-ene-1,4-diols used as important intermediates for the preparation of ampelomins and deoxy-carbasugars was studied. These olefins were obtained in few steps from a chiral cis-diol resulting from microbial oxidation of toluene. Although the stereoselective hydrogenation of this type of substrates is difficult, high yields were obtained for heterogeneous hydrogenation using Adam’s catalyst, where steric hindrance controlled the stereochemical outcome of the process. On the other hand, for homogeneous hydrogenation of similar olefins using Crabtree’s catalyst, coordination with the allylic alcohols allowed for a controlled hydrogen addition from the more hindered face. In this manner two protocols for the hydrogenation of these types of substrates resulting in complementary stereoselectivities are described. 相似文献
46.
Claudio Parra Patricio Muoz Luis Bustos Felipe Parra Mario J. Simirgiotis Hugo Escobar 《Molecules (Basel, Switzerland)》2021,26(7)
The Lamiaceae family is an important source of species among medicinal plants highly valued for their biological properties and numerous uses in folk medicine. Origanum is one of the main genera that belong to this family. The purpose of the study was to determine the phenolic composition of the Origanum vulgare extract and evaluate the antimicrobial, antioxidant, and inhibitory activities of this species that grows in the Andean region of the Atacama Desert. High-performance liquid chromatography was performed to determine the main phenols. Rosmarinic acid was identified as the predominant phenolic compound in this species (76.01 mg/100 g DW), followed by protocatechuic acid, which to our knowledge, no previous study reported similar concentrations in O. vulgare. The oregano extract exhibited a content of total phenolic (3948 mg GAE/100 g DW) and total flavonoid (593 mg QE/100 g DW) with a higher DPPH antioxidant activity (IC50 = 40.58 µg/mL), compared to the same species grown under other conditions. Furthermore, it was found to inhibit α-glucosidase activity with an IC50 value (7.11 mg/mL) lower than acarbose (129.32 mg/mL). Pseudomonas syringae and Pantoea agglomerans (both MIC 0.313 mg/mL and MBC 1.25 mg/mL) were the bacteria most susceptible to oregano extract with the lowest concentration necessary to inhibit bacterial growth. These results open the door for the potential use of this plant to manage chronic diseases, and they expand the knowledge of the species cultivated in arid environmental conditions. 相似文献
47.
Highly Enantioselective Construction of Tricyclic Derivatives by the Desymmetrization of Cyclohexadienones 下载免费PDF全文
Sandra del Pozo Dr. Alejandro Parra Dr. Sergio Díaz‐Tendero Dr. Rubén Mas‐Ballesté Dr. Silvia Cabrera Dr. José Alemán 《Angewandte Chemie (International ed. in English)》2014,53(31):8184-8189
The asymmetric synthesis of tricyclic compounds by the desymmetrization of cyclohexadienones is presented. The reaction tolerated a large variety of substituents at different positions of the cyclohexadienone, and heterocyclic rings of different sizes were accessible. Density functional theory calculations showed that the reaction proceeds through an asynchronous [4+2] cycloaddition. 相似文献
48.
Daniel Leibig Margarita Messerle Tobias Johann Christian Moers Farzaneh Kaveh Hans-Jürgen Butt Doris Vollmer Axel H. E. Müller Holger Frey 《Journal of polymer science. Part A, Polymer chemistry》2020,58(1):181-192
Well-defined polystyrene homopolymers with surface-adhesive triethoxysilyl end group were synthesized via living carbanionic polymerization, epoxide end-functionalization and subsequent hydrosilylation with triethoxysilane. Grafting-to performance of polymers with various molecular weight (Mn = 3000–14,000 g mol−1) to a silicon surface was examined in dependence of reaction time, polymer concentration, solvent and number of alkoxysilyl end groups. Crosslinkable polymers for surface modification were synthesized by statistical carbanionic copolymerization of 4-vinylbenzocyclobutene (4-VBCB) and styrene, followed by epoxide end-functionalization and triethoxysilane modification (Mn = 4000–14,000 g mol−1). The copolymers were characterized by 1H-NMR, THF-SEC, and matrix-assisted laser desorption and ionization time-of-flight mass spectrometry. In situ 1H-NMR kinetic studies in cyclohexane-d12 provided information regarding the monomer gradient in the polymer chains, with styrene being the more reactive monomer (rs = 2.75, r4-VBCB = 0.23). Thin polymer films on silicon wafers were prepared by grafting-to surface modification under conditions derived for the polystyrene homopolymer. The traceless, thermally induced crosslinking reaction of the benzocyclobutene units was studied by DSC in bulk as well as in 3–6 nm thick polymer films. Crosslinked films were analyzed by atomic force microscopy, ellipsometry, and nanoindentation, showing smooth polymer films with an increased modulus. © 2019 The Authors. Journal of Polymer Science published by Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 181–192 相似文献
49.
Lesslie Espinosa-Espinosa Leticia Garduo-Siciliano Mario Rodriguez-Canales Luis Barbo Hernandez-Portilla Maria Margarita Canales-Martinez Marco Aurelio Rodriguez-Monroy 《Molecules (Basel, Switzerland)》2022,27(1)
Mangifera indica can generate up to 60% of polluting by-products, including peels. However, it has been shown that flavonoids and mangiferin are mainly responsible for the antioxidant, anti-inflammatory, and antibacterial activities closely related to the wound-healing process. The chemical composition of MEMI (methanolic extract of M. indica) was analyzed by HPLC-DAD, as well as concentrations of total phenol (TPC) and flavonoids (TFC) and antioxidant activity (SA50). Wound-healing efficacy was determined by measurements of wound contraction, histological analysis, and tensiometric method; moreover, anti-inflammatory, antibacterial, and acute dermal toxicity (OECD 402) were also evaluated. Phenol, resorcinol, conjugated resorcinol, and mangiferin were detected. TPC, TFC, and SA50 were 136 mg GAE/g, 101.66 mg QE/g, and 36.33 µg/mL, respectively. Tensile strength and wound contraction closure did not show significant differences between MEMI and dexpanthenol groups. Histological analysis (after 14 days) shows a similar architecture between MEMI treatment and normal skin. MEMI exhibits a reduction in edema. Staphylococcus epidermidis had an MIC of 2 mg/mL, while Staphylococcus aureus, Pseudomonas aeruginosa, and Escherichia coli reached 4 mg/mL. The MEMI showed no signs of toxicity. Therefore, this study demonstrates multiple targets that flavonoids and mangiferin of MEMI may present during the healing process. 相似文献
50.
Margarita A. Epishina Alexander S. Kulikov Leonid L. Fershtat 《Molecules (Basel, Switzerland)》2022,27(8)
A series of novel 1,4-dihydrobenzo[1,2,4][e]triazines bearing an acetyl or ester moiety as a functional group at the C(3) atom of the 1,2,4-triazine ring were synthesized. The synthetic protocol is based on an oxidative cyclization of functionally substituted amidrazones in the presence of DBU and Pd/C. It was found that the developed approach is suitable for the preparation of 1,4-dihydrobenzo[e][1,2,4]triazines, but the corresponding Blatter radicals were isolated only in few cases. In addition, a previously unknown dihydrobenzo[e][1,2,4]triazolo[3,4-c][1,2,4]triazine tricyclic open-shell derivative was prepared. Studies of thermal behavior of the synthesized 1,4-dihydrobenzo[1,2,4][e]triazines revealed their high thermal stability (up to 240–250 °C), which enables their application potential as components of functional organic materials. 相似文献