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61.
早在本世纪初物理化学家们就已观察到,某些物质从其熔融态或溶液中结晶出来时,在某些条件下可形成周期性的宏观结晶条纹[1,2],这就是周期结晶现象,由于这种现象和晶体生长、材料物性以及成矿过程等重要问题紧密相关,很早就引起了人们的重视.近年来有关非平衡非线性系统中自发产生各种时空有序现象(自组织现象)的各种理论(如耗散结构理论)[3]的兴起,重新引起了人们对这类现象的兴趣.八十年代,Iwamoto等先后报道了甲基苄基氨基甲酸酯(MethylMesitylcarbamate)从氯仿溶液[4]和抗坏血酸(AscorbicAcid)从甲醇溶液[5]… 相似文献
62.
Five of the six possible aqueous two-salt mixtures from among NaCl, KCl, NaH2PO4,and KH2PO4 have been studied by the isopiestic method at 25°C. The sixth mixture, NaCl–KCl, has been studied previously. The deviations from ideal mixing behavior are described by a series of coefficients which were found by regression analysis. The coefficients were used to calculate the excess Gibbs energies of mixing for equal ionic strength fractions of each salt and the trace activity coefficient of each salt at an ionic strength of 2 mode-kg–1. The cross-square mixing rule is obeyed within experimental uncertainty for the excess Gibbs energies of mixing. 相似文献
63.
The morphology, crystallization behavior, and properties of an impact-modified polypropylene (PP) copolymer with or without
sodium benzoate were investigated. The contents of ethylene–propylene rubber (EPR) in the reactor-made PP copolymer is about
15 wt%. For comparison, blends of PP and EPR containing the same EPR composition were prepared by melt-mixing. Morphological
studies by scanning probe microscopy indicated that the impact-modified copolymer consists of three different phases, i.e.,
polyethylene, PP, and EPR phases, which is considerably different from the morphology of the conventional PP/EPR blend of
the corresponding composition. The impact-modified PP copolymer exhibited a higher crystallization rate in terms of the lower
crystallization half-time and thus higher thermal and mechanical properties, such as impact strength and hardness, than the
PP/EPR blend did. The addition of sodium benzoate as a nucleating agent to the copolymer increased the crystallization rate
and the mechanical properties.
Received: 4 June 2001 Accepted: 31 October 2001 相似文献
64.
Chiral salicylidenphenethylamines (R)‐HA or (S)‐HA , 2‐salicylidenfurfuryl‐imines HB , and 2‐salicylidenaminoethanol HC react with sodium hydride or sodium hexamethyldisilylamide to form the sodium complexes [Na(R)‐A] 4 · 0,5 Et 2 , [Na(S)‐A] 4 · 0,5 Et 2 O (1) , [NaB] 4 · 0,5 Ph‐Me (2) and [(dme)NaC] 4 (3) . In the presence of 18‐crown‐6 the complex [Na(18‐crown‐6)(thf) 2 ] 2 [Na 2 (C)] 4 · THF (4) can also be isolated. The crystal structure analyses of both 1 and 2 show that heterocubane structures with a Na4O4 frame work are formed. Additionally, the imine nitrogen atom is bonded at the Na atom which has the coordination number 4 in 1 . Additional coordination of the furfuryl oxygen atom results in the coordination number five for the sodium atom in 2 . In 3 which is also a tetramer, two Na2O2 units are connected via two imino‐ethanol bridges Na(1)‐N(=CH‐phenolat)‐CH2CH2‐OH‐Na(2A). The crystal structure analysis displays that 4 is an ionic compound consisting of two [(thf)2Na(18‐crown‐6)]+ cations and the dinuclear dianion [Na 2 (C) 4 ] 2? . Both 1 and 2 are carboxylation reagents which transfer CO2 to 2‐fluoropropiophenone. 1 is more active than 2 , but 3 and 4 are inactive. 相似文献
65.
Mixtures of dioctadecyldimethylammonium chloride (DODAC) cationic vesicle dispersions with aqueous micelle solutions of the anionic sodium cholate (NaC) were investigated by differential scanning calorimetry, DSC, turbidity and light scattering. Within the concentration range investigated (constant 1.0 mM DODAC and varying NaC concentration up to 4 mM), vesicle → micelle → aggregate transitions were observed. The turbidity of DODAC/NaC/water depends on time and NaC/DODAB molar concentration ratio R. At equilibrium, turbidity initially decreases smoothly with R to a low value (owing to the vesicle–micelle transition) when R = 0.5–0.8 and then increases steeply to a high value (owing to the micelle–aggregate transition) when R = 0.9–1.0. DSC thermograms exhibit a single and sharp endothermic peak at Tm ≈ 49 °C, characteristic of the melting temperature of neat DODAC vesicles in water. Upon addition of NaC, Tm initially decreases to vanish around R = 0.5, and the main transition peak broadens as R increases. For R > 1.0 two new (endo- and exothermic) peaks appear at lower temperatures indicating the formation of large aggregates since the dispersion is turbid. All samples are non-birefringent. Dynamic light scattering (DLS) data indicate that both DODAC and DODAC/NaC dispersions are highly polydisperse, and that the mean size of the aggregates tends to decrease as R increases. 相似文献
66.
Theodorus J.M. de Bruin Karoly Vekey Yves Gimbert Anne Milet 《Journal of organometallic chemistry》2006,691(20):4281-4288
The influence of carbon-carbon triple bond polarization on the regiochemistry of the Pauson-Khand reaction has been studied with the B3LYP functional. The regiochemistry determining step of this reaction, i.e., olefin insertion leading to cobaltacycle formation, has been examined with ethylene as the olefin and propyne, methyl 2-butynoate, and methyl propiolate as the acetylenes. From this study, it has been concluded that, in absence of overwhelming steric effects of an acetylene substituent, the regiochemistry is influenced by the polarization of the acetylenic bond, which arises from the different substituents. The initial C-C bond is preferentially formed with the acetylenic carbon that has the greater electron density: with propyne, this leads to a cyclopentenone having the methyl group in the α-position; with methyl 2-butynoate, to a cyclopentenone with the CO2Me in the β-position; with methyl propiolate, which is virtually unpolarized in the complex, to a cyclopentenone with the CO2Me in the α-position (a result of steric effects). These theoretical results are concordant with those observed experimentally with norbornene. The question of axial versus equatorial reactive positions for the coordinated olefin is also addressed and a kinetic simulation is presented. 相似文献
67.
<正> 光敏氧化效率是由敏化剂分子吸收光量子数及其产生单重态氧的量子产率决定的,这要求敏化剂的吸收光谱同光源的发射光谱很好地匹配。本文报道竹红菌甲素匹配高压钠灯有效地产生单重态氧,高效光敏氧化一系列具有不同反应活性的底物,成为单重态氧化学中一个新的光敏氧化体系。 相似文献
68.
Highly efficient kinetic resolution of racemic secondary alkyl diazoacetates in intramolecular carbon-hydrogen insertion reactions has been achieved using chiral dirhodium(ii) carboxamidates. Products formed from catalytic diazo decomposition of racemic 2-octyl diazoacetate and, separately, its (2R)- and (2S)-enantiomeric forms, as well as bothcis- andtrans-2-methylcyclohexyl diazoacetates, have been systematically evaluated. Enantioselectivities up to 99 %ee have been obtained for -lactone formation. -Lactone production has been observed and, although minor with cyclohexyl diazoacetates, is the major insertion pathway for diazo decomposition of 2-octyl diazoacetate.Dedicated to Academician of the RAS N. S. Zefirov (on his 60th birthday).Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1798–1803, September, 1995.Financial support for this research from the National Institutes of Health (GM 46503) and the National Science Foundation of the United States is gratefully acknowledged. We thank D. A. Pierson for her preparation of 2-methylcyclohexyl diazoacetates and preliminary studies of their diazo decomposition and A. Melekhov from the Higher College of Chemistry for his preparation and catalytic studies of rac-2-octyl diazoacetate. 相似文献
69.
V. A. Mamedov E. A. Berdnikov I. A. Litvinov L. G. Kuz'mina 《Russian Chemical Bulletin》1995,44(7):1247-1251
3,3-Dichloropentane-2,4-dione reacts with aromatic aldehydes under the conditions of Darzens reaction to give 4-acetoxy-4-aryl-3,3-dichlorobutan-2-ones, the products of insertion into the -C-C bond. The reaction of ethyl dichloroacetylacetate with benzaldehyde yields a derivative of tricyclo[5.1.0.03,5]octane, rather than 2,6-bis(1-chlorobenzylidene)cyclohexane-1,4-dione, as the by-product.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1294–1298, July, 1995. 相似文献
70.
C. Carlier-Pinasseau A. Astruc G. Lespes M. Astruc 《Journal of chromatography. A》1996,750(1-2):317-325
A reliable and rapid speciation method for the simultaneous determination of butyl- and phenyltin species in biological samples has been developed. Three extraction procedures are compared: enzymatic hydrolysis and solubilization by ethanoic and hydrochloric acids. Derivatization is performed by the one-step ethylation/extraction procedure using the sodium tetraethylborate reagent directly in the aqueous phase in the presence of an isooctane layer. Analysis is performed using capillary gas chromatography coupled to flame photometric detection. The detection limits are in the range of a few ng(Sn)/g. Analysis of the environmental samples and the certified reference material demonstrates the accuracy of the analytical method. 相似文献