Two hybrid systems based on oxygen-free graphene and AlCl- and Zn-phthalocyanines have been synthesized in aqueous-organic medium and comparatively studied by optical absorption method. N,N-Dimethylformamide was used as an organic solvent. It has been shown that the presence of oxygen-free graphene in the systems prevents the aggregation of phthalocyanines in aqua medium and contributes to their stabilization in monomeric form. The stability of the resulting hybrid complexes as well as the binding capacity of the components of the systems has been evaluated. The mechanisms of phthalocyanines and oxygen-free graphene interaction in aqueous-organic medium have been proposed.
The preparation method of porphyrin-polymer system -hemin-poly(3-hydroxybutyrate) (hemin-PHB) and its inhibitory effect on the growth of Gram-negative and Gram-positive microorganisms -Escherichia coli and Staphylococcus aureus, which are the common cause of wound infections, are presented. The assessment of antimicrobial activity was carried out by measuring of the inhibition zone diameters after bacterial daily incubation. It was shown that hemin-PHB efficiency was directly related to the hemin concentration. Thus, PHB containing 5% hemin (wt. %) inhibited E. coli and S. aureus significantly. The obtained porphyrin-polymer system can be recommended for use as the antiseptic material for wound treatment.
The process of aluminum phthalocyanine chloride (AlClPc) aggregation in water and water-organic media was studied both by quantum mechanical theoretical calculations and experimental methods of optical absorption and fluorescence spectroscopy. The structures of AlClPc in the monomeric and dimerized (H- and J-aggregates) states in the gas phase and in both N,N-dimethylformamide (DMF) and DMF-water binary solution were calculated by the electron density functional theory (DFT) method. The absorption and fluorescence spectra of these structures were calculated in time-dependent electron DFT approximation. Comparing all data obtained, conclusions about the change in the aggregation state of AlClPc were drawn. Results demonstrate depending AlClPc photophysical parameters on its monomer/dimer ratio in solution, which is determined by concentration of the dye and water in the system. The experimental results obtained for water-organic medium indicate the existence of a critical water concentration (~ 7.8 %), at which the ratio of monomers and dimers (J-aggregates) of AlClPc changes dramatically. In AlClPc-DMF system the dye is completely in monomeric form. The results of the study make it possible to predict the aggregation behavior of AlClPc complexes in water-organic media, as well as to control and manage their aggregation behavior.
Recently, it has become more and more obvious that the use of the unique physical properties of graphene is practically inexhaustible. In our work, we used the surface of oxygen-free graphene sheets to stabilize the AlClPc complex and prevent its agglomeration. A sonochemical method was developed for the preparation of stable suspensions of oxygen-free graphene in a DMF-aqua mixture, the composition and morphology of which were characterized using TEM, DLS, and Raman. Also, a method for the synthesis of hybrid structures based on AlClPc and graphene was developed, and new electrons interactions in them were determined by using of UV-VIS absorption spectroscopy. It was proved that these interactions are due to the graphene participation in surface complex with charge transfer. Graphene also prevents the agglomeration of the AlClPc complex, which is especially valuable for using the synthesized structure in biomedical research. The results obtained show how the use of molecular design techniques makes it possible to create new platforms for vector drag delivery and early diagnosis.
This paper analyzes the state of production of carbon fiber (CF) materials, including pitch-based CFs. It is shown that in Russia there is a significant potential for industrial production of pitch-based CFs. Considerable attention is paid to possible ways of modifying pitch-based CFs in order to improve their electrical properties. The efficiency of using gaseous bromine to reduce the electrical resistance of pitch-based CFs is shown. Based on the analysis of X-ray and Raman spectroscopy data, it is shown that a 7-fold decrease in electrical resistance during bromination is related to changes in the fiber structure.
We have obtained a new water-soluble form of boron(III) dipyrromethene luminophores using the example of 3,3',5,5'-tetraphenyl- ms -aza-2,2'-dipyrromethenate boron(III) (BODIPY) and Cremophor® (polyethylene glycol, PEG-40). The results of a study of the spectral-luminescent properties of the studied BODIPY–Cremophor®–aqueous–alcohol medium system are presented. It is found that Cremophor® is the only one of a series of investigated excipients (PEG-400, PEG-1000, polyvinylpyrrolidone, bovine serum albumin, sodium carboxymethylcellulose) providing solubilization of BODIPY in an aqueous medium, while maintaining its intense spectral characteristics, including fluorescence and luminophore, in the red region of the spectrum. The BODIPY–Cremophor® system is tested on two mouse cell lines: metastatic breast cancer and non-metastatic skin cancer. It is shown that the introduction of the BODIPY–Cremophor® system into both cell lines of mice leads to the detachment of cell cultures from the substrate and suppression of the development of cancerous tumors. The results obtained show that immobilization of BODIPY in PEG-40 in an aqueous-alcoholic medium makes it possible to obtain preparations with prolonged action, which can be used as photosensitizers (PSs) in photodynamic therapy and for bioimaging in cell biology.
In pure DMF, the graphene layering is mainly limited to 5 layers; in the aqua presence, partial association of the lightest graphene sheets with the highest surface energy occurs.
The synthesis methods as well as the data of spectral fluorescent properties of novel supramolecular systems based on chlorin e(6) (Ce-6) are presented. The effect of various biocompatible excipients such as hydrolyzed polyvinyl alcohol (PVP), potv-N-vinylpyrrolidone (PVP), sodium salt of carboxymethyl cellulose (Na-KMC), dimethylsulfoxide (DMSO), Cremophor (R) PEG-40 (PEG) on the optical absorption and fluorescence of chlorin e(6) is demonstrated. A red shift of the chlorin e(6) absorption spectrum when using all presented here excipients is a good prerequisite for increasing tissue permeability for visible light. The fluorescence quantum yield phi(k) of chlorin e(6) in systems with all excipients has been calculated. It has been proven, that in all obtained biocompatible systems, except DMSO - Ce-6 system, Ce-6 molecules disaggregate and charge transfer complexes "excipient - Ce-6" are formed. The high efficiency of such systems as PEG - Ce-6, PVP - Ce-6 and Na-KMC - Ce-6 for fluorescent diagnosis and photodynamic therapy is noted. The conclusions made in the work can be useful during the new photosensitizer controlled aggregation method development.
The spectral luminescent and electrophysical properties of polymer films based on poly-N-vinylpyrrolidone with the stabilized derivatives of tetraphenylporphyrin in various aggregation states (monomers, J- and H-aggregates) were investigated. Films containing a monomolecular form of porphyrins are characterized by intensive fluorescence. For films with J-aggregates an electric response that was not practically observed in the case of H-aggregates was detected. The films obtained are also characterized by optical and electric response to pH change, particularly in the presence of ammonia and hydrogen chloride vapors. The obtained data allow polymeric films with immobilized porphyrins to be considered as potential material for the creation of film systems for sensor applications, photovoltaics, molecular electronics, and photocatalysis. The variability of the film synthesis methodology allows the aggregation state of the immobilized porphyrins to be changed directionally, which provides the possibility of obtaining films of hybrid organic materials with the desired photophysical properties.
New hybrid graphene and aluminum phthalocyanine structures are synthesized (graphene is prepared with the sonochemical method in N,N-dimethylformamide). The physicochemical properties of these hybrid systems are studied with transmission electron microscopy, Raman spectroscopy, and optical spectroscopy. We show that graphene in the system prevents the aggregation of aluminum phthalocyanine and leads to its stabilization in monomeric form. The results may be used to obtain new materials for various sciences and technologies.
The present study was undertaken to investigate and characterize the structure, the electrical conductivity in the temperature range 10-300 K, thermogravimetric analysis (TGA) data and micro-Raman spectroscopy data of pitch-based graphite fibers during the bromination process. All the results are explained by the structural changes, the appearance of bromine in two main states, namely, as an intercalated bromine and as a bromine bound to the carbon network by a C-Br bond, by the degradation of graphite network and by the growth of the content of the amorphous phase during the bromination.
The effect of the filler content on the optical absorption spectra, electroconductivity, and surface morphology of thin nanoocomposite films based on poly( n -xylylene)–tin (PPX–Sn) has been studied. The films under study are prepared in vacuum by cryochemical synthesis on polished quartz, glass-ceramics, and silicon substrates. After completing the preparation, the samples are exposed to air for some time prior to measurements. With an increase in the filler content, a nonmonotonic change in both surface morphology of films (by atomic force microscopy) and adsorption spectra is found. An analysis of the spectra shows that, at the filler concentration C ≤ 9 vol %, tin in the composite is in the oxidized form of SnO 2 , while at C = 12 vol % it is in a metal state, respectively. With an increase in C from 4 to 12 vol %, the increase in conductivity of nanocomposites is more than 7 decimal orders, with a sharp change in the region of C ≈ 9–12 vol %. The conductivity of the film consisting of nanoparticles ( C = 100 vol %) is found to be low and comparable with that for composites with C = 4–5 vol %. With a decrease in the temperature from 300 to 15 K, the resistance of the sample with C = 12 vol % is found to decrease, while that for all other samples increases by the activation law. The activation energy with an increase in the filler concentration to 9 vol % is found to decrease, while that for the sample with C = 100 vol % increases by almost an order of magnitude. The most significant changes in the properties and morphology of the surface of nanocomposites are observed at a concentration of ~9 vol %, which apparently is the percolation threshold.
The spectral-fluorescent properties of various supramolecular systems based on chlorin e 6 (Ce 6 ) are determined to facilitate the development of new medicines for photodynamic therapy and diagnostics. The effect of various excipients, such as poly- N -vinylpyrrolidone (PVP), polyethylene glycol (PEG), bovine serum albumin (BSA), chitosan, Triton X-100 (TX-100), sodium hexametaphosphate (SHMP), and poly(dimethyldiallylammonium chloride) chloride (PDDAC), on the optical absorption and fluorescence of Ce 6 is demonstrated. In the Ce 6 −PVP, Ce 6 −PEG, Ce 6 −BSA, Ce 6 −TX-100, Ce 6 −SHMP, and Ce 6 −PDDAC systems, Ce 6 molecules are disaggregated and complexes thereof with excipients are formed. The quantum yield of Ce 6 fluorescence in supramolecular systems is close to that of the free-form photosensitizer, in the absence of excipients. The results suggest that supramolecular complexes of Ce 6 are promising for the development of medicines with controllable photodynamic activity.
The novel supramolecular systems based on chlorine e 6 (Ce 6 ) are presented, and their optical absorption and fluorescence have been investigated. The influence of different excipients as poly-N-vinylpyrrolidone (PVP), polyethyleneglycol (PEG), bovine serum albumin (BSA), chitosan, Triton X-100 (TX-100) on spectral characteristics of these systems has been studied. The obtained spectral-fluorescence characteristics of Ce 6 -PVP, Ce 6 -PEG, Ce 6 -BSA, Ce 6 -TX-100 indicate disaggregation of chlorine e 6 molecules and their consecutive interaction with excipients in solutions and formation of molecular associates and molecular complexes. The system Ce 6 -chitosan is characterized by aggregation of pigments in solution that reduces photochemical activity of a photosensitizer. The fluorescence quantum yield j k of mentioned above supramolecular systems has been calculated. The results can be useful during the new method of controlled aggregation of photosensitizers as a part of supramolecular complexes development as well as for the purposes of new medicines of predictable photodynamic activity creation.