全文获取类型
收费全文 | 4182篇 |
免费 | 234篇 |
国内免费 | 16篇 |
专业分类
化学 | 3465篇 |
晶体学 | 16篇 |
力学 | 67篇 |
数学 | 425篇 |
物理学 | 459篇 |
出版年
2023年 | 50篇 |
2022年 | 138篇 |
2021年 | 177篇 |
2020年 | 141篇 |
2019年 | 120篇 |
2018年 | 59篇 |
2017年 | 56篇 |
2016年 | 176篇 |
2015年 | 179篇 |
2014年 | 163篇 |
2013年 | 236篇 |
2012年 | 338篇 |
2011年 | 371篇 |
2010年 | 210篇 |
2009年 | 172篇 |
2008年 | 292篇 |
2007年 | 259篇 |
2006年 | 254篇 |
2005年 | 181篇 |
2004年 | 189篇 |
2003年 | 148篇 |
2002年 | 125篇 |
2001年 | 27篇 |
2000年 | 29篇 |
1999年 | 26篇 |
1998年 | 19篇 |
1997年 | 21篇 |
1996年 | 24篇 |
1995年 | 20篇 |
1994年 | 16篇 |
1993年 | 5篇 |
1991年 | 6篇 |
1990年 | 6篇 |
1989年 | 9篇 |
1988年 | 5篇 |
1987年 | 8篇 |
1986年 | 10篇 |
1985年 | 19篇 |
1984年 | 18篇 |
1983年 | 16篇 |
1982年 | 17篇 |
1981年 | 18篇 |
1980年 | 10篇 |
1979年 | 8篇 |
1978年 | 7篇 |
1977年 | 13篇 |
1976年 | 7篇 |
1975年 | 6篇 |
1974年 | 7篇 |
1973年 | 4篇 |
排序方式: 共有4432条查询结果,搜索用时 15 毫秒
941.
Zuccaccia D Pirondini L Pinalli R Dalcanale E Macchioni A 《Journal of the American Chemical Society》2005,127(19):7025-7032
The interionic structure, kinetic stability, and degree of anion encapsulation of coordination cages 1 were studied by PGSE, NOE, and EXSY NMR techniques. The rate constants for the formation/dissociation processes at 296 K were obtained independently via (1)H-NOESY and (19)F-NOESY experiments giving, respectively, k(obs) = 0.30 +/- 0.04 s(-1) in CDCl(3) and k(obs) = 5.2 +/- 0.8 s(-1) in CD(3)NO(2)/CDC(13) (7.1) mixture with the proton probe, and k(obs) = 0.33 +/- 0.06 s(-1) in CDCl(3) and k(obs) = 5.0 +/- 0.8 s(-1) in CD(3)NO(2)/CDC(13) (7/1 mixture) with the (19)F probe. PGSE experiments showed that in CDCl(3) not only the encapsuled anion but also the external anions translate with the same rate as the cage. (19)F,(1)H-HOESY experiments indicated that an average of five external triflate anions are located in the equatorial sites close to the palladium moieties, while two of them approach the polar pockets formed by the alkyl chains. In a CD(3)NO(2)/CDCl(3) (7/1) mixture only one or two anions are in close proximity with the cage, while the others are solvated. In all the considered solvents (benzene, chloroform, methylene chloride, and nitromethane) the inclusion of a single unsolvated triflate anion in the cage is quantitative. (19)F,(1)H-HOESY experiments indicated that the charged guest head points toward one metal center. Therefore, while the ionic aggregation level and kinetic stability of coordination cages 1 are solvent dependent, anion encapsulation is not. 相似文献
942.
Spiegel DA Wiberg KB Schacherer LN Medeiros MR Wood JL 《Journal of the American Chemical Society》2005,127(36):12513-12515
Trialkylboranes (BMe3, BEt3, and BBu3) have been shown to mediate reductive deoxygenation reactions of O-alkyl-S-methyl dithiocarbonates (methyl xanthates) in which water or deuterium oxide functions as the source of hydrogen or deuterium. This method has proven versatile with regard to substrate scope and is capable of providing protio- or deuterioalkane products in high yields with excellent levels of D-incorporation. Ab initio calculations suggest that the trialkylborane-water complex possesses an unusually low O-H bond dissociation energy (73 kcal/mol) and support a radical chain mechanism for this process. Taken together, this report provides evidence for fundamentally novel and previously overlooked modes of reactivity for water and trialkylboranes of wide ranging importance in both theoretical and applied investigations. 相似文献
943.
A thin chip microsprayer system coupled to Fourier transform ion cyclotron resonance mass spectrometry for glycopeptide screening 总被引:1,自引:0,他引:1
Bindila L Froesch M Lion N Vukelić Z Rossier JS Girault HH Peter-Katalinić J Zamfir AD 《Rapid communications in mass spectrometry : RCM》2004,18(23):2913-2920
A thin polymer microchip was coupled with a Fourier transform ion cyclotron resonance (FTICR) 9.4 T mass spectrometer and the method was optimized in negative ion mode for glycopeptide screening. The interface between the polymer microchip and FTICR mass spectrometer consists of an in-laboratory conceived and designed mounting system that exhibits robust and controllable alignment of the chip toward the inlet of the mass spectrometer. The particular attribute of the polymer chip coupled to the FTICR mass spectrometer, to achieve an increase in ionization efficiency and sensitivity under the premise of high mass accuracy of detection, is highlighted by the large number of major and minor glycopeptide structures detected and identified in highly heterogeneous mixtures obtained from urine matrices. Glycoforms expressing various saccharide chain lengths ranging from tri- to dodecasaccharide, bearing up to three sialic acid moieties, could be detected and assigned based on the accuracy of the mass measurement (average mass deviation below 6 ppm) of their molecular ions. -Thin chipESI-FTICRMS is a potent novel system for glycomic screening of complex mixtures, as demonstrated for identification of singly sialylated O-glycosylated amino acids and peptides from urine matrices, and could be considered for general applicability in the glycoanalytical field. 相似文献
944.
Laura Ribeiro Francisco Veiga 《Journal of inclusion phenomena and macrocyclic chemistry》2002,44(1-4):251-256
Inclusion complexation between -cyclodextrin (-CD),hydroxypropyl--cyclodextrin (HP--CD), water-solublepolymers (PVP and HPMC) and vinpocetine was studied in aqueous solution and in the solid state.Phase solubility studies were used to evaluate the complexation in aqueous solution at roomtemperature. Stability constants (Kc) of binary and ternary complexes were determined spectrophotometrically. Differential scanning calorimetry (DSC)was used to characterize kneaded, co-evaporated and lyophilised binary and ternary systems.The Kc values obtained were 70.14 M-1 and 35.01 M-1 for vinpocetine--CD and vinpocetine-HP--CD and increased in a range of 17% to 94%by addition of water-soluble polymers. Some preliminary evidences ofinclusion complexation were obtained from DSC suggesting that co-evaporated and lyophilised binary andternary systems were truly inclusion complexes. 相似文献
945.
The U+O chemi-ionization reaction has been investigated by quantum chemical methods. Potential-energy curves have been calculated for several electronic states of UO and UO(+). Comparison with the available spectroscopic and thermodynamic values for these species is reported and a mechanism for the chemi-ionization reaction U+O-->UO(+)+e(-) is proposed. The U+O and Sm+O chemi-ionization reactions are the first two metal-plus-oxidant chemi-ionization reactions to be studied theoretically in this way. 相似文献
946.
Giorgi G Salvini L Attanasi OA Guidi B Santeusanio S 《Journal of mass spectrometry : JMS》2002,37(2):169-178
Electron ionisation mass spectrometry was usefully used to characterize structurally 2-aryl-5-acetylthiazole derivatives in the gas phase. The compounds show characteristic fragmentation pathways depending on the chemical nature of the substituent at position 2, consisting mainly in the cleavage of both the 1,2- and 3,4-bonds of the thiazole ring. Liquid secondary ion mass spectrometry was applied to study the effects of protonation on the gas-phase unimolecular reactions of this class of compound. Tandem mass spectrometric experiments, carried out on molecular and protonated molecular ions, and also on fragment ions produced in the source, allowed the elucidation of gas-phase decompositions of low-internal energy ions. 相似文献
947.
Bordiga S Vitillo JG Ricchiardi G Regli L Cocina D Zecchina A Arstad B Bjørgen M Hafizovic J Lillerud KP 《The journal of physical chemistry. B》2005,109(39):18237-18242
Hydrogen storage is among the most demanding challenges in the hydrogen-based energy cycle. One proposed strategy for hydrogen storage is based on physisorption on high surface area solids such as metal-organic frameworks (MOFs). Within this class of materials, MOF-5 has been the first structure studied for hydrogen storage. The IR spectroscopy of adsorbed H2 performed at 15 K and ab initio calculations show that the adsorptive properties of this material are mainly due to dispersive interactions with the internal wall structure and to weak electrostatic forces associated with O13Zn4 clusters. Calculated and measured binding enthalpies are between 2.26 and 3.5 kJ/mol, in agreement with the H2 rotational barriers reported in the literature. A minority of binding sites with higher adsorption enthalpy (7.4 kJ/mol) is also observed. These species are probably associated with OH groups on the external surfaces present as termini of the microcrystals. 相似文献
948.
Laura Hermosilla Paloma Calle Carlos Sieiro Nuria García Pilar Tiemblo Julio Guzmn 《Chemical physics》2007,340(1-3):237-244
The EPR spectral pattern observed in the bulk polymerization of methacrylic monomers was theoretically investigated by DFT methodology. The conformational analysis of the propagating radical by the rotation around the C–Cβ bond, was performed using the B3LYP/6-31G* computational scheme. To obtain accurate values of the isotropic hyperfine coupling constants (hfccs) a higher level protocol, B3LYP/TZVP//B3LYP/6-31G*, was applied. The experimental 13-line spectrum registered at the first stage of the polymerization was assumed to correspond to a free rotating radical in a fluid medium and it was simulated just considering the most stable conformation. The 9-line spectrum registered at high conversions was interpreted in terms of highly hindered rotational conformers frozen in the very viscous medium. This spectrum was well reproduced by a model which considers the sum of the individual spectra of the conformations spread around the most probable. Each of these contributing spectra was obtained on the basis of the computed hfccs for the considered conformations and weighted by his relative Boltzmann population according to the DFT analysis. Besides, the calculated hfccs showed an excellent agreement with those predicted by the Heller–McConnell relationship, which confirms the coherence of the DFT methodology for this kind of calculations. 相似文献
949.
The synthesis, structure, and physical properties of a series of oxo-bridged dinuclear Fe(III) complexes containing pendant naphthalene groups are described. The compounds [Fe(2)O(O(2)CCH(2)-C(10)H(7))(tren)(2)](BPh(4))(NO(3))(2) (8), [Fe(2)O(O(2)CCH(2)-C(10)H(7))(TPA)(2)](ClO(4))(3) (9), Fe(2)O(O(2)CCH(2)-C(10)H(7))(2)(Tp)(2) (10), and Fe(2)O((O(2)CCH(2)CH(2))(2)-C(10)H(6))(Tp)(2) (11) (where tren is tris(2-aminoethyl)amine, TPA is tris(2-pyridyl)amine, and Tp is hydrotrispyrazolylborate) have been characterized in terms of their structural, spectroscopic, magnetic, and photophysical properties. All four complexes exhibit moderately strong intramolecular antiferromagnetic exchange between the high-spin ferric ions (ca. -130 cm(-)(1) for H = -2JS(1).S(2)). Room-temperature steady-state emission spectra for compounds 8-11 in deoxygenated CH(3)CN solution reveal spectral profiles similar to methyl-2-naphthyl acetate and [Zn(2)(OH)(O(2)CCH(2)-C(10)H(7))(2)(TACN-Me(3))(2)](ClO(4)) (13, where TACN-Me(3) is N,N,N-1,4,7-trimethyltriazacyclononane) but are significantly weaker in intensity relative to these latter two compounds. Time-resolved emission data for the iron complexes following excitation at 280 nm can be fit to simple exponential decay models with tau(obs)(S)()1 = 36 +/- 2, 32 +/- 4, 30 +/- 5, and 39 +/- 3 ns for compounds 8-11, respectively. The decays are assigned to the S(1) --> S(0) fluorescence of naphthalene; all of the lifetimes are less than that of the zinc model complex (tau(obs)(S)()1 = 45 +/- 2 ns), indicating quenching of the S(1) state by the iron-oxo core. Nanosecond time-resolved absorption data on [Zn(2)(OH)(O(2)CCH(2)-C(10)H(7))(2)(TACN-Me(3))(2)](ClO(4)) reveal a feature at lambda(max) = 420 nm that can be assigned as the T(1) --> T(n) absorption of the naphthalene triplet; the rise time of 50 +/- 10 ns corresponds to an intersystem crossing rate of 2 x 10(7) s(-1). A similar feature (though much weaker in intensity) is also observed for compound 8. The order-of-magnitude reduction in the T(1) lifetime of the pendant naphthalene for all of the iron-oxo complexes (tau(obs)(T)1 = 5 +/- 2 micros vs 90 +/- 10 micros for [Zn(2)(OH)(O(2)CCH(2)-C(10)H(7))(2)(TACN-Me(3))(2)](ClO(4))) indicates quenching of the naphthalene triplet with an efficiency of >90%. Neither the naphthalene radical cation nor the reduced Fe(II)Fe(III) species were observed by transient absorption spectroscopy, implying that energy transfer is the most likely origin for the quenching of both the S(1) and T(1) states. Spectral overlap considerations strongly support a F?rster (i.e., dipolar) mechanism for energy transfer from the S(1) state, whereas the lack of phosphorescence from either the free naphthyl ester or the Zn model complex suggests Dexter transfer to the diiron(III) core as the principal mechanism of triplet quenching. The notion of whether spin exchange within the diiron(III) core is in part responsible for the unusual ability of the iron-oxo core to engage in energy transfer from both the singlet and triplet manifolds of naphthalene is discussed. 相似文献
950.
Maria Laura Di Lorenzo 《European Polymer Journal》2005,41(3):569-575
This article contains a detailed analysis of the crystallization behavior of poly(l-lactic acid) (PLLA). Crystallization rates of PLLA have been measured in a wide temperature range, using both isothermal and non-isothermal methods. The combined usage of multiple thermal treatments allowed to obtain information on crystallization kinetics of PLLA at temperatures almost ranging from glass transition to melting point. Crystallization rate of PLLA is very high at temperatures between 100 and 118 °C, showing a clear deviation from the usual bell-shaped curve. This discontinuity has been ascribed to a sudden acceleration in spherulite growth, and is not associated to morphological changes in the appearance of PLLA spherulites. Experimental data of spherulite growth rates of PLLA have been analyzed with Hoffman-Lauritzen method. Applicability and limitations of this theoretical treatment have been discussed. 相似文献