UVA-LED-Assisted Activation of the Ferrate(VI) Process for Enhanced Micropollutant Degradation: Important Role of Ferrate(IV) and Ferrate(V).

This paper investigated ultraviolet A light-emitting diode (UVA-LED) irradiation to activate Fe(VI) for the degradation of micropollutants (e.g., sulfamethoxazole (SMX), enrofloxacin, and trimethoprim). UVA-LED/Fe(VI) could significantly promote the degradation of micropollutants, with rates that were 2.6-7.2-fold faster than for Fe(VI) alone. Comparatively, UVA-LED alone hardly degraded selected micropollutants. The degradation performance was further evaluated in SMX degradation via different wavelengths (365-405 nm), light intensity, and pH. Increased wavelengths led to linearly decreased SMX degradation rates because Fe(VI) has a lower molar absorption coefficient at higher wavelengths. Higher light intensity caused faster SMX degradation, owing to the enhanced level of reactive species by stronger photolysis of Fe(VI). Significantly, SMX degradation was gradually suppressed from pH 7.0 to 9.0 due to the changing speciation of Fe(VI). Scavenging and probing experiments for identifying oxidative species indicated that high-valent iron species (Fe(V)/Fe(IV)) were responsible for the enhanced degradation. A kinetic model involving target compound (TC) degradation by Fe(VI), Fe(V), and Fe(IV) was employed to fit the TC degradation kinetics by UVA-LED/Fe(VI). The fitted results revealed that Fe(IV) and Fe(V) primarily contributed to TC degradation in this system. In addition, transformation products of SMX degradation by Fe(VI) and UVA-LED/Fe(VI) were identified and the possible pathways included hydroxylation, self-coupling, bond cleavage, and oxidation reactions. Removal of SMX in real water also showed remarkable promotion by UVA-LED/Fe(VI). Overall, these findings could shed light on the understanding and application of UVA-LED/Fe(VI) for eliminating micropollutants in water treatments.

Programmable Payload Release from Transient Polymer Microcapsules Triggered by a Specific Ion Coactivation Effect.

Stimuli-responsive materials activated by a pair of molecular or ionic species are of interest in the design of chemical logic gates and signal amplification schemes. There are relatively few materials whose coactivated response has been well-characterized. Here, we demonstrate a specific ion coactivation (SICA) effect at the interfaces of transient polymer solids and liquid solutions. We found that depolymerization of the transient polymer, cyclic poly(phthalaldehyde) (cPPA), exhibited a SICA effect when the cPPA core-shell microcapsules were suspended in ion-containing acidic methanol solutions. Significant acceleration in cPPA depolymerization rate is triggered by the combination of acid and ion coactivators. Intriguingly, the SICA effect is related to the Hofmeister behavior. The SICA effect is primarily determined by anions, and cations exhibit a secondary effect that modulates the coactivation strength. Based on these observations, we developed cPPA programmable microcapsules whose payload release rates depend on the composition and concentration of the salt/acidic-methanol solutions.

Highly adhesive chitosan/poly(vinyl alcohol) hydrogels via the synergy of phytic acid and boric acid and their application as highly sensitive and widely linear strain sensors.

In recent years, flexible strain sensors have attracted increasing interest, and accurate sensing and comfortable wearables are highly demanded. However, current flexible strain sensors fail to have wide linearity and high sensitivity simultaneously, and their adhesion is insufficient for convenient wear and precise motion monitoring. Herein, chitosan/poly(vinyl alcohol) hydrogels with phytic acid (PA) and boric acid (BA) as crosslinkers (CS/PVA-PA-BA hydrogels) were fabricated. The synergy of phytic acid and boric acid not only improved the mechanical properties of the obtained hydrogels (1070% of fracture strain and 0.83 MPa of fracture stress), but also provided them with outstandingly strong adhesion. Their adhesive strength was up to 527 kPa for a variety of materials, including glass, silica rubber, steel, polytetrafluoroethylene (PTFE), and skin. In addition, the hydrogel-based strain sensor demonstrated high sensitivity (gauge factor = 4.61), a wide linear strain range (up to 1000%, R2 = 0.996), fast response time (90 ms), and good stability. A flexible strain sensor with such high sensitivity and wide linear range simultaneously, to the best of our knowledge, has never been reported before. The development of CS/PVA-PA-BA hydrogels is expected to inspire a novel method for high-adhesive and high-sensing-performance wearable electronics.

Conductive Hydrogels with Ultrastretchability and Adhesiveness for Flame- and Cold-Tolerant Strain Sensors.

Hydrogel strain sensors with extreme temperature tolerance have recently gained great attention. However, the sensing ability of these hydrogel strain sensors changes with temperature, resulting in the variety of output signals that causes signal distortion. In this study, double-network hydrogels comprising SiO2 nanoparticles composed of polyacrylamide and phytic acid-doped polypyrrole were prepared and applied on strain sensors with a wide sensing range, high adhesiveness, and invariable strain sensitivity under flame and cold environments. The hydrogels had stable conductivity, excellent adhesive strength of up to 79.7 kPa on various substrates, and high elongation of up to 1896% at subzero temperature and after heating. They also exhibited effective flame retardancy with low surface temperature (71.2 °C) after 1200 s of heating (200 °C) and antifreezing properties at a low temperature of -20 °C. Remarkably, even under cold temperature and heat treatment, the hydrogel-based strain sensor displayed consistent sensing behaviors in detecting human motions with a broad strain range (up to 500%) and steady gauge factor (GF, ∼2.90). Therefore, this work paves the way for the applications of hydrogel sensors in robotic skin, human-mechanical interfaces, and health monitoring devices under harsh operating environments.

Enhanced removal of organoarsenic by chlorination: Kinetics, effect of humic acid, and adsorbable chlorinated organoarsenic.

In this study, the effective removal of organoarsenic by the combined process of "chlorination + Fe(II)" was achieved. Chlorine could effectively degrade roxarsone (ROX) over pH from 5 to 10. The fitting results of acid-base protonation model proved that the degradation of ROX was mainly attributed to the reaction of HOCl and deprotonated ROX. The transformation of arsenic species conformed to the fitting results of two-channel kinetic model, in which 32.4% of ROX was oxidized to As(V) via electron transfer pathway (ii) and the rest was converted into monochloro-ROX via electrophilic substitution pathway (i). Humic acid inhibited the degradation of ROX due to the competitive consumption of chlorine and the restraint on the pathway ii. Subsequently, an enhanced removal of total arsenic achieved after chlorination, due to that the generating As(V) and monochloro-ROX were easier adsorbed compared with ROX, over 97.8% of total arsenic was removed by ferric (oxyhydr)oxides which in-situ formed from the oxidation of Fe(II). Additionally, toxicity studies indicated that the acute toxicity was significantly eliminated by adding Fe(II) after chlorination, likely due to the removal of As(V) and chlorinated products. Furthermore, organoarsenic was also effectively removed by the combined process of "chlorination + Fe(II)" in real water.

Photochromic Metal-Organic Framework for High-Resolution Inkless and Erasable Printing.

Inkless and erasable printing as a new technology has received intense attention in reducing paper waste and environmental hazards caused by the use of large amounts of ink. However, achieving high-resolution printing by inkless and erasable printing for practical applications remains a huge challenge. Herein, a new metal-organic framework (MOF) has been synthesized, which exhibits a reversible photochromic behavior. None of the unpaired electrons of metal ions and a unique three-dimensional network hinder electron transfer between the ligands and metal nodes, as well as between the ligands themselves, which are conducive to prolonging the photo-generated color lifetime and suitable for inkless and erasable printing. By virtue of the proper photo-generated color lifetime, strong contrast color before and after light irradiation, and reversible color transformation, a high-resolution printing content for inkless and erasable printing can be achieved by light irradiation. Notably, the paper coated with this MOF can be used for printing not only simple patterns such as pictures but also even texts for practical applications, surpassing other photochromic MOF materials for inkless and erasable printing, and almost comparable to ink and laser printing in terms of practicality and resolution. In addition, the MOF-coated paper can be reused for multiple cycles without significant deterioration.

UV/chlorine process for degradation of benzothiazole and benzotriazole in water: Efficiency, mechanism and toxicity evaluation.

Benzothiazole (BZA) and benzotriazole (BTZ) as emerging contaminants were found persistent in aquatic environments and toxic to aquatic organisms. The degradation of BZA and BTZ by UV/chlorine was systematically investigated in this study, and the results showed that BZA and BTZ can be remarkably removed by UV/chlorine compared with UV alone and dark chlorination. The radical quenching tests showed that degradation of BZA and BTZ by UV/chlorine involved the participation of reactive chlorine species (RCS), hydroxyl radical (HO·), and UV photolysis. HO· dominated BZA degradation at neutral and alkalinity, while RCS dominated BTZ degradation. The second-rate order constants for ClO· and BZA and BTZ were 2.22 × 108 M-1 s-1, and 2.40 × 108 M-1 s-1, respectively. Besides, the second-order rate constants for HO· and BZA and BTZ were also determined at pH 5.0, 7.0, and 9.0, respectively. The degradation efficiency of BZA by UV/chlorine was substantially promoted at acidic conditions, while the degradation efficiency of BTZ was promoted at both acidic and specific alkaline range mainly due to the reactivity of radical species and deprotonated form. The influence of Cl- was negligible, but the suppression effect of humic acid was slight during the BZA and BZT degradation by UV/chlorine. The transformation products were detected and the possible pathways were proposed. Seven disinfection by-products (DBPs) were identified both in BZA and BTZ degradation and trichloromethane was the main DBP. The toxicity assessment performed by luminescent bacteria and ECOSAR analysis indicated that the detoxification of BZA could be achieved by UV/chlorine, whereas the toxicity of BTZ was increased mainly due to the formation of intermediates. The findings from this study demonstrated UV/chlorine is likewise efficient for BZA and BTZ removal but the toxicity should be considered in the BTZ degradation.

Metallohydrogel with Tunable Fluorescence, High Stretchability, Shape-Memory, and Self-Healing Properties.

Aiming at the problem that the reported smart optical metallohydrogels were limited with poor mechanical properties, we reported here a novel smart optical metallohydrogel (Al-hydrogel) with excellent elongation, shape-memory ability, self-healing property, and controllable fluorescence intensity. The Al-hydrogel was obtained by the HHPMA-Al3+ and carboxylate-Al3+ coordination after one-pot micellar copolymerization of acrylic acid (AAc), acrylamide (AAm), and hydrophobic arylhydrazone-based ligand (HHPMA). This hydrogel was able to extend up to 5000% of its original length without fracture. Its emission intensity was tunable by OH-/H+ or Zn2+/AAc and increased by 500% with 0.1 M OH- or Zn2+. Its tunable fluorescence enabled us to repeatedly pattern it. A reversible system consisting of Fe3+/H+, was implemented to control the shape of the Al-hydrogel, endowing the Al-hydrogel with shape-memory ability. This highly stretchable and multifunctional Al-hydrogel has potential applications in information transmission, wearable devices, and flexible sensors.

Self-Healing and Multistimuli-Responsive Hydrogels Formed via a Cooperation Strategy and Their Application in Detecting Biogenic Amines.

We reported here a new platform of supramolecular hydrogels cross-linked by the cooperation of metal-ligand coordination and hydrophobic interaction. A salicylaldehyde benzoyl hydrazone-terminal poly(ethylene glycol) (2SBH-PEG) was synthesized and formed small micelles in an aqueous environment. Addition of Ni2+ connected the low-molecular-weight 2SBH-PEG into a metallopolymer via metal-ligand coordination and led to micelle aggregation, resulting in gelation due to the enhancement of hydrophobic interaction. The forming hydrogel, Ni-PEGel, exhibited rapid self-healing ability and reversible pH-responsive property. Because of the containing metal coordination bond, it was also sensitive to the strong competing ligands, such as ethylenediaminetetraacetic acid (EDTA) and pyridine. In addition, Ni-PEGel showed colorimetric changes when exposed to biogenic amine (BA) vapor. The color development of Ni-PEGel toward BAs makes it a good candidate in monitoring food spoilage.