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.

Bactericidal Pectin/Chitosan/Glycerol Films for Food Pack Coatings: A Critical Viewpoint.

Pectin and chitosan films containing glycerol (Gly) at 5, 10, 15, 20, 30, and 40 wt % were prepared in an aqueous HCl solution (0.10 M) by the solvent evaporation method. The unwashed film (UF) containing 40 wt % Gly (UF40) had elongation at break (ε, %) of 19%. Washed films (WFs) had high tensile strength (σ > 46 MPa) and low elongation at break (ε, <5.0%), enabling their use in food packaging applications. The polymers' self-assembling occurred during the washing, increasing the stiffness. The XPS analysis suggests that some HCl is lost during the drying process, resulting in a low acid content on the UF surfaces. The UF40 (at 5.0 mg/mL) exhibits cytocompatibility toward mammalian cells and antimicrobial and anti-adhesive properties against Escherichia coli. The remaining HCl in the UF40 can be a disadvantage for food packaging applications; the UF40 (∅ = 8.5 mm; 55 µm thickness) releases H3O+/HCl, reducing the pH to approximately 3.0 when kept in 200 mL distilled water for approximately 30 min. Therefore, we propose the use of UF40 to coat commercial food packaging. The UF40 has low permeability to water vapor and oxygen and works as a barrier against ultraviolet light. The UF40 is also colorless and completely transparent. The UF40 maintained tomatoes' structural integrity for 18 days at room temperature with no oxidation or microorganism contamination. This paper presents a critical viewpoint concerning chitosan-based films with antimicrobial activities.

Zinc oxide nanoparticle-reinforced pectin/starch functionalized films: A sustainable solution for biodegradable packaging.

Environmental pollution caused by non-biodegradable plastic pollutants adversely affects various ecosystems. This study proposes the development of novel functional and biodegradable films based on corn starch (CST) and pectin (PEC) containing zinc oxide nanoparticles (ZnONPs) from the casting method. The films exhibited processability, transparency, low water vapor permeation, and desirable mechanical properties for food packaging and coating applications. The ZnONPs acted as a plasticizer, enhancing the film elongation at the break, increasing the pec25-1 (PEC 25 wt% and ZnONPs 1 wt%) elongation from 79.85 to 162.32 %. The improved film elasticity supported by ZnONPs reduced the material stiffness. However, the films still demonstrated an average tensile strength (0.69 MPa) 17-fold higher than the tensile strength (0.04 MPa) of the non-biodegradable commercial film based on poly(vinyl chloride). Furthermore, the ZnONPs enhanced the UV-blocking capabilities of the films, leading to wettable materials with water contact angles lower than 90°. The films showed high biodegradation rates under natural disposal conditions. The results indicated that the pec25-1/ZnONPs film is a promising eco-friendly coating in food preservation due to its biodegradability, suitable mechanical properties, low water vapor permeability, and UV-blocking properties.

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).

Polysaccharide-Based Materials Created by Physical Processes: From Preparation to Biomedical Applications.

Polysaccharide-based materials created by physical processes have received considerable attention for biomedical applications. These structures are often made by associating charged polyelectrolytes in aqueous solutions, avoiding toxic chemistries (crosslinking agents). We review the principal polysaccharides (glycosaminoglycans, marine polysaccharides, and derivatives) containing ionizable groups in their structures and cellulose (neutral polysaccharide). Physical materials with high stability in aqueous media can be developed depending on the selected strategy. We review strategies, including coacervation, ionotropic gelation, electrospinning, layer-by-layer coating, gelation of polymer blends, solvent evaporation, and freezing-thawing methods, that create polysaccharide-based assemblies via in situ (one-step) methods for biomedical applications. We focus on materials used for growth factor (GFs) delivery, scaffolds, antimicrobial coatings, and wound dressings.

Application of a polyelectrolyte complex based on biocompatible polysaccharides for colorectal cancer inhibition.

Strategies for incorporating water-insoluble photosensitisers (PS) in drug delivery systems have been extensively studied. In this work, we evaluate the formation, characterisation, drug sorption studies, and cytotoxicity of chitosan (CHT)/chondroitin sulphate (CS) polyelectrolyte complexes (PECs) coated with polystyrene-block-poly(acrylic acid) (PS-b-PAA) nanoparticles (NPs) loaded with chloroaluminum phthalocyanine (AlClPc). The PECs were characterised by infrared spectroscopy (FTIR), differential scanning calorimetric (DSC), X-ray diffraction (XRD), and scanning electron microscopy (SEM). The PS-b-PAA NPs on the PEC surface was confirmed by scanning electron microscopy (SEM). Additionally, optical images distinguished the PEC structures containing PS-b-PAA or PS-b-PAA/AlClPc from the unloaded PEC. Kinetic and equilibrium studies investigate the sorption capacity of the PEC/PS-b-PAA toward AlClPc. The encapsulation efficiency reached 95% at 190 µg mL-1 AlClPc after only 15 min. The Brunauer-Emmett-Teller (BET) isotherm and pseudo-second-order kinetic fitted well to the experimental data. The PS-b-PAA NPs on the PEC surfaces increase the AlClPc bioavailability and the PEC structure stabilizes the PS-b-PAA/AlClPc nanostructures. The materials were cytocompatible upon healthy VERO (kidney epithelial cells), and cytotoxic against colorectal cancerous cells (HT-29 cells). For the first time, we associate PS-b-PAA/AlClPc with a hydrophilic and cytocompatible polysaccharide matrix. We suggest the use of these materials in strategies to treat cancer by using photodynamic therapy.

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.

Prevalence of intestinal parasites versus knowledge, attitudes, and practices of inhabitants of low-income communities of Campos dos Goytacazes, Rio de Janeiro State, Brazil.

Intestinal parasites are the causative agents of common infections responsible for significant public health problems in developing countries and generally linked to lack of sanitation, safe water, and improper hygiene. More than two billion people throughout the world live with unrelenting illness due to intestinal parasitic infections (IPIs). The purposes of this study are to assess knowledge, attitudes, and practices on IPIs and investigate the relationship with prevalence of intestinal parasites among a low-income group of inhabitants from two communities of the Travessão District area, Campos dos Goytacazes, north of Rio de Janeiro State, Brazil. The two communities are known as "Parque Santuário," which is an urban slum with miserable living conditions, and "Arraial," where the socioeconomic and educational levels are better, neither having a sanitary infrastructure with an excreta collection system. Questionnaires revealed that both communities had local and specific codification to denominate the intestinal parasites and present correct knowledge on the theme but ignored some aspects of IPI transmission, with the Arraial population being better informed (p < 0.05). The overall prevalence of IPIs in Parque Santuário (49.7%) was greater than in Arraial (27.2%) (p < 0.001; prevalence ratio/95% confidence interval 1.83/1.50-2.23). This study reports the real IPI situation in the Travessão District and also reinforces the need to continue the investigation on the impact of combined prophylactic methods, educational measures, and socioeconomic and sanitary improvements by governmental authorities and the local popular organization.

Pectin-capped gold nanoparticles synthesis in-situ for producing durable, cytocompatible, and superabsorbent hydrogel composites with chitosan.

Studies report the production of gold nanoparticles (AuNPs) and polysaccharides-based composites. However, there are few reports about AuNPs synthesis in-situ followed by the formation of hydrogel composites. Here, we show AuNPs synthesis in-situ into the pectin solutions to yield cytocompatible pectin-capped AuNPs/chitosan hydrogel composites. Visible spectroscopy and dynamic light scattering measurements confirm the AuNPs synthesis. The hydrodynamic radius of the pectin-capped AuNPs ranges from approximately 510 to 721 nm, while the Zeta potential is around -43 mV. Scanning electron microscopy shows that the composites present compact structures. Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy characterize the composites as well. Hydrogels (with or without AuNPs) containing the highest pectin content (at 4.12 pectin/chitosan weight ratio) have low stability (disintegrates approximately 60% after 14 days in phosphate buffer). Composites obtained at 3.75 pectin/chitosan weight ratio disintegrate between 25 and 30% after 14 days in phosphate buffer (physiological condition = pH 7.4). The AuNPs reinforce the hydrogel structures, increasing the elastic modulus (from 3.5 to 7.6 Pa) and decreasing the water uptake from 4465 to 2976%. 3.75 PT/CS weight ratio and 3.0 × 10-4 M Au(III) content provide a durable, cytocompatible, and superabsorbent hydrogel composite. These properties can support materials for drug delivery purposes.

Composite materials based on chitosan/gold nanoparticles: From synthesis to biomedical applications.

Conventional strategies (Turkevich's, and modified Turkevich's methods) often synthesize gold nanoparticles (AuNPs). These pathways produce AuNPs using toxic chemistries to reduce Au(III) and stabilize Au(0) atoms upon the AuNP surfaces. To overcome the disadvantages of conventional approaches, chitosan and chitosan-based materials associate with Au(III) to produce composites. Chitosan and derivatives reduce Au(III) and stabilize AuNPs, promoting biocompatibility to the composites, following approaches in-situ. In this review, we report methods to develop chitosan/AuNPs-based composites. The main criticism is about the mechanism of composite formation. Also, we highlight applications of chitosan/AuNPs-based devices in the biomedical arena. We report the synthesis of biosensors, drug delivery devices, scaffolds, antimicrobial coatings, and others. The major criticism is concerning the material design and the lack of data regarding the composite biocompatibility. We support a critical viewpoint.

Chitosan/gellan gum ratio content into blends modulates the scaffolding capacity of hydrogels on bone mesenchymal stem cells.

Here, we have demonstrated the production and characterization of hydrogel scaffolds based on chitosan/gellan gum (CS/GG) assemblies, without any covalent and metallic crosslinking agents, conventionally used to yield non-soluble polysaccharide-based materials. The polyelectrolyte complexes (physical hydrogels called as PECs) are characterized by Fourier-transform infrared spectroscopy, wide-angle X-ray scattering, and scanning electron microscopy. Hydrogels containing chitosan (CS) excesses (ranging from 60 to 80 wt%) were created. Durable polysaccharide-based scaffolds with structural homogeneity and interconnecting pore networks are developed by modulating the CS/GG weight ratio. The CS/GG hydrogel prepared at 80/20 CS/GG weight ratio (sample CS/GG80-20) is cytocompatible, supporting the attachment, growth, and spreading of bone marrow mesenchymal stem cells (BMSCs) after nine days of cell culture. The cytocompatibility is correlated to the swelling capacity of the PEC in PBS buffer (pH 7.4). By controlling the CS content, we can tune the water uptake of the material, enhancing the capacity to serve as a three-dimensional cell scaffold for BMSCs. This work presents for the first time that CS/GG hydrogels can be applied as scaffolds for tissue engineering purposes.

Poly(vinyl alcohol)/cationic tannin blend films with antioxidant and antimicrobial activities.

This study reports the synthesis, characterization and biological properties of films based on poly(vinyl alcohol) (PVA) and a cationic tannin polymer derivative (TN). Films are obtained from polymeric blends by tuning the PVA/TN weight ratios. The materials are characterized through infrared spectroscopy, X-ray photoelectron spectroscopy, contact angle measurements, mechanical analyses, and scanning electron microscopy. More hydrophilic surfaces are created by modulating the PVA and TN concentrations in the blends. Disintegration tests showed that the films present durability in phosphate buffer (pH 7.4) and low stability in simulated gastric fluid (pH 1.2). The film created at 90/10 PVA/TN weight ratio and crosslinked at 109 PVA/glutaraldehyde molar ratio (sample PVA10/TN10) supports the attachment and proliferation of bone marrow mesenchymal stem cells after 7 days of culture. The scaffolding capacity of the PVA10/TN10 surface is compared with titanium, one of the most important biomedical materials used in bone replacements. Also, the PVA/TN films exhibited cytocompatibility, antioxidant and antimicrobial activity against Staphylococcus aureus and Pseudomonas aeruginosa. These properties make PVA/TN films are candidates for biomedical applications in the tissue engineering field.

Prevalence of autoimmune thyroid disease and thyroid dysfunction in young Brazilian patients with type 1 diabetes.

Patients with an autoimmune condition are known to be at higher risk of developing other autoimmune disorders. Type 1 diabetes may be associated with additional autoimmune disorders including autoimmune thyroid disease. The aim of this study was to investigate the prevalence of thyroid autoantibodies in a group of children, adolescents, and young adults with type 1 diabetes from northeastern Brazil as well as their significance for the development of thyroid disorders. The study design was cross-sectional and descriptive, analyzing young people with a previous type 1 diabetes diagnosis. Two hundred and fourteen children and adolescents with prior diagnosis of type 1 diabetes were evaluated. Antibodies to thyroperoxidase (anti-TPO) were determined in all patients and thyroid-stimulating hormone (TSH) levels. The anti-TPO antibody test was positive in 54 out of the 214 patients studied, resulting in an overall prevalence of 25.2%. Among the anti-TPO-positive subjects, females were predominant (72%) over males (28%) (p < 0.001). A total of 55.5% patients with positive anti-TPO antibodies had abnormal TSH levels. Clinically significant hypothyroidism was found in 29.6% and subclinical hypothyroidism in 22.2% of patients with positive anti-TPO. Hyperthyroidism was present in only 3% of them. Our results demonstrate the high prevalence of autoimmune thyroiditis in patients with type 1 diabetes and the need for these patients of regular screening to make a precocious diagnosis of thyroid dysfunction.

Cross-sectional study of anal intraepithelial lesions in women with cervical neoplasia without HIV.

OBJECTIVE: To evaluate the prevalence of anal intraepithelial lesions and associated risk factors in women with cervical neoplasia. METHODS: The present cross-sectional study enrolled patients with intraepithelial or invasive cervical neoplasia who had been referred to the lower genital tract pathology outpatient department of the Instituto de Medicina Integral Prof. Fernando Figueira, Recife, Brazil, between December 1, 2008, and December 31, 2009; patients with HIV infections were excluded. All participants underwent anal cytology and high-resolution anoscopy; sociodemographic and clinical risk factors were identified using multivariate analysis. RESULTS: There were 324 patients included and 37 (11.4%) had anal intraepithelial neoplasia. Factors associated with anal intraepithelial neoplasia in the multivariate analysis were being older than 35 years of age (P=0.002), having completed no more than 4 years of education (P=0.012), anomalous anal cytology (P=0.003), and anomalous high-resolution anoscopy findings (P<0.001); subclinical HPV lesions on vulvoscopy (P=0.057) were not associated with anal intraepithelial neoplasia. CONCLUSION: The prevalence of anal intraepithelial neoplasia was high among patients with cervical neoplasia who did not have HIV, particularly patients older than 35 years.

Mannose binding lectin gene polymorphisms are associated with type 1 diabetes in Brazilian children and adolescents.

Mannose-binding lectin is an important constituent of the innate immune system, the serum levels of which are greatly affected by polymorphisms of the MBL2 gene: three polymorphisms in exon 1, as well as nucleotide variations in the promoter region of the gene, have been associated with protein deficiency and some infectious and autoimmune disease. The aim of this study was to investigate a possible association between MBL2 gene polymorphisms in patients who have developed type 1 diabetes during childhood and adolescence. We evaluated MBL2 gene polymorphisms in 214 children and adolescents with type 1 diabetes and compared them with a healthy control group, finding significant differences in genotypic and allelic frequencies (p = 0.004 and p = 0.0008, respectively). Our results suggest that patients with type 1 diabetes possessing the 0 allele have a higher risk for developing type 1 diabetes during childhood and adolescence, and that this risk factor is not related to age at diagnosis.

Chitosan/chondroitin sulfate hydrogels prepared in [Hmim][HSO4] ionic liquid.

[Hmim][HSO4] ionic liquid (IL) and bio-renewable sources as chitosan (CHT) and chondroitin sulfate (CS) were used to yield hydrogel-based materials (CHT/CS). The use of IL to solubilize both polysaccharides was considered an innovative way based on "green chemistry" principle, aiming the production of CHT/CS blended systems. CHT/CS hydrogels were carried out in homogeneous medium from short dissolution times. The hydrogels were characterized and achieved with excellent stabilities (in the 1.2-10pH range), larger swelling capacities, as well as devoid of cytotoxicity towards the normal VERO and diseased HT29 cells. The CHT/CS hydrogels carried out in [Hmim][HSO4] could be applied in many technological purposes, like medical, pharmaceutical, and environmental fields.

Preparation and cytotoxicity of N-modified chitosan nanoparticles applied in curcumin delivery.

Nanoparticles (NPs) based on N,N-dimethyl chitosan (DMC) and N,N,N-trimethyl chitosan (TMC), physical crosslinked with sodium tripolyphosphate (TPP) were successful obtained, using water/benzyl alcohol emulsion system. NPs morphologies were evaluated by Scanning Electron Microscopy and Transmission Electron Microscopy. NPs were characterized by Infrared Spectroscopy (FTIR), Thermogravimetric Analysis, Zeta Potential, Differential Scanning Calorimetry and Wide-angle X-ray Scattering. Curcumin (CUR) was loaded onto NPs and controlled release studies were evaluated in simulated intestinal fluid and in simulated gastric fluid. Cytotoxicity assays showed only loaded TMC/TPP particles containing CUR were slightly cytotoxic on human cervical tumor cells (SiHa cells), concerning unloaded TMC/TPP particles. Conversely, loaded NPs (TMC/TPP/CUR and DMC/TPP/CUR), especially TMC/TPP/CUR sample presented greater biocompatibility toward healthy VERO cells than unloaded NPs (TMC/TPP and DMC/TPP).

N,N-Dimethyl chitosan/heparin polyelectrolyte complex vehicle for efficient heparin delivery.

Polysaccharide-based device for oral delivery of heparin (HP) was successfully prepared. Previously synthesized N,N-dimethyl chitosan (DMC) (86% dimethylated by (1)H NMR spectroscopy) was complexed with HP by mixing HP and DMC aqueous solutions (both at pH 3.0). The polyelectrolyte complex (PEC) obtention was confirmed by infrared spectroscopy (FTIR), thermogravimetric analysis (TGA/DTG) and wide-angle X-ray scattering (WAXS). In vitro controlled release assays of HP from PEC were investigated in the simulated intestinal fluid (SIF) and simulated gastric fluid (SGF). The PEC efficiently protected the HP in SGF condition in which HP is degraded. On the other hand, in SIF PEC promoted the releasing of 80 ± 1.5% of loaded HP. The promissory results indicated that the PEC based on DMC/HP presented potential as drug-carrier matrix, since biological activity of HP was improved at pH close to physiological condition.