Insect-Inspired Strategy for Conferring Reversible, High Responsivity on Microgels to Dilute-Source CO2.

We described an insect-inspired strategy for conferring reversible, high responsivity on polymer microgels to dilute-source CO2 (≤5000 ppm in gas mixtures). This is demonstrated on oligo(ethylene oxide)-based microgels that contain tertiary amines on the polymer chains with proper organic small molecular carbonates in the polymer-solvent system. Similar to the synergistic contribution of the CO2 receptor subunits in mosquitoes for CO2 response, laser light scattering and related studies indicated that the CO2-response of the microgels in terms of the volume changes works through the coordination of different functional moieties in the system, making it different from the conventional CO2-response mechanism. While this pushes the lower response threshold of CO2 concentration down to ca. 1000 ppm, this unique strategy can also satisfy the urge to achieve both effective CO2 capture and facile CO2 release, making it possible to couple the detection with the capture and utilization of indoor excess CO2.

Reversible Regulating the Substrate Specificity of Enzymes in Microgels by a Phase Transition in Polymer Networks.

Here, we report a distinct approach for regulating the substrate specificity of enzymes immobilized in microgels by a phase transition in polymer networks. The finding is demonstrated on glucose oxidase that is immobilized in thermoresponsive poly(N-isopropylacrylamide)-based microgels. Laser light scattering and enzymatic oxidation tests indicate that the broadened specificity appears at low temperatures, at which the gel matrix is in the relatively swollen state relative to its state at microgel synthesis temperature; upon heating to the relative higher temperatures, the gel matrix is not able to shrink further that offers a tight space in which the enzyme resides to retain high glucose specificity. It is proposed that polymer phase transition in the gel matrix mainly alter protein gates that control passage of substrates into active sites, making them open or close to a certain extent that enable reversible regulating the substrate specificity. The finding is also observed on bulk gels under a rational design, making it of potential interest in enzymatic biofuel cell applications.

Mussel-Inspired Approach to Constructing Dual Network Coated Layered Clay for Enhanced Barrier and Antibacterial Properties of Poly(vinyl alcohol) Nanocomposites.

Inspired by complexation and mussel adhesion of catechol groups in tannic acid (TA), organophilic layered double hydroxides (LDHs@TA-Ti) were synthesized by forming a one-pot assembled TA-titanium (Ti) dual network coating on the surface of layered clay for the first time. LDHs@TA-Ti/poly(vinyl alcohol) (PVA) nanocomposites were prepared by the solution casting method. The results show that TA-Ti(IV) and TiO2 coordination compounds are simultaneously formed due to hydrolysis of titanium tetrachloride and complexation of TA in aqueous solution. Upon TA-Ti coatings onto the surface of LDHs, the antibacterial rate of LDHs@TA-Ti is up to 99.98%. Corresponding LDHs@TA-Ti/PVA nanocomposites also show outstanding antibacterial properties. Compared with pure PVA, LDHs@TA-Ti/PVA nanocomposites show a 40.9% increase in tensile strength, a 17.5% increase in elongation at break, a 35.9% decrease in oxygen permeability and a 26.0% decrease in water vapor permeability when adding 1 wt % LDHs@TA-Ti. UV transmittance (at 300 nm) of LDHs@TA-Ti/PVA nanocomposites decrease by 99.4% when the content of LDHs@TA-Ti reaches 3 wt %. These results indicate that PVA matrix incorporated with LDHs@TA-Ti could be used as a potential active packaging material to extend the shelf life of food products.

Insight into Hyper-Branched Aluminum Phosphonate in Combination with Multiple Phosphorus Synergies for Fire-Safe Epoxy Resin Composites.

Epoxy resin (EP) has widespread applications in thermosetting materials with great versatility and desirable properties such as high electrical resistivity and satisfactory mechanical properties. At present, 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) is widely applied to EP matrix for high flame resistance. Nevertheless, EP/DOPO composites acquire highly toxic decomposition products and smoke particles produced during combustion due to the gaseous fire-inhibition mechanism, which will be a major problem. To address this concern, an effective hyper-branched aluminum phosphonate (AHPP) was rationally designed and then coupled with DOPO into EP matrix to fabricate the fire-safe epoxy resin composites. On the basis of the results, significant increment in limiting oxygen index value (an achievement of 32% from 23.5% for pristine EP) and reduction in peak heat release rate and total heat release (59.4% and 45.6%) with the DOPO/AHPP ratio of 2:1 were recorded. During the cone calorimeter test, both the smoke production and total CO yield of EP-4 composite with the DOPO/AHPP ratio of 1:2 were dramatically decreased by 42.7% and 53.6%, which was mainly associated with the excellent catalytic carbonization of AHPP submicro-particles for EP composite. Future applications of submicro-scaled flame-retardant with various phosphorus oxidation states will have good prospects for development.

Salt-Enhanced CO2-Responsiveness of Microgels.

Here, we report a distinct mechanism for harnessing CO2-responsiveness through enhancing CO2 capture ability. The finding is demonstrated on the microgels that are composed of oligo(ethylene glycol) and sulfonate moieties. Laser light scattering studies on dilute aqueous dispersion of these microgels indicated a low CO2-responsivity, which can be significantly enhanced by adding NaCl and other salts. This salt-enhanced CO2-responsiveness of microgels can be elucidated by the antipolyelectrolyte behavior and its superposition of forming cross-links physically with CO2 as an intermediate. Further results of the filtration experiments on microgel translocation through pores suggest the feasibility of the explanation. The finding is also supported by the CO2 capture-release experiments on the dispersion, which can reversibly absorb and desorb CO2.

Immobilization of sulfur in microgels for lithium-sulfur battery.

Immobilization of sulfur in microgels is achieved via free radical polymerization of commercial poly(ethylene glycol) dimethacrylate in the solution of sulfur-terminated poly(3-oligo(ethylene oxide)4-thiophene), a copolymer prepared by the inverse vulcanization of S8 with allyl-terminated poly(3-oligo(ethylene oxide)4-thiophene). This microgelation leads to enhanced Li-S battery performance over the sulfur-terminated polymer.

Enhanced enzymatic hydrolysis of cellulose in microgels.

A cellulose-based microgel, where an individual microgel contains approximately one cellulose chain on average, is synthesized via free radical polymerization of a difunctional small-molecule N,N'-methylenebisacrylamide in cellulose solution. This microgelation leads to a low-ordered cellulose, favoring enzymatic hydrolysis of cellulose to generate glucose.

Temperature sensitivity and drug encapsulation of star-shaped amphiphilic block copolymer based on dendritic poly(ether-amide).

The star-shaped amphiphilic block copolymer (DPEA-PCL-PNIPAAms) with different PCL block lengths was prepared through ring opening polymerization of epsilon-caprolactone (CL) initiated by hydroxyl end-capped dendritic poly(ether-amide) (DPEA-OH), and then coupling with carboxyl end-capped linear poly(N-isopropylacrylamide) (PNIPAAm-COOH) via an esterification process. The molecular structure was characterized by FT-IR, (1)H NMR, and GPC analysis. As the copolymer dissolved in water, the core-shell structural nanoparticle was formed as a micelle. The fluorescence, (1)H NMR, and dynamic light scattering (DLS) techniques were utilized to confirm the formation of micelles. The optical transmittance and US-DSC measurements demonstrated that the micelles performed the reversible dispersion/aggregation behavior in response to temperature through the outer PNIPAAm polymer shell. The micelles loaded with daidzein showed a very rapid drug release speed at temperatures above the lower critical solution temperature (LCST) due to the temperature-induced structural change of the polymeric micelles.