全文获取类型
收费全文 | 1204篇 |
免费 | 24篇 |
国内免费 | 2篇 |
专业分类
化学 | 887篇 |
晶体学 | 5篇 |
力学 | 22篇 |
数学 | 64篇 |
物理学 | 252篇 |
出版年
2021年 | 8篇 |
2020年 | 9篇 |
2019年 | 14篇 |
2018年 | 8篇 |
2017年 | 7篇 |
2016年 | 21篇 |
2015年 | 18篇 |
2014年 | 19篇 |
2013年 | 70篇 |
2012年 | 55篇 |
2011年 | 53篇 |
2010年 | 30篇 |
2009年 | 30篇 |
2008年 | 62篇 |
2007年 | 54篇 |
2006年 | 64篇 |
2005年 | 59篇 |
2004年 | 50篇 |
2003年 | 60篇 |
2002年 | 44篇 |
2001年 | 41篇 |
2000年 | 26篇 |
1999年 | 18篇 |
1998年 | 6篇 |
1997年 | 14篇 |
1996年 | 7篇 |
1995年 | 8篇 |
1994年 | 18篇 |
1993年 | 7篇 |
1992年 | 26篇 |
1991年 | 18篇 |
1990年 | 24篇 |
1989年 | 16篇 |
1988年 | 15篇 |
1987年 | 16篇 |
1986年 | 22篇 |
1985年 | 32篇 |
1984年 | 13篇 |
1983年 | 13篇 |
1982年 | 12篇 |
1981年 | 13篇 |
1980年 | 15篇 |
1979年 | 12篇 |
1978年 | 10篇 |
1977年 | 14篇 |
1976年 | 10篇 |
1975年 | 13篇 |
1974年 | 7篇 |
1973年 | 10篇 |
1968年 | 5篇 |
排序方式: 共有1230条查询结果,搜索用时 62 毫秒
951.
Koyama J Morita I Kawanishi K Tagahara K Kobayashi N 《Chemical & pharmaceutical bulletin》2003,51(4):418-420
The simultaneous separation and determination of the major anthraquinones, emodin, chrysophanol, and their glucosides, of Rumex japonicus HOUTT., and emodin and emodin glucoside, of Cassia tora L., Rhamnus purshiana DC., Polygonum multiflorum THUNB., and P. cuspidatum SIEB. et ZUCC., were achieved by cyclodextrin modified capillary zone electrophoresis. The running electrolyte used in this method was 0.005 M alpha-cyclodextrin in 0.03 M borate buffer (pH 10.5) containing 10% acetonitrile, with an applied voltage of 20 kV. 相似文献
952.
Six new bicyclic peptides, celogentins D-H (1-5) and J (6) have been isolated from the seeds of Celosia argentea, and the structures including its absolute stereochemistry were determined by using extensive NMR methods and chemical means. Celogentins E-H (2-5) and J (6) showed potent inhibition of tubulin polymerization, while the inhibitory activity of celogentin D (1) was modest. Structure-activity relationship study indicates that ring size of the bicyclic ring system including unusual βs-Leu, Trp, and His residues would be important for their biological activity. 相似文献
953.
Masayuki Morita Atsushi Kishimoto Nobuko Yoshimoto Minato Egashira 《Research on Chemical Intermediates》2006,32(5):523-532
The surface processes at carbon and platinum electrodes have been studied using the electrochemical quartz crystal microbalance
technique in organic electrolyte solutions for lithium ion batteries. The changes in resonance frequency were analyzed as
a function of the electrode potential, indicating that the process depended not only on the electrode material but also on
the cathode potential. In the solution containing LiBF4 as the electrolyte, the main product at the platinum surface was Li2CO3 and LiF, whereas formation of lithium alkylcarbonates was the primary process at the platinum and carbon electrodes in LiPF6 solution. 相似文献
954.
T Hayashi K Hayashi K Uchida S Niwayama N Morita 《Chemical & pharmaceutical bulletin》1990,38(1):239-242
Scopadulcic acid B derivatives were synthesized and their antiviral activities against herpes simplex virus type 1 (HSV-1) were examined. All the derivatives synthesized showed lower inhibitory activities against HSV-1 than scopadulcic acid B (2). Five compounds, 7, 8, 15, 16, and 18, however, had in vitro therapeutic indexes larger than 7 and were considered to merit further investigation. 相似文献
955.
Shinsuke Nishida Yasushi Morita Tomohiro Ohba Kazunobu Sato Kazuhiro Nakasuji 《Tetrahedron》2007,63(32):7690-7695
3-Oxophenalenoxyl derivatives, neutral π-radicals having two oxygen atoms at 1,3-position on a phenalenyl skeleton, possess most of their spin densities at the two oxygen atoms and the 2-position, featuring in easy dimerization at the 2-position. For the decrease in spin density at the 2-position by invoking spin-delocalization into the 2-substituted π-systems, we have designed 2-thienyl-3-hydroxyphenalenone derivatives as synthetic precursors of neutral π-radicals, and conducted their oxidation reactions by using a variety of oxidants. The chemical structures of the dimer obtained were unambiguously determined by FABMS, IR, and NMR spectra with help of density functional theory calculations, showing the formation of the bonds on the thienyl moieties. These observations and DFT calculations illustrate the occurrence of a considerable amount of spin-delocalization into the 2-substituted-thienyl moieties from the 3-oxophenalenoxyl skeletons. 相似文献
956.
The potential energy curves of hydrogen-bonded systems were calculated for the water, methanol, and formic acid dimers and for the hydrogen maleate ion by a modified CNDO/2 method, the core resonance integrals between-electrons being distinguished from those between-electrons, the different bonding parameters being used for -O- and =O, and the core potential integralsV
AB
c
for O-H, C=O, and O...O being determined semi-empirically. Consequently, the following results were obtained: 1) a potential energy curve with a single minimum atr(O-H)=0.95 Å and with a concavity near 1.70 Å for the linear chain dimers of water and methanol; 2) a symmetrical potential energy curve with two minima atr(O-H)=0.95 and 1.78 Å for the cyclic dimer of formic acid; 3) a flat-bottomed symmetrical potential energy curve for the hydrogen maleate ion. The configuration analysis method was applied to the hydrogen-bonded systems; the contributions of the covalent ((O-H-O)–1) and ionic (O–H+O–) structures being 54% and 39%, respectively, for the symmetrical hydrogen bonding of the hydrogen maleate ion.
Zusammenfassung Die Kurven potentieller Energie von Systemen mit H-Brücken wurden im Fall von H2O-, CH3OH- und HCOOH-Dimeren und für das Hydrogen-Maleatanion mittels eines modifizierten CNDO-Verfahrens berechnet, wo für Rumpf-- und --Elektronen jeweils verschiedene Resonanzintegrale und verschiedene Bindungsparameter für =O und -O- verwendet und wo die Rumpfpotential-Integrale für O-H, C=O und O...O semiempirisch bestimmt werden.Die Resultate sind 1) eine Potentialkurve mit einem einfachen Minimum für lineare Ketten von H2O und CH3OH, 2) eine symmetrische Potentialkurve mit zwei Minima für das cyclische Diniere von HCOOH und 3) eine Potentialkurve mit einem flachen Minimum für das Maleatanion. Konfigurationsanalyse ergab einen Beitrag von 39% für die ionischen Strukturen.相似文献
957.
Molecular rectification of a helical peptide with a redox group in the metal-molecule-metal junction
A helical hexadecapeptide immobilized on gold via a thiophenyl group at the N-terminal was analyzed by scanning tunneling microscopy under ultrahigh vacuum to obtain the I-V response at a molecular level. The attenuation factor of the electron transfer through the hexadecapeptide was determined by applying the Simons model to the I-V response to show better molecular conductance of the hexadecapeptide than dodecanethiol. Chemical modification at the C-terminal of the hexadecapeptide with a ferrocene unit, on the other hand, brought about significant changes in the I-V response, where the helical peptide became more conductive at the negative bias voltage. The molecular rectification behavior is due to the ferrocene unit regulating the direction of the electron transfer at the metal-molecule junction. 相似文献
958.
Ito S Inabe H Okujima T Morita N Watanabe M Harada N Imafuku K 《The Journal of organic chemistry》2001,66(21):7090-7101
1,2-Di(6-azulenyl)tetraphenylbenzenes and (6-azulenyl)pentaphenylbenzenes were synthesized by Diels-Alder reactions of di(6-azulenyl)acetylenes and 6-(phenylethynyl)azulenes with tetraphenylcyclopentadienone. Cobalt-mediated cyclooligomerization of mono- and di(6-azulenyl)acetylenes afforded 1,3,5- and 1,2,4-tri(6-azulenyl)benzene derivatives together with (eta(5)-cyclopentadienyl)[tetra- and di(6-azulenyl)cyclobutadiene]cobalt complexes. The redox behavior of these novel (6-azulenyl)benzene derivatives and [tetra- and di(6-azulenyl)cyclobutadiene]cobalt complexes was examined by cyclic voltammetry (CV). Mono(6-azulenyl)benzenes exhibited a reduction wave upon CV. In contrast, 1,2-di(6-azulenyl)benzenes showed a two-step reduction wave at the similar potential region upon CV, which revealed the formation of a dianion stabilized by 6-azulenyl substituents under electrochemical reduction conditions. Three 6-azulenyl substituents on benzene in a 1,2,4 relationship also increased electron-accepting properties because of the formation of a closed-shell dianionic structure, whereas 1,3,5-tri(6-azulenyl)benzenes were reduced stepwise. 相似文献
959.
Shingo Minato Tetsuo Osa Masahiko Morita Asao Nakamura Hiroshi Ikeda Fujio Toda Akihiko Ueno 《Photochemistry and photobiology》1991,54(4):593-597
The intramolecular excimer formation of 6A,6B-, 6A,6C-, 6A,6D-, and 6A,6E-bis(2-naphthyl-sulfonyl)-γ-cyclodextrins (1, 2, 3, and 4, respectively) and 6A.6B-, 6A,6C-, and 6A,6D-bis(2-naphthyl-sulfonyl)-β-cyclodextrins (5, 6, and 7, respectively) has been studied in 10% ethylene glycol aqueous solution. The two naphthyl rings are co-included in the γ-cyclodextrin cavities of1–4, and marked excimer emission was observed for 2, 3, and 4. On the other hand, almost pure monomer emission was observed for 5, 6, and 7 due to inclusion of one of two naphthyl rings in the β-cyclodextrin cavities. Compounds 2, 3, 6, and 7 showed remarkable guest-induced enhancement in the excimer emission, and this property was used for detecting several organic compounds with remarkable molecular recognition. 相似文献
960.
This paper describes the synthesis and chemical properties of some 2- and 3-substituted furo[2,3-b]pyridines. Reaction of ethyl 2-chloronicotinate 1 with sodium ethoxycarbonylmethoxide or 1-ethoxycarbonyl-1-ethoxide gave β-keto ester 2 or ketone 5 , respectively. Ketonic hydrolysis of 2 afforded ketone 3, from which furo[2,3-b]pyridine 4 was obtained by the method of Sliwa. While, 2-methyl derivative 7 was prepared from 5 by reduction, O-acetylation and the subsequent pyrolysis. Reaction of ketone 3 with methyllithium gave tertiary alcohol 8 which was O-acetylated and pyrolyzed to give 3-methyl derivative 9 . Formylation of 4 , via lithio intermediate, with DMF yielded 2-formyl derivative 10 , from which 7 , was obtained by Wolff-Kishner reduction. Dehydration of the oxime 11 of 10 gave 2-cyano derivative 12 , which was hydrolyzed to give 2-carboxylic acid 13 . Reaction of 3-bromo compound 14 with copper(I) cyanide gave 3-cyano derivative 15 . Alkaline hydrolysis of 15 afforded compound 16 and 17 , while acidic hydrolysis gave carboxamide 18 . Reduction of 15 with DIBAL-H afforded 3-formyl derivative 19 . Wolff-Kishner reduction of 19 gave no reduction product 9 but hydrazone 20 . Reduction of tosylhydrazone 21 with sodium borohydride in methanol afforded 3-methoxymethylfuro[2,3-b]pyridine 22 . 相似文献