Preparation of 3D crimped ZnO/PAN hybrid nanofiber mats with photocatalytic activity and antibacterial properties by blow-spinning

Zinc oxide (ZnO) nanostructures have received widespread attention due to their unique structure and broad application possibilities, but high preparation costs and agglomeration limit their usage. In this article, low-cost and environmentally friendly cellulose and ZnCl₂ are used to synthesize ZnO nanoparticles (ZnO NPs). Subsequently, multifunctional ZnO/polyacrylonitrile hybrid nanofiber mats (ZnO/PAN@NFMs) with mechanical stability suitable for large-scale application are prepared via solution blow-spinning. The synthesized ZnO/PAN@NFMs exhibit higher photodegradation of organic dyes than earlier reported semiconductors and good recycling performance with an organic dye degradation above 94%–98% after five cycles, which is ascribed to fixation of the ZnO NPs in the nanofibers. In addition, the inhibition rate for Escherichia coli and Staphylococcus aureus is above 99.9% and the bacteriostatic rate against E. coli remains as high as 99% after 10 cycles. From these properties, the synthesized composite ZnO/PAN@NFMs are promising for wastewater cleaning and antibacterial fabrics.     

Evaluation of the removal of n-butanol vapor by the poly(lactic acid)-zeolite-TiO2 composite and formation of by-products

The use of polymeric films incorporated with zeolite-TiO₂ composites associated with UV radiation can be an alternative in the removal of volatile organic compounds (VOCs) through the adsorption and photodegradation processes. This study produced poly(lactic acid) (PLA) films incorporated with 13× zeolite, TiO₂, and 13×-TiO₂ zeolite composite to remove n-butanol and evaluate the by-products generated in the process. The results showed that 13× zeolite and TiO₂ added individually or as a composite to PLA, gave the polymer matrix a significant increase in the removal capacity of n-butanol. The best performance was presented by the zeolite-TiO₂, composite, confirming a synergistic effect. However, the formation of CO and CO₂ exceeded the expected values, with the verification that the polymeric matrix underwent photodegradation action by TiO₂. The polymeric film only containing zeolite is the most suitable for the removal of VOCs, as it did not present degradation of the PLA, generating a lower concentration of by-products.     

Natural Polysaccharides as Multifunctional Components for One-Step 3D Printing Tough Hydrogels

Natural polysaccharides (NPS) are regarded as biomolecular and structural components for preparing high-performance tough hydrogels. But the one-step fabrication of NPS-containing hydrogels in seconds and the template-free design of complicated high-resolution structures are still significant challenges in this field. To meet these requirements, various NPS-containing tough hydrogels are fabricated and processed into 2D/3D structures via the combination of Ru(bpy)₃²⁺-mediated photochemistry and extrusion 3D printing technique. The whole fabrication process is one-step, completed in tens of seconds under visible light irradiation. It is found that the used NPS plays a key role in achieving the fabrication of high-performance structured tough hydrogels. The high reactivity of functional groups in the used NPS can shorten their gelation times. Long rigid chains of the used NPS, their hierarchical assemblies, and contrasting multinetworks benefit from the efficient dissipation of mechanical energy and enhancement of its operational stability. Strong supramolecular interactions enable hydrogel precursors to have high viscosities, therefore providing good controllability to design high-resolution and complicated tough hydrogel structures via extrusion 3D printing. It is anticipated that this straightforward fabrication strategy and findings will open new horizons for NPS-containing materials.     

UV‐Cured Polysiloxane Epoxy Coatings Containing Titanium Dioxide as Photosensitive Semiconductor

UV‐cured polysiloxane epoxy coatings containing titanium dioxide were prepared by means of a cationic photopolymerization process. A good distribution of the inorganic filler was achieved within the polymeric network with an average size dimension of around 500 nm. UV‐vis analysis performed on organic dye (methylene blue) stained coatings showed a high efficiency of the titania photocatalytic activity: a complete degradation of the dye on the coating surface is reached after 60 min of UV irradiation without affecting the matrix photo‐degradation.

     

Model for reaction‐assisted polymer dissolution in LIGA

A new chemically oriented mathematical model for the development step of the LIGA process is presented (LIGA is an acronym for the German words Lithographie, Galvanoformung, and Abformung). The key assumption is that the developer can react with the polymeric resist material to increase the solubility of the latter, thereby partially overcoming the need to reduce the polymer size. The ease with which this reaction takes place is assumed to be determined by the number of side‐chain scissions that occur during the X‐ray exposure phase of the process. The dynamics of the dissolution process are simulated by the solution of the reaction diffusion equations for this three‐component, two‐phase system, the three species being the unreacted and reacted polymers and the solvent. The mass fluxes are described by multicomponent diffusion (Stefan–Maxwell) equations, and the chemical potentials are assumed to be given by the Flory–Huggins theory. Sample calculations are used to determine the dependence of the dissolution rate on key system parameters such as the reaction rate constant, polymer size, solid‐phase diffusivity, and Flory–Huggins interaction parameters. A simple photochemistry model is used to relate the reaction rate constant and the polymer size to the absorbed X‐ray dose. The resulting formula for the dissolution rate as a function of the dose and temperature is fit to an extensive experimental database to evaluate a set of unknown global parameters. The results suggest that reaction‐assisted dissolution is very important at low doses and low temperatures, the solubility of the unreacted polymer being too small for it to be dissolved at an appreciable rate. However, at high doses or at higher temperatures, the solubility is such that the reaction is no longer needed, and dissolution can take place via the conventional route. These results provide an explanation for the observed dependences of both the rate of dissolution and its activation energy on the absorbed dose. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 25–37, 2005     

Photochemical Mechanism of an Atypical Algal Phytochrome

Phytochromes are bilin‐containing photoreceptors that are typically sensitive to the red/far‐red region of the visible spectrum. Recently, phytochromes from certain eukaryotic algae have become attractive targets for optogenetic applications because of their unique ability to respond to multiple wavelengths of light. Herein, a combination of time‐resolved spectroscopy and structural approaches across picosecond to second timescales have been used to map photochemical mechanisms and structural changes in this atypical group of phytochromes. The photochemistry of an orange/far‐red light‐sensitive algal phytochrome from Dolihomastix tenuilepis has been investigated by using a combination of visible, IR and X‐ray scattering probes. The entire photocycle, correlated with accompanying structural changes in the cofactor/protein, are reported. This study identifies a complex photocycle for this atypical phytochrome. It also highlights a need to combine outcomes from a range of biophysical approaches to unravel complex photochemical and macromolecular processes in multi‐domain photoreceptor proteins that are the basis of biological light‐mediated signalling.     

Effects of aging on poly(1‐trimethylsilyl‐1‐propyne) membranes irradiated with vacuum ultraviolet radiation for gas separation

In this study, we investigated the effects of physical aging on the surface and gas‐transport properties of highly gas permeable poly(1‐trimethylsilyl‐1‐propyne) membranes irradiated with vacuum ultraviolet (VUV) radiation. VUV excimer lamp irradiation was performed on one side of the membrane for 6 or 60 min. The gas permeabilities for carbon dioxide (CO₂) and nitrogen (N₂) were determined through a volumetric measurement method at 23 °C. The gas permeabilities for CO₂ and N₂ increased temporarily at 7 days after 6 and 60 min of VUV irradiation of the membranes. The change in the gas permeability for N₂ was more remarkable than that for CO₂. These changes were related to the C?O or SiO_x ratio. The C?O ratio was related to the gas permeability of the membranes VUV‐irradiated for 6 min, whereas the SiO_x ratio was related to the gas permeability of the membranes VUV‐irradiated for 60 min. These changes affected the gas selectivities of the membranes. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45973.     

Photopolymerizable multifunctional monomers and their evaluation as reactive Bis‐GMA eluents

Bis‐GMA {2,2‐bis[4‐(2′‐hydroxy‐3′‐methacryloyloxy‐propoxy)‐phenyl]‐propane}, TEGDMA <2‐{2‐[2‐(2‐methylprop‐2‐enoyloxy)ethoxy]ethoxy}ethyl‐2‐methylprop‐2‐enoate>, and methyl methacrylate (MMA) are some of the most commonly used monomers in the field of restorative dentistry. These compounds are characterized by having one or two terminal double bonds. Besides the effort to synthesize new monomers, several problems still affect the clinical behavior of contemporary dental materials. In this work, two monomers with three terminal double bonds, 5A13DA and 5A13DMA, were synthesized. Both monomers were used to completely replace TEGDMA as reactive diluent of photopolymerizable dental resin composites containing Bis‐GMA. The effects of 5A13DA and 5A13DMA on flexural properties, double bond conversion, water sorption, solubility, and polymerization shrinkage were evaluated. In addition, both monomers were evaluated as crosslinking agents for methylmethacrylate, resulting in copolymers with enhanced thermal stability. The results obtained suggest that newly synthesized monomers are potential substitutes for TEGDMA in the formulation of dental composites, providing 50% lower volumetric shrinkage than the composite resin used as control and adequate mechanical properties. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46240.