全文获取类型
收费全文 | 2571篇 |
免费 | 58篇 |
国内免费 | 20篇 |
专业分类
化学 | 1867篇 |
晶体学 | 40篇 |
力学 | 31篇 |
综合类 | 1篇 |
数学 | 124篇 |
物理学 | 586篇 |
出版年
2021年 | 21篇 |
2020年 | 13篇 |
2019年 | 30篇 |
2018年 | 19篇 |
2017年 | 20篇 |
2016年 | 34篇 |
2015年 | 36篇 |
2014年 | 51篇 |
2013年 | 153篇 |
2012年 | 92篇 |
2011年 | 135篇 |
2010年 | 63篇 |
2009年 | 82篇 |
2008年 | 144篇 |
2007年 | 153篇 |
2006年 | 144篇 |
2005年 | 135篇 |
2004年 | 152篇 |
2003年 | 137篇 |
2002年 | 107篇 |
2001年 | 65篇 |
2000年 | 50篇 |
1999年 | 25篇 |
1998年 | 20篇 |
1997年 | 19篇 |
1996年 | 23篇 |
1995年 | 32篇 |
1994年 | 33篇 |
1993年 | 32篇 |
1992年 | 37篇 |
1991年 | 30篇 |
1990年 | 31篇 |
1989年 | 24篇 |
1988年 | 37篇 |
1987年 | 28篇 |
1986年 | 19篇 |
1985年 | 47篇 |
1984年 | 44篇 |
1983年 | 23篇 |
1982年 | 26篇 |
1981年 | 22篇 |
1980年 | 23篇 |
1979年 | 33篇 |
1978年 | 35篇 |
1977年 | 25篇 |
1976年 | 19篇 |
1974年 | 18篇 |
1973年 | 20篇 |
1972年 | 10篇 |
1967年 | 11篇 |
排序方式: 共有2649条查询结果,搜索用时 15 毫秒
1.
Ryuto Yasui Dr. Daiki Shimizu Prof. Kenji Matsuda 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(27):e202104242
The single-molecular conductance between two π-conjugated wires with and without a radical substituent has been compared. Specifically, methyl- and iminonitroxide-substituted 4-(biphenyl-4-yl)pyridine wires bound onto a porphyrin template were subjected to scanning tunneling microscopy (STM) apparent-height measurement at the interface between highly oriented pyrolytic graphite (HOPG) and octan-1-oic acid. Statistical analysis of the STM images revealed that the radical-substituted wire has 3.2±1.7-fold higher conductance than the methyl-substituted reference. Although density functional theory (DFT) calculation suggests that only 17 % of the SOMO is distributed on the wire moiety, the effect was significant. This study presents the potential of radical substituents to achieve high conductivity in molecular wires. 相似文献
2.
Annals of the Institute of Statistical Mathematics - Wasserstein geometry and information geometry are two important structures to be introduced in a manifold of probability distributions.... 相似文献
3.
Minoru Koyama Dr. Takafumi Kawakami Dr. Takashi Okazoe Prof. Dr. Kyoko Nozaki 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(46):10913-10917
Methacrylic esters, represented by methyl methacrylate (MMA), are widely used as commodity chemicals. Here, the one-pot synthesis of methacrylic esters from acetone, a haloform and alcohols in the presence of an organic base is described. Using DBU as the organic base for the reaction of acetone, chloroform and methanol in acetonitrile afforded MMA in 66 % yield. When the solvent was replaced by benzonitrile, the product MMA was successfully purified by distillation. Applicability of this process to various alcohols was also investigated to show ethyl, phenyl, CF3CH2, and n-C6F13CH2CH2 esters were obtained in moderate yields. The use of bromoform instead of chloroform resulted in the improvement of the yield, for example, methyl and n-C6F13CH2CH2 esters up to 81 and 70 %, respectively. The reaction with deuterated starting materials acetone-d6 and MeOH-d4, with DBU in acetonitrile afforded deuterated MMA (MMA-d8) in 70 % yield. 相似文献
4.
Shofu Matsuda Yuuki Okuda Yoshiki Obu Norio Nagayama Minoru Umeda 《Electroanalysis》2019,31(12):2466-2471
With the objective of understanding the kinetic redox properties of triphenylamine derivatives in association with chemical reactions, for their future application in functional organic semiconductor devices, the electrochemical characteristics of 4‐(2,2‐diphenylethenyl)‐N,N‐bis(4‐methylphenyl)‐benzenamine (TPA) were evaluated. Based on cyclic voltammograms of TPA on Pt disk electrodes with diameters of 300 μm and 10 μm at slow and fast scan rates in an acetonitrile solution, the TPA.+ is stable, while the TPA2+ is unstable. Importantly, the unstable TPA2+ appears to break down by a subsequent chemical reaction. A Cottrell plot analysis from chronoamperometry of a solution containing TPA reveals that both the first and second oxidations are one‐electron reactions. Concerning the stabilization mechanism of the first oxidation state of TPA, the results of molecular orbital calculations indicate that the electrons of the HOMO level are distributed in the triphenylamine group, which induces a resonance‐stabilized TPA.+. Based on these results, TPA/TPA.+ is suggested to have a sufficient stability for further application in organic semiconductor devices. 相似文献
5.
Chikako Matsuda Ryo Igarashi Prof. Dr. Hiroshi Katagiri Dr. Takashi Murase 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(19):e202200132
Tri- and tetra-fluorinated [7]helicenes are photolabile and undergo a double fluorine atom transfer. Herein, we show that the transferred product further undergoes a skeletal transformation on silica gel. The transformation begins with activation of the allylic C−F bond on the silanol surface. Then, the resulting carbocation readily undergoes a regioselective nucleophilic aromatic substitution with water, depending on the position of the fluorine substituents. Hexafluoro-2-propanol also activated the allylic C−F bond and acted as a nucleophile. These findings support the generation of a highly reactive cationic electrophilic intermediate in the successive transformations involving fluorine atoms. 相似文献
6.
7.
Investigation on the Surface‐Confined Self‐Assembly Stabilized by Hydrogen Bonds of Urea and Amide Groups: Quantitative Analysis of Concentration Dependence of Surface Coverage 下载免费PDF全文
Formation of a hydrogen‐bond network via an amide group is a key driving force for the nucleation–elongation‐type self‐assembly that is often seen in biomolecules and artificial supramolecular assemblies. In this work, rod‐coil‐like aromatic compounds bearing an amide ( 1 a – 3 a ) or urea group ( 1 u – 3 u ) were synthesized, and their self‐assemblies on a 2‐D surface were investigated by scanning tunneling microscopy (STM). According to the quantitative analysis of the concentration dependence of the surface coverage, it was revealed that the strength of the hydrogen bond (i.e., amide or urea) and the number of non‐hydrogen atoms in a molecular component (i.e., size of core and length of alkyl side chain) play a primary role in determining the stabilization energy during nucleation and elongation processes of molecular ordering on the HOPG surface. 相似文献
8.
We point out that it is immediate by our character formula that in the case of a boundary level the characters of admissible representations of affine Kac–Moody algebras and the corresponding W-algebras decompose in products in terms of the Jacobi form . 相似文献
9.
Prof. Dr. Tsutomu Ishi-i Honoka Tanaka Rihoko Kichise Christopher Davin Takaaki Matsuda Dr. Naoya Aizawa Dr. In Seob Park Prof. Dr. Takuma Yasuda Taisuke Matsumoto 《化学:亚洲杂志》2021,16(15):2136-2145
The regulation of multicolor fluorescence changes in mechanochromic fluorescence (MCF) remains a challenging task. Herein, we report the regulation of MCF using a donor-acceptor structure. Two crystal polymorphs, BTD-pCHO(O) and BTD-pCHO(R) produced by the introduction of formyl groups to an MCF dye, respond to a mechanical stimulus, allowing a three-color fluorescence change. Specifically, the orange-colored fluorescence of the metastable BTD-pCHO(O) polymorph changed to a deep-red color in the amorphous-like state to finally give a red color in the stable BTD-pCHO(R) polymorph. This change occurred by mechanical grinding followed by vapor fuming. The two different crystal packing patterns were selectively regulated by the electronic effect of the introduced functional groups. The two types of selectively formed crystals in BTD(F)-pCHO bearing fluorine atoms, and BTD(OMe)-pCHO bearing methoxy groups, respond to mechanical grinding, allowing for the regulation of multicolor MCL from a three-color change to two different types of two-color changes. 相似文献
10.