全文获取类型
收费全文 | 14972篇 |
免费 | 672篇 |
国内免费 | 62篇 |
专业分类
化学 | 10705篇 |
晶体学 | 107篇 |
力学 | 353篇 |
数学 | 2192篇 |
物理学 | 2349篇 |
出版年
2023年 | 106篇 |
2022年 | 212篇 |
2021年 | 312篇 |
2020年 | 293篇 |
2019年 | 305篇 |
2018年 | 274篇 |
2017年 | 246篇 |
2016年 | 601篇 |
2015年 | 460篇 |
2014年 | 528篇 |
2013年 | 917篇 |
2012年 | 1069篇 |
2011年 | 1164篇 |
2010年 | 662篇 |
2009年 | 575篇 |
2008年 | 1020篇 |
2007年 | 985篇 |
2006年 | 843篇 |
2005年 | 822篇 |
2004年 | 639篇 |
2003年 | 530篇 |
2002年 | 495篇 |
2001年 | 289篇 |
2000年 | 257篇 |
1999年 | 190篇 |
1998年 | 140篇 |
1997年 | 144篇 |
1996年 | 182篇 |
1995年 | 133篇 |
1994年 | 117篇 |
1993年 | 137篇 |
1992年 | 98篇 |
1991年 | 95篇 |
1990年 | 64篇 |
1989年 | 63篇 |
1988年 | 51篇 |
1987年 | 49篇 |
1986年 | 52篇 |
1985年 | 99篇 |
1984年 | 91篇 |
1983年 | 55篇 |
1982年 | 66篇 |
1981年 | 43篇 |
1980年 | 29篇 |
1979年 | 13篇 |
1978年 | 33篇 |
1977年 | 28篇 |
1976年 | 20篇 |
1975年 | 18篇 |
1974年 | 20篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
111.
Kar S Chanda N Mobin SM Urbanos FA Niemeyer M Puranik VG Jimenez-Aparicio R Lahiri GK 《Inorganic chemistry》2005,44(5):1571-1579
The reaction of cis-Ru(acac)2(CH3CN)2 (acac = acetylacetonate) with 2,2'-dipyridylamine (L) in ethanolic medium resulted in facile one-pot synthesis of stable [(acac)2RuIII(L)]ClO4 ([1]ClO4), trans-[(acac)2RuII(L)2] (2), trans-[(acac)2RuIII)L)2]ClO4 ([2]ClO4), and cis-[(acac)2RuII(L)2] (3). The bivalent congener 1 was generated via electrochemical reduction of [1]ClO4. Although in [1]+ the dipyridylamine ligand (L) is bonded to the metal ion in usual bidentate fashion, in 2/[2]+ and 3, the unusual monodentate binding mode of L has been preferentially stabilized. Moreover, in 2/[2]+ and 3, two such monodentate L's have been oriented in the trans- and cis-configurations, respectively. The binding mode of L and the isomeric geometries of the complexes were established by their single-crystal X-ray structures. The redox stability of the Ru(II) state follows the order 1 < 2 < 3. In contrast to the magnetic moment obtained for [1]ClO4, mu = 1.84 muB at 298 K, typical for low-spin Ru(III) species, the compound [2]ClO4 exhibited an anomalous magnetic moment of 2.71 muB at 300 K in the solid state. The variable-temperature magnetic measurements showed a pronounced decrease of the magnetic moment with the temperature, and that dropped to 1.59 muB at 3 K. The experimental data can be fitted satisfactorily using eq 2 that considered nonquenched spin-orbit coupling and Weiss constant in addition to the temperature-independent paramagnetism. [1]ClO4 and [2]ClO4 displayed rhombic and axial EPR spectra, respectively, in both the solid and the solution states at 77 K. 相似文献
112.
A systematic study of the bulk and surface geometrical and electronic properties of a series of transition-metal carbides (TMC with TM = Ti, V, Zr, Nb, Mo, Hf, Ta, and W) by first-principles methods is presented. It is shown that in these materials the chemical bonding is strongly covalent, the cohesive energies being directly related to the bonding-antibonding gap although the shift of the center of the C(2s) band related peak in the density of states with respect to diamond indicates that some metal to carbon charge transfer does also take place. The (001) face of these metal carbides exhibits a noticeable surface rumpling which grows along the series. It is shown that neglecting surface relaxation results in very large errors on the surface energy and work function. The surface formation induces a significant shift of electronic energy levels with respect to the corresponding values in the bulk. The extent and nature of the shift can be understood from simple bonding-antibonding arguments and is enhanced by the structural rippling of this surface. 相似文献
113.
Burguera JL Quintana IA Salager JL Burguera M Rondón C Carrero P Anton de Salager R Petit de Peña Y 《The Analyst》1999,124(4):593-599
An on-line time based injection system used in conjunction with cold vapor generation atomic absorption spectrometry and microwave-aided oxidation with potassium persulfate has been developed for the determination of the different mercury species in fish-eggs oil samples. A three-phase surfactant-oil-water emulsion produced an advantageous flow when a peristaltic pump was used to introduce the highly viscous sample into the system. The optimum proportion of the oil-water mixture ratio was 2:3 v/v with a Tween 20 surfactant concentration in the emulsion of 0.008% v/v. Inorganic mercury was determined after reduction with sodium borohydride while total mercury was determined after an oxidation step with persulfate prior to the reduction step to elemental mercury with the same reducing agent. The difference between total and inorganic mercury determined the organomercury content in samples. A linear calibration graph was obtained in the range 0.1-20 micrograms l-1 of Hg2+ by injecting 0.7 ml of samples. The detection limits based on 3 sigma of the blank signals were 0.11 and 0.12 microgram l-1 for total and inorganic mercury, respectively. The relative standard deviation of ten independent measurements were 2.8 and 2.2% for 10 micrograms l-1 and 8.8 and 9.0% for 0.1 microgram l-1 amounts of total and inorganic mercury, respectively. The recoveries of 0.3, 0.6 and 8 micrograms l-1 of inorganic and organic mercury added to fish-eggs oil samples ranged from 93.0 to 94.8% and from 100 to 106%, respectively. Good agreement with those values obtained for total mercury content in real samples by electrothermal atomic absorption spectrometry was also obtained, differences between mean values were < 7%. With the proposed procedure, 22 proteropterous catfish-eggs oil samples from the northwestern coast of Venezuela were measured; while the organic mercury lay in the range 2.0 and 3.3 micrograms l-1, inorganic mercury was not detected. 相似文献
114.
del Mar Graciani M Rodríguez A Muñoz M Moyá ML 《Langmuir : the ACS journal of surfaces and colloids》2005,21(16):7161-7169
Micellization in water-ethylene glycol (EG) N-dodecyl, N-tetradecyl, and N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (SB3-12, SB3-14, and SB3-16, respectively) micellar solutions, with the weight percent of EG changing within the range 0-40, was studied by means of surface tension measurements. Information about the influence of the added EG on the aggregation number of the sulfobetaine micelles and on the polarity of the interfacial region of micelles was obtained through fluorescence and spectroscopic measurements. Surface tension measurements also provide information about the dependence of the surface excess concentration, the minimum area per surfactant molecule, the surface pressure at the cmc, and the standard Gibbs energy of adsorption on the added weight percent of the organic solvent. The Gordon parameter of the water-EG mixtures was also estimated by means of surface tension measurements. The thermodynamic and structural changes originated by the presence of EG control the micellar kinetic effects observed in the reaction methyl 4-nitrobenzenesulfonate + Br(-) occurring in the water-EG sulfobetaine micellar solutions. Information about the distribution of bromide ions between the bulk and micellar pseudophases was obtained through conductivity measurements. The kinetic micellar effects were quantitatively explained by using the pseudophase kinetic model. 相似文献
115.
Reinoso S Vitoria P Gutiérrez-Zorrilla JM Lezama L San Felices L Beitia JI 《Inorganic chemistry》2005,44(26):9731-9742
Reaction of in situ generated copper(II)-monosubstituted Keggin polyoxometalates and copper(II)-bipyridine-oxalate complexes in the corresponding alkaline acetate buffer led to the formation of hybrid metal organic-inorganic compounds K(2)[{SiW(11)O(39)Cu(H(2)O)}{Cu(2)(bpy)(2)(H(2)O)(2)(mu-ox)}(2)].14H(2)O (1), K(14)[{SiW(11)O(39)Cu(H(2)O)}{Cu(2)(bpy)(2)(mu-ox)}](2)[SiW(11)O(39)Cu(H(2)O)].55H(2)O (2), (NH(4))(4)[{SiW(11)O(39)Cu(H(2)O)}{Cu(2)(bpy)(2)(mu-ox)}].10H(2)O (3), and Rb(4)[{SiW(11)O(39)Cu(H(2)O)}{Cu(2)(bpy)(2)(mu-ox)}].10H(2)O (4). Their structures have been established by single-crystal X-ray diffraction. The main structural feature of these compounds is the presence of copper(II)-monosubstituted alpha-Keggin polyoxoanions as inorganic building blocks, on which the mu-oxalatodicopper metalorganic blocks are supported. Compound 1contains the discrete hybrid polyanion [{SiW(11)O(39)Cu(H(2)O)}{Cu(2)(bpy)(2)(H(2)O)(2)(mu-ox)}(2)](2)(-), whereas the polymeric hybrid polyanion [{SiW(11)O(39)Cu(H(2)O)}{Cu(2)(bpy)(2)(mu-ox)}(2)](n)(4)(n)(-) gives a monodimensional character to compounds 2-4. Magnetic and EPR results are discussed with respect to the crystal structure of the compounds. DFT calculations on both the [Cu(2)(bpy)(2)(H(2)O)(4)(mu-ox)](2+) cationic complex and the metalorganic blocks have been performed in order to determine the optimized geometry and the magnetic coupling constants, respectively. 相似文献
116.
Gregorio Snchez Francisco Ruiz Joaquín Garcia M. Ramírez Carmen de Arellano Gregorio Lpez 《Helvetica chimica acta》1997,80(8):2477-2485
The hydroxo complex (Bu4N)2[Ni2(C6F5)4(μ-OH)2]reacts with 2,3,4,5,6-pentafluoro benzenamine (C6F5-NH2), 1,3-diaryltriaz-1-enes (ArNH? N=N? Ar, Ar = Ph, 4-MeC6H4, 4-MeOC6H4), 7-aza-1H-indole (= 1H-pyrrolo[2.3-b]pyridine; Hazind), N-phenylpyridin-2-amine(pyNHPh), and N-phenylpyridine-2-carboxamide (py-CONHPh) at room temperature in acetone to give the binuclear complexes (Bu4N)2[Ni2(C6F5)4(μ-C6F5NH)2] ( 1 ) and (Bu4N)2[{Ni(C6F5)2} 2(μ-OH)(μ-azind)] ( 2 ) and the mononuclear complexes Bu4N[Ni(C6F5)2(ArN3Ar)] ( 3 – 5 ), Bu4N[Ni(C6F5)2(pyNPh)] ( 6 ), and Bu4N[Ni(C6F5)2(pyCONPh)] ( 7 ). The hydroxo.complex (Bu4N)2[{Ni(C6F5)2-(μ-OH)}2] promotes the nucleophilic addition of water to pyridine-2-carbonitrile, 2-aminoacetonitrile, and 2-(dimethylamino)acetonitrile, and complexes 8 – 10 containing pyridine-2-carboxamidato, 2-aminoacetamidato and 2-(dimethylamino)acetamidato ligands are formed. Analytical (C, H, N) and spectroscopic (IR, 1H and 19F-NMR, and FAB-MS) data were used for structural assignments. A single-crystal X-ray diffraction study of (Bu4N)2[{Ni(C6F5)2}2(μ-OH)(μ-azind)] ( 2 ) established the binuclear nature of the anion; the two Ni-atoms are bridged by an OH group and a 7-aza-7H-indol-7-yl group, but the central Ni? O? Ni? N? C? N ring is not planar, the dihedral angle between the Ni? O? Ni and Ni? N? C? N? Ni planes being 84.4°. 相似文献
117.
M. Angel Mateos Rocío Gálvez F. Javier Manuel de Villena José M. Pingarrón 《Mikrochimica acta》1995,120(1-4):339-349
An electroanalytical study of the herbicide propazine's reduction process in micellar solutions and oil-in-water emulsions is reported. The anionic surfactant sodium pentanesulphonate was chosen as the most suitable. The differential pulse polarograms of micellar solutions had two reduction peaks below pH 2.0, whereas only one peak was obtained above pH 2.O. Ethyl acetate was chosen as the organic solvent to form propazine emulsions. Unlike in micellar solutions, the DPP polarograms of propazine emulsions showed only one peak even at pH < 2.0, suggesting that propazine hydrolysis was hindered in the emulsified medium. The limiting current is diffusion-controlled and the electrode process is irreversible. Propazine can be determined by differential pulse polarography over the 1.0 × 10–1 – 1.0 × 10–1moll–1 and 1.0 × 10–15 – 4.0 × 10–1 moll–1 concentration ranges and the limit of detection was 2.8 × 10–1 moll–1. Of the potential interferents simazine, methoprotryne and terbutryn (alls-triazines), thiram (a dithiocarbamate), dinoseb (nitrophenolic), and heptachlor (chlorinated cyclo-diene herbicide), only the first two were significant (10% error for equimolar concentrations). The method was applied to the determination of propazine in spiked drinking water. At a concentration level of 2.0 × 10–1 moll–1 a recovery of 94 ± 6% was obtained, after tenfold concentration on Sep-Pak. 相似文献
118.
119.
A simple spectrofluorimetric method for the determination of the fungicide benomyl in grapes is described. Benomyl is rapidly solvolysed in organic solvents to give the highly fluorescent metabolite carbendazim. Solvent effects on the spectral shape and their influence on analytical performance are studied. DMF was found to be the best solvent. The method is sensitive to 12 ng/ml benomyl, and has an RSD at the 0.5 g/ml level of 2.2%. The method is suitable for determining benomyl in spiked grapes, with recoveries in the range 97 to 104%. 相似文献
120.
Elías Molins Amílcar Labarta Javier Tejada Amparo Caubet Santiago Alvarez 《Transition Metal Chemistry》1983,8(6):377-380
Summary Magnetic moments and57Fe Mössbauer spectra at room temperature and at liquid nitrogen temperature of polynuclear ligand-bridged iron phthalocyanines, FePcL (L = pyrazine and 4,4-bipyridyl), are reported. The experimental data are in agreement with a pseudo-octahedral environment around the iron(II) cation. Partially oxidized derivatives, FePc(pz)I0.26 and FePc(bipy)I1.06 have been synthesized and their57Fe Mössbauer spectra and magnetic moments within the same temperature range obtained. Oxidation is shown to be metal centred and the iodine is found to be in I– form for FePc(pz)0.26 and as both I– and I
3
–
species for FePc(bipy)I1.06. While the magnetic moment of FePc(pz) increases upon oxidation, the opposite occurs for FePc(bipy). 相似文献