Stability of endoglucanases from mesophilic fungus and thermophilic bacterium in acidified polyols

Recent developments in chemical pretreatments of lignocellulosic biomass using polyols as co-solvents (e.g., glycerol and ethylene glycol) at temperatures less than 100 °C may allow the effective use of thermostable and non-thermostable cellulases in situ during the saccharification process. The potential of biomass saccharifying enzymes, endoglucanases (EG) from a thermophilic bacterium (Thermotoga maritima) and a mesophilic fungus (Trichoderma longibrachiatum), to retain their activity in aqueous buffer, acidified glycerol, and acidified ethylene glycol used as co-solvents at pretreatment temperatures at or below 100 °C were examined. The results show that despite its origin, T. longibrachiatum EG (Tl-EG) retained 75% of its activity after exposure to 100 °C for 5 min in aqueous buffer while T. maritima EG (Tm-EG) retained only 5% activity. However, at 90 °C both enzymes retained over 87% of their activity. In acidified (0.1% (w/w) H2SO4) glycerol, Tl-EG retained similar activity (80%) to that obtained in glycerol alone, while Tm-EG retained only 35%. With acidified ethylene glycol under these conditions, both Tl-EG and Tm-EG retained 36% of their activity. The results therefore show that Tl-EG is more stable in both acidified glycerol and ethylene glycol than Tm-EG. A preliminary kinetic study showed that pure glycerol improved the thermal stability of Tl-EG but destabilized Tm-EG, relative to the buffer solution. The half-lives of both Tl-EG and Tm-EG are 4.5 min in acidified glycerol, indicating that the effectiveness of these enzymes under typical pretreatment times of greater than 15 min will be considerably diminished. Attempts have been made to explain the differences in the results obtained between the two enzymes.

Preparation and characterization of potato starch films plasticized with polyols

The present study investigated the potato starches and polyols which were used to prepare edible films. The amylose content and the gelatinization properties of various potato starches extracted from different potato cultivars were determined. The amylose content of potato starches varied between 11.9 and 20.1%. Onset temperatures of gelatinization of potato starches in excess water varied independently of the amylose content from 58 to 61°C determined using differential scanning calorimetry (DSC). The crystallinity of selected native starches with low, medium and high amylose content was determined by X-ray diffraction. The relative crystallinity was found to be around 10 13% in selected native potato starches containing 13 17% water. The glass transition temperature, crystallization melting behavior and relaxations of polyols, erythritol, sorbitol and xylitol, were determined using (DSC), dielectric analysis (DEA) and dynamic mechanical analysis (DMA). The glass transition temperatures of xylitol and sorbitol decreased as a result of water plasticization. Anhydrous amorphous erythritol crystallized rapidly. Edible films were obtained from solutions containing gelatinized starch, plasticizer (polyol or binary polyol mixture) and water by casting and evaporating water at 35°C. The present study investigated effects of plasticizer type and content on physical and mechanical properties of edible films stored at various relative water vapor pressures (RVP). The crystallinity of edible films with low, medium and high amylose content was determined by X-ray diffraction and they were found to be practically amorphous. Water sorption and water vapor permeability (WVP) of films was affected by the type and content of plasticizer. Water vapor permeability of films increased with increasing plasticizer content and storage RVP. Generally, Young's modulus and tensile strength decreased with increasing plasticizer and water content with a concurrent increase in elongation at break of films. High contents of xylitol and sorbitol resulted in changes in physical and mechanical properties of films probably due to phase separation and crystallization of xylitol and sorbitol which was not observed when binary polyol mixtures were used as plasticizers. The mechanical properties and the water vapor permeability (WVP) of the films were found to be independent of the amylose content.

Buildup of gold nanoparticle multilayer thin films based on the covalent-bonding interaction between boronic acids and polyols

A novel method for the fabrication of gold nanoparticle multilayer films based on the covalent-bonding interaction between boronic acid and polyols, poly(vinyl alcohol) (PVA), was developed. The multilayer buildup was monitored by UV-vis absorbance, spectroscopy, which showed a linear increase of the film absorbance with the number of adsorbed Au layers and indicated the stepwise and uniform assembling process. The atomic force microscopy (AFM) image showed that a compact gold multilayer thin film was successfully assembled. The residual boronic acid group on the surface of thin film Could incorporate glycosylated-protein horseradish peroxidase (HRP), and good catalytic activity for H2O2 could be observed.

Phosphorylated polyols, pyrophosphates, and derivatives thereof having biological activity

The present invention provides phosphorylated and pyrophosphate derivatives of polyols, and structural derivatives of these compounds, and provides pharmaceutical compositions comprising the same. The compounds and compositions disclosed herein have various biological activities, including for example, as allosteric effectors of hemoglobin and/or as kinase inhibitors. The present invention further provides methods for therapy in human or mammalian patients, and methods for synthesis of biologically active compounds and their intermediates.

A rapid HPLC protocol for detection of polyols and trehalose

A procedure was developed to extract polyols and trehalose (protectants against stress) from fungal conidia. Conidia were sonicated (120 s) and immersed in a boiling water bath (5.5 min) to optimize extraction of polyols and trehalose, respectively. A rapid method was developed to separate and detect low-molecular-weight polyols and trehalose using high-performance liquid chromatography (HPLC). An ion exchange column designed for standard carbohydrate analysis was used in preference to one designed for sugar alcohol separation. This resulted in rapid elution (less than 5 min), without sacrificing peak resolution. The use of a pulsed electrochemical detector (gold electrode) resulted in limits of reliable quantification as low as 1.6 μg ml-1 for polyols and 2.8 μg ml-1 for trehalose. This is very sensitive and rapid method by which these protectants can be analysed. It avoids polyol derivatization that characterizes analysis by gas chromatography and the long run times (up to 45 min) that typify HPLC analysis using sugar alcohol columns.

Boron influence on concentration of polyols and other sugars in Eucalyptus

Embora a função do elemento Boro (B) nas plantas ainda não tenha sido bem esclarecida, várias hipóteses vêm sido levantadas. Uma das funções atribuídas a esse elemento é a síntese de carboidratos. Com o objetivo de avaliar o efeito do B sobre a síntese de alguns polióis e açúcares em Eucalyptus grandis e híbridos urograndis, estes foram submetidos à situação de suprimento e restrição de B. O experimento foi conduzido em casa de vegetação de acordo com o delineamento de blocos casualizados com cinco repetições, e os elementos nutricionais, assim como o B, foram fornecidos na forma de solução nutritiva. Não se observou diferença significativa nos teores de manitol, sorbitol, myo-inositol e scyllo-inositol e dos açúcares α-glicose e β-glicose entre E. grandis e híbridos. Arabinose foi o único a apresentar maior teor em E. grandis em restrição de B. O efeito da presença do B foi bastante expressivo, mas em suprimento do elemento as plantas apresentaram acréscimo significativo na síntese dos compostos avaliados.

Influence of the concentration of polyols on the rheological and spectral characteristics of guar gum

Polyols are widely used as sugar substitutes and provide texture to foods. Guar gum has many applications in food industry such as increasing product viscosity and improving texture. Knowledge of rheological properties of gum/polyol systems is important to permit replacing sugar while maintaining product texture. In this work, rheological properties of 0.1, 0.5 and 1 g/100 g guar solutions containing 10 and 40 g/100 g of maltitol, sorbitol, or xylitol were studied. The behavior of these mixtures was evaluated by steady and oscillatory shear measurements, and after a freezing/thawing cycle. Apparent viscosity of guar solutions increased with addition of polyols and with the increase in their concentrations, except for 40 g/100 g sorbitol addition to 1 g/100 g guar gum, in which the apparent viscosity decreased. Addition of polyols also increased the dynamic moduli of the systems. In mixtures of guar with 40 g/100 g polyol, the phase angle (δ) was below unity, but was dependent on frequency, which is characteristic of concentrated solutions with a certain degree of structuring. FTIR spectroscopy was studied to provide information on possible interactions between guar gum and polyols. Analyses carried out after freezing/thawing showed no changes in the viscoelastic behavior of the solutions. © 2013 Elsevier Ltd.

Leaf-cutter ant fungus gardens are biphasic mixed microbial bioreactors that convert plant biomass to polyols with biotechnological applications

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Hyperbranched polyether polyols as building blocks for complex macromolecular architectures

The present thesis deals with the development of new branched polymer architectures containing hyperbranched polyglycerol. Materials investigated include hyperbranched oligomers, hyperbranched polyglycerols containing functional initiator-cores at the focal point, well-defined linear-hyperbranched block copolymers and also negatively charged hyperbranched polyelectrolytes.rnHyperbranched oligoglycerols (DPn = 7 and 14) have been synthesized for the first time. The materials show narrow polydispersity (Mw/Mn ca. 1.45) and a very low content in cyclic homopolymers. 13C NMR evidences the dendritic structure of the oligomers and the DB could be calculated (44% and 52%). These new oligoglycerols were compared with the industrial products obtained by polycondensation which exhibit narrow polydispersity (Mw/Mn<1.3) butrnmultimodal distribution in SEC. Detailed 13C NMR and Maldi-ToF studies reveal the presence of branched units and cyclic compounds. In comparison, the hyperbranched oligoglycerols comprise a very low proportion of cyclic homopolymer which render them very interesting materials for biomedical applications for example.rnThe site isolation of the core moiety in dendritic structure offers intriguing potential with respect to peculiar electro-optical properties. Various initiator-cores (n-alkyl amines, UVabsorbing amines and benzophenone) for the ROMBP of glycidol have been tested. The bisglycidolized amine initiator-cores show the best control over the molecular weight and the molecular weight distribution. The photochemical analyses of the naphthalene containingrnhyperbranched polyglycerols show a slight red shift, a pronounced hypochromic effect (decrease of the intensity of the band) compared with the parent model compound and the formation of a relative compact structure. The benzophenone containing polymers adopt an open structure in polar solvents. The fluorescence measurements show a clear “dendritic effect” on the fluorescence intensities and the quantum yield of the encapsulated benzophenone.rnA convenient 3-step strategy has been developed for the preparation of well-defined amphiphilic, linear-hyperbranched block copolymers via hypergrafting. The procedure represents a combination of carbanionic polymerization with the alkoxide-based, controlled ring-opening multibranching polymerization of glycidol. Materials consisting of a polystyrene linear block and a hyperbranched polyglycerol block exhibit narrow polydispersity (1.01-1.02rnfor 5.4% to 27% wt. PG and 1.74 for 52% wt. PG) with a high grafting efficiency. The strategy was also extended to materials with a linear polyisoprene block.rnDetailed investigations of the solution properties of the block copolymers with linear polystyrene blocks show that block copolymer micelles are stabilized by the highly branched block. The morphology of the aggregates is depending on the solvent: in chloroform monodisperse spherical shape aggregates and in toluene ellipsoidal aggregates are formed. On graphite these aggregates show interesting features, giving promising potential applications with respect to the presence of a very dense, functional and stable hyperbranched block.rnThe bulk morphology of the linear-hyperbranched block copolymers has been investigated. The materials with a linear polyisoprene block only behave like complex liquids due to the low Tg and the disordered nature of both components. For the materials with polystyrene, only the sample with 27% wt. hyperbranched polyglycerol forms some domains showing lamellae.rnThe preparation of hyperbranched polyelectrolytes was achieved by post-modification of the hydroxyl groups via Michael addition of acrylonitrile, followed by hydrolysis. In aqueous solution materials form large aggregates with size depending on the pH value. After deposition on mica the structures observed by AFM show the coexistence of aggregates andrnunimers. For the low molecular weight sample (PG 520 g·mol-1) extended and highly ordered terrace structures were observed. Materials were also successfully employed for the fabrication of composite organic-inorganic multilayer thin films, using electrostatic layer-bylayer self-assembly coupled with chemical vapor deposition.

Polyamines from polyols - Pathways to azamacrocycles with hydroxymethyl pendent groups

Several pathways to macromonocylic polyamine ligands with pendent hydroxymethyl substituents have been explored. The new ligands have all been characterised by single-crystal, X-ray structure determinations on their complexes with Co(III) (one case) and Cu(II). As in some related systems, four-membered ring species, here oxetanes rather than azetidines, appear to be involved as reaction intermediates and can be quite readily isolated, providing reactants of potential for the construction of even more complicated multidentate ligands. (C) 2005 Elsevier Ltd. All rights reserved.

Polyols in the crustose lichen Rhizocarpon geographicum

A lichen is an intimate association between an alga and a fungus and is regarded as one of the best examples of ‘mutualism’ or ‘symbiosis’ involving microorganisms. In lichens which have Trebouxia as the algal partner, photosynthesis by the algae results in the production of the soluble polyol ribitol which is then transported to the fungus where it is converted to arabitol and mannitol. Within the fungus, arabitol may act as a short-term carbohydrate reserve while mannitol may be involved in stress resistance. The crustose lichen Rhizocarpon geographicum (L.) DC., has an unusual thallus structure consisting of discrete granules (areolae) containing the algal component growing in association with a non-lichenised fungal hypothallus that extends beyond the areolae to form a marginal ring. The concentrations of ribitol, arabitol, and mannitol were measured, using gas chromatography, in the central areolae and marginal hypothallus of the crustose lichen Rhizocarpon geographicum (L.) DC. growing on slate rocks in north Wales, UK. The concentrations of all three polyols were greater in the central areolae than in the marginal hypothallus. In addition, the ratios of polyols in the marginal hypothallus to that in the central areolae varied through the year. The concentration of an individual poyol in the hypothallus was correlated primarily with the concentrations of the other polyols in the hypothallus and not to their concentrations in the areolae. Low concentration of ribitol, arabitol, and mannitol in the marginal hypothallus compared with the central areolae suggests either a lower demand for carbohydrate by the hypothallus or limited transport of polyols from areolae to hypothallus, and may explain the low growth rates of this species. In addition, polyols appear to be partitioned differently through the year with an increase in mannitol compared with arabitol in more stressful periods.

Polyols in the crustose lichen rhizocarpon geographicum

A lichen is an intimate association between an alga and a fungus and is regarded as one of the best examples of ‘mutualism’ or ‘symbiosis’ involving microorganisms. In lichens which have Trebouxia as the algal partner, photosynthesis by the algae results in the production of the soluble polyol ribitol which is then transported to the fungus where it is converted to arabitol and mannitol. Within the fungus, arabitol may act as a short-term carbohydrate reserve while mannitol may be involved in stress resistance. The crustose lichen Rhizocarpon geographicum (L.) DC., has an unusual thallus structure consisting of discrete granules (areolae) containing the algal component growing in association with a non-lichenised fungal hypothallus that extends beyond the areolae to form a marginal ring. The concentrations of ribitol, arabitol, and mannitol were measured, using gas chromatography, in the central areolae and marginal hypothallus of the crustose lichen Rhizocarpon geographicum (L.) DC. growing on slate rocks in north Wales, UK. The concentrations of all three polyols were greater in the central areolae than in the marginal hypothallus. In addition, the ratios of polyols in the marginal hypothallus to that in the central areolae varied through the year. The concentration of an individual poyol in the hypothallus was correlated primarily with the concentrations of the other polyols in the hypothallus and not to their concentrations in the areolae. Low concentration of ribitol, arabitol, and mannitol in the marginal hypothallus compared with the central areolae suggests either a lower demand for carbohydrate by the hypothallus or limited transport of polyols from areolae to hypothallus, and may explain the low growth rates of this species. In addition, polyols appear to be partitioned differently through the year with an increase in mannitol compared with arabitol in more stressful periods.