全文获取类型
收费全文 | 5072篇 |
免费 | 260篇 |
国内免费 | 12篇 |
专业分类
化学 | 3659篇 |
晶体学 | 28篇 |
力学 | 139篇 |
数学 | 787篇 |
物理学 | 731篇 |
出版年
2023年 | 48篇 |
2022年 | 63篇 |
2021年 | 105篇 |
2020年 | 102篇 |
2019年 | 102篇 |
2018年 | 106篇 |
2017年 | 89篇 |
2016年 | 217篇 |
2015年 | 165篇 |
2014年 | 171篇 |
2013年 | 325篇 |
2012年 | 424篇 |
2011年 | 475篇 |
2010年 | 226篇 |
2009年 | 207篇 |
2008年 | 355篇 |
2007年 | 345篇 |
2006年 | 307篇 |
2005年 | 277篇 |
2004年 | 237篇 |
2003年 | 184篇 |
2002年 | 165篇 |
2001年 | 95篇 |
2000年 | 96篇 |
1999年 | 66篇 |
1998年 | 48篇 |
1997年 | 28篇 |
1996年 | 42篇 |
1995年 | 18篇 |
1994年 | 35篇 |
1993年 | 29篇 |
1992年 | 30篇 |
1991年 | 21篇 |
1990年 | 15篇 |
1989年 | 18篇 |
1988年 | 17篇 |
1987年 | 8篇 |
1986年 | 9篇 |
1985年 | 12篇 |
1984年 | 12篇 |
1983年 | 10篇 |
1982年 | 6篇 |
1981年 | 4篇 |
1980年 | 6篇 |
1979年 | 3篇 |
1978年 | 2篇 |
1977年 | 6篇 |
1976年 | 3篇 |
1975年 | 3篇 |
1973年 | 4篇 |
排序方式: 共有5344条查询结果,搜索用时 15 毫秒
101.
García G Rodríguez JL Lacconi GI Pastor E 《Langmuir : the ACS journal of surfaces and colloids》2004,20(20):8773-8780
In the present paper, a systematic electrochemical investigation on thiourea (TU) electrooxidation was developed on polycrystalline and (111) single-crystal gold electrodes in 0.1 M perchloric acid. The combination of cyclic voltammetry with in situ Fourier transform infrared spectroscopy (FTIRS) and differential electrochemical mass spectrometry techniques have allowed the nature of the species formed during the electroadsorption and electrooxidation of TU to be established. FTIRS experiments were performed in D2O to clean up the region of the H2O bending around 1600 cm(-1). It was concluded that TU adsorbs tilted on the surface in the 0.05-0.40 VRHE potential range. A dual-path reaction mechanism was evidenced in the oxidation process. The first pathway takes place from adsorbed TU at E > 0.40 VRHE and implies the formation of [Au(I)-(TU)2]+, which is oxidized to NH2CN and S0 at E > 0.80 VRHE. In a following oxidation step at E > 1.20 V, N2, CO2, and HSO4-/SO4(2-) were produced. The second parallel reaction occurs from TU in solution at E > 0.50 VRHE to form (TU)2(2+). All these species were characterized from the spectroscopic experiments. Similar results were obtained for both surfaces. 相似文献
102.
Molecular mechanics (MM) calculations have been performed on the title compounds. For the MM minimum energy conformation obtained by conformational analysis, molecular orbital (MO) calculations (MNDO and AM1) have also been performed. The geometries obtained have been compared with the experimental ones extracted from the Cambridge Structural Database (CSD). A qualitative structure-activity relationship has been pointed out based on the electrostatic potentials calculated at different positions on the electronic surface. 相似文献
103.
Díez-Barra E García-Martínez JC del Rey R Rodríguez-López J Giacalone F Segura JL Martín N 《The Journal of organic chemistry》2003,68(8):3178-3183
New chiral, soluble binaphthyl derivatives that incorporate stilbenoid dendrons at the 6,6'-positions have been prepared. The synthesis of the new enantiopure dendrimers was performed in a convergent manner by Horner-Wadsworth-Emmons (HWE) reaction of the appropriately functionalized 1,1'-binaphthyl derivative (R)-1 and the appropriate dendrons (R)(2n)G(n)-CHO. Different electroactive units were incorporated in the peripheral positions of the dendrons in order to tune both the optical and electrochemical behavior of these systems. Fluorescence measurements on the chiral dendrimers reveal a strong emission with maxima between 409 and 508 nm depending upon the substitution pattern. Finally, the redox properties of the dendrimers were determined by cyclic voltammetry, showing the influence of the functional groups at the peripheral positions of the dendrimer on the redox behavior of these systems. 相似文献
104.
D. Zorrilla Cuenca J. Sánchez Márquez M. Fernández Núñez R. Rodríguez Huertas 《International journal of quantum chemistry》2007,107(4):879-893
This project consists of two parts. In the first part, a series of test calculations is performed to verify that the integrals involved in the determination of atomic and molecular properties by standard self‐consistent field (SCF) methods can be obtained through Halton, Korobov, or Hammersley quasi‐random integration procedures. Through these calculations, we confirm that all three methods lead to results that meet the levels of precision required for their use in the calculation of properties of small atoms or molecules at least at a Hartree–Fock level. Moreover, we have ensured that the efficiency of quasi‐random integration methods that we have tested is Halton=Korobov>Hammersley?pseudo‐random. We also find that these results are comparable to those yielded by ordinary Monte Carlo (pseudo‐random) integration, with a calculation effort of two orders of smaller magnitude. The second part, which would not have been possible without the integration method previously analyzed, contains a first study of atoms constrained in spherical boxes through SCF calculations with basis functions adapted to the features of the problem: Slater‐type orbitals (STOs) trimmed by multiplying them by a function that yields 1 for 0 < r < (R‐δ), polynomial values for (R‐δ) < r < R and null for r > R, R being the radius of the box and δ a variationally determined interval. As a result, we obtain a equation of state for electrons of small systems, valid just in the limit of low temperatures, but fairly simple. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献
105.
de Oliveira MC Scarpellini M Neves A Terenzi H Bortoluzzi AJ Szpoganics B Greatti A Mangrich AS de Souza EM Fernandez PM Soares MR 《Inorganic chemistry》2005,44(4):921-929
The crystal structures and redox and UV-vis/EPR spectroscopic properties of two new mononuclear copper(II) complexes, [Cu(HL1)Cl2] (1) and [Cu(L1)Cl] (2), prepared through the reaction between copper(II) chloride and the ligand 2-[(bis(pyridylmethyl)amino)methyl]-4-methyl-6-formylphenol (HL1) under distinct base conditions, are reported along with solution studies. Also, we demonstrate that these CuII complexes are able to cleave unactivated peptide bonds from bovine serum albumin (BSA) and the thermostable enzyme Taq DNA polymerase at micromolar concentration, under mild pH and temperature conditions. The cleavage activity seems to be specific with defined proteolytic fragments appearing after protein treatment. The location of the specific cleavage sites was tentatively assigned to solvent-accessible portions of the protein. These are two of the most active Cu(II) complexes described to date, since their cleavage activity is detected in minutes and evidence is here presented for a hydrolytic mechanism mediating protein cleavage by these complexes. 相似文献
106.
Guillena G Rodríguez G Albrecht M van Koten G 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(23):5368-5376
Arylplatinum(II) complexes have been covalently bonded to the N and C termini and to the alpha-carbon of various amino acid derivatives. These organometallic-functionalized amino acid compounds can be converted into the corresponding free amino acids under both basic and acidic conditions; this demonstrates the excellent stability properties of these biomolecules. Due to the NMR activity displayed by the 195Pt nucleus (natural abundance 33.8%, I = 1/2) these compounds are functional bio-markers. Furthermore, the ability of the arylplatinum functional group to bind SO2 gas, selectively and reversibly as indicated by changes in the spectroscopic properties (1H, 13C, 195Pt NMR and UV spectra) of these compounds, allows for the potential use of these complexes as in vitro biosensors. 相似文献
107.
Carabias-Martínez R Rodríguez-Gonzalo E Revilla-Ruiz P Domínguez-Alvarez J 《Journal of chromatography. A》2003,990(1-2):291-302
Micellar electrokinetic capillary chromatography (MEKC) with diode array detection was used for the separation of 13 compounds (eight herbicides widely used in agriculture: metribuzin, lenacil, ethofumesate, atrazine, terbutryn, isoproturon, chlorotoluron and linuron, and five of their principal degradation products; namely, deethylatrazine, 2-hydroxyatrazine, deethyl-2-hydroxyatrazine, deisopropylatrazine and 3-chloro-4-methylphenylurea). Peak separation for the 13 analytes was not successful when a single surfactant system was employed, neither sodium dodecyl sulfate (SDS) nor dioctyl sulfosuccinate (DOSS) sodium salt. However, a mixture of these herbicides was successfully separated using a mixed micellar system involving SDS–DOSS in less than 14 min. An application study of an on-line concentration technique for MEKC was carried out to enhance sensitivity. The optimized on-line stacking procedure consisted simply of the addition of 50 mM of sodium chloride to the injection sample, the stacking effect being more intensive as analyte polarity increased. When this stacking procedure was combined with an off-line sample preconcentration step, based on solid-phase extraction, analytes could be detected in the ppb range. The whole method was applied to ultra-high-quality and natural waters. Linear relationships between the analytical signal and the initial analyte concentration were found to be independent of the type of water, except for the more polar analytes for which small differences were observed. 相似文献
108.
González-Pérez A. Galán J. J. Rodríguez J. R. 《Journal of Thermal Analysis and Calorimetry》2003,72(2):741-749
The specific conductivities of dodecyldimethylbenzylammonium bromide (C12BBr) have been determined in aqueous butanol and
aqueous benzyl alcohol solutions in the temperature range of 5-40°C. From these data the temperature dependent critical micelle
concentration (cmc) was determined. The molar fraction of alcohol in the micelle was estimated using the theory suggested by Motomura et al. for surfactant binary mixtures. The thermal properties such as standard Gibbs free energy, enthalpy and entropy of solubilization
of alcohols in the micelles were estimated for the phase separation model. The change in heat capacity upon solubilization
of alcohol in the micelle has been estimated form the above properties.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
109.
D. Rodríguez P. Fernández C. Pérez-Conde A. Gutiérrez C. Cámara 《Fresenius' Journal of Analytical Chemistry》1994,349(6):442-446
A rapid and sensitive method has been developed for the determination of lead in water samples by flame atomic absorption spectrometry using on-line preconcentration on a microcolumn packed with silica gel treated with a mixture of Aliquat 336 and nitroso-R-salt. The lead is retained at pH 5.5. The preconcentrated lead is directly eluted from the column to the nebulizer-burner system using 150 L of 0.1 mol/L hydrochloric acid. The optimum preconcentration conditions are given and the retention efficiency achieved is higher than 80%. The enrichment factor is 37 and 100 for sample volumes of 5 and 30 mL, respectively. The limits of detection are 10.0, 6.0 and 4.0 ng/mL when 5, 10 and 30 mL of water is preconcentrated. 相似文献
110.
Vicente J González-Herrero P Pérez-Cadenas M Jones PG Bautista D 《Inorganic chemistry》2005,44(20):7200-7213
Platinum(II) complexes with (fluoren-9-ylidene)methanedithiolato and its 2,7-di-tert-butyl- and 2,7-dimethoxy-substituted analogues were obtained by reacting different chloroplatinum(II) precursors with the piperidinium dithioates (pipH)[(2,7-R2C12H6)CHCS2] [R = H (1a), t-Bu (1b), or OMe (1c)] in the presence of piperidine. The anionic complexes Q2[Pt{S(2)C=C(C12H6R(2)-2,7)}2] [R = H, (Pr(4)N)(2)2a; R = t-Bu, (Pr4N)(2)2b, (Et4N)(2)2b; R = OMe, (Pr4N)(2)2c] were prepared from PtCl(2), piperidine, the corresponding QCl salt, and 1a-c in molar ratio 1:2:2:2. In the absence of QCl, the complexes (pipH)(2)2b and [Pt(pip)(4)]2b were isolated depending on the PtCl(2):pip molar ratio. The neutral complexes [Pt{S2C=C(C12H6R(2)-2,7)L(2)] [L = PPh(3), R = H (3a), t-Bu (3b), OMe (3c); L = PEt(3), R = H (4a), t-Bu (4b), OMe (4c); L(2) = dbbpy, R = H (5a), t-Bu (5b), OMe (5c) (dbbpy = 4,4'-di-tert-butyl-2,2'-bipyridyl)] were similarly prepared from the corresponding precursors [PtCl2L2] and 1a-c in the presence of piperidine. Oxidation of Q(2)2b with [FeCp2]PF6 afforded the mixed Pt(II)-Pt(IV) complex Q2[Pt2{S2C=C[C12H6(t-Bu)(2)-2,7]}4] (Q(2)6, Q = Et4N+, Pr4N+). The protonation of (Pr4N)(2)2b with 2 equiv of triflic acid gave the neutral dithioato complex [Pt2{S2CCH[C12H6(t-Bu)(2)-2,7]}4] (7). The same reaction in 1:1 molar ratio gave the mixed dithiolato/dithioato complex Pr4N[Pt{S2C=C[C12H6(t-Bu)(2)-2,7]}{S2CCH[C12H6(t-Bu)(2)-2,7]}] (Pr(4)N8) while the corresponding DMANH+ salt was obtained by treating 7 with 2 equiv of 1,8-bis(dimethylamino)naphthalene (DMAN). The crystal structures of 3b and 5c.CH2Cl2 have been solved by X-ray crystallography. All the platinum complexes are photoluminescent at 77 K in CH2Cl2 or KBr matrix, except for Q(2)6. Compounds 5a-c and Q8 show room-temperature luminescence in fluid solution. The electronic absorption and emission spectra of the dithiolato complexes reveal charge-transfer absorption and emission energies which are significantly lower than those of analogous platinum complexes with previously described 1,1-ethylenedithiolato ligands and in most cases compare well to those of 1,2-dithiolene complexes. 相似文献