Synthesis and characterization of poly(N‐isopropylacrylamide)s initiated with siloxane oligomer–(NH4)2Ce(NO3)6 redox pair

Poly(N‐isopropylacrylamide)s (PNIPAAM)s were synthesized via free‐radical polymerization using a ceric ammonium nitrate, Ce(IV)–α‐ω‐dihydroxy(polydimethylsiloxane) (Tegomer H‐Si 2111, PDMS) redox pair in hexane at 30°C in a nitrogen atmosphere. The dependence of the initiation and termination steps on the [NIPAAM]/[Ce(IV)] and [NIPAAM]/[PDMS] ratios were studied using gravimetry and FTIR, ¹H‐NMR, UV‐vis, and GFAA spectroscopy techniques. Gravimetric results indicated that, in the case of high concentrations of PDMS, the percentage of the solid portions of the products decreased while the amount of the oligomeric NIPAAM chains increased, that is, as the amount of PDMS in hexane was increased, the number of the short NIPAAM chains having PDMS segments at the two ends, also increased. UV‐vis results showed that the LCST of PNIPAAM initiated with Ce(IV) alone was higher than those of the ones that were synthesized using common initiator systems such as an ammonium persulfate–N,N,N′,N′‐tetramethylethylenediamine redox pair and azobis(isobutyronitrile). Further, it was observed that both siloxane blocks and ? NH? groups forming coordination bonds with free Ce(IV) ions and/or metal–ligand complexes had an important effect on the aggregation process of the chains. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1248–1254, 2003     

Reconfigurable Dual Peptide Tethered Polymer System Offers a Synergistic Solution for Next Generation Dental Adhesives

Resin-based composite materials have been widely used in restorative dental materials due to their aesthetic, mechanical, and physical properties. However, they still encounter clinical shortcomings mainly due to recurrent decay that develops at the composite-tooth interface. The low-viscosity adhesive that bonds the composite to the tooth is intended to seal this interface, but the adhesive seal is inherently defective and readily damaged by acids, enzymes, and oral fluids. Bacteria infiltrate the resulting gaps at the composite-tooth interface and bacterial by-products demineralize the tooth and erode the adhesive. These activities lead to wider and deeper gaps that provide an ideal environment for bacteria to proliferate. This complex degradation process mediated by several biological and environmental factors damages the tooth, destroys the adhesive seal, and ultimately, leads to failure of the composite restoration. This paper describes a co-tethered dual peptide-polymer system to address composite-tooth interface vulnerability. The adhesive system incorporates an antimicrobial peptide to inhibit bacterial attack and a hydroxyapatite-binding peptide to promote remineralization of damaged tooth structure. A designer spacer sequence was incorporated into each peptide sequence to not only provide a conjugation site for methacrylate (MA) monomer but also to retain active peptide conformations and enhance the display of the peptides in the material. The resulting MA-antimicrobial peptides and MA-remineralization peptides were copolymerized into dental adhesives formulations. The results on the adhesive system composed of co-tethered peptides demonstrated both strong metabolic inhibition of S. mutans and localized calcium phosphate remineralization. Overall, the result offers a reconfigurable and tunable peptide-polymer hybrid system as next-generation adhesives to address composite-tooth interface vulnerability.     

Colour changes of heat‐treated woods of red‐bud maple,European hophornbeam and oak

Colour evolution and colour changes were analyzed from small specimens of three heat treated wood species using the CIE L*a*b* colour space. Upon heat exposure, the wood substance became darker of species; this was accompanied by a steady reduction in lightness. As treatment conditions (e.g., time and temperature) increase, various shades of yellow were favoured for the surface of red‐bud maple wood (Δb = 1.22–9.79). For European hophornbeam wood, increased times at elevated temperatures make a blue (?b) colour the better choice. The total colour difference (ΔE) of the surfaces of wood substrates appear to be well correlated with the treatment temperature and time. The FTIR spectra suggest that the level of modification was insufficient for removing the major cell wall constituents of the wood substrates. All heat‐treated samples showed much less stability against colour difference in outdoor conditions. For red‐bud maple, the greatest improvement was achieved for samples that were treated at 150°C for 2 h (ΔE = 3.12). However, heat‐treated oak wood hadmuch less stability of colour difference for treatment conditions of 150°C for 10 h. © 2010 Wiley Periodicals, Inc. Col Res Appl, 2010.     

Morphological characterization and electrochemical/electrical properties of poly(N‐vinyl carbazole)/montmorillonite composites

A series of poly(N‐vinyl carbazole) (PNVCz)/sodium montmorillonite (Na⁺MMT) and PNVCz/organo‐MMT composite materials have been successfully prepared by in situ free radical polymerization with cerium ammonium nitrate (CAN) as initiator in the presence of inorganic nanolayers of hydrophilic Na⁺MMT or organophilic organo‐MMTs, modified with octadecylamine (ODA) and trimethyl stearyl ammonium (TMSA). The synthesized materials were subsequently characterized by Fourier transform infrared spectroscopy (FTIR), X‐ray diffraction (XRD), and differential scanning calorimetry (DSC). The distribution of MMT layers in the PNVCz matrix was also studied through polarized optical microscope (POM). Their electrochemical and electrical properties were investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The results showed that the type of intercalation agent and mixing method was affected on the structures and properties of composite materials. Both the interlayer spacing of clays and glass transition temperature of PNVCz was increased nearly from 1.18 nm to 3.53 nm and from 140°C to 185°, respectively. Their conductivities also increased relatively to that of the PNVCz homopolymer (10⁻¹¹–10⁻¹⁵ S/cm) and varied in the range of 10⁻¹⁰–10⁻⁵ S/cm, inversely dependent on the amount of MMT loading. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

The discrete fractional Fourier transform

We propose and consolidate a definition of the discrete fractional Fourier transform that generalizes the discrete Fourier transform (DFT) in the same sense that the continuous fractional Fourier transform generalizes the continuous ordinary Fourier transform. This definition is based on a particular set of eigenvectors of the DFT matrix, which constitutes the discrete counterpart of the set of Hermite-Gaussian functions. The definition is exactly unitary, index additive, and reduces to the DFT for unit order. The fact that this definition satisfies all the desirable properties expected of the discrete fractional Fourier transform supports our confidence that it will be accepted as the definitive definition of this transform     

Compressive moduli and network parameters of N‐isopropylacrylamide hydrogels copolymerized by monoesters of itaconic acid and crosslinked with tetraallylammonium bromide

The present study focuses on the mechanical properties of hydrophilically or hydrophobically modified poly(N‐isopropylacrylamide) (PNIPAAm) hydrogels, and all discussions on their improved mechanical strengths are based on the conformational effects of hydrophobic side chains attached to the comonomers and the structural differences between the crosslinkers. Three different types of monoalkyl itaconates, bearing octyl (Oc), cetyl (Ce), and cyclohexyl (CH) groups as comonomers, were used to prepare the copolymeric PNIPAAm hydrogels crosslinked with N,N′‐methylenebisacrylamide (BIS) and tetraallylammonium bromide (TAB) as neutral tetrafunctional and ionic octafunctional crosslinkers, respectively. The most striking result is the compressive E modulus of TAB‐crosslinked PNIPAAm hydrogel containing 10 mol % of mOcI. It reaches nearly 1.0 MPa and is independent of the temperature and pH of the swelling/shrinking medium. The result was discussed in terms of the inter/intramolecular interactions between hydrophobic octyl groups adopting a rod‐like conformation in the case of 25 °C/distilled deionized water (DDW) and 37 °C/DDW combinations. Further, it was observed that the electrostatic repulsive forces between the carboxylate groups on mOcI units could be suppressed even at 37 °C and pH 9 due to the rod‐like conformations of C₈H₁₇ groups. Its micrographs under bright‐field and polarized light supported the presence of an ordered anisotropic phase and multiple associations of extended, hydrophobic side chains. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45039.     

Molecular biomimetics: nanotechnology through biology

Proteins, through their unique and specific interactions with other macromolecules and inorganics, control structures and functions of all biological hard and soft tissues in organisms. Molecular biomimetics is an emerging field in which hybrid technologies are developed by using the tools of molecular biology and nanotechnology. Taking lessons from biology, polypeptides can now be genetically engineered to specifically bind to selected inorganic compounds for applications in nano- and biotechnology. This review discusses combinatorial biological protocols, that is, bacterial cell surface and phage-display technologies, in the selection of short sequences that have affinity to (noble) metals, semiconducting oxides and other technological compounds. These genetically engineered proteins for inorganics (GEPIs) can be used in the assembly of functional nanostructures. Based on the three fundamental principles of molecular recognition, self-assembly and DNA manipulation, we highlight successful uses of GEPI in nanotechnology.     

Effect of ceramic particle size and applied pressure on time to complete infiltration of liquid aluminium into SiC powder compacts

Monitoring of pressurized advance of liquid aluminium into SiC particle compacts of mean particle sizes 12.8, 22.8 and 36.7 m was carried out under applied pressures of 400 to 900 kPa. Infiltration time of liquid aluminium in the compact was recorded by computer logging the output from pairs of open ended wires with a potential difference between them. Results showed that time necessary to complete infiltration in the compacts decreased with increasing particle size and increasing applied pressure. Experimental results are in reasonably good agreement with model predictions.     

Mechanical properties and biocompatibility of plasma-nitrided laser-cut 316L cardiovascular stents

The effect of surface modification of laser-cut 316L cardiovascular stents by low-T plasma nitriding was evaluated in terms of mechanical properties and biocompatibility of the stents. The plasma nitriding was performed at 400, 450 or 500 °C using various ratios of nitrogen–hydrogen gas mixtures. The flexibility and radial strength were measured in crimped and expanded state of the stents, respectively. The mechanical properties could be adjusted and improved by plasma nitriding conducted at temperatures lower than 450 °C and/or nitrogen content less than 10% in the treatment gas. An osteoblast cell culture model system was utilized to investigate the effect of plasma nitriding of the stents on the biological response towards the stents, using biological criteria such as cell viability, alkaline phosphatase and nitric oxide production. In terms of cell viability and alkaline phosphatase production, the plasma nitriding procedure did not appear to negatively affect the biocompatibility of the 316L steel stents. However, in terms of nitric oxide production that was slightly increased in the presence of the plasma-nitrided stents, an indirect improvement in the biocompatibility could possibly be expected.