Ink-Based Additive Manufacturing of a Polymer/Coal Composite: A Non-Traditional Reinforcement.

Coal, a crucial natural resource traditionally employed for generating carbon-rich materials and powering global industries, has faced escalating scrutiny due to its adverse environmental impacts outweighing its utility in the contemporary world. In response to the worldwide shift toward sustainability, the United States alone has witnessed an approximate 50% reduction in coal consumption. Nevertheless, the ample availability of coal has spurred interest in identifying alternative sustainable applications. This research delves into the feasibility of utilizing coal as a nonconventional carbon-rich reinforcement in direct ink writing (DIW)-based 3D printing techniques. Our investigation here involves a thermosetting resin serving as a matrix, incorporating pulverized coal (250 µm in size) and carbon black as the reinforcement and a viscosity modifier, respectively. The ink formulation is meticulously designed to exhibit shear-thinning behavior essential for DIW 3D printing, ensuring uniform and continuous printing. Mechanical properties are assessed through the 3D printing of ASTM standard specimens to validate the reinforcing impact. Remarkably, the study reveals that a 2 wt % coal concentration in the ink leads to a substantial improvement in both tensile and flexural properties, resulting in enhancements of 35 and 12.5%, respectively. Additionally, the research demonstrates the printability of various geometries with coal as reinforcement, opening up new possibilities for coal utilization while pursuing more sustainable manufacturing and applications.

Bactericidal Chitosan Derivatives and Their Superabsorbent Blends with ĸ-Carrageenan.

The aim of this work is research dedicated to the search for new bactericidal systems for use in cosmetic formulations, dermocosmetics, or the production of wound dressings. Over the last two decades, chitosan, due to its special biological activity, has become a highly indispensable biopolymer with very wide application possibilities. Reports in the literature on the antibacterial effects of chitosan are very diverse, but our research has shown that they can be successfully improved through chemical modification. Therefore, in this study, results on the synthesis of new chitosan-based Schiff bases, dCsSB-SFD and dCsSB-PCA, are obtained using two aldehydes: sodium 4-formylbenzene-1,3-disulfonate (SFD) and 2-pyridine carboxaldehyde (PCA), respectively. Chitosan derivatives synthesized in this way demonstrate stronger antimicrobial activity. Carrying out the procedure of grafting chitosan with a caproyl chain allowed obtaining compatible blends of chitosan derivatives with κ-carrageenan, which are stable hydrogels with a high swelling coefficient. Furthermore, the covalently bounded poly(ε-caprolactone) (PCL) chain improved the solubility of obtained polymers in organic solvents. In this respect, the Schiff base-containing polymers obtained in this study, with special hydrogel and antimicrobial properties, are very promising materials for potential use as a controlled-release formulation of both hydrophilic and hydrophobic drugs in cosmetic products for skin health.

Polyethylene terephthalate (PET) micro- and nanoplastic particles affect the mitochondrial efficiency of human brain vascular pericytes without inducing oxidative stress.

The objective of this investigation was to evaluate the influence of micro- and nanoplastic particles composed of polyethylene terephthalate (PET), a significant contributor to plastic pollution, on human brain vascular pericytes. Specifically, we delved into their impact on mitochondrial functionality, oxidative stress, and the expression of genes associated with oxidative stress, ferroptosis and mitochondrial functions. Our findings demonstrate that the exposure of a monoculture of human brain vascular pericytes to PET particles in vitro at a concentration of 50 µg/ml for a duration of 3, 6 and 10 days did not elicit oxidative stress. Notably, we observed a reduction in various aspects of mitochondrial respiration, including maximal respiration, spare respiratory capacity, and ATP production in pericytes subjected to PET particles for 3 days, with a mitochondrial function recovery at 6 and 10 days. Furthermore, there were no statistically significant alterations in mitochondrial DNA copy number, or in the expression of genes linked to oxidative stress and ferroptosis, but an increase of the expression of the gene mitochondrial transcription factor A (TFAM) was noted at 3 days exposure. These outcomes suggest that, at a concentration of 50 µg/ml, PET particles do not induce oxidative stress in human brain vascular pericytes. Instead, at 3 days exposure, PET exposure impairs mitochondrial functions, but this is recovered at 6-day exposure. This seems to indicate a potential mitochondrial hormesis response (mitohormesis) is incited, involving the gene TFAM. Further investigations are warranted to explore the stages of mitohormesis and the potential consequences of plastics on the integrity of the blood-brain barrier and intercellular interactions. This research contributes to our comprehension of the potential repercussions of nanoplastic pollution on human health and underscores the imperative need for ongoing examinations into the exposure to plastic particles.

Bactericidal Biodegradable Linear Polyamidoamines Obtained with the Use of Endogenous Polyamines.

The work presents the synthesis of a series of linear polyamidoamines by polycondensation of sebacoyl dichloride with endogenous polyamines: putrescine, spermidine, spermine, and norspermidine-a biogenic polyamine not found in the human body. During the synthesis carried out via interfacial reaction, hydrophilic, semi-crystalline polymers with an average viscosity molecular weight of approximately 20,000 g/mol and a melting point of approx. 130 °C were obtained. The structure and composition of the synthesized polymers were confirmed based on NMR and FTIR studies. The cytotoxicity tests performed on human fibroblasts and keratinocytes showed that the polymers obtained with spermine and norspermidine were strongly cytotoxic, but only in high concentrations. All the other examined polymers did not show cytotoxicity even at concentrations of 2000 µg/mL. Simultaneously, the antibacterial activity of the obtained polyamides was confirmed. These polymers are particularly active against E. Coli, and virtually all the polymers obtained demonstrated a strong inhibitory effect on the growth of cells of this strain. Antimicrobial activity of the tested polymer was found against strains like Staphylococcus aureus, Staphylococcus epidermidis, and Pseudomonas aeruginosa. The broadest spectrum of bactericidal action was demonstrated by polyamidoamines obtained from spermine, which contains two amino groups in the repeating unit of the chain. The obtained polymers can be used as a material for forming drug carriers and other biologically active compounds in the form of micro- and nanoparticles, especially as a component of bactericidal creams and ointments used in dermatology or cosmetology.

3D Printing-Enabled Design and Manufacturing Strategies for Batteries: A Review.

Lithium-ion batteries (LIBs) have significantly impacted the daily lives, finding broad applications in various industries such as consumer electronics, electric vehicles, medical devices, aerospace, and power tools. However, they still face issues (i.e., safety due to dendrite propagation, manufacturing cost, random porosities, and basic & planar geometries) that hinder their widespread applications as the demand for LIBs rapidly increases in all sectors due to their high energy and power density values compared to other batteries. Additive manufacturing (AM) is a promising technique for creating precise and programmable structures in energy storage devices. This review first summarizes light, filament, powder, and jetting-based 3D printing methods with the status on current trends and limitations for each AM technology. The paper also delves into 3D printing-enabled electrodes (both anodes and cathodes) and solid-state electrolytes for LIBs, emphasizing the current state-of-the-art materials, manufacturing methods, and properties/performance. Additionally, the current challenges in the AM for electrochemical energy storage (EES) applications, including limited materials, low processing precision, codesign/comanufacturing concepts for complete battery printing, machine learning (ML)/artificial intelligence (AI) for processing optimization and data analysis, environmental risks, and the potential of 4D printing in advanced battery applications, are also presented.

Biodegradable Polymers and Polymer Composites with Antibacterial Properties.

Antibiotic resistance is one of the greatest threats to global health and food security today. It becomes increasingly difficult to treat infectious disorders because antibiotics, even the newest ones, are becoming less and less effective. One of the ways taken in the Global Plan of Action announced at the World Health Assembly in May 2015 is to ensure the prevention and treatment of infectious diseases. In order to do so, attempts are made to develop new antimicrobial therapeutics, including biomaterials with antibacterial activity, such as polycationic polymers, polypeptides, and polymeric systems, to provide non-antibiotic therapeutic agents, such as selected biologically active nanoparticles and chemical compounds. Another key issue is preventing food from contamination by developing antibacterial packaging materials, particularly based on degradable polymers and biocomposites. This review, in a cross-sectional way, describes the most significant research activities conducted in recent years in the field of the development of polymeric materials and polymer composites with antibacterial properties. We particularly focus on natural polymers, i.e., polysaccharides and polypeptides, which present a mechanism for combating many highly pathogenic microorganisms. We also attempt to use this knowledge to obtain synthetic polymers with similar antibacterial activity.

Biodegradable Block Poly(ester amine)s with Pendant Hydroxyl Groups for Biomedical Applications.

The article presents the results of the synthesis and characteristics of the amphiphilic block terpolymers, built of a hydrophilic polyesteramine block, and hydrophobic blocks made of lactidyl and glycolidyl units. These terpolymers were obtained during the copolymerization of L-lactide with glycolide carried out in the presence of previously produced macroinitiators with protected amine and hydroxyl groups. The terpolymers were prepared to produce a biodegradable and biocompatible material containing active hydroxyl and/or amino groups, with strong antibacterial properties and high surface wettability by water. The control of the reaction course, the process of deprotection of functional groups, and the properties of the obtained terpolymers were made based on 1H NMR, FTIR, GPC, and DSC tests. Terpolymers differed in the content of amino and hydroxyl groups. The values of average molecular mass oscillated from about 5000 g/mol to less than 15,000 g/mol. Depending on the length of the hydrophilic block and its composition, the value of the contact angle ranged from 50° to 20°. The terpolymers containing amino groups, capable of forming strong intra- and intermolecular bonds, show a high degree of crystallinity. The endotherm responsible for the melting of L-lactidyl semicrystalline regions appeared in the range from about 90 °C to close to 170 °C, with a heat of fusion from about 15 J/mol to over 60 J/mol.

The Level of Fear in the Polish Police Population during the COVID-19 Pandemic with the Impact of Sociodemographic Variables.

This study has a twofold objective. First, we aim to measure the levels of fear among Polish police officers using the COVID-19 Fear Scale (FCV-19S) that has a stable unidimensional structure allowing for the provision of additional data by combining variables. This structure allows the second objective to be met to measure the correlation with sociodemographic variables. The utilitarian objective of the study is to provide information for updating support policies for stress management in the service. The questionnaire was completed by 1862 people with a mean age of 38.75 years with a good Cronbach's alpha (0.89). The perceived level of fear associated with COVID-19 should be considered relatively low. Caring for the elderly does not affect the level of fear. The factors of gender, age and having children statistically significantly differentiate the perceptions of fear. Therefore, there is a necessity to focus on building support for police officers who are over 50 years old, as well as for women, where higher levels of fear in both men and women can translate into the development of psychosomatic illnesses.

Dewetting Dynamics of Sheared Thin Polymer Films: An Experimental Study.

An experimental investigation is reported on the effect of shear on the bursting of molten ultrathin polymer films embedded in an immiscible matrix. By use of an optical microscope coupled with a shearing hot stage, the dewetting dynamics, i.e., the growth of dewetting holes, is monitored over time at various shear rates. It is observed that their circularity is modified by shear and that for all temperatures and thicknesses studied the growth speed of the formed holes rapidly increases with increasing shear rate. A model balancing capillary forces and viscous dissipation while taking into account shear thinning is then proposed and captures the main features of the experimental data, such as the ellipsoid shape of the holes and the faster dynamics in the direction parallel to the shear. This research will help to understand the instabilities occurring during processing of layered polymeric structures, such as multilayer coextrusion.

Gallic Acid Based Black Tea Extract as a Stabilizing Agent in ZnO Particles Green Synthesis.

In this work, zinc oxide particles (ZnO NPs) green synthesis with the application of black tea extract (BT) is presented. A thorough investigation of the properties of the extract and the obtained materials was conducted by using Fourier transform infrared spectroscopy (FTIR), liquid chromatography-mass spectrometry (LC-MS), X-ray diffraction (XRD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and quadrupole mass spectroscopy (QMS). The obtained results indicated that the amount of used BT strongly influenced the morphology, chemical, and crystalline structure of the obtained particles. The investigation demonstrated that the substance present in black tea (BT) extract, which was adsorbed on the ZnO surface, was in fact gallic acid. It was found that gallic acid controls the crystallization process of ZnO by temporarily blocking the zinc cations. Additionally, these organic molecules interact with the hydroxide group of the precipitant. This blocks the dehydration process stabilizing the zinc hydroxide forms and hinders its transformation into zinc oxide. Performed measurements indicated that obtained ZnO particles have great antioxidant and antimicrobial properties, which are significantly correlated with ZnO-gallic acid interactions.

Pectin-organophilized ZnO nanoparticles as sustainable fillers for high-density polyethylene composites.

A series of nanocomposites made of high-density polyethylene (HDPE) and 10 wt% zinc oxide nanoparticles (ZnO NPs) were produced by extrusion and injection molding. The nanoparticles were prepared via a green way using the pectin-based banana peel extract as the stabilizer and a proper dispersion-providing agent. The fillers were well-dispersed in the matrix and the composites exhibited improved functional characteristics such as increased thermal stability and mechanical properties. The presence of the pectin-organophilized filler had a significant impact on the crystallization process of HDPE. The kinetics of the degradation process was also altered in comparison to the pure polymer. The fire properties of the composites were enhanced as the amount of the gas products produced during their degradation was reduced, what was confirmed by thermogravimetric analysis coupled with gas products analyses (TGA/FTIR/QMS). The structure and morphology of the materials were characterized by scanning electron microscope (SEM), infrared spectroscopy (FTIR), X-ray diffraction (XRD), and differential scanning calorimetry (DSC). Additionally, the mechanical properties were tested by tensile tests. An in-depth analysis revealed that the HDPE-pectin-ZnO interactions are crucial for the structural and performance properties of the final composite. The used biopolymer reacts with ZnO via ionic interaction and through hydrogen bond in the case of HDPE.

Triple-Shape Memory Behavior of Modified Lactide/Glycolide Copolymers.

The paper presents the formation and properties of biodegradable thermoplastic blends with triple-shape memory behavior, which were obtained by the blending and extrusion of poly(l-lactide-co-glycolide) and bioresorbable aliphatic oligoesters with side hydroxyl groups: oligo (butylene succinate-co-butylene citrate) and oligo(butylene citrate). Addition of the oligoesters to poly (l-lactide-co-glycolide) reduces the glass transition temperature (Tg) and also increases the flexibility and shape memory behavior of the final blends. Among the tested blends, materials containing less than 20 wt % of oligo (butylene succinate-co-butylene citrate) seem especially promising for biomedical applications as materials for manufacturing bioresorbable implants with high flexibility and relatively good mechanical properties. These blends show compatibility, exhibiting one glass transition temperature and macroscopically uniform physical properties.

Pectin based banana peel extract as a stabilizing agent in zinc oxide nanoparticles synthesis.

Various amounts of banana peel extract were successfully used as a stabilizing agent in the co-precipitation of zinc oxide nanoparticles. The obtained materials were characterized by means of Fourier transform infrared spectroscopy (FTIR), gel permeation chromatography (GPC), X-ray diffraction (XRD), photoluminescence spectroscopy (PL), scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDS), N2 physisorption, thermogravimetric analysis (TGA), and quadrupole mass spectroscopy (QMS). On account of using such a broad spectrum of analytic methods, a thorough description of the interactions between the organic ingredients of the extract and ZnO particles was presented. It was indicated that the banana peel extract is based on pectin. These carbohydrate macromolecules adsorb on ZnO surface due to presence of active carboxylic groups. By increasing the concentration of polysaccharides, pectin-pectin interactions were also observed. The amount of the extract used for the synthesis significantly influenced the crystalline structure of zinc oxide particles along with their size and morphology. The shape and size were varying from thin flakes (450 × 24 nm) when the smallest amount of the extract was used, through nanocones with pointed tips (210 × 120 nm) agglomerated in a flower-like structure, until cubic-shaped nanoparticles (20-40 nm) agglomerated in a pinecone-like structure (430 × 180 nm) when the biggest amount of the extract was applied. The obtained particles have displayed apromising antimicrobial activity against Gram-positive (Staphylococcus aureus) and Gram-negative (Pseudomonas aeruginosa) bacteria, and fungus (Candida albicans). The highest activity was demonstrated against S. aureus pathogen.

Analysis of the Effectiveness of Decontamination Fluids on the Level of Biological Contamination of Firefighter Suits.

The scope of tasks of chemical and ecological rescue procedures includes prevention of terrorist attacks with biological weapons. After each action, firefighters are obliged to clean and disinfect their outfits to prevent the potential spreading of harmful microorganisms. This study aimed to analyze the effectiveness of decontamination fluids used to disinfect firefighter's suits. Two types of clothes were analyzed: special combat clothing (NOMEX), and the heavy gas-tight chemical type 1a suit. Swabbed places were cut out and sterilized mechanically using detergent and alcohol. Each time, smears were made on sterile glass, fixed in pure ethanol and stained using the Gram method. After this, the staining samples were air dried and photographed under a light microscope at magnification 1000×. Each smear was made in triplicate and the relative number of stained microorganisms was analyzed using ImageJ software. The results showed that detergent significantly decreased the number of pathogens in the chest area on the NOMEX suit and the type 1a-gas-tight clothing and was more effective than alcohol, especially in case of the NOMEX suit. In conclusion, the detergent was more efficient in decontaminating the NOMEX outfit than the heavy gas-tight clothing, whose surface was better cleaned by the alcohol.

Synthesis and Properties of Bioresorbable Block Copolymers of l-Lactide, Glycolide, Butyl Succinate and Butyl Citrate.

The paper presents the course of synthesis and properties of a series of block copolymers intended for biomedical applications, mainly as a material for forming scaffolds for tissue engineering. These materials were obtained in the polymerization of l-lactide and copolymerization of l-lactide with glycolide carried out using a number of macroinitiators previously obtained in the reaction of polytransesterification of succinic diester, citric triester and 1,4-butanediol. NMR, FTIR and DSC were used to characterize the materials obtained; wettability and surface free energy were assessed too. Moreover, biological tests, i.e., viability and metabolic activity of MG-63 osteoblast-like cells in contact with synthesized polymers were performed. Properties of obtained block copolymers were controlled by the composition of the polymerization mixture and by the composition of the macroinitiator. The copolymers contained active side hydroxyl groups derived from citrate units present in the polymer chain. During the polymerization of L-lactide in the presence of polyesters with butylene citrate units in the chain, obtained products of the reaction held a fraction of highly branched copolymers with ultrahigh molecular weight. The reason for this observed phenomenon was strong intermolecular transesterification directed to lactidyl side chains, formed as a result of chain growth on hydroxyl groups related to the quaternary carbons of the citrate units. Based on the physicochemical properties and results of biological tests it was found that the most promising materials for scaffolds formation were poly(l-lactide-co-glycolide)-block-poly(butylene succinate-co-butylene citrate)s, especially those copolymers containing more than 60 mol % of lactidyl units.

The impact of shape memory test on degradation profile of a bioresorbable polymer.

The semicrystalline poly(L-lactide) (PLLA) belongs to the materials with shape memory effect (SME) and as a bioresorbable and biocompatible polymer it have found many applications in medical and pharmaceutical field. Assessment of the SME impact on the polymer degradation profile plays crucial role in applications such as drug release systems or in regenerative medicine. Herein, the results of in vitro degradation studies of PLLA samples after SME full test cycle are presented. The samples were loaded and deformed in two manners: progressive and non-progressive. The performed experiments illustrate also influence of the material mechanical damages, caused e.g. during incorrect implantation of PLLA product, on hydrolytic degradation profile. Apparently, degradation profiles are significantly different for the material which was not subjected to the deformation and the deformed ones. The materials after deformation of 50% (in SME cycle) was characterized by non-reversible morphology changes. The effect was observed in deformed samples during the SME test which were carried out ten times.

The effect of polymeric membrane surface on HaCaT cell properties.

The control of the surface properties is an important issue for applicability of polymer membranes interacting with cells. In this work, the influence of surface roughness and stiffness of two polymer membranes on viability and mechanical properties of keratinocytes was studied. Terpolimer polyglicolide, polycaprolactone and polylactide, (PGA-PCL-PLA) and copolymer polycaprolactone, polyglicolide (PGA-PCL) substrates were used for membranes fabrication. Surface modification - the hydrolysis of the obtained membranes was carried out. The analysis of membranes' surface properties revealed that RMS surface roughness and roughness factor of PGA-PCL-PLA membrane decreased after hydrolysis while its stiffness increased. In contrast, the PGA-PCL membrane stiffness was only slightly affected by NaOH treatment. Immortalized human keratinocytes (HaCaT) were grown under standard conditions on the surface of the studied membranes and characterized by means of atomic force microscopy and fluorescence microcopy. The results showed the substrate-dependent effect on cells' properties.

Crystallinity as a tunable switch of poly(L-lactide) shape memory effects.

Materials with shape memory effect (SME) have already been widely used in the medical field. The interesting part of this group is represented by double function materials. The bioresorption and SME ability are common in polyesters implants. The first information about vascular stent made of bioresorbable polyester with SME was published in 2000. However, there are not many investigations about SME control of elements in the aspect of material processing. In the present work, the ability to control the shape memory (SM) of bioresorbable and semicrystalline poly(L-lactide) (PLLA) is investigated. The studies are based on the unexpected effect of material orientation which was demonstrated even at low percentage deformation in crystallized mould injected material. The presented studies revealed that the different degrees of crystallinity obtained during processing might be a useful switch to create a tailored SME for a specific application. The prepared samples of variable morphology revealed a possibility to control the value of material stress during permanent shape recovery. The degree of shape recovery of the prepared samples was also controlable. The highest stress value observed during permanent shape recovery reached 10MPa for the sample annealed 60min at 115°C even when the sample was only deformed in 8%. The other significant aspect of this work is to present the problem of slow crystallization of the material during and after processing (cooling rate) as well as the possibility of negative SME change during the shelf life of the fabric.

Influence of Radiation Sterilization on Properties of Biodegradable Lactide/Glycolide/Trimethylene Carbonate and Lactide/Glycolide/ε-caprolactone Porous Scaffolds with Shape Memory Behavior.

The aim of the study was the evaluation of gamma irradiation and electron beams for sterilization of porous scaffolds with shape memory behavior obtained from biodegradable terpolymers: poly(l-lactide-co-glycolide-co-trimethylene carbonate) and poly(l-lactide-co-glycolide-co-ɛ-caprolactone). The impact of mentioned sterilization techniques on the structure of the scaffolds before and after the sterilization process using irradiation doses ranged from 10 to 25 kGy has been investigated. Treatment of the samples with gamma irradiation at 15 kGy dose resulted in considerable drop in glass transition temperature (Tg) and number average molecular weight (Mn). For comparison, after irradiation of the samples using an electron beam with the same dose, no significant changes in structure or properties of examined scaffolds have been noticed. Higher doses of irradiation via electron beam caused essential changes of the scaffolds' pores resulting in partial melting of their surface. Nevertheless, obtained results have revealed that sterilization with electron beam, when compared to gamma irradiation, is a better method because it does not affect significantly the physicochemical properties of the scaffolds. Both used methods of sterilization did not influence the shape memory behavior of the examined materials.