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.     

Photochromic properties of color‐matching,double‐shelled microcapsules covalently bonded onto cotton fabric and applications to outdoor clothing

In this research, we aimed to apply color‐matching, double‐shelled microcapsules to deal with outdoor‐clothing sunscreen‐indicator identifications on cotton fabrics with a covalent‐bonding coating method; this method allows one to display both the UV intensity and a warning. The color‐property characteristics of color‐matching‐double‐shelled‐photochromic‐microcapsule–treated patterns on cotton fabrics under various sunshine irradiation intensities are very close to those of inkjet‐printing color‐gradation patterns, which indicate sunshine irradiation intensities. Color‐matching, double‐shelled microcapsules were obtained by the addition of red double‐shelled microcapsules into yellow double‐shelled microcapsules. We increased the weight ratio of the red microcapsules and added blue double‐shelled microcapsules into the red double‐shelled microcapsules when the weight ratio of blue microcapsules was increased. Color‐matching, double‐shelled photochromic microcapsules, whose yellow/red/blue weight ratios were 5.6/0/0, 4.8/0.8/0, 2.4/3.2/0, and 0.8/4.8/0–0/0/5.6, presented distinct color‐property characteristic changes under various irradiation intensities and presented a good color identification; a rather dark, bright color; and good laundering durability of covalent bonding on cotton fabrics. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44698.     

Fabrication and photocatalytic behavior of a novel nanocomposite hydrogels containing Fe‐octacarboxylic acid phthalocyanine

A novel poly(ethylene glycol)‐based nanocomposite hydrogels containing Fe‐octacarboxylic acid phthalocyanine (FeOCAP)/magnetic attapulgite was successfully synthesized by in situ polymerization. Fourier transform infrared spectroscopy result showed the FeOCAP/magnetic attapulgite was successfully introduced into the hydrogels matrix. Besides, the hydrogen bond interactions existed between FeOCAP/attapulgite and hydrogels, which acted as the crosslink points in the hydrogels network, and meanwhile, stabilized the nanoparticles in hydrogel without phase separation. Photocatalytic activity studies confirmed that the as‐prepared nanocomposite hydrogels had excellent photocatalytic activity for rhodamine B photodegradation, as compared to the pure hygrogels. The rhodamine B removal percentage of the hydrogels could reach nearly 100% and the kinetics of photocatalytic degradation reaction was described by the Langmuir–Hinshelwood kinetics models. The hydrogels could be reused more than five times without losing any photodegradation ability, which indicated that the hydrogels would be potentially useful in dyes wastewater treatments. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45428.     

Activatable Photosensitizers: Agents for Selective Photodynamic Therapy

Recent developments in the design of bifunctional and activatable photosensitizers rejuvenate the aging field of photodynamic sensitization and photodynamic therapy. While systematic studies have uncovered new dyes that can serve as potential photosensitizers, the most promising results have come from studies aimed at gaining precise control over the location and rate of cytotoxic singlet oxygen generation. As a consequence, higher selectivities and efficiencies in photodynamic treatment protocols are now within reach. This feature article highlights the variety of approaches that have been pursued to improve photodynamic therapy and to transform simple photosensitizers into smarter theranostic agents.     

Native Chemical Ligation Directed by Photocleavable Peptide Nucleic Acid (PNA) Templates

A novel peptide–peptide ligation strategy is introduced that has the potential to provide peptide libraries of linearly or branched coupled fragments and will be suited to introduce simultaneous protein modifications at different ligation sites. Ligation is assisted by templating peptide nucleic acid (PNA) strands, and therefore, ligation specificity is solely encoded by the PNA sequence. PNA templating, in general, allows for various kinds of covalent ligation reactions. As a proof of principle, a native chemical ligation strategy was elaborated. This PNA‐templated ligation includes easy on‐resin procedures to couple linkers and PNA to the respective peptides, and a traceless photocleavage of the linker/PNA oligomer after the ligation step. A 4,5‐dimethoxy‐2‐nitrobenzaldehyde‐based linker that allowed the photocleavable linkage of two bio‐oligomers was developed.