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排序方式: 共有162条查询结果,搜索用时 15 毫秒
11.
The first 1,3-dipolar reaction of azomethine ylides with optically pure vinyl sulfoxide are reported. The presence of the sulfinyl group increase the reactivity of the acrylate moiety as a dipolarophile, and the reactions evolve with complete regio- and endo-selectivities. Nevertheless, mixtures of the two diastereoisomers 4 and 5 (75-88% de) resulting from the anti dipole/s-cis dipolarophile and syn dipole/s-trans dipolarophile approaches, respectively, are obtained. The stereoselectivity can be controlled by using THF or MeCN as solvents or by changing the reaction temperature in MeCN. After separation of the cycloadducts, optically pure 2,5-dihydro-1H-pyrroles are easily obtained by pyrolytic desulfinylation. 相似文献
12.
We present a new type of flow cytometer that can operate underwater for a long time, as long as days, for measuring the size distribution, concentration, and biomass of marine phytoplankton. The major improvement of the instrument over existing techniques is the elimination of sample preparation, which is achieved with a laser Doppler crossed-beam arrangement for both defining a measurement volume and measuring the speed of the particle traversing it. By simultaneously sampling the laser-induced fluorescence signal and the Doppler signals, the technique can discriminate sizes of phytoplankton. 相似文献
13.
Alberto Castro-Muñiz Amelia Martínez-Alonso Juan M.D. Tascón 《Polymer Degradation and Stability》2009,94(10):1890-1894
The main objective of this work was to investigate the development of porosity in solid residues from the thermal decomposition of the polymer, poly(p-phenylene terephthalamide) (PPTA). PPTA chars were prepared at different temperatures and characterized by X-ray diffraction and physical adsorption of CO2 at 0 °C. The carbonization temperatures were selected on the basis of thermogravimetric analysis results. The effect of introducing an isothermal treatment at 500 °C on the characteristics of the resulting chars was also studied. It was found that this pre-treatment lowers the decomposition temperature of PPTA and yields a somewhat less ordered material than in the case of pyrolysis under a constant heating rate. The micropore volume increases with increasing heat treatment temperature for both series of samples. The mean micropore size decreases for the two series of chars until the 700-800 °C interval; above these temperatures, this evolution is reversed. The micropore volume of the samples submitted to the isothermal treatment is higher than when PPTA is treated under a constant heating rate. Likewise, the pore size distribution is more heterogeneous when the intermediate isothermal treatment at 500 °C is introduced during PPTA pyrolysis. Some differences between porosity development in chars from PPTA and other high thermal stability polymers were explained on the basis of different mechanistic features in polymer pyrolysis. 相似文献
14.
Azomethine ylides, derived from iminoesters 1 and DBU in the presence of silver salts, react with (S)-2-p-tolylsulfinyl-2-cyclopentenone 2 in a completely regio- and endoselective manner but with a low facial selectivity, affording a mixture of two cycloadducts 3 and 4. When the ylides were prepared with LHMDS, only one diastereoisomer 3 was obtained in an almost quantitative yield. A nucleophilic addition/ring closure process easily accounts for the stereochemical results. Compounds 3 were transformed into optically pure 4-oxocyclopenta[c]dihydropyrroles and tetrahydropyrroles by elimination of the sulfinyl group. 相似文献
15.
Kim J Welch LA Olivas A Podkolzin SG Koel BE 《Langmuir : the ACS journal of surfaces and colloids》2010,26(21):16401-16411
Adsorption and decomposition of cyclohexanone (C(6)H(10)O) on Pt(111) and on two ordered Pt-Sn surface alloys, (2 × 2)-Sn/Pt(111) and (√3 × √3)R30°-Sn/Pt(111), formed by vapor deposition of Sn on the Pt(111) single crystal surface were studied with TPD, HREELS, AES, LEED, and DFT calculations with vibrational analyses. Saturation coverage of C(6)H(10)O was found to be 0.25 ML, independent of the Sn surface concentration. The Pt(111) surface was reactive toward cyclohexanone, with the adsorption in the monolayer being about 70% irreversible. C(6)H(10)O decomposed to yield CO, H(2)O, H(2), and CH(4). Some C-O bond breaking occurred, yielding H(2)O and leaving some carbon on the surface after TPD. HREELS data showed that cyclohexanone decomposition in the monolayer began by 200 K. Intermediates from cyclohexanone decomposition were also relatively unstable on Pt(111), since coadsorbed CO and H were formed below 250 K. Surface Sn allowed for some cyclohexanone to adsorb reversibly. C(6)H(10)O dissociated on the (2 × 2) surface to form CO and H(2)O at low coverages, and methane and H(2) in smaller amounts than on Pt(111). Adsorption of cyclohexanone on (√3 × √3)R30°-Sn/Pt(111) at 90 K was mostly reversible. DFT calculations suggest that C(6)H(10)O adsorbs on Pt(111) in two configurations: by bonding weakly through oxygen to an atop Pt site and more strongly through simultaneously oxygen and carbon of the carbonyl to a bridged Pt-Pt site. In contrast, on alloy surfaces, C(6)H(10)O bonds preferentially to Sn. The presence of Sn, furthermore, is predicted to make the formation of the strongly bound C(6)H(10)O species bonding through O and C, which is a likely decomposition precursor, thermodynamically unfavorable. Alloying with Sn, thus, is shown to moderate adsorptive and reactive activity of Pt(111). 相似文献
16.
A regio- and stereoselective iodination has been performed on vicinal diols located on ketopyranose templates using the controlled- Garegg conditions. 3-O-Benzyl-1,2-O-isopropylidene-β-d-fructo- or psicopyranoses (1 or 4) were selectively iodinated, respectively, at C-5 or C-4 of the ketoses to afford the l-sorbo or d-sorbo iodohydrins. 相似文献
17.
Luca Pasquini Elsa Callini Matteo Brighi Federico Boscherini Amelia Montone Torben R. Jensen Chiara Maurizio Marco Vittori Antisari Ennio Bonetti 《Journal of nanoparticle research》2011,13(11):5727-5737
We report on the hydrogen storage behaviour of Mg nanoparticles (NPs) (size range 100 nm–1 μm) with metal-oxide core–shell
morphology synthesized by inert gas condensation and decorated by transition metal (TM) (Pd or Ti) clusters via in situ vacuum
deposition. The structure and morphology of the as-prepared and hydrogenated NPs is studied by electron microscopy, X-ray
diffraction including in situ experiments and X-ray absorption spectroscopy, in order to investigate the relationships with
the hydrogen storage kinetics measured by the volumetric Sieverts method. With both Pd and Ti, the decoration deeply improves
the hydrogen sorption properties: previously inert NPs exhibit complete hydrogenation with fast transformation kinetics, good
stability and reversible gravimetric capacity that can attain 6 wt%. In the case of Pd-decoration, the occurrence of Mg–Pd
alloying is observed at high temperatures and in dependence of the hydrogen pressure conditions. These structural transformations
modify both the kinetics and thermodynamics of hydride formation, while Ti-decoration has an effect only on the kinetics.
The experimental results are discussed in relation with key issues such as the amount of decoration, the heat of mixing between
TM and Mg and the binding energy between TM and hydrogen. 相似文献
18.
Amelia Carolina Sparavigna Mauro Maria Baldi 《International Journal of Mathematical Education in Science & Technology》2017,48(2):306-316
The regular pentagon had a symbolic meaning in the Pythagorean and Platonic philosophies and a subsequent important role in Western thought, appearing also in arts and architecture. A property of regular pentagons, which was probably discovered by the Pythagoreans, is that the ratio between the diagonal and the side of these pentagons is equal to the golden ratio. Here, we will study some relations existing between a regular pentagon and this ratio. First, we will focus on the group of fivefold rotational symmetry, to find the position in the complex plane of the vertices of this geometric figure. Then, we will propose an analytic method to solve the same problem based on the Cartesian coordinates, a method where we find the golden ratio without any specific geometric consideration. This study shows a comparison of the use of complex numbers, symmetries and analytic methods, applied to a subject which can be interesting for general education in mathematics. In fact, the proposed approach can convey and link several concepts, requiring only a general pre-college education, showing at the same time the richness that mathematics can offer in solving geometric problems. 相似文献
19.
Amelia Torcello-Gómez Miguel Wulff-Pérez María José Gálvez-RuizAntonio Martín-Rodríguez Miguel Cabrerizo-VílchezJulia Maldonado-Valderrama 《Advances in colloid and interface science》2014
Triblock copolymers (also known as Pluronics or poloxamers) are biocompatible molecules composed of hydrophobic and hydrophilic blocks with different lengths. They have received much attention recently owing to their applicability for targeted delivery of hydrophobic compounds. Their unique molecular structure facilitates the formation of dynamic aggregates which are able to transport lipid soluble compounds. However, these structures can be unstable and tend to solubilize within the blood stream. The use of nanoemulsions as carriers for the lipid soluble compounds appears as a new alternative with improved protection against physiological media. The interfacial behavior of block copolymers is directly related to their peculiar molecular structure and further knowledge could provide a rational use in the design of poloxamer-stabilized nanoemulsions. This review aims to combine the new insights gained recently into the interfacial properties of block copolymers and their performance in nanoemulsions. Direct studies dealing with the interactions with physiological media are also reviewed in order to address issues relating metabolism degradation profiles. A better understanding of the physico-chemical and interfacial properties of block copolymers will allow their manipulation to modulate lipolysis, hence allowing the rational design of nanocarriers with efficient controlled release. 相似文献
20.
Perez AA Sánchez CC Patino JM Rubiolo AC Santiago LG 《Colloids and surfaces. B, Biointerfaces》2011,85(2):50-315
Milk whey proteins (MWP) and pectins (Ps) are biopolymer ingredients commonly used in the manufacture of colloidal food products. Therefore, knowledge of the interfacial characteristics of these biopolymers and their mixtures is very important for the design of food dispersion formulations (foams and/or emulsions). In this paper, we examine the adsorption and surface dilatational behaviour of MWP/Ps systems under conditions in which biopolymers can saturate the air-water interface on their own. Experiments were performed at constant temperature (20 °C), pH 7 and ionic strength 0.05 M. Two MWP samples, β-lactoglobulin (β-LG) and whey protein concentrate (WPC), and two Ps samples, low-methoxyl pectin (LMP) and high-methoxyl pectin (HMP) were evaluated. The contribution of biopolymers (MWP and Ps) to the interfacial properties of mixed systems was evaluated on the basis of their individual surface molecular characteristics. Biopolymer bulk concentration capable of saturating the air-water interface was estimated from surface pressure isotherms. Under conditions of interfacial saturation, dynamic adsorption behaviour (surface pressure and dilatational rheological characteristics) of MWP/Ps systems was discussed from a kinetic point of view, in terms of molecular diffusion, penetration and configurational rearrangement at the air-water interface. The main adsorption mechanism in MWP/LMP mixtures might be the MWP interfacial segregation due to the thermodynamic incompatibility between MWP and LMP (synergistic mechanism); while the interfacial adsorption in MWP/HMP mixtures could be characterized by a competitive mechanism between MWP and HMP at the air-water interface (antagonistic mechanism). The magnitude of these phenomena could be closely related to differences in molecular composition and/or aggregation state of MWP (β-LG and WPC). 相似文献