全文获取类型
收费全文 | 555篇 |
免费 | 18篇 |
国内免费 | 1篇 |
专业分类
化学 | 493篇 |
晶体学 | 1篇 |
力学 | 4篇 |
数学 | 47篇 |
物理学 | 29篇 |
出版年
2023年 | 8篇 |
2022年 | 24篇 |
2021年 | 26篇 |
2020年 | 10篇 |
2019年 | 21篇 |
2018年 | 10篇 |
2017年 | 9篇 |
2016年 | 24篇 |
2015年 | 21篇 |
2014年 | 18篇 |
2013年 | 37篇 |
2012年 | 26篇 |
2011年 | 29篇 |
2010年 | 24篇 |
2009年 | 24篇 |
2008年 | 38篇 |
2007年 | 28篇 |
2006年 | 26篇 |
2005年 | 30篇 |
2004年 | 21篇 |
2003年 | 31篇 |
2002年 | 15篇 |
2001年 | 10篇 |
2000年 | 7篇 |
1999年 | 3篇 |
1998年 | 10篇 |
1997年 | 4篇 |
1996年 | 4篇 |
1995年 | 5篇 |
1994年 | 3篇 |
1993年 | 3篇 |
1990年 | 2篇 |
1989年 | 2篇 |
1988年 | 4篇 |
1986年 | 2篇 |
1985年 | 1篇 |
1984年 | 2篇 |
1982年 | 3篇 |
1980年 | 3篇 |
1977年 | 1篇 |
1976年 | 3篇 |
1974年 | 1篇 |
1972年 | 1篇 |
排序方式: 共有574条查询结果,搜索用时 15 毫秒
21.
The complexation equilibria of the hydrogen salicylate ion, HL(-), have been studied, at 25 degrees C, by potentiometric measurements with a glass electrode in 1 M NaClO4 for uranyl and Nd(III) ions and in 3 M NaClO4 for Pb(II) ion. The ligand concentration (CL) was varied between 10(-3) and 0.05 M. In the system with U(VI) the concentrations ranged between: 10(-3) < or = [U(VI)] < or = 0.01 M, 0.5 < or = CL /[U(VI)] < or = 10 and 10(-2) < or = [H+] < or = 10(-5) M; for neodymium system: 2 x 10(-3) < or = [Nd(III)] < or = 0.01, 1 < or = CL /[Nd(III)] < or = 10 and 10(-2) < or = [H+] < or = 10(-7) M; for lead system: 10(-3) < or = [Pb(II) < or = 3 x 10(-3), 1 < or = CL /Pb(II)] < or = 2 and 10(-5) < or = [H+] < or = 10(-7.3) M. The experimental data have been explained with the formation of UO2HL+, UO2L, UO2(OH)L(-), (UO2)2(OH)L2(-) UO2(HL)L(-), NdHL(2+), NdL(+), Nd(OH)L, PbHL(+), PbL and PbL2(2-). Equilibrium constants are given for the investigated ionic media and at infinite dilution. 相似文献
22.
Petar Todorov Emilia Naydenova Rosica Petrova Boris Shivachev Kolio Troev 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(11):o661-o662
The title compound, C6H12NO5P, was synthesized as an intermediate phase in a search for new N‐(phosphonomethyl)glycine derivatives. The molecules are held together by O—H⋯O hydrogen bonds, forming chains along the b axis in the crystal structure. The observed molecular structure is compared with that calculated by the density functional theory method. 相似文献
23.
Maria Bocheska Maria Hoffmann Urszula Lesiska Emilia Luks Wanda Radecka-Paryzek 《Tetrahedron》2005,61(52):12307-12313
New compounds: 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis(3-diisopropoxyphosphorylpropoxy)calix[4]arene (1) and 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis(3-methoxyethoxyphosphorylpropoxy)calix[4]arene (2) were synthesized and their ionophoric properties in ion-selective membrane electrodes were studied in comparison with already described by us 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis(3-diethoxyphophorylpropoxy)calix[4]arene (3). Complexes of 1 with calcium(II), lanthanum(III), europium(III) and gadolinium(III) nitrates were prepared in direct reaction of the ligand and appropriate metal salts. They were characterized by spectral data (IR, UV/Vis, luminescence, NMR, ESI-MS) and elemental analysis. The similarity in complexing behavior of the (dialkoxyphosphoryl)propoxy-calix[4]arenes toward calcium and some lanthanides was observed. 相似文献
24.
Francesco Dallavalle Emilia Fisicaro Roberto Corradini Rosangela Marchelli 《Helvetica chimica acta》1989,72(7):1479-1486
Protonation and Cu(II) complexation equilibria of L -phenyhilaninamide, N2-methyl-L-phenylalaninamide, N2, N2-dimethyl-L-phenylalaninamide, L -valinamide, and L -prolinamide have been studied by potentiometry in aqueous solution. The formation constants of the species observed, CuL2+, CuL, CuLH, CuL2H and CuL2H?2, are discussed in relation to the structures of the ligands. Possible structures of bisamidato complexes are proposed on the ground of VIS and CD spectra. Since Cu(II) complexes of the present ligands (pH range 6–8) perform chiral resolution of dansyl- and unmodified amino acids in HPLC (reversed phase), it is relevant for the investigation of the resolution mechanism to know which are the species potentially involved in the recognition process. 相似文献
25.
26.
Carballo R Casas JS García-Martínez E Pereiras-Gabián G Sánchez A Sordo J Vázquez-López EM 《Inorganic chemistry》2003,42(20):6395-6403
The reactions of methylacetoacetate and ethyl 2-methylacetoacetate thiosemicarbazones (H(2)L(A) and H(2)L(B), respectively) with [ReX(CO)(5)] and [ReX(CO)(3)(CH(3)CN)(2)] (X = Cl, Br) were explored under various experimental conditions. Besides the adducts fac-[ReX(CO)(3)(H(2)L)], in which the rhenium is coordinated to three carbonyl groups, the X anion, and the N,S-bidentate thiosemicarbazone ligand, the following complexes were also isolated: fac-[ReBr(CO)(3)(Hpyz(B))], the tetrameric complexes fac-[Re(pyz(A))(CO)(3)](4) and fac-[Re(pyz(B))(CO)(3)](4), and fac-[Re(pyz(B))(CO)(3)(H(2)O)] (where Hpyz(A) and Hpyz(B) are pyrazolones derived by cyclization of H(2)L(A) and H(2)L(B), respectively). The cyclization reactions were monitored by (1)H NMR spectroscopy and the complexes isolated were identified by elemental analysis, mass spectrometry, IR and (1)H NMR spectroscopy, and in some cases by X-ray diffractometry. The isolation and the full structural identification of the rather unusual fac-[ReBr(CO)(3)(Hpyz(B))], which contains the enol form of the pyrazolone ligand, affords new insight into the cyclization of thiosemicarbazones derived from beta-keto esters. 相似文献
27.
Giorgio Pifferi Luigi Fontanella Emilia Occelli Riccardo Monguzzi 《Journal of heterocyclic chemistry》1972,9(6):1209-1214
o- Aminomethylbeiizyl alcohols (X) easily cyclize with phosgene in an aqueous alkaline medium to form 4,5-dihydro-2,4-benzoxazepin-3(1H)ones (IV) and with aldehydes in acidic conditions to yield 1,3,4,5-tetrahydro-2,4-benzoxazepines (V). The characteristics and chemical behaviour of these new heterocyclic ring systems are reported. 相似文献
28.
Grzegorz Mlostoń Aneta Wróblewska Emilia Obijalska Heinz Heimgartner 《Tetrahedron: Asymmetry》2013,24(15-16):958-965
Starting with (S)-1-benzylprolinamine and α-hydroxyimino ketones, enantiomerically pure bisheterocyclic imidazole N-oxides bearing the (S)-configured N-benzyl(pyrrolidin-2-yl)methyl residue were prepared. These N-oxides reacted with 2,2,4,4-tetramethylcyclobutane-1,3-dithione to give the corresponding optically active imidazole-2-thione derivatives via a sulfur transfer reaction. Reduction of the N-oxides with Raney-nickel led to deoxygenation, whereas catalytic hydrogenation (Pd/C) in ethanol occurred with simultaneous deoxygenation and debenzylation, leading to optically active 1-(pyrrolidin-2-yl)methyl-1H-imidazoles. Alkylation of the prepared imidazole N-oxides and their respective imidazoles with butyl and hexyl bromide and subsequent anion exchange gave optically active N-alkoxy- and N-alkylimidazolium tetrafluoroborates, respectively, with the properties of ‘room temperature ionic liquids’. 相似文献
29.
30.