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.

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.

Pineapple Agro-Industrial Biomass to Produce Biomedical Applications in a Circular Economy Context in Costa Rica.

Pineapple is a highly demanded fruit in international markets due to its unique appearance and flavor, high fiber content, vitamins, folic acid, and minerals. It makes pineapple production and processing a significant source of income for producing countries, such as Costa Rica. This review collects bibliographic information dating back to the beginnings of pineapple production in Costa Rica to the state of the market today. It details the impacts of its production chain and proposes a biorefinery as a solution to environmental problems. Besides the potentiality of new sustainable markets to contribute to the post-COVID-19 economy in Costa Rica is highlighted. The general characteristics of pineapple by-products -cellulose, hemicellulose, lignin, and other high-value products like bromelain y saponin- are described, as well as the primary processes for their ex-traction via biorefinery and main applications in the medical field. Finally, a brief description of the main works in the literature involving modeling and simulation studies of pineapple by-products properties is included.

Biomolecule-mimetic nanomaterials for photothermal and photodynamic therapy of cancers: Bridging nanobiotechnology and biomedicine.

Nanomaterial-based phototherapy has become an important research direction for cancer therapy, but it still to face some obstacles, such as the toxic side effects and low target specificity. The biomimetic synthesis of nanomaterials using biomolecules is a potential strategy to improve photothermal therapy (PTT) and photodynamic therapy (PDT) techniques due to their endowed biocompatibility, degradability, low toxicity, and specific targeting. This review presents recent advances in the biomolecule-mimetic synthesis of functional nanomaterials for PTT and PDT of cancers. First, we introduce four biomimetic synthesis methods via some case studies and discuss the advantages of each method. Then, we introduce the synthesis of nanomaterials using some biomolecules such as DNA, RNA, protein, peptide, polydopamine, and others, and discuss in detail how to regulate the structure and functions of the obtained biomimetic nanomaterials. Finally, potential applications of biomimetic nanomaterials for both PTT and PDT of cancers are demonstrated and discussed. We believe that this work is valuable for readers to understand the mechanisms of biomimetic synthesis and nanomaterial-based phototherapy techniques, and will contribute to bridging nanotechnology and biomedicine to realize novel highly effective cancer therapies.

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.

Self-assembly study of type I collagen extracted from male Wistar Hannover rat tail tendons.

BACKGROUND: Collagen, the most abundant protein in the animal kingdom, represents a promising biomaterial for regenerative medicine applications due to its structural diversity and self-assembling complexity. Despite collagen's widely known structural and functional features, the thermodynamics behind its fibrillogenic self-assembling process is still to be fully understood. In this work we report on a series of spectroscopic, mechanical, morphological and thermodynamic characterizations of high purity type I collagen (with a D-pattern of 65 nm) extracted from Wistar Hannover rat tail. Our herein reported results can be of help to elucidate differences in self-assembly states of proteins using ITC to improve the design of energy responsive and dynamic materials for applications in tissue engineering and regenerative medicine. METHODS: Herein we report the systematic study on the self-assembling fibrillogenesis mechanism of type I collagen, we provide morphological and thermodynamic evidence associated to different self-assembly events using ITC titrations. We provide thorough characterization of the effect of pH, effect of salts and protein conformation on self-assembled collagen samples via several complementary biophysical techniques, including circular dichroism (CD), Fourier Transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), atomic force microscopy (AFM), scanning electron microscopy (SEM), dynamic mechanical thermal analysis (DMTA) and thermogravimetric analysis (TGA). RESULTS: Emphasis was made on the use of isothermal titration calorimetry (ITC) for the thermodynamic monitoring of fibrillogenesis stages of the protein. An overall self-assembly enthalpy value of 3.27 ± 0.85 J/mol was found. Different stages of the self-assembly mechanism were identified, initial stages take place at pH values lower than the protein isoelectric point (pI), however, higher energy release events were recorded at collagen's pI. Denatured collagen employed as a control exhibited higher energy absorption at its pI, suggesting different energy exchange mechanisms as a consequence of different aggregation routes.

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.

Increased Fibroblast Metabolic Activity of Collagen Scaffolds via the Addition of Propolis Nanoparticles.

Propolis natural extracts have been used since ancient times due to their antioxidant, anti-inflammatory, antiviral, and antimicrobial activities. In this study, we produced scaffolds of type I collagen, extracted from Wistar Hanover rat tail tendons, and impregnated them with propolis nanoparticles (NPs) for applications in regenerative medicine. Our results show that the impregnation of propolis NPs to collagen scaffolds affected the collagen denaturation temperature and tensile strength. The changes in structural collagen self-assembly due to contact with organic nanoparticles were shown for the first time. The fibril collagen secondary structure was preserved, and the D-pattern gap increased to 135 ± 28 nm, without losing the microfiber structure. We also show that the properties of the collagen scaffolds depended on the concentration of propolis NPs. A concentration of 100 µg/mL of propolis NPs with 1 mg of collagen, with a hydrodynamic diameter of 173 nm, was found to be an optimal concentration to enhance 3T3 fibroblast cell metabolic activity and cell proliferation. The expected outcome from this research is both scientifically and socially relevant since the home scaffold using natural nanoparticles can be produced using a simple method and could be widely used for local medical care in developing communities.

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.

Biogenic silica-based microparticles obtained as a sub-product of the nanocellulose extraction process from pineapple peels.

Silica in plant tissues has been suggested as a component for enhancing mechanical properties, and as a physical barrier. Pineapples present in their shell and bracts rosette-like microparticles that could be associated to biogenic silica. In this study, we show for the first time that silica-based microparticles are co-purified during the extraction process of nanocellulose from pineapple (Ananas comosus). This shows that vegetable biomass could be an underappreciated source, not only for nanocellulose, but also for a highly valuable sub-product, like 10 µm biogenic rosette-like silica-based microparticles. The recovery yield obtained was 7.2 wt.%; based on the dried initial solid. Due to their size and morphology, the microparticles have potential applications as reinforcement in adhesives, polymer composites, in the biomedical field, and even as a source of silica for fertilizers.

Estudio preliminar de la obtención de compuestos híbridos de quitosano y polifenoles derivados de lignina a partir de subproductos agropecuarios y pesquería de camarón / Preliminary study of the production of hybrid compounds of chitosan and polyphenols derived from lignin from agroindustry and shrimp fishery

En este estudio se prepararon y caracterizaron microcápsulas híbridas del conjugado de polifenoles derivados de la lignina proveniente de la cáscara de piña, y el quitosano obtenido a partir de la quitina de la cáscara del camarón; ambos materiales fueron obtenidos como residuos de la industria agropecuaria y pesquería de camarón de Costa Rica. Con el objetivo de preparar compuestos fenólicos derivados de la lignina, y utilizarlos en la síntesis de las microcápsulas, se realizó la hidrólisis enzimática de la misma en un reactor a presión atmosférica a un pH de 6.8, en buffer de citrato 1 M, durante 6 h a 37ºC. Las enzimas utilizadas fueron extraídas de los cultivos de hongos de Gloeophyllum trabeum (Pers.) Murrill y Phanerochae chrysosporiumin Burdsall. Para la obtención del quitosano se realizó la desacetilación alcalina a partir de exoesqueletos del camarón Heterocarpus vicarius Fazon. Para la preparación de las microcápsulas se empleó una disolución de quitosano en ácido acético, el cual fue mezclado con una disolución acuosa del producto obtenido de la hidrólisis de la lignina y luego añadido a una disolución de vaselina para microemulsionar. Posteriormente, se agregó el glutaraldehído como agente entrecruzante. Se obtuvieron microcápsulas con tamaños entre 5 y 10 µm. Estas microcápsulas son un material promisorio ya que, mediante la formación del complejo, se puede aumentar la solubilidad del quitosano y estabilizar los polifenoles, manteniendo así sus propiedades antioxidantes. Los resultados preliminares obtenidos en esta investigación, muestran el potencial de este material para el encapsulamiento de fármacos y pesticidas.

Hybrid microcapsules of the conjugate of polyphenols derived from lignin were prepared and characterized. They were obtained from pineapple peel and chitin from shrimp shell from agroindustry or shrimp fishery of Costa Rica. The phenolic compounds were obtained by hydrolysis of lignin, using the enzyme derivatives from the fungus culture of Gloeophyllum trabeum (Pers.) Murrill and Phanerochaete chrysosporium Burdsall. The reaction was carried out in a reactor with atmospheric pressure, pH 6.8, with a citrate buffer of 1M, for 6 hours at 37°C. The chitosan was obtained by alkaline deacetylation of the Heterocarpus vicarious Fazon, shrimp exoskeletons. Microcapsules were prepared mixing a solution of chitosan dissolved in acetic acid and a solution of polyphenol derivatives from lignin. Afterwards, they were added to a vaseline aqueous solution for the microemulsion formation and glutaraldehyde was added as a crosslinking agent. Microcapsules with sizes between 5 to 10 µm were obtained. These microcapsules are a promising material to increase chitosan solubility and for preventing the oxidation of polyphenols. The preliminary results obtained in this research show the potential of this material for the encapsulation of drugs and pesticides.