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Thermally switchable ladder-like poly(silsesquioxane) (LPSQ) adhesives based on Diels–Alder reaction were prepared and utilized as reversible adhesion materials.

Defense against chemical warfare agents (CWAs) is regarded as a top priority for the protection of humanity, but it still depends on physical protection with severe limitations such as residual toxicity and post-treatment requirement. In this study, a strategically designed functional polymeric substrate was composited with a metal-organic framework catalyst to remove toxicity immediately. A series of PMMA-BPEI copolymers exhibited high processability as a coating and accelerated the catalytic activity of Zr(IV)-based metal-organic framework catalysts (UiO-66). Among them, PMB

Environment-friendly and robust nanocellulose/metal-organic framework aerogel composites were prepared for effective detoxification of chemical warfare agent simulants both in static and dynamic continuous flow systems. For this, we fabricated a durable porous composite of the UiO-66 catalyst and TEMPO-oxidized cellulose nanofibers (TOCN) to examine as a detoxification filter. Even with over 50 wt % UiO-66, the obtained cellulose aerogel composites exhibited high stability without leaking of UiO-66 for 4 weeks under an aqueous state. The cellulose aerogel composite with 54 wt % UiO-66 showed a quite high surface area (483 m2 g-1) despite the presence of TOCN, which caused fast degradation of methyl paraoxon (MPO), a nerve agent simulant, with a 0.7 min half-life in an aqueous solution with N-ethylmorpholine buffer. This aerogel composite was then examined as the detoxification filter in the continuous flow system under a 7.2 mL h-1 flow rate, which surprisingly decomposed 53.7 g of MPO within 1 h with 1 m2 of the effective area.

Metal organic frameworks (MOFs) have been suggested as promising materials for application in the degradation of chemical warfare agents, with the majority of studies to date focusing on nerve agents. One of the most prominent MOFs used in the detoxification of nerve agents is UiO-66, which is of interest as a future nerve agent decontaminant. However, blister agents, which constitute one of the most toxic and highly reactive categories of chemical agents, are yet to be examined as gas-phase decontamination targets using MOF structures. In this study, a novel type of UiO-66 with a smaller particle size, namely, UiO-66S, was used as a decontaminant for the blister agent simulant, 2-chloroethyl ethyl sulfide (2-CEES). The gas-phase chemical adsorption and decomposition of 2-CEES were demonstrated for the first time, with an estimated t1/2 of 1.34 h. This value is the highest reported value for an MOF in gas-phase reaction conditions. The obtained nontoxic degradation products were identified, and the reaction mechanism was studied using density functional theory calculations. Furthermore, the synthesized UiO-66S catalyst also exhibits superior catalytic ability toward nerve agent simulants (diisopropyl fluorophosphate).The results of the study provide a firm basis for the use of UiO-66S as a future decontaminant for both nerve and blister agents.

An acid-base bifunctional zeolitic imidazolate framework catalyst (ZIF8-A61-SO3H) with amine and sulfonic acid groups was successfully prepared through simple two step post-synthetic modification: preparation of amine-functionalized ZIF-8 with amine contents of 61% (ZIF8-A61) by the ligand exchange of 2-mIM with 3-amino-1,2,4-triazole (Atz), followed by the sulfonic acid functionalization by the ring-opening reaction of 1,3-propanesultone with –NH2 groups in ZIF8-A61. Amine-functionalized ZIF8-A materials with difference amine contents (15%, 34%, and 61%, respectively) were also prepared by controlling the synthesis time. All obtained ZIF catalysts evaluated as a heterogeneous catalyst for one-pot deacetalization-Knoevenagel condensation tandem reaction. Compared with ZIF-8 and amine-functionalized ZIF-8 catalysts, ZIF8-A61-SO3H catalyst showed good catalytic performance with 100% conversion of the reactant and 98% selectivity of the final Knoevenagel product. An enhanced catalytic activity can be attributed to the co-existence of site-isolated acid-base groups on the ZIF8-A61-SO3H catalyst in close proximity. The heterogeneous nature of the catalytic system was confirmed by a hot-filtering test and the catalyst also exhibited reusable in the five repeated cycles. A plausible catalytic mechanism of deacetalization-Knoevenagel condensation reaction over ZIF8-A61-SO3H was also proposed.

A catalytic hydrolysis rate of nerve agents can be a significant issue because of their severe toxicity which can lead to severe damage to human life. Regarding the issue, much effort has been given rise to the development of the various design of Zr(IV)-based MOF catalysts so that high catalytic performance. However, we still have feasibility issues. To this end, we turned our attention to develop the method for facile, scalable, and efficient synthesis of Zr(IV)-based MOFs (UiO-66) with high-performance hydrolysis by imparting enriched active sites to the catalysts, as well as to examine its feasibility using the combination of UiO-66 with the organic bases including 4-ethylmorpholine (4-EM) and linear-/ branch-type polyethyleneimine (PEI). The modulated UiO-66 catalysts were synthesized by varying the total reaction concentration. The synthesized three different UiO-66 catalysts were characterized and then applied for hydrolysis rates of the methylparaoxon (MPO) nerve agent simulant. From these investigations, we found that the highest concentration led to the smallest particle size (ca. 100 nm) and highest defect density (1.8 per cluster), resulting in 3-times higher catalytic activity (0.548 s−1) in turnover frequency (TOF) relative to that of the uncontrolled UiO-66 (ca. 580 nm and 1.6 per cluster) (0.188 s−1) which is prepared by the reported procedure. In addition, the reaction process significantly influenced on the catalytic activity of UiO-66, in which the simple change of the reagent mixing method led to a ca. 182-times difference in the catalytic activity for MPO hydrolysis despite using the same reagents including catalysts and bases. Importantly, we found that the reaction process-dependent catalytic activity of UiO-66 can be significantly associated with the chelation of Zr(IV) Lewis acidic active sites by base materials of 4-EM and PEI (Lewis base). Furthermore, the solid-state catalytic system based on the polymer composite of UiO-66S/LPEI10k on the cotton fabric was also examined for MPO hydrolysis at various relative humidity and temperature conditions to create actual atmosphere conditions, which gave the possibility for actual military applications such as protective suits and equipment. In addition, we schematically demonstrated the loss of active sites on UiO-66 by chelation effects based on experimental and density functional theory (DFT)-derived computational simulation because it is highly correlated to the feasibility of Zr(IV)-based MOF catalysts for detoxification of nerve agents. In addition, we carefully propose a plausible reaction mechanism step on the nucleophilic attack by hydroxide group on the basis of the computational simulation.

Development of new hole-transport layer (HTL) materials for organic photovoltaic (OPV) applications is one crucial issue to mitigate such limitations of low power efficiency, processibility, and stability derived from poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) as a common HTL material. To this end, poly(3-hexylthiophene) (P3HT)-based diblock copolymers including the different ratios between polystyrene (PSty) or/and poly(neopentyl styrene sulfonate) (PNSS) as a second block segment were designed and then used for incorporating with single wall carbon nanotubes (SWCNTs) to form potentially self-dopable nanocomposites. The structure of fabricated P3HT-based diblock copolymer/SWCNT nanocomposites was examined by microscopic and spectroscopic characterizations, exhibiting a charge transfer behavior between P3HT and SWCNT, and growth of the P3HT crystalline phase along the SWCNT surface with a form of the conducting path. The acquired SWCNT nanocomposites exhibited good solubility and dispersion in various organic solvents including toluene, chlorobenzene, THF, chloroform, and DMF, which are good solvents for the PSty or/and PNSS neutral second block. The concept for the neutralized second block by protecting groups can prevent the poisoning ITO substrate by water contamination as shown in the conventional aqueous PEDOT-PSS solution. Notably, the PNSS constituent in the nanocomposite was merely acidified to give in-situ sulfonic acid groups in PSty by simple thermolysis process at 160 °C for 30 min after a solution process for fabrication of a thin film. The thermolysis step provided efficient doping of P3HT by PSS, in which the thiophene groups worked as Bronsted base are protonated by taking protons from sulfonic acid groups and then lead to a form of ionic bonds between cationic thiophene and anionic sulfonate groups. In addition, the formed ionic bonds in the nanocomposites led to an insoluble thin film, which has a good advantage for the further solvent process without substantial damages. The beneficial features of the conducting path along SWCNT and the efficient doping of P3HT by PSS in the acquired nanocomposites led to ca. 5-fold higher electrical conductivity (3.16 S cm−1) and similar work function (5.1 eV) in comparison to water contained commercial PEDOT:PSS (0.6 S cm−1 and 5.0 eV, respectively). As such, the rationally designed potentially self-dopable SWCNT nanocomposites can be one of the promising alternatives beyond the commercial PEDOT: PSS HTL material.

As many people live in cities that lack green space, biodiversity in such areas is decreasing. Suwon, the study site, a city that strives to improve its biodiversity, is close to the capital city of the Republic of Korea (ROK), and has a large population. This study aims to identify habitat-suitable areas using the longitudinal distribution model in Suwon-si, examine habitat changes when rooftop greening scenarios are applied to various use areas, and distinguish efficient use areas to expand the number of forms. To establish a rooftop greening creation scenario, the area was calculated based on the rooftop greening promotion plan in the metropolitan area, and a representative use area where rooftop greening can be applied was selected. To generate a scenario for creating rooftop greening, the property of the green area was assigned to the corresponding use area, and it was produced as an environmental variable, while the species distribution model was driven. As a result of the study, the area of increase in habitat area according to the rooftop greening for each usage area was derived, and the efficiency of the increase in habitat area compared to the rooftop greening area for each usage area was derived. To improve biodiversity in Suwon-si, rooftop greening in residential areas was found to be the most efficient, and rooftop greening efficiency in commercial areas was the lowest. It is expected that information on the increase and efficiency of the habitat of the wild birds due to rooftop greening by area of use derived from this study will help establish a rooftop greening plan and support decision-making to promote biodiversity in the city.

Well-defined methacrylate based amphiphilic block copolymers (BCs) consisting of poly(methyl methacrylate) (PMMA) and poly(ethylene glycol) methacrylate (PPEGMA) were synthesized by atom transfer radical polymerization (ATRP) and used as additives in DMAc casting solution to fabricate poly(vinylidene fluoride) (PVDF) ultra-filtration (UF) membranes in non-solvent induced phase separation (NIPS) process, where the amphiphilic BC additives hydrophilically altered PVDF with PPEGMA block segment by strong interaction with the other PMMA block segment, which reduced water resistance to the PVDF polymer solution during phase separation. FT-IR and XPS studies showed carbonyl groups of BCs in the PVDF membranes, which were not changed even after IPA treatment, indicating that BCs in the membrane were very stable. Obtained PVDF membranes with BCs showed porous surface layer and finger-like pore structures with macrovoids on the sublayers, of which sizes were increased with the increase of BC contents, which were then compared to the pristine PVDF membranes and the PVDF membrane with corresponding other additives such as hydrophobic PMMA, hydrophilic PPEGMA, LiCl and BC/LiCl. Obtained PVDF membranes showed MWCO with 100 K PEO and the best water flux (140 LMH) was achieved in the PVDF membrane with BC/LiCl additive, which was almost 4 times higher than the pristine PVDF membrane. In addition, the PVDF membranes with BC and BC/LiCl additives improved the anti-fouling property for BSA protein, of which reversible fouling resistance ratio was ca. 7 times higher than that of the pristine PVDF membrane.

Various failure modes derived from the electrochemical migration (ECM) through the dielectric polymer layers have been considered critical issues in the electronic devices. Herein, we for the first time suggested the rationally designed epoxy/zeolitic imidazolate framework-8 (ZIF-8) nanocomposite materials for efficient suppression of copper ion migration based on the plausible reaction mechanisms of metal metathesis addressed by sequential cleaving and ligating between metal ions (Zn2+ and Cu2+) and 2-methylimidazole (2-mim) ligands. The fabrication process for epoxy/ZIF-8 (EZ) nanocomposites was first examined to optimize the crosslinking system. The capability of the metal ion capture in the EZ nanocomposites was examined using the aqueous solution containing Cu2+ ions. In addition, the ECM suppression properties were evaluated using the thermal humidity bias (THB) model testing. The representative model investigations with the EZ nanocomposites exhibited substantially enhanced copper ion adsorption and suppression of copper migration in comparison to those of epoxy. Hence, the EZ nanocomposites can be one promising material to alleviate the undesired ECM behavior in electronic device applications.

Two series of water-soluble metalloporphyrin-cored amphiphilic star block copolymers were synthesized by controlled radical polymerizations such as atom transfer radical polymerization (ATRP) and reversible addition fragmentation chain transfer (RAFT), which gave eight amphiphilic block copolymer arm chains consisting of poly(n-butyl acrylate-b-poly(ethylene glycol) methyl ether methacylate) (PnBA-b-PEGMEMA, Mn,GPC = 78,000, Mw/Mn = 1.2, 70 wt% of PPEGMEMA) and poly(styrene-b-2-dimethylamino ethyl acrylate) (PS-b-PDMAEA, Mn,GPC = 83,000, Mw/Mn = 1.2, 67 wt% of PDMAEA), yielding porphyrin(Pd)-(PnBA-b-PPEGMEMA)8 and porphyrin(Pd)-(PS-b-PDMAEA)8, respectively. Obtained metalloporphyrin polymer photocatalysts were homogeneously solubilized in water to apply to the removal of chlorophenols in water, and was distinguished from conventional water-insoluble small molecular metalloporphyrin photocatalysts. Notably, we found that the water-soluble star block copolymers with hydrophobic–hydrophilic core–shell structures more effectively decomposed the chlorophenol, 2,4,6-trichlorophenol (2,4,6-TCP), in water under visible light irradiation (k = 1.39 h−1, t1/2 = 0.5 h) in comparison to the corresponding water-soluble star homopolymer, because the hydrophobic core near the metalloporphyrin effectively captured and decomposed the hydrophobic chlorophenols in water.

The carbon fiber reinforced plastics (CFRP) are still limited the used in the automotive industry mainly by the weak interfacial adhesion between the fiber and polymer matrix. Herein, to improve interfacial interactions between the carbon fiber (CF) and polypropylene (PP) matrix, poly(dimethylaminoethyl methacrylate)-b-poly(methyl methacrylate) (PDMAEMA-b-PMMA, PDM) compatibilizers are applied to functionalize the CF surface through a covalent bonding with epoxide groups on the chemically modified CF surface with tertiary amines in the PDMAEMA block, which induced intermolecular entanglement with PP chains with the PMD compatibilizers. The acquired compatibilizer-functionalized CF (CECF) was applied to fabricate PP composites by a melt-mixing method. The highly improved interfacial adhesion between the CECF and PP was confirmed by evaluating thermal, morphological, rheological, and mechanical properties. Based on the significantly enhanced interfacial adhesion, notably, the tensile strength and modulus of the CECF/PP composite exhibited a massive increase by ca. 312% and 664%, respectively, relative to those of the PP resin. The Ashby plot facilitated understanding that the acquired mechanical properties of the CECF/PP composite showed a relatively ideal position compared to reported PP composites and centered on the commercially available region in automotive components.

Herein, environmentally benign chitin nanofiber (ChNF) membranes were fabricated by regulating suspension behavior. The introduction of zeolitic imidazole frameworks (ZIF-8) into the composite membranes led to the domain formation of ChNF derived by coordinative interaction, resulting in pore size-tunable membranes. Based on the rheological, morphological, and structural characterizations, the driving force of pore-size control was studied in the aqueous suspension of ChNF and ZIF-8 according to the relative concentration. At critical concentration, the 30-ChNF membrane presents superior water permeance (40 LMH h−1) while maintaining a high rejection rate (>80% for all organic dyes). Moreover, the molecular size cut-off of the composite membranes for dyes can be controlled in the range of less than 1 nm to 2 nm. The experimental results provide a simple strategy for the preparation of pore tunable ChNF membranes using MOF with high mechanical strength, good durability, high flux, dye rejection, and antifouling ability.

The facile tuning of the gate size and the chemical functionalization of zeolitic imidazolate frameworks (ZIFs) have been considered efficient strategies for various potential applications including gas membranes, sensors, and catalysts. Herein, we demonstrate the synthesis of amine-functionalized ZIF-8 (ZIF8-A) with 3-amino-1,2,4-triazole (Atz) by postsynthetic modification (PSM) towards two objectives: (1) CO2 selective adsorption by a combination of chemical interactions and controlled gate sizes and (2) potential for further chemical modifications. The acquired ZIF8-A substantially enhanced CO2/N2 and CO2/CH4 selectivity at 35 °C compared to ZIF-8 since the Atz conversion enhanced chemical interactions with CO2 due to the introduction of amine moieties while reducing both the surface area and pore volume. The gate size control of ZIF-8 by the replacement of Atz was thoroughly investigated by extensive transport experiments and density functional theory (DFT)-based computational simulations. In addition, the vinyl-functionalized ZIF-8, another versatile starting material, was successfully prepared by further chemical modifications of ZIF8-A with either methacrylic anhydride or glycidyl methacrylate through nucleophilic substitution reactions. As such, we believe that our current work can provide promising platforms for designing ZIF-based materials with versatile properties including precise control of the gate size and the incorporation of various functional groups.

Pourable and room temperature flowable ladder-structured polysilsesquioxanes were synthesized and applied as functional optical hard coatings. Organic functional group type (propyl, hexyl, octyl, dodecyl) and their copolymer composition with UV-curable methylacryloxypropyl group were selected as to control both pre-cured viscosity and final mechanical properties independent of molecular weight. Ladder-structured polysilsesquioxanes with longer alkyl side chains exhibited higher fluidity and flexibility while maintaining its optical property and mechanical strength. The solvent-free processability of our synthesized materials along with their superior optical and mechanical properties over commercial solvent-based hard coatings suggest the high value of our hybrid materials for the coatings industry.

To data, combination of Pt-based bimetallic nanocrysatals and the graphene support have significantly contributed to enhance the oxygen reduction reaction (ORR) performance relative to electrocatalysts based on monometallic Pt nanoparticles (NPs) primarily due to the unique ligand effects and benefits of the carbon support. In this study, we propose a new structure of bimetallic electrocatalysts to realize the synergistic effects on the ORR performance through effective integration of the fine-sized Pt NPs, PdPt bimetallic nanocrystals, and non-covalently functionalized graphene with ionic polymers. The facile wet-chemical methods were applied to synthesize fine-sized (2–5 nm) spherical Pt NPs doped large-sized (20–50 nm) non-spherical PdPt bimetallic NPs on the electronically negative ionic polymer-functionalized graphene support (Pt-on-PdPt/fG). This Pt-on-PdPt/fG with synergistic effects based on enlarged active surface area, ligand, and interfacial linking effects, exhibits substantially enhanced ORR activity (specific activity: 1.89 mA c m Pt − 2 at 0.9 VRHE) and durability in comparison to the commercial Pt/C (specific activity: 0.23 mA c m Pt − 2 at 0.9 VRHE). To this end, the effective integration of newly designed fine-sized Pt NPs doped bimetallic nanocrystals and unique graphene supports with the well-interactive ability could be a good platform to develop the advanced electrocatalysts for the efficient ORR.

A series of multi-crosslinkable, self-healing, ladder-structured polysilsesquioxane inorganic-organic hybrid materials were developed to enhance the mechanical properties through tandem UV-curing and Diels-Alder chemistry. The introduction of UV-curable acryl- or epoxy groups allowed for a higher degree of crosslink density while bringing the inorganic backbones closer together for highly efficient self-healing properties, all with a singular material as the ternary organic functional groups consisting of UV-curable function, diene, and dienophile were tethered to the well-defined inorganic backbone. Exceptional thermal stability (>400 °C), optical transparency (>95%), solution processability, as well as robust surface mechanical properties in both bulk (pencil hardness 6H) and nanoscale (elastic modulus > 9 GPa), properties which can be adroitly recovered through mild and rapid thermal treatment hold great promise for next generation hybrid smart coating materials for application in optoelectronic devices.

Heteroleptic ruthenium-complexed ladder-like structured polysilsesquioxane (LPSQ-Ru) was synthesized by post coordination reaction of bidentate ligand side chains in LPSQ with reactive Ru(II) complexes, which was well characterized by 1H and 29Si NMR, FT-IR, and spectroscopic techniques. The photophysical properties of LPSQ-Ru were examined by UV and PL analyses in both solution and solid states, comparing to analogous polymers of ruthenium-complexed polystyrene (PS-Ru). Obtained absorptions of LPSQ-Ru and PS-Ru were broadened ranging from 390-490 nm regardless of the states. However, LPSQ-Ru exhibited higher and shaper PL emission spectrum in comparison to that of PS-Ru, particularly in the solid state, because Ru-complexes in LPSQ were much effectively isolated, preventing their aggregations due to the rigid double strained siloxane backbone. This extinguished photophysical property in LPSQ-Ru kept after intensive thermal treatment at 250 °C for 90 min, which was not achieved in PS-Ru (~5-fold decrease). These differences originated from the backbone structures were also appeared in electrochemical properties in the solid states.

Developing polymeric membranes with propylene/propane separation performance surpassing the upper bound has been received much attention. Herein, a highly controlled thermal treatment process yielding microporous polyimide membranes made from dense brominated-polyimide membrane precursor via thermal debromination/cross-linking approach is demonstrated. We showed that facile thermal treatment could generate a narrow size distribution of micro-voids as well as covalent linkages between inter/intra polymer chains while the polyimide backbone structure remained intact. The thermally treated membranes were well-characterized by FTIR, TGA, WAXD, solid-state 13C NMR and N2 adsorption/desorption isotherm. Single gas propylene/propane (C3H6/C3H8) separation performance greatly improved in terms of both selectivity and permeability, surpassing the trade-off line while maintaining flexible membrane properties. A thermal cross-linking treatment at 380 °C for 5 h exhibited the best C3H6 permeability of 84.70 barrer and C3H6/C3H8 selectivity of 14.6 with high plasticization resistance.

Mixed matrix membranes (MMMs) are an attractive platform for challenging gas separations since they are the state-of-the-art scalable molecular sieve membranes. Here, the commercially attractive polysulfone (PSF) was grafted by poly(polyethylene glycol) methyl ether methacrylate (PEG) side chains to improve the interfacial interaction with zeolitic imidazolate framework-8 (ZIF-8) nanoparticles and the affinity towards C3H6 for enhanced C3H6/C3H8 separation performance. The PSFPEG graft copolymers monotonically increased the intersegmental distance of polymer chains with increasing the PEG contents based on the XRD results and the density functional theory calculations. Also, the cross-sectional SEM images of MMMs visualized that the interfacial adhesion between ZIF-8 and polymer was improved as the PEG content increased. Both DSC and FT-IR analyses revealed that such an enhanced interfacial adhesion was attributed to a combination of flexible nature of PEG side chains and various chemical interactions. More importantly, the PSFPEG73/ZIF-8 (65/35 vol/vol) MMM enhanced both C3H6 permeability and C3H6/C3H8 permselectivity compared to the PSF/ZIF-8 counterpart by 57% and 55%, respectively. Besides, the equimolar C3H6/C3H8 mixed gas permeation isotherm exhibited that the PSFPEG73/ZIF-8 (65/35 vol/vol) MMM enhanced the plasticization resistance against C3H6 compared to the PSF/ZIF-8 counterpart (e.g., C3H6-induced plasticization pressure of 5 vs. 3 atm), demonstrating the significance of the interfacial interaction.

The synthesis of metal-organic frameworks (MOFs) with in-built porphyrin units remains challenging. It takes long synthesis time under carefully controlled reaction conditions, and a mixed-phase with different crystal morphologies is still frequently observed. In this work, Zr-based porphyrinic MOF-525 and MOF-545 in high purity and uniform size were produced through a sonochemical route in 2.5 and 0.5 h, respectively, using zirconyl chloride octahydrate and tetrakis (4-carboxyphenyl) porphyrin. Benzoic acid was used as a modulator for MOF-525, and trifluoroacetic acid for MOF-545. The physicochemical properties of the MOF products were examined by X-ray diffraction, scanning electron microscopy, and N2 adsorption-desorption isotherms. Additionally, the defect sites in the MOF samples were analyzed by UV–vis spectrometry, thermogravimetric analysis, and inductively coupled plasma mass spectrometer. The sonochemically synthesized MOF samples had more defect sites than the conventionally prepared ones and exhibited improved textural properties. In particular, the MOF-545 had a significantly smaller (ca. 1.0 μm) particle size than the conventionally prepared sample (ca. 4.8 μm). The MOF-525 and MOF-545 prepared by the sonochemical route exhibited enhanced hydrolysis of the chemical warfare simulant dimethyl-4-nitrophenyl phosphate (DMNP) and a faster and higher bisphenol-A adsorption than the conventionally prepared MOF samples.

An in-depth examination of the self-healing properties of both dienophile and diene functionalized ladder-like structured polysilsesquioxane copolymers and terpolymers was investigated. Through functionalization of both diene and dienophile on the double-stranded siloxane backbone with ternary n-alkyl functional groups acting as chain mobility control, the effect of chain mobility and chemical structure on self-healing and mechanical properties were elucidated. All of the single component self-healing hybrid materials exhibited fast healing times (∼5 min), and their de-crosslinked adducts exhibited exceptional retention of solubility in common organic solvents for good reusability, all while having inherent high thermal stability and optical transparency.

Porous-structured noble metal electrocatalysts offer activity and durability benefits based on a high surface area and interconnected nanostructure, respectively. However, conventional technical methods used for synthesizing a porous structure are still difficult as well as resulting in defects in the structure. Here we report a facile route for the synthesis of uniform, large-area mesoporous platinum thin films based on ionic polymer doped graphene, which exhibit substantially enhanced activity and durability for oxygen reduction relative to commercial Pt/C. Notably, a remarkable durability (≥95% retention of electrochemical activities after 30 000 cycles of intensive accelerated durability tests) is acquired which is ascribed to the synergistic effects derived from the interconnected Pt structure (morphology) and ionic polymer-doped graphene (support). The suggested robust concept for a controlled mesoporous-structured platinum thin film on graphene could be a great breakthrough for obtaining a highly durable electrocatalyst.

Palladium nanoparticles on ionic polymer-doped graphene (Pd–IPG) nanocomposite catalysts have been investigated for efficient Suzuki coupling reactions. This combination effected highly accelerated Suzuki coupling reactions due to several advantageous features associated with the flanking ionic polymer part of the catalyst system. These include a high level of Pd incorporation, excellent dispersion stability, and increased accessibility and diffusion of the substrates onto the surface of Pd NPs. The enhanced availability of the Pd catalyst to the reacting substrates is believed to allow for ca. 16-fold higher catalytic activity than that of Pd–graphene without the ionic polymer. Moreover, high recycling capability of the catalyst (10 times) in combination with excellent product yields (>96%) and no significant leaching of the catalyst upon hot-filtration test suggest that the Pd–IPG nanocomposite catalysts have high reusability with significant retention (>95%) of the Pd species.

An investigation into the hydrolysis kinetics of an aqueous base-catalyzed sol-gel reaction yielding ladder-like polysilsesquioxanes was studied using NMR. Under various variables of monomer concentration, water concentration, solvent type, and monomer type, the various effects on molecular weight and degree of condensation were elucidated. Moreover, the various rate orders and rate constants were calculated and compared with previous reports of the hydrolysis of organosilane precursors. Through this study we were able to ascertain the optimal conditions of hydrolysis-polycondensation for obtaining highly condensed, high molecular weight ladder-like polysilsesquioxanes.

The incorporation of pyrene-functionalized poly(methyl methacrylate)-b-poly(dimethylaminoethyl methacrylate) (PMMA-b-PDMAEMA) ionic block copolymer-wrapped carbon nanotubes (PBCNTs) with graphene oxide (GO) allows compact decoration of metal nanoparticles (NP) for use as robust catalysts. This well-tailored concept of the PBCNT-GO functional carbon support provides various features, including a two-dimensional (2D) structure, dimensional stability, versatile solubility (from toluene to water), enhanced diffusion of reagents, and recyclability. Among the various compositions of GO and PBCNT, 50 wt% of the PBCNT additive-containing support (PBCGO55) showed great hybridization potential for Ag, Au, and Pd NPs. In particular, the hybridization of PBCGO55 with Pd NPs (Pd-PBCGO55) displayed superior morphological features with compact decoration of ultra-fine NPs (1–3 nm), larger surface area, higher density of edge and corner atoms, better dispersion stability, and lesser aggregation of the decorated Pd NPs in comparison with the other hybrid catalysts. In the catalytic reduction of 4-nitrophenol (4-NP), the Pd-PBCGO55 hybrid catalyst exhibited the best catalytic performance, resulting in highly enhanced reaction rate constant (k) of 9.73 min−1 and catalytic activity of 141.8 mol mol−1 min−1, exhibiting a 50-fold increased rate constant and 30-fold increased catalytic activity in comparison to Ag-GO without PBCNT (k = 0.19 min−1, catalytic activity = 4.58 mol mol−1 min−1).

We present a new strategy to strongly and effectively immobilize silver nanoparticles (AgNPs) on polyamide thin film composite membranes to endow antibacterial activity. This method relies on the immobilization of relatively large silica particles (SiO 2 , ~400 nm in diameter), where AgNPs of ~30 nm in diameter are tightly and densely bound (AgNP@SiO 2 ), on the membrane surface using cysteamine as a covalent linker. The formation of multiple Ag–S chemical bonds between a “bumpy” AgNP@SiO 2 and the rough membrane surface provides a great leaching stability of AgNPs and AgNP@SiO 2 . AgNP@SiO 2 particles were well distributed over the entire membrane surface without severe aggregation. The surface coverage of the membrane by AgNP@SiO 2 was tuned by adjusting the deposition time and AgNP@SiO 2 particle concentration. The AgNP@SiO 2 -immobilized membrane showed excellent antibacterial properties against Escherichia coli , Pseudomonas aeruginosa and Staphylococcus aureus, even with a relatively low particle coverage. Importantly, the separation performance (water flux and salt rejection) of the membrane was not impaired by particle immobilization. These beneficial effects are attributed mainly to the sparse and good distribution of AgNP@SiO 2 , which can reinforce the antibacterial activity of AgNPs while having a negligible impact on the hydraulic resistance.

A novel inorganic–organic hybrid crosslinker was prepared through synthesis of a fully condensed, high molecular weight ladder-like poly(methacryloxypropyl)silsesquioxane (LPMASQ) in one pot with a facile, base-catalysed system. The fully condensed LPMASQ revealed good thermal (∼380 °C) and electrochemical stability (∼5.0 V) due to the absence of uncondensed silanol groups. LPMASQ also revealed good solubility in various organic solvents and fully gelated 1 M LiPF6 in ethyl carbonate–diethyl carbonate (EC–DEC, 3/7, v/v) electrolyte solution through fast thermal and photocuring even at a very low concentration of 2 wt%. These observations were attributed to the polymeric nature of LPMASQ containing over one hundred methacryl moieties on the rigid double-stranded siloxane backbone. To the best of our knowledge, formation of a gel polymer electrolyte with 2 wt% gelator is the smallest gelation concentration that has ever been reported. This leads to high ionic conductivity (∼6.0 mS cm−1), excellent Coulombic efficiency and battery cell performance, comparable with those of the neat liquid electrolyte. The small crosslinker content, thermal and electrochemical stability, fast thermal and photocuring and facile processing of the LPMASQ based GPEs, as well as excellent Li battery cell performances strongly hold great promise for future industrial battery applications.

A region suffering from an attack of a nerve agent requires not only a highly sorptive material but also a fast-acting catalyst to decontaminate the lethal chemical present. The product should be capable of high sorptive capacity, selectivity and quick response time to neutralize the long lasting harmful effects of nerve agents. Herein, we have utilized organophosphorus hydrolase (OPH) as a non-toxic bio-catalytic material held in with the supporting matrix of poly-β-cyclodextrin (PCD) as a novel sorptive reinforced self-decontaminating material against organophosphate intoxication. OPH coated PCD (OPH-PCD) will not only be providing support for holding enzyme but also would be adsorbing methyl paraoxon (MPO) used as a simulant, in a host-guest inclusion complex formation. Sorption trend for PCD revealed preference towards the more hydrophobic MPO against para-nitrophenol (pNP). The results show sorption capacity of 1.26 mg/g of 100 μM MPO with PCD which was 1.7 times higher compared to pNP. The reaction rate with immobilized OPH-PCD was found to be 23% less compared to free enzyme. With the help of OPH-PCD, continuous hydrolysis (100%) of MPO into pNP was observed for a period of 24 h through packed bed reactor with good reproducibility and stability of enzyme. The long-term stability also confirmed its stable nature for the investigation period of 4 days where it maintained activity. Combined with its fast and reactive nature, the resulting self-decontaminating regenerating material provides a promising strategy for the neutralization of nerve agents and preserving the environment.

A series of well-defined hard–soft–hard triblock copolymers were synthesized by Ru-based atom transfer radical polymerization (ATRP) (MWD < 1.26) in order to examine their electromechanical properties under electric fields. The obtained methacrylate based triblock copolymers consisted of poly(dodecyl methacrylate) (PDMA) soft middle block segments and three different hard block segments with poly(methyl methacrylate) (PMMA), poly(tert-butyl methacrylate) (PtBMA), and their random copolymers (PMTDTMTs). Polar acidified triblock copolymers were also prepared by deprotecting tert-butyl groups in tBMA-incorporating hard block segments through simple thermal treatment at 200 °C for 120 min, which in situ gave poly(methacrylic acid) (PMAA) and its random copolymers (PAMDMA) in the hard block segments. SAXS and AFM studies indicated that these triblock copolymers showed well-organized phase separations with different domain sizes, which were strongly dependent on the amount of bulky PtBMA or polar PMAA in the hard block segments. In addition, these triblock copolymers had a variety of morphologies affecting their mechanical (elastic modulus) and electrical (dielectric constant) properties, leading to a tuning of their electromechanical properties. The transverse strains of these triblock random copolymers as a function of an applied electric field indicated that the PTMDMT series possessed the best electromechanical properties, exhibiting an 11-fold enhancement relative to the corresponding acidified polymer PAMDMA at 50 Vpp μm−1 due to a dramatic decrease of the elastic modulus from 4.04 to 0.05 MPa in spite of an increase of the dielectric constant from 3.6 to 5.1. In situ SAXS analysis under an electric field showed that these bulk strains originated from nano-structured microdomain changes.