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431.
Hongmei Shi Shipeng Liu Shigang Shen Shuying Huo Weijun Kang 《Transition Metal Chemistry》2009,34(8):821-826
Kinetics of oxidation of dl-pipecolinate by bis(hydrogenperiodato)argentate(III) complex anion, [Ag(HIO6)2]5−, has been studied in aqueous alkaline medium in the temperature range of 25–40 °C. The oxidation kinetics is first order
in the silver(III) and pipecolinate concentrations. The observed second-order rate constant, decreasing with increasing [periodate]
is virtually independent of [OH−]. α-Aminoadipate as the major oxidation product of pipecolinate has been identified by chromatographic analysis. A reaction
mechanism is proposed that involves a pre-equilibrium between [Ag(HIO6)2]5− and [Ag(HIO6)(H2O)(OH)]2−, a mono-periodate coordinated silver(III) complex. Both Ag(III) complexes are reduced in parallel by pipecolinate in rate-determining
steps (described by k
1 for the former Ag(III) species and k
2 for the latter). The determined rate constants and their associated activation parameters are k
1 (25 °C) = 0.40 ± 0.02 M−1 s−1, ∆H
1≠ = 53 ± 2 kJ mol−1, ∆S
1≠ = −74 ± 5 J K−1 mol−1 and k
2 (25 °C) = 0.64 ± 0.02 M−1 s−1, ∆H
2≠ = 41 ± 2 kJ mol−1, ∆S
2≠ = −110 ± 5 J K−1 mol−1. The time-resolved spectra, a positive dependence of the rate constants on ionic strength of the reaction medium, and the
consistency of pre-equilibrium constants derived from different reaction systems support the proposed reaction mechanism. 相似文献
432.
Oxidation of 3-(4-methoxyphenoxy)-1,2-propanediol (MPPD) by bis(hydrogenperiodato) argentate(III) complex anion, [Ag(HIO6)2]5− has been studied in aqueous alkaline medium by use of conventional spectrophotometry. The major oxidation product of MPPD
has been identified as 3-(4-methoxyphenoxy)-2-ketone-1-propanol by mass spectrometry. The reaction shows overall second-order
kinetics, being first-order in both [Ag(III)] and [MPPD]. The effects of [OH−] and periodate concentration on the observed second-order rate constants k′ have been analyzed, and accordingly an empirical expression has been deduced:
where [IO4
−]tot denotes the total concentration of periodate and k
a = (0.19 ± 0.04) M−1 s−1, k
b = (10.5 ± 0.3) M−2 s−1, and K
1 = (5.0 ± 0.8) × 10−4 M at 25.0 °C and ionic strength of 0.30 M. Activation parameters associated with k
a and k
b have been calculated. A mechanism is proposed, involving two pre-equilibria, leading to formation of a periodato–Ag(III)–MPPD
complex. In the subsequent rate-determining steps, this complex undergoes inner-sphere electron-transfer from the coordinated
MPPD molecule to the metal center by two paths: one path is independent of OH−, while the other is facilitated by a hydroxide ion. 相似文献
433.
Solid-state and solution analysis shows that dialkyl substituents on the central phenyl ring of bis(dioxaborole)s, such as , do not have an appreciable effect on the planarity but do significantly alter the supramolecular assembly of these compounds. 相似文献
434.
We present a novel broadband dispersion compensating photonic crystal fiber with defected core in this paper. The small central defect of air hole can flexibly control the chromatic dispersion properties of this kind of photonic crystal fiber. This kind of fiber has broadband large negative chromatic dispersion, and the chromatic dispersion coefficient varies from -440 to -480 ps/(nm.km) in the measured wavelength range of 1500 - 1625 nm. The calculated chromatic dispersion curve is well matched to the measured chromatic dispersion coefficient in the range of 1500 - 1625 nm. The proposed photonic crystal fiber can be used to design the dispersion compensating fiber in the desired wavelength range by adjusting its structural parameters. 相似文献
435.
Onset of metallic behavior in magnesium clusters 总被引:1,自引:0,他引:1
We have measured the photoelectron spectra of mass-selected magnesium cluster anions, Mg- n, over the size range, n=3-35. Their s-p band gaps were observed to close at n=18, signaling the onset of metallic behavior. Electronic shell structure was implicated by gap "reopenings" and mass spectral magic numbers. Complementary calculations are presented in the companion paper [P. H. Acioli and J. Jellinek, Phys. Rev. Lett. 89, 213402 (2002)]]. 相似文献
436.
自从1990年用电弧法成功地制备出宏观量的C60和C70以来,富勒烯的电化学研究有了迅速的发展.理论研究指出,在一个C60簇化合物中,有六个吡喃环烯单元,可分别得到一个电子使五元环芳香化,从而形成C(n=1~6)阴离子.Haufler首先报导了C60可逆的两步单电子还原,之后一些作者陆续得到了三步、四步和五步单电子电还原过程.直到达1992年,在使用混合溶剂并控制低温-10℃至5℃和-88℃至60℃条件下,才得到了C60的六步电还原伏安图.富勒烯的微电极伏安法的研究极少见报导.杨汉西等用铂微电极得到了C60三步电还原的稳态伏安图.本文在… 相似文献
437.
KI-醚类催化剂催化二氧化碳和环氧乙烷合成碳酸乙烯酯反应研究 总被引:7,自引:0,他引:7
合成了5个含有金属铁的环醚Fe(CO)3L(L1=Ph2P(CH2CH2O)2CH2CH2PPh2,L2=Ph2P(CH2CH2O)4CH2CH2PPh2,L3=OPh[(OCH2CH2)PPh2]2,L4=OPh[OCH2CH2)2PPh2]2)和[Fe(CO3)]2L5(L5=[Ph2PCH2CH2OCH2CH2PPh2]2).对它们进行了元素分析,并用红外光谱和核磁共振谱进行了结构表征.用KI+醚类为催化剂,催化二氧化碳与环氧乙烷反应生成碳酸乙烯酯,反应选择性大于96.9%.催化机理为碱催化,催化剂的活性受醚的影响.能和K+形成稳定配合物的醚可提高催化剂的活性.含金属铁的环醚和普通醚类相似,可以和钾离子作用,提高阴离子的亲核催化性能. 相似文献
438.
发光多孔硅的化学传感特征 总被引:2,自引:0,他引:2
发光多孔是一种新型的光电器件材料。其荧光的猝灭或增敏,以及其电学特性的变化可作为化学伟感信息用于电化学传感技术。本文评述了自发光多孔硅首次报道以来在化学传感领域的应用研究进展。 相似文献
439.
This paper describes the DSC study of 4-trifluorocoumarin derivatives, C_(481), C_(485), C_(500) and C_(480), providing their DSC thermograms and thermodynamic parameters during the phase transitions of these compounds. Singlemelting peaks were observed on DSC thermogram respectively.Experimental results show the existence of certain correlations between the melting point, heat of fusion and molecular structure for this series of compounds. 相似文献
440.
Dey S Karukurichi KR Shen W Berkowitz DB 《Journal of the American Chemical Society》2005,127(24):8610-8611
Described is a new method for the screening of an array of catalysts, in situ, to estimate enantioselectivity and relative rates. We term this approach "double-cuvette ISES (in situ enzymatic screening)". The Co(III)-salen mediated hydrolytic kinetic resolution (HKR) of (+/-)-propylene oxide is used as a model reaction to demonstrate proof of principle. In two parallel cuvettes, a lower CHCl3-based organic layer is loaded with the epoxide and the chiral salen catalyst. Aqueous reporting layers, containing distinct "reporting enzymes" and their nicotinamide cofactors, are layered above the organic layers. The 1,2-propanediol enantiomers formed by the chiral catalyst diffuse into the aqueous layer and are oxidized there by the reporting enzymes at rates dependent upon the diol concentration, the R:S ratio of the diol, and the enantioselectivity of the reporting enzymes. A focused chiral salen library was constructed from seven chiral 1,2-diamines, derived from amino acid, terpenoid, and carbohydrates skeletons, and seven salicylaldehyde derivatives. Double-cuvette ISES identified a couple of interesting combinatorial hits in this salen array, wherein either the sense or magnitude of enantioselection for a given chiral diamine depends significantly upon the choice of "salicylaldehyde" partner. A comparison of predicted ee's and relative rates using this new screening tool with those independently measured is provided. 相似文献