Conjugated Block Copolymers for Functional Nanostructures.

Conjugated polymers have been actively studied as an alternative to inorganic semiconductors for their unique optical and electrical properties and low-cost solution processability. However, typical conjugated polymer films contain numerous defects that negatively affect their transport properties, which remains a major issue despite much effort to develop ways to improve the molecular packing structure. In principle, conjugated block copolymers (BCPs) composed of a rod-type conjugated polymer and a coil-type insulating polymer can assemble into various types of ordered nanostructures based on the microphase segregation of two polymer blocks. However, such assembly typically requires a relatively large volume fraction of the coil block or modification of the rod block, both of which tend to impede charge transport. As an alternative, we and others have fabricated nanoscale assemblies of conjugated BCPs via solution-phase self-assembly, which can be used as building blocks for construction of extended nanoarrays of conjugated polymers. In particular, BCPs containing poly(3-hexylthiophene) (P3HT), a conjugated polymer widely used for its high hole mobility, form highly ordered and technologically relevant one-dimensional (1D) nanowires with controlled lengths. A range of well-defined assembly structures such as square plates, ribbons, vesicles, and helices have been prepared from various conjugated BCPs, resembling those of peptide self-assembly, forming diverse nanostructures through combinations of π-π stacking, hydrogen bonding, and hydrophobic interactions.When the self-assembly of P3HT BCPs takes place at an air-water interface, the initially formed polymer nanowires further assemble into hierarchical two-dimensional (2D) nanoarrays with solvent evaporation. The fluidic nature of the water subphase allows fabrication of highly ordered assembly structures from P3HT BCPs with high P3HT content. The ultrathin free-standing film integrated in a field effect transistor (FET) showed orders of magnitude higher current and hole mobility compared to that fabricated by conventional spin-coating. Furthermore, binary self-assembly of a P3HT BCP and quantum dots (QDs) at the air-water interface generates well-ordered 2D films of alternating P3HT nanowires and 1D QD arrays. Unlike coil-coil BCP systems, QDs reside at the interface between P3HT and coil blocks for a broad range of QD sizes due to the strong P3HT packing interactions and the flexible water subphase, forming tight p-n junctions for enhanced photocurrent. Incorporation of magnetic nanoparticles can further improve the degree of order, enabling fabrication of long-range order and direction-controlled P3HT nanoarrays through magnetic-field induced self-assembly.The conjugated BCP approach is highly modular and can be combined with various types of functional molecules, polymers, and nanoparticles, offering a powerful platform for fabrication of functional polymer nanostructures with desired morphologies and properties. This Account introduces recent advances in the self-assembly of π-conjugated BCPs, describes how they differ from prototypical coil-coil type BCPs, and discusses current issues and future outlooks.

Evaluation of Osteoblast-Like Cell Viability and Differentiation on the Gly-Arg-Gly-Asp-Ser Peptide Immobilized Titanium Dioxide Nanotube via Chemical Grafting.

This study examined the effect of the immobilization of the Gly-Arg-Gly-Asp-Ser (GRGDS) peptide on titanium dioxide (TiO2) nanotube via chemical grafting on osteoblast-like cell (MG-63) viability and differentiation. The specimens were divided into two groups; TiO2 nanotubes and GRGDS-immobilized TiO2 nanotubes. The surface characteristics of GRGDS-immobilized TiO2 nanotubes were observed by using X-ray photoelectron spectroscopy (XPS) and a field emission scanning electron microscope (FE-SEM). The morphology of cells on specimens was observed by FE-SEM after 2 hr and 24 hr. The level of cell viability was investigated via a tetrazolium (XTT) assay after 2 and 4 days. Alkaline phosphatase (ALP) activity was evaluated to measure the cell differentiation after 4 and 7 days. The presence of nitrogen up-regulation or C==O carbons con- firmed that TiO2 nanotubes were immobilized with GRGDS peptides. Cell adhesion was enhanced on the GRGDS-immobilized TiO2 nanotubes compared to TiO2 nanotubes. Furthermore, significantly increased cell spreading and proliferation were observed with the cells grown on GRGDS-immobilized TiO2 nanotubes (P < .05). However, there was no significant difference in ALP activity between GRGDS-immobilized TiO2 nanotubes and TiO2 nanotubes. These results suggest that the GRGDS-immobilized TiO2 nanotubes might be effective in improving the osseointegration of dental implants.

Combined effects of mineral trioxide aggregate and human placental extract on rat pulp tissue and growth, differentiation and angiogenesis in human dental pulp cells.

OBJECTIVE: The aim of this study was to evaluate the combined effects of mineral trioxide aggregate (MTA) and human placental extract (HPE) on cell growth, differentiation and in vitro angiogenesis of human dental pulp cells (HDPCs) and to identify underlying signal transduction mechanisms. In vivo dental pulp responses in rats for a pulp-capping agent were examined. MATERIALS AND METHODS: MTS assay. ALP activity test, alizarin red S staining and RT-PCR for marker genes were carried out to evaluate cell growth and differentiation. HUVEC migration, mRNA expression and capillary tube formation were measured to evaluate angiogenesis. Signal transduction was analysed using Western blotting and confocal microscopy. The pulps of rat maxillary first molars were exposed and capped with either MTA or MTA plus HPE. Histologic observation and scoring were performed. RESULTS: Compared to treatment of HDPCs with either HPE or MTA alone, the combination of HPE and MTA increased cell growth, ALP activity, mineralized nodules and expression of marker mRNAs. Combination HPE and MTA increased migration, capillary tube formation and angiogenic gene expression compared with MTA alone. Activation of Akt, mammalian target of rapamycin (mTOR), p38, JNK and ERK MAPK, Akt, and NF-κB were significantly increased by combining HPE and MTA compared with MTA alone. Pulp capping with MTA plus HPE in rats showed superior dentin bridge formation, odontoblastic layers and dentinal tubules and lower inflammatory cell response, compared to the MTA alone group. CONCLUSIONS: This study demonstrates for the first time that the use of MTA with HPE promotes cell growth, differentiation and angiogenesis in HDPCs, which were associated with mTOR, MAPK and NF-κB pathways. Direct pulp capping with HPE plus MTA showed superior results when compared with MTA alone. Thus, the combination of MTA and HPE may be useful for regenerative endodontics.

Analysis of Removal Torque of Injection Molded Zirconia Implants; An Experimental Study on Beagles.

This study compared the removal torque between injection molded zirconia implants and titanium implants with resorbable blast media (RBM) surfaces in beagle humeri. Fifteen screw-shaped implants were classified into 3 groups; titanium implant with RBM surface (Group RT), injection molded zirconia implant (Group Zr) and injection molded zirconia implant with sand-blasted surface (Group ZrS). Implants were inserted into beagle humeri. After 12 weeks, removal torque values were measured. The Zr group has a slightly higher removal torque value than the RT and ZrS groups but there were no significant differences among groups. Zirconia implants shows a similar removal torque to RBM titanium implants. This in vivo study showed injection molded zirconia implants could be an alternative to RBM titanium implants in terms of removal torque.

Shear bond strength between resin cement and colored zirconia made with metal chlorides.

STATEMENT OF PROBLEM: Although the application of zirconia in esthetic prostheses has increased, the shear bond strength (SBS) between colored zirconia and resin cement has not been investigated. PURPOSE: The purpose of this study was to compare the SBS between resin cement and colored zirconia made with metal chlorides. MATERIAL AND METHODS: Sixty-four zirconia specimens were divided into 2 groups: one in which the specimens were bonded with resin cement, including 4-META (4-methacryloxyethyl trimellitic anhydride), and one in which the specimens were bonded with resin cement (SEcure, Sun Medical) after being processed with zirconia primer (Zirconia Liner), including 4-META. Each group was then divided into 4 subgroups depending on the coloring liquid. The subgroups were noncolored (control), commercial coloring liquid VITA In-Ceram 2000 YZ LL1, aqueous chromium chloride solution 0.1 wt%, and aqueous molybdenum chloride solution 0.1 wt%. Composite resin cylinders (Filtek Z250, 3M ESPE) were fabricated and bonded to the surface of the zirconia specimen with resin cement (SEcure). All specimens were stored in 37°C distilled water for 24 hours, and the SBS was measured with a universal testing machine. All data were analyzed statistically with 2-way ANOVA and tested post hoc with the Tukey test (α=.05). RESULTS: Significant differences were observed among the SBS values of the colored zirconia depending on the coloring liquid (P<.001) and whether they were processed with zirconia primer (P<.001). The SBS between colored zirconia and resin cement was significantly higher than that of noncolored zirconia and resin cement in groups processed with zirconia primer (P<.05). Colored zirconia immersed in aqueous molybdenum chloride solution showed a significantly higher SBS. CONCLUSIONS: Coloring liquid enhanced the SBS between resin cement and zirconia processed with zirconia primer. In particular, colored zirconia immersed in aqueous molybdenum chloride solution showed the highest SBS.

The core composition of DNA block copolymer micelles dictates DNA hybridization properties, nuclease stabilities, and cellular uptake efficiencies.

Here, we report how the nature of the hydrophobic core affects the molecular interactions of DNA block copolymer assemblies. Three different amphiphilic DNA block copolymers, DNA-b-polystyrene (DNA-b-PS), DNA-b-poly(2-vinylpyridine) (DNA-b-P2VP), and DNA-b-poly(methyl acrylate) (DNA-b-PMA) were synthesized and assembled into spherical micelles composed of a hydrophobic polymer core and DNA corona. Interestingly, DNA block copolymer micelles having different hydrophobic cores exhibited markedly different molecular and biological interactions. DNA-b-PS exhibited higher melting temperature, sharper melting transition, higher stability to nuclease-catalyzed DNA degradation, and higher cellular uptake efficiency compared to DNA-b-P2VP and DNA-b-PMA. The investigation of the self-assembly behavior revealed a much higher aggregation number and DNA density for DNA-b-PS micelles, which explains the superior properties of DNA-b-PS. These results demonstrate that the type of the hydrophobic core polymer, which has been largely overlooked, has a profound impact on the molecular and biological interactions of the DNA shell.

Odontogenic stimulation of human dental pulp cells with bioactive nanocomposite fiber.

The aim of the present study was to investigate the effects of a composite nanofibrous matrix made of biopolymer blend polycaprolactone-gelatin (BP) and mesoporous bioactive glass nanoparticles (BGNs) on the odontogenic differentiation of human dental pulp cells (HDPCs). BGN-BP nanomatrices, with BGN content of up to 20 wt%, were produced via electrospinning. The differentiation of the HDPCs was evaluated by using an ALP activity assay, calcified nodule formation, and mRNA expression for markers. Integrin and its underlying signal pathways were assessed via reverse transcriptase-polymerase chain reaction and Western blot analysis. Although cell growth and attachment on the BGN-BP nanomatrix was similar to that on BP, ALP activity, mineralized nodule formation, and mRNA, expressions involving ALP, osteocalcin, osteopontin, dentin sialophosphoprotein, and dentin matrix protein-1 were greater on BGN-BP. BGN-BP upregulated the key adhesion receptors (integrin components α1, α2, α5, and ß1) and activated integrin downstream pathways, such as phosphorylated-focal adhesion kinase (p-FAK), and p-paxillin. In addition, BGN-BP activated BMP receptors, BMP-2 mRNA, and p-Smad 1/5/8, and such activation was blocked by the BMP antagonist, noggin. Furthermore, BGN-BP induced phosphorylation of extracellular signal-regulated kinase, protein kinase 38, and c-Jun-N-terminal kinase mitogen-activated protein kinases and activated expression of the transcription factors Runx2 and Osterix in HDPCs. Collectively, the results indicated for the first time that a BGN-BP composite nanomatrix promoted odontogenic differentiation of HDPCs through the integrin, BMP, and mitogen-activated protein kinases signaling pathway. Moreover, the nanomatrix is considered to be promising scaffolds for the culture of HDPCs and dental tissue engineering.