Thermo- and pH-Responsive Gelatin/Polyphenolic Tannin/Graphene Oxide Hydrogels for Efficient Methylene Blue Delivery.

Gelatin (GE), amino-functionalized polyphenolic tannin derivative (TN), and graphene oxide (GO) were associated to yield thermo- and pH-responsive hydrogels for the first time. Durable hydrogel assemblies for drug delivery purposes were developed using the photosensitizer methylene blue (MB) as a drug model. The cooling GE/TN blends provide brittle physical assemblies. To overcome this disadvantage, different GO contents (between 0.31% and 1.02% wt/wt) were added to the GE/TN blend at 89.7/10.3 wt/wt. FTIR and RAMAN spectroscopy analyses characterized the materials, indicating GO presence in the hydrogels. Incorporation studies revealed a total MB (0.50 mg/mL) incorporation into the GE/TN-GO hydrogel matrices. Additionally, the proposed systems present a mechanical behavior similar to gel. The GO presence in the hydrogel matrices increased the elastic modulus from 516 to 1650 Pa. SEM revealed that hydrogels containing MB present higher porosity with interconnected pores. Dissolution and swelling degree studies revealed less stability of the GE/TN-GO-MB hydrogels in SGF medium (pH 1.2) than SIF (pH 6.8). The degradation increased in SIF with the GO content, making the polymeric matrices more hydrophilic. MB release studies revealed a process controlled by Fickian diffusion. Our results point out the pH-responsible behavior of mechanically reinforced GE/TN-GO-MB hydrogels for drug delivery systems purposes.

Methacrylate saccharide-based monomers for dental adhesive systems.

The aim of this in vitro study was to synthesize three new methacrylate monomers based on the modification of saccharides structures (glucose-Gluc, sucrose-Sucr and chitosan-Chit) with glycidyl methacrylate, and to use them in the composition of dental adhesives. Three methacrylate saccharide monomers were synthesized and characterized by mid-IR, 1H and 13C NMR, antioxidant activity and cytotoxic effect. Monomers included: one monosaccharide - Gluc-MA; one disaccharide - Sucr-MA; and one polysaccharide - Chit-MA. Primers containing HEMA, methacrylate saccharide monomers at concentrations of 0 (control), 1, 2 or 4 wt%, 60 wt% ethanol aqueous solution (pH3.0) and initiator system were formulated. Primers were used in conjunction with a bond step and composite paste to restore caries-free third molars, and dentin bond strength (24 hours and 6 month of storage in water), and antimicrobial activity (Alamar Blue test) were tested. Degree of conversion (DC) and maximum rate of polymerization (Rpmax) of the primers themselves were also analyzed. The mid-IR, 1H and 13C spectrum confirmed the presence of vinyl group on the structure of saccharides. Chit-MA showed low antioxidant activity and did not present a cytotoxic effect. Gluc-MA and Sucr-MA possess antioxidant and cytotoxic activity, concentration dependent. In the presence of methacrylate saccharide monomers, the primers showed DC comparable to the control group, except Gluc-MA4%, Sucr-MA4% and Chit-MA1%, which showed a range of 64.6 from 58.5 %DC. Rpmax was not statistically different for all the groups (p = 0.01). The bond strength of Sucr-MA1% increased from 25.7 (±2.8) to 40.6 (±5.3) MPa after 6 months of storage. All the synthesized monomers showed some antimicrobial activity after polymerization. Gluc-MA and Chit-MA 4% and Sucr-MA 1, 2 and 4% led to decrease bacterial metabolism. Sucr-MA 1% showed better results regarding the decrease in bacterial metabolism and increasing the bond strength after 6 months of storage.

SPR platform based on image acquisition for HER2 antigen detection.

HER2 antigen is a marker used for breast cancer diagnosis and prevention. Its determination has great importance since breast cancer is one of the most insidious types of cancer in women. HER2 antigen assessment in human serum is traditionally achieved by enzyme-linked immunosorbent assay (ELISA method), but it has some disadvantages, such as suppressing the thermodynamic-kinetic studies regarding the antibody-antigen interaction, and the use of labeled molecules that can promote false positive responses. Biosensors based on surface plasmon resonance (SPR) are sensitive optical techniques widely applied on bioassays. The plasmonic devices do not operate with labeled molecules, overcoming conventional immunoassay limitations, and enabling a direct detection of target analytes. In this way, a new SPR biosensor to assess HER2 antigen has been proposed, using nanohole arrays on a gold thin film by signal transduction of transmitted light measurements from array image acquisitions. These metallic nanostructures may couple the light directly on surface plasmons using a simple collinear arrangement. The proposed device reached an average sensitivity for refractive index (RI) variation on a metal surface of 4146 intensity units/RIU (RIU = RI units). The device feasibility on biomolecular assessment was evaluated. For this, 3 ng ml-1 known HER2 antigen concentration was efficiently flowed (using a microfluidic system) and detected from aqueous solutions. This outcome shows that the device may be a powerful apparatus for bioassays, particularly toward breast cancer diagnosis and prognosis.

Silver Nanoparticles In Situ Synthesized and Incorporated in Uniaxial and Core-Shell Electrospun Nanofibers to Inhibit Coronavirus.

In the present study, we sought to develop materials applicable to personal and collective protection equipment to mitigate SARS-CoV-2. For this purpose, AgNPs were synthesized and stabilized into electrospinning nanofiber matrices (NMs) consisting of poly(vinyl alcohol) (PVA), chitosan (CHT), and poly-ε-caprolactone (PCL). Uniaxial nanofibers of PVA and PVA/CHT were developed, as well as coaxial nanofibers of PCL[PVA/CHT], in which the PCL works as a shell and the blend as a core. A crucial aspect of the present study is the in situ synthesis of AgNPs using PVA as a reducing and stabilizing agent. This process presents few steps, no additional toxic reducing agents, and avoids the postloading of drugs or the posttreatment of NM use. In general, the in situ synthesized AgNPs had an average size of 11.6 nm, and the incorporated nanofibers had a diameter in the range of 300 nm, with high uniformity and low polydispersity. The NM's spectroscopic, thermal, and mechanical properties were appropriate for the intended application. Uniaxial (PVA/AgNPs and PVA/CHT/AgNPs) and coaxial (PCL[PVA/CHT/AgNPs]) NMs presented virucidal activity (log's reduction ≥ 5) against mouse hepatitis virus (MHV-3) genus Betacoronavirus strains. In addition to that, the NMs did not present cytotoxicity against fibroblast cells (L929 ATCC® CCL-1TM lineage).

Poly(butylene adipate-co-terephthalate)/Poly(lactic acid) Polymeric Blends Electrospun with TiO2-R/Fe3O4 for Pollutant Photodegradation.

This work aimed to use the electrospinning technique to obtain PBAT/PLA polymer fibers, with the semiconductors rutile titanium dioxide (TiO2-R) and magnetite iron oxide (Fe3O4), in order to promote the photocatalytic degradation of environmental contaminants. The parameters used in the electrospinning process to obtain the fibers were distance from the needle to the collecting target of 12 cm, flow of 1 mL h-1 and voltage of 14 kV. The best mass ratio of semiconductors in the polymeric fiber was defined from a 22 experimental design, and the values obtained were 10% TiO2-R, 1% Fe3O4 at pH 7.0. Polymer fibers were characterized by Scanning Electron Microscopy (SEM), Differential Scanning Calorimetry (DSC), X-ray Diffraction (XRD), Thermogravimetric Analysis (TGA) and Fourier Transform Infrared (FTIR) techniques. SEM measurements indicated a reduction in fiber diameter after the incorporation of semiconductors; for the PBAT/PLA fiber, the average diameter was 0.9466 ± 0.2490 µm, and for the fiber with TiO2-R and Fe3O4 was 0.6706 ± 0.1447 µm. In the DSC, DRX, TGA and FTIR analyses, it was possible to identify the presence of TiO2-R and Fe3O4 in the fibers, as well as their interactions with polymers, demonstrating changes in the crystallinity and degradation temperature of the material. These fibers were tested against Reactive Red 195 dye, showing an efficiency of 64.0% within 24 h, showing promise for photocatalytic degradation of environmental contaminants.

Electrospinning in personal protective equipment for healthcare work.

Protection in many service areas is mandatory for good performance in daily activities of workers, especially health areas. Personal protective equipment (PPE) is used to protect patients and health workers from contamination by harmful pathogens and body fluids during clinical attendance. The pandemic scenario caused by SARS-CoV-2 has shown that the world is not prepared to face global disease outbreaks, especially when it comes to the PPE of healthcare workers. In the last years, the world has faced a deficiency in the development of advanced technologies to produce high-quality PPE to attend to the exponential increasing demand. Electrospinning is a technology that can be used to produce high-quality PPE by improving the protective action of clothing. In the face of this concern, this manuscript presents as focus the potential of electrospinning to be applied in protective clothing. PPE mostly used by healthcare workers are also presented. The physico-chemical characteristics and production processes of medical textiles for PPE are addressed. Furthermore, an overview of the electrospinning technique is shown. It is important to highlight most research about electrospinning applied to PPE for health areas presents gaps and challenges; thus, future projections are also addressed in this manuscript.

Polycaprolactone nanofibers colonized by HeLa cells: an alternative for in vitro investigation of fungal infection.

Introduction: In vitro 3D equivalent tissues can be used for studies of fungal infections. Objectives: To develop 3D electrospun nanofibers using polycaprolactone (PCL) colonized by HeLa cells as a possible in vitro model for the investigation of fungal infection. Materials & methods: A PCL solution was synthesized and electrospun. HeLa cells were cultured on the nanostructured PCL scaffolds, forming a 3D structure. Physicochemical, biological and Candida albicans infection assays were performed in this model. Results: The nanostructured PCL scaffolds showed favorable physicochemical characteristics and allowed the colonization of HeLa cells, which showed indications of extracellular matrix production. Conclusions: Fungal infection was evidenced in the 3D nanostructured PCL scaffolds, being viable, economical and compatible to study fungal infections in vitro.

Experimental data for green synthesis of Zn-abietate complex from natural resin.

This data article is associated with the work "Ecofriendly synthesis of Zn-abietate complex derived from Pinus elliottii resin and its application as an antibacterial pigment against S. aureus and E. coli". The characterization data of the Zn-abietate complex obtained from Pinus elliottii resin and their reactional intermediary (Na-abietate) are reported. The Na-abietate was prepared with purified Pinus resin and sodium hydroxide (≥ 99%) in a stoichiometric ratio of 1:1. For the Zn-abietate synthesis was used ZnSO4 and Na-abietate solutions were at mild temperature and stirring without using organic solvents to ensuring the green character of the synthesis. Spectroscopic and structural characterization was consistent with an octahedral complex involving three carboxylate ligands per metal ion. X-ray photoelectron spectroscopy (XPS) analysis of the Na-abietate salt confirms the presence of carbonyl groups, carbon-oxygen atoms simple bonds (O-C/O=C), and carboxylate groups oxygen atoms (O-C=O). Analysis of the Zn LMM Auger, for the Zn-abietate complex, indicates the presence of zinc atoms with oxidation state Zn2+, this is supported by the distance between Zn 2p3/2 and 1p1/2 in the XPS spectrum. Together, these data will be useful for the structural representation of the samples.

Antimicrobial and cytocompatible chitosan, N,N,N-trimethyl chitosan, and tanfloc-based polyelectrolyte multilayers on gellan gum films.

In this work free-standing gels formed from gellan gum (GG) by solvent evaporation are coated with polysaccharide-based polyelectrolyte multilayers, using the layer-by-layer approach. We show that PEMs composed of iota-carrageenan (CAR) and three different natural polycationic polymers have composition-dependent antimicrobial properties, and support mammalian cell growth. Cationic polymers (chitosan (CHT), N,N,N-trimethyl chitosan (TMC), and an amino-functionalized tannin derivative (TN)) are individually assembled with the anionic iota-carrageenan (CAR) at pH 5.0. PEMs (15-layers) are alternately deposited on the GG film. The GG film and coated GG films with PEMs are characterized by infrared spectroscopy with attenuated total reflectance (FTIR-ATR), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and water contact angle (WCA) measurements. The TN/CAR coating provides a hydrophobic (WCA = 127°) and rough surface (Rq = 243 ± 48 nm), and the TMC/CAR coating provides a hydrophilic surface (WCA = 78°) with the lowest roughness (Rq = 97 ± 12 nm). Polymer coatings promote stability and durability of the GG film, and introduce antimicrobial properties against Gram-negative (Salmonella enteritidis) and Gram-positive (Staphylococcus aureus) bacteria. The films are also cytocompatible. Therefore, they have properties that can be further developed as wound dressings and food packaging.

A urethane-based multimethacrylate mixture and its use in dental composites with combined high-performance properties.

OBJECTIVES: To synthesize and characterize different molar weight urethane multimethacrylates with a single stage (one-pot) procedure. To prepare and characterize the properties of related composites. METHODS: Two methacrylate precursors were initially synthesized. Then, these precursors and the multimethacrylate system formed by their coupling were characterized by FTIR and (1)H NMR. The final product was used as a matrix (with TEGDMA and SiO2 silanized microparticles) in the preparation of composites and their physical and mechanical properties were compared to those of a bis-GMA-based resin. Water sorption and solubility measurements of the composites were also performed. RESULTS: FTIR and NMR suggested that the proposed synthesis route yields a mixture of mainly urethane-di, -tri, and tetramethacrylates. The composites presented low polymerization shrinkage (e.g. 1.88±0.08% for a resin with 70% of SiO2) and high flexural strength (e.g. 124.74±9.68 MPa for a resin with 65% of SiO2) when compared to the bis-GMA based resin and other composites found to date. Water sorption and solubility results show that the composites were deemed compliant with ISO 4049 requirements. SIGNIFICANCE: The mixture containing different molar weight of urethane multimethacrylates showed to be an excellent substitute for bis-GMA, achieving an equilibrium of properties (unlike reports elsewhere which show the enhancement of some parameters in detriment to others) and composites with low polymerization shrinkage, suitable microhardness and degree of conversion, and up to standard water sorption/solubility and flexural strength.

Effect of the photoinitiator system on the properties of a dental material based on a hybrid polymer / Efeito do sistema fotoiniciador sobre as propriedades de um material dentário baseado em um polímero híbrido

Objetivo: Nesse estudo, foram avaliados os efeitos de dois diferentes protocolos de cura sobre as propriedades de um compósito usando um polímero híbrido como resina dentária. Material e Métodos: Dois compósitos diferentes foram preparados, um contendo uma mistura de TEGDMA/Bis-GMA (50:50) e, outro contendo uma mistura de TEGDMA/p-MEMO (50:50), [p-MEMO: precursor oligomérico inorgânico]. Ambos compósitos foram reticulados com lucirin e canforoquinona. Os compósitos foram preparados com 70% em massa de carga inorgânica. Resistência flexural foi avaliada com uma máquina de testes universal e o grau de conversão calculado por espectroscopia na região do infravermelho. Um picnômetro a gás hélio foi usado para obter os dados de contração de polimerização. Testes de sorção foram feitos e microscopia eletrônica de varredura foi usada para avaliar efeitos deletérios sobre as superfícies das resinas. Resultados: A amostra constituída com TEGDMA/p-MEMO reticulada com lucirin (L-T/p) apresentou os melhores valores das propriedades monitoradas. Conclusão: Lucirin é o sistema fotoiniciador mais adequado para compostos dentários contendo polímeros híbridos.

Objective: In this study, the effects of two different cure protocols upon the properties of composites using a hybrid-polymer as dental resin were evaluated. Material and Methods: Two distinct dental composites were prepared, one containing a mixture of TEGDMA/bis-GMA (50:50) and, another containing a mixture of TEGDMA/p MEMO (50:50), [p-MEMO: oligomeric inorganic precursor]. Both composites were polymerized with lucirin and canphorquinone as photoinitiators. The composites were made with a 70 % wt of inorganic filler. Flexural strength was evaluated with a universal test machine and the degree of conversion was measured by infrared spectroscopy. A helium pycnometer was used to obtain polymer shrinkage data. Sorption tests were performed and SEM microscopy was used to show deleterious effects upon the resins’ surfaces. Results: The sample based on TEGDMA/p-MEMO polymerized with lucirin (L-T/p) showed the best values of the monitored properties. Conclusion: Lucirin is the most suitable photoinitiator for dental composites containing hybrid polymers.

Integrando ciência e arte com resinas compostas: reabilitação estética anterior, aspectos químicos e análise em MEV - Microscopia Eletrônica de Varredura / Science and art with dental composite: anterior esthetic rehabilitation, chemical aspects and analysis with SEM - Scanning Electron Microscopy

Atualmente, o desenvolvimento observado nas resinas compostas proporciona ao cirurgião-dentista a oportunidade de reproduzir com grande fidelidade os dentes naturais. As propriedades químicas têm melhorado constantemente, proporcionando maior durabilidade, resistência e estética satisfatória. O presente artigo teve como objetivo apresentar passo-a-passo uma reabilitação estética com resinas compostas em dentes anteriores, discutir alguns aspectos gerais sobre suas características químicas, bem como analisar o compósito utilizado através de MEV - microscopia eletrônica de varredura.