全文获取类型
收费全文 | 1020篇 |
免费 | 159篇 |
国内免费 | 531篇 |
专业分类
化学 | 1107篇 |
晶体学 | 23篇 |
力学 | 23篇 |
综合类 | 19篇 |
数学 | 230篇 |
物理学 | 308篇 |
出版年
2023年 | 2篇 |
2022年 | 35篇 |
2021年 | 33篇 |
2020年 | 32篇 |
2019年 | 8篇 |
2018年 | 25篇 |
2017年 | 55篇 |
2016年 | 49篇 |
2015年 | 76篇 |
2014年 | 101篇 |
2013年 | 119篇 |
2012年 | 186篇 |
2011年 | 159篇 |
2010年 | 91篇 |
2009年 | 78篇 |
2008年 | 93篇 |
2007年 | 114篇 |
2006年 | 36篇 |
2005年 | 70篇 |
2004年 | 74篇 |
2003年 | 46篇 |
2002年 | 34篇 |
2001年 | 18篇 |
2000年 | 28篇 |
1999年 | 18篇 |
1998年 | 25篇 |
1997年 | 20篇 |
1996年 | 23篇 |
1995年 | 4篇 |
1994年 | 9篇 |
1993年 | 8篇 |
1992年 | 4篇 |
1991年 | 7篇 |
1990年 | 6篇 |
1989年 | 8篇 |
1988年 | 5篇 |
1987年 | 2篇 |
1986年 | 3篇 |
1985年 | 3篇 |
1984年 | 2篇 |
1983年 | 1篇 |
排序方式: 共有1710条查询结果,搜索用时 609 毫秒
11.
12.
在H6TeO6/KOH水溶液中以臭氧为氧化剂,将二价铜化合物氧化成三价铜化合物,并获得一个新的三价铜化合物Ba4K[Cu(H2TeO6)2](OH)4.6H2O;描述了碱性溶液中“Cu(Ⅲ)/Cu(Ⅲ)”循环伏安图。对铜(Ⅲ)化合物,Na4H[H2TeO6)2].17H2O以及相应的铜(Ⅱ)配合物的电子光谱和Cu2pXPS进行了研究,给出了其配位场场强参数和Cu2PXPX的电子结合能。由于价态升高 相似文献
13.
呋喃甲醛缩二乙撑三胺希夫碱铜配合物的合成及结构(英) 总被引:1,自引:0,他引:1
A novel copper(Ⅱ) complex CuL(NO3)2(where L=N,N′-bis(furaldehyde)-diethylenetriamine) was synthesized and characterized by X-ray crystallography analysis. The crystal belongs to monoclinic, space group C2/c with cell parameters a=1.924 0(6) nm, b=0.792 8(3) nm, c=2.504 1(8) nm, β=111.163(5)°, and Z=8. The coordination geometry around Cu(Ⅱ) is a distorted trigonal-bipyramid,and one-dimensional chain is formed through intermolecular hydrogen bonds. CCDC: 255629. 相似文献
14.
A copper(Ⅱ) complex 1 of a novel macrocyclic polyamine ligand with hydroxylethyl pendant groups, 4,11-bis(hydroxylethyl)-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane (L) has been synthesized and characterized. Rate enhancement for hydrolysis of p-nitrophenyl picolinate (PNPP) catalyzed by 1 was studied kinetically under Brij35 micellar condition. For comparision, the catalytic activity of corresponding copper(Ⅱ) complex 2 of non-substituted macrocyclic polyamine ligand, 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraaza-cyclotetradecane (L') toward the hydrolysis of PNPP was also investigated. The results indicate that the macrocyclic polyamine copper(Ⅱ) complex 1 effectively catalyzed the hydrolysis of PNPP, and the pendant ligand hydroxyl group or deprotonated pendant ligand hydroxyl group can act as catalytically active species in the reaction. A ternary Complex kinetic model involving metal ion, ligand and substrate has been proposed, and the results confirmed the reasonability of such kinetic model. 相似文献
15.
N-亚水杨基苄胺过渡金属配合物的合成、结构与抑菌性能研究(英) 总被引:7,自引:0,他引:7
N-salicylidene-benzylamineato M(Ⅱ) complexes (ZnL2, CuL2 and CdL2) were synthesized, characterized and valued for antimicrobial activities against bacterial strands using the agar diffusion method. The crystal of ZnL2 was determined by X-ray diffraction. It crystallizes in the Monoclinic system, space group C2/c with a=2.269 1(3), b=0.918 2(1), c=1.239 5(2) nm, β=117.89(2), Z=4, R1=0.049 4, wR2=0.138 2. The complexes were found to be active against Staphylococcus aureus and Eschierichia Coli. CCDC: 249474. 相似文献
16.
The title compound, [Mn4O2(O2CMe)6(MeOH)2(dbm)2]·2MeCOOH·2CH2Cl2 (Hdbm = dibenzoylmethane), has been synthesized and structurally determined by single-crystal X-ray diffraction. The crystal belongs to triclinic, space group P(-l), with a = 10.729(3), b = 12.269(3), c =13.085(4) (A), a = 106.367(3), β = 107.643(2), γ = 94.771(2)°, V = 1547.9(7) (A)3, Z = 1,C50H64Cl4Mn4O24, Mr= 1410.57, Dc= 1.513 g/em3, F(000) = 724, Rint = 0.0147, T = 293(2) K and μ = 1.046 mm-1. The fimal R = 0.0359 and wR = 0.0938 for 5791 observed reflections with I > 2( )I).The structure of the complex consists of one [Mn4(μ3-O)2]8+ core with four coplanar Mn atoms disposed in an extended "butterfly-like" arrangement and two O atoms triply bridging each "wing",and the peripheral ligation is provided by six μ2-MeCO2-, two terminalμ2-dbm- groups at the two hydrogen bonding interactions are found within the structure of the compound. 相似文献
17.
One novel complex [Co(p-MBA)2(2,2'-bipy)(H2O)]·(H2O) has been synthesized by the reaction of p-methylbenzoic acid with 2,2'-bipyridine in the solvent mixture of water and methanol. It crystallizes in triclinic, space group P-1 with a=0.70479(14), b=1.1211(2), c=1.6718(3) nm, α=103.806(3), β=90.795(3), γ=104.207(3)°, V=1.2399(4) nm3, Mr=512.41, Dc=1.373 g/cm3, Z=2, F(000)=532, μ=0.733 mm-1, R=0.0432 and wR=0.0957. The crystal structural analysis shows that the cobalt atom is coordinated with three oxygen atoms from two p-methylbenzoic acids and one water molecule and two nitrogen atoms from one 2,2'-bipyridine,forming a distorted square-pyramidal coordination geometry. The cyclic voltammetry behavior of the complex is also reported. 相似文献
18.
A polynuclear complex [Cd(endc)(H2O)]n·nH2O (endc = endo-norbomene-cis5,6-dicarboxylate anion) has been synthesized by the hydrothermal reaction of cadmium nitrate tetrahydrate with endo-norbomene-cis-5,6-dicarboxylic acid in 1:1 molar ratio,and structurally characterized by single-crystal X-ray diffraction.It crystallizes in monoclinic,space group P21/c with a = 1.16471(7),b = 0.95334(7),c = 0.91109(9) nm,Z = 4,V= 1.01035(14)nm3,Dc.= 2.160 g/cm3,μ= 2.172 mm-1,F(000) = 648,R =0.0302 and wR = 0.0752.According to structural analysis,each Cd(Ⅱ) ion is coordinated to six O atoms from three endc anions and one water molecule,giving a distorted octahedral geometry.Two- dimensional layer arrangement of the title complex is constructed from the bridging nature of endc.It is worth notice that adjacent two-dimensional layers are joined together to form a three-dimensional supramolecular framework via intermolecular hydrogen bonding interactions. 相似文献
19.
A novel complex [Pb(qina)2(DMSO)]·H2O was synthesized, of which qina- is the quinaldic acid radical and DMSO the dimethyl sulfoxide. Elemental analysis, IR spectra, and X-ray single-crystal diffraction were carried out to determine the composition and crystal structure. This complex belongs to monoclinic system, space group P121/n1, with a = 7.1553(17), b = 17.543(2), c = 17.306(2)(A),β = 91.671(4)°, C22H20N2O6PbS, Mr = 647.65, Z = 4, V= 2171.5(6)(A)3, Dc= 1.981g/cm3,μ = 7.908 mm-1, F(000) = 1248, -9≤h≤6, -23≤k≤ 19, -22≤l≤22, R= 0.0221 and wR =0.0488. Weak coordinate bond is formed between oxygen atom in DMSO and Pb(Ⅱ ). There are also weak interactions, such as π-π interaction, hydrogen bonds and so on, among the complex molecules. 相似文献
20.
A novel coordination polymer [{Cd(hmbdc)(H2O)3}·2H2O]n (hmbdc=5-hydroxy- isophthalic acid) has been synthesized and characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P21/c, with a=9.599(3), b=18.699(5), c=7.557(2) (A), β= 108.198(4)°, V=1288.6(6) (A)3, Z=4, Mr=382.60, Dc=1.972 g/cm3, F(000)=760, μ=1.740, the final R=0.0555 and wR=0.0995 for 1732 observed reflections with Ⅰ > 2σ(Ⅰ). The structural analysis shows that the intermolecular hydrogen bonds and π-π interactions result in a three-dimensional supramolecular framework. 相似文献