Thermally stabilized and subsequently carbonized nanofibers are a promising material for many technical applications in fields such as tissue engineering or energy storage. They can be obtained from a variety of different polymer precursors via electrospinning. While some methods have been tested for post-carbonization doping of nanofibers with the desired ingredients, very little is known about carbonization of blend nanofibers from two or more polymeric precursors. In this paper, we report on the preparation, thermal treatment and resulting properties of poly(acrylonitrile) (PAN)/poly(vinylidene fluoride) (PVDF) blend nanofibers produced by wire-based electrospinning of binary polymer solutions. Using a wide variety of spectroscopic, microscopic and thermal characterization methods, the chemical and morphological transition during oxidative stabilization (280 °C) and incipient carbonization (500 °C) was thoroughly investigated. Both PAN and PVDF precursor polymers were detected and analyzed qualitatively and quantitatively during all stages of thermal treatment. Compared to pure PAN nanofibers, the blend nanofibers showed increased fiber diameters, strong reduction of undesired morphological changes during oxidative stabilization and increased conductivity after carbonization.
Carbon suboxide (C3O2) is a unique molecule able to polymerize spontaneously into highly conjugated light‐absorbing structures at temperatures as low as 0 °C. Despite obvious advantages, little is known about the nature and the functional properties of this carbonaceous material. In this work, the aim is to bring “red carbon,” a forgotten polymeric semiconductor, back to the community's attention. A solution polymerization process is adapted to simplify the synthesis and control the structure. This allows one to obtain this crystalline covalent material at low temperatures. Both spectroscopic and elemental analyses support the chemical structure represented as conjugated ladder polypyrone ribbons. Density functional theory calculations suggest a crystalline structure of AB stacks of polypyrone ribbons and identify the material as a direct bandgap semiconductor with a medium bandgap that is further confirmed by optical analysis. The material shows promising photocatalytic performance using blue light. Moreover, the simple condensation–aromatization route described here allows the straightforward fabrication of conjugated ladder polymers and can be inspiring for the synthesis of carbonaceous materials at low temperatures in general.
The combined benefits of moisture-stable phosphonic acids and mesoporous silica materials (SBA-15 and MCM-41) as large-surface-area solid supports offer new opportunities for several applications, such as catalysis or drug delivery. We present a comprehensive study of a straightforward synthesis method via direct immobilization of several phosphonic acids and phosphoric acid esters on various mesoporous silicas in a Dean–Stark apparatus with toluene as the solvent. Due to the utilization of azeotropic distillation, there was no need to dry phosphonic acids, phosphoric acid esters, solvents, or silicas prior to synthesis. In addition to modeling phosphonic acids, immobilization of the important biomolecule adenosine monophosphate (AMP) on the porous supports was also investigated. Due to the high surface area of the mesoporous silicas, a possible catalytic application based on immobilization of an organocatalyst for an asymmetric aldol reaction is discussed.
27 February 2025 in International Journal of Biological Macromolecules
We developed a formulation of long double-stranded RNA (dsRNA) using interpolyelectrolyte complexes (IPECs) composed of the biopolymers chitosan and alginate, in order to protect the dsRNA from biotic and abiotic factors. Our primary objectives were to enhance stability of dsRNA against environmental nucleases and, secondarily, to mitigate the negative charge of the dsRNA, which may promote foliar uptake. Our approach relies on submicron particles with adjustable surface charge being either positive or negative. Following this approach, we obtained a high encapsulation efficiency of 94 %. Subsequently, we investigated the influence of the charge ratio and total polymer content on the size, size distribution and ζ-potential of the IPECs. We discovered that formulating at low polymer concentrations ≤0.05 g/L with charge ratios of ≤0.9 (+/-) and ≥ 1.25 (+/-), respectively, produced <100 nm particles. Furthermore, the IPEC formulation protected dsRNA from enzymatic degradation by RNase III and micrococcal nuclease. In addition, we observed outstanding protection of formulated dsRNA from heat degradation. Experiments on Nicotiana benthamiana plants showed that formulated dsRNA offered protection against tobacco mosaic virus. In essence, this formulation demonstrates versatility for the production of IPECs with customizable size, surface charge, and nucleic acid content.
Spray-induced gene silencing (SIGS) employing double-stranded RNA (dsRNA) offers a promising, species-specific approach for protecting crops from insect pests such as the cabbage stem flea beetle (Psylliodes chrysocephala). However, the environmental instability of dsRNA presents a major limitation to its field application. In this study, we evaluate two distinct dsRNA formulation strategies for improved stability and delivery: a bottom-up approach using chitosan-based interpolyelectrolyte complexes (IPEC) and a top-down approach employing functionalized mesoporous silica carriers (SBA-15). Both systems were comprehensively characterized in terms of size, surface potential, porosity, and release behavior. The results revealed that IPECs exhibited release kinetics that were approximately one order of magnitude faster than those of SBA-15 across all tested conditions. The two formulations significantly improved dsRNA stability against UV and heat exposure compared to free dsRNA. In feeding assays with P. chrysocephala, both carriers achieved comparable gene silencing efficacy, though dsRNA@IPEC induced more immediate effects, while dsRNA@SBA-15 displayed delayed but ultimately stronger reduction in consumed leaf area, consistent with its slower release kinetics. We demonstrate that despite structural and mechanistic differences, both delivery platforms effectively stabilized and delivered dsRNA, and offered distinct advantages depending on application needs. This work highlights how formulation strategies are key to successful SIGS and supports the development of robust, field-adaptable formulation technologies for sustainable pest management.