Study on the Biodegradation Process of D-Mannose Glycopolymers in Liquid Media and Soil.

Polymers derived from natural raw materials have become of great interest due to their increased biodegradable features and possible biocompatibility. Our group has successfully synthesized and characterized polymers derived from D-mannose oligomer (M), 2-hydroxy propyl acrylate (HPA), and methacrylate (HPMA) in different weight ratios. Their biodegradation was studied in liquid media with pure Proteus mirabilis inoculum for the samples with the most sugar residue, and the results show that the methacrylate derivative M_HPMA1 lost about 50% of its weight during incubation. SEM/EDX techniques were employed to display the modifications of the samples during the biodegradation process. The glycopolymers were buried in garden soil, and the experiment proved that more than 40% of the weight of the M_HPA1 sample was lost during biodegradation, while the other samples encountered an average of about 32% weight loss. The biodegradation profile was fitted against linear and polynomial mathematical models, which enabled an estimate of about a year for the total degradation of the D-mannose glycopolymers sample in soil.

An Empirical Model for Predicting Biodegradation Profiles of Glycopolymers.

Pollution caused by plastic materials has a great impact on the environment. The biodegradation process is a good treatment solution for common polymers and biodegradation susceptible ones. The present work introduces new insight into the biodegradation process from a mathematical point of view, as it envisions a new empirical model for this complex process. The model is an exponential function with two different time constants and a time delay, which follows the weight loss profile of the polymer during the biodegradation process. Moreover, this function can be generated as the output variable of a dynamic exogenous system described through state equations. The newly developed models displayed a good fit against the experimental data, as shown by statistical indicators. In addition, the new empirical model was compared to kinetics models available in the literature and the correlation coefficients were closest to 1 for the new empirical model in all discussed cases. The mathematical operations were performed in the MATLAB Simulink environment.

Biodegradation Pattern of Glycopolymer Based on D-Mannose Oligomer and Hydroxypropyl Acrylate.

Glycopolymers are polymers with sugar moieties which display biodegradable and/or biocompatible character. They have emerged as an environmentally-friendly solution to classical synthetic polymers and have attracted significant research interest in the past years. Herein, we present the synthesis of a D-mannose based glycopolymer with biodegradable features. The glycopolymer was synthesized by radical copolymerization between a D-mannose oligomer bearing polymerizable double bonds and 2-hydroxypropyl acrylate, in a weight ratio of 1:2. The copolymerization kinetics was investigated by differential scanning calorimetry (DSC) and the activation energy of the process was comparatively assessed by Kissinger-Akahira-Sunose and Flynn-Wall-Ozawa methods. The obtained glycopolymer displayed good thermal behavior, fact proven by thermogravimetrical (TG) analysis and it was submitted to biodegradation inside a bioreactor fed with water from the Bega River as the source of microbial inoculum. The glycopolymer sample degraded by approximately 60% in just 23 days. The biodegradation pattern of the glycopolymer was successfully fitted against a modified sigmoidal exponential function. The kinetic model coefficients and its accuracy were calculated using Matlab and the correlation coefficient is more than promising. The changes inside glycopolymer structure after biodegradation were studied using TG and FTIR analyses, which revealed that the sugar moiety is firstly attacked by the microbial consortia as nutrient source for proliferation.

2,2'-Spirobis[chromene] Derivatives Chemistry and Their Relation with the Multistate System of Anthocyanins.

The chemistry of 2,2'-spirobis[chromene] derivatives is intimately related to the one of anthocyanins and similar compounds. The 2,2'-spirobis[chromene] species plays a central role in the network of chemical reactions connecting two different flavylium-based multistate systems. In the present work, a new asymmetric 2,2'-spirobis[chromene] intermediate possessing a constrained propylenic bridge between carbons 3 and 3' was isolated and its role as a pivot in the anthocyanins-type multistate of chemical reactions was investigated by the conjugation of absorption spectroscopy, stopped-flow, NMR, and X-ray crystallography. It was confirmed that the propylenic bridge is essential to stabilize the spirobis[chromene] species. Furthermore, under acidic conditions, two cis-trans styrylflavylium isomers were identified, which could be interconverted directly into one another with light. This is the first report of styrylflavylium cations with photoisomerization on the styryl moiety.

Chemistry and photochemistry of 2,6-bis(2-hydroxybenzilidene)cyclohexanone. An example of a compound following the anthocyanins network of chemical reactions.

The kinetics and thermodynamics of the 2,6-bis(2-hydroxybenzilidene)cyclohexanone chemical reactions network was studied at different pH values using NMR, UV-vis, continuous irradiation, and flash photolysis. The chemical behavior of the system partially resembles anthocyanins and their analogue compounds. 2,6-Bis(2-hydroxybenzilidene)cyclohexanone exhibits a slow color change from yellow to red styrylflavylium under extreme acidic conditions. The rate constant for this process (5 × 10(-5) s(-1)) is pH independent and controlled by the cis-trans isomerization barrier. However, the interesting feature is the appearance of the colorless compound, 7,8-dihydro-6H-chromeno[3,2-d]xanthene, isolated from solutions of acid to neutral range, characterized by (1)H NMR and single crystal X-ray diffraction. Light absorption by 2,6-bis(2-hydroxybenzilidene)cyclohexanone solutions immediately after preparation exclusively results in cis-isomer as photoproduct, which via hemiketal formation yields (i) red styrylflavylium by dehydration under extremely acidic solutions (pH < 1) and (ii) colorless 7,8-dihydro-6H-chromeno[3,2-d]xanthene by cyclization in solutions of acid to neutral range.