Modification of xylan via an oxidation-reduction reaction

Xylan is a biopolymer readily available from forest resources. Various modification methods, including oxidation with sodium periodate, have been shown to facilitate the engineering applications of xylan. However, modification procedures are often optimized for semicrystalline high molecular weight polysaccharide cellulose rather than for lower molecular weight and amorphous polysaccharide xylan. This paper elucidates the procedure for the periodate oxidation of xylan into dialdehyde xylan and its further reduction into a dialcohol form and is focused on the modification work up. The oxidation–reduction reaction decreased the molecular weight of xylan while increased the dispersity more than 50%. Unlike the unmodified xylan, all the modified grades could be solubilized in water, which we see essential for facilitating the future engineering applications of xylan. The selection of quenching and purification procedures and pH-adjustment of the reduction step had no significant effect on the degree of oxidation, molecular weight and only a minor effect on the hydrodynamic radius in water. Hence, it is possible to choose the simplest oxidation-reduction route without time consuming purification steps within the sequence.Peer reviewe

The electrochemical response of core-functionalized naphthalene Diimides (NDI) – a combined computational and experimental investigation

Aqueous organic redox flow batteries (AORFBs) have attracted increased interest as sustainable energy storage devices due to the desire of increasing electricity production from renewable energy sources. Several organic systems have been tested as redox active systems in AORFBs but few fundamental electrochemical studies exist. This article provides reduction potentials and acid constants, pKa, of nine different core-substituted naphthalene diimides (NDI), calculated using density functional theory (DFT). Reduction potentials were acquired at each oxidation state for the nine species and were used to achieve a correlation between the electron donating ability of the substituents and the potential. Cyclic voltammograms were simulated using the scheme-of-squares framework to include both electron and proton transfer processes. The results show that the anion radical is unprotonated in the entire pH range, while the dianion can be protonated in one or two steps depending on the substituent. The core substituentsmay also have acid-base properties. and optimization of the redox properties for battery applications can therefore be obtained both by changing the core substituent and by changing pH of the electrolyte. Three core-substituted NDI molecules were studied experimentally and good qualitative agreement with the theoretically predicted behaviour was demonstrated. For 2,6-di(dimethylamino)-naphthalene diimide (2DMA-NDI), the calculations showed that one of the DMA substituents could be protonated in the accessible pH range and pKa was determined to 3.95 using 1H NMR spectroscopy. The redox mechanism of each molecule was explored and the qualitative agreement between theory and experiment clearly shows that this combination provides a better understanding of the systems and offers opportunities for further developments. The applicability of NDI for redox flow batteries is finally discussed.Peer reviewe

Polyanhydride Microcapsules Exhibiting a Sharp pH Transition at Physiological Conditions for Instantaneous Triggered Release

Stimulus-responsive microcapsules pose an opportunity to achieve controlled release of the entire load instantaneously upon exposure to an external stimulus. Core-shell microcapsules based on the polyanhydride poly(bis(2-carboxyphenyl)adipate) as a shell were formulated in this work to encapsulate the model active substance pyrene and enable a pH-controlled triggered release. A remarkably narrow triggering pH interval was found where a change in pH from 6.4 to 6.9 allowed for release of the entire core content within seconds. The degradation kinetics of the shell were measured by both spectrophotometric detection of degradation products and mass changes by quartz crystal microbalance with dissipation monitoring and were found to correlate excellently with diffusion coefficients fitted to release measurements at varying pH values. The microcapsules presented in this work allow for an almost instantaneous triggered release even under mild conditions, thanks to the designed core-shell morphology. The Swedish Research Council FORMAS (2018-02284) is acknowledged for funding. The authors would like to thank Sofie Ekström, Ellen Emanuelsson, Sebastian Ladisic, and Emma Pettersson for their contributions to the laboratory work.</p

Differences in Backbone Dynamics of Two Homologous Bacterial Albumin-binding Modules: Implications for Binding Specificity and Bacterial Adaptation.

Proteins G and PAB are bacterial albumin-binding proteins expressed at the surface of group C and G streptococci and Peptostreptococcus magnus, respectively. Repeated albumin-binding domains, known as GA modules, are found in both proteins. The third GA module of protein G from the group G streptococcal strain G148 (G148-GA3) and the second GA module of protein PAB from P.magnus strain ALB8 (ALB8-GA) exhibit 59% sequence identity and both fold to form three-helix bundle structures that are very stable against thermal denaturation. ALB8-GA binds human serum albumin with higher affinity than G148-GA3, but G148-GA3 shows substantially broader albumin-binding specificity than ALB8-GA. The (15)N nuclear magnetic resonance spin relaxation measurements reported here, show that the two GA modules exhibit mobility on the picosecond-nanosecond time scale in directly corresponding regions (loops and termini). Most residues in G148-GA3 were seen to be involved in conformational exchange processes on the microsecond-millisecond time scale, whereas for ALB8-GA such motions were only identified for the beginning of helix 2 and its preceding loop. Furthermore, and more importantly, hydrogen-deuterium exchange and saturation transfer experiments reveal large differences between the two GA modules with respect to motions on the second-hour time scale. The high degree of similarity between the two GA modules with respect to sequence, structure and stability, and the observed differences in dynamics, binding affinity and binding specificity to different albumins, suggest a distinct correlation between dynamics, binding affinity and binding specificity. Finally, it is noteworthy in this context that the module G148-GA3, which has broad albumin-binding specificity, is expressed by group C and G streptococci known to infect all mammalian species, whereas P.magnus with the ALB8-GA module has been isolated only from humans