New fluorinated oxazoline block copolymer lowers the adhesion of platelets on polyurethane surfaces

We have prepared an amphiphilic oxazoline block copolymer of hydrophilic poly(2-methyl-2-oxazoline) and hydrophobic poly[2-(2-perfluorooctyl)ethyl-2-oxazoline] chains. By controlling the length and composition of polymer chains, we found that this fluorinated block copolymer can be readily dissolved in water. Furthermore, we can achieve a stable surface coating of the fluorinated block copolymer by dissolving the copolymer in water, then coating the aqueous copolymer solution onto surfaces of nonwater-soluble polymers. This is a simple and useful method of modifying the surface character of polymer substrates. We have found that the polyether urethane (PEU) coated by block copolymer has a different surface chemistry and biological reactivity than the uncoated PEU. From XPS analysis, we found the fluorinated copolymer was coated on PEU (atomic % of F: 31.3 on coated PEU, 0.3 on uncoated). The two surfaces have different affinities for biological molecules. Specifically, the fibrinogen adsorption on the fluorinated copolymer-coated PEU was 62 ± 39 ng/cm², compared to a value of 156 ± 99 ng/cm² for uncoated PEU. In an ex vivo evaluation of platelet adhesion, the surface of coated PEU attached a few white cells while uncoated PEU was covered with activated platelets. © 1994 John Wiley & Sons, Inc.     

Morphology study of layered silicate/chitosan nanohybrids

Modification of clay with biopolymers has been of high interest in recent years. These new materials may be used for drug delivery systems and as biomaterials due to their high biocompatible properties and because they have the advantage of being biodegradable. The modification of montmorillonite (MMT) with chitosan was done in solution, at ratio 1:2 and at room temperature, or at stages of high temperature, and subjected to a microwave treatment. The influence of pH was observed upon the intercalation process.The obtained materials were characterized through X‐ray diffraction (XRD), thermogravimetrical analyses (TGA), Fourier transform infrared spectroscopy (FTIR), atomic force microscopy (AFM), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Using such a mixed treatment, the basal distance of modified MMT increased up to 3.6 nm. The results show the intercalation of chitosan between the layers of MMT and obtaining of intercalated and partial exfoliated nanocomposites. Copyright © 2011 John Wiley & Sons, Ltd.     

Conditions for Cracking and Debond Development at Partially Bonded Bimaterial Half-Planes

Fracture phenomena at the debond tip of partially bonded bimaterial half-planes subjected to concentrated normal forces, couples, and uniform tension are considered. The crack initiation conditions are described by the stress distribution before the initiation and the energy release rate of the crack immediately after the initiation. The debond development conditions are described by the stress distribution and the energy release rate of the debond before its initiation. When both the crack and the debond have chances to occur, or when cracks can arise in both the materials, the fracture phenomena are predicted by comparing the ratio of energy release rates and the ratio of fracture toughnesses.     

Nature‐Inspired Bacterial Cellulose/Methylglyoxal (BC/MGO) Nanocomposite for Broad‐Spectrum Antimicrobial Wound Dressing

Bacterial cellulose (BC) is a natural material produced by Acetobacter xylinum, widely used in wound dressings due to the high water‐holding capacity and great mechanical strength. In this paper, a novel antimicrobial dressing made from BC/methylglyoxal (MGO) composite with a dip‐coating method inspired by naturally antimicrobial Manuka honey is proposed, which to our best knowledge, has not yet to be reported. Characterizations by scanning electron microscope and atomic force microscopy show the interconnected nanostructure of BC and MGO and increase surface roughness of the BC/MGO composite. Thermal analysis indicates high temperature stability of both BC and BC/MGO, while compared with BC, BC/MGO exhibits slightly weaker thermal stability possibly due to reduction of hydrogen bonding and increase of crystallinity. Mechanical test confirms the strong mechanical property of BC and BC/MGO nanocomposite. From the disk diffusion antimicrobial test, the BC/MGO nanocomposite with highest MGO concentration (4%) shows great zone inhibition diameter (around 14.3, 12.3, 17.1, and 15.5 mm against Micrococcus luteus, Pseudomonas aeruginosa, Staphylococcus aureus, and Escherichia coli). Compared with other antimicrobial wound dressing composite materials, the proposed BC/MGO nanocomposite has among the greatest antimicrobial property against broad‐spectrum bacteria, making it a promising antimicrobial dressing in chronic wounds care.     

Insights into the polymerization kinetics of thermoresponsive polytrimethylene carbonate bearing a methoxyethoxy side group

The ring-opening polymerization kinetics of 5-[2-(2-methoxyethoxy)-ethoxymethyl]-5-methyl-1,3-dioxa-2-one (TMOE-2) and 5-[2-{2-(2-methoxyethoxy)ethyoxy}-ethoxymethyl]-5-methyl-1,3-dioxa-2-one (TMOE-3) was investigated using different catalysts with the aim to improve control over molecular weight. The possibility of monomer impurities driving the variability in molecular weight that has been seen in different reports, was assessed and evidence of catalysis via an imidazole impurity was found. The catalysts 1,5,7-triazobicyclo(4.4.0)dec-5-ene (TBD), hydrogen chloride in diethyl ether (HCl·Et₂O), stannous 2-ethylhexanoate (SnOct₂), and catalyst free thermal polymerizations were conducted to understand the mechanisms influencing the molecular weight. TBD and HCl·Et₂O consistently achieved high conversion of the monomer; however, molecular weights greater than 7,000 Da could not be achieved due to competing side reactions. SnOct₂ catalyzed and catalyst free thermal polymerizations were highly influenced by monomer purity and achieved lower conversion than TBD and HCl·Et₂O. Understanding these mechanisms will guide future synthesis of poly(TMOE-2) and poly(TMOE-3) for biomedical applications.     

Surface modification of poly(2‐hydroxyethyl methacrylate) hydrogel for contact lens application

The present study examined poly(2‐hydroxyethyl methacrylate) (PHEMA)‐based hydrogels that have been extensively used in biomedical applications, including contact lens. In this research, we aimed to reduce adsorption of protein components from tears and bacterial deposition by surface modification of the hydrogel with different functional groups that included carboxylic acid, primary amine, and quaternary ammonium. The PHEMA was treated with a solution of sulfuric acid for partial hydrolysis of the HEMA ester groups to induce acid groups on the surface of the hydrogel. Carboxylic acid groups of the modified PHEMA were converted to primary amine and quaternary ammonium groups via carbodiimide chemistry. The surface physical and chemical properties of different samples were investigated by atomic force microscopy and X‐ray photoelectron spectroscopy, respectively. We conducted the bicinchoninic acid assay to evaluate protein deposition from artificial tear fluid on samples. Antibacterial properties of the modified hydrogels were investigated with a culture of Staphylococcus aureus, one of the major causes of eye infections. Our data showed that positively charged amine and ammonium groups efficiently resisted protein adsorption and bacterial deposition compared to alcohol and carboxylic acid groups.     

聚苯乙烯共价键合磷铵两性离子的结构修饰及血液相容性

利用形成碳-氧键将磷铵两性离子(1)共价键合到聚苯乙烯(PS)材料表面, 改善其抗凝血性能. 首先对PS进行氯甲基化反应, 生成苄氯结构, 然后通过自合成化合物1中的-OH与氯甲基化聚苯乙烯的-CH₂Cl反应形成醚键, 将两性离子接枝在PS上. 表征了产物结构, 并通过水接触角和血小板黏附实验对结构修饰前后材料的亲水性和抗凝血性能进行了比较. 结果表明, 磷铵两性离子结构修饰的聚苯乙烯材料可以有效地提高其血液相容性.     

Self‐Assembling Peptide Gels for 3D Prostate Cancer Spheroid Culture

Progress in prostate cancer research is presently limited by a shortage of reliable in vitro model systems. The authors describe a novel self‐assembling peptide, bQ13, which forms nanofibers and gels useful for the 3D culture of prostate cancer spheroids, with improved cytocompatibility compared to related fibrillizing peptides. The mechanical properties of bQ13 gels can be controlled by adjusting peptide concentration, with storage moduli ranging between 1 and 10 kPa. bQ13's ability to remain soluble at mildly basic pH considerably improved the viability of encapsulated cells compared to other self‐assembling nanofiber‐forming peptides. LNCaP cells formed spheroids in bQ13 gels with similar morphologies and sizes to those formed in Matrigel or RADA16‐I. Moreover, prostate‐specific antigen (PSA) is produced by LNCaP cells in all matrices, and PSA production is more responsive to enzalutamide treatment in bQ13 gels than in other fibrillized peptide gels. bQ13 represents an attractive platform for further tailoring within 3D cell culture systems.     

One-pot synthesis of a chitosan-based hydrogel as a potential device for magnetic biomaterial

This describes the cross-linking/co-polymerization reaction of chitosan (CS), acrylic acid (AAc), and N, N′-methylenebisacrylamide (MBA) in the presence of citrate-covered-γ-Fe₂O₃ nanoparticules. A gelling process was verified by means of spectroscopic methods; Fourier transform infrared (FT-IR) and solid-state ¹³C-CP/MAS nuclear magnetic resonance (NMR). The corresponding signals of the gelling process, in the ¹³C NMR spectra, for the magnetic hydrogel were shifted to lower values due to embedding of the citrate-covered-γ-Fe₂O₃ nanoparticules. The X-ray diffraction (XRD) confirmed that the crystallinity of the magnetic hydrogel exhibited a different crystalline structure to that without magnetic properties. The Mössbauer and magnetization analysis revealed that the magnetic hydrogel displays a high lattice strain, due to bonded iron atom covalence and superparamagnetism. From scanning electronic microscope (SEM) micrographs, no separation phase coexists between the magnetic nanoparticules and cross-linked hydrogel, indicating an excellent dispersion throughout the hydrogel. The swelling rate was dependent on the cross-linking degree of the hydrogel and ionic strength of the aqueous solution.