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31.
Potential applications of nanoporous thermosetting polymers include polyelectrolytes in fuel cells, separation membranes, adsorption media, and sensors. Design of nanoporous polymers for such applications entails controlling permeability by tailoring pore size, structure, and interface chemistry. Nanoporous thermosetting polymers are often synthesized via free radical mechanisms using solvents that phase separate during polymerization. In this work, a novel technique for the synthesis of nanoporous thermosets is presented that is based on the reactive encapsulation of an inert solvent using step-growth cross-linking polymerization without micro/macroscopic phase separation. The criteria for selecting such a monomer-polymer-solvent system are discussed based on FTIR analysis, observed micro/macroscopic phase separation, and thermodynamics of swelling. Investigation of resulting network pore structures by scanning electron microscopy (SEM) and small-angle X-ray scattering following extraction and supercritical drying using carbon dioxide showed that nanoporous polymeric materials with pore sizes ranging from 1 to 50 nm can be synthesized by varying the solvent content. The differences in the porous morphology of these materials compared to more common free radically polymerized analogues that exhibit phase separation were evident from SEM imaging. Furthermore, it was demonstrated that the chemical activity of the nanoporous materials obtained by our method could be tailored by grafting appropriate functional groups at the pore interface. 相似文献
32.
Giuseppe Trapani Andrea Latrofa Antonia Reho Massimo Franco Gaetano Liso 《Journal of heterocyclic chemistry》1992,29(5):1155-1159
The title compounds 3a-j together with the N-alkylacylketene S,N-acetals 12a-j were obtained by reaction of N,N'-dialkyldithiodianilines with β-ketoesters compounds. A possible reaction pathway is suggested. 相似文献
33.
Enza Di Gregorio Luciano Lattuada Alessandro Maiocchi Silvio Aime Giuseppe Ferrauto Eliana Gianolio 《Chemical science》2021,12(4):1368
The set-up of reversible binding interactions between the hydrophobic region of macrocyclic GBCAs (Gadolinium Based Contrast Agents) and SO3−/OH containing pyrene derivatives provides new insights for pursuing relaxivity enhancements of this class of MRI contrast agents. The strong binding affinity allows attaining relaxation enhancements up to 50% at pyrene/GBCA ratios of 3 : 1. High resolution NMR spectra of the Yb-HPDO3A/pyrene system fully support the formation of a supramolecular adduct based on the set-up of hydrophobic interactions. The relaxation enhancement may be accounted for in terms of the increase of the molecular reorientation time (τR) and the number of second sphere water molecules. This effect is maintained in blood serum and in vivo, as shown by the enhancement of contrast in T1w-MR images obtained by simultaneous injection of GBCA and pyrene derivatives in mice.The set-up of reversible binding interactions between the hydrophobic region of macrocyclic gadolinium based contrast agents and SO3−/OH containing pyrene derivatives provides new insights for pursuing relaxivity enhancement of MRI contrast agents. 相似文献
34.
Raffaele P. Bonomo Vincenzo Cucinotta Franca D' Allessandro Giuseppe Impellizzeri Giuseppe Maccarrone Enrico Rizzarelli Graziella Vecchio 《Journal of inclusion phenomena and macrocyclic chemistry》1993,15(2):167-180
The functionalized cyclodextrin 6-deoxy-6-[1-(2-amino)ethylamino]--cyclodextrin was synthesized, and an NMR, EPR, pH-metric, and calorimetric investigation was carried out in aqueous solution in order to ascertain its behaviour towards protonation and copper(II) complex formation. The thermodynamic parameters of the ternary complex formation with alanine, phenylalanine and tryptophan enantiomeric pairs were also determined (25° C andI=0.1 mol dm–3). No thermodynamic enantioselectivity was observed in these systems, while a chiral, though poor, discrimination was observed in LEC: c.d. spectra also show enantiomeric stereoselectivity. The results of the present investigation, compared with previously reported results, suggest the occurence of acis-complex trans-complex equilibrium in such systems. 相似文献
35.
Tedesco E Della F Favaretto L Barbarella G Albesa-Jové D Pisignano D Gigli G Cingolani R Harris KD 《Journal of the American Chemical Society》2003,125(40):12277-12283
The "rigid-core" material 3,5-dimethyl-2,3'-bis(3-methylthiophene)-dithieno[3,2-b:',3'-d]thiophene-4,4-dioxide (DTTOMe4) has the highest photoluminescence ever reported for thiophene-based molecules in the solid state. We report the structure of this material, determined directly from powder X-ray diffraction data using the Genetic Algorithm method for structure solution, followed by Rietveld refinement, and the structural properties are discussed in relation to the structures of the corresponding subsystems DTTO and DTTOMe. While the crystal structures of the latter compounds contain cofacial dimers, the crystal structure of DTTOMe4 comprises layers of molecules aligned in an antiparallel fashion. Intermediate neglect of differential overlap with single configuration interaction (INDO/SCI) calculations on the intermolecular interactions in the three crystal structures show that the different solid-state photoluminescence efficiencies of DTTOMe4, DTTOMe, and DTTO cannot be correlated with the different types of dipole-dipole alignment in the solid state. Instead, photoluminescence efficiencies correlate well with the rate of formation of nonradiatively decaying charge-transfer pairs upon photoexcitation. Because of larger intermolecular distances in DTTOMe4, the photoluminescence is less effectively quenched by charge-transfer processes than in DTTOMe and DTTO. 相似文献
36.
PHOTOCHEMISTRY and PHOTOBIOLOGY WITHOUT LIGHT 总被引:3,自引:0,他引:3
Abstract— This review covers the literature since 1980 on chemically and enzymatically generated electronically excited species. The emphasis lies on triplet states of carbonyl products that are derived from dioxetanes and dioxetanones as precursors or from suitable enzymatic oxygenations. Singlet oxygen, an important excited state species in biological processes, is not explicitly treated. The utilization of triplet excited carbonyl products to promote photochemical and photobiological transformations by energy transfer are of primordial interest and not the photomechanistic behavior, photophysical properties and inherent photochemical reactions of such excited state species. Thus, the coverage concentrates on photodamage of DNA and RNA, the photochemistry of flavins, vitamin D, tryptophan, arachidonic acid, chlorophyll, lipid peroxidation, urocanase activation, excitation of chlorophlasts, and the aerobic oxidation of Schiff bases derived from amino acids and proteins. The potential perspectives of employing authentic dioxetanes and enzymatically generated dioxetane intermediates as effective photon equivalents in photochemotherapy, phototoxicity, photoaffinity labeling and photogenotoxicity are pointed out, in the hope of stimulating more intensive activity in this emerging and novel bioorganic and photobiological field. 相似文献
37.
Gualtiero Plazzogna Valerio Peruzzo Giuseppe Tagliavini 《Journal of organometallic chemistry》1973,60(2):229-232
The reaction between pentadeuteriophenyllithium and hexaphenyldilead combined with new measurements of isotopic exchange between Ph6Pb2 (labelled with RaD) and Ph4Pb, have shown that the dilead compound is undissociated in solution. These results cast doubt upon the previously reported equilibrium: Ph6Pb2Ph4Pb+Ph2Pb. 相似文献
38.
Graziano Guella Ines Mancini Giuseppe Chiasera Francesco Pietra 《Helvetica chimica acta》1992,75(1):310-322
39.
40.
Graziano Guella Giuseppe Chiasera Ibrahima N'Diaye Francesco Pietra 《Helvetica chimica acta》1994,77(5):1203-1221
Kinetic and equilibrium studies show that typical xenicanes such as dictyolactone ( 1 ) and 4-hydroxydictyolactone ( 3 ) undergo slow conformation medium-ring flipping between the predominant trans-( 1a or 3a ; Me(20) trans to H–C(3)) and the minor cis-conformers ( 1b or 3b ; Me(20) cis to H–C(3); see Scheme 1). The formation of the latter is inhibited in heterocyclic-ring-opened congeners such as 18-acetoxy-4-hydroxydictyo-19-al ( 7 ). Molecular-mechanics calculations suggest that typical-xenicane cis-conformers are disfavoured by mainly C(4)–C(5) torsional strain. This is confirmed by the observation of two sizably populated cis-and trans-conformers for the unnatural 4-oxoxenicanes 10–12 . Unusually facile thermal (E)→(Z) isomerization of xenicanes 1,3,10–12 , and 7 is also observed (→ 13–17 and 9 , resp.; Scheme 3), reflecting great strain relief in the transition state. Conflicting results in the literature now fit into this scheme which provides a basis for unravelling recognition phenomena with these biologically active systems. 相似文献