全文获取类型
收费全文 | 6065篇 |
免费 | 209篇 |
国内免费 | 46篇 |
专业分类
化学 | 3736篇 |
晶体学 | 24篇 |
力学 | 195篇 |
数学 | 1215篇 |
物理学 | 1150篇 |
出版年
2023年 | 60篇 |
2022年 | 136篇 |
2021年 | 182篇 |
2020年 | 162篇 |
2019年 | 156篇 |
2018年 | 132篇 |
2017年 | 121篇 |
2016年 | 247篇 |
2015年 | 232篇 |
2014年 | 247篇 |
2013年 | 345篇 |
2012年 | 419篇 |
2011年 | 474篇 |
2010年 | 275篇 |
2009年 | 255篇 |
2008年 | 386篇 |
2007年 | 343篇 |
2006年 | 319篇 |
2005年 | 306篇 |
2004年 | 241篇 |
2003年 | 192篇 |
2002年 | 200篇 |
2001年 | 79篇 |
2000年 | 52篇 |
1999年 | 66篇 |
1998年 | 53篇 |
1997年 | 64篇 |
1996年 | 52篇 |
1995年 | 50篇 |
1994年 | 47篇 |
1993年 | 38篇 |
1992年 | 30篇 |
1991年 | 29篇 |
1990年 | 21篇 |
1989年 | 19篇 |
1988年 | 23篇 |
1987年 | 25篇 |
1986年 | 19篇 |
1985年 | 26篇 |
1984年 | 23篇 |
1983年 | 13篇 |
1982年 | 24篇 |
1981年 | 14篇 |
1980年 | 16篇 |
1979年 | 15篇 |
1978年 | 15篇 |
1977年 | 10篇 |
1976年 | 9篇 |
1975年 | 6篇 |
1973年 | 7篇 |
排序方式: 共有6320条查询结果,搜索用时 15 毫秒
61.
Jos L. Marco 《Journal of heterocyclic chemistry》1986,23(1):287-288
From (S)-pyroglutamic acid ( 1 ) the asymmetric synthesis of (S)-5-ethyl-2-pyrrolidinone ( 5 ) in 30% yield is described. 相似文献
62.
The reactions of perfluoroalkyl- and perfluoroacyl-iminosulfur difluorides with chlorine monofluoride result in the preparation of perfluoroalkyldichloroamines and a new class of compounds N,N-dichloroperfluoroamides, RfC(O)NCl2, via the elimination of SF4. The amides, FC(O)NCl2 and CF3C(O)NCl2, in addition to 1,2-bis-(dichloroamino)tetrafluoroethane, Cl2NCF2CF2NCl2, are reported and characterized. The reactions of CIF with other sulfur(IV) imines proceed in an analogous manner to form perfluoroalkyl-dichloroamines via the elimination of the corresponding sulfur(IV) fluoride. 相似文献
63.
Galli C Gentili P Lanzalunga O Lucarini M Pedulli GF 《Chemical communications (Cambridge, England)》2004,(20):2356-2357
Characterisation of the aminoxyl (>N-O*) radical BTNO, generated from 1-hydroxybenzotriazole (HBT) by the one-electron oxidant CAN (a Ce(IV) salt), confirms BTNO as the reactive intermediate in oxidations run with the laccase/HBT system. 相似文献
64.
Treatment of the five-coordinate ferrous dialkyl complex, (iPrPDI)Fe(CH2SiMe3)2 (iPrPDI = ((2,6-CHMe2)2C6H3N=CMe)2C5H3N), with [PhMe2NH][BPh4] in the presence of diethyl ether or tetrahydrofuran furnished the corresponding alkyl cations, where the donor ligand is coordinated in the basal plane of a distorted square pyramidal iron(II) alkyl cation. Performing the same reaction with the neutral Lewis acid, B(C6F5)3, induced methide abstraction from a silicon atom followed by rearrangement to afford the base free ferrous alkyl cation, [(iPrPDI)Fe(CH2SiMe2CH2SiMe3)][MeB(C6F5)3]. This complex is active for the polymerization of ethylene and yields polymers that are of higher molecular weight and narrower polydispersity than traditional methylalumoxane-activated catalysts. 相似文献
65.
Reaction kinetics data were collected for isobutane conversion over a series of ultra stable Y (USY) zeolite catalysts with and without rare earth cations and subjected to various extents of dealumination by steaming. We conducted these reaction studies at low temperatures (523-573 K) using isobutane feed streams containing known levels of isobutylene (100-400 ppm) so that the kinetics were controlled by bimolecular hydride transfer and oligomerization/beta-scission processes with little or no participation of monomolecular initiation reactions. These experimental conditions led to stable catalyst performance with the main products of isobutane conversion being propane, n-butane, and isopentane, with smaller amounts of propylene, trans-2-butene, and cis-2-butene. The rates of formation of these products per Br?nsted acid site (as counted by pyridine adsorption) depended exponentially on Br?nsted acid site density, regardless of whether the catalyst contained rare earth cations. Kinetic modeling showed an exponential dependence of hydride transfer and oligomerization/ beta-scission reaction rates on Br?nsted acid site density which translated into composite activation energies for these reactions having a linear relationship with site density. Based on results in the literature from theoretical calculations, we suggest that increasing Br?nsted acid site density in zeolite Y leads to larger zeolite elasticity, increased stabilization of cationic transition states, and lower composite activation barriers for hydride transfer and beta-scission steps. The role of rare earth cations, therefore, is to ensure the retention of high Br?nsted acid site density under hydrothermal conditions, such as in fluid catalytic cracking (FCC) regenerators, where steam would dealuminate the Y zeolite framework and reduce this site density. It is for this reason that hydride transfer reaction rates are high in the presence of rare earth cations and lead to higher yields of less olefinic gasoline during FCC. 相似文献
66.
67.
Marengo E Liparota MC Robotti E Bobba M Gennaro MC 《Analytical and bioanalytical chemistry》2005,381(4):884-895
A new method has been developed for monitoring the degradation of paintings. Two inorganic pigments (ultramarine blue and red ochre) were blended with linseed oil and spread on canvas. Each canvas was subjected to simulated accelerated ageing in the presence of typical degradation agents (UV radiation and acidic solution). Periodically the painted surfaces were analysed by FT-Raman, to investigate the status of the surface. The data obtained were analysed by principal component analysis (PCA). Finally the Shewhart and cumulative sum control charts based on the relevant principal components (PC) and the so called scores monitoring and residuals tracking (SMART) charts were built. The method based on the use of PC to describe the process was found to enable identification of the presence of relevant modification occurring on the surface of the samples studied.Electronic supplementary material Supplementary material is available for this article at 相似文献
68.
Laura Gagliardi Giorgio Orlandi Fernando Bernardi Alessandro Cembran Marco Garavelli 《Theoretical chemistry accounts》2004,111(2-6):363-372
In the present paper we report the results of a multiconfigurational computational study on potential-energy curves of azobenzene along the NN twisting to clarify the role of this coordinate in the decay of the S2(*) and S1(n*) states. We have found that there is a singlet state, S3 at the trans geometry, on the basis of the doubly excited configuration n2*2, that has a deep minimum at about 90° of twisting, where it is the lowest excited singlet state. The existence of this state provides an explanation for the short lifetime of S2(*) and for the wavelength-dependence of azobenzene photochemistry. We have characterized the S1(n*) state by calculating its vibrational frequencies, which are found to correspond to the recently observed transient Raman spectrum. We have also computed the potential-energy curve for the triplet T1(n*) at the density functional theory B3LYP level, which indicates that in this state the isomerization occurs along the twisting coordinate.Acknowledgement The financial support from MIUR (project Modellistica delle proprietà spettroscopiche di sistemi molecolari complessi funds ex 60% and project Dinamiche molecolari in sistemi di interesse chimico funds ex 40%), from the University of Bologna (Funds for Selected Research Topics) is gratefully acknowledged.Contribution to the Jacopo Tomasi Honorary Issue 相似文献
69.
Karen Wright Marco CrismaClaudio Toniolo Roland TörökAntal Péter Michel WakselmanJean-Paul Mazaleyrat 《Tetrahedron letters》2003,44(16):3381-3384
Amination of 3-carboxymethyl-1-oxyl-2,2,6,6-tetramethyl-4-piperidone with (R)-α-methylbenzylamine, NaBH3CN reduction of the resulting enamine and removal of the chiral auxiliary from the separated diastereoisomers, led to enantiomerically pure (3S,4S) and (3R,4R) methyl 4-amino-1-oxyl-2,2,6,6-tetramethylpiperidine-3-carboxylates. 相似文献
70.
Compounds A3M5 (A = alkaline earth, M = triel/tetrel): A Case Study on Structural and Electronic Factors Stabilizing Polar Intermetallics Starting from the non electron precise binary compounds Ca3Ga5/Sr3In5 (Hf3Ni2Si3 type) and Ba3Al5 at one hand and Ba3Pb5 (Pu3Pd5 type) at the other hand, a series of new ternary intermetallics of the general formula A3M5 (A: alkaline earth, M: triel/tetrel) has been synthesized, structurally characterized and studied by band structure calculations. The chemical substitution of M in A3M5 allows, via the continous variation of the radius ratio (rA:rM) and the valence electron number (VE/M) the detection of the geometrically and electronically determined stability ranges of the three structure types formed by the binary compounds. At values of rA:rM between 1.30 and 1.52 in the triel rich region of A3M′xM″5?x the Hf3Ni2Si3 type (orthorhombic, space group Cmcm) is formed: In Ca3Ga5 up to 1.8 Ga can be substituted by Al, in Sr3In5 similar amount of In can be replaced by either Al or Ga. The mixed trielide Sr3Al2.6Ga2.4 (a = 468.4(1), b = 1132.5(1), c = 1570.0(2) pm, R1 = 0.0261) can be obtained, although both corresponding binary phases are not known. At larger values of the ratio rA/rM as in Ba3Al3Ga2 (Ba3Al5 type, hexagonal, space group P63/mmc, a = 598.9(1), c = 1456.0(3) pm, R1 = 0.0353) layers of condensed M5 building blocks with Al‐Al partial bonds are formed. Substituting one In position in Sr3In5 against Pb results in the isotypic, but electron precise Zintl compound Sr3In4Pb (a = 506.1(1), b = 1191.8(3), c = 1650.2(4) pm, R1 = 0.0286), where the Fermi level in shifted into a distinct minimum of the density of states. Conversely, at the tetrele rich end of the series A3InxPb5?x, characterized by compounds of the Pu3Pd5 type (orthorhombic, space group Cmcm) with almost isolated nido clusters M5, a minimum of the DOS can be reached, if Pb is partially substituted by In (A3InxPb5?x with A = Sr/Ba: x = 0.7/0.6; a = 1084.6(2)/1118.6(2), b = 867.1(2)/904.4(1), c = 1104.8(2)/1133.9(2) pm, R1 = 0.0394/0.0434). 相似文献