全文获取类型
收费全文 | 2491篇 |
免费 | 88篇 |
国内免费 | 11篇 |
专业分类
化学 | 1919篇 |
晶体学 | 26篇 |
力学 | 37篇 |
数学 | 163篇 |
物理学 | 445篇 |
出版年
2023年 | 14篇 |
2021年 | 16篇 |
2020年 | 31篇 |
2019年 | 61篇 |
2018年 | 23篇 |
2017年 | 27篇 |
2016年 | 49篇 |
2015年 | 34篇 |
2014年 | 42篇 |
2013年 | 123篇 |
2012年 | 154篇 |
2011年 | 146篇 |
2010年 | 65篇 |
2009年 | 92篇 |
2008年 | 132篇 |
2007年 | 133篇 |
2006年 | 142篇 |
2005年 | 119篇 |
2004年 | 82篇 |
2003年 | 85篇 |
2002年 | 76篇 |
2001年 | 48篇 |
2000年 | 34篇 |
1999年 | 29篇 |
1998年 | 26篇 |
1997年 | 20篇 |
1996年 | 23篇 |
1995年 | 16篇 |
1993年 | 27篇 |
1992年 | 29篇 |
1991年 | 27篇 |
1990年 | 38篇 |
1989年 | 26篇 |
1988年 | 27篇 |
1987年 | 23篇 |
1986年 | 34篇 |
1985年 | 32篇 |
1984年 | 41篇 |
1983年 | 30篇 |
1982年 | 34篇 |
1981年 | 33篇 |
1980年 | 35篇 |
1979年 | 29篇 |
1978年 | 36篇 |
1977年 | 31篇 |
1976年 | 23篇 |
1975年 | 20篇 |
1974年 | 25篇 |
1973年 | 23篇 |
1972年 | 14篇 |
排序方式: 共有2590条查询结果,搜索用时 15 毫秒
1.
Saqib Kamal Arif I. Inamdar Kuan-Ru Chiou Batjargal Sainbileg Muhammad Usman Jenq-Wei Chen Tzuoo-Tsair Luo Michitoshi Hayashi Chen-Hsiung Hung Wen-Feng Liaw Kuang-Lieh Lu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(30):e202103905
The dielectric properties of coordination polymers has been a topic of recent interest, but the role of different functional groups on the dielectric properties of these polymers has not yet been fully addressed. Herein, the effects of electron-donating (R=NH2) and electron-withdrawing (R=NO2) groups on the dielectric behavior of such materials were investigated for two thermally stable and guest-free Zn-based coordination polymers, [Zn(L1)(L2)]n ( 1 ) and [Zn(L1)(L3)]n ( 2 ) [L1=2-(2-pyridyl) benzimidazole (Pbim), L2=5-aminoisophthalate (Aip), and L3=5-nitroisophthalate (Nip)]. The results of dielectric studies of 1 revealed that it possesses a high dielectric constant (κ=65.5 at 1 kHz), while compound 2 displayed an even higher dielectric constant (κ=110.3 at 1 kHz). The electron donating and withdrawing effects of the NH2 and NO2 substituents induce changes in the polarity of the polymers, which is due to the inductive effect from the aryl ring for both NO2 and NH2. Theoretical results from density functional theory (DFT) calculations, which also support the experimental findings, show that both compounds have a distinct electronic behavior with diverse wide bandgaps. The significance of the current work is to provide information about the structure-dielectric property relationships. So, this study promises to pave the way for further research on the effects of different functional groups on coordination polymers on their dielectric properties. 相似文献
2.
3.
4.
Kengo Sugita Prof. Dr. Makoto Yamashita 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(20):4520-4523
The reaction between a dialkyl-substituted alumanyl anion and [Y(CH2SiMe3)2(thf)3][BPh4] resulted in the formation of (dialkylalumanyl)yttrium complex 2 , which exhibits the first 2-center–2-electron (2 c-2 e) Al−Y bond. The 1H and 13C NMR spectra of 2 together with an X-ray crystallographic analysis indicated a C2v symmetrical structure. DFT calculations on 2 revealed that its LUMO consists of overlapping 3 p- and 4 d-orbitals of the Al and Y atoms, respectively, and that the HOMO–LUMO gap is narrow. The UV/Vis spectrum of 2 exhibited a visible absorption at 432 nm, which suggests that the strong σ-donating and π-accepting character of the three-coordinate dialkylalumanyl ligand generates a colored d0-complex that does not contain any π-electrons. 相似文献
5.
Dr. Hironobu Hayashi Nao Hieda Dr. Mitsuaki Yamauchi Yee Seng Chan Prof. Dr. Naoki Aratani Prof. Dr. Sadahiro Masuo Prof. Dr. Hiroko Yamada 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(66):15079-15083
The photo-induced generation of unstable molecules generally requires stringent conditions to prevent oxidation and the concomitant decomposition of the products. The visible-light-induced conversion of two heptacene precursors to heptacene was studied. Single crystals of bis- and mono-α-diketone-type heptacene precursors ( 7-DK2 and 7-DK1 , respectively), were prepared to investigate the effect of precursor structure on reactivity. The photoirradiation of a 7-DK2 single crystal cleaved only one α-diketone group, forming an intermediate bearing a pentacene subunit, while that of a 7-DK1 single crystal gave rise to characteristic absorption peaks of heptacene and their increase in intensity with photoirradiation time, indicating the generation of heptacene without decomposition. Heptacene production was not observed when the precursors were photoirradiated in solution, implying that the single crystal interior provided isolation from the external environment, thus preventing heptacene oxidation. 相似文献
6.
Naoto Sato Taiki Hayashi Kazuma Tochigi Prof. Hiroaki Wada Prof. Atsushi Shimojima Prof. Kazuyuki Kuroda 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(33):7860-7865
Eight corners of a double-four ring cage-type germanoxane, containing a fluoride ion, were successfully silylated by the combination of chlorosilanes and silazanes. Three different silyl groups, trimethylsilyl, dimethylsilyl, and dimethylvinylsilyl, were attached on the corners of germanoxane cage. The solubility and reactivity of the cage modified with dimethylvinylsilyl groups were significantly increased, allowing for further reaction. Hydrosilylation reaction between dimethylvinylsilylated cage geramanoxanes and dimethylsilylated cage siloxanes afforded porous solids. Functionalization of the corners of germanoxanes with silyl groups should provide valuable building blocks in various functional materials. 相似文献
7.
Prof. Kengo Hanaya Kaho Yamoto Prof. Kazuaki Taguchi Prof. Kazuaki Matsumoto Prof. Shuhei Higashibayashi Prof. Takeshi Sugai 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(47):e202201677
The chemical modification of proteins is an effective technique for manipulating the properties and functions of proteins, and for creating protein-based materials. The N-terminus is a promising target for single-site modification that provides modified proteins with uniform structures and properties. In this paper, a copper(II)-mediated aldol reaction with 2-pyridinecarboxaldehyde (2-PC) derivatives is proposed as an operationally simple method to selectively modify the N-terminus of peptides and proteins at room temperature and physiological pH. The copper(II) ion activates the N-terminal amino acids by complexation with an imine of the N-terminal amino acid and 2-PCs, realizing the selective formation of the nucleophilic intermediate at the N-terminus. This results in a stable carbon-carbon bond between the 2-PCs and the α-carbon of various N-terminal amino acids. The reaction is applied to four different proteins, including biopharmaceuticals such as filgrastim and trastuzumab. The modified trastuzumab retains the human epidermal growth factor receptor 2 recognition activity. 相似文献
8.
Optical Review - This paper proposes a novel steganography method to show an aerial image that is formed with aerial imaging by retro-reflection by use of dual transparent balls made of acrylic... 相似文献
9.
10.
Aromaticity Relocation in Perylene Derivatives upon Two‐Electron Oxidation To Form Anthracene and Phenanthrene 下载免费PDF全文
Akinobu Matsumoto Dr. Mitsuharu Suzuki Dr. Hironobu Hayashi Dr. Daiki Kuzuhara Dr. Junpei Yuasa Prof. Dr. Tsuyoshi Kawai Prof. Dr. Naoki Aratani Prof. Dr. Hiroko Yamada 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(41):14462-14466
We prepared perylene dications 1 2+ and 2 2+ by using “capped” perylene derivatives, and for the first time, successfully obtained single crystals of a perylene dication 1 2+ that enabled us to perform its structural analysis. We realized that the substituted aryl groups on perylene control the positions of positive charges, thus the remaining electronic system satisfies Clar's sextet rule toward the highest number of localized sextets. Experimental and theoretical evidence proved that Clar's aromatic π‐sextet rule could be applied even for the dicationic perylenes in a very simple way. 相似文献