全文获取类型
收费全文 | 3471篇 |
免费 | 111篇 |
国内免费 | 24篇 |
专业分类
化学 | 2174篇 |
晶体学 | 13篇 |
力学 | 91篇 |
数学 | 774篇 |
物理学 | 554篇 |
出版年
2023年 | 35篇 |
2022年 | 80篇 |
2021年 | 91篇 |
2020年 | 63篇 |
2019年 | 85篇 |
2018年 | 64篇 |
2017年 | 67篇 |
2016年 | 139篇 |
2015年 | 105篇 |
2014年 | 121篇 |
2013年 | 199篇 |
2012年 | 250篇 |
2011年 | 286篇 |
2010年 | 158篇 |
2009年 | 173篇 |
2008年 | 232篇 |
2007年 | 222篇 |
2006年 | 201篇 |
2005年 | 162篇 |
2004年 | 159篇 |
2003年 | 100篇 |
2002年 | 95篇 |
2001年 | 40篇 |
2000年 | 42篇 |
1999年 | 29篇 |
1998年 | 27篇 |
1997年 | 24篇 |
1996年 | 32篇 |
1995年 | 15篇 |
1994年 | 19篇 |
1993年 | 16篇 |
1992年 | 27篇 |
1991年 | 14篇 |
1990年 | 28篇 |
1989年 | 13篇 |
1988年 | 12篇 |
1987年 | 11篇 |
1986年 | 16篇 |
1985年 | 21篇 |
1984年 | 23篇 |
1983年 | 10篇 |
1982年 | 7篇 |
1981年 | 14篇 |
1980年 | 8篇 |
1979年 | 9篇 |
1978年 | 6篇 |
1974年 | 8篇 |
1973年 | 5篇 |
1971年 | 6篇 |
1963年 | 5篇 |
排序方式: 共有3606条查询结果,搜索用时 15 毫秒
191.
192.
Vicente M Bastida R Lodeiro C Macías A Parola AJ Valencia L Spey SE 《Inorganic chemistry》2003,42(21):6768-6779
The synthesis of a new oxaaza macrocyclic ligand, L, derived from O(1),O(7)-bis(2-formylphenyl)-1,4,7-trioxaheptane and tren containing an amine terminal pendant arm, and its metal complexation with alkaline earth (M = Ca(2+), Sr(2+), Ba(2+)), transition (M = Co(2+), Ni(2+), Cu(2+), Zn(2+), Cd(2+)), post-transition (M = Pb(2+)), and Y(3+) and lanthanide (M = La(3+), Er(3+)) metal ions are reported. Crystal structures of [H(2)L](ClO(4))(2).3H(2)O, [PbL](ClO(4))(2), and [ZnLCl](ClO(4)).H(2)O are also reported. In the [PbL] complex, the metal ion is located inside the macrocyclic cavity coordinated by all N(4)O(3) donor atoms while, in the [ZnLCl] complex, the metal ion is encapsulated only by the nitrogen atoms present in the ligand. pi-pi interactions in the [H(2)L](ClO(4))(2).3H(2)O and [PbL](ClO(4))(2) structures are observed. Protonation and Zn(2+), Cd(2+), and Cu(2+) complexation were studied by means of potentiometric, UV-vis, and fluorescent emission measurements. The 10-fold fluorescence emission increase observed in the pH range 7-9 in the presence of Zn(2+) leads to L as a good sensor for this biological metal in water solution. 相似文献
193.
A simple differential titrator for automatic potentiometric titration at zero current, with two identical indicator electrodes, is described. The autoburette is a normal microburette connected to one tube of a peristaltic pump, and the differentiating system is a closed-flow circuit in a second tube of the pump, this tube containing two electrodes 5 cm apart. The apparatus has been applied to the determination of halides and sulphide-disulphide mixtures, with electrodes coated with an appropriate silver salt. 相似文献
194.
Jorge Rosales 《Fresenius' Journal of Analytical Chemistry》1972,260(5):361-363
Tertiäre Amine und Salze organischer Säuren werden in Acetanhydrid mit 5% Essigsäure durch anodische Proton-Erzeugung auf Platin in Gegenwart von Hydrochinon mit Hilfe der biamperometrischen Endpunkttechnik mit einem Wismutelektrodenpaar quantitativ bestimmt. Mengen von 0,5–0,9 mg wurden mit einer mittleren Abweichung von <1% analysiert. Die Ergebnisse stimmten zufriedenstellend mit denen aus thermometrischen und photometrischen Titrationen überein.Summary Tertiary amines and salts of organic acids have been quantitatively determined in acetic anhydride with 5% of acetic acid by means of anodic generation of protons on platinum in the presence of hydroquinone, applying a biamperometric end-point detection using an indicating system of bismuth electrodes. Amounts of 0.5–0.9 mg have been analysed with average deviations of <1%. Good agreement was obtained with the results of thermometric and photometric titrations.
Coulometrische Bestimmung von schwachen Basen unter Anwendung eines Wismut-Elektrodenpaars als Indicatorsystem相似文献
195.
196.
Maria J. Ortiz Antonia R. Agarrabeitia Gonzalo Duran-Sampedro Jorge Bañuelos Prieto Teresa Arbeloa Lopez Walter A. Massad Hernán A. Montejano Norman A. García Iñigo Lopez Arbeloa 《Tetrahedron》2012,68(4):1153-1162
A theoretical and experimental study on the iodination of BODIPY dyes with different degrees of substitution has been developed. Polyhalogenated BODIPYs synthesized in this work are the first examples of this type of dyes with more than two halogen atoms in the BODIPY core and they can be selectively functionalized. Surprisingly, the position in which halogen is attached has a marked effect in the photophysical properties and modulates the fluorescence capacity of the resulting BODIPY. These iodinated BODIPYs are efficient singlet oxygen generators. 相似文献
197.
Gerardo Cáceres Montenegro Carolina G. Gutierrez Santiago E. Vaillard Roque J. Minari Jorge R. Vega Luis M. Gugliotta 《大分子反应工程》2017,11(3)
The synthesis of poly(acrylic acid) (PAA) of low molar mass under safe conditions is difficult due to the high polymerization rate of acrylic acid (AA) and the fast heat generation. The aqueous‐solution “semibatch” polymerization of non‐ionized AA in almost starved conditions involves high initiator loads when low molar masses are required. This article proposes the simultaneous feeding of AA and nonconventional chain transfer agents (CTA) as a strategy aimed at controlling both the molar masses and the generated heat rate. Three CTAs are investigated: 2‐mercaptoethanol, thioglycolic acid, and isopropyl alcohol. Even when PAA of relatively low molar mass can be produced by adequately selecting the flow rates and concentrations of both AA and CTA, it is found that the nature of CTA can have a significant effect on the polymerizations kinetics. The mechanisms responsible for these effects are discussed with the help of a representative mathematical model.
198.
The solvothermal reaction of (N(C(4)H(9))(4))(2)[Re(2)Cl(8)] with trifluoroacetic acid and acetic anhydride leads to the new rhenium trifluoroacetate dimer N(C(4)H(9))(4)[Re(2)(OOCCF(3))Cl(6)] (1) and to the rhenium carbonyl dimer Re(2)(mu(2)-Cl)(2)(CO)(8) as the rhenium-reduced byproduct. The reaction of the precursor complex, N(C(4)H(9))(4)[Re(2)(OOCCF(3))Cl(6)] (1), with the organometallic carboxylic acid (CO)(6)Co(2)HCCCOOH leads to the cluster of clusters compound Re(2)(OOCCCHCo(2)(CO)(6))(4)Cl(2) (2), which has the dimer structure of Re(2)(OOCR)(4)Cl(2). Cyclic voltammetric measurements show that Re(2)(OOCCCHCo(2)(CO)(6))(4)Cl(2) (2) has one reduction centered on the dirhenium core and a reduction centered on the cobalt atoms. DFT calculations have been used to rationalize the observed displacements of the voltammetric signals in Re(2)(OOCCCHCo(2)(CO)(6))(4)Cl(2) (2) compared to the parent ligand (CO)(6)Co(2)HCCCOOH and rhenium pivalate. 相似文献
199.
Inside Cover: Seeding Molecular Rotators on a Passivated Silicon Surface (ChemPhysChem 2/2014) 下载免费PDF全文
200.
Jorge A. Vila Yelena A. Arnautova Osvaldo A. Martin Harold A. Scheraga 《Journal of computational chemistry》2014,35(4):309-312
The goal of this study is twofold. First, to investigate the relative influence of the main structural factors affecting the computation of the 13C′ shielding, namely, the conformation of the residue itself and the next nearest‐neighbor effects. Second, to determine whether calculation of the 13C′ shielding at the density functional level of theory (DFT), with an accuracy similar to that of the 13Cα shielding, is feasible with the existing computational resources. The DFT calculations, carried out for a large number of possible conformations of the tripeptide Ac‐G XY ‐NMe, with different combinations of X and Y residues, enable us to conclude that the accurate computation of the 13C′ shielding for a given residue X depends on the: (i) (?,ψ) backbone torsional angles of X ; (ii) side‐chain conformation of X ; (iii) (?,ψ) torsional angles of Y ; and (iv) identity of residue Y . Consequently, DFT‐based quantum mechanical calculations of the 13C′ shielding, with all these factors taken into account, are two orders of magnitude more CPU demanding than the computation, with similar accuracy, of the 13Cα shielding. Despite not considering the effect of the possible hydrogen bond interaction of the carbonyl oxygen, this work contributes to our general understanding of the main structural factors affecting the accurate computation of the 13C′ shielding in proteins and may spur significant progress in effort to develop new validation methods for protein structures. © 2013 Wiley Periodicals, Inc. 相似文献