A Facile Surface Modification Scheme for Medical-Grade Titanium and Polypropylene Using a Novel Mussel-Inspired Biomimetic Polymer with Cationic Quaternary Ammonium Functionalities for Antibacterial Application.

Medical device-associated infection remains a critical problem in the healthcare setting. Different clinical- or device-related methods have been attempted to reduce the infection rate. Among these approaches, creating a surface with bactericidal cationic functionality has been proposed. To do so, a sophisticated multi-step chemical procedure would be needed. Instead, a simple immersion approach was utilized in this investigation to render the titanium and polypropylene surface with the quaternary ammonium functionality by using a mussel-inspired novel lab-synthesized biomimetic catechol-terminated polymer, PQA-C8. The chemical oxidants, CuSO4/H2O2, as well as dopamine, were added into the novel PQA-C8 polymer immersion solution for one-step surface modification. Additionally, a two-step immersion scheme, in which the polypropylene substrate was first immersed in the dopamine solution and then in the PQA-C8 solution, was also attempted. Surface analysis results indicated the surface characteristics of the modified substrates were affected by the immersion solution formulation as well as the procedure utilized. The antibacterial assay has shown the titanium substrates modified by the one-step dopamine + PQA-C8 mixtures with the oxidants added and the polypropylene modified by the two-step scheme exhibited bacterial reduction percentages greater than 90% against both Gram-positive S. aureus and Gram-negative E. coli and these antibacterial substrates were non-cytotoxic.

Studies of Mercaptosuccinic Acid-Crosslinked Chitosan Hydrogel with Grafted Cinnamaldehyde and Silver Nanoparticles for Antibacterial Biomedical Application.

For the effective clinical antibacterial application of biomaterials, such as for wound management and tissue repair, the biomaterials need to show proper antibacterial capability as well as non-cytotoxicity. Furthermore, the material needs to have suitable mechanical characteristics for further medical use. Chitosan hydrogel is a potential candidate for various antibacterial biomedical applications due to its amine functionalities that lead to antimicrobial characteristics. Nevertheless, its antimicrobial capability is dependent upon the degree of protonation of amine groups caused by the pH value. Moreover, its mechanical compressive strength may not be high enough for clinical use if not chemically or physically crosslinked. This study utilized a novel chemical crosslinker, mercaptosuccinic acid, to improve its mechanical characteristics. The natural antibacterial agent, cinnamaldehyde, was grafted onto the crosslinked chitosan to improve its antimicrobial capability. Meanwhile, to take advantage of the thiol functionality in the mercaptosuccinic acid, the bactericidal silver nanoparticles were incorporated through silver-thiol covalent bounding. NMR analyses indicated the chitosan was successfully mercaptosuccinic acid-crosslinked and grafted with cinnamaldehyde at different ratios. Combined the results from the mechanical assessment, swelling experiments, antimicrobial assessment, and cytotoxicity assay, the chitosan hydrogel with the highest crosslinked degree and grafted with cinnamaldehyde and silver nanoparticles is of great promise for further clinical uses.

Enhancing Resin Cement Adhesion to Zirconia by Oxygen Plasma-Aided Silicatization.

The combinations of alumina particle air abrasion (AA) and a 10-methacryloyloxyidecyl-dihyidrogenphosphate (MDP) primer and a tribochemical silica coating (TSC) and a silane-base primer are contemporary pre-cementation treatments for zirconia restorations for bonding with resin cements. However, the stability of zirconia resists the mechanical or chemical preparations. The purpose of this study was to develop an atmospheric-pressure oxygen plasma (OP)-aided silicatization method to enhance the adhesion of resin cements to zirconia. Zirconia discs were prepared to receive surface treatments of different combinations: (1) AA or TSC (2) with or without OP treatment, and (3) a chemical primer (no primer, silane, or a silane-MDP mixture). The surface morphology, hydrophilicity, and chemical compositions were characterized, and the resin-zirconia bond strengths were examined either after 24 h or a thermocycling test. The results indicated that the OP treatment after the TSC facilitated the homogeneous distribution of silane and crosslinking of silica particles, and effectively improved the hydrophilicity. The OP increased the O and Si and reduced the C elemental contents, while the combination of TSC, OP, and silane induced SiOx generation. Among the groups, only the TSC-OP-silane treatment effectively enhanced the bond strength and maintained the adhesion after thermocycling. With these results, the OP aided the silicatization protocol effectively, generated silane crosslinking, and resulted in superior resin-zirconia bond strength and durability compared to the current treatments.

Interaction of silane with 10-MDP on affecting surface chemistry and resin bonding of zirconia.

OBJECTIVE: To investigate the effect of silane contents on their chemical interaction with 10-methacryloyloxydecyl-dihydrogen phosphate (MDP), and affecting the bonding of MDP to zirconia by time-of-flight secondary ion mass spectrometry (TOF-SIMS) and solid-state nuclear magnetic resonance (SSNMR) spectroscopy. METHODS: Zirconia (Cercon ht, Dentsply) slabs were prepared and fully sintered. Experimental primers SE-5 and SE-10 were formulated by adding 5 wt% and 10 wt% γ-methacryloxypropyltrimethoxysilane to an MDP-based primer SE BOND (SE), respectively. SE, SE-5, and SE-10 were applied on the assigned zirconia slabs. The chemical compositions on the surface and adhesive interfaces were examined by TOF-SIMS in a depth-profiling mode. Hydrophilicity and resin affinity of treated zirconia were analyzed. The bond strengths to resin cylinder were examined either after 24-h storage or thermocycles. In addition, zirconia powders treated with three primers were assessed by SSNMR spectrometry for the adsorption of MDP. RESULTS: TOF-SIMS analysis showed that SE treatment generated the greatest amount of P-O-Zr related ions, which reduced in SE-5 and SE-10 groups. The 3D ion-images illustrated the generation of ZrO2(OH)- ions with silane contents. The SSNMR analysis revealed that the chemical bonding was mainly P-O-Zr ionic bonds in SE but shifted to P-OH-Zr hydrogen bonds in SE-5 and SE-10. SE-5 and SE-10 treated zirconia presented higher hydrophilicity and affinity to resin compared to Zr did. SE showed the highest initial bond strength which significantly decreased after thermocycling. SIGNIFICANCE: MDP adsorption onto zirconia via P-O-Zr ionic bond promotes bonding with resin. The silane enhances the hydroxylation of zirconia and impairs the adsorption of MDP, but does not adversely affect the bond durability.

Investigations of silane-MDP interaction in universal adhesives: A ToF-SIMS analysis.

OBJECTIVES: The purposes of this study were to investigate whether the presence of silane in universal adhesives affects the functions of 10-methacryloyloxydecyl dihydrogen phosphate (MDP) and adhesion to zirconia. METHODS: Two silane-containing universal adhesives (Scotchbond Universal (SBU) and Clearfil Universal-Bond (CUB)) and two silane-free adhesives (All-Bond Universal (ABU) and SE-Bond primer (SE)) were individually applied on zirconia disks. Time-of-flight secondary-ion-mass-spectrometry (ToF-SIMS) examined the distributions of MDP- and silane-related ions, as well as evidence of zirconium phosphate (ZrP) compounds, on the surface and interfacial regions using a depth profiling mode. The hydrophilicity and resin wettability of the treated zirconia were examined using a contact angle test. For the shear bond strength (SBS) test, the zirconia disks were air-blasted, treated with the assigned adhesives, and bonded with pre-cured composite cylinders using a resin cement. These resin-zirconia assemblies received a bond test after 24-h storage. RESULTS: Both SBU and CUB exhibited silane-related ions and ZrO2(OH)-, but fewer PO- ions in the interfacial regions. CUB had more siloxane-related ions. SE-treated zirconia had abundant PO- ions and particularly high PO3-- and ZrP- related ions in the interfacial regions. The silane-free adhesives exhibited a higher affinity to both water and adhesive liquids. SE showed significantly higher SBSs compared to ABU, while SBU and CUB were not statistically different. SIGNIFICANCE: The silane content may cause hydroxylation of zirconia and affect MDP adsorption. An acidic pH accelerated the condensation of silanol. The bond performance of the MDP-based adhesive could be influenced by the silane content and other components.

Novel Polymerization of Dental Composites Using Near-Infrared-Induced Internal Upconversion Blue Luminescence.

Blue light (BL) curing on dental resin composites results in gradient polymerization. By incorporating upconversion phosphors (UP) in resin composites, near-infrared (NIR) irradiation may activate internal blue emission and a polymerization reaction. This study was aimed to evaluate the competency of the NIR-to-BL upconversion luminance in polymerizing dental composites and to assess the appropriate UP content and curing protocol. NaYF4 (Yb3+/Tm3+ co-doped) powder exhibiting 476-nm blue emission under 980-nm NIR was adapted and ball-milled for 4-8 h to obtain different particles. The bare particles were assessed for their emission intensities, and also added into a base composite Z100 (3M EPSE) to evaluate their ability in enhancing polymerization under NIR irradiation. Experimental composites were prepared by dispensing the selected powder and Z100 at different ratios (0, 5, 10 wt% UP). These composites were irradiated under different protocols (BL, NIR, or their combinations), and the microhardness at the irradiated surface and different depths were determined. The results showed that unground UP (d50 = 1.9 µm) exhibited the highest luminescence, while the incorporation of 0.4-µm particles obtained the highest microhardness. The combined 20-s BL and 20-120-s NIR significantly increased the microhardness on the surface and internal depths compared to BL correspondents. The 5% UP effectively enhanced the microhardness under 80-s NIR irradiation but was surpassed by 10% UP with longer NIR irradiation. The combined BL-NIR curing could be an effective approach to polymerize dental composites, while the intensity of upconversion luminescence was related to specific UP particle size and content. Incorporation of 5-10% UP facilitates NIR upconversion polymerization on dental composites.

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.

Effect of alkyl chain length and fluorine content on the surface characteristics and antibacterial activity of surfaces grafted with brushes containing quaternized ammonium and fluoro-containing monomers.

Although considerable efforts have been made to vary the alkyl chain length in the quaternary ammonium compounds (QACs) for optimizing the antibacterial activity, only few researchers have systematically investigated the combinatory effects of alkyl chain length and another acryl monomers with the different chemical configuration on the antibacterial activity of the modified substrate. In this study, by surface grafting of various copolymeric brushes, different modified cotton substrates were prepared by surface-initiated reversible addition-fragmentation chain transfer (RAFT) polymerization reaction for exploring the effects of alkyl chain length of QACs and the fluorine content on antibacterial and anti-microbial adhesion characteristics. The quaternized monomers used were prepared by quaternization of 2-(dimethylamino) ethyl methacrylate (DMAEMA) with 1-bromooctane (DMAEMA + 8), and 1-bromopropane (DMAEMA + 3). The fluoro-containing monomer was 2,2,2-Trifluoroethyl methacrylate (TFEMA). Ethyl methacrylate (EMA) was also used for comparison. Results have shown that the optimal antibacterial and anti-microbial adhesion characteristics were noted on the substrates grafted with DMAEMA + 8 and TFEMA. This can be attributed to the enhanced degree of surface quaternization due to the hydrophobic interactions between the grafted TFEMA and DMAEMA + 8 chains, leading to an increase in antibacterial efficacy of modified cotton substrates.

Studies of the Sulfonated Hydrogenated Styrene-Isoprene-Styrene Block Copolymer and Its Surface Properties, Cytotoxicity, and Platelet-Contacting Characteristics.

Styrenic thermoplastic elastomers (TPEs) consist of styrenic blocks. They are connected with other soft segments by a covalent linkage and are widely used in human life. However, in biomedical applications, TPEs need to be chemically hydrogenated in advance to enhance their properties such as strong UV/ozone resistance and thermal-oxidative stability. In this study, films composed of sulfonated hydrogenated TPEs were evaluated. Hydrogenated tert-butyl styrene-styrene-isoprene block copolymers were synthesized and selectively sulfonated to different degrees by reaction with acetyl sulfate. By controlling the ratio of the hydrogenated tert-butyl styrene-styrene-isoprene block copolymer and acetyl sulfate, sulfonated films were optimized to demonstrate sufficient mechanical integrity in water as well as good biocompatibility. The thermal plastic sulfonated films were found to be free of cytotoxicity and platelet-compatible and could be potential candidates in biomedical film applications such as wound dressings.

Studies of surface grafted collagen and transforming growth factor ß1 combined with cyclic stretching as a dual chemical and physical stimuli approach for rat adipose-derived stem cells (rADSCs) chondrogenesis differentiation.

The adipose-derived stem cell has been used in various regenerative medicine research due to its multiple differentiation capabilities. Developing a stable and quick approach for the differentiation of stem cells is a critical issue in tissue regenerative field. In this investigation, rat adipose-derived stem cells (rADSCs) were seeded onto the type I collagen/transforming growth factor ß1 (TGF-ß1) immobilized polydimethylsiloxane (PDMS) substrate and then combined with short term dynamic stretching stimulation (intermittent or continuous stretching for 6 h) to induce the rADSCs chondrogenesis differentiation using the induction medium without growth factors added in vitro. Via regulating the extracellular chemical- and mechano-receptors of the cultured rADSCs, the chondrogenic differentiation was examined. After 72 h of static culture, proteoglycan secretion was noted on the surfaces modified by collagen with or without TGF-ß1. After different stretching stimulations, significant proteoglycan secretion was noted on the surface modified by both collagen and collagen/TGF-ß1, especially after the intermittent stretching culturing. Nonetheless, genetic expression of the chondrogenic markers: SOX-9, Col2a1, and aggrecan, instead, were dependent upon the surface grafted layer and the stretching mode utilized. These findings suggested that the surface chemical characteristics and external mechanical stimulation could synergistically affect the efficacy of chondrogenic differentiation of rADSCs.

Studies of zwitterionic sulfobetaine functionalized polypropylene surface with or without polyethylene glycol spacer: surface characterization, antibacterial adhesion, and platelet compatibility evaluation.

Microbial adhesion reduction as well as platelet compatibility improvement have been suggested as the key requirements for developing blood-contacting synthetic biomaterials. Surface grafting of hydrophilic polyethylene glycol chains or alkyl chains with zwitterionic terminal ends has been proposed for reducing microbial or platelet adhesion. Nonetheless, none has been reported to incorporate both polyethylene glycol and zwitterionic terminal functionality on the same surface-grafted alkyl chain. In this investigation, a novel surface modification scheme was reported for grafting zwitterionic alkyl chains with or without polyethylene glycol as the spacer. It was noted the bacterial adhesion reduction capability on the zwitterionic modified surface was dependent upon the use of polyethylene glycol spacer or not and the strain of microbe tested. Besides, the zwitterionic modified ones all showed greater antimicrobial adhesion capability than the surface modified with polyethylene glycol alone. On the other hand, significantly reduced platelet adhesion and activation were found, but with no statistical differences noted among the polyethylene glycol-modified surface and zwitterionic ones, with or without polyethylene glycol spacer. These suggested that the use of polyethylene glycol spacer on the zwitterionic terminated surface could further enhance the antimicrobial adhesion against gram-negative bacterial while still keeping its platelet compatibility.

Sulfonation and Characterization of Tert-Butyl Styrene/Styrene/Isoprene Copolymer and Polypropylene Blends for Blood Compatibility Applications.

Hydrogenated styrenic block copolymers (HSBCs) have been used in medical tubing for many years due to their high clarity, flexibility, kink resistance, and toughness. However, when it comes to blood storage applications, HSBC compounds' market has been limited because of their high hydrophobicity, which may trigger platelet adhesion when contacting with blood. HSBC needs to be physically or chemically modified in advance to make it blood compatible; however, HSBC has strong UV/ozone resistance, thermooxidative stability, and excellent processing capability, which increases the difficulty of the chemical modification process as unsaturated dienes has been converted to saturated stable midblocks. Moreover, medical HSBC-containing compounds primarily make up with the non-polar, hydrophobic nature and benign characteristics of other common ingredients (U.S. Pharmacopeia (USP) grades of mineral oil and polypropylene), which complicates the realization of using HSBC-containing compounds in blood-contacting applications, and this explains why few studies had disclosed chemical modification for biocompatibility improvement on HSBC-containing compounds. Sulfonation has been reported as an effective way to improve the material's blood/platelet compatibility. In this study, hydrogenated tert-butyl styrene (tBS)-styrene-isoprene block copolymers were synthesized and its blends with polypropylene and USP grades of mineral oil were selectively sulfonated by reaction with acetyl sulfate. By controlling the ratio of the hydrogenated tBS-styrene-isoprene block copolymer in the blend, sulfonated films were optimized to demonstrate sufficient physical integrity in water as well as thermal stability, hydrophilicity, and platelet compatibility.

Studies of proliferation and chondrogenic differentiation of rat adipose stem cells using an anti-oxidative polyurethane scaffold combined with cyclic compression culture.

The adipose stem cell is a potential candidate for the autologous chondrocytes repairing approach because of the abundance of fat in the animal body and its versatile differentiation capability. In this study, rat adipose stem cells (rASCs) were seeded into anti-oxidative N-acetylcysteine (NAC) grafted polyurethane (PU) scaffold and then combined with short dynamic compressive stimulation (24 h) to induce rASCs chondrogenesis differentiation in vitro. The inner pore surface of the PU scaffold was first modified via alginate and type I collagen to promote rASCs adherence. The modified layers crosslinked by genipin showed outstanding stability after ultrasonic treatment, indicating the modified layers were stable and can keep the cells adhesion well during dynamic compressive stimulation. After inner pore surface modification and 10 mM NAC grafting, the PU scaffold-A-C-G (graft 10 mM NAC) has shown the best proliferation efficiency with homogeneous cell distribution after 72hr static culture. After short term dynamic compressive stimulation, significant gene expression in chondrogenic markers, Sox-9, and Aggrecan, were noted in both PU scaffold-A-C-G and PU scaffold-A-C-G (graft 10 mM NAC). Considering the cell proliferation efficiency and gene expression, the anti-oxidative NAC grafted PU scaffold combined with short term dynamic compressive stimulation could be useful for cell culturing in stem cell therapy.

Studies of polypropylene surface modified with novel beta-thiopropionate-based zwitterionic polymeric brush: synthesis, surface characterization, and significantly reduced fouling characteristics evaluation.

Creating a surface with anti- or reduced fouling characteristics can lead to a reduction in nonspecific protein adsorption as well as the bacterial adhesion and platelet adhesion/activation that occur as follows. A zwitterionic polymer that consists of both cationic and anionic functionalities have been reported as an effective material to achieve these goals, likely resulted from the strongly-adsorbed hydration layer after being immersed in the physiological environment. In this investigation, a novel beta-thiopropionate-based zwitterionic monomer, 2-ammonio-3-((3-(2-hydroxy-3-(methacryloyloxy)propoxy)-3-oxopropyl)thio)-3-methylbutanoate (DPAMA), was synthesized through a facial process. And then the hydrophobic polypropylene was surface modified with this novel zwitterionic polymer through the surface-initiated atom transfer radical polymerization technique. Surface characterization analyses have been employed to investigate the modified surface properties in each reaction stage. In vitro protein adsorption, bacterial adhesion, and platelet compatibility evaluations have shown the polyDPAMA-modified polypropylene surface has significantly reduced fouling characteristics and good hemocompatibility. Henceforth, this novel zwitterionic polyDPAMA grafting PP and the associated grafting reaction scheme have great potential for future clinical applications.

Studies of PET nonwovens modified by novel antimicrobials configured with both N-halamine and dual quaternary ammonium with different alkyl chain length.

This work describes the synthesis of novel antimicrobial agents consisting of N-halamine and dual quaternary ammonium with different alkyl chain lengths and their antimicrobial applications for PET nonwovens. The antimicrobial agents were grafted onto PET nonwovens via esterification with a crosslinker, 1,2,3,4-butanetetracarboxylic acid (BTCA). The cyclic amide structure in the antimicrobial agents could be easily converted to N-halamine after immersion in a diluted chlorine bleach solution. Variations in surface chemical composition of the modified PET nonwovens were examined by XPS. Antimicrobial activities of the nonwovens/fabrics were tested against S. aureus (Gram-positive) and E. coli (Gram-negative) strains. Systematic investigation showed the antibacterial activities were dependent upon the alkyl chain length. The synergism of N-halamine and dual quaternary ammonium could lead to significant antimicrobial activity with inactivation of up to 90% of S. aureus and E. coli after 10 minute contact. This work suggested that the novel composite biocides with N-halamine and dual quaternary ammonium groups and the associated surface modification methods could be of use for further developing antimicrobial nonwoven applications.

A facile novel fluorocarbon copolymer solution coating process for improving platelet compatibility of titanium.

Titanium (Ti) and its alloys possess mechanical properties that are desirable in many biomedical applications compared to other metals. Furthermore, the native metal oxide layer that prevents further oxidation is also known to be biocompatible. However, clinical findings have shown that titanium and its alloys are prone to adverse bioreactions such as platelet adhesion and activation which could lead to thrombogenic complications. It has been found that surfaces modified with fluorocarbons could reduce the degree of both platelet adhesion and activation. Nevertheless, direct fluorocarbon deposition onto titanium substrates would require significant technical efforts. Instead, this research utilized a facile coating process with novel copolymers containing 2,2,2-trifluoroethyl methacrylate (TFEMA) and vinylphosphonic acid (VPA) to modify the titanium surface, giving the surface lower surface energy and higher hydrophobicity, significantly reducing the thrombus formation while exhibiting good cytocompatibility. The anchorage group, phosphonic acid provided by VPA, can be covalently bound to the oxide surface of titanium metal. Via free radical polymerization, VPA and TFEMA formed copolymers with different hydrophobicity were then used to modify titanium substrates, on which a series of surface characterization, in vitro platelet adhesion tests, and cytotoxicity assays were performed. Nuclear magnetic resonance (NMR) and X-ray photoelectron spectroscopy (XPS) confirmed the synthesis of the copolymers and the modification of Ti substrates. The platelet adhesion tests showed significantly reduced amount of adherent platelets on certain copolymer-modified Ti substrates with low degrees of activation. The in vitro cytotoxicity assays further highlighted that the modifications conducted on Ti does not induce cytotoxicity.

Effects of silane- and MDP-based primers application orders on zirconia-resin adhesion-A ToF-SIMS study.

OBJECTIVE: To evaluate the 3-methacryloyloxypropyltrimethoxysilane (MPS)- and 10-methacryloyloxydecyl-dihydrogen-phosphate (MDP)-base primers, in their single or sequential applications, with regard to modifying zirconia surfaces and improving resin-zirconia adhesion. METHODS: Zirconia disks received different treatments: without primer (Zr), MPS-base primer (S), MDP-base primer (M), MPS/MDP mixture (SMmix), MPS followed by MDP (SM), and MDP followed by MPS (MS). The compositions and chemical interactions of the coatings to zirconia were analyzed using time-of-flight secondary ion mass spectrometry (ToF-SIMS) and reconstructed 3D ion images. Surface wettability of these coatings to water and resin adhesive was assessed. The shear bond strength (SBS) between resin and the treated zirconia was also examined before and after thermocycling. RESULTS: Groups S and MS presented substantial OH- ions in the coatings and zirconia substrate. PO2- and PO3- fragments existed in all MDP-treatment groups with various proportions and distributions, while groups M and SM showed higher proportions of PO3- and the zirconium phosphate related ions. In 3D ion images, PO3- in groups M and SM was denser and segregated to the interface, but was dispersed or overlaid above PO2- in SMmix and MS. All the primers increased the surface wettability to water and resin, with M and SM presenting superhydrophilic surfaces. All MDP-treatment groups showed improved SBS before thermocycling, while M and SM retained higher SBS after this. SIGNIFICANCE: The MDP-base primer shows a relevant function in facilitating POZr bonding and enhancing resin-zirconia bonding. The co-treated MPS impairs the chemical activity of MDP, especially if it is the final coat.

Studies of magnetic alginate-based electrospun matrices crosslinked with different methods for potential hyperthermia treatment.

The magnetic electrospun mats were lately established as an innovative biomaterial for hyperthermic cancer treatment. Unlike those surface-modified magnetic nanoparticles that may not firmly adhere onto the tumor for long-term duration, the magnetic mats with nanofibrous structure can promote cell adhesion and kill the tumor directly within an alternating magnetic field. However, most magnetic electrospun mats were fabricated using non-biodegradable polymers and organic solvents, causing the problems of removal after therapy and the suspected biotoxicity associated with residual solvent. Alginate (SA) was utilized in this investigation as the main material for electrospinning because of being biodegradable and water-soluble. The alginate-based electrospun mats were then treated by an ionic or a covalent crosslinking method, and then followed by chelation with Fe(2+)/Fe(3+) for chemical coprecipitation of Fe3O4 magnetic nanoparticles. Significant less cytotoxicity was noted on both liquid extracts from the ionic-crosslinked (Fe3O4-SA/PEO) and covalent-crosslinked (Fe3O4-SA/PVA) magnetic electrospun mats as well as the surface of Fe3O4-SA/PVA. In vitro hyperthermia assay indicated that the covalent-crosslinked magnetic alginate-based mats reduced tumor cell viability greater than Fe3O4 nanoparticles. Such magnetic electrospun mats are of potential for hyperthermia treatment by endoscopic/surgical delivery as well as serving as a supplementary debridement treatment after surgical tumor removal.

Genetic Polymorphisms in Inflammasome-Dependent Innate Immunity among Pediatric Patients with Severe Renal Parenchymal Infections.

BACKGROUND: Inflammasome innate immune response activation has been demonstrated in various inflammatory diseases and microbial infections. However, to our knowledge, no study has examined the inflammasome-dependent pathways in patients with urinary tract infection. Defective or variant genes associated with innate immunity are believed to alter the host's susceptibility to microbial infection. This study investigated genetic polymorphisms in genes encoding inflammasomes and the subsequent released cytokines in pediatric patients with severe renal parenchymal infections. METHODOLOGY: This study included patients diagnosed with acute pyelonephritis (APN) and acute lobar nephronia (ALN) who had no underlying disease or structural anomalies other than vesicoureteral reflux (VUR). Single nucleotide polymorphism (SNP) genotyping was performed in the genes associated with inflammasome formation and activation (NLRP3, CARD8) and subsequent IL-1ß cytokine generation (IL-1ß). PRINCIPAL FINDINGS: A total of 40 SNPs were selected for initial genotyping. Analysis of samples from 48 patients each and 96 controls revealed that only nine SNPs (five SNPs in NLRP3; three SNPs in CARD8; one SNP in IL-1ß) had heterozygosity rates >0.01. Hardy-Weinberg equilibrium was satisfied for the observed genotype frequencies of these SNPs. Analysis excluding patients with VUR, a well-known risk factor for severe UTIs, revealed a lower frequency of the CC genotype in NLRP3 (rs4612666) in patients with APN and ALN than in controls. Correction for multiple-SNP testing showed that the non-VUR subgroup of the APN+ALN combined patient groups remained significantly different from the control group (P < 0.0055). CONCLUSIONS: This study is the first to suggest that the inflammasome-dependent innate immunity pathway is associated with the pathogenesis of pediatric severe renal parenchymal infections. Further investigation is warranted to clarify its pathogenic mechanism.

Surface modification of titanium substrate with a novel covalently-bound copolymer thin film for improving its platelet compatibility.

Despite of its widely uses in various clinical applications, the titanium-based material still faces different challenges, such as hemocompatibility and anti-biofouling characteristics required in various situations. The objective of this investigation was to develop a novel surface modification strategy for titanium-based material to improve the platelet compatibility that is important in rigorous blood-contacting cardiovascular applications. In this work, a series of copolymers, which composed of novel 6-acryloyloxy hexyl phosphonic acid (AcrHPA) and sulfobetaine methacrylate (SBMA) was synthesized. The phosphonic acid group in these copolymers can impart covalent binding to the titanium substrate while the zwitterionic sulfobetaine functionality is considered being able to reduce the platelet adhesion and activation on the modified titanium substrate. NMR analyses suggested that copolymerization reaction is likely not an ideal statistical reaction but to add the monomers in a random order. Studies have shown that the composition of the monomers affected the surface characteristics and platelet compatibility of these covalent-bound AcrHPA-SBMA copolymers on titanium substrate. Contact angle analysis has shown the addition of SBMA can increase surface hydrophilicity of the spun-coated copolymers. In addition, AFM analyses have revealed that the surface roughness of the spun-coated copolymer layer were varied with the ratio of AcrHPA and SBMA. The most platelet compatible surface was noted on the one modified by the highest amount of SBMA added (i.e. 70 mol%) in copolymerization. In summary, the surface modification scheme presented here would be of potential as well as manufacturing process applicable for future development in blood-contacting titanium-based biomedical devices.