全文获取类型
收费全文 | 178篇 |
免费 | 6篇 |
国内免费 | 1篇 |
专业分类
化学 | 125篇 |
晶体学 | 6篇 |
数学 | 1篇 |
物理学 | 53篇 |
出版年
2022年 | 1篇 |
2021年 | 2篇 |
2020年 | 4篇 |
2019年 | 6篇 |
2017年 | 4篇 |
2016年 | 3篇 |
2015年 | 5篇 |
2014年 | 5篇 |
2013年 | 11篇 |
2012年 | 10篇 |
2011年 | 11篇 |
2010年 | 11篇 |
2009年 | 8篇 |
2008年 | 11篇 |
2007年 | 10篇 |
2006年 | 12篇 |
2005年 | 5篇 |
2004年 | 6篇 |
2003年 | 7篇 |
2002年 | 5篇 |
2001年 | 1篇 |
2000年 | 5篇 |
1999年 | 2篇 |
1998年 | 2篇 |
1997年 | 1篇 |
1996年 | 2篇 |
1995年 | 3篇 |
1994年 | 2篇 |
1990年 | 1篇 |
1988年 | 3篇 |
1986年 | 2篇 |
1985年 | 2篇 |
1984年 | 3篇 |
1982年 | 2篇 |
1981年 | 1篇 |
1980年 | 2篇 |
1978年 | 3篇 |
1976年 | 2篇 |
1975年 | 1篇 |
1973年 | 4篇 |
1972年 | 1篇 |
1971年 | 2篇 |
1968年 | 1篇 |
排序方式: 共有185条查询结果,搜索用时 15 毫秒
11.
Makoto Nagai Atsuo Nishioka 《Journal of polymer science. Part A, Polymer chemistry》1968,6(6):1655-1660
The NMR spectra of stereoblock poly(methyl methacrylate) in several solvents were measured. It is concluded from the following experimental results that the solute–solvent complexes are formed in benzene solution: the chemical shifts measured in C6H6 go to a lower field than do those in CDCl3, except those of the ester methyl group, which splits into three resonances, and the shifts in the aromatic solvents are so different from those in the aliphatic solvents that Buckingham's theory cannot be applied to the results. The analysis of the temperature dependence of the chemical shifts of PMMA in benzene solution gave the heat of formation of the complex: ΔH = 2.8 ± 0.5 kcal./mole. 相似文献
12.
Shirokawa S Kamiyama M Nakamura T Okada M Nakazaki A Hosokawa S Kobayashi S 《Journal of the American Chemical Society》2004,126(42):13604-13605
A highly regio- and diastereoselective TiCl4-mediated vinylogous Mukaiyama aldol reaction using the chiral vinylketene silyl N,O-acetal has been developed. The present vinylogous Mukaiyama aldol reaction provides a unique and effective means of controlling remote asymmetric induction. The methyl group at the alpha-position is important in achieving a high level of stereoselectivity. From a synthetic point of view, this methodology can provide a one-step construction of delta-hydroxy-alpha,gamma-dimethyl-alpha,beta-unsaturated carbonyl unit that is seen in many natural polyketide products. 相似文献
13.
Reliability of mean transit time obtained using perfusion-weighted MR imaging; comparison with positron emission tomography 总被引:2,自引:0,他引:2
Mihara F Kuwabara Y Tanaka A Yoshiura T Sasaki M Yoshida T Masuda K Matsushima T 《Magnetic resonance imaging》2003,21(1):33-39
The purpose of this project was to assess the reliability of the cerebral mean transit time (MTT) obtained using perfusion-weighted MR imaging by comparing it with the MTT obtained when performing positron emission tomography (PET). Ten patients with chronic occlusive cerebrovascular disease were investigated. They had either unilateral internal carotid artery occlusion or middle cerebral artery occlusion. The regions-of-interest were placed in non-infarcted areas within the territory of the middle cerebral artery on the affected side. Control regions-of-interest were placed in mirrored regions of the contralateral side. Linear regression analyses were performed using the parameters of the MTT obtained with perfusion-weighted MR imaging and the MTT, cerebral blood flow, vascular reactivity, and oxygen extraction fraction obtained with PET. The respective MTTs of the affected and non-affected sides obtained with perfusion-weighted MR imaging versus those with PET were 7.3 +/- 2.2 s and 6.0 +/- 1.2 s versus 8.2 +/- 3.0 s and 6.4 +/- 1.7 s. The MTT obtained using perfusion-weighted MR imaging and PET demonstrated statistically significant correlation (r = 0.87, p < 0.0001). The MTT obtained with perfusion-weighted MR imaging correlated statistically with cerebral blood flow (r = -0.74, p < 0.001), vascular reactivity (r = -0.73, p < 0.001) and oxygen extraction fraction (r = 0.61, p < 0.01). Similarly, the MTT obtained using PET statistically correlated with cerebral blood flow (r = -0.78, p < 0.0001), vascular reactivity (r = -0.51, p < 0.05) and oxygen extraction fraction (r = 0.68, p < 0.01). The reliability of the MTT obtained using perfusion-weighted MR imaging appears to be approximately equal to that obtained with positron emission tomography. 相似文献
14.
New atom-economical catalytic systems consisting of [Cp∗IrCl2]2/NaOAc (Cp∗=pentamethylcyclopentadienyl) for the N-alkylation of carbamates and amides using alcohols as alkylating agents under solvent-free conditions have been developed. For example, the reaction of n-butyl carbamate with benzyl alcohol in the presence of [Cp∗IrCl2]2 (5.0 mol % Ir) and NaOAc (5.0 mol %) at 130 °C under the absence of solvent gives n-butyl N-benzylcarbamate in the yield of 94%. The present catalytic system is applicable to not only carbamates but also amides, and only harmless water is produced as co-product. 相似文献
15.
Atsuo Yamada Kazuyuki Saka Makiko Uehara Sou Taminato Ryoji Kanno Fabrice Mauvy Claude Grenier 《Electrochemistry communications》2010,12(12):1690-1693
Electrode–electrolyte hetero-epitaxial systems for solid oxide fuel cells (SOFCs) with two different configuration of Nd2NiO4 + δ(110)//YSZ(100) and Nd2NiO4 + δ(100)//YSZ(110) were successfully fabricated by pulsed laser deposition. Thin films of Nd2NiO4 + δ approximately 20 nm thick were grown on a commercial single crystal of YSZ. The preferred two-dimensional diffusion paths of the oxide ions were perpendicular to the substrate for both configurations and showed oxygen reduction capability different from each other. This opens up new research direction focusing on the details of anisotropic catalytic activity of SOFC cathode depending on the crystalline surface. 相似文献
16.
Superstructure in the Metastable Intermediate‐Phase Li2/3FePO4 Accelerating the Lithium Battery Cathode Reaction
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Shin‐ichi Nishimura Ryuichi Natsui Prof. Atsuo Yamada 《Angewandte Chemie (International ed. in English)》2015,54(31):8939-8942
LiFePO4 is an important cathode material for lithium‐ion batteries. Regardless of the biphasic reaction between the insulating end members, LixFePO4, x≈0 and x≈1, optimization of the nanostructured architecture has substantially improved the power density of positive LiFePO4 electrode. The charge transport that occurs in the interphase region across the biphasic boundary is the primary stage of solid‐state electrochemical reactions in which the Li concentrations and the valence state of Fe deviate significantly from the equilibrium end members. Complex interactions among Li ions and charges at the Fe sites have made understanding stability and transport properties of the intermediate domains difficult. Long‐range ordering at metastable intermediate eutectic composition of Li2/3FePO4 has now been discovered and its superstructure determined, which reflected predominant polaron crystallization at the Fe sites followed by Li+ redistribution to optimize the Li? Fe interactions. 相似文献
17.
Iron–Oxalato Framework with One‐Dimensional Open Channels for Electrochemical Sodium‐Ion Intercalation
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Xianfen Wang Ryosuke Kurono Dr. Shin‐ichi Nishimura Dr. Masashi Okubo Prof. Atsuo Yamada 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(3):1096-1101
Discovery of a new class of ion intercalation compounds is highly desirable due to its relevance to various electrochemical devices, such as batteries. Herein, we present a new iron–oxalato open framework, which showed reversible Na+ intercalation/extraction. The hydrothermally synthesized K4Na2[Fe(C2O4)2]3 ? 2 H2O possesses one‐dimensional open channels in the oxalato‐bridged network, providing ion accessibility up to two Na+ per the formula unit. The detailed studies on the structural and electronic states revealed that the framework exhibited a solid solution state almost entirely during Na+ intercalation/extraction associated with the reversible redox of Fe. The present work demonstrates possibilities of the oxalato frameworks as tunable and robust ion intercalation electrode materials for various device applications. 相似文献
18.
Fujiki S Iwao Y Kobayashi M Miyagishima A Itai S 《Chemical & pharmaceutical bulletin》2011,59(5):553-558
It has been reported that tablets of clarithromycin (CAM), a 14-membered macrolide antibiotic, are especially stable under low pH conditions such as in gastric fluid, and showed excellent antibacterial efficiency even though CAM molecules themselves are rapidly decomposed. Therefore, we aimed to clarify the stabilization mechanism of CAM tablets under low pH conditions. From the results of stability and dissolution tests, the optimal decomposition rate constant (K(dec)) and dissolution rate constant (K(dis)) at various pH values were calculated by curve-fitting to consecutive reactions. Consequently, log(K(dec)) increased as pH decreased. On the other hand, log(K(dis)) increased as pH decreased from 3.0 to 1.5, but decreased as pH decreased from 1.5 to 1.0. In addition, the disintegration time of commercially available tablets at pH 1.0 and 1.2 was found to be delayed, resulting in a decrease of K(dis). Furthermore, from powder X-ray diffraction, HPLC and elemental analysis, the delay in disintegration time might be attributable to the formation of a transparent gel, formed by the reaction between CAM molecule and hydrochloric acid under low pH conditions, on the surface of CAM tablet. On the basis of these results, this report can be considered the first case where a transparent gel prevents gastric fluid from penetrating the tablet, resulting in reduced decomposition of CAM following oral administrating. 相似文献
19.
Iwasaki Y Matsui R Suzuki T Nakazaki A Kobayashi S 《Chemical & pharmaceutical bulletin》2011,59(4):522-524
We have developed a high-yielding and stereoselective vinylogous Mukaiyama aldol reaction (VMAR) of α-haloenals. Contrary to the simple α,β-unsaturated aldehyde, α-haloenals were found to be reactive affording the corresponding VMAR adducts in excellent yields. Some transformations of VMAR adducts by Pd-mediated cross-coupling were also examined in order to demonstrate the synthetic utility of VMAR of α-haloenals. 相似文献
20.
We study the analytic Bethe, ansatz in solvable vertex models associated with the YangianY(X
r
) or its quantum affine analogueU
q
(X
r
(1)
) forX
r
=B
r
,C
r
andD
r
. Eigenvalue formulas are proposed for the transfer matrices related to all the fundamental representations ofY(X
r
). Under the Bethe ansatz equation, we explicitly prove that they are pole-free, a crucial property in the ansatz. Conjectures are also given on higher representation cases by applying theT-system, the transfer matrix functional relations proposed recently. The eigenvalues are neatly described in terms of Yangian analogues of the semi-standard Young tableaux. 相似文献