全文获取类型
收费全文 | 5247篇 |
免费 | 190篇 |
国内免费 | 38篇 |
专业分类
化学 | 3417篇 |
晶体学 | 12篇 |
力学 | 198篇 |
数学 | 1069篇 |
物理学 | 779篇 |
出版年
2023年 | 29篇 |
2022年 | 99篇 |
2021年 | 131篇 |
2020年 | 126篇 |
2019年 | 125篇 |
2018年 | 109篇 |
2017年 | 89篇 |
2016年 | 224篇 |
2015年 | 184篇 |
2014年 | 221篇 |
2013年 | 363篇 |
2012年 | 393篇 |
2011年 | 408篇 |
2010年 | 213篇 |
2009年 | 252篇 |
2008年 | 331篇 |
2007年 | 326篇 |
2006年 | 254篇 |
2005年 | 233篇 |
2004年 | 235篇 |
2003年 | 167篇 |
2002年 | 124篇 |
2001年 | 56篇 |
2000年 | 47篇 |
1999年 | 42篇 |
1998年 | 42篇 |
1997年 | 46篇 |
1996年 | 56篇 |
1995年 | 26篇 |
1994年 | 36篇 |
1993年 | 19篇 |
1992年 | 35篇 |
1991年 | 23篇 |
1990年 | 25篇 |
1989年 | 24篇 |
1988年 | 24篇 |
1987年 | 19篇 |
1986年 | 17篇 |
1985年 | 37篇 |
1984年 | 31篇 |
1983年 | 29篇 |
1982年 | 30篇 |
1981年 | 16篇 |
1980年 | 20篇 |
1979年 | 15篇 |
1978年 | 21篇 |
1977年 | 14篇 |
1976年 | 18篇 |
1974年 | 13篇 |
1972年 | 8篇 |
排序方式: 共有5475条查询结果,搜索用时 15 毫秒
41.
Francesco De Sarlo Antonio Guarna Andrea Goti Alberto Brandi 《Journal of organometallic chemistry》1984,269(2):115-121
Organomercury fulminates react with acetylene derivatives to give unstable 3-(organomercurio)isoxazoles, which isomerize to 2-cyanoenolates. These are hydrolyzed with hydrochloric acid to the corresponding enols and are cleaved by water at the double bond. With monosubstituted acetylenes, substitution at the free position by the organomercury residue is predominant. 相似文献
42.
43.
Alberto Avenoza Jesús H Busto Carlos Cativiela Francisco Corzana Jesús M Peregrina María M Zurbano 《The Journal of organic chemistry》2002,67(2):598-601
A short and efficient asymmetric synthesis of the (6R,7S)-7-tert-butoxycarbonylamino-2-ketocarbacepham is described. The key step involves the hetero Diels-Alder reaction of the benzylimine derived from the enantiomer of Garner's aldehyde with Danishefsky's diene. 相似文献
44.
45.
Poschalko A Lancelot N Marin J Larras V Limal D Elbayed K Raya J Piotto M Briand JP Guichard G Bianco A 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(18):4532-4537
A novel resin called DEUSS (perdeuterated poly(oxyethylene)-based solid support) has been prepared by anionic polymerization of deuterated [D4]ethylene oxide, followed by cross-linking with deuterated epichlorohydrin. DEUSS can be suspended in a wide range of solvents including organic and aqueous solutions, in which it displays a high swelling capacity. As measured by proton HRMAS of the swollen polymer, the signal intensity of the oxyethylene protons is reduced by a factor of 110 relative to the corresponding nondeuterated poly(oxyethylene)poly(oxypropylene) (POEPOP) resin, thus facilitating detailed HRMAS NMR studies of covalently linked molecules. This 1H NMR invisible matrix was used for the solid-phase synthesis of peptides, oligoureas, and a series of amides as well as their characterization by HRMAS NMR spectroscopy. On-bead NMR spectra of high quality and with resolution comparable to that of liquid samples were obtained and readily interpreted. The complete absence of the parasite resin signals will be of great advantage, for example, for the optimization of multistep solid-phase stereoselective reactions, and for the conformational study of resin-bound molecules in a large variety of solvents. 相似文献
46.
Valentina Domenici Carlo Alberto Veracini Katalin Fodor-Csorba Giacomo Prampolini Ivo Cacelli Andrjia Lebar Bostjan Zalar 《Chemphyschem》2007,8(16):2321-2330
The orientational properties of the banana-shaped liquid crystal 4-chloro-1,3-phenylenebis{4-[4'-(10-undecenyloxy)]benzoyloxy} benzoate (ClPbis11BB) are reported in the nematic phase under the effect of an external magnetic field. A new hypothesis, which states that the central ring of the aromatic core is oriented perpendicularly to the external magnetic field, is proposed. In support of this hypothesis, a series of studies based on (2)H NMR spectroscopy, both in the bulk and in solution, are discussed. (2)H NMR measurements on three selectively deuterium-labelled isotopomers are presented, together with DFT results from B3LYP/cc-pvDz calculations performed on the aromatic core. The rather flat shape of the investigated intramolecular energy surface allows for several different conformations to be populated, the computed magnetic susceptibilities of which are consistent with the proposed hypothesis of peculiar orientation of banana-shaped molecules. Moreover, the orientation of the magnetic susceptibility tensor is shown to be strongly dependent on the internal conformation of the banana-shaped molecules. 相似文献
47.
Alberto Cavicchioli 《Geometriae Dedicata》1986,20(3):345-348
We construct a countable set of prime non-homeomorphic homology spheres with Heegaard genus 2.
Work performed under the auspicies of the G.N.S.A.G.A. of the C.N.R. (National Research Council of Italy) and within the project Geometria delle Varietà Differenziabili of the M.P.I. (Italy). 相似文献
Sunto Si prova l'esistenza di una classe numerabile di sfere omologiche prime non omeomorfe con genere di Heegaard 2.
Work performed under the auspicies of the G.N.S.A.G.A. of the C.N.R. (National Research Council of Italy) and within the project Geometria delle Varietà Differenziabili of the M.P.I. (Italy). 相似文献
48.
J. C. Masini Oswaldo E. S. Godinho Luiz M. Aleixo 《Fresenius' Journal of Analytical Chemistry》1998,360(1):104-111
A linearization method based on modified Gran functions, and a general nonlinear regression program were used to study potentiometric
titration curves of denatured ovalbumin and lysozyme in 6 mol L–1 guanidine hydrochloride medium with the aim of determining the ionizable species. With both numerical techniques it was possible
to determine the sum of the carboxylic groups, the imidazol, the α-amine, and the sum of ɛ-amine, phenolic and sulfhydryl
groups, if the protein is completely denatured, and assumes a randomly coiled conformation. A total of 87.8 ± 2.5 and 20.7
± 0.6 groups per mol were determined in the ovalbumin and lysozyme, respectively. These values are very close to the 88 and
21 groups expected by aminoacid composition of both proteins, indicating that all ionizable groups were exposed to the solvent.
For ovalbumin the distribution of groups was very similar to that expected by the aminoacid composition, but for lysozyme
some anomalies were observed, suggesting the existence of interactions between ionizable groups, altering the dissociation
constants.
Received: 9 December 1996 / Revised: 27 February 1997 / Accepted: 4 March 1997 相似文献
49.
Carlos Cativiela Maria D. Diaz De Villegas Jos A. Mayoral Alberto Avenoza Miguel A. Roy 《Journal of heterocyclic chemistry》1988,25(3):851-855
3(5)-Carbomethoxy-4-hetarylpyrazoles 3 can be obtained by the aromatization of the corresponding cis-3-benzamido-3-carbomethoxy-4-hetaryl-Δ1-pyrazolines 2 obtained by 1,3-dipolar cycloaddition of diazo-methane with methyl Z-2-benzamido-3-hetarylpropenoates 1. An explanation, based on FMO theory, for the different reactivity of the dipolarophiles with diazomethane is given. 相似文献
50.
Maria do Carmo B. Pimentel Eduardo Henrique M. Melo José Luiz Lima Filho William M. Ledingham Nelson Durán 《Applied biochemistry and biotechnology》1997,66(2):185-195
This work is a study of lipase production by a Brazilian strain ofPenicillium citrinum using an inexpensive and simple medium without organic nitrogen sources and of some important industrial properties, including
thermostability in relation to ionic strength. The maximal lipase activity (1585 U/L) was obtained whenPenicillium citrinum was cultured on 0.75% ammonium sulfate complemented with minerals salts instead of yeast extract. Although this activity
was about 55% lower than that produced in medium with yeast extract (2850 U/L), the specific activity (7.8 U/mg proteins)
was higher than that obtained with the yeast extract (4.9 U/mg proteins). The morphology of fungus changed totally, with yeast
extract there are smooth, solid, and spherical pellets whereas on ammonium sulfate there are small “hairy” pellets uniformly
suspended in the medium. The effect of ferrous (Fe++) ions was carried out using medium MA with and without Fe++ ions. Lipase production byPenicillium citrinum in medium MA requires Fe++ ions, the absence of which caused a decreased of about 50% in the specific activity (3.5 U/mg proteins). The utilization
of commercial, locally available oils as carbon sources, such as soybean oil (236 U/L) and corn oil (74 U/L) resulted in lower
activity compared to olive oil, showing that lipase production byPenicillium citrinum is specifically induced by olive oil. Potassium concentration in the medium can effects the production of lipase (1 mM (1585
U/L), 10 mM (1290 U/L), and 30 mM (1238 U/L), 50 mM (195 U/L), and 100 mM (2 U/L). The crude culture filtered was susceptable
to thermal deactivation. It was stable at pH 6.0, but was not stable at the optimum pH (8.0-8.5) at 50 mM. At the low ionic
concentration (1-25 mM) this lipase was stable at low pH (3.5-4.0). The activation energy was 22.4 ±2.2 Kcal. mol 1. 相似文献