全文获取类型
收费全文 | 727篇 |
免费 | 12篇 |
国内免费 | 7篇 |
专业分类
化学 | 520篇 |
晶体学 | 8篇 |
力学 | 16篇 |
数学 | 26篇 |
物理学 | 176篇 |
出版年
2021年 | 7篇 |
2020年 | 14篇 |
2019年 | 17篇 |
2018年 | 9篇 |
2017年 | 7篇 |
2016年 | 12篇 |
2015年 | 9篇 |
2014年 | 11篇 |
2013年 | 30篇 |
2012年 | 37篇 |
2011年 | 42篇 |
2010年 | 17篇 |
2009年 | 19篇 |
2008年 | 42篇 |
2007年 | 37篇 |
2006年 | 39篇 |
2005年 | 30篇 |
2004年 | 26篇 |
2003年 | 20篇 |
2002年 | 26篇 |
2001年 | 9篇 |
2000年 | 16篇 |
1999年 | 8篇 |
1998年 | 6篇 |
1997年 | 8篇 |
1996年 | 7篇 |
1995年 | 7篇 |
1994年 | 15篇 |
1993年 | 14篇 |
1992年 | 11篇 |
1991年 | 11篇 |
1990年 | 16篇 |
1989年 | 10篇 |
1988年 | 8篇 |
1987年 | 17篇 |
1986年 | 25篇 |
1985年 | 15篇 |
1984年 | 7篇 |
1983年 | 3篇 |
1982年 | 5篇 |
1981年 | 12篇 |
1980年 | 6篇 |
1979年 | 9篇 |
1978年 | 9篇 |
1977年 | 11篇 |
1976年 | 5篇 |
1975年 | 3篇 |
1974年 | 10篇 |
1971年 | 2篇 |
1969年 | 3篇 |
排序方式: 共有746条查询结果,搜索用时 15 毫秒
21.
The discovery that supporting electrolytes can be effectively confined in typical organic solvents in a c-Hex-based multiphase electrolyte solution has led to the development of a novel heterogeneous continuous flow synthetic system. PTFE fiber functions as a separation filter that can efficiently isolate the c-Hex phase from multiphase electrolyte solutions. This system has demonstrated both electrochemical solvating and carbon-carbon bond forming reactions. Hydrophobic substrates can be introduced into the reactor as c-Hex solutions, which are then electrochemically transformed into the target hydrophobic products that pass through the PTFE fiber as c-Hex solutions. 相似文献
22.
Taishi Nakanishi Dr. Jun Kikuchi Dr. Atsushi Kaga Prof. Dr. Shunsuke Chiba Prof. Dr. Masahiro Terada 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(37):8230-8234
A catalytic enantioselective synthesis of β-amino secondary amides was achieved using vinyl azides as the enamine-type nucleophile and chiral N-Tf phosphoramide as the chiral Brønsted acid catalyst through a five-step sequential transformation in one pot. The established sequential transformation involves an enantioselective [4+2] cycloaddition reaction of vinyl azides with N-acyl imines as the key stereo-determining step that is efficiently accelerated by a chiral N-Tf phosphoramide catalyst in a highly enantioselective manner in most cases. Further generation of the iminodiazonium ion intermediate through ring opening of the cycloaddition product and subsequent skeletal rearrangement involving Schmidt-type 1,2-aryl group migration followed by recyclization of the resulting nitrilium ion were also initiated by the same acid catalyst. Final acid hydrolysis of the recyclized products in the same pot gave rise to enantioenriched β-amino amides through C−C bond formation at the α-position of the secondary amides. 相似文献
23.
Kanna Adachi Tomoshi Yamada Hayate Ishizuka Mana Oki Shunsuke Tsunogae Noriko Shimada Osamu Chiba Tatsuya Orihara Prof. Dr. Masafumi Hidaka Prof. Dr. Takatsugu Hirokawa Dr. Minami Odagi Prof. Dr. Keiichi Konoki Prof. Dr. Mari Yotsu-Yamashita Prof. Dr. Kazuo Nagasawa 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(9):2025-2033
A novel series of C12-keto-type saxitoxin (STX) derivatives bearing an unusual nonhydrated form of the ketone at C12 has been synthesized, and their NaV-inhibitory activity has been evaluated in a cell-based assay as well as whole-cell patch-clamp recording. Among these compounds, 11-benzylidene STX ( 3 a ) showed potent inhibitory activity against neuroblastoma Neuro 2A in both cell-based and electrophysiological analyses, with EC50 and IC50 values of 8.5 and 30.7 nm , respectively. Interestingly, the compound showed potent inhibitory activity against tetrodotoxin-resistant subtype of NaV1.5, with an IC50 value of 94.1 nm . Derivatives 3 a – d and 3 f showed low recovery rates from NaV1.2 subtype (ca 45–79 %) compared to natural dcSTX ( 2 ), strongly suggesting an irreversible mode of interaction. We propose an interaction model for the C12-keto derivatives with NaV in which the enone moiety in the STX derivatives 3 works as Michael acceptor for the carboxylate of Asp1717. 相似文献
24.
Bailly J. L. Caso C. Chiba Y. Dibon H. Epp B. Ferrando A. Fontanelli F. Ganguli S. N. Gémesy T. Gurtu A. Hamatsu R. Hidas P. Hirose T. Hrubec J. Ivanyshenkov Yu. Kageya T. Khalatyan N. Kistenev E. Kita I. Kitamura S. Kubik V. MacNaughton J. Malhotra P. K. Matsumoto S. Mittra I. S. Montanet L. Neuhofer G. Pinter G. Porth P. Raghavan R. Rodrigo T. Singh J. Squarcia S. Takahashi K. Tanaka R. Tikhonova L. A. Trevisan U. Yamagata T. Zholobov G. Zotkin S. A. 《Zeitschrift fur Physik C Particles and Fields》1989,43(3):341-348
Zeitschrift für Physik C Particles and Fields - Correlations among identically charged pions were measured for pions produced inp p collisions at 360 GeV/c using the EHS spectrometer. The... 相似文献
25.
The dynamic stability of a vertically standing cantilevered beam simultaneously excited in both horizontal and vertical directions at its base is studied theoretically. The beam is assumed to be an inextensible Euler–Bernoulli beam. The governing equation of motion is derived using Hamilton's principle and has a nonlinear elastic term and a nonlinear inertia term. A forced horizontal external term is added to the parametrically excited system. Applying Galerkin's method for the first bending mode, the forced Mathieu–Duffing equation is derived. The frequency response is obtained by the harmonic balance method, and its stability is investigated using the phase plane method. Excitation frequencies in the horizontal and vertical directions are taken as 1:2, from which we can investigate the influence of the forced response under horizontal excitation on the parametric instability region under vertical excitation. Three criteria for the instability boundary are proposed. The influences of nonlinearities and damping of the beam on the frequency response and parametric instability region are also investigated. The present analytical results for instability boundaries are compared with those of experiments carried out by one of the authors. 相似文献
26.
Derek Yiren Ong Zhihao Yen Asami Yoshii Julia RevilloImbernon Ryo Takita Shunsuke Chiba 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(15):5046-5051
New protocols for controlled reduction of carboxamides to either alcohols or amines were established using a combination of sodium hydride (NaH) and zinc halides (ZnX2). Use of a different halide on ZnX2 dictates the selectivity, wherein the NaH‐ZnI2 system delivers alcohols and NaH‐ZnCl2 gives amines. Extensive mechanistic studies by experimental and theoretical approaches imply that polymeric zinc hydride (ZnH2)∞ is responsible for alcohol formation, whereas dimeric zinc chloride hydride (H?Zn?Cl)2 is the key species for the production of amines. 相似文献
27.
Simon Rohrbach Andrew J. Smith Jia Hao Pang Darren L. Poole Tell Tuttle Shunsuke Chiba John A. Murphy 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(46):16518-16540
Jüngste Entwicklungen in der experimentellen und theoretischen Chemie haben zur Identifizierung einer schnell wachsenden Klasse von nukleophilen aromatischen Substitutionsreaktionen geführt, die einem konzertierten Mechanismus (cSNAr) folgen, und nicht dem klassischen, zweistufigen SNAr‐Mechanismus. Während klassische SNAr‐Reaktionen auf die substantielle Aktivierung des aromatischen Ringes durch elektronenziehende Substituenten angewiesen sind, ist eine solche Aktivierung für den konzertierten Reaktionsverlauf nicht zwingend nötig. 相似文献
28.
Summary A set of hydrophilicity parameters in a normal-phase liquid chromatography of peptides is presented in order to clarify the
contribution of individual amino acid residues to peptide retention and to predict retention times. The retention of 100 peptides
was studied using normal-phase liquid chromatography on amide, diol and silica columns. An acetonitrile-water mixed solution
containing 0.2% trifluoroacetic acid +0.2% triethylamine was used as the mobile phase in a linear gradient elution system.
The contribution of each residue upon retention was calculated by linear multiple regression analysis. This paper described
the contribution values as “hydrophilicity retention coefficients”. Using these hydrophilicity retention coefficients, retention
times could be predicted for peptides of known amino acid content and sequence. A set of hydrophilicity retention coefficients
on each column was successfully explained by contributions to the degree of retention. 相似文献
29.
Sol-Gel Processing of Transparent PLZT((Pb,La)(Zr,Ti)O3) Fibers 总被引:1,自引:0,他引:1
Kitaoka Kenji Takahara Koji Kozuka Hiromitsu Yoko Toshinobu 《Journal of Sol-Gel Science and Technology》1999,16(1-2):183-193
PLZT((Pb,La)(Zr,Ti)O3) ceramic fibers were prepared by the sol-gel method from a solution of lead acetate trihydrate, lanthanum isopropoxide, zirconium n-propoxide and titanium isopropoxide containing 2-methoxyethanol as the solvent. The as-drawn gel fibers were pretreated in an autoclave and preheated in flowing H2O vapor prior to the heat-treatment for crystallization. The effects of autoclaving and preheating in flowing H2O vapor on the structure and composition of the resultant fibers were investigated. Optically transparent single phase perovskite PLZT fibers of 5–15 m in thickness and 5 cm in length were successfully prepared when the autoclave-treatment and the preheating in flowing H2O vapor were conducted prior to crystallization. These treatments are thought to promote hydrolysis of the organic groups and polycondensation reaction in the gel fibers, leading to the successful formation of dense, crack-free transparent PLZT fibers. 相似文献
30.
In this letter, we report synthesis of branched polysaccharide 2 by glycosylation of glucal-type monomer 1 with two free hydroxy groups at position 3 and 4. Monomer 1 polymerized with N-halosuccinimide promoter in acetonitrile solvent at room temperature--50 degrees C. The product was isolated as a petroleum ether insoluble fraction. The structure was determined by 1H and 13C NMR spectra as well as elemental analysis to be a polysaccharide consisting of 2-halo-2-deoxy-alpha-D-mannoside units, indicating that the polymerization proceeded via stereoregular glycosylation manner. The molecular weights determined by GPC with DMF were 3,300-4,000. The degree of branching was estimated by the NMR data of the product from the reaction of 2 with 3,5-dinitrobenzoyl chloride. 相似文献