全文获取类型
收费全文 | 261篇 |
免费 | 6篇 |
国内免费 | 1篇 |
专业分类
化学 | 235篇 |
数学 | 3篇 |
物理学 | 30篇 |
出版年
2022年 | 2篇 |
2021年 | 1篇 |
2020年 | 8篇 |
2019年 | 4篇 |
2018年 | 3篇 |
2017年 | 1篇 |
2016年 | 2篇 |
2015年 | 3篇 |
2014年 | 6篇 |
2013年 | 14篇 |
2012年 | 13篇 |
2011年 | 16篇 |
2010年 | 13篇 |
2009年 | 3篇 |
2008年 | 12篇 |
2007年 | 15篇 |
2006年 | 14篇 |
2005年 | 14篇 |
2004年 | 18篇 |
2003年 | 11篇 |
2002年 | 7篇 |
2001年 | 7篇 |
2000年 | 8篇 |
1999年 | 7篇 |
1998年 | 1篇 |
1997年 | 3篇 |
1996年 | 3篇 |
1995年 | 1篇 |
1994年 | 2篇 |
1991年 | 2篇 |
1990年 | 3篇 |
1989年 | 1篇 |
1988年 | 3篇 |
1987年 | 8篇 |
1986年 | 4篇 |
1985年 | 4篇 |
1984年 | 8篇 |
1983年 | 2篇 |
1982年 | 3篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1979年 | 4篇 |
1978年 | 4篇 |
1976年 | 1篇 |
1974年 | 1篇 |
1972年 | 1篇 |
1971年 | 1篇 |
1966年 | 1篇 |
1960年 | 1篇 |
1913年 | 2篇 |
排序方式: 共有268条查询结果,搜索用时 15 毫秒
111.
Spherical silica particles were synthesized using the sol‐gel method by hydrolyzing tetraethyl orthosilicate (TEOS) with an alkali catalyst, and it was investigated how the experimental conditions (the reaction temperature, the concentration and dropping rate of the hydrolysis catalyst solution) affected the size and morphology of silica particles. Furthermore, the silica particles were doped with sodium fluoride to measure their ion release ability. The mean diameters of the silica particles changed according to the reaction temperature and the dropping rate of the hydrolysis catalyst, namely the higher the reaction temperature or the slower the dropping rate the smaller are the mean diameters. The surface area of the silica particles was significantly different depending on the dropping rate of the hydrolysis catalyst, namely the slower the dropping rate the larger the specific surface area. The specific heat capacity and thermal reduction (TG) of the silica particles were significantly different according to the reaction temperature, namely the higher the reaction temperature the lower the specific heat capacity and the TG. It was found that the fluoride‐retaining ability was proportional to the surface area of silica particles. The fluoride ion release was equilibrated on elapsing 5 min. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
112.
Kakiuchi F Matsuura Y Kan S Chatani N 《Journal of the American Chemical Society》2005,127(16):5936-5945
When the reaction of aromatic ketones with arylboronates (arylboronic acid esters) using RuH(2)(CO)(PPh(3))(3) (3) as a catalyst was conducted in toluene, the corresponding arylation product was obtained in moderate yields. In this case, a nearly equivalent amount of a benzyl alcohol derived from a reduction of an aromatic ketone was also formed. The use of aliphatic ketones, such as pinacolone and acetone, as an additive or a solvent dramatically suppressed the reduction of the aromatic ketones and, as a result, ortho-arylation products were obtained in high yield based on the aromatic ketones. In these reactions, the aliphatic ketone functioned as a scavenger of ortho-hydrogens of the aromatic ketones and the B(OR)(2) moiety of the arylboron compound (HB species). A variety of aromatic ketones, such as acetophenones, acetonaphthones, tetralones, and benzosuberone, could also be used in this coupling reaction. Several arylboronates containing electron-donating (NMe(2), OMe, and Me) and -withdrawing (CF(3) and F) groups were also applicable to this coupling reaction. Intermolecular competitive reaction using pivalophenone-d(0)() and -d(5) and intramolecular competitive reaction using pivalophenone-d(1) were carried out using 3 as a catalyst. The k(H)/k(D) value for the intermolecular competitive reaction was substantially different, compared with intramolecular competitive reaction. This strongly suggests the production of an intermediate where the ketone carbonyl is coordinated to the ruthenium involved in this catalytic reaction. (1)H and (11)B NMR studies using 2'-methylacetophenone, phenylboronate (2), and pinacolone (6) indicate that 6 functions effectively as a scavenger of the HB species. 相似文献
113.
The molecular weights of isopoly(L-Iysine), poly(L-ornithine), and poly(L-, -diaminobutylic acid), the homologues of poly (L-lysine), were determined by the sedimentation equilibrium method in aqueous solutions of 1.0 M NaCl or 0.1 M Na2CO3. In every sample the molecular weights in the presence of carbonate ions was twice that in NaCl solution. In a previous paper we reported that poly(L-lysine) behaved as a dimer at concentrations higher than 0.4 g/dl in the presence of carbonate ions and as a monomer in dilute solution, and these two forms were related by a monomer-dimer equilibrium. The homologues did not have a monomer-dimer equilibrium relationship under the conditions of the measurements that we carried out. The CD spectrum of isopoly(L-lysine) in water showed a uniform increase with a decrease in the wave length in the presence of carbonate ions. However, in the alkaline region in NaOH solution, the spectrum changed and a small minimum at 212 nm was found. When additional carbonate ions were added a large minimum at 205 nm was observed. This result can be explained by a change in the conformation from a random coil to a regular structure. We could not compare isopoly(L-lysine) with other polypeptides, because it does not have peptide bonds. The CD spectra of poly(L-ornithine) and poly(L-, -diaminobutylic acid) in NaOH or Na2CO3 solutions showed only slightly regular structures. It was also confirmed that the dimer-structures of the poly (L-lysine) homologues do not have regular structures.This paper was presented at the VI. Symposium on Analytical Ultracentrifugation, Marburg, FRG, February 16–17,1989. 相似文献
114.
115.
The structure of 12Be is investigated using a microscopic α+α+4n model based on the molecular-orbit (MO) model. It is shown that the remark-able α-clustering and the contribution of the spin-orbit interaction make the binding of the state with the (3/2?)2(1/2+)2 configuration for the valence neutrons properly stronger in comparison with the closed p-shell (3/2?)2(1/2?)2 configuration. The molecular-like structure of the C isotopes is also investigated using a microscopic α+α+α+n+n+... model. 相似文献
116.
N Chatani T Asaumi S Yorimitsu T Ikeda F Kakiuchi S Murai 《Journal of the American Chemical Society》2001,123(44):10935-10941
Catalytic reactions which involve the cleavage of an sp(3) C-H bond adjacent to a nitrogen atom in N-2-pyridynyl alkylamines are described. The use of Ru(3)(CO)(12) as the catalyst results in the addition of the sp(3) C-H bond across the alkene bond to give the coupling products. A variety of alkenes, including terminal, internal, and cyclic alkenes, can be used for the coupling reaction. The presence of directing groups, such as pyridine, pyrimidine, and an oxazoline ring, on the nitrogen of the amine is critical for a successful reaction. This result indicates the importance of the coordination of the nitrogen atom to the ruthenium catalyst. In addition, the nature of the substituents on the pyridine ring has a significant effect on the efficiency of the reaction. Thus, the substitution of an electron-withdrawing group on the pyridine ring as well as a substitution adjacent to the sp(2) nitrogen in the pyridine ring dramatically retards the reaction. Cyclic amines are more reactive than acyclic ones. The choice of solvent is also very important. Of the solvents examined, 2-propanol is the solvent of choice. 相似文献
117.
Yukio Kitagawa Daisuke Hobara Masahiro Yamamoto Takashi Kakiuchi 《Journal of Solid State Electrochemistry》2008,12(4):461-469
The electrochemical reductive desorption of the self-assembled monolayers of 3-mercaptopropionic acid in an aqueous alkaline
solution gives a sharp peak with the full width at half maximum of about 20 mV irrespective of the type of cations in a linear
scan voltammogram. This suggests that a strong attractive interaction exists between negatively charged carboxylate groups
in the self-assembled monolayer surface due to the counterion binding, which not only simply stabilizes the adsorbed carboxylates
but also makes the interaction between the adsorbed thiolates even attractive possibly by forming a two-dimensional ionic
crystal. The effect of tetraalkylammonium ions on the shape of the voltammograms was also examined.
Dedicated to Professor Oleg Petrii on the occasion of his 70th birthday. 相似文献
118.
Ken Tsutsumi Dr. Yuuki Yanagisawa Akinori Furutani Dr. Tsumoru Morimoto Dr. Kiyomi Kakiuchi Prof. Takehiko Wada Prof. Tadashi Mori Dr. Yoshihisa Inoue Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(25):7448-7455
Upon diastereodifferentiating the [2+2] photocycloaddition of ethylene to a series of p‐substituted (?)‐8‐phenylmenthyl cyclohexenonecarboxylates, the diastereoselectivity was critically controlled by the nature of the substituent introduced to the chiral auxiliary, and the p‐nitro‐substituted substrate afforded the cycloadducts in 90 % diastereomeric excess (de) and with 97 % isolated yield. Detailed experimental and theoretical conformation analyses revealed that the stacking interaction of the aromatic auxiliary with the cyclohexenone moiety plays the decisive role in determining the substrate conformation and is, therefore, responsible for the dramatic enhancement of the de. Of particular interest, the product de was directly related to the ellipticity of the substrate, enabling us to “predict” the de prior to photoirradiation. 相似文献
119.
Gopinath SC Awazu K Fujimaki M Shimizu K Mizutani W Tsukagoshi K 《The Analyst》2012,137(15):3520-3527
The surfaces of silica-based sensor chips, designed for evanescent-field-coupled waveguide-mode sensors, were functionalized using various surface chemistries. The immobilization of molecular entities on the functionalized silica surfaces was monitored using various microscopic techniques (scanning electron, fluorescence, and atomic force microscopies). Further, gold nanoparticle-based signal enhancement analyses were performed with protein conjugation on different functionalized surfaces using a waveguide-mode sensor. Based on these analyses, the sensor surfaces modified with glutaraldehyde (Glu) and carbonyldiimidazole were found to be good for molecules of different sizes. In addition, it can be inferred that the Glu-modified surface may be suitable for small molecules with diameters around 5 nm owing to its surface roughness. The modified surface with carbonyldiimidazole is suitable for the direct immobilization of larger molecules especially for biomolecular assemblies without intermediate chemical modifications. 相似文献
120.
Ade Arsianti Hiroki Tanimoto Tsumoru Morimoto Anton Bahtiar Tatsuo Takeya Kiyomi Kakiuchi 《Tetrahedron》2012,68(13):2884-2891
A novel polyhydroxylated 18-membered analogue of antimycin A3 was synthesized. Our synthesis commenced with Boc-l-threonine and was achieved by way of one-pot homocoupling/ring-closing olefin metathesis reaction cascade and Sharpless asymmetric dihydroxylation. The analogue exhibited a greater anticancer activity against HeLa cells, breast MDA-MB-231 cells, and prostate PC-3 cells compared to the original antimycin A3. 相似文献