Deposition and release of chlorhexidine from non-ionic and anionic polymer matrices

Therapeutic activity of locally applied drugs depends on both the thermodynamic activity of the active molecule and the pharmaceutical system which enables the release of the molecule; also the vasoconstrictive activity of vessels plays an important role. In this study, the release of chlorhexidine was assessed considering the use of ionic and non-ionic polymeric carriers at temperatures in the range between 22°C and 42°C, including the temperature of 32°C as the reference surface body temperature. The obtained release rates and concentrations of chlorhexidine, loaded to methylcellulose and poly(acrylic acid) gels, were compared with respective viscositiy, pH, and conductivity of the assessed systems. The deposition patterns of chlorhexidine in the polymeric matrix were studied using energy dispersive X-ray spectrometry to evaluate the possible influence of chlorhexidine distribution in/on the carrier on the respective release rates. This study is significant for patients with various skin temperature conditions, who are required to receive local biocides applied on skin or into the oral cavity. The obtained precipitate of polyacrylic acid-chlorhexidine preparation was extensively studied to evaluate the chlorhexidine release and to develop an application in skin and dental care.     

Charge-transfer photolysis of copper(II) dithiocarbamate mixed-ligand complexes in toluene/alcohol solutions

Charge-transfer (CT)-photolysis of Cu(II) dithiocarbamate mixed-ligand complexes Cu(II)(Et2dtc)X (X = Cl-, Br-) and Cu(II)(Et2dtc)(+)...Y- (Y = ClO4-, NO3-) has been studied in toluene/ROH and compared with our previous data obtained in chloromethane/ROH solutions, where chloromethane = CCl4, CHCl3 or CH2Cl2 and ROH = MeOH, EtOH, i-PrOH or i-BuOH. An EPR evidence is obtained about the formation of a new copper(II) dithiocarbamate mixed-ligand complex during simultaneous photolyses of Cu(II)(Et2dtc)+ and Cu(II)(Et2dtc)2 species in toluene/ROH. The role of the solvent is discussed from the combined analysis of spectrophotometric and EPR data and quantum yield results.     

Molecular basis of Celmer's rules: stereochemistry of catalysis by isolated ketoreductase domains from modular polyketide synthases

A system is reported for the recombinant expression of individual ketoreductase (KR) domains from modular polyketide synthases (PKSs) and scrutiny of their intrinsic specificity and stereospecificity toward surrogate diketide substrates. The eryKR(1) and the tylKR(1) domains, derived from the first extension module of the erythromycin PKS and the tylosin PKS, respectively, both catalyzed reduction of (2R, S)-2-methyl-3-oxopentanoic acid N-acetylcysteamine thioester, with complete stereoselectivity and stereospecificity, even though the substrate is not tethered to an acyl carrier protein or an intact PKS multienzyme. In contrast, and to varying degrees, the isolated enzymes eryKR(2), eryKR(5), and eryKR(6) exercised poorer control over substrate selection and the stereochemical course of ketoreduction. These data, together with modeling of diketide binding to KR(1) and KR(2), demonstrate the fine energetic balance between alternative modes of presentation of ketoacylthioester substrates to KR active sites.     

Invertible bimodule categories over the representation category of a Hopf algebra

For any finite-dimensional Hopf algebra H   we construct a group homomorphism BiGal(H)→BrPic(Rep(H))$\mathrm{BiGal}(H)\to \text{BrPic}(\mathrm{Rep}(H))$, from the group of equivalence classes of H  -biGalois objects to the group of equivalence classes of invertible exact Rep(H)$\mathrm{Rep}(H)$-bimodule categories. We discuss the injectivity of this map. We exemplify in the case H=_Tq$H=T_q$ is a Taft Hopf algebra and for this we classify all exact indecomposable Rep(_Tq)$\mathrm{Rep}(T_q)$-bimodule categories.     

A Sequence to Compute the Brauer Group of Certain Quasi-Triangular Hopf Algebras

A deeper understanding of recent computations of the Brauer group of Hopf algebras is attained by explaining why a direct product decomposition for this group holds and describing the non-interpreted factor occurring in it. For a Hopf algebra B in a braided monoidal category ${{\mathcal C}}$ , and under certain assumptions on the braiding (fulfilled if ${{\mathcal C}}$ is symmetric), we construct a sequence for the Brauer group ${{\rm{BM}}}({{\mathcal C}};B)$ of B-module algebras, generalizing Beattie’s one. It allows one to prove that ${{\rm{BM}}}({{\mathcal C}};B) \cong {{\rm{Br}}}({{\mathcal C}}) \times {\operatorname{Gal}}({{\mathcal C}};B)$ , where ${{\rm{Br}}}({{\mathcal C}})$ is the Brauer group of ${{\mathcal C}}$ and ${\operatorname{Gal}}({{\mathcal C}};B)$ the group of B-Galois objects. We also show that ${{\rm{BM}}}({{\mathcal C}};B)$ contains a subgroup isomorphic to ${{\rm{Br}}}({{\mathcal C}}) \times {\operatorname{H^2}}({{\mathcal C}};B,I),$ where ${\operatorname{H^2}}({{\mathcal C}};B,I)$ is the second Sweedler cohomology group of B with values in the unit object I of ${{\mathcal C}}$ . These results are applied to the Brauer group ${{\rm{BM}}}(K,B \times H,{{\mathcal R}})$ of a quasi-triangular Hopf algebra that is a Radford biproduct B × H, where H is a usual Hopf algebra over a field K, the Hopf subalgebra generated by the quasi-triangular structure ${{\mathcal R}}$ is contained in H and B is a Hopf algebra in the category ${}_H{{\mathcal M}}$ of left H-modules. The Hopf algebras whose Brauer group was recently computed fit this framework. We finally show that ${{\rm{BM}}}(K,H,{{\mathcal R}}) \times {\operatorname{H^2}}({}_H{{\mathcal M}};B,K)$ is a subgroup of ${{\rm{BM}}}(K,B \times H,{{\mathcal R}})$ , confirming the suspicion that a certain cohomology group of B × H (second lazy cohomology group was conjectured) embeds into it. New examples of Brauer groups of quasi-triangular Hopf algebras are computed using this sequence.     

EPR study on the photoinduced electron transfer in the ternary complex (dithiocarbamato,dithiophosphato)copper(II)

The EPR study on equimolar solutions of Cu(dtc)₂ and Cu(dtp)₂ in aerated acetone, toluene and chloroalkane (CHCl₃ and CCl₄) solutions indicates that Cu(dtc)(dtp) is the only complex species present in solution. The analysis of the EPR spectra recorded after photo-irradiation in aerated acetone solutions enables the characterization of the intermediate paramagnetic species and provides a reasonable explanation.     

Colloid-chemical processes in the growth and design of the bio-inorganic aragonite structure in the scleractinian coral Cladocora caespitosa

This study describes the morphological properties and discusses the colloid-chemical mechanisms of the formation of hierarchically structured aragonite fibers in the exoskeleton structure of the Mediterranean zooxanthellate scleractinian coral Cladocora caespitosa. The study is based on a detailed structural and morphological examination of the coral exoskeleton and on a preliminary biochemical and molecular identification of the isolated soluble proteinaceus organic matrix. The biomineral structure was examined by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM) and atomic-force microscopy (AFM), while the isolated protein organic constituents were analyzed by sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) and mass spectrometry (MALDI-TOF-MS). The SDS-PAGE analysis of the soluble protein matrix showed three major protein bands at 15, 41, and 80kDa. Based on the MALDI-TOF-MS analyses, the identified peptides tend to exhibit an acidic character. The results obtained confirm and complement the existing hypotheses relating to the significant role of the soluble acidic protein matrix and the biologically induced colloid-chemical processes in the phase formation and growth of scleractinian submicrometer fibrous aragonite units. It was also shown that the general strategy for the morphogenesis of fibrous structured aragonite lies in the nanoscale aggregation and subsequent coalescence processes that occur simultaneously. The subsequent morphological conversion of the initially formed submicrometer fibrous aragonite units into well-defined, micrometer-sized, prismatic facets in the skeletal structures of the corals is demonstrated.     

Bismuth titanate thin films prepared by wet-chemical techniques: effect of sol ageing time

In this work, layered perovskite bismuth titanate (Bi₄Ti₃O₁₂) thin films were fabricated on α-alumina substrates by spin coating process. Precursor sol was prepared by sol–gel process from bismuth nitrate and titanium butoxide in concentrated acetic acid, with diethylamine as a stabilizer. Processes occurring in the precursor sol were followed in the ageing period of 20 days. Thin films prepared from the as-synthesized and aged sols are crack-free, with the thickness of ~1 μm, uniform surface texture and rounded grains having grain size in nanometer range. Sintering of thin films was performed at various temperatures, and sintered thin films exhibited dense structure, fully crystallized with typical Aurivillius phase and without any preferred orientation and impurity phase. The influence of ageing of the precursor sol on the microstructure of obtained thin films was also investigated. Direct relation between hydrodynamic diameter of precursor particles and the morphology and the grain size of the obtained films was observed.     

Sintered Silicon Carbide: A New Ceramic Vessel Material for Microwave Chemistry in Single‐Mode Reactors

Silicon carbide (SiC) is a strongly microwave absorbing chemically inert ceramic material that can be utilized at extremely high temperatures due to its high melting point and very low thermal expansion coefficient. Microwave irradiation induces a flow of electrons in the semiconducting ceramic that heats the material very efficiently through resistance heating mechanisms. The use of SiC carbide reaction vessels in combination with a single‐mode microwave reactor provides an almost complete shielding of the contents inside from the electromagnetic field. Therefore, such experiments do not involve electromagnetic field effects on the chemistry, since the semiconducting ceramic vial effectively prevents microwave irradiation from penetrating the reaction mixture. The involvement of electromagnetic field effects (specific/nonthermal microwave effects) on 21 selected chemical transformations was evaluated by comparing the results obtained in microwave‐transparent Pyrex vials with experiments performed in SiC vials at the same reaction temperature. For most of the 21 reactions, the outcome in terms of conversion/purity/product yields using the two different vial types was virtually identical, indicating that the electromagnetic field had no direct influence on the reaction pathway. Due to the high chemical resistance of SiC, reactions involving corrosive reagents can be performed without degradation of the vessel material. Examples include high‐temperature fluorine–chlorine exchange reactions using triethylamine trihydrofluoride, and the hydrolysis of nitriles with aqueous potassium hydroxide. The unique combination of high microwave absorptivity, thermal conductivity, and effusivity on the one hand, and excellent temperature, pressure and corrosion resistance on the other hand, makes this material ideal for the fabrication of reaction vessels for use in microwave reactors.