Processing and Properties of Nanofibrous Bacterial Cellulose-Containing Polymer Composites: A Review of Recent Advances for Biomedical Applications

Abstract

Bacterial cellulose (BC) is an extracellular natural polymer produced by many microorganisms and its properties could be tailored via specific fabrication methods and culture conditions. There is a growing interest in BC derived materials due to the main features of BC such as porous fibrous structure, high crystallinity, impressive physico-mechanical properties, and high water content. However, pristine BC lacks some features, limiting its practical use in varied applications. Thus, fabrication of BC composites has been attempted to overcome these constraints. This review article overviews most recent advance in the development of BC composites and their potential in biomedicine including wound dressing, tissue engineering scaffolds, and drug delivery. Special emphasis is placed on the fabrication and applications of BC-containing nanofibrous composites for biomedical usage. It summarizes electrospinning of BC-based nanofibers and their surface modification with an outline on challenges and future perspective.     

An unprecedented highly efficient solvent-free oxidation of alkynes to α,β-acetylenic ketones with tert-butyl hydroperoxide catalyzed by water-soluble copper complex

The catalytic system composed of CuCl₂ and 2,2′-biquinoline-4,4′-dicarboxylic acid dipotassium salt (BQC) was found to be highly efficient for the selective α-oxidation of internal alkynes to the corresponding α,β-acetylenic ketones, with aqueous tert-butyl hydroperoxide under mild conditions. For the first time, full conversions of alkynes were reached with excellent selectivities, and propargylic tert-butylperoxy ethers were observed and suggested as the reaction intermediates. In the case of terminal alkynes, the oxidations are sluggish and low yields ranging from 32% to 40% were obtained.     

正己烷在Pt-Ce促进的氧化硅担载的杂多酸金属氧酸盐上的异构化

制备了用于正己烷临氢异构化的氧化硅担载的Keggin型杂多酸和还原态Pt-Ce氧化物催化剂.这些混合氧化物催化剂或单独使用,或与氧化硅担载的杂多酸催化剂一起使用.用X射线衍射、傅里叶变换红外光谱、傅里叶变换拉曼光谱、热重和N2物理吸附等方法表征在氧化、还原态和催化实验后的催化剂状态.本文的目的是在最佳反应条件(反应温度、还原温度和流量等)下,筛选出具有最好异构化收率的催化剂.结果表明,还原氧化物的存在不但有利于消除积炭,而且在反应期间能有效地维持氧化硅担载杂多酸的结构.从这些催化剂样品中,可以找到具有更好异构化活性和选择性的催化剂.     

Regioselective bond cleavage in the dissociative electron transfer to benzyl thiocyanates: the role of radical/ion pair formation

Important aspects of the electrochemical reduction of a series of substituted benzyl thiocyanates were investigated. A striking change in the reductive cleavage mechanism as a function of the substituent on the aryl ring of the benzyl thiocyanate was observed, and more importantly, a regioselective bond cleavage was encountered. A reductive alpha-cleavage (CH(2)-S bond) was seen for cyano and nitro-substituted benzyl thiocyanates leading to the formation of the corresponding nitro-substituted dibenzyls. With other substituents (CH(3)O, CH(3), H, Cl, and F), both the alpha (CH(2)-S) and the beta (S-CN) bonds could be cleaved as a result of an electrochemical reduction leading to the formation of the corresponding substituted monosulfides, disulfides, and toluenes. These final products are generated through either a protonation or a nucleophilic reaction of the two-electron reduction-produced anion on the parent molecule. The dissociative electron transfer theory and its extension to the formation/dissociation of radical anions, as well as its extension to the case of strong in-cage interactions between the produced fragments ("sticky" dissociative electron transfer (ET)), along with the theoretical calculation results helped rationalize (i) the observed change in the ET mechanism, (ii) the dissociation of the radical anion intermediates formed during the electrochemical reduction of the nitro-substituted benzyl thiocyanates, and more importantly (iii) the regioselective reductive bond cleavage.     

Utility of 2‐[4‐(3‐oxobenzo[f]‐2H‐chromen‐2‐yl)‐1,3‐thiazol‐2‐yl]ethanenitrile in heterocyclic synthesis

Pyrazolo[4,3‐d]pyrimidines, pyrazolo[4,3‐d]triazolino[4,3‐a]pyrimidines, 3‐(2‐thiazolyl)thiophenes, thiazolo[3,2‐a]pyridine and pyrazolo[1,5‐a]pyrimidines were synthesized from 2‐[4‐(3‐oxobenzo[f]‐2H‐chromen‐2‐yl)‐1,3‐thiazol‐2‐yl]ethanenitrile. The newly synthesized compounds were elucidated by elemental analysis, spectral data, chemical transformation and alternative synthesis route whenever possible.     

Hydroformylation of Olefins Catalyzed by Rhodium Trichloride Anchored on Ti-HMS

Rhodium trichloride supported on Ti-hexagonal mesoporous silica (Ti-HMS), via a bipyridyl group, is an efficient catalyst for the hydroformylation of olefins at 120 °C and 40.8 atm of CO/H₂ (CO/H₂=2/1). The catalyst is selective leading to high ratios of linear or branched aldehydes from functionalized olefins, and high activity in the case of propene which gave a turnover frequency of 6209 mol/mol(Rh)/h.     

Water increases rates of epoxidation by Mn(III)porphyrins/imidazole/IO4(-) in CH2Cl2. Analogy with peroxidase and chlorite dismutase

Manganese(III)-meso-tetraphenylporphyrin [Mn(TPP)] and manganese(III)-meso-tetrakis(pentafluorophenyl)porphyrin [Mn(TPFPP)] catalyse the epoxidation of cyclooctene by IO(4)(-) in the presence of excess imidazoles, in both dry CH(2)Cl(2) and CH(2)Cl(2) saturated with H(2)O. The reaction rates of the electron deficient Mn(TPFPP) are a factor 24 less than those of Mn(TPP); however, the former increases 15-30 times in the presence of water, while those of Mn(TPP) do so by a factor of 2-3. The most striking catalytic enhancement caused by the addition of water was observed with 2-methylimidazole and Mn(TPFPP). As deprotonation of imidazoles may play a significant role in the presence of water, we found that manganese(III)-meso-tetrakis(phenyl-4-sulfonato)porphyrin [Mn(TPPS)] decreases the NH proton pK(a) of axially coordinated imidazole from 14.2 to 9.5. We conclude that the imidazole ligand is partially deprotonated in the presence of water. The latter enables the solvation of imidazolium ions that are formed simultaneously. The imidazolate form of the co-catalyst is a much stronger donor than the imidazole itself, providing electron density to Mn(III) and thus promoting oxygen transfer. The failure of N-methylimidazole to increase the reaction rates upon addition of water supports this hypothesis. A functionally related deprotonation has been shown to occur in horseradish peroxidase (J. S. de Ropp, V. Thanabal, G. N. La Mar, J. Am. Chem. Soc. 1985, 107, 8270-8272) and in chlorite dismutase (B. R. Goblirsch, B. R. Streit, J. L. Dubois, C. M. Wilmot, J. Biol. Inorg. Chem. 2010, 15, 879-888). Mn(III)porphyrins in combination with imidazoles and water constitute a functional biomimetic model of peroxidases.     

Raman active jagged-shaped gold-coated magnetic particles as a novel multimodal nanoprobe

The creation of novel engineered multimodal nanoparticles (NPs) is a key focus in bionanotechnology and can lead to deep understanding of biological processes at the molecular level. Here, we present a multi-component system made of gold-coupled core-shell SPIONs, as a new nanoprobe with signal enhancement in surface Raman spectroscopy, due to its jagged-shaped gold shell coating.     

Stabilizing and suicide-peroxide protecting effect of Ni2+ on horseradish peroxidase

The present research discusses the structure stabilizing and protecting effects of Ni²⁺ against suicide-peroxide inactivation of horseradish peroxidase (HRP). Suicide inactivation of HRP by hydrogen peroxide (3 mM) was monitored by measuring change in the absorbance of the colored product (tetraguaiacol) of the catalytic reaction cycle at 470 nm. Progress curves of the catalytic reaction cycle were obtained at 27 °C, phosphate buffer (5 mM), pH 7.0. The corresponding kinetic parameters (e.g., initial enzyme activity (α_o) and the apparent rate constant (k_i) of suicide inactivation of HRP by peroxide) were evaluated using a kinetic equation derived in this study. Comparative activatory and inhibitory effects of Ni²⁺ on the kinetics of suicide-peroxide inactivation of HRP are discussed.     

Sulfur multilayer formation on Au(111): new insights from the study of hexamethyldisilathiane

Hexamethyldisilathiane was successfully used as a new precursor for the formation of S layers on Au and to study their interaction. Characterization of the S modified gold surface was done by X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), and scanning tunneling microscopy (STM). Key findings include the direct observation by STM of (i) coexistence of different phases, (ii) multiple sulfur layers formation, (ii) formation of rectangular structures not only on the adlayer but also on the top layer, and (iv) rectangular structure mobility on different layers. These results provide clear evidence regarding the adsorbate nature of the rectangular structures, solving a highly debated question.