32‐Hetero‐5,6‐dimethoxyphenanthrisapphyrins—macrocycles that link structural features of polycylic aromatic hydrocarbons and expanded porphyrins—were obtained in a straightforward [3+1] condensation reaction of dimethoxyphenanthritripyrrane and 2,5‐bis(arylhydroxymethyl)heterocyclopentadienes. The highly folded conformation of formally 4 n π‐electron macrocycles causes them to manifest only limited macrocyclic π conjugation as explored by means of NMR spectroscopic and X‐ray structural analyses, and supported by DFT calculations. Although protonation does not change their π‐conjugation characteristics, the cleavage of ether groups at the phenanthrenylene moiety yields nonaromatic 32‐hetero‐5,6‐dioxophenanthrisapphyrins. 相似文献
In the paper we consider the Bessel differential operator in half‐line , , and its Dirichlet heat kernel . For , by combining analytical and probabilistic methods, we provide sharp two‐sided estimates of the heat kernel for the whole range of the space parameters and every , which complements the recent results given in 1 , where the case was considered. 相似文献
Preparation of 1-(4-hydroxy-iminomethylpyridinium)-3-pyridiniumpropane dibromide is described. This compound represents a new acetylcholinesterase (AChE) reactivator, which has no substituents on the second pyridinium ring as found in other commonly used AChE reactivators. The reactivation ability of this reactivator was tested on tabun- and cyclosarin-inhibited AChE. According to the results obtained, the new compound (without substitution and with decreased molecule size) showed increased reactivation potency in case of cyclosarin inhibited AChE. A potent oxime for treatment of tabun and cyclosarin-caused intoxications was thus obtained via slight modification of the reactivator structure (compared to trimedoxime and K027). 相似文献
Dioleoylphosphatidylcholine unilamellar vesicles made by extrusion technique (LUVETs) were studied as the delivery system for lipophilic water-insoluble potential photosensitizers for photodynamic therapy (PDT). Two azaphthalocyanines (AzaPcs) with hydrophobic substituents only and two also possessing two charged amino groups were introduced into the study. All compounds are insoluble in water and form aggregates in PBS with tetrahydrofuran as cosolvent. The size of these aggregates depends on the concentration of AzaPc in solution. AzaPcs with tert-butyl substituents were found to be incorporated into the lipid bilayer of vesicles in the monomeric form even at high concentrations. The stability of LUVETs with incorporated AzaPc was excellent for at least 4 weeks. Therefore, they are suitable for use as a delivery system for these water-insoluble photosensitizers. Very low amount of AzaPc with n-octyl substituents incorporated into LUVETs due to its stronger self-aggregation. Values of binding constants determined for all AzaPcs showed inverse order than expected from their lipophilicities. However, the binding constants followed the order of the strength of aggregation forces. Aggregation of AzaPcs in water medium plays a very important role in the interaction of AzaPcs with LUVETs. 相似文献
The efficient and straightforward NHC-rhodium-catalyzed thiol-silane and thiol-germanane coupling reactions, leading to new classes of functionalized SQ-based materials, are presented for the first time. The proposed strategies use commercially available reagents and show a broad functional groups tolerance, which opens a possibility of effective synthetic procedures of biologically active compounds. 相似文献
A novel, 100% water-soluble chalcone based chemosensing receptor {1-[3-(2-Hydroxy-phenyl)-3-oxo-propenyl]-naphthalen-2-yloxy}-acetic acid, L was synthesized and characterized. The receptor L is designed based on the chelation enhanced fluorescence (CHEF) mechanism. The chemosensing properties of L were evaluated by UV–vis and fluorescence spectrometric methods. It exhibits highly selective recognition ability towards aluminum ions in water over other metal ions. The binding stoichiometry of L? Al3+ complex is 2:1 by means of Job’s plot and the detection limit is 5.66?×?10??8 M. 相似文献
Three tetracationic porphyrins differing in the position of charged nitrogen atoms on the peripheral substituents — 5,10,15,20-tetrakis(N-methylpyridinium-4-yl)porphyrin (TMPyP4), 5,10,15,20-tetrakis(N-methylpyridinium-2-yl)porphyrin (TMPyP2), 5,10,15,20-tetrakis(4-trimethylammoniophenyl) porphyrin (TMAPP), and hydrophobic 5,10,15,20-tetraphenylporphyrin (TPP), were immobilized by adsorption
and encapsulation in poly(hydroxymethylsiloxane) (PHOMS). The so prepared porphyrin-PHOMS composites were characterized by
porosimetry, scanning electron microscopy, fluorescence and diffuse reflectance UV-VIS spectroscopy. It was found that porphyrins
are immobilized in the PHOMS matrix in the free base monomer form Their irradiation produced singlet oxygen O2(1Δg) with the lifetime of 10–30 μs. 相似文献
The interaction between bis(hexadecyldimethylammonium)hexane dibromide (16-6-16), bis(tetradecyldimethylammonium)hexane dibromide (14-6-14), their conventional counterparts cetyltrimethylammonium bromide (CTAB) and tetradecyltrimethylammonium bromide (TTAB) with polyvinylpyrrolidone (PVP) was investigated using the conductivity technique. The results show that gemini surfactants interact strongly with PVP as compared to conventional surfactants. The results also reveal that the surfactants with shorter hydrocarbon chain interact weakly as those of longer hydrocarbon chain. The interactions of 16-6-16 and 14-6-14 and their conventional counterparts with PVP were also studied using dynamic light scattering (DLS) measurements. We have also highlighted the effect of surfactant–polymer interactions on the dispersion force in the solution. Critical aggregation concentration (cac) and critical micelle concentration (cmc) were obtained using the conductivity data. The degrees of micelle ionization and free energies associated with aggregation, micellization, and transfer have also been evaluated and discussed. 相似文献
Click to view : Glycopolymers can be used to display glycans on microarrays in native‐like architectures. The structurally uniform alkyne‐terminated mucin mimetic glycopolymers (see picture; TR=fluorophore) were printed on azide‐functionalized chips by microcontact printing in the presence of a copper catalyst. The surface‐bound glycopolymers bind lectins in a ligand‐specific manner.