Manganese dioxide-coated biocarbon for integrated adsorption-photocatalytic degradation of formaldehyde in indoor conditions.

Formaldehyde is a common indoor air pollutant with hazardous effects on human health. This study investigated the efficiency of biocarbon (BC) functionalized with variable contents of MnO2 for formaldehyde removal in ambient conditions via integrated adsorption-photocatalytic degradation technology. The sample with the highest formaldehyde removal potential was used to prepare a functional coating made of acrylic binder mixed with 20 wt% of the particles and applied on beech (Fagus sylvatica L) substrate. SEM images showed that MnO2 was deposited around and inside the pores of the BC. EDX spectra indicated the presence of Mn peaks and increased content of oxygen in the doped BC compared to pure BC, which indicated the successful formation of MnO2. Raman spectra revealed that the disorder in the BC's structure increased with increasing MnO2 loadings. FTIR spectra of BC-MnO2 samples displayed additional peaks compared to the BC spectrum, which were attributed to MnO vibrations. Moreover, the deposition of increased MnO2 loadings decreased the porosity of the BC due to pores blockage. The BC sample containing 8 % Mn exhibited the highest formaldehyde removal efficiency in 8 h, which was 91 %. A synergetic effect between BC and MnO2 was observed. The formaldehyde removal efficiency and capacity of the coating reached 43 % and 6.1 mg/m2, respectively, suggesting that the developed coating can be potentially used to improve air quality in the built environment.

Advance Analysis of the Obtained Recycled Materials from Used Disposable Surgical Masks.

The production of personal protective equipment (PPE) has increased dramatically in recent years, not only because of the pandemic, but also because of stricter legislation in the field of Employee Protection. The increasing use of PPE, including disposable surgical masks (DSMs), is putting additional pressure on waste collectors. For this reason, it is necessary to find high-quality solutions for this type of waste. Mechanical recycling is still the most common type of recycling, but the recyclates are often classified as low-grade materials. For this reason, a detailed analysis of the recyclates is necessary. These data will help us to improve the properties and find the right end application that will increase the value of the materials. This work represents an extended analysis of the recyclates obtained from DSMs, manufactured from different polymers. Using surface and morphology tests, we have gained insights into the distribution of different polymers in polymer blends and their effects on mechanical and surface properties. It was found that the addition of ear loop material to the PP melt makes the material tougher. In the polymer blends obtained, PP and PA 6 form the surface (affects surface properties), while PU and PET are distributed mainly inside the injection-molded samples.

Pullulan-based films impregnated with silver nanoparticles from the Fusarium culmorum strain JTW1 for potential applications in the food industry and medicine.

Introduction: Biopolymers, such as pullulan, a natural exopolysaccharide from Aureobasidium pullulans, and their nanocomposites are commonly used in the food, pharmaceutical, and medical industries due to their unique physical and chemical properties. Methods: Pullulan was synthesized by the A. pullulans ATCC 201253 strain. Nanocomposite films based on biosynthesized pullulan were prepared and loaded with different concentrations of silver nanoparticles (AgNPs) synthesized by the Fusarium culmorum strain JTW1. AgNPs were characterized by transmission electron microscopy, Zeta potential measurements, and Fourier-transform infrared spectroscopy. In turn, the produced films were subjected to physico-chemical analyses such as goniometry, UV shielding capacity, attenuated total reflection-Fourier-transform infrared spectroscopy, scanning electron microscopy, and X-ray photoelectron spectroscopy, and their mechanical and degradation properties were assessed. The antibacterial assays of the nanoparticles and the nanocomposite films against both food-borne and reference pathogens, including Listeria monocytogenes, Salmonella infantis, Salmonella enterica, Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, and Klebsiella pneumoniae, were performed using standard methods. Results: AgNPs were small (mean 15.1 nm), spherical, and displayed good stability, being coated with protein biomolecules. When used in higher concentrations as an additive to pullulan films, they resulted in reduced hydrophilicity and light transmission for both UV-B and UV-A lights. Moreover, the produced films exhibited a smooth surface. Therefore, it can be concluded that the addition of biogenic AgNPs did not change the morphology and texture of the films compared to the control film. The nanoparticles and nanocomposite films demonstrated remarkable antibacterial activity against both food-borne and reference bacteria. The highest activity of the prepared films was observed against L. monocytogenes. Discussion: The obtained results suggest that the novel nanocomposite films prepared from biosynthesized pullulan and AgNPs can be considered for use in the development of medical products and food packaging. Moreover, this is the first report on pullulan-based nanocomposites with mycogenic AgNPs for such applications.

Fabrication of Polysaccharide-Based Halochromic Nanofibers via Needle-Less Electrospinning and Their Characterization: A Study of the Leaching Effect.

Responsive materials, i.e., smart materials, have the ability to change their physical or chemical properties upon certain external signals. The development of nanofibrous halochromic materials, specifically combining the pH-sensitive functionality and unique nanofiber properties, could yield interesting new applications, especially when the common problem of dye leaching is successfully tackled. Therefore, in this article, we studied the fabrication process of polysaccharide-based halochromic nanofibrous materials by using a combination of various halochromic dyes (bromothymol blue, bromocresol green, and thymol blue) and cellulose acetate in a spinning solution using a one-pot strategy. The inhibition of leaching was addressed by using a complexing agent: poly-diallyl-dimethylammonium chloride (PDADMAC). The preparation of hybrid spinning solutions, their characterization, and ability to form continuous nanofibers were studied using a high production needle-less electrospinning system. The produced hybrid solutions and nanofibers were characterized, in terms of their rheological properties, chemical structure, morphology, and functionality. Fabricated nanofibrous halochromic structures show a clear color change upon exposure to different pH values, as well as the reduced leaching of dyes, upon the addition of a complexing agent. The leaching decreased by 61% in the case of bromocresol green, while, in the case of bromothymol blue and thymol blue, the leaching was reduced by 95 and 99%, respectively.

Succinylation of Polyallylamine: Influence on Biological Efficacy and the Formation of Electrospun Fibers.

Succinylation of proteins is a commonly encountered reaction in biology and introduces negatively charged carboxylates on previously basic primary amine groups of amino acid residues. In analogy, this work investigates the succinylation of primary amines of the synthetic polyelectrolyte polyallylamine (PAA). It investigates the influence of the degree of succinylation on the cytotoxicity and antibacterial activity of the resulting polymers. Succinylation was performed in water with varying amounts of succinic anhydride and at different pH values. The PAA derivatives were analyzed in detail with respect to molecular structure using nuclear magnetic resonance and infrared absorbance spectroscopy. Polyelectrolyte and potentiometric charge titrations were used to elucidate charge ratios between primary amines and carboxylates in the polymers. The obtained materials were then evaluated with respect to their minimum inhibitory concentration against Staphylococcus aureus and Pseudomonas aeruginosa. The biocompatibility was assessed using mouse L929 fibroblasts. The degree of succinylation decreased cytotoxicity but more significantly reduced antibacterial efficacy, demonstrating the sensitivity of the fibroblast cells against this type of ampholytic polyelectrolytes. The obtained polymers were finally electrospun into microfiber webs in combination with neutral water-soluble polyvinyl alcohol. The resulting non-woven could have the potential to be used as wound dressing materials or coatings.

Metallisation of Textiles and Protection of Conductive Layers: An Overview of Application Techniques.

The rapid growth in wearable technology has recently stimulated the development of conductive textiles for broad application purposes, i.e., wearable electronics, heat generators, sensors, electromagnetic interference (EMI) shielding, optoelectronic and photonics. Textile material, which was always considered just as the interface between the wearer and the environment, now plays a more active role in different sectors, such as sport, healthcare, security, entertainment, military, and technical sectors, etc. This expansion in applied development of e-textiles is governed by a vast amount of research work conducted by increasingly interdisciplinary teams and presented systematic review highlights and assesses, in a comprehensive manner, recent research in the field of conductive textiles and their potential application for wearable electronics (so called e-textiles), as well as development of advanced application techniques to obtain conductivity, with emphasis on metal-containing coatings. Furthermore, an overview of protective compounds was provided, which are suitable for the protection of metallized textile surfaces against corrosion, mechanical forces, abrasion, and other external factors, influencing negatively on the adhesion and durability of the conductive layers during textiles' lifetime (wear and care). The challenges, drawbacks and further opportunities in these fields are also discussed critically.

Efficient Chitosan/Nitrogen-Doped Reduced Graphene Oxide Composite Membranes for Direct Alkaline Ethanol Fuel Cells.

Herein, we prepared a series of nanocomposite membranes based on chitosan (CS) and three compositionally and structurally different N-doped graphene derivatives. Two-dimensional (2D) and quasi 1D N-doped reduced graphene oxides (N-rGO) and nanoribbons (N-rGONRs), as well as 3D porous N-doped graphitic polyenaminone particles (N-pEAO), were synthesized and characterized fully to confirm their graphitic structure, morphology, and nitrogen (pyridinic, pyrrolic, and quaternary or graphitic) group contents. The largest (0.07%) loading of N-doped graphene derivatives impacted the morphology of the CS membrane significantly, reducing the crystallinity, tensile properties, and the KOH uptake, and increasing (by almost 10-fold) the ethanol permeability. Within direct alkaline ethanol test cells, it was found that CS/N rGONRs (0.07 %) membrane (Pmax. = 3.7 mWcm-2) outperformed the pristine CS membrane significantly (Pmax. = 2.2 mWcm-2), suggesting the potential of the newly proposed membranes for application in direct ethanol fuel cells.

Comparison of Trimethylsilyl Cellulose-Stabilized Carbonate and Hydroxide Nanoparticles for Deacidification and Strengthening of Cellulose-Based Cultural Heritage.

Herein, colloidal dispersions of alkaline nanoparticles (NPs: CaCO3 and Mg(OH)2) are stabilized by trimethylsilyl cellulose (TMSC) in hexamethyldisiloxane and employed to treat historical wood pulp paper by an effortless dip-coating technique. Both alkaline NPs exhibit high stability and no size and shape changes upon stabilization with the polymer, as shown by UV-vis spectroscopy and transmission electron microscopy. The long-term effect of NP/TMSC coatings is investigated in detail using accelerated aging. The results from the pH-test and back-titration of coated papers show a complete acid neutralization (pH ∼ 7.4) and introduction of adequate alkaline reserve even after prolonged accelerated aging. Scanning electron microscopy-energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and infrared and water contact angle measurements showed the introduction of a thin and smooth hydrophobic NP/TMSC coating on the paper fibers. Acid-catalyzed desilylation of TMSC was observed by declining C-Si infrared absorbance peaks upon aging. The CaCO3 coatings are superior to Mg(OH)2 with respect to a reduced yellowing and lower cellulose degradation upon aging as shown by colorimetric measurements and degree of polymerization analysis. The tensile strength and folding endurance of coated and aged papers are improved to 200-300 and 50-70% as illustrated by tensile strength and double folding endurance measurements.

Electrospun nanofibrous composites from cellulose acetate / ultra-high silica zeolites and their potential for VOC adsorption from air.

The optimized preparation of novel electrospun nanofibrous composites from cellulose acetate (CA) and ultra-high silica zeolites (UHSZ) are reported as a promising material for the adsorption of Volatile Organic Compound (VOCs). Two types of UHSZs, i.e. silicalite and USY were prepared by hydrothermal crystallization while the fabrication of composites was performed using single needle and needle-less electrospinning systems, demonstrating the scalability of the composite fibres' manufactured. Herein, factors such as properties of spinning solutions and electrospinning process parameters were studied, as well as interactions between the CA and UHSZs. In addition, Quartz Crystal Microbalance - Dissipation technique (QCM-D) was employed with an aim to study the adsorption behaviour of newly developed composites using ammonia as a model pollutant. The QCM-D data revealed that the presence of UHSZs in the CA materials increased adsorption capacity, designating CA/UHSZ composites as potential materials suitable for a large-scale removal of VOCs from polluted air.

Functional dextran amino acid ester particles derived from N-protected S-trityl-L-cysteine.

This work describes the derivatization of dextran using N-(tert-butyloxycarbonyl)-S-(trityl)-L-cysteine in the presence of N,N'-carbonyldiimidazole (CDI) as a coupling agent. Homogeneous reactions in dimethyl sulfoxide allowed for an efficient coupling of the amino acid derivative to the polymer backbone. Derivatization was confirmed by infrared and 13C NMR spectroscopy, size exclusion chromatography and elemental analysis. The presence of hydrophobic protecting groups resulted in a product that can be shaped into water-insoluble particles stable in an aqueous environment and non-toxic for lung epithelial cells. It is suggested that materials composed of ester bonds between amino acids and polysaccharides are useful for targeted drug delivery, bio-imaging or surface functionalization.

Microstructured and Degradable Bacterial Cellulose⁻Gelatin Composite Membranes: Mineralization Aspects and Biomedical Relevance.

Bacterial cellulose (BC)⁻gelatin (GEL) membranes were processed by successive periodate oxidation and a freeze-thawing/carbodiimide crosslinking procedure, first facilitating a Schiff-base reaction among respective aldehyde and hydroxyl groups, and later GEL stabilization and microstructuring. The formation of highly microporous structures within the GEL portion, with significant differences between bottom and top, was elucidated, and pores in the 27.6 ± 3 µm⁻108 ± 5 µm range were generated, exceeding the threshold value of ~10 µm sufficient for cell trafficking. During a relatively short (6 h) exhaustion procedure in supersaturated simulated body fluid solution, the membranes accommodated the combination of biologically relevant minerals, i.e., flake-like octacalcium phosphate (OCP) and (amorphous) apatite, onto their surface, forming a membrane with intensive swelling (650⁻1650%) and up to 90% weight loss in a 4-week period. The membranes´ 6-day eluates did not evoke any cytotoxic effects toward human fibroblast, MRC-5 cells. The same type of cells retained their morphology in direct contact with the membrane, attaching to the GEL porous site, while not attaching to the GEL thin-coated BC side, most probably due to combined, ablation effect of dominant ß-sheet conformation and carbodiimide crosslinking. Together with arrested proliferation through the BC side, the membranes demonstrated beneficial properties for potential guided tissue regeneration (GTR) applications.

A green approach to obtain stable and hydrophilic cellulose-based electrospun nanofibrous substrates for sustained release of therapeutic molecules.

Stable and (bio)-compatible nanofibrous matrices showing effective incorporation and release of nonsteroidal anti-inflammatory drugs (NSAIDs) hold a huge potential in tissue regeneration and wound healing. Herein, a two-step, water-based and needleless electrospinning method is used to fabricate thermally cross-linked multifunctional nanofibrous substrates from a hydrophilic cellulose derivative, i.e. carboxymethyl cellulose (CMC), and polyethylene glycol (PEG) with an in situ incorporated NSAID, diclofenac (DCF). Electrospun bi-component blend nanofibers, strongly linked together by ester bonds, with different degrees of cross-linking density are achieved by varying the concentrations of butanetetracarboxylic acid (BTCA, a green polycarboxylic cross-linker) and the sodium hypophosphite (SHP) catalyst, and the temperature. The results demonstrated that not only the dimensional stability and swelling properties could be better controlled but also the morphology, fiber diameter, surface area, pore volume, pore size, and functionality of the cross-linked nanofibers. Release kinetics of DCF from the nanofibrous substrates are controlled and prolonged up to 48 h, and the overall released mass of DCF decreased linearly with increasing cross-linking degree of BTCA and SHP. Fitting of release data using various kinetic models revealed that the release of DCF follows a non-Fickian (diffusion and erosion controlled) to Fickian mechanism (only diffusion-controlled process). Cell viability testing based on crystal violet dyeing showed that the DCF-incorporating nanofibers have excellent biocompatibility and no toxic effect on human skin fibroblast cells. Overall, the reported DCF-incorporating nanofibrous substrate demonstrates high potential to be used as a smart drug delivery system in wound healing, especially due to its noninvasive characteristics.

Novel electrospun fibers with incorporated commensal bacteria for potential preventive treatment of the diabetic foot.

AIM: A novel electrospun biocompatible nanofibrous material loaded with commensal bacteria for potential preventive treatment of the diabetic foot was developed. MATERIALS & METHODS: Two biocompatible polymers (carboxymethylcellulose and polyethylene oxide) were combined with a bacterium isolate from the skin located between the toes of a healthy adult (identified using a matrix-assisted laser desorption/ionization mass spectrometry-based method as a strain of Staphylococcus epidermidis). Higher bacteria loads in the material were assured through their encapsulation in polyethylenimine. The nanofibrous material was characterized using scanning electron microscopy, zeta-potential measurements and through evaluation of cell growth and viability. RESULTS & DISCUSSION: nanometer formation was confirmed using scanning electron microscopy, while the zeta-potential measurements revealed successful bacteria encapsulation. Viable and sufficiently growing cells were confirmed prior and after their incorporation. CONCLUSION: The prepared materials were proven suitable to deliver viable commensal bacteria in a comparable share to the Staphylococcaceae in the foot microbiome making this approach promising for preventive diabetic foot treatment.

Thermal, Mechanical and Optical Features of Aluminosilicate-Coated Cotton Textiles via the Crosslinking Method.

The presented study focuses on the development of a pad-dry-thermofix functional coating process using a mixture of microporous aluminosilicate particles in diverse bath formulations to impart UV-ray-blocking, thermal stability and easy-care properties to the cotton fabric. The results of Scanning Electron Microscopy (SEM) and X-ray powder Diffraction (XRD) revealed the presence of three different types of zeolites within the examined sample, i.e., the largest amount being zeolite A, followed by the zeolite X, and the zeolite ZSM-5. The surface characterization results of zeolite-coated/cross-linked textiles provided evidence of acceptable UV-ray-blocking properties and increased thermal stability, as well as enhanced tensile strength and breaking tenacity without considerably decreasing the whiteness degree. Moreover, the dry crease recovery angle increased for the cotton fabric cross-linked via an mDMDHEU, and decreased significantly using 30 g/L zeolites negatively influencing qualitative values. TG/DTA results have proven the enlarged thermal stability of aluminosilicate-coated cotton, although combustion was not prevented.

Nanofibrous polysaccharide hydroxyapatite composites with biocompatibility against human osteoblasts.

Regenerative medicine has a high demand for defined scaffold materials that promote cell growth, stabilize the tissue during maturation and provide a proper three dimensional structure that allows the exchange of nutrients. In many instances nanofiber composites have already shown their potential for such applications. This work elaborates the development of polysaccharide based nanofibers with integrated hydroxyapatite nanoparticles. A detailed study on the formation of electrospun nanofibres from aqueous mixtures of carboxymethyl cellulose polyethylene oxide was performed. The influence of different processing conditions and spinning solution properties using a nozzle-less electrospinning device was systematically studied. Optimized parameters were used to incorporate hydroxyapatite nanoparticles into the fibers. Nanofibers were additionally hydrophobized with alkenyl succinic anhydride (ASA) to render them insoluble in water. The nanofiber webs were thoroughly investigated with respect to morphology, chemical composition and inorganic content. Time dependent biocompatibility testing of the materials with human bone-derived osteoblasts showed no significant reduction in cell viability for the developed materials composed of carboxymethyl cellulose/polyethyleneoxide. Cells grown on hydrophobized materials show similar viability as those grown on a commercial collagen/apatite matrix.

Environmentally friendly procedure for in-situ coating of regenerated cellulose fibres with silver nanoparticles.

This study introduces a novel green in-situ procedure for introduction of silver nanoparticles (Ag NPs) on and into cellulose fibres in a three-stage process. First-stage of the process includes the activation of cellulose fibres in alkaline solution, followed by reduction of silver nitrate to Ag NPs in the second stage, while the last stage of process involves washing and neutralization of fibres. Efficiency of the method towards incorporation of silver particles into the fibres' internal structure was characterized; the coatings' morphology and determination of spatial presence of Ag particles were imagining by the scanning electron microscopy and accompanying energy dispersive x-ray spectroscopy analysis; prepared fibres have superior durability of particles' coating against washing and excellent antimicrobial activity even after 20 washing cycles. Additionally, the water retention of silver treated fibres was improved, while the mechanical properties were not significantly impaired.

Tuning of cellulose fibres' structure and surface topography: Influence of swelling and various drying procedures.

Presented study deals with the pre-treatment of cellulose fibres with the aim to activate their surface and to enlarge their pore system, leading to an enhancement of fibres' affinity for subsequent functionalization processes. Swelling of fibres in aqueous solutions of sodium hydroxide opens their fibrillar structure, while freezing and freeze-drying retain this enlargement of the pore system, in contrast with conventional air or elevated temperature drying. Effect of different pre-treatment procedures on fibres' supramolecular structure, enlargement of their pore system, surface topography, zeta potential and mechanical properties was investigated. Degree of enhancement of the pore system depends on the concentration of sodium hydroxide and type of freezing; higher alkali concentrations are more effective, but at the cost of extensive deterioration of mechanical properties. Swelling of fibres in lower concentrations of NaOH, in combination with freeze drying, offers an acceptable compromise between enhancement of the fibres' pore system, changes in surface potential and tensile properties of treated fibres. Design of a suitable regime of swelling and drying of cellulose fibres results in an effective procedure for controlled tuning of their surface topography in combination with an increase of the available internal surface area and pore volume.

Enhanced catalytic activity of the surface modified TiO2-MWCNT nanocomposites under visible light.

Fusing multiwall carbon nanotubes (MWCNTs) with TiO2 at the nano-scale level promotes the separation of those electron-hole charges generated upon UV and daylight irradiation. In this study, we investigated facile sonochemical synthesis, combined with the calcination process for the preparations of TiO2-MWCNT composites with different mole ratios of titanium and carbon. In order to produce stable nano dispersions we exploited an innovative biotechnology-based approach for the covalent functionalizations of TiO2-MWCNTs with in-situ synthesized soluble phenoxazine dye molecules. The none and functionalized TiO2-MWCNTs composites were analyzed by a range of analytical techniques including XRD, Raman, XPS, SEM and UV-vis diffuse reflectance spectroscopy (DRS), and dynamic light scattering (DLS). The photocatalytic activity was evaluated toward the liquid-phase degradation of MB in aqueous solution under both UV and visible light irradiation. TiO2-MWCNTs with optimized mole ratio exhibit much higher photocatalytic activity and stability than bare TiO2. The as-prepared TiO2-MWCNTs photocatalyst possessed good adsorptivity of dyes, extended light absorption range and efficient charge separation properties simultaneously. The results indicated that the soluble phenoxazine dyes and amino-benzenesulfonic acid monomers were covalently grafted on to the surfaces of TiO2-MCNTs, which promoted good aquatic dispersibility and extended light absorption, resulting in increased photocatalytic efficiency.

Antifouling coating of cellulose acetate thin films with polysaccharide multilayers.

In this investigation, partially deacetylated cellulose acetate (DCA) thin films were prepared and modified with hydrophilic polysaccharides with the layer-by-layer (LbL) technique. As polysaccharides, chitosan (CHI) and carboxymethyl cellulose (CMC) were used. DCA thin films were manufactured by exposing spin coated cellulose acetate to potassium hydroxide solutions for various times. The deacetylation process was monitored by attenuated total reflectance-infrared spectroscopy, film thickness and static water contact angle measurements. A maximum of three bilayers was created from the alternating deposition of CHI and CMC on the DCA films under two different conditions namely constant ionic strengths and varying pH values of the CMC solutions. Precoatings of CMC at pH 2 were used as a base layer. The sequential deposition of CMC and CHI was investigated with a quartz crystal microbalance with dissipation, film thickness, static water contact angle and atomic force microscopy (AFM) measurements. The versatility and applicability of the developed functional coatings was shown by removing the multilayers by rinsing with mixtures containing HCl/NaCl. The developed LbL coatings are used for studying the fouling behavior of bovine serum albumin (BSA).