Highly Adhesive and Self-Healing Zwitterionic Hydrogels as Antibacterial Coatings for Medical Devices.

Bacterial infection of medical devices has caused incalculable losses to maintenance costs and health care. A single coating with antibacterial function cannot guarantee the long-term use of the device, because the coating will be damaged and fall off during reuse. To solve this problem, the development of coatings with high adhesion and self-healing ability is a wise direction. In this paper, a multifunctional polyzwitterionic antibacterial hydrogel coating (PZG) composed of amphozwitterion monomer, anionic monomer, and quaternary ammonium cationic monomer was synthesized by dipping UV photoinitiated polymerization. The structure of PZGs was characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy. Ascribing to the hydrogel internal electrostatic interaction, hydrogen bond, and cation-π interaction, the obtained PZGs exhibited high ductility (>1200% strain) and appropriate strength (>189 kPa). Remarkably, PZGs could also adhere firmly on different substrates through noncovalent interaction, and their adhesion could be controlled by adjusting the amount of zwitterionic. Reversible physical interactions in polymer networks endowed hydrogels with excellent self-healing properties. In addition, PZGs exhibit good antibacterial activity and biocompatibility due to the synergistic effect of quaternary ammonium cation and amphozwitterion monomer. This work provides a multifunctional antibacterial coating for medical equipment and has broad application prospects in the biomedical field.

A One-Pot Strategy to Synthesize Block Copolyesters from Monomer Mixtures Using a Hydroxy-Functionized Ionic Liquid.

One-pot transformation of monomer mixtures into block copolymers remains a key challenge. Herein, a metal-free route to prepare block copolymers from monomer mixtures by a hydroxyl functionalized ionic liquid of 3-(2-hydroxyl-ethyl)-1-methylimidazolium bromide (HEMIMB) is described. HEMIMB can bridge two catalytic cycles including ring-opening alternating copolymerization (ROAC) of phthalic anhydride (PA) with epoxides and ring-opening polymerization (ROP) of L-lactide (LA), and enable a selective copolymerization from PA, LA, and epoxides. The selective copolymerization depends on the presence of PA in mixed feedstocks, exhibits the first ROAC of PA with epoxides and then ROP of LA to the formation of block polyesters in one-pot strategy. This work is beneficial to the development of metal-free catalysts for sequence-controlled polymerization that enable block architectures from mixtures of monomers.

Preparation of grafting copolymer of acrylic acid onto loess surface and its adsorption behavior.

Loess is a typical natural mineral particle distributed widely around the world, and it is inexpensive, readily accessible, and harmless to the environment. In this study, loess was modified by surface grafting copolymerization of functional monomers, such as acrylic acid, N-vinyl pyrrolidone, and N,N-methylenebisacrylamide as a cross-linking agent, which afforded a novel loess-based grafting copolymer (LC-PAVP). After being characterized by scanning electron microscopy, thermal gravimetric analysis and Fourier-transform infrared spectroscopy, its adsorption capacity and mechanism of removing lead ions (Pb2+) were investigated. With the study of the optimal experimental conditions, it was demonstrated that the removal rate of Pb2+ by LC-PAVP can reach up to 99.49% in 60 min at room temperature. It was also found that the kinetic characteristics of the adsorption capacity due to the pseudo-second-order kinetic model and the thermodynamics conformed well with the Freundlich model. In summary, as a lost-cost and eco-friendly loess-based adsorbent, LC-PAVP is a good potential material for wastewater treatment.

Preparation of Thermo-Responsive Poly(ionic liquid)s-Based Nanogels via One-Step Cross-Linking Copolymerization.

In this study, thermo-responsive polymeric nanogels were facilely prepared via one-step cross-linking copolymerization of ethylene glycol dimethacrylate/divinylbenzene and ionic liquid (IL)-based monomers, 1,n-dialkyl-3,3'-bis-1-vinyl imidazolium bromides ([CnVIm]Br; n = 6, 8, 12) in selective solvents. The results revealed that stable and blue opalescent biimidazolium (BIm)-based nanogel solutions could be obtained without any precipitation when the copolymerizations were conducted in methanol. Most importantly, these novel nanogels were thermo-response, and could reversibly transform to precipitation in methanol with temperature changes. Turbidity analysis and dynamic light scatting (DLS) measurement illustrated that PIL-based nanogel solutions presented the phase transform with upper critical solution temperature (UCST) in the range of 5-25 °C. The nanogels were characterized using Fourier transform infrared (FTIR), thermogravimetric analyses (TGA), and scanning electron microscopy (SEM). In addition, BIm-based nanogels could also be used as highly active catalysts in the cycloaddition reaction of CO2 and epoxides. As a result, our attributes build a robust platform suitable for the preparation of polymeric nanomaterials, as well as CO2 conversion.

Construction of hexagonal spindle-shaped Fe-MOFs induced by cationic copolymer and its application for effective wastewater treatment.

The environment and human health are in danger due to the long-term enrichment and buildup of organic pesticides, dyes, and harmful microbes in wastewater. The development of functional materials that are efficient for treating wastewater remains a significant problem. Eco-friendly hexagonal spindle-shaped Fe-MOFs (Hs-FeMOFs) were created in this study under the influence of cationic copolymer (PMSt). The mechanism of crystal growth and development of its unique morphology were described after looking into impact factors for the ideal circumstances and being characterized by XRD, TEM, XPS, and other techniques. It revealed that Hs-FeMOFs possess an enormous supply of adsorption active sites, a strong electropositivity, and the nanometer tip. Then, typical organic pollutants, such as herbicides and mixed dyes, as well as biological pollutants bacteria, were chosen to assess its efficacy in wastewater treatment. It was discovered that the pendimethalin could be quickly removed in wastewater and the removal rate reached 100% within 10 min. In separation of mixed dyes, the retention rate of malachite green (MG) reached 92.3% in 5 min and with a minimum inhibitory concentration of 0.8 mg/mL and demonstrated strong activity due to the presence of cationic copolymers. In actual water matrix, Hs-FeMOF could also play excellent adsorption and antibacterial activity. In summary, a novel, environmentally friendly MOF material with good activity was successfully created by cationic copolymer induction. It offers a fresh approach to develop functional materials in wastewater treatment.

Nano-assemblies of phosphonium-functionalized diblock copolymers with fabulous antibacterial properties and relationships of structure-activity.

As a novel antimicrobial material, quaternary phosphonium salts (QPSs) have been drawing close attention because of their excellent antimicrobial capacity with high activity and low bacterial survivability. Polymeric QPSs (PQPSs) also exhibit selectivity and long-term stability, however the polymerization of QPSs is severely challenged by low controllability and narrow selectivity of cation type. In this study, high-conversion RAFT polymerization is employed to prepare innovative phosphonium-functionalized diblock copolymers (PFDCs) with desired molecular weights and particle sizes. The excellent antibacterial activity of the PFDCs achieves lowest MIC values of 40 and 60 µg mL-1 (i.e., 1.4 and 2.2 µmol L-1) against E. coli and S. aureus, respectively. Mixing with an ink, dye, and latex coating does not weaken the antibacterial activity of the PFDCs, which inhibited 99.9% E. coli, showing broad applicability in different media. The effects of the cation type, synthesis medium, crosslinking content, and particle size on the morphology and antibacterial activity are studied. In summary, the RAFT polymerization of QPSs through the versatile design of ionic liquid monomers and the polymerization-induced self-assembly (PISA) method for constructing nano-assemblies with various micromorphology and particle size provides an exceedingly efficient way to build up multifunctional and multi-morphological polymeric nano-objects that open up vast possibilities in the fields of antibiotics, drug delivery, templated synthesis, and catalysis.

Synthesis of Ag@chitosan/copolymer with dual-active centers for high antibacterial activity.

The prevention and treatment of microorganism contamination on substrate surfaces have recently generated significant concern of scientists. In this paper, a novel diblock copolymer containing antibacterial quaternary ammonium groups as pendant groups, poly(3-(methacryloylamino) propyltrimethyl ammonium chloride)-b-poly(styrene) (PMS), was synthesized by interfacial polymerization. Also, PMS anisotropic particles (APs) could be successfully obtained based on different assembly behaviors by adjusting the ratios of monomers and the toluene/styrene (Tol/St). Moreover, silver loaded chitosan (Ag@CS) and PMS APs were combined to prepare natural/synthetic polymer antibacterial materials with dual-active centers (Ag@CS/PMS-4 APs), aiming to expand the application of carbohydrate polymers and improve the antibacterial activity of composite materials. Remarkably, the resulting series of PMS particles, especially worm-like PMS-4 APs, and Ag@CS/PMS-4 APs composite film ((Ag@CS/PMS-4 APs)-F) exhibited excellent antibacterial properties, which can be employed as interface materials to prevent the transmission of infectious diseases caused by microorganism contamination.

Reutilization of discarded biomass for preparing functional polymer materials.

Biomass is abundant and recyclable on the earth, which has been assigned numerous roles to human beings. However, over the past decades, accompanying with the rapid expansion of man-made materials, such as alloy, plastic, synthetic rubber and fiber, a great number of natural materials had been neglected and abandoned, such as straw, which cause a waste of resource and environmental pollution. In this review, based on introducing sources of discarded biomass, the main composition and polymer chains in discarded biomass materials, the traditional treatment and novel approach for reutilization of discarded biomass were summarized. The discarded biomass mainly come from plant wastes generated in the process of agriculture and forestry production and manufacturing processes, animal wastes generated in the process of animal husbandry and fishery production as well as the residual wastes produced in the process of food processing and rural living garbage. Compared with the traditional treatment including burning, landfill, feeding and fertilizer, the novel approach for reutilization of discarded biomass principally allotted to energy, ecology and polymer materials. The prepared functional materials covered in composite materials, biopolymer based adsorbent and flocculant, carrier materials, energy materials, smart polymer materials for medical and other intelligent polymer materials, which can effectively serve the environmental management and human life, such as wastewater treatment, catalyst, new energy, tissue engineering, drug controlled release, and coating. To sum up, the renewable and biodegradable discarded biomass resources play a vital role in the sustainable development of human society, as well as will be put more emphases in the future.

Loess clay based copolymer for removing Pb(II) ions.

Functional monomers, such as acrylic acid and 2-hydroxyethyl methacrylate were supported into loess clay in situ polymerization, which afforded loess clay based copolymer (LC/PAAHM), a new kind of polymer adsorbent for removing Pb(II) ions from aqueous solution. Characterization of the polymer adsorbent was carried out by different sophisticated methods, such as Fourier transformation infrared spectrometry (FTIR), scanning electron microscopy (SEM), X-ray diffractometry (XRD), thermogravimetric analysis (TGA), and Zetasizer. Batch experiments were carried out to evaluate the factors affecting the removal efficiency, in which the pH, the adsorbent dosage, temperature and initial Pb(II) concentration all found in positive relevance to the increase of Pb(II) removal efficiency. The removal rate of Pb(II) got to 99% at room temperature and the adsorption capacity got to 356.9 mg/g. The pseudo-first-order and pseudo-second-order kinetic models were applied to test the experimental data, and Langmuir and Freundlich models have been applied to study the adsorption equilibrium, respectively.

A facile one-step synthesis to cross-linked polymeric nanoparticles as highly active and selective catalysts for cycloaddition of CO2 to epoxides.

A very convenient one-step synthesis to cross-linked polymeric nanoparticles by conventional radical copolymerization without the addition of stabilizers or surfactants was explored. Moreover, these nanoparticles exhibited excellent stability, activity and selectivity in the cycloaddition reaction of CO(2) to epoxides and could be separated from the products easily and reused.

Poly(ethylene glycol)-conjugated human serum albumin including iron porphyrins: surface modification improves the O2-transporting ability.

Artificial O2-carrying hemoprotein composed of human serum albumin including tetrakis(o-amidophenyl)porphinatoiron(II) (Fe4P or Fe3P) [HSA-FeXP] has been modified by maleimide- or succinimide-terminated poly(ethylene glycol) (PEG), and the formed PEG bioconjugates have been physicochemically characterized. 2-Iminothiolane (IMT) reacted with the amino groups of Lys to create active thiol groups, which bind to alpha-maleimide-omega-methoxy PEG [Mw: 2-kDa (PEG(M2)), 5-kDa (PEG(M5))]. On the other hand, alpha-succinimidyl-omega-methoxy PEG [Mw: 2-kDa (PEG(S2)), 5-kDa (PEG(S5))] directly binds to Lys residues. MALDI-TOF MS of the PEG-conjugated HSA-FeXP showed distinct molecular ion peaks, which provide an accurate number of the PEG chains. In the case of PEG(MY)(HSA-FeXP), the spectroscopic assay of the thiol groups also provided the mean of the binding numbers of the polymers, and the degree of the modification was controlled by the ratio of [IMT]/[HSA]. The viscosity and colloid osmotic pressures of the 2-kDa PEG conjugates (phosphate-buffered saline solution, [HSA] = 5 g dL(-1)) were almost the same as that of the nonmodified one, whereas the 5-kDa PEG binding increased the rheological parameters. The presence of flexible polymers on the HSA surface retarded the association reaction of O2 to FeXP and stabilized the oxygenated complex. Furthermore, PEG(MY)(HSA-FeXP) exhibited a long circulation lifetime of FeXP in rats (13-16 h). On the basis of these results, it can be concluded that the surface modification of HSA-FeXP by PEG has improved its comprehensive O2-transporting ability. In particular the PEG(MY)(HSA-FeXP) solution could be a promising material for entirely synthetic O2-carrying plasma expander as a red cell substitute.