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51.
Maria Luisa Moyá Antonio Barrios Maria del Mar Graciani Rafael Jiménez Ernestina Muñoz Francisco Sánchez John Burgess 《Transition Metal Chemistry》1991,16(2):165-168
Summary The kinetics of replacement of 4,4-bipyridine, (4,4-bipy), and 4-cyanopyridine, (4-CNpy), by cyanide in [Fe(CN)5-(4,4-bipy)]3-. at 298 K have been studied in binary aqueous mixtures containing different amounts of t-butanol, methanol, glycerol, ethyleneglycol and sucrose. The plots of logarithms of the limiting rate constantsversus the mole fraction of water are linear over the entire composition range studied, showing the importance of solvation phenomena. A different straight line of log (kL/s–1)versus XH2O is obtained for each mixture, indicating the influence of other solvent parameters on the reaction rate. A multiparameter regression of G
exp
with A (acidity vector), B (basicity vector) and GE is used for both reactions; plots of G
calc
versus G
exp
are linear with slopes of near unity. 相似文献
52.
2-and 4-Ethoxymethoxybenzyl methyl ethers were employied as useful starting materials for the synthesis of 1,2- or 1,4-dicarbo-substituted benzenes. The proposed reaction sequence involves connection between the reductive lithiation of benzyl alkyl ethers and the metal-catalyzed cross-coupling reaction of aromatic triflates. 相似文献
53.
Pilar Campíns-Falcó Adela Sevillano-Cabeza Luisa Gallo-Martínez Francisco Bosch-Reig Isidro Monzó-Mansanet 《Mikrochimica acta》1997,126(3-4):207-215
This paper discusses the spectrophotometric determination of cephalexin as the intact cephalexin or as its acid-induced degradation product. Cephalexin can be determined in the range 1 × 10–5–18 × 10–5
M with relative standard deviations of 5-1%. The limits of quantitation and detection were 10–5 and 0.3 × 10–5
M, respectively. These procedures were compared with reversed-phase HPLC determination. No interference was observed in the presence of common pharmaceutical adjuvants. The H-point standard additions method was applied in order to correct for the possible presence of the cephalexin precursor, 7-aminocephalosporanic acid; this improves the selectivity of the UV-vis spectrophotometric method. 相似文献
54.
A simple and fast analytical procedure has been developed for the determination of As, Sb, Se, Te and Bi in milk samples by hydride generation atomic fluorescence spectrometry (HG-AFS). Samples were treated with aqua regia for 10 min in an ultrasound water bath and pre-reduced with KBr for total Se and Te determination or with KI and ascorbic acid for total As and Sb, the determination of Bi being possible in all with or without pre-reduction. Slurries of samples, in the presence of antifoam A, were treated with NaBH4 in HCl medium to obtain the corresponding hydrides, and AFS measurements were processed in front of external calibrations prepared and measured in the same way as samples. Results obtained by the developed procedure compare well with those found after microwave-assisted complete digestion of samples. The proposed method is simple and fast, and only 1 ml of milk is needed. The values obtained for detection limit are 2.5, 1.6, 3, 6 and 7 ng l−1 for As, Sb, Se, Te and Bi respectively in the diluted samples, with average relative standard deviation values of 3.8, 3.1, 1.9, 6.4 and 1.2% for three independent analysis of a series of commercially available samples of different origin. Data found in Spanish market samples varied from 3.2±0.3 to 11.3±0.2 ng g−1 As, from 3.1±0.2 to 11.6±0.4 ng g−1 Sb, from 10.7±0.5 to 25.5±0.4 ng g−1 Se, from 0.9±0.2 to 9.4±0.6 ng g−1 Te and from 11.5±0.1 to 27.7±0.4 ng g−1 Bi. 相似文献
55.
Welter S Salluce N Benetti A Rot N Belser P Sonar P Grimsdale AC Müllen K Lutz M Spek AL De Cola L 《Inorganic chemistry》2005,44(13):4706-4718
In the search for light-addressable nanosized compounds we have synthesized 10 dinuclear homometallic trisbipyridyl complexes of linear structure with the general formula [M(bpy)3-BL-M(bpy)3]4+ [M = Ru(II) or Os(II); BL = polyphenylenes (2, 3, 4, or 5 units) or indenofluorene; bpy = 2,2'-bipyridine]. By using a "chemistry on the complex" approach, different sizes of rodlike systems have been obtained with a length of 19.8 and 32.5 A for the shortest and longest complex, respectively. For one of the ruthenium precursors, [Rubpy-ph2-Si(CH3)3][PF6]2, single crystals were obtained by recrystallization from methanol. Their photophysical and electrochemical properties are reported. All the compounds are luminescent both at room and low temperature with long excited-state lifetimes due to an extended delocalization. Nanosecond transient absorption showed that the lowest excited state involves the chelating unit attached to the bridging ligand. Electrochemical data indicated that the first reduction is at a slightly more positive potential than for the reference complexes [M(bpy)3]2+ (M = Ru, Os). This result confirms that the best acceptor is the bipyridine moiety connected to the conjugated spacers. The role of the tilt angle between the phenylene units, in the two series of complexes, for the ground and excited states is discussed. 相似文献
56.
Dirksen A Kleverlaan CJ Reek JN De Cola L 《The journal of physical chemistry. A》2005,109(24):5248-5256
A photoactive supramolecular assembly that is based on the hydrogen-bonded system H1.G2, consisting of a methyl viologen-functionalized barbiturate host (H1) (1-(N-(3,5-bis[[(6-tert-butylacetylamino-2-pyridyl)amino]carbonyl])-phenylacetamide)-1'-methyl-4,4'-bipyridium) and a [Re(Br)(CO)3(barbi-bpy)] (barbi-bpy = 5-[4-(4'-methyl)-2,2'-bipyridyl]methyl-2,4,6-(1H,3H,5H)-pyrimidinetrione) complex as the guest (G2) is described. The host molecule contains a well-known electron accepting group (methyl viologen), whereas the guest system can act as an efficient electron donor in the excited state. Upon self-assembly, the resulting adduct (H1.G2) represents an interesting noncovalently linked donor-acceptor system. The H1.G2 complex has been characterized in acetonitrile-d3 using 1H NMR and diffusion-ordered NMR spectroscopy (DOSY). The photophysical properties of the components and of the assembly have been studied in dichloromethane, in which the assembly has a high binding constant (Kass > or = 2 x 10(5) M(-1)), using time-resolved fluorescence and transient absorption spectroscopy. A detailed investigation of the hydrogen-bonded complex H1.G2 revealed that, upon excitation of the rhenium compound G2, an ultrafast electron-transfer process occurs from the metal-based component to the acceptor unit. The kinetics of the forward and back electron-transfer processes have been determined. 相似文献
57.
Daniel Carmona Joaquina Ferrer María Pilar Lamata Luis A. OroHans-Heinrich Limbach Gerd SchererJos Elguero María Luisa Jimeno 《Journal of organometallic chemistry》1994,470(1-2):271-274
The Arrhenius equation corresponding to the process P---Ag+P*---Ag*→---P---Ag*+P*---Ag has been determined for [(η6-p-cymene)Ru(μ-pz)3Ag(PPh3)] (1) by complete line-shape analysis of the 31P NMR spectra between −40°C and +30°C. It has the form K = 1011.8± e(−46±5 kJ mol−1/RT). The preexponential term, log A = 11.8 corresponds to a small activation entropy, whereas the activation energy, 46 kJ mol−1 is comparable to those determined for other phosphorus—metal compounds. 相似文献
58.
Luisa Carini 《Rendiconti del Circolo Matematico di Palermo》1979,28(2):220-228
We introduce in a U. F. D.,A, and in its quotient fieldK two metricsd and \(\bar d\) connected to the (p)-adic topology onA and its extension toK; we prove that: \(\bar d\left( {\frac{x}{y},\frac{{x'}}{{y'}}} \right) = \inf \left( {\frac{{d(xy',yx')}}{{2d(yy',0)}},1} \right)\) . 相似文献
59.
Tingke Rao Prof. Maria Luisa Saladino Prof. Yuanxing Fang Prof. Xinchen Wang Dr. Cristina Giordano 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(72):16676-16682
A versatile synthetic strategy for the preparation of multimetallic oxynitrides has been designed and here exemplarily discussed considering the preparation of nanoscaled zinc–gallium oxynitrides and zinc–gallium–indium oxynitrides, two important photocatalysts of new generation, which proved to be active in key energy related processes from pollutant decomposition to overall water splitting. The synthesis presented here allows the preparation of small nanoparticles (less than 20 nm in average diameter), well-defined in size and shape, yet highly crystalline and with the highest surface area reported so far (up to 80 m2 g−1). X-ray diffraction studies show that the final material is not a mixture of single oxides but a distinctive compound. The photocatalytic properties of the oxynitrides have been tested towards the decomposition of an organic dye (as a model reaction for the decomposition of air pollutants), showing better photocatalytic performances than the corresponding pure phases (reaction constant 0.22 h−1), whereas almost no reaction was observed in absence of catalyst or in the dark. The photocatalysts have been also tested for H2 evolution (semi-reaction of the water splitting process) with results comparable to the best literature values but leaving room for further improvement. 相似文献
60.
Umar Farid Maria Luisa Aiello Prof. Stephen J. Connon 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(43):10074-10079
A new catalytic methodology was developed to promote an efficient one-pot kinetic resolution of racemic aldehydes with selectivity (s*) of up to 91 (99:1 d.r., >99 % ee) in a cycloaddition reaction with enolizable anhydrides to afford dihydroisocoumarin products (a core prevalent in natural products and molecules of medicinal interest) containing three contiguous stereocentres. 相似文献