Laccase-Treated Polystyrene Surfaces with Caffeic Acid, Dopamine, and L-3,4-Dihydroxyphenylalanine Substrates Facilitate the Proliferation of Melanocytes and Embryonal Carcinoma Cells NTERA-2.

This study presents the effects of treating polystyrene (PS) cell culture plastic with oxidoreductase enzyme laccase and the catechol substrates caffeic acid (CA), L-DOPA, and dopamine on the culturing of normal human epidermal melanocytes (NHEMs) and human embryonal carcinoma cells (NTERA-2). The laccase-substrate treatment improved PS hydrophilicity and roughness, increasing NHEM and NTERA-2 adherence, proliferation, and NHEM melanogenesis to a level comparable with conventional plasma treatment. Cell adherence dynamics and proliferation were evaluated. The NHEM endpoint function was quantified by measuring melanin content. PS surfaces treated with laccase and its substrates demonstrated the forming of polymer-like structures. The surface texture roughness gradient and the peak curvature were higher on PS treated with a combination of laccase and substrates than laccase alone. The number of adherent NHEM and NTERA-2 was significantly higher than on the untreated surface. The proliferation of NHEM and NTERA-2 correspondingly increased on treated surfaces. NHEM melanin content was enhanced 6-10-fold on treated surfaces. In summary, laccase- and laccase-substrate-modified PS possess improved PS surface chemistry/hydrophilicity and altered roughness compared to untreated and plasma-treated surfaces, facilitating cellular adherence, subsequent proliferation, and exertion of the melanotic phenotype. The presented technology is easy to apply and creates a promising custom-made, substrate-based, cell-type-specific platform for both 2D and 3D cell culture.

Biomineralization and remineralizing potential of toothpastes containing nanosized ß-calcium glycerophosphate: an in vitro study.

To evaluate the effect of 1100 ppm F toothpastes supplemented with micrometric or nanosized ß-CaGP (ß-CaGPm/ß-CaGPn) on artificial enamel remineralization, using a pH cycling model. Enamel blocks with artificial caries were randomly allocated into ten groups (n = 10), according to the toothpastes: without fluoride/ß-CaGPm/ß-CaGPn (negative control); 1100 ppm F (1100F); 1100F plus 0.125%, 0.25%, 0.5%, and 1.0% of ß-CaGPm or ß-CaGPn. The blocks were treated 2×/day with slurries of toothpastes. After pH cycling, the percentage of surface hardness recovery (%SHR); integrated loss of subsurface hardness (ΔKHN); integrated mineral loss (ΔIMR); fluoride (F), calcium (Ca), and phosphorus (P) concentrations in the enamel; polydispersity index (PdI); and zeta potential (Zp) were determined. The data were analyzed by ANOVA (p < 0.001). For Zp/PdI, no significance was observed when comparing the means (p > 0.001). The treatment with 1100F-0.25%ß-CaGPn led to %SHR ∼57 higher when compared to the 1100F group (p < 0.001). The lowest ΔKHN was observed for the 1100F-0.25%ß-CaGPn group (p < 0.001). The ΔIMR was lower (∼201%) for the 1100F-0.25%ß-CaGPn when compared to 1100F (p < 0.001). The association of ß-CaGPm and ß-CaGPn to 1100F did not influence its F concentration (p > 0.001). The highest increase in Ca and P was observed for 1100F-0.25%ß-CaGPn (p < 0.001). The addition of 0.25%ß-CaGPn to 1100F toothpaste was able to promote an additional remineralizing effect of artificial caries lesions.

Enzymatically Driven Mineralization of a Calcium-Polyphosphate Bleaching Gel.

To examined alkaline phosphatase enzyme (ALP) activity and the effects of incorporating it in the thickener solution of a hydrogen-peroxide-based bleaching gel containing calcium-polyphosphate (CaPP) on the orthophosphate (PO43-) levels, bleaching effectiveness, and enamel microhardness. ALP activity was assessed at different pH levels and H2O2 concentrations, and in H2O- and Tris-based thickeners. Circular dichroism (CD) was used to examine the ALP secondary structure in water-, Tris-, or H2O2-based mediums. The PO43- levels were evaluated in thickeners with and without ALP. Enamel/dentin specimens were allocated into the following groups: control (without bleaching); commercial (Whiteness-HP-Maxx); Exp-H (H2O-based); CaPP-H; ALP-H (CaPP+ALP); Exp-T (Tris-based); CaPP-T; and ALP-T (CaPP+ALP). Color changes (ΔE/ΔE00) and the bleaching index (ΔWID) were calculated, and surface (SMH) and cross-sectional microhardness (CSMH) were assessed. The two-way ANOVA and Tukey's post-hoc tests were used to compare ALP and PO43- levels; generalized linear models were used to examine: ΔE/ΔE00/SMH/CSMH; and Kruskal-Wallis and Dunn's tests were used for ΔWID (α = 5%). The ALP activity was higher at pH 9, lower in H2O2-based mediums, and similar in both thickeners. The CD-spectra indicated denaturation of the enzyme upon contact with H2O2. The PO43- levels were higher after incorporating ALP, and the ΔE/ΔE00/ΔWID were comparable among bleached groups. SMH was lower after bleaching in Exp-H, while CSMH was highest in ALP-T.

Effect of incorporation of calcium polyphosphate sub-microparticles in low-concentration bleaching gels on physical properties of dental enamel.

AIM: To evaluate the bleaching efficacy and effects on enamel properties of experimental gels with carbamide peroxide (CP; 10%) or hydrogen peroxide (HP; 6%) containing calcium polyphosphate sub-microparticles (CaPPs). METHODS: A total of 216 bovine tooth specimens were divided for microhardness and color analyses (n = 108) and block randomized into nine groups (n = 12): (G1) commercial CP (Whiteness Perfect, FGM; Brazil); (G2) experimental CP; (G3) CP-0.5%CaPPs; (G4) CP-1.5%CaPPs; (G5) commercial HP (Potenza Bianco, PHS; Brazil); (G6) experimental HP; (G7) HP-0.5%CaPPs; (G8) HP-1.5%CaPPs; (G9) artificial saliva. The gels' pH values were determined with a bench pH meter. Color (ΔE, ΔE00, ΔWID) and microhardness variation were evaluated before and after the therapy. Part of the specimens used for microhardness was submitted to the scanning electron microscopy (SEM) (n = 3) and energy-dispersive X-ray spectroscopy EDX (n = 3) analyses. Statistical analyses were performed in the R statistical software (α = 0.05). Linear mixed models for repeated measures in time were used to analyze microhardness and L* values. Generalized linear models were used to analyze the a*, b*, ΔE, ΔE00, and ΔWID, considering a group effect. The EDX data were analyzed using a one-way ANOVA with Tukey's test. RESULTS: The gels' pH remained over 6,0. All gels effectively bleached the specimens and did not differ significantly. When compared to the control group, the hardness was significantly lower in the G1, G2, G6, and G7 groups. The G3, G4, G5, and G8 groups did not differ significantly (p > 0.05). CONCLUSION: The incorporation of CaPPs in low-concentration whitening gels reduces its negative effects on microhardness without interfering with their bleaching efficacy.

Functionalization of breast implants by cyclodextrin in-situ polymerization: a local drug delivery system for augmentation mammaplasty.

Mammaplasty is a widely performed surgical procedure worldwide, utilized for breast reconstruction, in the context of breast cancer treatment, and aesthetic purposes. To enhance post-operative outcomes and reduce risks (hematoma with required evacuation, capsular contracture, implant-associated infection and others), the controlled release of medicaments can be achieved using drug delivery systems based on cyclodextrins (CDs). In this study, our objective was to functionalize commercially available silicone breast implants with smooth and textured surfaces through in-situ polymerization of two CDs: ß-CD/citric acid and 2-hydroxypropyl-ß-CD/citric acid. This functionalization serves as a local drug delivery system for the controlled release of therapeutic molecules that potentially can be a preventive treatment for post-operative complications in mammaplasty interventions. Initially, we evaluated the pre-treatment of sample surfaces with O2 plasma, followed by chitosan grafting. Subsequently, in-situ polymerization using both types of CDs was performed on implants. The results demonstrated that the proposed pre-treatment significantly increased the polymerization yield. The functionalized samples were characterized using microscopic and physicochemical techniques. To evaluate the efficacy of the proposed system for controlled drug delivery in augmentation mammaplasty, three different molecules were utilized: pirfenidone (PFD) for capsular contracture prevention, Rose Bengal (RB) as anticancer agent, and KR-12 peptide (KR-12) to prevent bacterial infection. The release kinetics of PFD, RB, and KR-12 were analyzed using the Korsmeyer-Peppas and monolithic solution mathematical models to identify the respective delivery mechanisms. The antibacterial effect of KR-12 was assessed against Staphylococcus epidermidis and Pseudomonas aeruginosa, revealing that the antibacterial rate of functionalized samples loaded with KR-12 was dependent on the diffusion coefficients. Finally, due to the immunomodulatory properties of KR-12 peptide on epithelial cells, this type of cells was employed to investigate the cytotoxicity of the functionalized samples. These assays confirmed the superior properties of functionalized samples compared to unprotected implants.

Maintenance of enamel properties after bleaching with high-concentrated hydrogen-peroxide gel containing calcium polyphosphate sub-microparticles.

OBJECTIVE: To assessed the physical and chemical properties of human-enamel after treatment with an experimental bleaching gel containing 35%-hydrogen peroxide (HP) and calcium polyphosphate sub-microparticles (CaPP). MATERIALS AND METHODS: Enamel/dentin specimens (4 × 4 × 3 mm) were obtained (n = 120) and allocated to different groups: control (saliva only); experimental (HP35%); commercial (whiteness-HP-Maxx); CaPP0.5% (HP35% + CaPP0.5wt%); CaPP1.5% (HP35% + CaPP1.5wt%). Three sessions were performed. The specimens' color was assessed using a spectrophotometer and the color (ΔE/ΔE00) and bleaching index (ΔWID) determined. The surface roughness and microhardness were assessed with a roughness tester and Knoop indenter. Raman spectroscopy was performed to obtain the ratios between the areas under the 431, 580, and 1070 cm-1 and the 960 cm-1 bands (430:960, 580:960, 1070:960). Kruskal-Wallis and Dunn compared the color, Ra, and SMH data. The Raman data was analyzed with Kruskal-Wallis and Dunn (α = 5%). RESULTS: The ΔE, ΔE00, and ΔWID were similar among the bleached groups (p > 0.05). The roughness was not different between the groups (p > 0.05). After the 3rd session, CaPP0.5% had higher microhardness than the experimental (p < 0.05). The 1070:960 was higher in the experimental than in the CaPP1.5% and control (p < 0.05). CONCLUSIONS: In human enamel, CaPP did not alter the bleaching effectiveness or roughness, and additionally, CaPP-containing gels increased the microhardness and preserved the mineral content when compared to the experimental without CaPP. CLINICAL RELEVANCE: Experimental bleaching gels containing calcium polyphosphate sub-microparticles as a mineral source reduce the mineral content alteration and superficial microhardness reduction, known potential side effects of the in-office bleaching treatments.

Calcium-Polyphosphate Submicroparticles (CaPP) Improvement Effect of the Experimental Bleaching Gels' Chemical and Cellular-Viability Properties.

The aim of this research was to develop and characterize the chemical and cellular-viability properties of an experimental high-concentration bleaching gel (35 wt%-H2O2) containing calcium-polyphosphate particles (CaPP) at two concentrations (0.5 wt% and 1.5 wt%). The CaPP submicroparticles were synthesized by coprecipitation, keeping a Ca:P ratio of 2:1. The CaPP morphology, size, and chemical and crystal profiles were characterized through scanning and transmission electron microscopy, energy-dispersive X-ray analysis, and X-ray diffraction, respectively. The assessed bleaching gels were experimental (without CaPP); 0.5% CaPP; 1.5% CaPP; and commercial. The gels' pH values and H2O2 concentrations (iodometric titration) were determined. The odontoblast-like cell viability after a gel's exposure was assessed by the MTT assay. The pH and H2O2 concentration were compared through a repeated-measures analysis of variance (ANOVA) and a Tukey's test and the cell viability through a one-way ANOVA and a Tukey's test using a GraphPad Prism (α < 0.05). The CaPP particles were spherical (with Ca and P, 135.7 ± 80.95 nm size) and amorphous. The H2O2 concentration decreased in all groups after mixing (p < 0.001). The 0.5% CaPP resulted in more-stable pH levels and higher viability levels than the experimental one (p < 0.05). The successful incorporation of CaPP had a positive impact on the bleaching gel's chemical and cellular-viability properties when compared to the experimental gel without these particles.

Encapsulated salts in velvet worm slime drive its hardening.

Slime expelled by velvet worms entraps prey insects within seconds in a hardened biopolymer network that matches the mechanical strength of industrial polymers. While the mechanic stimuli-responsive nature and building blocks of the polymerization are known, it is still unclear how the velvet worms' slime hardens so fast. Here, we investigated the slime for the first time, not only after, but also before expulsion. Further, we investigated the slime's micro- and nanostructures in-depth. Besides the previously reported protein nanoglobules, carbohydrates, and lipids, we discovered abundant encapsulated phosphate and carbonate salts. We also detected CO2 bubbles during the hardening of the slime. These findings, along with further observations, suggest that the encapsulated salts in expelled slime rapidly dissolve and neutralize in a baking-powder-like reaction, which seems to accelerate the drying of the slime. The proteins' conformation and aggregation are thus influenced by shear stress and the salts' neutralization reaction, increasing the slime's pH and ionic strength. These insights into the drying process of the velvet worm's slime demonstrate how naturally evolved polymerizations can unwind in seconds, and could inspire new polymers that are stimuli-responsive or fast-drying under ambient conditions.

Application of Poly-L-Lysine for Tailoring Graphene Oxide Mediated Contact Formation between Lithium Titanium Oxide LTO Surfaces for Batteries.

When producing stable electrodes, polymeric binders are highly functional materials that are effective in dispersing lithium-based oxides such as Li4Ti5O12 (LTO) and carbon-based materials and establishing the conductivity of the multiphase composites. Nowadays, binders such as polyvinylidene fluoride (PVDF) are used, requiring dedicated recycling strategies due to their low biodegradability and use of toxic solvents to dissolve it. Better structuring of the carbon layers and a low amount of binder could reduce the number of inactive materials in the electrode. In this study, we use computational and experimental methods to explore the use of the poly amino acid poly-L-lysine (PLL) as a novel biodegradable binder that is placed directly between nanostructured LTO and reduced graphene oxide. Density functional theory (DFT) calculations allowed us to determine that the (111) surface is the most stable LTO surface exposed to lysine. We performed Kubo-Greenwood electrical conductivity (KGEC) calculations to determine the electrical conductivity values for the hybrid LTO-lysine-rGO system. We found that the presence of the lysine-based binder at the interface increased the conductivity of the interface by four-fold relative to LTO-rGO in a lysine monolayer configuration, while two-stack lysine molecules resulted in 0.3-fold (in the plane orientation) and 0.26-fold (out of plane orientation) increases. These outcomes suggest that monolayers of lysine would specifically favor the conductivity. Experimentally, the assembly of graphene oxide on poly-L-lysine-TiO2 with sputter-deposited titania as a smooth and hydrophilic model substrate was investigated using a layer-by-layer (LBL) approach to realize the required composite morphology. Characterization techniques such as X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), Kelvin probe force microscopy (KPFM), scanning electron microscopy (SEM) were used to characterize the formed layers. Our experimental results show that thin layers of rGO were assembled on the TiO2 using PLL. Furthermore, the PLL adsorbates decrease the work function difference between the rGO- and the non-rGO-coated surface and increased the specific discharge capacity of the LTO-rGO composite material. Further experimental studies are necessary to determine the influence of the PLL for aspects such as the solid electrolyte interface, dendrite formation, and crack formation.

Multivalent non-covalent interactions lead to strongest polymer adhesion.

Multivalent interactions play a leading role in biological processes such as the inhibition of inflammation or virus internalization. The multivalent interactions show enhanced strength and better selectivity compared to monovalent interactions, but they are much less understood due to their complexity. Here, we detect molecular interactions in the range of a few piconewtons to several nanonewtons and correlate them with the formation and subsequent breaking of one or several bonds and assign these bonds. This becomes possible by performing atomic force microcopy (AFM)-based single molecule force spectroscopy of a multifunctional polymer covalently attached to an AFM cantilever tip on a substrate bound polymer layer of the multifunctional polymer. Varying the pH value and the crosslinking state of the polymer layer, we find that bonds of intermediate strength (non-covalent), like coordination bonds, give the highest multivalent bond strength, even outperforming strong (covalent) bonds. At the same time, covalent bonds enhance the polymer layer density, increasing in particular the number of non-covalent bonds. In summary, we can show that the key for the design of stable and durable polymer coatings is to provide a variety of multivalent interactions and to keep the number of non-covalent interactions at a high level.

Nonirritant and Cytocompatible Tinospora cordifolia Nanoparticles for Topical Antioxidant Treatments.

Tinospora cordifolia extract contains antioxidants such as polyphenols, and thus, it has been used as a natural phytochemical antioxidant therapeutic agent. Many of these compounds are insoluble or only partially soluble in water. In this study, we produced a novel aqueous nanoparticle formulation, with an average particle size of 182.9 ± 3.8 nm, to improve the dispersion of the bioactive compounds in water and to increment its bioavailability. The nanoparticles are composed of polyphenols, alkaloids, and glycosides. We studied the effect of this nanoparticle formulation on mouse 3T3 fibroblast cell viability and New Zealand rabbit dermal irritability tests. Concentrations of 2.5, 25, and 250 µg/mL resulted in similar cell viability to cells in culture media. An intermediate concentration of 12.45 mg/ml was used for the acute dermal irritability test. There were no severe alterations that compromised animal health. These results represent a precedent for application of such nanoparticles derived from plant stems, such as Tinospora cordifolia, in biomedicine and in antiaging cosmetic treatments.

Bioinspired catechol chemistry for dentin remineralization: A new approach for the treatment of dentin hypersensitivity.

OBJECTIVE: Dentin remineralization is of considerable clinical interest for dentin hypersensitivity and developing biomimetic analogs that can regulate hydroxyapatite (HAp) nucleation and growth remains a challenge. This study aimed to evaluate in vitro the potential for dentin remineralization using the following biomimetic in situ prepared poly(catechols): poly(dopamine), poly(DOPA), poly(caffeic acid) and a synthesized DOPA-peptide possessing collagen and calcium-binding domains (DOPA-Ahx-(Gly)3-(Glu)5). METHODS: Dentin samples were immersed in a freshly prepared phosphate-buffered saline (PBS) containing the respective catechol and laccase. After the reaction, they were immersed in calcium and phosphate remineralization solution, which was changed every day for 10 days. Samples of intact and demineralized dentin were used as control groups and kept in deionized water under the same experimental conditions. The remineralized dentin was characterized by scanning electron microscopy (SEM), Micro-energy dispersion X-ray fluorescence spectroscopy (µEDX) and X-ray diffraction (XRD). RESULTS: The application of different poly(catechols) and DOPA-peptide promoted crystal nucleation and the formation of HAp, which partially covered both the dentin surface and dentinal tubules walls. SIGNIFICANCE: By mimicking the role of charged non-collagenous proteins in vivo, polymers consisting of catechol groups showed the ability to modify demineralized dentin surface properties, promoting mineral formation. The use of poly(catechols) may be encouraged for the development of a therapeutic technique for dentin hypersensitivity.

New details of assembling bioactive films from dispersions of amphiphilic molecules on titania surfaces.

Tailoring the surface properties of materials for biomedical applications is important to avoid clinical complications. Forming thin layers of amphiphilic molecules with apolar regions that facilitate attractive intermolecular interactions, can be a suitable and versatile approach to achieve hydrophobic surface modification and provide functional antibacterial properties. Aiming to correlate layer structure and properties starting from film formation, octadecylphosphonic acid (ODPA) and dimethyloctadecyl (3-trimethoxysilylpropyl) ammonium chloride (DMOAP) layers were adsorbed onto smooth titania surfaces. Then the films were studied by atomic force microscopy (AFM) and X-ray Photoelectron Spectroscopy (XPS), and their interactions with aqueous environments were characterized by contact angle and zeta potential measurements. In addition, antibacterial assays were performed using E. coli and S. mutants to reveal the antibacterial properties effected by the surface modification. Immediately after sputter deposition, titania was hydrophilic; however, after air storage and adsorption of DMOAP or ODPA, an increase in the water contact angle was observed. XPS investigations after layer formation and after antibacterial tests revealed that the attachment of layers assembled from ODPA on titania substrates is considerably stronger and more stable than that observed for DMOAP films. Heat treatment strongly affects DMOAP layers. Furthermore, DMOAP layers are not stable under biological conditions.

Two-Step Fractionation of a Model Technical Lignin by Combined Organic Solvent Extraction and Membrane Ultrafiltration.

A fractionation method for technical lignin was developed, combining organic solvent extraction and membrane ultrafiltration of the solvent soluble component. This method was validated on a commercial wheat straw/Sarkanda grass lignin (Protobind 1000) using 2-butanone (MEK) as the solvent for both the extraction and the ultrafiltration operations. The parent lignin and the different obtained fractions were fully characterized in terms of chemical composition and physicochemical properties by gel permeation chromatography, gas chromatography/mass spectrometry (GC/MS), pyrolysis-GC/MS, total phenol contents, 31P nuclear magnetic resonance (31P NMR), thermogravimetric analysis, differential scanning calorimetry analysis, and Fourier-transform infrared spectroscopy. The results show that the proposed process allows a straightforward recovery of the different lignin fractions as well as a selective control over their molecular mass distribution and related dependent properties. Moreover, the operating flexibility of the Soxhlet/ultrafiltration process allows the treatment of lignins from different feedstocks using the same installation just by modulating the choice of the solvent and the membrane porosity with the best characteristics. This is one of the most important features of the proposed strategy, which represents a new fractionation approach with the potential to improve lignin valorization for materials science and preparative organic chemistry applications.

Functionalization of hydrophobic surfaces with antimicrobial peptides immobilized on a bio-interfactant layer.

The design of functionalized polymer surfaces using bioactive compounds has grown rapidly over the past decade within many industries including biomedical, textile, microelectronics, bioprocessing and food packaging sectors. Polymer surfaces such as polystyrene (PS) must be treated using surface activation processes prior to the attachment of bioactive compounds. In this study, a new peptide immobilization strategy onto hydrocarbonaceus polymer surfaces is presented. A bio-interfactant layer made up of a tailored combination of laccase from trametes versicolor enzyme and maltodextrin is applied to immobilize peptides. Using this strategy, immobilization of the bio-inspired peptide KLWWMIRRWG-bromophenylalanine-3,4-dihydroxyphenylalanine-G and KLWWMIRRWG-bromophenylalanine-G on polystyrene (PS) was achieved. The interacting laccase layers allows to immobilize antimicrobial peptides avoiding the chemical modification of the peptide with a spacer and providing some freedom that facilitates different orientations. These are not strongly dominated by the substrate as it is the case on hydrophobic surfaces; maintaining the antimicrobial activity. Films exhibited depletion efficiency with respect to the growth of Escherichia coli bacteria and did not show cytotoxicity for fibroblast L929. This environmentally friendly antimicrobial surface treatment is both simple and fast, and employs aqueous solutions. Furthermore, the method can be extended to three-dimensional scaffolds as well as rough and patterned substrates.

Bio-interfactants as double-sided tapes for graphene oxide.

We present a versatile and highly substrate-independent approach for preparing multisandwich layers based on thermally reduced Graphene Oxide (rGO) which gets strongly attached by bio-interfactants using a layer-by-layer (LBL) aqueous dipping and rinsing process. The process allows for the deposition of homogeneous ultra-thin films (∼5.5 nm) in distinct surface topographies, thicknesses and compositions by varying the bio-interfactant layer(s). The layers formed on quartz or other semi conductive material are electrically conductive, flexible, and transparent. The here-developed approach could be applied for the fabrication of wearables, sensors, and antistatic transparent films.

Structural and tribometric characterization of biomimetically inspired synthetic "insect adhesives".

Background: Based on previous chemical analyses of insect tarsal adhesives, we prepared 12 heterogeneous synthetic emulsions mimicking the polar/non-polar principle, analysed their microscopical structure and tested their adhesive, frictional, and rheological properties. Results: The prepared emulsions varied in their consistency from solid rubber-like, over soft elastic, to fluid (watery or oily). With droplet sizes >100 nm, all the emulsions belonged to the common type of macroemulsions. The emulsions of the first generation generally showed broader droplet-size ranges compared with the second generation, especially when less defined components such as petrolatum or waxes were present in the lipophilic fraction of the first generation of emulsions. Some of the prepared emulsions showed a yield point and were Bingham fluids. Tribometric adhesion was tested via probe tack tests. Compared with the "second generation" (containing less viscous components), the "first generation" emulsions were much more adhesive (31-93 mN), a finding attributable to their highly viscous components, i.e., wax, petrolatum, gelatin and poly(vinyl alcohol). In the second generation emulsions, we attained much lower adhesivenesses, ranging between 1-18 mN. The adhesive performance was drastically reduced in the emulsions that contained albumin as the protein component or that lacked protein. Tribometric shear tests were performed at moderate normal loads. Our measured friction forces (4-93 mN in the first and 0.1-5.8 mN in the second generation emulsions) were comparatively low. Differences in shear performance were related to the chemical composition and emulsion structure. Conclusion: By varying their chemical composition, synthetic heterogeneous adhesive emulsions can be adjusted to have diverse consistencies and are able to mimic certain rheological and tribological properties of natural tarsal insect adhesives.

Adsorption mechanism and valency of catechol-functionalized hyperbranched polyglycerols.

Nature often serves as a model system for developing new adhesives. In aqueous environments, mussel-inspired adhesives are promising candidates. Understanding the mechanism of the extraordinarily strong adhesive bonds of the catechol group will likely aid in the development of adhesives. With this aim, we study the adhesion of catechol-based adhesives to metal oxides on the molecular level using atomic force microscopy (AFM). The comparison of single catechols (dopamine) with multiple catechols on hyperbranched polyglycerols (hPG) at various pH and dwell times allowed us to further increase our understanding. In particular, we were able to elucidate how to achieve strong bonds of different valency. It was concluded that hyperbranched polyglycerols with added catechol end groups are promising candidates for durable surface coatings.

In situ sonochemical synthesis of ZnO particles embedded in a thermoplastic matrix for biomedical applications.

Zinc oxide particles were synthesized and dispersed in situ in a polystyrene (PS) matrix using ultrasound. PS ultrasonic degradation was investigated at different polymer concentrations in organic solvent in contact with aqueous media prior to the particle synthesis. Decrease in weight-average molecular weight (Mw) was strongly dependent on polymer concentration in organic solvent and sonication time: degradation occurred less at higher polymer concentration, yet increased with longer times of more than 30min. The ZnO particles with a 800nm flower-like morphology were dispersed in the polystyrene matrix in situ; the composite presented both a lower average molecular weight (Mw) and lower number average molecular weight Mn when compared to pristine polystyrene, however thermal degradation temperature and Young's modulus were similar to the pristine polystyrene. The composite prepared in situ presented lower particle aggregation in comparison with ZnO commercially dispersed with ultrasound under the same conditions. Antibacterial activity of the ZnO/PS coating was tested against Escherichia coli (Gram-negative bacteria; DMS No. 10290) by evaluating bacterial growth inhibition after 20h on contact with the film surface. The results indicated that bacterial growth was inhibited in the medium in contact with the composite prepared in situ compared to the film of composite prepared by mixing and the pristine PS. This study showed the potential use of ZnO/PS composite prepared in situ as antibacterial coatings.

Structural manipulation of colloidal silica.

Structural properties of the nanosized silica Ludox TMA with novel functionalizations have been investigated. Silica is stabilized in aqueous solution at a pH value higher than the pK(a) of silicic acid. A surface modification consisting of poly(p-benzamide)s functionalized with derivatized nucleobases on the C-terminus and cationic pyridinium functions on the N-terminus of the polymer chain was carried out. Due to the negatively charged surface, strong physisorption of the cationic pyridinium functions occurs. It is possible to stabilize diluted solutions of silica without agglomeration in solvents with various polarities by using pyridinium cations. Defined structures could be created according to the hydrogen donor/acceptor potential of the introduced nucleobase. Surprisingly the interactions between the same nucleobases are already sufficient for strong particle-particle interactions. Dramatic effects on the structural behavior are characterized by PCS, (S)TEM and EFTEM.