Progressing Ultragreen, Energy-Efficient Biobased Depolymerization of Poly(ethylene terephthalate) via Microwave-Assisted Green Deep Eutectic Solvent and Enzymatic Treatment

Effective interfacing of energy-efficient and biobased technologies presents an all-green route to achieving continuous circular production, utilization, and reproduction of plastics. Here, we show combined ultragreen chemical and biocatalytic depolymerization of polyethylene terephthalate (PET) using deep eutectic solvent (DES)-based low-energy microwave (MW) treatment followed by enzymatic hydrolysis. DESs are emerging as attractive sustainable catalysts due to their low toxicity, biodegradability, and unique biological compatibility. A green DES with triplet composition of choline chloride, glycerol, and urea was selected for PET depolymerization under MW irradiation without the use of additional depolymerization agents. Treatment conditions were studied using Box-Behnken design (BBD) with respect to MW irradiation time, MW power, and volume of DES. Under the optimized conditions of 20 mL DES volume, 260 W MW power, and 3 min MW time, a significant increase in the carbonyl index and PET percentage weight loss was observed. The combined MW-assisted DES depolymerization and enzymatic hydrolysis of the treated PET residue using LCC variant ICCG resulted in a total monomer conversion of ≈16% (w/w) in the form of terephthalic acid, mono-(2-hydroxyethyl) terephthalate, and bis-(2-hydroxyethyl) terephthalate. Such high monomer conversion in comparison to enzymatically hydrolyzed virgin PET (1.56% (w/w)) could be attributed to the recognized depolymerization effect of the selected DES MW treatment process. Hence, MW-assisted DES technology proved itself as an efficient process for boosting the biodepolymerization of PET in an ultrafast and eco-friendly manner.

Physical/Mechanical and Antibacterial Properties of Orthodontic Adhesives Containing Calcium Phosphate and Nisin

Enamel demineralization around orthodontic adhesive is a common esthetic concern during orthodontic treatment. The aim of this study was to prepare orthodontic adhesives containing monocalcium phosphate monohydrate (MCPM) and nisin to enable mineralizing and antibacterial actions. The physicomechanical properties and the inhibition of S. mutans growth of the adhesives with added MCPM (5, 10 wt %) and nisin (5, 10 wt %) were examined. Transbond XT (Trans) was used as the commercial comparison. The adhesive containing a low level of MCPM showed significantly higher monomer conversion (42–62%) than Trans (38%) (p < 0.05). Materials with additives showed lower monomer conversion (p < 0.05), biaxial flexural strength (p < 0.05), and shear bond strength to enamel than those of a control. Additives increased water sorption and solubility of the experimental materials. The addition of MCPM encouraged Ca and P ion release, and the precipitation of calcium phosphate at the bonding interface. The growth of S. mutans in all the groups was comparable (p > 0.05). In conclusion, experimental orthodontic adhesives with additives showed comparable conversion but lesser mechanical properties than the commercial material. The materials showed no antibacterial action, but exhibited ion release and calcium phosphate precipitation. These properties may promote remineralization of the demineralized enamel.

Radiolytic synthesis of gold nanoparticles in HEMA-based hydrogels: Potentialities for imaging nanocomposites

This article reports on the radiolytic synthesis of nanocomposites containing gold nanoparticles (AuNPs) within two types of hydrogels based on 2-hydroxyethyl methacrylate (HEMA): (i) plain networks with various contents in ethylene glycol dimethacrylate (EGDMA), as a cross-linker and (ii) stimuli-responsive (SR) networks prepared from these monomers copolymerized with [2-(methacryloyloxy)ethyl]trimethylammonium chloride (MADQUAT) to confer pH-switchable swelling. Hydrogels were prepared by photopolymerization with well-defined composition and a high degree of monomer conversion using two experimental procedures, as xerogels or in aqueous solution. Besides MADQUAT, acrylic acid (AA) or N-isopropylacrylamide have been tested as copolymers, yielding pHor temperature-sensitive hydrogels, respectively. Isothermal swelling in water was affected by monomer composition. Electron beam (EB) irradiation at doses up to 100 kGy of poly(HEMA) xerogels and water-swollen networks prepared with 0.5 wt% of EGDMA had a moderate impact on swelling characteristics and thermomechanical properties of the plain materials, whereas small amounts of extractables were formed. Poly(HEMA)-based nanocomposites containing AuNPs were successfully obtained by EB irradiation of samples swollen by aqueous solutions of Au(III). The effects of dose and cross-linking density on the formation of AuNPs were monitored by UV-visible spectroscopy. Irradiation at well-defined temperatures of the Au(III)-loaded SR hydrogels induced the formation of nanoparticles with size-dependent features, whereas the efficiency of Au(III) reduction at 10 kGy was not significantly affected by the network structure. EB-induced reduction of Au(III) in poly(HEMA) hydrogels using a lead mask to generate well-defined patterns yielded coloured and long-lasting images in the zones where the nanocomposite was formed.

Assessment of Degree of Conversion and Knoop Microhardness of Different Resin Cementing Agents

Background: There are still controversies in the literature as to which is the best resinous cementing agent. Due to this fact and the immense availability of types and brands of cementing agents, further studies are needed to evaluate the properties of these important dental materials. Objective: To assess the degree of monomer conversion (DC) and Knoop microhardness (KHN) of four resin cements: two conventional dual-cured resin cements (EnForce and RelyXARC); one self-etching cement (RelyXU100); and one chemically-activated cement (Cement-Post). Methods: 20 Pieces were made to assess KHN, and 20 to assess DC (n = 5). The DC was analyzed using a Fourier-transform infrared spectrometer, and KHN of the base and the top of the pieces were assessed using the Future-Tech microhardness tester. The data of KHN were statistically analyzed by two-factor ANOVA, and data related to DC were analyzed by the Kruskal-Wallis non-parametric test. The analysis of the correlation between KHN and DC of the cementing agents was performed by linear regression. Results: Dual-cured cements exhibited lower average KHN values at the base than at the top of the pieces (p <0.05). The self-etching cement had a significantly higher average KHN value than the other assessed cements (p <0.05). The DC of the dual-cured cement did not differ (p >0.05). The chemically-activated cement exhibited the lowest averages of KHN and DC values (p <0.05). Linear regression analysis indicated a strong correlation between DC and KNH (p = 0.043; R2 = 0.96); however, a specific hardness value could not be correlated to a specific DC value. Conclusion: Preferably, dual-cured resin cements (conventional or self-etching) should be used. Chemically-activated resin cements should be avoided due to their lower averages of DC and KHN values.

Effects of Color Modifier on Degree of Monomer Conversion, Biaxial Flexural Strength, Surface Microhardness, and Water Sorption/Solubility of Resin Composites

Color modifiers can be mixed with resin composites to mimic the shade of severely discolored tooth. The aim of this study was to assess the effects of a color modifier on the physical and mechanical properties of a resin composite. The composite was mixed with a color modifier at 0 wt% (group 1), 1 wt% (group 2), 2.5 wt% (group 3), or 5 wt% (group 4). The degree of monomer conversion (DC) was examined after light curing for 20 or 40 s. Biaxial flexural strength (BFS)/modulus (BFM), surface microhardness (SH), and water sorption (Wsp)/solubility (Wsl) were also tested. The DC of group 1 was significantly higher than that of groups 3 and 4. The increase in curing time from 20 to 40 s increased the DC by ~10%. The BFS, BFM, Wsp, and Wsl of all the groups were comparable. A negative correlation was detected between the concentration of color modifier and the BFS and DC, while a positive correlation was observed with Wsp. In conclusion, the color modifier reduced the DC of composites, but the conversion was improved by extending the curing time. The increase in color modifier concentration also correlated with a reduction in strength and the increase in the water sorption of the composites.

Preparation of Monodisperse Poly(Methyl Methacrylate)/Polystyrene Composite Particles by Seeded Emulsion Polymerization Using a Sequential Flow Process

We develop a sequential flow process for the production of monodisperse poly (methyl methacrylate) (PMMA)/polystyrene (PS) composite particles through a soap-free emulsion polymerization of methyl methacrylate (MMA) using the first water-in-oil (W/O) slug flow and a subsequent seeded emulsion polymerization of styrene (St) using the second W/O slug flow. In this process, monodisperse PMMA seed particles are first formed in the dispersed aqueous phase of the first W/O slug flow. Subsequently, removal of the oil phase from the slug flow is achieved through a porous hydrophobic tubing, resulting in a single flow of the aqueous phase containing the seed particles. The aqueous phase is then mixed with an oil phase containing St monomer to form the second W/O slug flow. Finally, monodisperse PMMA/PS composite particles are obtained by a seeded emulsion polymerization of St using the second W/O slug flow. We compared the reaction performance between the slug flow and the batch processes in terms of particle diameter, monomer conversion, particle size distribution, and the number of particles in the system. We found that internal circulation flow within the slugs can enhance mass transfer efficiency between them during polymerization, which results in monodisperse PMMA/PS composite particles with a large particle diameter and a high monomer conversion in a short reaction time, compared to those prepared using the batch process. We believe that this sequential microflow process can be a versatile strategy to continuously produce monodisperse composite particles or core-shell particles in a short reaction time.

Experimental Design in Polymer Chemistry—A Guide towards True Optimization of a RAFT Polymerization Using Design of Experiments (DoE)

Despite the great potential of design of experiments (DoE) for efficiency and plannability in academic research, it remains a method predominantly used in industrial processes. From our perspective though, DoE additionally provides greater information gain than conventional experimentation approaches, even for more complex systems such as chemical reactions. Hence, this work presents a comprehensive DoE investigation on thermally initiated reversible addition–fragmentation chain transfer (RAFT) polymerization of methacrylamide (MAAm). To facilitate the adaptation of DoE for virtually every other polymerization, this work provides a step-by-step application guide emphasizing the biggest challenges along the way. Optimization of the RAFT system was achieved via response surface methodology utilizing a face-centered central composite design (FC-CCD). Highly accurate prediction models for the responses of monomer conversion, theoretical and apparent number averaged molecular weights, and dispersity are presented. The obtained equations not only facilitate thorough understanding of the observed system but also allow selection of synthetic targets for each individual response by prediction of the respective optimal factor settings. This work successfully demonstrates the great capability of DoE in academic research and aims to encourage fellow scientists to incorporate the technique into their repertoire of experimental strategies.

AimR Adopts Preexisting Dimer Conformations for Specific Target Recognition in Lysis-Lysogeny Decisions of Bacillus Phage phi3T

A bacteriophage switches between lytic and lysogenic life cycles. The AimR-AimP-AimX communication system is responsible for phage lysis-lysogeny decisions during the infection of Bacillus subtilis. AimX is a regulator biasing phage lysis, AimR is a transcription factor activating AimX expression, and AimP is an arbitrium peptide that determines phage lysogeny by deactivating AimR. A strain-specific mechanism for the lysis-lysogeny decisions is proposed in SPbeta and phi3T phages. That is, the arbitrium peptide of the SPbeta phage stabilizes the SPbeta AimR (spAimR) dimer, whereas the phi3T-derived peptide disassembles the phi3T AimR (phAimR) dimer into a monomer. Here, we find that phAimR does not undergo dimer-to-monomer conversion upon arbitrium peptide binding. Gel-filtration, static light scattering (SLS) and analytical ultracentrifugation (AUC) results show that phAimR is dimeric regardless of the presence of arbitrium peptide. Small-angle X-ray scattering (SAXS) reveals that the arbitrium peptide binding makes an extended dimeric conformation. Single-molecule fluorescence resonance energy transfer (smFRET) analysis reveals that the phAimR dimer fluctuates among two distinct conformational states, and each preexisting state is selectively recognized by the arbitrium peptide or the target DNA, respectively. Collectively, our biophysical characterization of the phAimR dynamics underlying specific target recognition provides new mechanistic insights into understanding lysis-lysogeny decisions in Bacillus phage phi3T.

Synergistic Enzyme Mixtures to Realize Near-Complete Depolymerization in Biodegradable Polymer/Additive Blends

Embedding catalysts inside of plastics affords accelerated chemical modification with programmable latency and pathways. Nanoscopically embedded enzymes can lead to near complete degradation of polyesters via chain-end mediated processive depolymerization. The overall degradation rate and pathways have a strong dependence on the morphology of semi-crystalline polyesters. Yet, most studies to date focus on pristine polymers instead of mixtures with additives and other components despite their nearly universal uses in plastic production. Here, additives are introduced to purposely change the morphology of polycaprolactone (PCL) by increasing the bending and twisting of crystalline lamellae. These morphological changes immobilize chain-ends preferentially at the crystalline/amorphous interfaces and limit chain-end accessibility by the embedded processive enzyme. This chain end redistribution reduces the polymer-to-monomer conversion from >95% to less than 50%, causing formation of highly crystalline plastic pieces including microplastics. By synergizing both random chain scission and processive depolymerization, it is feasible to navigate morphological changes in polymer/additive blends and to achieve near complete depolymerization. The random scission enzymes in the amorphous domains create new chain ends that are subsequently bound and depolymerized by processive enzymes. Present studies further highlight the importance to consider host polymer morphological effects on the reactions catalyzed by embedded catalytic species.