Polycaprolactone (PCL) Chains Grafting on the Surface of Cellulose Nanocrystals (CNCs) during <i>In Situ</i>Polymerization of <i>ε</i>-Caprolactone at Room Temperature

This work aimed at investigating the feasibility of surface modification of cellulose nanocrystals (CNCs) using in situ ring opening polymerization of ε-caprolactone (ε-CL) at room temperature. Residues of flax and milkweed (Asclepias syriaca) stem fibers were used as a source of cellulose to obtain and isolate CNCs. The cationic ring opening polymerization (CROP) of the monomer ε-CL was used to covalently graft polycaprolactone (PCL) chains at the CNCs surface. Silver hexafluoroantimonate (AgSbF6) was used in combination with the extracted CNCs to initiate, at room temperature, the polymerization and the grafting reactions with no other stimulus. Fourier-Transform InfraRed (FTIR), X-ray Photoelectron Spectrometry (XPS), UV/visible absorption and Gel Permeation Chromatography (GPC) analyses evidenced the presence of PCL chains covalently grafted at CNCs surface, the formation of Ag(0) particles as well as low or moderate molecular weight free PCL chains.

Thermal and mechanical properties and micro-mechanism of SiO_(2)/epoxy nanodielectrics

In addition to electrical insulation properties,the thermal properties of nanodielectrics,such as glass transition temperature,thermal expansion coefficients,thermal conductivity,and mechanical properties,including Young's modulus,bulk modulus,and shear modulus,are also very important.This paper describes the molecular dynamics simulations of epoxy resin doped with SiO_(2)nanoparticles and with SiO_(2)nanoparticles that have been surface grafted with hexamethyldisilazane(HMDS)at 10%and 20%grafting rates.The results show that surface grafting can improve certain thermal and mechanical properties of the system.Our analysis indicates that the improved thermal performance occurs because the formation of thermal chains becomes easier after the surface grafting treatment.The improved mechanical properties originate from two causes.First,doping with SiO_(2)nanoparticles inhibits the degree of movement of molecular chains in the system.Second,the surface grafting treatment weakens the molecular repulsion between SiO_(2)and epoxy resin,and the van der Waals excluded region becomes thinner.Thus,the compatibility between SiO_(2)nanoparticles and polymers is improved by the grafting treatment.The analysis method and conclusions in this paper provide guidance and reference for the future studies of the thermal and mechanical properties of nanodielectrics.

Grafting of PEG400 onto the surface of LLDPE/SMA film

Linear low-density polyethylene(LLDPE)was melt and blended with styrene-maleic anhydride copolymer(SMA).The blending films were then immersed in poly(ethylene glycol)400(PEG400)at room temperature.The surface composition of the blend films was determined by Fourier transform infra-red spectroscopy coupled with a variable incidence angle attenuated total reflection accessory(ATR-FTIR).Results show that PEG400 can be grafted onto the surface of the films via esterification with SMA.The immersion of PEG promotes the enrichment of SMA onto the surface of the films.The water contact angle data show that grafting of PEG400 onto PE can greatly improve the hydro-philicity of the PE surface.These experiments show that sur-face functionalization of polyethylene films by blending SMA and then surface grafting of PEG is feasible,which suggest an effective and simple route for PE surface modification via blending and grafting.

Smart biomaterials: Surfaces functionalized with proteolytically stable osteoblast-adhesive peptides

Engineered scaffolds for bone tissue regeneration are designed to promote cell adhesion,growth,proliferation and differentiation.Recently,covalent and selective functionalization of glass and titanium surfaces with an adhesive peptide(HVP)mapped on[351e359]sequence of human Vitronectin allowed to selectively increase osteoblast attachment and adhesion strength in in vitro assays,and to promote osseointegration in in vivo studies.For the first time to our knowledge,in this study we investigated the resistance of adhesion sequences to proteolytic digestion:HVP was completely cleaved after 5 h.In order to overcome the enzymatic degradation of the native peptide under physiological conditions we synthetized three analogues of HVP sequence.A retro-inverted peptide D-2HVP,composed of D amino acids,was completely stable in serum-containing medium.In addition,glass surfaces functionalized with D-2HVP increased human osteoblast adhesion as compared to the native peptide and maintained deposition of calcium.Interestingly,D-2HVP increased expression of IBSP,VTN and SPP1 genes as compared to HVP functionalized surfaces.Total internal reflection fluorescence microscope analysis showed cells with numerous filopodia spread on D-2HVP-functionalized surfaces.Therefore,the D-2HVP sequence is proposed as new osteoblast adhesive peptide with increased bioactivity and high proteolytic resistance.

Thermo-responsive cellulose papers grafted with poly(di(ethylene glycol)methyl ether methacrylate)

Novel thermo-responsive cellulose papers were prepared via grafting poly(di(ethylene glycol)methyl ether methacrylate)(PDEGMA)by activators regenerating electron transfer(ARGET)and atom transfer radical polymerization(ATRP).Attenuated total refraction Fourier-transform infrared spectroscopy(ATR-FTIR)and scanning electron microscopy(SEM)measurements of the modified paper showed that PDEGMA brushes were successfully grafted on the paper surface.The thermal stability of the papers before and after grafting was evaluated by thermogravimetric analysis(TGA).The PDEGMA-grafted paper exhibited a two-step thermal degradation process,and presented thermo-responsive characteristics.It was hydrophilic at room temperature but changed rapidly to highly hydrophobic when the temperature rose above 50℃.

Structure, mechanical and thermal properties of BMI/E-44/CNTs ternary composites via amination method

Multi-walled carbon nanotubes(CNTs) were modified by an amination treatment with hexamethylenediamine(HMD), and then bismaleimide(BMI)/epoxy(E-44)/CNTs ternary composites were prepared using modified CNTs as the reinforcement via a simple mixing and curing molding method. The results show that the surfaces of CNTs are grafted polymer with the thickness of 3 nm and the dispersity of surface grafted carbon nanotubes(SG-CNTs) in the resin composites can be improved. The prepared composites contain C-C, C-N, C=O and-COOH groups and can keep a smooth surface. In addition, the composites have the flexural strength of 152 MPa, the tensile strength of 73 MPa and the impact strength of 87 k J m^(-2),respectively, when the weight ratio of BMI to E-44 is 1:8 and the content of SG-CNTs is 2 wt%. However,the thermal stability of the composites with SG-CNTs is a little lower than that of the composites without SG-CNTs.