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61.
Oxophilic synthetic receptors were designed and synthesized using a porphyrin scaffold, with the aim of constructing a preorganized complementary binding site for phenols and carbohydrates. We pursued three strategies for phenol recognition: (1) Lewis acid/Lewis base combinations serving as a hydrogen bond donor and acceptor for the OH group, (2) Lewis base/pi-pi stacking, targeting both the OH group and the aromatic moiety of phenols, and (3) exchange of the axial hydroxyl ligand on a trivalent and oxophilic metal center of aluminum porphyrin. For the recognition of acidic phenols, the most promising recognition motif was Lewis base/pi-pi stacking, which can bind to phenols with a hydrogen bond and pi-pi stacking interactions. [5-(8-Quinolyl)-10,15,20-triphenylporphyrinato]zinc binds to p-nitrophenol with a binding constant of 540 M(-)(1) in CHCl(3) at 25 degrees C. For carbohydrate recognition, we designed the metalloporphyrin receptor having 8-quinolyl groups and o-carbomethoxymethoxyphenyl groups, where these Lewis basic parts serve as the cooperative hydrogen bonding sites for the hydroxyl groups of glucoside. The receptor binds to beta-octyl glucoside with a binding constant of 7.35 x 10(4) M(-)(1) in CHCl(3) at 15 degrees C, demonstrating importance of formation of a highly ordered hydrogen bonding network between the receptor and the guest. These binding features have significant implications for the rational design of oxophilic artificial receptors. 相似文献
62.
Selective Generation of Formamides through Photocatalytic CO2 Reduction Catalyzed by Ruthenium Carbonyl Compounds 下载免费PDF全文
Dr. Katsuaki Kobayashi Dr. Takashi Kikuchi Prof. Susumu Kitagawa Prof. Koji Tanaka 《Angewandte Chemie (International ed. in English)》2014,53(44):11813-11817
The selective formation of dialkyl formamides through photochemical CO2 reduction was developed as a means of utilizing CO2 as a C1 building block. Photochemical CO2 reduction catalyzed by a [Ru(bpy)2(CO)2]2+ (bpy: 2,2′‐bipyridyl)/[Ru(bpy)3]2+/Me2NH/Me2NH2+ system in CH3CN selectively produced dimethylformamide. In this process a ruthenium carbamoyl complex ([Ru(bpy)2(CO)(CONMe2)]+) formed by the nucleophilic attack of Me2NH on [Ru(bpy)2(CO)2]2+ worked as the precursor to DMF. Thus Me2NH acted as both the sacrificial electron donor and the substrate, while Me2NH2+ functioned as the proton source. Similar photochemical CO2 reductions using R2NH and R2NH2+ (R=Et, nPr, or nBu) also afforded the corresponding dialkyl formamides (R2NCHO) together with HCOOH as a by‐product. The main product from the CO2 reduction transitioned from R2NCHO to HCOOH with increases in the alkyl chain length of the R2NH. The selectivity between R2NCHO and HCOOH was found to depend on the rate of [Ru(bpy)2(CO)(CONR2)]+ formation. 相似文献
63.
TiO2(B) nanowires and TiO2 anatase nanowires were synthesized by the hydrothermal processing in 10 M NaOH aq. at 150 °C followed by the post-heat treatment at 300-800 °C. As-synthesized Na-free titanate nanowires (prepared by the hydrothermal treatment and repeated ion exchanging by HCl (aq.) were transformed into TiO2(B) structure with maintaining 1-D morphology at 300-500 °C, and further transformed into anatase structure at 600-800 °C with keeping 1-D shape. At 900 °C, they transformed into rod-shaped rutile grains. Microstructure of these 1-D TiO2 nanomaterials is reported. 相似文献
64.
Yasuhiro Tachibana Ryusuke Muramoto Hajime Matsumoto Susumu Kuwabata 《Research on Chemical Intermediates》2006,32(5):575-583
We investigated the photoelectrochemical characteristics and photo-stability of Cu2O layered on a copper plate using a hydrophobic ionic liquid. Our findings revealed that Cu2O is stable under white light irradiation, provided water is removed from the electrolyte. Methyl viologen derivative, a well-established
electron acceptor, was introduced to the ionic liquid electrolyte, allowing the photo-induced electron transfer reaction at
the Cu2O/electrolyte interface to be characterized. The methyl viologen derivative exhibited two distinct redox reactions at −0.56
V and −0.98 V vs. Ag/AgCl, clearly indicating that no dimer formation or co-proportionation reaction occurred. The excessive photocurrents
being continuously generated resulted from a viable photo-induced electron transfer reaction from the Cu2O to the acceptor. However, in contrast, the reduction of the Cu2O by water in the aqueous solution causes this electron transfer to be inhibited. We further demonstrate that these findings
are vital to understanding the role of the Cu2O and its photoelectrochemical applications. 相似文献
65.
Homohelicity induction of a series of propylene-linked zinc bilinone (ZnBL; linear tetrapyrrople-zinc(II) complex) dimers upon complexation with chiral amine and α-amino esters was investigated. Introduction of substituents such as dimethyl and diisobutyl to the central carbon of the propylene spacer gave rise to stabilization of the homohelical (PP and MM) conformers rather than the heterohelical (PM) conformer. As bulkiness of the substituent increased, stability of the homohelical conformers was raised. The preorganization of the homohelical structures led to significantly amplified homohelicity induction upon complexation with chiral amine and α-amino esters. 相似文献
66.
Seiichi Ohta Susumu Inasawa Yukio Yamaguchi 《Journal of Polymer Science.Polymer Physics》2012,50(12):863-869
When a mixture of liquid crystal (LC) and photo reactive monomer is irradiated by UV light, polymerization occurs and LC droplets form through phase separation, producing polymer dispersed LCs (PDLCs). Although size control of LC droplets and reduced amounts of LC in PDLC films are important in applications, precise size control of LC droplets at a low LC fraction has not yet been accomplished. In this study, the phase diagrams of the LC/initial monomer and the LC/polymer during polymerization were used to control LC droplet size at various LC fractions. Both the relative position of the sample in the initial phase diagram and the shift of the phase separation line during polymerization were shown to be important in determining the size of LC droplets. Our results are expected to provide a new strategy for precise size control of LC droplets especially at a low LC fraction range, which would be a great help for PDLC applications. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012 相似文献
67.
68.
Susumu Ohira 《合成通讯》2013,43(3-4):561-564
Dimethyl (1-diazo-2-oxopropyl) phosphonate (3) was transformed to dimethyl (diazomethyl)—phosphonate (4), which was used for the synthesis of enol ether or alkyne without isolation. 相似文献
69.
70.
Noriyuki Yoshii Yoshimichi Andoh Susumu Okazaki 《Journal of computational chemistry》2020,41(9):940-948
We derived a new expression for the electrostatic interaction of three-dimensional charge-neutral systems with two-dimensional periodic boundary conditions (slab geometry) using a fast multipole method (FMM). Contributions from all the image cells are expressed as a sum of real and reciprocal space terms, and a self-interaction term. The reciprocal space contribution consists of two parts: zero and nonzero terms of the absolute value of the reciprocal lattice vector. To test the new expressions, electrostatic interactions were calculated for a randomly placed charge distribution in a cubic box and liquid water produced by molecular dynamics calculation. The accuracy could be controlled by the degree of expansion of the FMM. In the present expression, the computational complexity of the electrostatic interaction of N-particle systems is order N, which is superior to that of the conventional two-dimensional periodic Ewald method for a slab geometry and the particle mesh Ewald method with a large empty space at an interface of the unit cell. © 2020 Wiley Periodicals, Inc. 相似文献