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1.
ACS Biomater Sci Eng ; 10(8): 4791-4801, 2024 Aug 12.
Artigo em Inglês | MEDLINE | ID: mdl-39012256

RESUMO

Scaffolds for the filling and regeneration of osteochondral defects are a current challenge in the biomaterials field, and solutions with greater functionality are still being sought. The novel approach of this work was to obtain scaffolds with biologically active additives possessing microstructural, permeability, and mechanical properties, mimicking the complexity of natural cartilage. Four types of scaffolds with a gelatin/alginate matrix modified with hydroxyapatite were obtained, and the relationship between the modifiers and substrate properties was evaluated. They differed in the type of second modifier used, which was hydrated MgCl2 in two proportions, ZnO, and nanohydroxyapatite. The samples were obtained by freeze-drying by using two-stage freezing. Based on microstructural observations combined with X-ray microanalysis, the microstructure of the samples and the elemental content were assessed. Permeability and mechanical tests were also performed. The scaffolds exhibited a network of interconnected pores and complex microarchitecture, with lower porosity at the surface (15 ± 7 to 29 ± 6%) and higher porosity at the center (67 ± 8 to 75 ± 8%). The additives had varying effects on the pore sizes and permeabilities of the samples. ZnO yielded the most permeable scaffolds (5.92 × 10-11 m2), whereas nanohydroxyapatite yielded the scaffold with the lowest permeability (1.18 × 10-11 m2), values within the range reported for trabecular bone. The magnesium content had no statistically significant effect on the permeability. The best mechanical parameters were obtained for ZnO samples and those containing hydrated MgCl2. The scaffold's properties meet the criteria for filling osteochondral defects. The developed scaffolds follow a biomimetic approach in terms of hierarchical microarchitecture and mechanical parameters as well as chemical composition. The obtained composite materials have the potential as biomimetic scaffolds for the regeneration of osteochondral defects.


Assuntos
Hidrogéis , Cloreto de Magnésio , Alicerces Teciduais , Óxido de Zinco , Óxido de Zinco/química , Alicerces Teciduais/química , Cloreto de Magnésio/química , Hidrogéis/química , Porosidade , Alginatos/química , Durapatita/química , Permeabilidade , Gelatina/química , Teste de Materiais
2.
Biosensors (Basel) ; 14(6)2024 Jun 10.
Artigo em Inglês | MEDLINE | ID: mdl-38920608

RESUMO

Agricultural products are vitally important for sustaining life on earth and their production has notably grown over the years worldwide in general and in Brazil particularly. Elevating agricultural practices consequently leads to a proportionate increase in the usage of pesticides that are crucially important for enhanced crop yield and protection. These compounds have been employed excessively in alarming concentrations, causing the contamination of soil, water, and air. Additionally, they pose serious threats to human health. The current study introduces an innovative tool for producing appropriate materials coupled with an electrochemical sensor designed to measure carbendazim levels. The sensor is developed using a molecularly imprinted polymer (MIP) mounted on a glassy carbon electrode. This electrode is equipped with multi-walled carbon nanotubes (MWCNTs) for improved performance. The combined system demonstrates promising potential for accurately quantifying carbendazim. The morphological characteristics of the synthesized materials were investigated using field emission scanning electron microscopy (FESEM) and the Fourier-transform infrared (FTIR) technique. The analytical curve was drawn using the electrochemical method in the range of 2 to 20 ppm while for HPLC 2-12 ppm; the results are presented as the maximum adsorption capacity of the MIP (82.4%) when compared with NIP (41%) using the HPLC method. The analysis conducted using differential pulse voltammetry (DPV) yielded a limit of detection (LOD) of 1.0 ppm and a repeatability of 5.08% (n = 10). The results obtained from the analysis of selectivity demonstrated that the proposed electrochemical sensor is remarkably efficient for the quantitative assessment of carbendazim, even in the presence of another interferent. The sensor was successfully tested for river water samples for carbendazim detection, and recovery rates ranging from 94 to 101% were obtained for HPLC and 94 to 104% for the electrochemical method. The results obtained show that the proposed electrochemical technique is viable for the application and quantitative determination of carbendazim in any medium.


Assuntos
Benzimidazóis , Carbamatos , Técnicas Eletroquímicas , Nanotubos de Carbono , Praguicidas , Carbamatos/análise , Benzimidazóis/análise , Praguicidas/análise , Nanotubos de Carbono/química , Técnicas Biossensoriais , Eletrodos , Materiais Biomiméticos/química , Limite de Detecção
3.
Biomimetics (Basel) ; 9(6)2024 May 21.
Artigo em Inglês | MEDLINE | ID: mdl-38921187

RESUMO

In the complex and dynamic landscape of cyber threats, organizations require sophisticated strategies for managing Cybersecurity Operations Centers and deploying Security Information and Event Management systems. Our study enhances these strategies by integrating the precision of well-known biomimetic optimization algorithms-namely Particle Swarm Optimization, the Bat Algorithm, the Gray Wolf Optimizer, and the Orca Predator Algorithm-with the adaptability of Deep Q-Learning, a reinforcement learning technique that leverages deep neural networks to teach algorithms optimal actions through trial and error in complex environments. This hybrid methodology targets the efficient allocation and deployment of network intrusion detection sensors while balancing cost-effectiveness with essential network security imperatives. Comprehensive computational tests show that versions enhanced with Deep Q-Learning significantly outperform their native counterparts, especially in complex infrastructures. These results highlight the efficacy of integrating metaheuristics with reinforcement learning to tackle complex optimization challenges, underscoring Deep Q-Learning's potential to boost cybersecurity measures in rapidly evolving threat environments.

4.
Chem Biodivers ; 21(8): e202400668, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-38763894

RESUMO

The cytochrome P450 is a superfamily of hemoproteins mainly present in the liver and are versatile biocatalysts. They participate in the primary metabolism and biosynthesis of various secondary metabolites. Chemical catalysts are utilized to replicate the activities of enzymes. Metalloporphyrins and Salen complexes can contribute to the products' characterization and elucidate biotransformation processes, which are investigated during pre-clinical trials. These catalysts also help discover biologically active compounds and get better yields of products of industrial interest. This review aims to investigate which natural product classes are being investigated by biomimetic chemical models and the functionalities applied in the use of these catalysts. A limited number of studies were observed, with terpenes and alkaloids being the most investigated natural product classes. The research also revealed that Metalloporphyrins are still the most popular in the studies, and the identity and yield of the products obtained depend on the reaction system conditions.


Assuntos
Produtos Biológicos , Sistema Enzimático do Citocromo P-450 , Metaloporfirinas , Produtos Biológicos/química , Produtos Biológicos/metabolismo , Metaloporfirinas/química , Metaloporfirinas/metabolismo , Catálise , Sistema Enzimático do Citocromo P-450/metabolismo , Etilenodiaminas/química , Biomimética , Terpenos/química , Terpenos/metabolismo , Materiais Biomiméticos/química , Materiais Biomiméticos/metabolismo , Complexos de Coordenação/química
5.
Bioengineering (Basel) ; 11(1)2024 Jan 16.
Artigo em Inglês | MEDLINE | ID: mdl-38247960

RESUMO

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.

6.
Biomimetics (Basel) ; 8(7)2023 Oct 26.
Artigo em Inglês | MEDLINE | ID: mdl-37999150

RESUMO

Dry fruits and nutshells are biological capsules of outstanding toughness and strength with biomimetic potential to boost fiber-reinforced composites and protective structures. The strategies behind the Betholletia excelsa fruit mechanical performance were investigated with C-ring and compression tests. This last test was monitored with shearography and simulated with a finite element model. Microtomography and digital and scanning electron microscopy evaluated crack development. The fruit geometry, the preferential orientation of fibers involved in foam-like sclereid cells, promoted anisotropic properties but efficient energy dissipating mechanisms in different directions. For instance, the mesocarp cut parallel to its latitudinal section sustained higher forces (26.0 ± 2.8 kN) and showed higher deformation and slower crack propagation. The main toughening mechanisms are fiber deflection and fiber bridging and pullout, observed when fiber bundles are orthogonal to the crack path. Additionally, the debonding of fiber bundles oriented parallel to the crack path and intercellular cracks through sclereid and fiber cells created a tortuous path.

7.
J Mech Behav Biomed Mater ; 146: 106082, 2023 10.
Artigo em Inglês | MEDLINE | ID: mdl-37619285

RESUMO

Functionalization of calcium phosphates with biomimetic peptides is a promising strategy to increase cellular response for bone tissue repair. In this work, biphasic calcium phosphate pellets were functionalized with the hydroxyapatite-binding peptide pVTK by dropping a suspension of the peptide on the pellet surface. The bioactivity tests were performed in vitro by using McCoy culture medium. Cytotoxicity tests were also performed to assess cell viability. The material was characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy with field emission gun (FEG-SEM). The results showed that functionalization with the biomimetic peptide was most effective in inducing precipitation of bone-like apatite on the pellets surface, when compared to the control groups (two positive control groups and one negative control group). Cytotoxicity tests showed that all samples are biocompatible but the pellets with peptide showed the highest values of cell viability.


Assuntos
Biomineralização , Fosfatos de Cálcio , Apatitas , Biomimética , Peptídeos/farmacologia
8.
Biomimetics (Basel) ; 8(3)2023 Jul 19.
Artigo em Inglês | MEDLINE | ID: mdl-37504205

RESUMO

Degenerative diseases and injuries that compromise hand movement reduce individual autonomy and tend to cause financial and psychological problems to their family nucleus. To mitigate these limitations, over the past decade, hand exoskeletons have been designed to rehabilitate or enhance impaired hand movements. Although promising, these devices still have limitations, such as weight and cost. Moreover, the movements performed are not kinematically compatible with the joints, thereby reducing the achievements of the rehabilitation process. This article presents the biomimetic design of a soft hand exoskeleton actuated using artificial tendons designed to achieve low weight, volume, and cost, and to improve kinematic compatibility with the joints, comfort, and the sensitivity of the hand by allowing direct contact between the hand palm and objects. We employed two twisted string actuators and Bowden cables to move the artificial tendons and perform the grasping and opening of the hand. With this configuration, the heavy part of the system was reallocated to a test bench, allowing for a lightweight set of just 232 g attached to the arm. The system was triggered by the myoelectric signals of the biceps captured from the user's skin to encourage the active participation of the user in the process. The device was evaluated by five healthy subjects who were asked to simulate a paralyzed hand, and manipulate different types of objects and perform grip strength. The results showed that the system was able to identify the intention of movement of the user with an accuracy of 90%, and the orthosis was able to enhance the ability of handling objects with gripping force up to 1.86 kgf.

9.
Pharmaceutics ; 15(3)2023 Mar 14.
Artigo em Inglês | MEDLINE | ID: mdl-36986804

RESUMO

Inducing immunogenic cell death (ICD) during cancer therapy is a major challenge that might significantly improve patient survival. The purpose of this study was to develop a theranostic nanocarrier, capable both of conveying a cytotoxic thermal dose when mediating photothermal therapy (PTT) after its intravenous delivery, and of consequently inducing ICD, improving survival. The nanocarrier consists of red blood cell membranes (RBCm) embedding the near-infrared dye IR-780 (IR) and camouflaging Mn-ferrite nanoparticles (RBCm-IR-Mn). The RBCm-IR-Mn nanocarriers were characterized by size, morphology, surface charge, magnetic, photophysical, and photothermal properties. Their photothermal conversion efficiency was found to be size- and concentration-dependent. Late apoptosis was observed as the cell death mechanism for PTT. Calreticulin and HMGB1 protein levels increased for in vitro PTT with temperature around 55 °C (ablative regime) but not for 44 °C (hyperthermia), suggesting ICD elicitation under ablation. RBCm-IR-Mn were then intravenously administered in sarcoma S180-bearing Swiss mice, and in vivo ablative PTT was performed five days later. Tumor volumes were monitored for the subsequent 120 days. RBCm-IR-Mn-mediated PTT promoted tumor regression in 11/12 animals, with an overall survival rate of 85% (11/13). Our results demonstrate that the RBCm-IR-Mn nanocarriers are great candidates for PTT-induced cancer immunotherapy.

10.
Front Bioeng Biotechnol ; 11: 1120179, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-36815878

RESUMO

Introduction: Cell membrane-covered biomimetic nanosystems have allowed the development of homologous nanostructures to bestow nanoparticles with enhanced biointerfacing capabilities. The stability of these structures, however, still represents a challenge for the scientific community. This study is aimed at developing and optimizing cell derived membrane-coated nanostructures upon applying design of experiments (DoE) to improve the therapeutic index by homotypic targeting in cancer cells. Methods: Important physicochemical features of the extracted cell membrane from tumoral cells were assessed by mass spectrometry-based proteomics. PLGA-based nanoparticles encapsulating temozolomide (TMZ NPs) were successfully developed. The coating technology applying the isolated U251 cell membrane (MB) was optimized using a fractional two-level three-factor factorial design. All the formulation runs were systematically characterized regarding their diameter, polydispersity index (PDI), and zeta potential (ZP). Experimental conditions generated by DoE were also subjected to morphological studies using negative-staining transmission electron microscopy (TEM). Its short-time stability was also assessed. MicroRaman and Fourier-Transform Infrared (FTIR) spectroscopies and Confocal microscopy were used as characterization techniques for evaluating the NP-MB nanostructures. Internalization studies were carried out to evaluate the homotypic targeting ability. Results and Discussion: The results have shown that nearly 80% of plasma membrane proteins were retained in the cell membrane vesicles after the isolation process, including key proteins to the homotypic binding. DoE analysis considering acquired TEM images reveals that condition run five should be the best-optimized procedure to produce the biomimetic cell-derived membrane-coated nanostructure (NP-MB). Storage stability for at least two weeks of the biomimetic system is expected once the original characteristics of diameter, PDI, and ZP, were maintained. Raman, FTIR, and confocal characterization results have shown the successful encapsulation of TMZ drug and provided evidence of the effective coating applying the MB. Cell internalization studies corroborate the proteomic data indicating that the optimized NP-MB achieved specific targeting of homotypic tumor cells. The structure should retain the complex biological functions of U251 natural cell membranes while exhibiting physicochemical properties suitable for effective homotypic recognition. Conclusion: Together, these findings provide coverage and a deeper understanding regarding the dynamics around extracted cell membrane and polymeric nanostructures interactions and an in-depth insight into the cell membrane coating technology and the development of optimized biomimetic and bioinspired nanostructured systems.

11.
Biomimetics (Basel) ; 8(1)2023 Jan 26.
Artigo em Inglês | MEDLINE | ID: mdl-36810383

RESUMO

Buildings must adapt and respond dynamically to their environment to reduce their energy loads and mitigate environmental impacts. Several approaches have addressed responsive behavior in buildings, such as adaptive and biomimetic envelopes. However, biomimetic approaches lack sustainability consideration, as conducted in biomimicry approaches. This study provides a comprehensive review of biomimicry approaches to develop responsive envelopes, aiming to understand the connection between material selection and manufacturing. This review of the last five years of building construction and architecture-related studies consisted of a two-phase search query, including keywords that answered three research questions relating to the biomimicry and biomimetic-based building envelopes and their materials and manufacturing and excluding other non-related industrial sectors. The first phase focused on understanding biomimicry approaches implemented in building envelopes by reviewing the mechanisms, species, functions, strategies, materials, and morphology. The second concerned the case studies relating to biomimicry approaches and envelopes. Results highlighted that most of the existing responsive envelope characteristics are achievable with complex materials requiring manufacturing processes with no environmentally friendly techniques. Additive and controlled subtractive manufacturing processes may improve sustainability, but there is still some challenge to developing materials that fully adapt to large-scale and sustainability needs, leaving a significant gap in this field.

12.
Biomimetics (Basel) ; 8(1)2023 Feb 02.
Artigo em Inglês | MEDLINE | ID: mdl-36810392

RESUMO

The study and application of biological knowledge favor the creation of innovative projects in several areas, so it is necessary to better understand the use of these resources specifically in the field of design. Thus, a systematic review was undertaken to identify, describe, and analyze the contributions of biomimicry to design. For this purpose, the integrative systematic review model, called the Theory of Consolidated Meta-Analytical Approach, was used, carrying out a search on the Web of Science with the descriptors "design" and "biomimicry". For the period from 1991 to 2021, 196 publications were retrieved. The results were organized according to areas of knowledge, countries, journals, institutions, authors, and years. Citation, co-citation, and bibliographic coupling analyses were also performed. The investigation highlighted the following research emphases: the conception of products, buildings, and environments; the exploration of natural structures and systems to create materials and technologies; the use of biomimetic creative tools in product design; and projects focused on saving resources and implementing sustainability. It was noted that there was a tendency for authors to adopt a problem-based approach. It was concluded that the study of biomimicry can stimulate the development of multiple skills in design, improving creativity, and enhancing the potential integration of sustainability into production cycles.

13.
Biomimetics (Basel) ; 8(1)2023 Feb 12.
Artigo em Inglês | MEDLINE | ID: mdl-36810408

RESUMO

This study investigates biomimetic sensors for the detection of methotrexate contaminants in environmental samples. Sensors inspired by biological systems are the focus of this biomimetic strategy. Methotrexate is an antimetabolite that is widely used for the treatment of cancer and autoimmune diseases. Due to the widespread use of methotrexate and its rampant disposal into the environment, the residues of this drug are regarded as an emerging contaminant of huge concern, considering that exposure to the contaminant has been found to lead to the inhibition of some essential metabolic processes, posing serious risks to humans and other living beings. In this context, this work aims to quantify methotrexate through the application of a highly efficient biomimetic electrochemical sensor constructed using polypyrrole-based molecularly imprinted polymer (MIP) electrodeposited by cyclic voltammetry on a glassy carbon electrode (GCE) modified with multi-walled carbon nanotubes (MWCNT). The electrodeposited polymeric films were characterized by infrared spectrometry (FTIR), scanning electron microscopy (SEM), and cyclic voltammetry (CV). The analyses conducted using differential pulse voltammetry (DPV) yielded a detection limit of 2.7 × 10-9 mol L-1 for methotrexate, a linear range of 0.01-125 µmol L-1, and a sensitivity of 0.152 µA L mol-1. The results obtained from the analysis of the selectivity of the proposed sensor through the incorporation of interferents in the standard solution pointed to an electrochemical signal decay of only 15.4%. The findings of this study show that the proposed sensor is highly promising and suitable for use in the quantification of methotrexate in environmental samples.

14.
J Esthet Restor Dent ; 35(1): 7-18, 2023 01.
Artigo em Inglês | MEDLINE | ID: mdl-36744374

RESUMO

OBJECTIVES: For decades, the dental community has discussed which materials would be the ideal substitutes for lost tooth structure. Initially, the biomimetic approach advocated that feldspathic ceramics would be the material of choice for enamel. However, given the complexity of obtaining excellent dental technicians and the financial cost, are composite resins a suitable replacement? The optical properties with opalescence and fluorescence effects, as well as this material's high fracture toughness, indicate it as a long-lasting restorative material. However, because this material depends on the operator's expertise, knowledge of layering techniques and the selection of each material for the different layers is required. Thus, knowledge of the polychromatic technique through a bioinspired approach is necessary to obtain results of life-like restorations. This article aims to review the polychromatic layering technique (PLT), considering the optical and mechanical properties of dentin and enamel and correlating these properties with current composite resins to guide clinicians in selecting the most suitable restoratives for their clinical challenges. CLINICAL CONSIDERATIONS: The polychromatic layering technique is revisited, cross-referencing the properties of dentin and enamel with current composite resin restoratives and their biomimetic properties. The effectiveness and predictability of the PLT are corroborated in clinical cases of varying degrees of difficulty requiring different layering strategies. CONCLUSION: After the bio-inspired analysis, using nature as a model to be understood and followed, it is possible to note how the polychromatic technique remains current and viable in mimicking nature, providing esthetic and natural results in the layering of composite resins. CLINICAL SIGNIFICANCE: Composite resins effectively replicate the optical and mechanical characteristics of natural dentin and enamel through the bioinspired approach presented by the polychromatic layering technique.


Assuntos
Resinas Compostas , Restauração Dentária Permanente , Resinas Compostas/química , Restauração Dentária Permanente/métodos , Cor , Materiais Dentários/química , Esmalte Dentário
15.
Int J Biol Macromol ; 233: 123223, 2023 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-36639070

RESUMO

Tailoring magnetic nanocarriers with tunable properties is of great significance for the development of multifunctional candidate materials in numerous fields. Herein, we report a one-pot biomimetic silicification-based method for the synthesis of silica-coated magnetic nanoparticles. The synthesis process was mild, low cost, and highly efficient, which took only about 21 min compared with 4.5-120 h in other literature. Then, the carriers had been characterized by VSM, SEM, TEM, XRD, FT-IR, and EDS to confirm their function. To evaluate the usefulness of the carriers, they were adopted to couple the purification and immobilization of ß-1,3-xylanase from the cell lysate in a single step with high immobilization yield (92.8 %) and high activity recovery (82.4 %). The immobilized enzyme also retained 58.4 % of the initial activity after 10 cycles and displayed good storage properties, and improved thermal stability, which would be promising in algae biomass bioconversion as well as other diverse applications.


Assuntos
Nanopartículas de Magnetita , Nanopartículas , Dióxido de Silício , Espectroscopia de Infravermelho com Transformada de Fourier , Enzimas Imobilizadas/metabolismo , Fenômenos Magnéticos , Estabilidade Enzimática , Concentração de Íons de Hidrogênio , Temperatura
16.
Biomimetics (Basel) ; 8(1)2023 Jan 11.
Artigo em Inglês | MEDLINE | ID: mdl-36648815

RESUMO

Soft robotics have broken the rigid wall of interaction between humans and robots due to their own definition and manufacturing principles, allowing robotic systems to adapt to humans and enhance or restore their capabilities. In this research we propose a dexterous bioinspired soft active hand prosthesis based in the skeletal architecture of the human hand. The design includes the imitation of the musculoskeletal components and morphology of the human hand, allowing the prosthesis to emulate the biomechanical properties of the hand, which results in better grips and a natural design. CAD models for each of the bones were developed and 3D printing was used to manufacture the skeletal structure of the prosthesis, also soft materials were used for the musculoskeletal components. A myoelectric control system was developed using a recurrent neural network (RNN) to classify the hand gestures using electromyography signals; the RNN model achieved an accuracy of 87% during real time testing. Objects with different size, texture and shape were tested to validate the grasping performance of the prosthesis, showing good adaptability, soft grasping and mechanical compliance to object of the daily life.

17.
J Inorg Biochem ; 237: 112026, 2022 12.
Artigo em Inglês | MEDLINE | ID: mdl-36270893

RESUMO

A mononuclear Mn(III) complex of a clickable ligand, [Mn(hbpapn)(H2O)2]ClO4·4.5H2O, where H2hbpapn = 1,3-bis[(2-hydroxybenzyl)(propargyl)amino]propane, has been prepared and fully characterized. The complex catalyzes the dismutation of superoxide employing a Mn(III)/Mn(IV) redox cycle, with catalytic rate constant of 3.9 × 106 M-1 s-1 determined through the nitro blue tetrazolium photoreduction inhibition assay, in aqueous medium of pH 7.8. The alkyne function of the ligand was used for the covalent attachment of the catalyst to azide modified mesoporous silicas with different texture and morphology, through click chemistry. In these materials the catalyst is essentially linked to the inner pore walls, isolated and protected from the external medium. The hybrid materials can be recycled, and retain or improve the superoxide dismutase activity of the free catalyst with the pore size of the solid matrix playing a role on the activity of the catalyst.


Assuntos
Manganês , Dióxido de Silício , Manganês/química , Ligantes , Dióxido de Silício/química , Biomimética , Superóxido Dismutase/química
18.
Polymers (Basel) ; 14(18)2022 Sep 19.
Artigo em Inglês | MEDLINE | ID: mdl-36146056

RESUMO

Polyaniline (PANI) composites have gained momentum as supercapacitive materials due to their high energy density and power density. However, some drawbacks in their performance remain, such as the low stability after hundreds of charge-discharge cycles and limitations in the synthesis scalability. Herein, we report for the first time PANI-Graphitic oxidized carbon nitride composites as potential supercapacitor material. The biomimetic polymerization of aniline assisted by hematin, supported by phosphorous and oxygen-modified carbon nitrides (g-POCN and g-OCN, respectively), achieved up to 89% yield. The obtained PAI/g-POCN and PANI/g-OCN show enhanced electrochemical properties, such as conductivity of up to 0.0375 S/cm, specific capacitances (Cs) of up to 294 F/g (at high current densities, 5 A/g) and a stable operation after 500 charge-discharge cycles (at 3 A/g). In contrast, the biomimetic synthesis of Free PANI, assisted by stabilized hematin in cosolvents, exhibited lower performance properties (65%). Due to their structural differences, the electrochemical properties of Free PANI (conductivity of 0.0045 S/cm and Cs of up to 82 F/g at 5 A/g) were lower than those of nanostructured PANI/g-POCN and g-OCN supports, which provide stability and improve the properties of biomimetically synthesized PANI. This work reveals the biomimetic synthesis of PANI, assisted by hematin supported by modified carbon nitrides, as a promising strategy to produce nanostructured supercapacitors with high performance.

19.
Prog Biomater ; 11(3): 263-271, 2022 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-35739413

RESUMO

We evaluated the influence of the open porosity of alumina (Al2O3) substrates on the phase formation of calcium phosphates deposited onto it surface. The Al2O3 substrates were prepared with different porosities by the foam-gelcasting method associated with different amounts of polyethylene beads. The substrates were coated biomimetically for 14 and 21 days of incubation in a simulated body fluid (SBF). Scanning electron microscopy characterisation and X-ray computed microtomography showed that the increase in the number of beads provided an increase in the open porosity. The X-ray diffraction and infrared spectroscopy showed that the biomimetic method was able to form different phases of calcium phosphates. It was observed that the increase in the porosity favoured the formation of ß-tricalcium phosphate for both incubation periods. The incubation period and the porosity of the substrates can influence the phases and the amount of calcium phosphates formed. Thus, it is possible to target the best application for the biomaterial produced.

20.
Sci Technol Adv Mater ; 23(1): 300-321, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-35557509

RESUMO

The rice leaf, combining the surface properties of lotus leaves and shark skin, presents outstanding superhydrophobic properties motivating its biomimesis. We created a novel biomimetic rice-leaf superhydrophobic surface by a three-level hierarchical structure, using for a first time stereolithographic (SLA) 3D printed channels (100µm width) with an intrinsic roughness from the printing filaments (10µm), and coated with TiO2 nanoparticles (22 and 100nm). This structure presents a maximum advancing contact angle of 165° characterized by lower both anisotropy and hysteresis contact angles than other 3D printed surfaces, due to the presence of air pockets at the surface/water interface (Cassie-Baxter state). Dynamic water-drop tests show that the biomimetic surface presents self-cleaning, which is reduced under UV-A irradiation. The biomimetic surface further renders an increased floatability to 3D printed objects meaning a drag-reduction due to reduced water/solid contact area. Numerical simulations of a channel with a biomimetic wall confirm that the presence of air is essential to understand our results since it increases the average velocity and decreases the friction factor due to the presence of a wall-slip velocity. Our findings show that SLA 3D printing is an appropriate approach to develop biomimetic superhydrophobic surfaces for future applications in anti-fouling and drag-reduction devices.

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