全文获取类型
收费全文 | 2454篇 |
免费 | 55篇 |
国内免费 | 18篇 |
专业分类
化学 | 1525篇 |
晶体学 | 12篇 |
力学 | 76篇 |
数学 | 490篇 |
物理学 | 424篇 |
出版年
2021年 | 22篇 |
2020年 | 26篇 |
2019年 | 14篇 |
2018年 | 27篇 |
2017年 | 14篇 |
2016年 | 46篇 |
2015年 | 32篇 |
2014年 | 41篇 |
2013年 | 107篇 |
2012年 | 94篇 |
2011年 | 132篇 |
2010年 | 69篇 |
2009年 | 68篇 |
2008年 | 109篇 |
2007年 | 126篇 |
2006年 | 133篇 |
2005年 | 146篇 |
2004年 | 129篇 |
2003年 | 109篇 |
2002年 | 108篇 |
2001年 | 51篇 |
2000年 | 35篇 |
1999年 | 19篇 |
1998年 | 25篇 |
1997年 | 27篇 |
1996年 | 45篇 |
1995年 | 30篇 |
1994年 | 20篇 |
1993年 | 35篇 |
1992年 | 25篇 |
1991年 | 27篇 |
1990年 | 16篇 |
1989年 | 20篇 |
1988年 | 29篇 |
1987年 | 21篇 |
1986年 | 18篇 |
1985年 | 38篇 |
1984年 | 30篇 |
1983年 | 26篇 |
1982年 | 38篇 |
1981年 | 47篇 |
1980年 | 39篇 |
1979年 | 29篇 |
1978年 | 28篇 |
1977年 | 25篇 |
1976年 | 30篇 |
1975年 | 23篇 |
1974年 | 27篇 |
1973年 | 30篇 |
1972年 | 20篇 |
排序方式: 共有2527条查询结果,搜索用时 765 毫秒
51.
B.M.Ratnayake Bandara Arthur J. Birch Brian Chauncy Lawrence F. Kelly 《Journal of organometallic chemistry》1981,208(2):C31-C35
Complexation commencing with some substituted 1,3- or 1,4-cyclohexadienes with Fe(CO)5 indicates that the steric direction is controlled by classical hindrance with groups such as alkyl, but probably involves transmission of the entering group through intermediate complexation with CO2Me. The results help to define methods of obtaining desired stereoisomers in the series. 相似文献
52.
The successful realization of a stereospecific chloride degenerative transfer living Ziegler-Natta polymerization process that provides isotactic polyolefins of narrow polydispersity (Mw/Mn = 1.05) is documented. Variable-temperature NMR studies confirm the configurational stability of all species with respect to metal-centered epimerization and large magnitudes for both kbeta and k-beta. Additional kinetic analyses with an increasing concentration of the dormant state establish that kbeta is larger than k-beta. Finally, [Et3Si][B(C6F5)4] has been shown to be an effective substoichiometric halide abstractor for chloride degenerative transfer Ziegler-Natta polymerization. 相似文献
53.
J. V. Crivello J. L. Lee D. A. Conlon 《Journal of polymer science. Part A, Polymer chemistry》1987,25(12):3293-3309
All aromatic polyimides bearing diarylsulfide linkages in the main chain were prepared either by condensation of a sulfur containing dianhydride with an aromatic diamine or the condensation of a sulfur containing aromatic diamine with a dianhydride. Phenylation with diphenyl iodonium salts was then used to convert the diarylsulfide groups to triarylsulfonium salts. The resulting photosensitive polyimides were shown to undergo main chain cleavage during photolysis using UV irradiation. These new polyimides are candidates for positive working, high temperature photoresist materials. 相似文献
54.
W. Clark Still Lawrence J. Macpherson Toshiro Harada James F. Callahan Arnold L. Rheingold 《Tetrahedron》1984,40(12):2275-2281
The conformations of macrocyclic intermediates provide a useful medium through which distant chiral centers may control chemical reactions. In this paper, we show that macrocycles made by cyclization of simple acyclic starting materials with an auxiliary spacer may be used to prepare stereochemically complex acyclic products. 相似文献
55.
Hot water extracts of Ginkgo biloba seeds were analyzed for the presence of ginkgotoxin (4'-O-methylpyridoxine) by reversed-phase liquid chromatography (LC) using methanol-0.05M KH2PO4 (1 + 9, v/v) adjusted to pH 3 as mobile phase. Detection was by fluorescence (excitation 280 nm, emission 370 nm). A straight line calibration curve was obtained for the 10-100 ng injected. After addition of beta-glucosidase (37 degrees C/h), an earlier eluting peak disappeared and the ginkgotoxin peak increased. The identity of the ginkgotoxin was confirmed by LC/MS and LC/MS/MS. LC/MS/MS also confirmed the 5'-glucoside by comparison with the 3-glucoside. This is the first identification of a glucoside of ginkgotoxin in Ginkgo biloba. An unknown compound of MW 267 also observed in the Ginkgo biloba seed extract was shown not to be 3,5'-diacetylginkgotoxin by its different LC retention time. Extraction of ground Ginkgo biloba seeds with boiling water in a Soxhlet for 2 x 2 h yielded a total of 179 microg/g of free ginkgotoxin. The concentration in powder from Ginkgo biloba capsules was several times lower than this (17-64 microg/g) in 3 samples but higher in another (457 microg/g). Canned ginkgo seeds (white nuts) contained no detectable free ginkgotoxin but the glucoside was present. Different extraction times were studied: 0.5 h gave only 52 microg/g free ginkgotoxin in the ginkgo seeds. However, boiling an extract for 4 h showed about 15% loss of ginkgotoxin and its glucoside. 相似文献
56.
Mohammad A. Khadim Lawrence D. Colebrook Laurance D. Hall 《Journal of heterocyclic chemistry》1980,17(4):651-656
Proton spin-lattice relaxation rates (R1 values) have been measured, at 270 MHz, for a series of N-aryl isoindolinones. A normalization procedure has been used to enable comparison of R1 values in different compounds by minimizing the effects on relaxation rates of changes in motional correlation times accompanying changes in substitution patterns. A substantial (4.3-fold) dynamic range of R1 values has been observed, and individual values have been correlated with the molecular environments of the nuclei. There is evidence for an interring relaxation process. 相似文献
57.
Gas-phase activation energies were calculated for three lithium enolate reactions by using several different ab initio and density functional theory (DFT) methods to determine which levels of theory generate acceptable results. The reactions included an aldol-type addition of an enolate to an aldehyde, a proton transfer from an alcohol to a lithium enolate, and an S(N)2 reaction of an enolate with chloromethane. For each reaction, the calculations were performed for both the monomeric and dimeric forms of the lithium enolate. It was found that transition state geometry optimization with B3LYP followed by single point MP2 calculations generally provided acceptable results compared to higher level ab initio methods. 相似文献
58.
A series of gold(III) cations of the type cis-[CH3)2AuL2]+ X? where L Ph3, PMePh2, PMe2Ph, PMe3, AsPh3, AsPh3, SbPh3, H2NCH2CH2NH2, Ph2PCH2CH2-PPh2, Ph2AsCH2CH2AsPh2, and o-C6H4(AsMe2)2 and X BF4?, PF6?, ClO4?, and F3CSO3? has been prepared. In addition, the cis complexes [(CH3)(CD3)-Au(PPh3)2]F3CSO3, [(C2H5)2Au(PPh3)2]F3CSO and [(n-C4H9)2Au(PPh3)2]F3-CSO3 have been synthesized. All have been characterized by PMR, Raman and infrared spectroscopy. These [R2AuL2]X compounds yield only ethane, butane, or octane via reductive elimination, and no disproportionation is observed. The alkane eliminations have been studied in CHCl3, CH3Cl2, and CH3COCH3 solution as a function of temperature, concentration of the complex, and concentration of added ligand L. Elimination is fastest when L is bulky (PPh3 > PMePh2 > PMe2Ph > PMe3), decreases in the sequence SbPh3 > AsPh3 > PPh3, is slow with chelating ligands, is inhibited by excess ligand, and there is small anion effect as X is varied. As R is varied, the rate of elimination decreases Bu ? Et > Me. An intramolecular dissociative mechanism is proposed which involves rapid elimination of alkane from an electron deficient dialkylgold(III) complex with nonequivalent gold—carbon bonds and produces the corresponding [AuL2]X complex. 相似文献
59.
Abstract— The lowest-lying triplet states of a variety of aromatic molecules and complexes have been generated by the irradiation of these compounds in solvent glasses with plane-polarized light. Measurements of the allowed (Δ M=± 1) ESR transitions clearly demonstrate that the triplets so formed are oriented with respect to the external magnetic field. By this method the triplet zero-field splitting parameters, D and E , can be evaluated simply and reliably. Intramolecular energy transfer is postulated to explain the triplet spectra of Zn( o -phen)2 (NO3 )2 and Zn( o -phen)3 (NO3 )2 . It was observed that in triplet-triplet energy transfer from benzophenone to naphthalene there is no apparent orientation requirement between the donor and acceptor molecules. Further areas of significance and application of this technique are suggested. 相似文献
60.
L. G. Chalmet R. L. Francis J. F. Lawrence 《Journal of Optimization Theory and Applications》1980,32(2):135-149
An example of design might be a warehouse floor (represented by a setS) of areaA, with unspecified shape. Givenm warehouse users, we suppose that useri has a known disutility functionf
isuch thatH
i(S), the integral off
iover the setS (for example, total travel distance), defines the disutility of the designS to useri. For the vectorH(S) with entriesH
i(S), we study the vector minimization problem over the set {H(S) :S a design} and call a design efficient if and only if it solves this problem. Assuming a mild regularity condition, we give necessary and sufficient conditions for a design to be efficient, as well as verifiable conditions for the regularity condition to hold. For the case wheref
iis thel
p-distance from warehouse docki, with 1<p<, a design is efficient if and only if it is essentially the same as a contour set of some Steiner-Weber functionf
=1
f
1++
m
f
m
,when the
i
are nonnegative constants, not all zero.This research was supported in part by the Interuniversity College for PhD Studies in Management Sciences (CIM), Brussels, Belgium; by the Army Research Office, Triangle Park, North Carolina; by a National Academy of Sciences-National Research Council Postdoctorate Associateship; and by the Operations Research Division, National Bureau of Standards, Washington, D.C. The authors would like to thank R. E. Wendell for calling Ref. 16 to their attention. 相似文献