全文获取类型
收费全文 | 4129篇 |
免费 | 212篇 |
国内免费 | 19篇 |
专业分类
化学 | 3150篇 |
晶体学 | 33篇 |
力学 | 101篇 |
综合类 | 1篇 |
数学 | 513篇 |
物理学 | 562篇 |
出版年
2023年 | 38篇 |
2022年 | 37篇 |
2021年 | 62篇 |
2020年 | 93篇 |
2019年 | 79篇 |
2018年 | 48篇 |
2017年 | 46篇 |
2016年 | 145篇 |
2015年 | 142篇 |
2014年 | 152篇 |
2013年 | 211篇 |
2012年 | 257篇 |
2011年 | 311篇 |
2010年 | 187篇 |
2009年 | 150篇 |
2008年 | 242篇 |
2007年 | 246篇 |
2006年 | 228篇 |
2005年 | 215篇 |
2004年 | 174篇 |
2003年 | 131篇 |
2002年 | 151篇 |
2001年 | 91篇 |
2000年 | 88篇 |
1999年 | 71篇 |
1998年 | 54篇 |
1997年 | 46篇 |
1996年 | 41篇 |
1995年 | 45篇 |
1994年 | 39篇 |
1993年 | 41篇 |
1992年 | 28篇 |
1991年 | 48篇 |
1990年 | 40篇 |
1989年 | 32篇 |
1988年 | 9篇 |
1987年 | 22篇 |
1986年 | 12篇 |
1985年 | 17篇 |
1984年 | 20篇 |
1983年 | 19篇 |
1982年 | 16篇 |
1981年 | 12篇 |
1980年 | 21篇 |
1979年 | 14篇 |
1978年 | 15篇 |
1977年 | 25篇 |
1975年 | 11篇 |
1974年 | 12篇 |
1973年 | 10篇 |
排序方式: 共有4360条查询结果,搜索用时 15 毫秒
61.
Beller M Thiel OR Trauthwein H Hartung CG 《Chemistry (Weinheim an der Bergstrasse, Germany)》2000,6(14):2513-2522
A new catalytic amination of aromatic olefins with anilines is presented. In a domino reaction, substituted quinoline derivatives are obtained in the presence of cationic rhodium complexes, such as [Rh(cod)2]BF4, and PPh3. Ethylbenzene is formed as a by-product in this new oxidative reaction. The first transition metal catalyzed anti-Markovnikov hydroamination of styrene with anilines occurs as a side reaction. Mechanistic investigations strongly support the regioselective oxidative amination of styrene as the key reaction step. 相似文献
62.
Feth MP Bolm C Hildebrand JP Köhler M Beckmann O Bauer M Ramamonjisoa R Bertagnolli H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(6):1348-1359
XANES and EXAFS spectroscopic studies at the Mn-K- and Br-K-edge of reaction products of (S,S)-(+)-N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminomanganese(III) chloride ([(salen)Mn(III)Cl], 1) and (S,S)-(+)-N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminomanganese(III) bromide ([(salen)Mn(III)Br], 2) with 4-phenylpyridine N-oxide (4-PPNO) and 3-chloroperoxybenzoic acid (MCPBA) are reported. The reaction of the Mn(III) complexes with two equivalents of 4-PPNO leads to a hexacoordinated compound, in which the manganese atom is octahedrally coordinated by four oxygen/nitrogen atoms of the salen ligand at an average distance of approximately 1.90 A and two additional, axially bonded oxygen atoms of the 4-PPNO at 2.25 A. The oxidation state of this complex was determined as approximately +IV by a comparative study of Mn(III) and Mn(V) reference compounds. The green intermediate obtained in reactions of MCPBA and solutions of 1 or 2 in acetonitrile was investigated with XANES, EXAFS, UV/Vis, and Raman spectroscopy, and an increase of the coordination number of the manganese atoms from 4 to 5 and the complete abstraction of the halide was observed. A formal oxidation state of IV was deduced from the relative position of the pre-edge 1s-->3d feature of the X-ray absorption spectrum of the complex. The broad UV/Vis band of this complex in acetonitrile with lambda(max)=648 nm was consistent with a radical cation structure, in which a MCPBA molecule was bound to the Mn(IV) central atom. An oxomanganese(V) or a dimeric manganese(IV) species was not detected. 相似文献
63.
64.
Huang S Xiao Z Wang F Zhou J Yuan G Zhang S Chen Z Thiel W von Ragué Schleyer P Zhang X Hu X Chen B Gan L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(18):5449-5456
[60]Fullerene mixed peroxides C60(O)(OOtBu)4 exhibit chemo- and regioselective reactions under mild conditions. The epoxy moiety is opened by ferric chloride to form vicinal hydroxy chloride C60Cl(OH)(OOtBu)4. BF3 is also effective in opening the epoxy moiety. The O-O bond of the fullerene mixed peroxide is cleaved by aluminum chloride to form both [5,6]- and [6,6]-fullerene hemiketals (oxohomo[60]fullerenes). A Hock-type rearrangement is proposed for the formation of the hemiketals, in which a fullerene C-C bond is cleaved. Lewis acids and/or visible light can initiate isomerization of the hemiketal isomers. Single-crystal X-ray analysis and theoretical calculations confirmed the results. 相似文献
65.
A recently proposed extension of the MNDO formalism to d orbitals has been parameterized for the halogens CI, Br, and I. Extensive test calculations indicate slight consistent improvements for normalvalent molecules and dramatic improvements for hypervalent molecules, in comparison with established MNDO -type methods without d orbitals. The mean absolute errors in calculated heats of formation are 3.9 kcal/mol for 155 normalvalent compounds and 2.8 kcal/mol for 23 hypervalent compounds. The predicted structures of the hypervalent molecules are qualitatively correct, with a mean absolute error of 2° in 19 bond angles. 相似文献
66.
Coloring linear hypergraphs: the Erdős–Faber–Lovász conjecture and the Combinatorial Nullstellensatz
Designs, Codes and Cryptography - The long-standing Erdős–Faber–Lovász conjecture states that every n-uniform linear hypergaph with n edges has a proper vertex-coloring using... 相似文献
67.
Oliver Pretzel 《Order》1995,12(2):135-147
We prove generalizations to chain groups, of Minty's Arc Colouring Lemma and its extension, the well-known Farkas Lemma. In these the orientation of the edges is replaced by an arbitrary chain.A function on a chain groupN isrepresentable if there exists a chainR such that (X)=R·X for allXN. Anorientation is a chain with values ±1. We prove that for a regular chain group a linear function that is representable by an orientation for each chainXN locally, is representable by an orientation globally. 相似文献
68.
Summary Multiflorine (1) — a minor lupine alkaloid — treated by methyl lithium or methyl magnesium iodide affords 4S-4-hydroxy-4-methyl-2,3-didehydrosparteine (2) and 2S-2-methyl-4-oxosparteine (3), respectively, as the dominating products. Their steric structure, determined by1H and13C NMR techniques, points to stereospecific preferences of these reactions. The observed nucleophilic 1,2- and 1,4-additions indicate that regiospecificity of the action of MeLi or MeMgI on multiflorine is different from that of the so far known similar alkylation of other enamino ketones.
Die räumliche Struktur von Methylierungsprodukten des Multiflorins
Zusammenfassung Multiflorin (1), ein Lupin-Nebenalkaloid, ergibt bei Umsetzung mit Methyllithium oder Methylmagnesiumiodid 4S-4-Hydroxy-4-methyl-2,3-didehydrospartein (2) und 2S-2-Methyl-4-oxospartein (3) als Hauptprodukte. Ihre NMR-spektroskopisch (1H und13C) aufgeklärte räumliche Struktur weist auf eine Stereoselektivität der erwähnten Reaktionen hin. Die beobachteten nucleophilen 1,2- und 1,4-Additionen zeigen, daß sich die Regiospezifität der Einwirkung von MeLi oder MeMgl auf Multiflorin von jener bis jetzt bekannter Alkylierungen von Enaminoketonen unterscheidet.相似文献
69.
The production of ultrafine silica particles is examined by modelling the processes in a flow plasma reactor. The model is based on the authors' experimental data on silica sand processing by use of thermal arc plasma. The free-molecular coagulation is assumed to be the dominant process for particle growth. This is carried out at fast cooling of the vapour, during its mixing with oxygen. The particle size distribution functions are calculated, and the influence of the chemical monomer generation and the mixing on their behavior is investigated. Comparison of the calculated and the experimental mean particle size is made.List of symbols
C
nl
collision frequency function, cm3/s
-
d
m
mean median diameter, nm
-
F
LN(d)
integral form of the particle size distribution function,%
-
g(t)
mixing function
-
k
Boltzmann's constant
-
k
1,k,k
rate coefficients, cm3/s
-
k
2,k
3
rate coefficiens, cm6/s
-
m
mass of the monomer, g
-
M
number of groups
-
T
absolute temperature, K
-
T
0
temperature of the hot vapour, K
-
T
E
temperature of SiO2 condensation, K
-
t
time, s
-
t
m
mixing time, s
-
t
c
colling time, s
-
z
0
monomer concentration, cm–3
-
z
n
,z
l
concentrations of particles in groups, cm–3
- z
n
total number concentration of particles (n=0, 1, M), cm–3
-
z
n
/(z
n
)(log d
n+1
–logd
n)
differential form of particle size distribution function
-
w
i
reaction rates (i=1, 2, 3), cm–3/s
- ,
cooling rates, K/s
-
coefficient of proportionality
- SiO
conversion rate of SiO,%
-
coefficient determined from the cooling rate, s–1
-
mass density of the particles, g/cm3
-
standard deviation
The authors gratefully acknowledge Prof. L. S. Polak from the Institute of Petrol Chemical Synthesis, Russian Academy of Science, for helpful discussions. 相似文献
70.