全文获取类型
收费全文 | 664篇 |
免费 | 21篇 |
国内免费 | 2篇 |
专业分类
化学 | 532篇 |
晶体学 | 10篇 |
力学 | 3篇 |
数学 | 44篇 |
物理学 | 98篇 |
出版年
2023年 | 5篇 |
2022年 | 4篇 |
2021年 | 25篇 |
2020年 | 15篇 |
2019年 | 15篇 |
2018年 | 18篇 |
2017年 | 17篇 |
2016年 | 30篇 |
2015年 | 16篇 |
2014年 | 30篇 |
2013年 | 51篇 |
2012年 | 43篇 |
2011年 | 59篇 |
2010年 | 30篇 |
2009年 | 34篇 |
2008年 | 38篇 |
2007年 | 39篇 |
2006年 | 36篇 |
2005年 | 25篇 |
2004年 | 43篇 |
2003年 | 21篇 |
2002年 | 25篇 |
2001年 | 8篇 |
2000年 | 11篇 |
1999年 | 3篇 |
1998年 | 1篇 |
1997年 | 3篇 |
1996年 | 10篇 |
1995年 | 1篇 |
1994年 | 3篇 |
1993年 | 6篇 |
1992年 | 1篇 |
1990年 | 1篇 |
1985年 | 5篇 |
1984年 | 3篇 |
1982年 | 2篇 |
1981年 | 2篇 |
1980年 | 3篇 |
1979年 | 1篇 |
1978年 | 3篇 |
1977年 | 1篇 |
排序方式: 共有687条查询结果,搜索用时 171 毫秒
31.
Anna Matveeva Zoya Starikova Margarita Passechnik Irina Odinets Tatyana Mastryukova 《Phosphorus, sulfur, and silicon and the related elements》2013,188(8-9)
The enols R 1 R 2 P(E)(CN)C = CR 3 OH (E = O or S) gave in solutions either neutral metal complexes ML x or M(OH) y L x . The anionic ambidentate ligands are coordinated through E and O atoms in solutions, and O, E, and N atoms in in crystals. 相似文献
32.
The Thorpe-Ziegler reaction has been used in the preparation of enaminonitriles and cyclic ketones for many years. A wide variety of bases1 have been employed to acomplish this reaction, the most effective being the alkali metal salts of aralkyl amines. The reaction conditions vary from room temperature to toluene reflux temperature for long periods of time1. 相似文献
33.
34.
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
35.
Gold nanoparticles functionalized with a triarylcarbinol derivative have been used as colorimetric molecular probes for the naked-eye detection of the nerve agent simulants DCNP and DFP. The detection process is based on the compensation of charges at the surface of the nanoparticles which triggers their aggregation in solution with the resulting change in their plasmon band. 相似文献
36.
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
37.
Imaging the Magnetic Reversal of Isolated and Organized Molecular‐Based Nanoparticles using Magnetic Force Microscopy 下载免费PDF全文
Elena Pinilla‐Cienfuegos Samuel Mañas‐Valero Josep Canet‐Ferrer Laure Catala Talal Mallah Alicia Forment‐Aliaga Eugenio Coronado 《Particle & Particle Systems Characterization》2015,32(6):693-700
In the race towards miniaturization in nanoelectronics, magnetic nanoparticles (MNPs) have emerged as potential candidates for their integration in ultrahigh‐density recording media. Molecular‐based materials open the possibility to design new tailor‐made MNPs with variable composition and sizes, which benefit from the intrinsic properties of these materials. Before their implementation in real devices is reached, a precise organization on surfaces and a reliable characterization and manipulation of their individual magnetic behavior are required. In this paper, it is demonstrated how molecular‐based MNPs are accurately organized on surfaces and how the magnetic properties of the individual MNPs are detected and tuned by means of low‐temperature magnetic force microscopy (LT‐MFM) with variable magnetic field. The magnetization reversal on isolated and organized MNPs is investigated; in addition, the temperature dependence of their magnetic response is evaluated. 相似文献
38.
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
39.
Orthogonally diprotected l-glyceraldehyde was efficiently prepared from readily available starting materials, allowing to obtain a highly stable and synthetically versatile chiral building block compared to known symmetrically protected derivatives. 相似文献
40.
Multiscale Approach to the Study of the Electronic Properties of Two Thiophene Curcuminoid Molecules 下载免费PDF全文
Alvaro Etcheverry‐Berríos Ignacio Olavarría Dr. Mickael L. Perrin Raúl Díaz‐Torres Domingo Jullian Dr. Ingrid Ponce Dr. José H. Zagal Dr. Jorge Pavez Dr. Sergio O. Vásquez Dr. Herre S. J. van der Zant Dr. Diana Dulić Dr. Núria Aliaga‐Alcalde Dr. Monica Soler 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(36):12808-12818
We studied the electronic and conductance properties of two thiophene–curcuminoid molecules, 2‐thphCCM ( 1 ) and 3‐thphCCM ( 2 ), in which the only structural difference is the position of the sulfur atoms in the thiophene terminal groups. We used electrochemical techniques as well as UV/Vis absorption studies to obtain the values of the HOMO–LUMO band gap energies, showing that molecule 1 has lower values than 2 . Theoretical calculations show the same trend. Self‐assembled monolayers (SAMs) of these molecules were studied by using electrochemistry, showing that the interaction with gold reduces drastically the HOMO–LUMO gap in both molecules to almost the same value. Single‐molecule conductance measurements show that molecule 2 has two different conductance values, whereas molecule 1 exhibits only one. Based on theoretical calculations, we conclude that the lowest conductance value, similar in both molecules, corresponds to a van der Waals interaction between the thiophene ring and the electrodes. The one order of magnitude higher conductance value for molecule 2 corresponds to a coordinate (dative covalent) interaction between the sulfur atoms and the gold electrodes. 相似文献