Cellulose Acetate Membranes Modification by Aminosilane Grafting in Supercritical Carbon Dioxide towards Antibiofilm Properties

The study explores the grafting of cellulose acetate microfiltration membranes with an aminosilane to attain antibiofilm properties. The grafting reaction was performed in the supercritical carbon dioxide used as a transport and reaction medium. The FTIR analyses and dissolution tests confirmed the covalent bonding between the aminosilane and polymer. The membranes’ microstructure was investigated using a dual-beam SEM and ion microscopy, and no adverse effects of the processing were found. The modified membranes showed a more hydrophilic nature and larger water permeate flow rate than the neat cellulose acetate membranes. The tests in a cross-filtration unit showed that modified membranes were considerably less blocked after a week of exposure to Staphylococcus aureus and Escherichia coli than the original ones. Microbiological investigations revealed strong antibiofilm properties of the grafted membranes in experiments with Staphylococcus aureus, Listeria monocytogenes, Escherichia coli, and Salmonella Enteritidis.

Synthesis and nanoscale characterization of hierarchically assembled molecular nanosheets

Chemical functionalization of molecular two-dimensional (2D) materials towards the assembly of hierarchical functional nanostructures is of great importance for nanotechnology including areas like artificial photocatalytic systems, nanobiosensors or ultrafiltration. To achieve the desired functionality of 2D materials, these need to be characterized down to the nanoscale. However, obtaining the respective chemical information is challenging and generally requires the application of complementary experimental techniques. Here, we demonstrate the synthesis and chemical characterization of hierarchically assembled molecular nanosheets based on about 1 nm thin, molecular carbon nanomembrane (CNM) and covalently grafted, single-molecule layer cobalt(III) catalysts for the light-driven hydrogen evolution reaction (HER). We employ X-ray photoelectron spectroscopy (XPS) and tip-enhanced Raman spectroscopy (TERS) to access both the transversal and lateral chemical information of the synthesized nanosheets with nanometer resolution. TERS and XPS data provide detailed information on the average and local surface distribution of the catalyst as well as mechanistic details of the grafting reaction. The proposed approach represents a general route towards a nanoscale structural analysis for a variety of molecular 2D materials - a rapidly growing materials class with broad prospects for fundamental science and applications.

Electron-Beam-Induced Grafting of Chitosan onto HDPE/ATZ Composites for Biomedical Applications

The surface functionalisation of high-density polyethylene (HDPE) and HDPE/alumina-toughened zirconia (ATZ) surfaces with chitosan via electron-beam (EB) irradiation technique was exploited for preparing materials suitable for biomedical purposes. ATR–FTIR analysis and wettability measurements were employed for monitoring the surface changes after both irradiation and chitosan grafting reaction. Interestingly, the presence of ATZ loadings beyond 2 wt% influenced both the EB irradiation process and the chitosan functionalisation reaction, decreasing the oxidation of the surface and the chitosan grafting. The EB irradiation induced an increase in Young’s modulus and a decrease in the elongation at the break of all analysed systems, whereas the tensile strength was not affected in a relevant way. Biological assays indicated that electrostatic interactions between the negative charges of the surface of cell membranes and the –NH3+ sites on chitosan chains promoted cell adhesion, while some oxidised species produced during the irradiation process are thought to cause a detrimental effect on the cell viability.

Addition of divinyl benzene comonomer to glycidyl methacrylate grafting to cyclic natural rubber

The process of thermally grafting glycidyl methacrylate (GMA) on cyclic natural rubber (CNR) compared to the addition of an initiator of organic peroxide, dicumyl peroxide (DCP) and using cross-linker divinyl benzene (DVB) has been carried out by means of melt processing. The main aims of the modified GMA grafted to CNR was to increase the polarity of the polymer to be used as a compatibiliser agent in asphalt modification. The addition of DVB comonomer in the processing was to increase the amount of GMA implanted in cyclic rubber as measured by the degree of GMA grafting. The grafting method was carried out by melting polymer (melt processing) at high temperatures in the reactor internal mixer (Brabender model). The grafting reaction took place at a temperature of 160°C, 60 rpm rotor rotation for 10 minutes of mixing. To determine the GMA grafting reaction on cyclic rubber, characterization was carried out with Fourier Transformed Infra Red (FT-IR) while the degree of GMA grafting on natural rubber was determined by acid-base titration method in organic solvents. It was found that the GMA grafting process on cyclic natural rubber could easily occur in the melting phase at high temperatures and increase with the addition of dicumyl peroxide (DCP) peroxide. Although the addition of divinyl benzene (DVB) comonomer can increase the degree of grafting of GMA on CNR, the addition of comonomer can cause high cross-linking.

Novel Poly(Methylenelactide-g-L-Lactide) Graft Copolymers Synthesized by a Combination of Vinyl Addition and Ring-Opening Polymerizations

In this work, a novel poly (methylenelactide-g-L-lactide), P(MLA-g-LLA) graft copolymer was synthesized from poly(methylenelactide) (PMLA) and L-lactide (LLA) using 0.03 mol% liquid tin(II) n-butoxide (Sn(OnBu)2) as an initiator by a combination of vinyl addition and ring-opening polymerization (ROP) at 120 °C for 72 h. Proton and carbon-13 nuclear magnetic resonance spectroscopy (1H- and 13C-NMR) and Fourier-transform infrared spectroscopy (FT-IR) confirmed the grafted structure of P(MLA-g-LLA). The P(MLA-g-LLA) melting temperatures (Tm) range of 144–164 °C, which was lower than that of PLA (170–180 °C), while the thermal decomposition temperature (Td) of around 314–335 °C was higher than that of PLA (approx. 300 °C). These results indicated that the grafting reaction could widen the melt processing range of PLA and in doing so increase PLA’s thermal stability during melt processing. The graft copolymers were obtained with weight-average molecular weights (M¯w) = 4200–11,000 g mol−1 and a narrow dispersity (Đ = 1.1–1.4).

Flame Retardancy and Dispersion of Functionalized Carbon Nanotubes in Thiol-Ene Nanocomposites

A polysilicone flame retardant (PA) was synthesized and covalently grafted onto the surface of carbon nanotubes (CNTs) via amide linkages to obtain modified CNTs (CNTs-PA). The grafting reaction was characterized by Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectrometer (XPS), Transmission electron microscopy (TEM) and Thermogravimetric analysis (TGA), and the resultant CNTs-PA was soluble and stable in polar solvents Chloroform. Thiol-ene (TE)/CNTs-PA nanocomposites were prepared via Ultraviolet curing. The flame retardancy of thiol-ene nanocomposites was improved, especially for the heat release rate. Moreover, the results from Scanning electron microscopy (SEM) and Dynamic mechanical thermal analysis (DMTA) showed that the CNTs-PA improved the dispersion of CNTs in thiol-ene and enhanced the interfacial interaction between CNTs-PA and thiol-ene matrix.

Surface Modification of Polyurethane Membrane with Various Hydrophilic Monomers and N-halamine: Surface Characterization and Antimicrobial Properties Evaluation

Reducing microbial infections associated with biomedical devices or articles/furniture noted in a hospital or outpatient clinic remains a great challenge to researchers. Due to its stability and low toxicity, the N-halamine compound has been proposed as a potential antimicrobial agent. It can be incorporated into or blended with the FDA-approved biomaterials. Surface grafting or coating of N-halamine was also reported. Nevertheless, the hydrophobic nature associated with its chemical configuration may affect the microbial interactions with the chlorinated N-halamine-containing substrate. In this study, a polymerizable N-halamine compound was synthesized and grafted onto a polyurethane surface via a surface-initiated atom transfer radical polymerization (SI-ATRP) scheme. Further, using the sequential SI-ATRP reaction method, different hydrophilic monomers, namely poly (ethylene glycol) methacrylate (PEGMA), hydroxyethyl methacrylate (HEMA), and [2-(methacryloyloxy) ethyl] dimethyl-(3-sulfopropyl) ammonium hydroxide (SBMA), were also grafted onto the polyurethane (PU) substrate before the N-halamine grafting reaction to change the surface properties of the N-halamine-modified substrate. It was noted that the chains containing the hydrophilic monomer and the polymerizable N-halamine compound were successfully grafted onto the PU substrate. The degree of chlorination was improved with the introduction of a hydrophilic monomer, except the HEMA. All of these hydrophilic monomer-containing N-halamine-modified PU substrates demonstrated a more than 2 log CFU reduction after microbial incubation. In contrast, the surface modified with N-halamine only exhibited significantly less antimicrobial efficacy instead. This is likely due to the synergistic effects caused by the reduced chlorine content, as well as the reduced surface interactions with the microbes.

Incorporation of amine functional group on surface of hydroxyapatite prepared fromstriped catfish (Pagasianodon hypophthalmus) bone

This study was conducted to incorporate amine functional groups on the surface of hydroxyapatite to enhance its potential application in biomedical materials. Hydroxyapatite particles (HA) were synthesized from striped catfish (Pagasianodon hypophthalmus) bone and surface modified by grafting with (3-aminopropyl)triethoxysilane (APTES). Important factors affected grafting efficiency such as concentration of APTES, water content, reaction temperature and reaction time were studied. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and Scanning electron microscopy (SEM) were used to confirm the grafting reaction on HA surfaces. Grafting efficiency was evaluated based on intensity of characteristic absorption peaks of APTES. The experimental results showed that amine functional groups were successfully introduced on HA surface at optimal condition of 0.2 M APTES, 0.75 wt.% water content, at 60°C and 12-hour reaction time.

Theoretical Study on the Grafting Reaction of Maleimide Containing 2-Hydroxy-Benzophenone Onto Polyethylene

A theoretical study on the multi-channel hydrogen addition of maleimide containing 2-hydroxy-benzophenone onto polyethylene in Ultra-Violet (UV) radiation cross-linking process was carried out using density functional theory (DFT) method at the B3LYP/6-311+G(d,p) level. The energetic information and the minimum energy path (MEP) are calculated of nine reaction channels. The electrophilic addition reactions at two positions in the target molecule (maleimide containing 2-hydroxy-benzophenone) were investigated, where are on the C atom of C=C groups and on the O atom of C=O groups. Frontier MOs and NBO charge population of the target molecule have been analyzed in detail. As a result, the reaction site of C in C=C group is more active than the site of O in C=O groups. The target molecule can be used as a multi-functional additive candidate. The predicted mechanism may provide a theoretical basis for the real application of XLPE high voltage insulation cables.