Insights into the roles of superficial lattice oxygen in formaldehyde oxidation on birnessite.

K+-modified birnessite materials were constructed to remove formaldehyde (HCHO) in this work. The introduction of K+ led to weakening of the Mn-O bonds and enhanced the migration of superficial lattice oxygen, resulting in improved redox properties and catalytic activity. MnO2-3K with the largest specific surface area and greatest abundance of superficial lattice oxygen showed the best catalytic performance at 30-130 °C. The operando analyses reveal that HCHO is primarily activated to dioxymethylene (DOM) and subsequently converted to formate species (*COOH). The accumulation of formate species caused a decline in catalytic performance during extended testing at 30 °C, a challenge that could be mitigated by raising the temperature. Theoretical studies disclose that the *COOH → *H2CO3 step with the largest energy barrier is the rate limiting step for HCHO deep decomposition. Molecular oxygen could be activated at oxygen vacancies to replenish the depleted lattice oxygen after decomposition of carbonate species (*H2CO3) and CO2 and H2O desorption. The adsorbed oxygen and water did not limit the deep oxidation of HCHO. This research presents a promising approach for designing highly efficient, non-noble metal catalysts for formaldehyde degradation.

Room-Temperature Columnar Liquid Crystals from Twisted and Macrocyclic 9,9'-Bifluorenylidene Mesogen with Ambipolar Carrier Transport Properties.

We herein report the synthesis and characterization of a series of twisted and conjugated 9,9'-bifluorenylidene (BF) derivatives and a ladder-shaped cyclic dimer (CBF) bearing eight long alkoxy chains at peripheral positions. These contorted aromatics formed hexagonal columnar liquid crystalline mesophases over a wide temperature range, including room temperature. Ambipolar carrier transport properties with electron and hole mobility values of approximately 10-4 and 10-5 cm2 V-1 s-1, respectively, were achieved for the BF derivatives forming a monodomain orientation at ambient temperature.

Recent Advances in Organic Molecular-to-Supramolecular Self-Assembled Room-Temperature Phosphorescent Materials for Biomedical Applications.

This minireview focuses on recent advancements in organic molecular-to-supramolecular self-assembled room-temperature phosphorescent (RTP) materials and their prospective biomedical applications. RTP materials, having their unique capacity to emit long-lasting phosphorescence at ambient temperature, have piqued researchers' interest in various biological applications, including biosensing, bioimaging, drug delivery, and photodynamic therapy (PDT). These materials have several benefits, including high sensitivity, remarkable photostability, and low cytotoxicity. RTP materials' self-assembly into supramolecular structures improves their performance and broadens their uses. Researchers have built organic RTP systems with long-lasting phosphorescence by leveraging weak noncovalent interactions in aquatic conditions. These materials have demonstrated incredible promise as biosensors that enable sensitive analyte detection and as photosensitizers in PDT that target and sensitize specific cell types. The review also outlines future directions and challenges in developing and utilizing pure organic RTP materials for biological imaging purposes, providing valuable guidelines for their future design and application.

Bismuth-Decorated Beta Zeolites Catalysts for Highly Selective Catalytic Oxidation of Cellulose to Biomass-Derived Glycolic Acid.

Catalytic conversion of cellulose to liquid fuel and highly valuable platform chemicals remains a critical and challenging process. Here, bismuth-decorated ß zeolite catalysts (Bi/ß) were exploited for highly efficient hydrolysis and selective oxidation of cellulose to biomass-derived glycolic acid in an O2 atmosphere, which exhibited an exceptionally catalytic activity and high selectivity as well as excellent reusability. It was interestingly found that as high as 75.6% yield of glycolic acid over 2.3 wt% Bi/ß was achieved from cellulose at 180 °C for 16 h, which was superior to previously reported catalysts. Experimental results combined with characterization revealed that the synergetic effect between oxidation active sites from Bi species and surface acidity on H-ß together with appropriate total surface acidity significantly facilitated the chemoselectivity towards the production of glycolic acid in the direct, one-pot conversion of cellulose. This study will shed light on rationally designing Bi-based heterogeneous catalysts for sustainably generating glycolic acid from renewable biomass resources in the future.

Preparation and Characterization of Graphene Oxide/Polyaniline/Polydopamine Nanocomposites towards Long-Term Anticorrosive Performance of Epoxy Coatings.

To address the challenging issues of metal materials corrosion in industries, which has caused huge economic losses and security threats to many facilities in marine environments, functional polymer coatings have been widely used and regarded as one of the simplest and most effective methods to prevent such an undesirable event. In this study, a new type of coating filler consisting of graphene oxide/polyaniline/polydopamine (GO-PANI-PDA) nanocomposites has been successfully synthesized. The morphology, structure, composition, and corrosion resistance performance of the GO-PANI-PDA (GPP) nanocomposites were investigated via a series of characterization methods. The results from our electrochemical impedance spectroscopy, potentiodynamic polarization curve and salt spray experiment showed that the best corrosion resistance performance of the coating is from GPP 21 with the epoxy/GO-PANI:PDA ratio of 2:1, which exhibited a positive corrosion potential (-0.51 V) shift from epoxy/GO-PANI coating (-0.64 V). The corrosion current density (3.83 × 10-8 A/cm2) of GPP 21 is nearly an order of magnitude lower than that of epoxy/GO-PANI (7.05 × 10-7 A/cm2). The good anti-corrosion performance was fascinatingly observed in salt spray tests even without obvious corrosion phenomenon after 30 days of testing. Due to these remarkable properties, GPP nanocomposites can be an outstanding candidate for the rapid development of broadband shielding and anticorrosive materials.

Backbone Effects on the Thermoelectric Properties of Ultra-Small Bandgap Conjugated Polymers.

Conjugated polymers with narrower bandgaps usually induce higher carrier mobility, which is vital for the improved thermoelectric performance of polymeric materials. Herein, two indacenodithiophene (IDT) based donor-acceptor (D-A) conjugated polymers (PIDT-BBT and PIDTT-BBT) were designed and synthesized, both of which exhibited low-bandgaps. PIDTT-BBT showed a more planar backbone and carrier mobility that was two orders of magnitude higher (2.74 × 10-2 cm2V-1s-1) than that of PIDT-BBT (4.52 × 10-4 cm2V-1s-1). Both exhibited excellent thermoelectric performance after doping with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, where PIDTT-BBT exhibited a larger conductivity (0.181 S cm-1) and a higher power factor (1.861 µW m-1 K-2) due to its higher carrier mobility. The maximum power factor of PIDTT-BBT reached 4.04 µW m-1 K-2 at 382 K. It is believed that conjugated polymers with a low bandgap are promising in the field of organic thermoelectric materials.

Zwitterionic liquid crystalline polythiophene as an antibiofouling biomaterial.

To address a key challenge of conjugated polymers in biomedical applications having poor antifouling properties that eventually leads to the failure and reduced lifetime of bioelectronics in the body, herein we describe the design, synthesis, and evaluation of our newly designed multifunctional zwitterionic liquid crystalline polymer PCBTh-C8C10, which is facilely synthesized using oxidative polymerization. A conjugated polythiophene backbone, a multifunctional zwitterionic side chain, and a mesogenic unit are integrated into one segment. By DSC and POM characterization, we verify that the introduction of 3,5-bis(2-octyl-1-dodecyloxy)benzene as a mesogenic unit into the polythiophene backbone allows the formation of the liquid crystalline mesophase of the resulting polymer. We also demonstrate that the PCBTh-C8C10 coated surface exhibits good conductivity, stability, hydrophilicity, and remarkable antibiofouling properties against protein adsorption, cell growth, and bacteria attachment. This new zwitterionic liquid crystalline polymer having good antibiofouling features will be widely recognized as a promising biomaterial that is applicable in implantable organic bioelectronics via inhibiting the foreign body response. A deep understanding of structure-property relationships of zwitterionic conjugated polymers has also been provided in this study.

Structure and Doping Optimization of IDT-Based Copolymers for Thermoelectrics.

π-conjugated backbones play a fundamental role in determining the thermoelectric (TE) properties of organic semiconductors. Understanding the relationship between the structure-property-function can help us screen valuable materials. In this study, we designed and synthesized a series of conjugated copolymers (P1, P2, and P3) based on an indacenodithiophene (IDT) building block. A copolymer (P3) with an alternating donor-acceptor (D-A) structure exhibits a narrower band gap and higher carrier mobility, which may be due to the D-A structure that helps reduce the charge carrier transport obstacles. In the end, its power factor reaches 4.91 µW m-1 K-2 at room temperature after doping, which is superior to those of non-D-A IDT-based copolymers (P1 and P2). These results indicate that moderate adjustment of the polymer backbone is an effective way to improve the TE properties of copolymers.

Zwitterionic Porous Conjugated Polymers as a Versatile Platform for Antibiofouling Implantable Bioelectronics.

Here, we describe the design, synthesis, and evaluation of two kinds of multifunctional zwitterionic linear poly(carboxybetaine thiophene) (PCBTh) and porous poly(carboxybetaine thiophene-co-9,9'-bifluoreneylidene) (PCBTh-coBF) polymers, which can be facilely synthesized using Yamamoto and Suzuki polycondensation, respectively. The integrations of zwitterionic polymer-based biomaterials that consist of conjugated polymer backbones, multifunctional zwitterionic side chains, and distorted units are designed and studied to address a key challenge of conjugated polymers in biomedical applications: biofouling phenomena that eventually lead to the failure and reduced lifetime of bioelectronics in the body. The introduction of a twisting unit into the polymer backbone allows us to tune the porosity, morphology, optical properties, and efficiency of antibiofouling features of resulting polymers. The PCBTh-coBF coated surface exhibits good conductivity, stability, hydrophilicity, and antibiofouling properties against protein adsorption, cell growth, and bacteria attachment, which may be useful for chronic in vivo bioelectronics applications by minimizing the foreign body response.

One-Step Large-Scale Nanotexturing of Nonplanar PTFE Surfaces to Induce Bactericidal and Anti-inflammatory Properties.

Here we demonstrate a simple and scalable nanotexturing method for both planar (films) and nonplanar (tubes) polytetrafluoroethylene (PTFE) surfaces using a commercial desktop oxygen plasma etcher. The simple process can generate semiordered nanopillar structures on both tubular and planar samples with high radial and axial uniformity. We found that the resulting surfaces exhibit good in vitro bactericidal and in vivo anti-inflammatory properties. When tested against Staphylococcus aureus, the nanotextured surfaces showed significantly decreased live bacteria coverage and increased dead bacteria coverage, demonstrating significant bactericidal functionality. Moreover, the etched planar PTFE films exhibited better healing and inflammatory responses in the subcutis of C57BL/6 mice over 7 and 21 days, evidenced by a thinner inflammatory band, lower collagen deposition, and decreased macrophage infiltration. Our results suggest the possibility of using this simple process to generate large scale biomimetic nanotextured surfaces with good antibiofouling properties to enhance the functionality of many implantable and other biomedical devices.

Pyrolytic preparation and modification of carbon black recovered from waste tyres.

The medium temperature pyrolysis process using a fixed-bed reactor at atmospheric pressure was utilised to recover carbon black from motorcycle and automobile tyres. Experimental results have shown that the ash and volatile contents of several recovered carbon blacks are high, the elongation at break of the vulcanised natural rubber filled with recovered carbon blacks from motorcycle tyres is better than that from motorcycle tyres and standard carbon black 7#, while the other mechanical properties are worse. In order to improve the reinforcing effect of recovered carbon blacks, the modification of recovered carbon black was performed by high-energy electron bombardment and non-oxidising acid. The specific surface area of the pyrolytic carbon blacks increased after high-energy electron bombardment. The ash content of the pyrolytic carbon black was reduced from 22.5% to 8.4% after rinsing with hydrochloric acid, and the tensile stress at 300% was increased by about 2.2 MPa.

Correction: Bismuth oxyiodide coupled with bismuth nanodots for enhanced photocatalytic bisphenol A degradation: synergistic effects and mechanistic insight.

Correction for 'Bismuth oxyiodide coupled with bismuth nanodots for enhanced photocatalytic bisphenol A degradation: synergistic effects and mechanistic insight' by Shunqin Luo et al., Nanoscale, 2017, DOI: 10.1039/c7nr05320g.

Bismuth oxyiodide coupled with bismuth nanodots for enhanced photocatalytic bisphenol A degradation: synergistic effects and mechanistic insight.

Bismuth based semiconductor photocatalysts are being generated as promising materials for photocatalysis. In this work, hydrothermal methods have been utilized to synthesize a bismuth oxyiodide semiconductor with deposited Bi nanodots (Bi-BiOI), which could create oxygen defects and accelerate photoinduced charge migration simultaneously. The resulting Bi-BiOI strongly demonstrates the high photocatalytic performance for bisphenol A and methylene blue degradation under visible light. 86% of BPA was degraded after an irradiation time of 4 hours. Electrospray ionization mass spectrometry was employed to detect the evolution of intermediates formed during the decomposition process of bisphenol A, and the following results suggested complete bisphenol A mineralization. Additionally, electron paramagnetic resonance results revealed the production of free radicals and the presence of oxygen vacancies. Furthermore, a distinctively increased photocurrent response and photoluminescence decay dynamics demonstrate that the interface between the Bi nanodots and BiOI semiconductor promotes the separation and migration of photoinduced electron-hole pairs. The lower valence band value (2.57 eV) of Bi-BiOI presented a higher oxidation potential, thus the production of hydroxyl radicals could be promoted considerably. Based on the experimental results, factors such as oxygen vacancies, effective charge migration, suppressed photoinduced electron-hole pair recombination and a high Bi-BiOI oxidation potential would result in advanced free radical production capacity, thereby enhancing the photocatalytic efficiency. The findings of our work will contribute to the fabrication of metal nanodot deposited semiconductor photocatalysts and pave the way for the utilization of advanced oxidation technology.

Red-Green-Blue Trichromophoric Nanoparticles with Dual Fluorescence Resonance Energy Transfer: Highly Sensitive Fluorogenic Response Toward Polyanions.

A red-green-blue (RGB) trichromophoric fluorescent organic nanoparticle exhibiting multi-colour emission was constructed; the blue-emitting cationic oligofluorene nanoparticle acted as an energy-donor scaffold to undergo fluorescence resonance energy transfer (FRET) to a red-emitting dye embedded in the nanoparticle (interior FRET) and to a green-emitting dye adsorbed on the surface through electrostatic interactions (exterior FRET). Each FRET event occurs independently and is free from sequential FRET, thus the resultant dual-FRET system exhibits multi-colour emission, including white, in aqueous solution and film state. A characteristic white-emissive nanoparticle showed visible responses upon perturbation of the exterior FRET efficiency by acceptor displacement, leading to highly sensitive responses toward polyanions in a ratiometric manner. Specifically, our system exhibits high sensitivity toward heparin with an extremely low detection limit.

Phosphorescence from a pure organic fluorene derivative in solution at room temperature.

A fluorene derivative having both bromo and formyl groups exhibited bright phosphorescence emission in common organic solvents at room temperature. The absolute phosphorescence quantum yield reached 5.9% in chloroform at 298 K. When the fluorene derivative was incorporated into a poly(methyl methacrylate) film, the phosphorescence emission was similarly observed even under air at room temperature for over five days.