全文获取类型
收费全文 | 725篇 |
免费 | 21篇 |
国内免费 | 4篇 |
专业分类
化学 | 568篇 |
晶体学 | 9篇 |
力学 | 2篇 |
数学 | 71篇 |
物理学 | 100篇 |
出版年
2023年 | 5篇 |
2021年 | 9篇 |
2020年 | 21篇 |
2019年 | 13篇 |
2018年 | 7篇 |
2017年 | 18篇 |
2016年 | 16篇 |
2015年 | 13篇 |
2014年 | 16篇 |
2013年 | 54篇 |
2012年 | 58篇 |
2011年 | 42篇 |
2010年 | 26篇 |
2009年 | 22篇 |
2008年 | 40篇 |
2007年 | 43篇 |
2006年 | 37篇 |
2005年 | 46篇 |
2004年 | 21篇 |
2003年 | 28篇 |
2002年 | 14篇 |
2001年 | 6篇 |
2000年 | 10篇 |
1999年 | 7篇 |
1998年 | 2篇 |
1997年 | 3篇 |
1996年 | 6篇 |
1994年 | 7篇 |
1992年 | 7篇 |
1991年 | 5篇 |
1990年 | 8篇 |
1989年 | 3篇 |
1988年 | 4篇 |
1987年 | 3篇 |
1986年 | 9篇 |
1985年 | 18篇 |
1984年 | 15篇 |
1983年 | 5篇 |
1982年 | 15篇 |
1981年 | 3篇 |
1980年 | 4篇 |
1979年 | 15篇 |
1978年 | 8篇 |
1977年 | 6篇 |
1974年 | 2篇 |
1973年 | 5篇 |
1968年 | 2篇 |
1967年 | 5篇 |
1966年 | 7篇 |
1965年 | 3篇 |
排序方式: 共有750条查询结果,搜索用时 31 毫秒
1.
The aim of the present study was to form a nitride layer on a titanium (Ti) substrate through a compact laser-nitriding system comprising a focused pulsed Nd:YAG laser and nitrogen gas blow. To obtain a high-quality layer, the effects of pulse frequency and gas flow rate on the surface characteristics were investigated by using plasma emission analysis as well as X-ray analyses. Optical emission spectra from the laser-induced plasma mainly consisted of ionic Ti lines, and their intensities when the pulse frequency was 15 Hz were much higher than those for 8 Hz. Similarly, the reflections from the δ-TiN phase in the X-ray diffraction (XRD) pattern were enhanced when using 15 Hz. On the other hand, the flow rate of nitrogen gas blow had a significant effect on the thickness of the thin oxide layer that formed above the nitride layer. Using a lower flow rate resulted in the formation of a thicker oxide layer. The higher pulse frequency and the faster flow rate were beneficial for obtaining a higher-quality layer because of the enhancement of nitridation and the suppression of oxidation, respectively. 相似文献
2.
3.
Dr. Wataru Suzuki Dr. Hiroaki Kotani Dr. Tomoya Ishizuka Prof. Dr. Takahiko Kojima 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(46):10480-10486
Selective two-electron reduction of dioxygen (O2) to hydrogen peroxide (H2O2) has been achieved by two saddle-distorted N,N’-dimethylated porphyrin isomers, an N21,N’22-dimethylated porphyrin ( anti -Me2P ) and an N21,N’23-dimethylated porphyrin ( syn -Me2P ) as catalysts and ferrocene derivatives as electron donors in the presence of protic acids in acetonitrile. The higher catalytic performance in an oxygen reduction reaction (ORR) was achieved by anti -Me2P with higher turnover number (TON=250 for 30 min) than that by syn -Me2P (TON=218 for 60 min). The reactive intermediates in the catalytic ORR were confirmed to be the corresponding isophlorins ( anti -Me2Iph or syn -Me2Iph ) by spectroscopic measurements. The rate-determining step in the catalytic ORRs was concluded to be proton-coupled electron-transfer reduction of O2 with isophlorins based on kinetic analysis. The ORR rate by anti -Me2Iph was accelerated by external protons, judging from the dependence of the observed initial rates on acid concentrations. In contrast, no acceleration of the ORR rate with syn -Me2Iph by external protons was observed. The different mechanisms in the O2 reduction by the two isomers should be derived from that of the arrangement of hydrogen bonding of a O2 with inner NH protons of the isophlorins. 相似文献
4.
Jie Wang Denan Li Honggui Yang Shufan Yao Prof. Qianqian Zhu Prof. Masahiro Sadakane Prof. Yanshuo Li Prof. Wataru Ueda Prof. Zhenxin Zhang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(41):e202200618
Zeolitic octahedral metal oxides are inorganic crystalline microporous materials with adsorption and redox properties. New ϵ-Keggin nickel molybdate–based zeolitic octahedral metal oxides have been synthesized. 31P NMR spectroscopy shows that reduction of MoVI-based molybdates forms an ϵ-Keggin polyoxometalate that immediately transfers to the solid phase. Investigation of the formation process indicates that a low Ni concentration, insoluble reducing agent, and long synthesis time are the critical factors for obtaining the zeolite octahedral metal oxides rather than the ϵ-Keggin polyoxometalate molecule. The synthesized zeolitic nickel molybdate with Na+ is used as the adsorbent, which effectively separates C2 hydrocarbon mixtures. 相似文献
5.
Synthesis and Metalation of Doubly o‐Phenylene‐Bridged Cyclic Bis(dipyrrin)s with Highly Bent Skeleton of Dibenzoporphyrin(2.1.2.1) 下载免费PDF全文
Dr. Daiki Kuzuhara Wataru Furukawa Aya Kitashiro Prof. Dr. Naoki Aratani Prof. Dr. Hiroko Yamada 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(30):10671-10678
Facile synthesis of dibenzoporphyrins(2.1.2.1) has been successfully reported by the simple condensation reaction of o‐dipyrrolylbenzene with various aldehydes in the presence of a Lewis acid. This reaction enables the preparation of various dibenzoporphyrin(2.1.2.1) derivatives with p‐substituted phenyl groups, five‐membered heterocycles, and ethynyl groups at the meso‐positions. Dibenzoporphyrins(2.1.2.1) consist of two dipyrrin units that are connected by o‐phenylene bridges, which adopt highly bent saddle‐shaped structures; this was confirmed by X‐ray diffraction analysis. We found that dibenzoporphyrin(2.1.2.1) can be described as a 20π antiaromatic conjugated system, but practically, it is not an antiaromatic macrocycle, which we revealed by 1H NMR spectroscopy. The redox potentials had good correlations with Hammett substituent constant (σp) of the substituents at the meso‐positions. The free‐base dibenzoporphyrin(2.1.2.1) was able to form the metal complexes with nickel(II), copper(II), palladium(II), platinum(II), and tin(IV) ions. These results suggested that dibenzoporphyrin(2.1.2.1) derivatives can be utilized as novel macrocyclic dianionic tetradentate ligands for various metal ions to give complexes with varying optical and electrochemical properties. 相似文献
6.
The aim of this paper is to find the global solutions of uncertain optimization problems having a quadratic objective function and quadratic inequality constraints. The bounded epistemic uncertainties in the constraint coefficients are represented using either universal or existential quantified parameters and interval parameter domains. This approach allows to model non-controlled uncertainties by using universally quantified parameters and controlled uncertainties by using existentially quantified ones. While existentially quantified parameters could be equivalently considered as additional variables, keeping them as parameters allows maintaining the quadratic problem structure, which is essential for the proposed algorithm. The branch and bound algorithm presented in the paper handles both universally and existentially quantified parameters in a homogeneous way, without branching on their domains, and uses some dedicated numerical constraint programming techniques for finding a robust, global solution. Several examples clarify the theoretical parts and the tests demonstrate the usefulness of the proposed method. 相似文献
7.
Keigo E. Yamada Dr. Iain A. Stepek Dr. Wataru Matsuoka Prof. Dr. Hideto Ito Prof. Dr. Kenichiro Itami 《Angewandte Chemie (International ed. in English)》2023,62(51):e202311770
Nanocarbons incorporating non-hexagonal aromatic rings - such as five-, seven-, and eight-membered rings - have various intriguing physical properties such as curved structures, unique one-dimensional packing, and promising magnetic, optical, and conductivity properties. Herein, we report an efficient synthetic approach to polycyclic aromatics containing seven-membered rings via a palladium-catalyzed intramolecular Ar−H/Ar−Br coupling. In addition to all-hydrocarbon scaffolds, heteroatom-embedded heptagon-containing polyarenes can be efficiently constructed with this method. Rhodium- and palladium-catalyzed sequential six- and seven-membered ring formations also afford complex heptagon-containing molecular nanocarbons from readily available arylacetylenes and biphenyl boronic acids. Detailed mechanistic analysis by DFT calculations showed the feasibility of seven-membered ring formation by a concerted metalation-deprotonation mechanism. This reaction can serve as a template for the synthesis of a wide range of seven-membered ring-containing molecular nanocarbons. 相似文献
8.
Dr. Thomas Lunkenbein Dr. Frank Girgsdies Anna Wernbacher Dr. Johannes Noack Dr. Gudrun Auffermann Akira Yasuhara Achim Klein‐Hoffmann Prof. Wataru Ueda Dr. Maik Eichelbaum Dr. Annette Trunschke Prof. Robert Schlögl Dr. Marc G. Willinger 《Angewandte Chemie (International ed. in English)》2015,54(23):6828-6831
Complex Mo,V‐based mixed oxides that crystallize in the orthorhombic M1‐type structure are promising candidates for the selective oxidation of small alkanes. The oxygen sublattice of such a complex oxide has been studied by annular bright field scanning transmission electron microscopy. The recorded micrographs directly display the local distortion in the metal oxygen octahedra. From the degree of distortion we are able to draw conclusions on the distribution of oxidation states in the cation columns at different sites. The results are supported by X‐ray diffraction and electron paramagnetic resonance measurements that provide integral details about the crystal structure and spin coupling, respectively. 相似文献
9.
Yoshida Go Ninomiya Kazuhiko Inagaki Makoto Higemoto Wataru Strasser Patrick Kawamura Naritoshi Shimomura Koichiro Miyake Yasuhiro Miura Taichi Kubo Kenya M. Shinohara Atsushi 《Journal of Radioanalytical and Nuclear Chemistry》2019,320(2):283-289
The role of valence electrons for the muon capture process by molecules is experimentally investigated with the aid of cascade calculations. Low-momentum muons are introduced to gas targets of CO, CO2, and COS below atmospheric pressure. The initial states of captured muons are determined from the measured muonic X-ray structure of the Lyman and Balmer series. We propose that the lone pair electrons in the carbon atom of CO significantly contribute to the capture of a muon with large angular momenta.
相似文献10.
Homo‐double helix formation of an optically active conjugated polymer bearing carboxy groups and amplification of the helicity upon complexation with achiral and chiral amines 下载免费PDF全文
Wataru Makiguchi Shinzo Kobayashi Keisuke Furukawa Hiroki Iida Yoshio Furusho Eiji Yashima 《Journal of polymer science. Part A, Polymer chemistry》2015,53(8):990-999
An optically active, m‐terphenyl‐based π‐conjugated polymer bearing carboxy groups was synthesized by the copolymerization of the diethynyl monomer bearing a carboxy group with (S,S)‐2,5‐bis(2‐methylbutoxy)‐1,4‐dibromobenzene using Sonogashira reaction. The copolymer showed a weak circular dichroism (CD) in the main‐chain chromophore region due to a homo‐double helix formation with an excess helical handedness biased by the chiral alkoxy substituents through self‐association. However, upon complexation with achiral amines, such as piperidine, the CD intensity of the polymer significantly increased resulting in the formation of a greater excess one‐handed homo‐double helix via hydrogen‐bonded inclusion complexation with the achiral amines between each strand, leading to the amplification of the helicity. A preferred‐handed homo‐double helix was also induced in the polymer in the presence of nonracemic amines. The effect of the achiral and chiral amines on the homo‐double helix formation was investigated by comparing the CD spectra of the polymer to those of its model dimer. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 990–999 相似文献