Aqueous photo-RAFT polymerization under ambient conditions: synthesis of protein-polymer hybrids in open air.

A photoinduced reversible addition-fragmentation chain-transfer (photo-RAFT) polymerization technique in the presence of sodium pyruvate (SP) and pyruvic acid derivatives was developed. Depending on the wavelength of light used, SP acted as a biocompatible photoinitiator or promoter for polymerization, allowing rapid open-to-air polymerization in aqueous media. Under UV irradiation (370 nm), SP decomposes to generate CO2 and radicals, initiating polymerization. Under blue (450 nm) or green (525 nm) irradiation, SP enhances the polymerization rate via interaction with the excited state RAFT agent. This method enabled the polymerization of a range of hydrophilic monomers in reaction volumes up to 250 mL, eliminating the need to remove radical inhibitors from the monomers. In addition, photo-RAFT polymerization using SP allowed for the facile synthesis of protein-polymer hybrids in short reaction times (<1 h), low organic content (≤16%), and without rigorous deoxygenation and the use of transition metal photocatalysts. Enzymatic studies of a model protein (chymotrypsin) showed that despite a significant loss of protein activity after conjugation with RAFT chain transfer agents, the grafting polymers from proteins resulted in a 3-4-fold recovery of protein activity.

Degradation of Polylactic Acid/Polypropylene Carbonate Films in Soil and Phosphate Buffer and Their Potential Usefulness in Agriculture and Agrochemistry.

Blends of poly(lactic acid) (PLA) with poly(propylene carbonate) (PPC) are currently in the phase of intensive study due to their promising properties and environmentally friendly features. Intensive study and further commercialization of PPC-based polymers or their blends, as usual, will soon face the problem of their waste occurring in the environment, including soil. For this reason, it is worth comprehensively studying the degradation rate of these polymers over a long period of time in soil and, for comparison, in phosphate buffer to understand the difference in this process and evaluate the potential application of such materials toward agrochemical and agricultural purposes. The degradation rate of the samples was generally accompanied by weight loss and a decrease in molecular weight, which was facilitated by the presence of PPC. The incubation of the samples in the aqueous media yielded greater surface erosions compared to the degradation in soil, which was attributed to the leaching of the low molecular degradation species out of the foils. The phytotoxicity study confirmed the no toxic impact of the PPC on tested plants, indicating it as a "green" material, which is crucial information for further, more comprehensive study of this polymer toward any type of sustainable application.

Comparison of Mechano- and PhotoATRP with ZnO Nanocrystals.

Zinc oxide (ZnO) was previously reported as an excellent cocatalyst for mechanically controlled atom transfer radical polymerization (mechanoATRP), but its photocatalytic properties in photoinduced ATRP (photoATRP) have been much less explored. Herein, well-defined ZnO nanocrystals were prepared via microwave-assisted synthesis and applied as a heterogeneous cocatalyst in mechano- and photoATRP. Both techniques yielded polymers with outstanding control over the molecular weight, but ZnO-cocatalyzed photoATRP was much faster than analogous mechanoATRP (conversion of 91% in 1 h vs 54% in 5 h). The kinetics of photoATRP was tuned by loadings of ZnO nanocrystals. PhotoATRP with ZnO did not require any excess of ligand versus Cu, in contrast to mechanoATRP, requiring an excess of ligand, acting as a reducing agent. ZnO-cocatalyzed photoATRP proceeded controllably without prior deoxygenation, since ZnO was involved in a cascade of reactions, leading to the rapid elimination of oxygen. The versatility and robustness of the technique were demonstrated for various (meth)acrylate monomers with good temporal control and preservation of end-group functionality, illustrated by the formation of tailored block copolymers.

Injection-Molded Isotactic Polypropylene Colored with Green Transparent and Opaque Pigments.

Polypropylene (PP) belongs among the most important commodity plastics due to its widespread application. The color of the PP products can be achieved by the addition of pigments, which can dramatically affect its material characteristics. To maintain product consistency (dimensional, mechanical, and optical), knowledge of these implications is of great importance. This study investigates the effect of transparent/opaque green masterbatches (MBs) and their concentration on the physico-mechanical and optical properties of PP produced by injection molding. The results showed that selected pigments had different nucleating abilities, affecting the dimensional stability and crystallinity of the product. The rheological properties of pigmented PP melts were affected as well. Mechanical testing showed that the presence of both pigments increased the tensile strength and Young's modulus, while the elongation at break was significantly increased only for the opaque MB. The impact toughness of colored PP with both MBs remained similar to that of neat PP. The optical properties were well controlled by the dosing of MBs, and were further related to the RAL color standards, as demonstrated by CIE color space analysis. Finally, the selection of appropriate pigments for PP should be considered, especially in areas where dimensional and color stability, as well as product safety, are highly important.

Stable Magnetorheological Fluids Containing Bidisperse Fillers with Compact/Mesoporous Silica Coatings.

A drawback of magnetorheological fluids is low kinetic stability, which severely limits their practical utilization. This paper describes the suppression of sedimentation through a combination of bidispersal and coating techniques. A magnetic, sub-micro additive was fabricated and sequentially coated with organosilanes. The first layer was represented by compact silica, while the outer layer consisted of mesoporous silica, obtained with the oil-water biphase stratification method. The success of the modification technique was evidenced with transmission electron microscopy, scanning electron microscopy/energy-dispersive X-ray spectroscopy and Fourier-transform infrared spectroscopy. The coating exceptionally increased the specific surface area, from 47 m2/g (neat particles) up to 312 m2/g, which when combined with lower density, resulted in remarkable improvement in the sedimentation profile. At this expense, the compact/mesoporous silica slightly diminished the magnetization of the particles, while the magnetorheological performance remained at an acceptable level, as evaluated with a modified version of the Cross model. Sedimentation curves were, for the first time in magnetorheology, modelled via a novel five-parameter equation (S-model) that showed a robust fitting capability. The sub-micro additive prevented the primary carbonyl iron particles from aggregation, which was projected into the improved sedimentation behavior (up to a six-fold reduction in the sedimentation rate). Detailed focus was also given to analyze the implications of the sub-micro additives and their surface texture on the overall behavior of the bidisperse magnetorheological fluids.

Biodegradable Films of PLA/PPC and Curcumin as Packaging Materials and Smart Indicators of Food Spoilage.

Bio-based and biodegradable packaging combined with chemical sensors and indicators has attracted great attention as they can provide protection combined with information on the actual freshness of foodstuffs. In this study, we present an effective, biodegradable, mostly bio-sourced material ideal for sustainable packaging that can also be used as a smart indicator of ammonia (NH3) vapor and food spoilage. The developed material comprises a blend of poly(lactic acid) (PLA) and poly(propylene carbonate) (PPC) loaded with curcumin (CCM), which is fabricated via the scalable techniques of melt extrusion and compression molding. Due to the structural similarity of PLA and PPC, they exhibited good compatibility and formed hydrogen bonds within their blends, as proven by Fourier transform infrared (FTIR) and X-ray diffraction (XRD). Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) analysis confirmed that the blends were thermally stable at the used processing temperature (180 °C) with minimal crystallinity. The rheological and mechanical properties of the PLA/PPC blends were easily tuned by changing the ratio of the biopolymers. Supplementing the PLA/PCC samples with CCM resulted in efficient absorption of UV radiation, yet the transparency of the films was preserved (T700 ∼ 68-84%). The investigation of CCM extract in ethanol with the DPPH• assay demonstrated that the samples could also provide effective antioxidant action, due to the tunable release of the CCM. Analyses for water vapor and oxygen permeability showed that the PPC improved the barrier properties of the PLA/PPC blends, while the presence of CCM did not hinder barrier performance. The capacity for real-time detection of NH3 vapor was quantified using the CIELab color space analysis. A change in color of the sample from a yellowish shade to red was observed by the naked eye. Finally, a film of PLA/PPC/CCM was successfully applied as a sticker indicator to monitor the spoilage of shrimps over time, demonstrating an evident color change from yellow to light orange, particularly for the PPC-containing blend. The developed system, therefore, has the potential to serve as a cost-effective, easy-to-use, nondestructive, smart indicator for food packaging, as well as a means for NH3 gas monitoring in industrial and environmental applications.

Comparative Study of PVDF Sheets and Their Sensitivity to Mechanical Vibrations: The Role of Dimensions, Molecular Weight, Stretching and Poling.

This paper is focused on the comparative study of the vibration sensing capabilities of poly(vinylidene fluoride) (PVDF) sheets. The main parameters such as molecular weight, initial sample thickness, stretching and poling were systematically applied, and their impact on sensing behavior was examined. The mechanical properties of prepared sheets were investigated via tensile testing on the samples with various initial thicknesses. The transformation of the α-phase to the electro-active ß-phase was analyzed using FTIR after applying stretching and poling procedures as crucial post-processing techniques. As a complementary method, the XRD was applied, and it confirmed the crystallinity data resulting from the FTIR analysis. The highest degree of phase transformation was found in the PVDF sheet with a moderate molecular weight (Mw of 275 kDa) after being subjected to the highest axial elongation (500%); in this case, the ß-phase content reached approximately 90%. Finally, the vibration sensing capability was systematically determined, and all the mentioned processing/molecular parameters were taken into consideration. The whole range of the elongations (from 50 to 500%) applied on the PVDF sheets with an Mw of 180 and 275 kDa and an initial thickness of 0.5 mm appeared to be sufficient for vibration sensing purposes, showing a d33 piezoelectric charge coefficient from 7 pC N-1 to 9.9 pC N-1. In terms of the d33, the PVDF sheets were suitable regardless of their Mw only after applying the elongation of 500%. Among all the investigated samples, those with an initial thickness of 1.0 mm did not seem to be suitable for vibration sensing purposes.

On the Use of Laser Fragmentation for the Synthesis of Ligand-Free Ultra-Small Iron Nanoparticles in Various Liquid Environments.

Traditionally, the synthesis of nanomaterials in the ultra-small size regime (1-3 nm diameter) has been linked with the employment of excessive amounts of hazardous chemicals, inevitably leading to significant environmentally detrimental effects. In the current work, we demonstrate the potential of laser fragmentation in liquids (LFL) to produce highly pure and stable iron ultra-small nanoparticles. This is carried out by reducing the size of carbonyl iron microparticles dispersed in various polar solvents (water, ethanol, ethylene glycol, polyethylene glycol 400) and liquid nitrogen. The explored method enables the fabrication of ligand-free iron oxide ultra-small nanoparticles with diameter in the 1-3 nm range, a tight size distribution, and excellent hydrodynamic stability (zeta potential > 50 mV). The generated particles can be found in different forms, including separated ultra-small NPs, ultra-small NPs forming agglomerates, and ultra-small NPs together with zero-valent iron, iron carbide, or iron oxide NPs embedded in matrices, depending on the employed solvent and their dipolar moment. The LFL technique, aside from avoiding chemical waste generation, does not require any additional chemical agent, other than the precursor microparticles immersed in the corresponding solvent. In contrast to their widely exploited chemically synthesized counterparts, the lack of additives and chemical residuals may be of fundamental interest in sectors requiring colloidal stability and the largest possible number of chemically active sites, making the presented pathway a promising alternative for the clean design of new-generation nanomaterials.

Magnetorheological fluids based on core-shell carbonyl iron particles modified by various organosilanes: synthesis, stability and performance.

Although smart materials, specifically magnetorheological (MR) fluids, have shown remarkable practical importance, their drawbacks such as an aggregation of magnetic fillers, insufficient compatibility with the carrier liquid, low resistance to corrosion and poor sedimentation stability still cause severe limitations for their broader utilization. To address this challenge, our study presents a facile concept for the coating of magnetic particles, leading to their enhanced utility properties and sufficient MR performance. This concentrates on the coating of magnetic carbonyl iron (CI) particles with a thin modifying layer as a surface shell utilizing four organosilanes; tetraethoxysilane, (3-aminopropyl)triethoxysilane, bis[3(trimethoxysilyl)propyl]amine and vinyltrimethoxysilane. Characterization of the modified particles and their suspensions was examined using various methods. XPS analysis confirmed the successful particle modification, while the surface free energy was evaluated by tensiometric measurements reflecting the better compatibility of particles with the dispersing medium. The lowest surface free energy possessed particles modified with (3-aminopropyl)triethoxysilane. The magnetization of the modified core-shell particles was not negatively affected by the organosilanes layer present on the particles resulting in comparable MR performance of the systems based on pure CI particles and their modified analogues as was proved by the fitting of the corresponding flow curves by the Robertson-Stiff model. Moreover, the modification of the particles improved their thermo-oxidation stability and chemical stability investigated via thermogravimetric analysis and acidic tests, respectively. Finally, the sedimentation stability of the modified particle-based systems expressed as a weight gain measured using a tensiometer device was enhanced in comparison with the pure CI particle-based system, which can be very positive in the intended applications.

Effect of Structure of Polymers Grafted from Graphene Oxide on the Compatibility of Particles with a Silicone-Based Environment and the Stimuli-Responsive Capabilities of Their Composites.

This study reports the utilization of controlled radical polymerization as a tool for controlling the stimuli-responsive capabilities of graphene oxide (GO) based hybrid systems. Various polymer brushes with controlled molecular weight and narrow molecular weight distribution were grafted from the GO surface by surface-initiated atom transfer radical polymerization (SI-ATRP). The modification of GO with poly(n-butyl methacrylate) (PBMA), poly(glycidyl methacrylate) (PGMA), poly(trimethylsilyloxyethyl methacrylate) (PHEMATMS) and poly(methyl methacrylate) (PMMA) was confirmed by thermogravimetric analysis (TGA) coupled with online Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). Various grafting densities of GO-based materials were investigated, and conductivity was elucidated using a four-point probe method. Raman shift and XPS were used to confirm the reduction of surface properties of the GO particles during SI-ATRP. The contact angle measurements indicated the changes in the compatibility of GOs with silicone oil, depending on the structure of the grafted polymer chains. The compatibility of the GOs with poly(dimethylsiloxane) was also investigated using steady shear rheology. The tunability of the electrorheological, as well as the photo-actuation capability, was investigated. It was shown that in addition to the modification of conductivity, the dipole moment of the pendant groups of the grafted polymer chains also plays an important role in the electrorheological (ER) performance. The compatibility of the particles with the polymer matrix, and thus proper particles dispersibility, is the most important factor for the photo-actuation efficiency. The plasticizing effect of the GO-polymer hybrid filler also has a crucial impact on the matrix stiffness and thus the ability to reversibly respond to the external light stimulation.

Poly(2-oxazoline)-based magnetic hydrogels: Synthesis, performance and cytotoxicity.

Research on the subject of smart biomaterials has become a cornerstone of tissue engineering and regenerative medicine. Herein, the authors report on developing magnetic hydrogels that combine high biocompatibility and remarkable activity in magnetic fields. We fabricated magnetic hydrogels based on poly(2-ethyl-2-oxazoline) (POx) via living ring-opening cationic polymerization with in-situ embedding of the carbonyl iron (CI) particles. Investigation was made as to the effect exerted by the concentration of CI on magnetic, viscoelastic/magnetorheological properties, the degree of equilibrium swelling, and cytotoxicity. The hydrogels exhibited an open pore structure, as evidenced by computed tomography (CT) imaging. Susceptibility measurements revealed the concentration-dependent field-induced particle restructuration indicating elongation/contraction of the material, thereby determining the potential for magneto-mechanical stimulation of the cells. The POx-based magnetic hydrogels were amphiphilic in character, showing decrease in their capability to hold liquid alongside increase in CI concentration. Viscoelastic measurements suggested that interaction occurred between the particles and matrix based on inconsistency between the experimental storage modulus and the Krieger-Dougherty model. The synthesized materials exhibited excellent biocompatibility toward the 3T3 fibroblast cell line in tests of extract toxicity and direct contact cytotoxicity (ISO standards). The unique combination of properties exhibited by the material - magneto-mechanical activity and biocompatibility - could prove favorable in fields such as biomedicine and biomechanics.

Tailoring Performance, Damping, and Surface Properties of Magnetorheological Elastomers via Particle-Grafting Technology.

A novel concept based on advanced particle-grafting technology to tailor performance, damping, and surface properties of the magnetorheological elastomers (MREs) is introduced. In this work, the carbonyl iron (CI) particles grafted with poly(trimethylsilyloxyethyl methacrylate) (PHEMATMS) of two different molecular weights were prepared via surface-initiated atom transfer radical polymerization and the relations between the PHEMATMS chain lengths and the MREs properties were investigated. The results show that the magnetorheological performance and damping capability were remarkably influenced by different interaction between polydimethylsiloxane chains as a matrix and PHEMATMS grafts due to their different length. The MRE containing CI grafted with PHEMATMS of higher molecular weight exhibited a greater plasticizing effect and hence both a higher relative magnetorheological effect and enhanced damping capability were observed. Besides bulk MRE properties, the PHEMATMS modifications influenced also field-induced surface activity of the MRE sheets, which manifested as notable changes in surface roughness.