全文获取类型
收费全文 | 524篇 |
免费 | 7篇 |
国内免费 | 5篇 |
专业分类
化学 | 386篇 |
晶体学 | 13篇 |
力学 | 5篇 |
数学 | 19篇 |
物理学 | 113篇 |
出版年
2022年 | 2篇 |
2021年 | 5篇 |
2020年 | 4篇 |
2019年 | 7篇 |
2018年 | 3篇 |
2016年 | 6篇 |
2015年 | 5篇 |
2014年 | 9篇 |
2013年 | 21篇 |
2012年 | 23篇 |
2011年 | 35篇 |
2010年 | 15篇 |
2009年 | 17篇 |
2008年 | 31篇 |
2007年 | 36篇 |
2006年 | 33篇 |
2005年 | 31篇 |
2004年 | 31篇 |
2003年 | 34篇 |
2002年 | 24篇 |
2001年 | 3篇 |
2000年 | 8篇 |
1999年 | 6篇 |
1997年 | 6篇 |
1996年 | 3篇 |
1995年 | 5篇 |
1994年 | 2篇 |
1993年 | 5篇 |
1992年 | 4篇 |
1991年 | 9篇 |
1990年 | 5篇 |
1989年 | 3篇 |
1988年 | 4篇 |
1987年 | 3篇 |
1986年 | 4篇 |
1985年 | 6篇 |
1984年 | 11篇 |
1983年 | 6篇 |
1982年 | 8篇 |
1981年 | 4篇 |
1980年 | 7篇 |
1979年 | 7篇 |
1978年 | 7篇 |
1977年 | 6篇 |
1976年 | 4篇 |
1975年 | 3篇 |
1974年 | 6篇 |
1973年 | 12篇 |
1965年 | 1篇 |
1927年 | 2篇 |
排序方式: 共有536条查询结果,搜索用时 31 毫秒
1.
2.
Control of chain ends of polyesters in polycondensation of AA and BB monomers by use of solid‐phase reagent 下载免费PDF全文
Toshihiko Sugiura Daisuke Yajima Kento Shoji Yoshihiro Ohta Tsutomu Yokozawa 《Journal of polymer science. Part A, Polymer chemistry》2015,53(11):1379-1386
For selective synthesis of linear polyester having a functional group at one end, polycondensation between 1,4‐butanediol ( 1a ) and sebacoyl chloride ( 2a ) and between 1,12‐dodecanediol ( 1b ) and isophthaloyl chloride ( 2b ) was conducted in the presence of oxime resin or oxime silica gel, followed by cleavage of the formed polyester from the solid‐phase support with aniline. Matrix‐assisted laser desorption ionization time‐of‐flight mass spectra and 1H NMR spectra of the cleaved polyester showed that the products contained not only polyester with anilide at one end ( poly 1 ), but also polyester with anilides at both ends ( poly 2 ). The product ratio of poly 1 to poly 2 ( poly 1 / poly 2 ) was dependent on monomers, monomer concentration, feed ratio of monomer to oxime moiety in the support, oxime content in the support, reaction solvent, and the nature of the support. Polyester with a high poly 1 / poly 2 ratio of 81/21 and moderate molecular weight (Mn = 1430 g/mol) was obtained by polycondensation of 1b and 2b in the presence of oxime silica gel in dichloromethane. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1379–1386 相似文献
3.
Palladium(0)/PAr3‐Catalyzed Intermolecular Amination of C(sp3)H Bonds: Synthesis of β‐Amino Acids 下载免费PDF全文
Jian He Toshihiko Shigenari Prof. Dr. Jin‐Quan Yu 《Angewandte Chemie (International ed. in English)》2015,54(22):6545-6549
An intermolecular C(sp3)? H amination using a Pd0/PAr3 catalyst was developed. The reaction begins with oxidative addition of R2N? OBz to a Pd0/PAr3 catalyst and subsequent cleavage of a C(sp3)? H bond by the generated Pd? NR2 intermediate. The catalytic cycle proceeds without the need for external oxidants in a similar manner to the extensively studied palladium(0)‐catalyzed C? H arylation reactions. The electron‐deficient triarylphosphine ligand is crucial for this C(sp3)? H amination reaction to occur. 相似文献
4.
5.
6.
Hiroshi Sakai Takashi Yamazaki Nobuya Machida Toshihiko Shigematsu Saburo Nasu 《Molecular Crystals and Liquid Crystals》2013,570(2):105-110
Abstract Mössbauer spectra of the FePS3-cobaltocene intercalation compound were measured in the temperature range of 300K to 10K. The spectra, distinct from those of pure FePS3, suggest the charge transfer from cobaltocene to Fe-S antibonding orbitals of the FePS3 host lattice. 相似文献
7.
To electrochemically sense lymphoma cells (U937), we fabricated a multifunctional peptide probe that consists of cell-penetrating/apoptosis-inducing/electron-transfer peptides. Electron-transfer peptides derive from cysteine residue combined with the C-terminals of four tyrosine residues (Y4). A peptide whereby Y4C is bound to the C-terminals of protegrin 1 (RGGRLCYCRRRFCVCVGR-NH2) is known to be an apoptosis-inducing agent against U937 cells, and is referred to as a peptide-1 probe. An oxidation response of the peptide-1 probe has been observed due to a phenolic hydroxyl group, and this response is decreased by the uptake of the peptide probe into the cells. To improve the cell membrane permeability against U937 cells, the RGGR at the N-terminals of the peptide-1 probe was replaced by RRRR (peptide-2 probe). In contrast, RNRCKGTDVQAWY4C (peptide-3 probe), which recognizes ovalbumin, was constructed as a control. Compared with the other probes, the change in the peak current of the peptide-2 probe was the greatest at low concentrations and occurred in a short amount of time. Therefore, the cell membrane permeability of the peptide-2 probe was increased based on the arginine residues and the apoptosis-inducing peptides. The peak current was linear and ranged from 100 to 1000 cells/ml. The relative standard deviation of 600 cells/ml was 5.0% (n = 5). Furthermore, the membrane permeability of the peptide probes was confirmed using fluorescent dye. 相似文献
8.
Photophysical Properties and Efficient,Stable, Electrogenerated Chemiluminescence of Donor–Acceptor Molecules Exhibiting Thermal Spin Upconversion 下载免费PDF全文
Dr. Ryoichi Ishimatsu Dr. Tomohiko Edura Prof. Chihaya Adachi Prof. Koji Nakano Prof. Toshihiko Imato 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(14):4889-4898
The photophysical properties and electrogenerated chemiluminescence (ECL) of three donor–acceptor molecules composed of dicyanobenzene and methyl‐, tert‐butyl‐, and phenyl‐substituted carbazolyl groups, 1,2,3,5‐tetrakis(3,6‐disubstituted‐carbazol‐9‐yl)‐4,6‐dicyanobenzene (4CzIPN‐Me, 4CzIPN‐tBu, and 4CzIPN‐Ph, respectively) are described. These molecules show delayed fluorescence as a result of thermal spin upconversion from the lowest triplet state to the lowest singlet state at room temperature. The three molecules showed yellow to yellowish–red ECL. Remarkably, the ECL efficiencies of 4CzIPN‐tBu in dichloromethane reached almost 40 %. Moreover, stable ECL was emitted from 4CzIPN‐tBu and 4CzIPN‐Ph. In case of 4CzIPN‐Me, the ECL intensity decreased during voltage cycles because of polymerization. Quantum chemical calculations revealed that polymerization was inhibited by the steric hindrance of the bulky tert‐butyl and phenyl groups on the carbazolyl moieties and lowered the spin density on the carbazolyl groups through electron conjugation for 4CzIPN‐Ph. 相似文献
9.
Naoki Kise Yosei Takenaga Yohei Ishikawa Yoichi Morikami Toshihiko Sakurai 《Tetrahedron letters》2012,53(15):1940-1945
The reductive coupling of N-methoxycarbonyl lactams with benzophenone by Zn-TiCl4 in THF gave cross-coupled products as cyclic α-diphenylidene-N-methoxycarbonylamines and ring-opening α,α-diphenyl-α-hydroxy-ω-(N-methoxycarbonyl)amino ketones selectively depending on the reduction conditions. The reductive coupling of N-methoxycarbonyl lactams with 9-fluorenone by Zn-TiCl4 gave cyclic α-(9H-fluoren-9-ylidene)-N-methoxycarbonylamines preferentially irrespective to the conditions. 相似文献
10.
Kazuharu Sugawara Sora Ishizaki Hideki Kuramitz Toshihiko Kadoya 《Electroanalysis》2020,32(2):207-216
We developed a highly sensitive electrochemical system for the sensing of ovalbumin (OVA). Lysozyme origin/tyrosine‐rich peptides (RNRCKGTDVQAWY4C) were immobilized on magnetic beads, and the competitive reaction between OVA and oligothreonine/OVA origin peptide probe (T8VLLPDEVSG) could then be measured. In a previous study, the detection of OVA at the 10?13 M level was achieved using RNRCKGTDVQAWY4C‐modified beads via a cross‐linker. To improve the sensitivity to OVA, this system uses T8VLLPDEVSG peptide probe to measure the interaction to RNRCKGTDVQAWY4C immobilized on magnetic beads. The peak of Y4C actually was an electron‐transfer peptide, which represented the oxidation of a phenolic hydroxyl group. First, we confirmed that the oxidation response of Y4C was increased based on an improvement in the electron transfer accessibility by oligothreonine. Next, T8VLLPDEVSG peptide probe was used for the electrochemical sensing of OVA in solutions that contained consistent amounts of RNRCKGTDVQAWY4C on magnetic beads. As a result, the peak current decreased as the concentration of OVA increased. The sensitivity to OVA was improved compared with the use of only RNRCKGTDVQAWY4C on magnetic beads. The OVA detection level was 10?14 M, which approximates the results from antibody‐antigen reactions. Consequently, the proposed system is a powerful new concept in protein sensing. 相似文献