全文获取类型
收费全文 | 122858篇 |
免费 | 1707篇 |
国内免费 | 637篇 |
专业分类
化学 | 47658篇 |
晶体学 | 1024篇 |
力学 | 7463篇 |
数学 | 37114篇 |
物理学 | 20182篇 |
无线电 | 11761篇 |
出版年
2022年 | 356篇 |
2021年 | 555篇 |
2020年 | 614篇 |
2019年 | 586篇 |
2018年 | 12134篇 |
2017年 | 11770篇 |
2016年 | 7804篇 |
2015年 | 1784篇 |
2014年 | 1334篇 |
2013年 | 2332篇 |
2012年 | 6219篇 |
2011年 | 14068篇 |
2010年 | 8049篇 |
2009年 | 7868篇 |
2008年 | 9353篇 |
2007年 | 11702篇 |
2006年 | 2437篇 |
2005年 | 3605篇 |
2004年 | 3459篇 |
2003年 | 3653篇 |
2002年 | 2447篇 |
2001年 | 731篇 |
2000年 | 733篇 |
1999年 | 569篇 |
1998年 | 572篇 |
1997年 | 550篇 |
1996年 | 726篇 |
1995年 | 506篇 |
1994年 | 412篇 |
1993年 | 408篇 |
1992年 | 362篇 |
1991年 | 338篇 |
1990年 | 279篇 |
1989年 | 283篇 |
1988年 | 310篇 |
1987年 | 289篇 |
1986年 | 276篇 |
1985年 | 420篇 |
1984年 | 401篇 |
1983年 | 295篇 |
1982年 | 375篇 |
1981年 | 385篇 |
1980年 | 374篇 |
1979年 | 337篇 |
1978年 | 312篇 |
1977年 | 270篇 |
1976年 | 238篇 |
1975年 | 237篇 |
1974年 | 226篇 |
1973年 | 247篇 |
排序方式: 共有10000条查询结果,搜索用时 10 毫秒
991.
Xiaodong Zhang Dexu Lin Zhengmin Liu 《Journal of Radioanalytical and Nuclear Chemistry》2005,266(1):149-151
Summary The elastic scattering cross sections of natural vanadium for protons have been measured for beam energies below 2.64 MeV in steps of 10 keV and in the angular 160° and 170°. The overall standard error (ΔσExp/σExp) in the measured cross sections is estimated to be better than ±3% at all the beam energies and angles. The results are presented in graphical and tabular forms that should be useful for those who wish to use the cross sections for material analysis. 相似文献
992.
Blackmore IJ Gibson VC Hitchcock PB Rees CW Williams DJ White AJ 《Journal of the American Chemical Society》2005,127(16):6012-6020
The 2,6-bis(alpha-iminoalkyl)pyridines 2,6-[ArNC(CR(3))](2)C(5)H(3)N [R = H, D; Ar = 2,6-i-Pr(2)C(6)H(3) (DIPP), 2,6-Me(2)C(6)H(3) (DMP)] react with MeLi in Et(2)O to give a binary mixture of products: the pyridine N-methylated species 2,6-[ArNC(CR(3))](2)C(5)H(3)N(Me)Li(OEt(2)) and the deprotonated/dedeuterated species 2-[ArNC(CR(3))],6-[ArNC(=CR(2))]C(5)H(3)NLi(OEt(2)). For R = D, the product ratio is 2:1 in favor of the N-methylated product, while, for R = H, the deprotonated product is favored by 5:1, increasing to 8:1 in toluene solvent. Warming solutions of the N-methylated species leads to clean conversion to the thermodynamically preferred deprotonated species. Crossover experiments show that MeLi is re-formed and dissociates from the terdentate ligand before deprotonating the ketimine methyl unit. For MgR(2) (R = Et, i-Pr) and ZnR(2) (R = Et) reagents, N-alkylation products are formed exclusively, but derivatives containing bulky aryl substituents are found to undergo further rearrangement to 2-alkylated species, arising by migration of the alkyl group of the N-alkyl moiety to the adjacent ring carbon atom. The reversibility of the N-alkylation process has been probed using deuterio-labeled Mg alkyl reagents and mixed alkyl zinc species. A cationic zinc derivative is shown to undergo "reverse" alkyl migration, from the heterocycle nitrogen atom to the zinc center. EPR spectroscopy reveals a paramagnetic intermediate in which the unpaired electron is delocalized over the heterocycle and di-imine moieties of the ligand, indicating that the N-alkylation reactions proceed via single electron-transfer processes. 相似文献
993.
Shah BK Neckers DC Shi J Forsythe EW Morton D 《The journal of physical chemistry. A》2005,109(34):7677-7681
Anthanthrene (1) derivatives substituted at the 4,10 and 6,12 positions (2-6) were synthesized as promising candidates for organic light emitting diodes (OLEDs). The emission of these compounds can be manipulated in the blue region (lambda(max) = 437-467 nm) through structural modifications. Photophysical and electrochemical properties (phi(F) = 0.20-0.47; tau(F) = 2.97-6.06 ns; HOMO-LUMO energy gap = 2.25-2.56 eV) as well as geometry optimized structures of 1-6 are reported. 相似文献
994.
Israel Cabasso Suresh K. Sahni David Vofsi 《Journal of polymer science. Part A, Polymer chemistry》1988,26(11):2997-3014
Phosphonic acid ester derivatives of glycerol, D -mannitol, D -sorbitol, pentaerythritol, and dipentaerythritol have been synthesized by transacetalation reactions with diethyl 2,2-diethoxyethylphosphonate. These phosphonated derivatives of polyols and carbohydrates have been esterified to from the corresponding methacrylates. All these compounds have been characterized on the basis of their elemental analysis and spectroscopic (infrared including FT–IR, 1H-, 13C-, 31P-NMR, and mass) methods. Transacetalation reactions with dialkyl 2,2-dialkoxyethylphosphonate lead to the synthesis of 1,3-dioxane derivatives in the case of D -mannitol, pentaerythritol, and dipentaerythritol, whereas a mixture of both 1,3-dioxane and 1,3-dioxolane derivatives is obtained with D -sorbitol and glycerol. The methacrylates of phosphonylated polyol derivatives show the capacity to dissolve and interact with metal salts such as bismuth bromide and uranyl nitrate. Some of the polymers obtained from these monomers have been characterized on the basis of their spectral and thermal (differential scanning calorimetry) properties. 相似文献
995.
Peter D van der Wal Maria Skowronska-Ptasinska Albert van den Berg Piet Bergveld Ernst J.R Sudhölter David N Reinhoudt 《Analytica chimica acta》1990
Several polymeric materials were studied as membrane materials for potassium-selective ion-sensitive field-effect transistors (ISFETs) to overcome the problems related with the use of conventional plasticized poly(vinyl chloride) membranes casted on ISFET gate surfaces. Several acrylate materials, such as ACE, Epocryl and derivatives, showed no reproducible results. Three room-temperature vulcanizing (RTV)-type silicone rubbers were tested. The addition-type RTV-2 silicone rubber was not suitable as a membrane material, but the condensation-type RTV-1 and especially the RTV-2 silicone rubber showed good results. ISFETs with a Silopren membrane showed a durability of at least 2 months. 相似文献
996.
T. Vlase Gabriela Vlase A. Chiriac N. Doca 《Journal of Thermal Analysis and Calorimetry》2005,80(1):87-90
Summary In order to obtain catalysts, the thermal decomposition of the precursors is a compulsory step. However, kinetic analysis of the decomposition data obtained under non-isothermal conditions lead very seldom to the intimate reaction mechanism. There is also a lack of information because in non-isothermal kinetics, the compensation effect, is rather a rule and unfortunately a source of debate. In order to discriminate between these processes, and the influence of conversion, respectively temperature on the reaction rate, the NPK (non-parametric kinetic - Sempere and Nomen) method was used. This method is based on the singular value decomposition algorithm (SVD) applied on the matrix of reaction rate at corresponding conversion and temperature. This method allows a less speculative determination of the conversion functions and of the kinetic parameters. 相似文献
997.
Szekeres E Acosta E Sabatini DA Harwell JH 《Journal of colloid and interface science》2005,287(1):273-287
Solubilization of dodecanol-limonene binary oil mixtures has been studied in saturated Winsor type I and III sodium dihexyl sulfosuccinate microemulsions. The systems showed different oil solubilization behavior below and above dodecanol volume fraction 0.2. Below 0.2 dodecanol volume fraction regular Winsor type microemulsions formed. The oil solubilization was characterized in this concentration range by the optimum salinity and the maximum characteristic length. Dodecanol showed Langmuirian-type surface excess adsorption at the vicinity of the surfactant layer. Variation of the optimum salinity and middle phase characteristic length with increasing dodecanol concentration could be linked to changes in the dodecanol surface excess. These relationships were used to develop new mathematical models for the optimum salinity and characteristic length as a function of oil phase composition. Both models yield excellent agreement with the data. Above dodecanol volume fraction 0.2 regular Winsor type III microemulsions are not formed. Therefore our new models are not applicable in this concentration range. 相似文献
998.
The synthesis of alkylarylphosphines is easily carried out by hydrophosphination of unactivated alkenes under mild thermal activation; gram scale amounts of products can be prepared by this simple methodology. 相似文献
999.
The synthesis of a new ligand system for mono- and bimetallic complexes based on a calixarene is described. Ligand BBPC (3, bis(bipyridine)-calix[4]arene) is obtained in three steps in 40% overall yield by first brominating one of the methyl groups of the 4,4'-dimethyl-2,2'-bipyridine in two steps and subsequently reacting it with p-tert-butylcalix[4]arene under basic conditions. Reaction of BBPC (3) with 2 equiv of [Rh(NBD)(2)]BF(4) or [Rh(NBD)(CH(3)CN)(2)]BF(4) (NBD = norbornadiene) produces the bimetallic compound BBPC[Rh(NBD)BF(4)](2) (4). Treatment of the ligand with PdCl(2)(CH(3)CN)(2) leads to the isolation of the bimetallic complex BBPC[PdCl(2)](2) (5). When the nickel precursor NiBr(2)(DME) (DME = dimethoxyethane) is reacted with BBPC, the bimetallic complex BBPC[NiBr(2)](2) (6) is isolated which, upon crystallization from methanol, gives the mononuclear bis(bipyridine) complex BBPC[NiBr(OMe)] (7). Full characterization includes X-ray structural studies of complexes 4, 5, and 7. The bimetallic compounds 4 and 5 show metal to metal distances of 4.334 A (for 4) and 3.224 A (for 5). For all three complexes, unique molecular packing arrangements were found, based on hydrophobic/hydrophilic interactions. 相似文献
1000.
Moein B. Sayed 《Journal of Solid State Electrochemistry》2003,7(4):223-231
Variable strength H-bonding affects the mobility and so electric conduction of protons differently. Also, variable extent
mesomerism modifies electric conduction with varying dielectric features. Both these molecular modifiers are properly cited
using azophenol derivatives as model compounds for discussion of their consequences in the varying features of electric conduction.
The electric permittivity shows low-frequency dispersion characteristic of ionic conduction over mobile charge carries; the
mobility shifts at a critical temperature T
c, being structure dependent. The frequency-dependent Z′′-Z′ layout changes with temperature from linear at low temperatures to semicircular above T
c within a frame of temperature-sensitive dipole-ionic mediated conduction. The a.c. conductivity, σac, increases with frequency and temperature and becomes frequency insensitive, like d.c. conductivity, σdc, above the T
c because of the escalating contribution from the d.c. conduction. The mesomeric structure seems to prompt a dipole-based electric
conduction of high relaxation energy over the strongly associated phenolic protons that may be thermally activated above the
T
c into a much lower relaxation energy protonic conduction of up to two orders higher conductivity. The protonic conduction
emerges at a T
c that falls with a drop in the relaxation energy following a similar order of increasing proton mobility and mesomerism in
the azophenol derivatives: azocatechol>azoquinol>azoresorcinol. On the molecular level, variable temperature infrared spectroscopy
reveals higher proton mobility and mesomerism for the azocatechol derivative that demonstrates its higher protonic conductivity
at lower T
c and relaxation energy, compared to the azoquinol and azoresorcinol derivatives. This is well verified in the light of conflicting
intramolecular H-bonding that assists the proton mobility in azocatechol whereas it associates the protons in azoresorcinol
more than in azoquinol.
Electronic Publication 相似文献