全文获取类型
收费全文 | 5233篇 |
免费 | 249篇 |
国内免费 | 52篇 |
专业分类
化学 | 3637篇 |
晶体学 | 60篇 |
力学 | 252篇 |
综合类 | 1篇 |
数学 | 605篇 |
物理学 | 979篇 |
出版年
2023年 | 43篇 |
2022年 | 145篇 |
2021年 | 324篇 |
2020年 | 239篇 |
2019年 | 239篇 |
2018年 | 206篇 |
2017年 | 168篇 |
2016年 | 274篇 |
2015年 | 153篇 |
2014年 | 208篇 |
2013年 | 454篇 |
2012年 | 328篇 |
2011年 | 325篇 |
2010年 | 203篇 |
2009年 | 175篇 |
2008年 | 217篇 |
2007年 | 227篇 |
2006年 | 185篇 |
2005年 | 138篇 |
2004年 | 144篇 |
2003年 | 124篇 |
2002年 | 141篇 |
2001年 | 63篇 |
2000年 | 45篇 |
1999年 | 39篇 |
1998年 | 35篇 |
1997年 | 25篇 |
1996年 | 36篇 |
1995年 | 34篇 |
1994年 | 37篇 |
1993年 | 29篇 |
1992年 | 35篇 |
1991年 | 36篇 |
1990年 | 25篇 |
1989年 | 45篇 |
1988年 | 37篇 |
1987年 | 28篇 |
1986年 | 31篇 |
1985年 | 28篇 |
1984年 | 35篇 |
1983年 | 26篇 |
1982年 | 18篇 |
1981年 | 20篇 |
1980年 | 22篇 |
1979年 | 18篇 |
1978年 | 23篇 |
1977年 | 18篇 |
1976年 | 14篇 |
1974年 | 11篇 |
1973年 | 11篇 |
排序方式: 共有5534条查询结果,搜索用时 31 毫秒
121.
3-[1′(1′H)-Substituent-pyrazol-5′-yl]benzo[5,6]coumarins and 3-(1′,2′-oxazol-5′-yl)benzo[5,6]coumarin were prepared via condensation of 3-(2′-formyl-1′-chlorovinyl)benzo[5,6] coumarin with hydrazine derivatives or hydroxylamine.Reaction of 3-[1′(1′H)-pyrazol-5′-yl]benzo[5,6]coumarin with alkyl halides,olefinic compunds or acid chlorides are described. 相似文献
122.
Cycloheptyne-dicobalt hexacarbonyl complexes, substituted by propargylic ether functions, undergo 2 + 2 + 2 cycloaddition reactions with alkynes to give tricyclic benzocycloheptanes; an all-intramolecular version of this transformation is also possible. 相似文献
123.
Mohamed GG Omar MM Hindy AM 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,62(4-5):1140-1150
Metal complexes of Schiff base derived from 2-thiophene carboxaldehyde and 2-aminobenzoic acid (HL) are reported and characterized based on elemental analyses, IR, 1H NMR, solid reflectance, magnetic moment, molar conductance and thermal analysis (TGA). The ligand dissociation as well as the metal-ligand stability constants were calculated pH metrically at 25 degrees C and ionic strength mu=0.1 (1M NaCl). The complexes are found to have the formulae [M(HL)2](X)n.yH2O (where M=Fe(III) (X=Cl, n=3, y=3), Co(II) (X=Cl, n=2, y=1.5), Ni(II) (X=Cl, n=2, y=1) and UO2(II) (X=NO3, n=2, y=0)) and [M(L)2] (where M=Cu(II) (X=Cl) and Zn(II) (X=AcO)). The molar conductance data reveal that Fe(III) and Co(II), Ni(II) and UO2(II) chelates are ionic in nature and are of the type 3:1 and 2:1 electrolytes, respectively, while Cu(II) and Zn(II) complexes are non-electrolytes. IR spectra show that HL is coordinated to the metal ions in a terdentate manner with ONS donor sites of the carboxylate O, azomethine N and thiophene S. From the magnetic and solid reflectance spectra, it is found that the geometrical structure of these complexes are octahedral. The thermal behaviour of these chelates shows that the hydrated complexes losses water molecules of hydration in the first step followed immediately by decomposition of the anions and ligand molecules in the subsequent steps. The activation thermodynamic parameters, such as, E*, DeltaH*, DeltaS* and DeltaG* are calculated from the DrTG curves using Coats-Redfern method. The synthesized ligands, in comparison to their metal complexes also were screened for their antibacterial activity against bacterial species, Escherichia coli, Pseudomonas aeruginosa, Staphylococcus pyogones and Fungi (Candida). The activity data show that the metal complexes to be more potent/antibacterial than the parent Schiff base ligand against one or more bacterial species. 相似文献
124.
A summary of the chemistry of the tetranuclear Au(I) amidinate complexes is presented. Tetranuclear Au(I) amidinate clusters are produced by the reaction of the sodium salt of a amidine ligand with the gold precursor Au(THT)Cl in a (1:1) stoichiometry. The structures of the tetranuclear Au4[ArNC(H)NAr]4, Ar = C6H4‐4‐OMe, C6H3‐3,5‐Cl, C6H4‐4‐Me, C6H4‐3‐CF3, C6F5, C10H7 and the tetranuclear Au4[(PhNC(Ph)NPh]4 and Au4[PhNC(CH3)NPh]4 have been characterized by X‐ray crystallography. The average Au···Au distance between adjacent Au(I) atoms is ?3.0 Å, typical of compounds having an aurophilic interaction. The four gold atoms are located at the corner of a rhomboid with the amidinate ligands bridged above and below the near plane of the four Au(I) atoms. The angles at Au···Au···Au in the cyclic units are between 70° and 116°. The tetranuclear gold(I) amidinate clusters each show different luminescence behavior. The tetranuclear clusters Au4[(ArNC(H)NAr]4, Ar = C6H4‐4‐OMe, Ar = C6H4‐3‐CF3, Ar = C6H4‐4‐Me and Ar = C6H4‐3,5‐Cl are the first tetranuclear gold(I) cluster species from group 11 elements that show fluorescence at room temperature. The tetranuclear naphthyl derivative Ar = C10H7 is luminescent only at 77 K. The pentafluorophenyl derivative Ar = C6F5 does not show any photoluminescence in the solid state nor in the solution. The lifetimes of the naphthyl and trifluoromethylphenyl complexes are in the millisecond range indicating phosphorescent processes. Electrochemical and chemical oxidation studies of the tetranuclear Au(I) amidinate clusters are presented. The tetranuclear complexes Au4[ArNC(H)NAr]4, Ar = C6H4‐4‐OMe, Ar = C6H4‐4‐Me, and Ar = C6H3‐3,5‐Cl, show three reversible waves at 0.75, 0.95, 1.09 V vs. Ag/AgCl at a scan rate of 500 mV/s in 0.1 M Bu4NPF6/CH2Cl2 at a Pt working electrode in CH2Cl2. Three reversible waves at 0.87, 1.19, 1.42 V vs. Ag/AgCl at a scan rate of 100 mV/s are also observed for the tetranuclear complex Au4[PhNC(Ph)NPh]4 in CH2Cl2. The pentafluorophenyl amidinate derivative, Au4[ArNC(H)NAr]4, Ar = C6F5 shows no oxidation wave below 1.8 V. Recently it has been shown that Au4[ArNC(H)NAr]4 is a very effective catalyst precursor for room temperature CO oxidation. 相似文献
125.
El-Hendawy Ahmed M. Alqaradawi Siham Y. Al-Madfa Homaid A. 《Transition Metal Chemistry》2000,25(5):572-578
The new complexes [RuIIIbpyL2](PF6) and [RuIIIbpyLCl2] [bpy = 2,2-bipyridine; HL = acetylacetone, trifluoroacetylacetone, benzoylacetone (Hbac), tropolone or maltol; HL = Hbac or dibenzoylmethane) have been prepared and characterized by spectroscopy. Their redox behaviour was studied by cyclic voltammetry. They effectively catalyze the oxidation of alcohols, alkanes and primary aromatic amines. 相似文献
126.
Mohammed A. Bari Siddiqui Shakeel Ahmed Musaed S. Al-Gharami Chistopher F. Dean 《Reaction Kinetics and Catalysis Letters》2007,91(1):61-67
Sulfur reduction ability of alumina supported zinc, gallium and zinc-gallium additives for fluid catalytic cracking catalysts
was evaluated in a micro-activity test unit (MAT). Gallium/alumina showed the highest sulfur reduction of 31%, but the cracking
activity of the catalyst was decreased. Zinc-gallium/alumina reduced sulfur in 24 wt.% without decreasing the base catalyst
activity. 相似文献
127.
An europium-sensitized time-resolved luminescence (TRL) method was developed to determine oxytetracycline (OTC) in cultivated catfish muscle. Extraction of OTC from fish muscle was performed with pH 4.0 ethylenediaminetetraacetic acid (EDTA)-McIlvaine buffer and clean up with hydrophilic-lipophilic balanced copolymer solid phase extraction (SPE) cartridges. The eluate was used without further concentration for TRL measurement in pH 9.0 micellar tris(hydroxylmethyl)aminomethane (TRIS) buffer. Cetyltrimethylammonium chloride (CTACl) was used as surfactant and EDTA as a co-ligand. The excitation and emission wavelengths were set at 388 and 615 nm, respectively. The linear dynamic range was 0-1000 ng g−1 (R2=0.9995). The recovery was 92-112% in the fortification range of 50-200 ng g−1 and the limits of detection (LOD) ranged from 3 to 7 ng g−1. Incurred catfish samples were used to demonstrate the performance of the method around 100 ng g−1, the European Union maximum residue level. 相似文献
128.
Ahmed H. Osman Amna S. A. Zidan Asma I. El-Said Aref A. M. Aly 《Transition Metal Chemistry》1993,18(1):34-36
Summary Mixed ligand complexes of the type K[Cu(x-HQA)Rxan] [x-HQA = 5-arylazo-8-hydroxyquinoline derivatives; Rxan = methyl or ethylxanthate] have been prepared and characterised by elemental analysis, spectral measurements and conductivity. Upon irradiation, solutions of these complexes photoeliminate dinitrogen and a mechanism for this reaction is proposed. The photosensitivity of the oxine ligand was found to be responsible for the observed photolysis of the complexes. 相似文献
129.
M. Rafi K. Ahmed I. A. Khan M. R. Husain 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1991,18(4):379-382
The ultraviolet spectra of Na2 and K2 molecules have been investigated. These studies were made in absorption in the second order of a 3.4 m Ebert Spectrograph with a reciprocal dispersion of 2.6 Å/mm. A number of new bands in the spectra of both the molecules not previously reported have been observed. Computer methods have been used to calculate the term values and to evaluate molecular constants. 相似文献
130.
Wack H France S Hafez AM Drury WJ Weatherwax A Lectka T 《The Journal of organic chemistry》2004,69(13):4531-4533
We detail the synthesis of a new C(2)-symmetric bis(cyclophane) ligand system that can be thought of as electronically analogous to binol, but which possesses the added "third dimension" of cyclophane chirality. The ligand synthesis involves a spontaneous (but unexpected) atropisomerization to the desired product. We have employed this ligand to form a metal complex that is an effective cocatalyst for the highly enantio- and diastereoselective catalytic asymmetric synthesis of a beta-lactam. 相似文献