Recent Progress in Polysaccharide-Based Materials for Energy Applications: A Review.

In recent years, polysaccharides have emerged as a promising alternative for the development of environmentally friendly materials. Polysaccharide-based materials have been mainly studied for applications in the food, packaging, and biomedical industries. However, many investigations report processing routes and treatments that enable the modification of the inherent properties of polysaccharides, making them useful as materials for energy applications. The control of the ionic and electronic conductivities of polysaccharide-based materials allows for the development of solid electrolytes and electrodes. The incorporation of conductive and semiconductive phases can modify the permittivities of polysaccharides, increasing their capacity for charge storage, making them useful as active surfaces of energy harvesting devices such as triboelectric nanogenerators. Polysaccharides are inexpensive and abundant and could be considered as a suitable option for the development and improvement of energy devices. This review provides an overview of the main research work related to the use of both common commercially available polysaccharides and local native polysaccharides, including starch, chitosan, carrageenan, ulvan, agar, and bacterial cellulose. Solid and gel electrolytes derived from polysaccharides show a wide range of ionic conductivities from 0.0173 × 10-3 to 80.9 × 10-3 S cm-1. Electrodes made from polysaccharides show good specific capacitances ranging from 8 to 753 F g-1 and current densities from 0.05 to 5 A g-1. Active surfaces based on polysaccharides show promising results with power densities ranging from 0.15 to 16 100 mW m-2. These investigations suggest that in the future polysaccharides could become suitable materials to replace some synthetic polymers used in the fabrication of energy storage devices, including batteries, supercapacitors, and energy harvesting devices.

Seamless Integration of Conducting Hydrogels in Daily Life: From Preparation to Wearable Application.

Conductive hydrogels (CHs) have received significant attention for use in wearable devices because they retain their softness and flexibility while maintaining high conductivity. CHs are well suited for applications in skin-contact electronics and biomedical devices owing to their high biocompatibility and conformality. Although highly conductive hydrogels for smart wearable devices are extensively researched, a detailed summary of the outstanding results of CHs is required for a comprehensive understanding. In this review, the recent progress in the preparation and fabrication of CHs is summarized for smart wearable devices. Improvements in the mechanical, electrical, and functional properties of high-performance wearable devices are also discussed. Furthermore, recent examples of innovative and highly functional devices based on CHs that can be seamlessly integrated into daily lives are reviewed.

Lignocellulosic Biomass for the Fabrication of Triboelectric Nano-Generators (TENGs)-A Review.

Growth in population and increased environmental awareness demand the emergence of new energy sources with low environmental impact. Lignocellulosic biomass is mainly composed of cellulose, lignin, and hemicellulose. These materials have been used in the energy industry for the production of biofuels as an eco-friendly alternative to fossil fuels. However, their use in the fabrication of small electronic devices is still under development. Lignocellulose-based triboelectric nanogenerators (LC-TENGs) have emerged as an eco-friendly alternative to conventional batteries, which are mainly composed of harmful and non-degradable materials. These LC-TENGs use lignocellulose-based components, which serve as electrodes or triboelectric active materials. These materials can be derived from bulk materials such as wood, seeds, or leaves, or they can be derived from waste materials from the timber industry, agriculture, or recycled urban materials. LC-TENG devices represent an eco-friendly, low-cost, and effective mechanism for harvesting environmental mechanical energy to generate electricity, enabling the development of self-powered devices and sensors. In this study, a comprehensive review of lignocellulosic-based materials was conducted to highlight their use as both electrodes and triboelectric active surfaces in the development of novel eco-friendly triboelectric nano-generators (LC-TENGs). The composition of lignocellulose and the classification and applications of LC-TENGs are discussed.

Per- and polyfluoroalkyl substances (PFASs) in consumable species and food products.

Per- and polyfluoroalkyl substances (PFASs) are a group of thousands of manmade chemicals widely used in consumer products and industrial processes. Toxicological studies have suggested that exposure to PFASs may lead to several adverse effects, including infertility and cancer development. In light of their widespread use, the contamination of food products has created health concerns in sites directly influenced by industrial and anthropogenic activity. In the present contribution, the current knowledge of PFAS contamination was systematically reviewed in order to provide with the knowledge gaps and main sources of contamination, as well as critically evaluate estimated dietary intake and relative risk values of the consulted studies. Legacy PFASs remain the most abundant despite their production restrictions. Edible species from freshwater bodies exhibit higher PFAS concentrations than marine species, probably due to low hydrodynamics and dilution in lentic ecosystems. Studies in food products from multiple sources, including aquatic, livestock, and agricultural, agree that the proximity to factories and fluorochemical industries rendered significantly higher and potentially hazardous PFAS contamination. Short-chain PFAS are suggested as chemicals of emerging concern to food security. However, the environmental and toxicological implications of short-chain congeners are not fully understood and, thus, much research is needed in this sense.

Carbon Quantum Dots Based on Marine Polysaccharides: Types, Synthesis, and Applications.

The marine environment offers a vast array of resources, including plants, animals, and microorganisms, that can be utilized to extract polysaccharides such as alginate, carrageenan, chitin, chitosan, agarose, ulvan, porphyra, and many more. These polysaccharides found in marine environments can serve as carbon-rich precursors for synthesizing carbon quantum dots (CQDs). Marine polysaccharides have a distinct advantage over other CQD precursors because they contain multiple heteroatoms, including nitrogen (N), sulfur (S), and oxygen (O). The surface of CQDs can be naturally doped, reducing the need for excessive use of chemical reagents and promoting green methods. The present review highlights the processing methods used to synthesize CQDs from marine polysaccharide precursors. These can be classified according to their biological origin as being derived from algae, crustaceans, or fish. CQDs can be synthesized to exhibit exceptional optical properties, including high fluorescence emission, absorbance, quenching, and quantum yield. CQDs' structural, morphological, and optical properties can be adjusted by utilizing multi-heteroatom precursors. Moreover, owing to their biocompatibility and low toxicity, CQDs obtained from marine polysaccharides have potential applications in various fields, including biomedicine (e.g., drug delivery, bioimaging, and biosensing), photocatalysis, water quality monitoring, and the food industry. Using marine polysaccharides to produce carbon quantum dots (CQDs) enables the transformation of renewable sources into a cutting-edge technological product. This review can provide fundamental insights for the development of novel nanomaterials derived from natural marine sources.

Mercury pollution in Peru: geographic distribution, health hazards, and sustainable removal technologies.

Peru is one of the great gold producers worldwide. However, a significant portion of the gold produced in Peru derives from artisanal small-scale gold mining (ASGM) in the Andes and Amazon. In ASGM, gold amalgamation with mercury (Hg) is a critical procedure to refine gold through the formation of Au-Hg alloys. Due to the rudimentary and improvised techniques conducted by small-scale and informal miners, Hg contamination has become of great concern and is strictly associated with ASGM. Multiple studies have evidenced notably high concentrations of Hg in consumable fish species, rivers, sediments, and air in locations where ASGM is one of the main sources of income to local communities and is carried out aggressively. In the present review, we have conducted a systematic search for national and international literature reporting the concentration and distribution of Hg pollution across environmental compartments, biota, and human samples in Peru. The results and data retrieved from the articles were quantitatively and qualitatively analyzed, and the distribution of Hg across environmental compartments was visualized through a geographic information system. Additionally, we reviewed the use of adsorption techniques as alternatives to treat Hg0 vapor from the gold shop and smelter flues, one of the main sources of hazardous levels of Hg exposure.

Synthesis, characteristics, and applications of modified starch nanoparticles: A review.

Nowadays, starch nanoparticles (SNPs) are drawing attention to the scientific community due to their versatility and wide range of applications. Although several works have extensively addressed the SNP production routes, not much is discussed about the SNPs modification techniques, as well as the use of modified SNPs in typical and unconventional applications. Here, we focused on the SNP modification strategies and characteristics and performance of the resulting products, as well as their practical applications, while pointing out the main limitations and recommendations. We aim to guide researchers by identifying the next steps in this emerging line of research. SNPs esterification and oxidation are preferred chemical modifications, which result in changes in the functional groups. Moreover, additional polymers are incorporated into the SNP surface through copolymer grafting. Physical modification of starch has demonstrated similar changes in the functional groups without the need for toxic chemicals. Modified SNPs rendered differentiated properties, such as size, shape, crystallinity, hydrophobicity, and Zeta-potential. For multiple applications, tailoring the aforementioned properties is key to the performance of nanoparticle-based systems. However, the number of studies focusing on emerging applications is fairly limited, while their applications as drug delivery systems lack in vivo studies. The main challenges and prospects were discussed.

Binational survey of personal protective equipment (PPE) pollution driven by the COVID-19 pandemic in coastal environments: Abundance, distribution, and analytical characterization.

In the present contribution, two nationwide surveys of personal protective equipment (PPE) pollution were conducted in Peru and Argentina aiming to provide valuable information regarding the abundance and distribution of PPE in coastal sites. Additionally, PPE items were recovered from the environment and analyzed by Fourier transformed infrared (FTIR) spectroscopy, Scanning electron microscopy (SEM) with Energy dispersive X-ray (EDX), and X-ray diffraction (XRD), and compared to brand-new PPE in order to investigate the chemical and structural degradation of PPE in the environment. PPE density (PPE m-2) found in both countries were comparable to previous studies. FTIR analysis revealed multiple polymer types comprising common PPE, mainly polypropylene, polyamide, polyethylene terephthalate, and polyester. SEM micrographs showed clear weathering signs, such as cracks, cavities, and rough surfaces in face masks and gloves. EDX elemental mapping revealed the presence of elemental additives, such as Ca in gloves and face masks and AgNPs as an antimicrobial agent. Other metals found on the surface of PPE were Mo, P, Ti, and Zn. XRD patterns displayed a notorious decrease in the crystallinity of polypropylene face masks, which could alter its interaction with external contaminants and stability. The next steps in this line of research were discussed.

Environmental pollution with antifouling paint particles: Distribution, ecotoxicology, and sustainable alternatives.

Antifouling paint particles (APPs) are a type of paint particle loaded with toxic biocidal compounds. The present review focused on the current knowledge in respect of the abundance, distribution, and ecotoxicological effects of APPs in the marine environment. Also, the recent advances in nontoxic biobased antifouling paints were discussed as potential alternatives to contemporary marine coatings. The presence of APPs is mainly associated with boat maintenance in boatyards and port areas. Conventional microplastic assessments showed a significant contribution of paint particles to the morphological composition. Moreover, recent ecotoxicological studies demonstrated that environmental concentrations of APPs induce mortality (LC50) in sediment dwellers and macroinvertebrates. Novel biocides from natural sources and biopolymer binders in the formulation of antifouling paints are proposed as potential alternatives to conventional antifouling paints. The toxicity of most natural biocides is negligible to nontargeted species, while biopolymers are expected to prevent the formation of APPs.

Marine macroinvertebrates inhabiting plastic litter in Peru.

Marine litter, such as plastic bags, bottles, fabrics, or fishing gear, serve as a shelter for many marine organisms that are likely to colonize artificial substrata. Such assemblages can potentially turn marine litter into vectors of alien invasive species (AIS). Here, we report the abundance and diversity of macroinvertebrates inhabiting marine litter in Peruvian beaches. Results indicate that most of the fouled items found came from land-based sources (81.5%) and Bivalvia was the most abundant class (53.5%), mainly composed of the mussel Semimytilus algosus. No significant differences were found in the abundance and diversity of macroinvertebrates (class level) among sampling sites or sources of litter. Polypropylene and low-density polyethylene items were most frequently found with fouled biota. Although none of the identified species were non-native to the coast of Peru, we discuss marine litter as a potential source of AIS in this region.

Influence of the source of starch and plasticizers on the environmental burden of starch-Brazil nut fiber biocomposite production: A life cycle assessment approach.

Amidst the global plastic pollution crisis, bio-based polymers have been proposed as a potential substitute to tackle this issue. Owed to their biodegradability, biopolymers are generally regarded as eco-friendly during the post-consumer (disposal) stage. However, the environmental burden of the many production processes biopolymers and their components undergo better reflect the sustainable nature of these materials. Previous studies evaluating the Life Cycle Assessment (LCA) of starch-based composites have focused on commercially available starches, although other non-conventional starches can also be used to produce biopolymers. To address this knowledge gap, in the present study we evaluated the LCA of starch-Brazil nut fiber biocomposites prepared with starch from three different sources, Andean potato, corn, and sweet potato, and applying two different plasticizers, glycerol and sorbitol. Results indicated that the starch-based biocomposites were less impacting than conventional PLA-Brazil nut fiber and PP-glass fiber composites. The type of starch and plasticizer significantly influenced the environmental load of the production of the composites. The main drivers of these differences were the multiple agricultural practices, such as irrigation and fertilization, and the crop efficiency for starch extraction. Sorbitol was found to be many times more impacting than glycerol in most categories, which is due to the complex processing of sorbitol and high content in biocomposites with similar mechanical properties than glycerol. Additionally, Brazil nut fibers are presented as an eco-friendly and low-burden natural filler due to their easy processing and agricultural waste origin. The limitations, applications, and significance of the results were discussed.

Sorption of chemical contaminants on degradable and non-degradable microplastics: Recent progress and research trends.

Microplastics (<5 mm) are ubiquitous contaminants of growing concern. These have been found in multiple environmental compartments, including remote sites where anthropogenic activity is null. Once released, microplastics interact with multiple chemicals in the environment, many of which are classified as organic contaminants or heavy metals. Some contaminants have an affinity for microplastics, attributed to certain sorption mechanisms, and thus become vectors of hazardous chemicals. Here, we focused on the sorption behavior of degradable and non-degradable microplastics, including field and laboratory experiments. We reviewed the sorption mechanisms, namely hydrophobic interactions, electrostatic interactions, pore-filling, Van der Waals forces, hydrogen bonding, and π-π interactions, and the factors strengthening or weakening these mechanisms. Then, we analyzed the literature investigating the sorption behavior of a wide range of chemicals contaminants on microplastics, and the current knowledge regarding the occurrence of organic contaminants and heavy metals on microplastics extracted from the environment. The future perspectives and research priorities were discussed. It is apparent that degradable microplastics, such as polylactic acid or polybutylene succinate, have a greater affinity for hydrophobic contaminants than conventional synthetic non-degradable microplastics according to recent studies. However, studies assessing degradable microplastics are scarce and much research is required to further prove this point. We stated several knowledge gaps in this new line of research and suggest the future studies to follow an integrative approach, allowing to comprehend the multiple factors involved, such as ecotoxicity, bioaccumulation, and fate of the chemical contaminants.

Polysaccharide-based triboelectric nanogenerators: A review.

Triboelectric nanogenerators (TENGs) are versatile electronic devices used for environmental energy harvesting and self-powered electronics with a wide range of potential applications. The rapid development of TENGs has caused great concern regarding the environmental impacts of conventional electronic devices. Under this context, researching alternatives to synthetic and toxic materials in electronics are of major significance. In this review, we focused on TENGs based on natural polysaccharide materials. Firstly, a general overview of the working mechanisms and materials for high-performance TENGs were summarized and discussed. Then, the recent progress of polysaccharide-based TENGs along with their potential applications reported in the literature from 2015 to 2020 was reviewed. Here, we aimed to present polysaccharide polymers as a promising and viable alternative to the development of green TENGs and tackle the challenges of recycling e-wastes.

Bacterial Cellulose-Graphene Based Nanocomposites.

Bacterial cellulose (BC) and graphene are materials that have attracted the attention of researchers due to their outstanding properties. BC is a nanostructured 3D network of pure and highly crystalline cellulose nanofibres that can act as a host matrix for the incorporation of other nano-sized materials. Graphene features high mechanical properties, thermal and electric conductivity and specific surface area. In this paper we review the most recent studies regarding the development of novel BC-graphene nanocomposites that take advantage of the exceptional properties of BC and graphene. The most important applications of these novel BC-graphene nanocomposites include the development of novel electric conductive materials and energy storage devices, the preparation of aerogels and membranes with very high specific area as sorbent materials for the removal of oil and metal ions from water and a variety of biomedical applications, such as tissue engineering and drug delivery. The main properties of these BC-graphene nanocomposites associated with these applications, such as electric conductivity, biocompatibility and specific surface area, are systematically presented together with the processing routes used to fabricate such nanocomposites.

Application of the Spider Silk Standardization Initiative (S3I) methodology to the characterization of major ampullate gland silk fibers spun by spiders from Pantanos de Villa wetlands (Lima, Peru).

Spider silk is a natural material with unique properties and a great potential for engineering and biomedical applications. In spite of its simple composition and highly conserved and stereotypical production, spider silks show a wide range of variability in their mechanical properties which, for long, have defied their classification and standardization. Here we propose to launch the Spider Silk Standardization Initiative (S3I), a methodology based on the definition of the α* parameter, in an attempt to define a systematic procedure to classify the tensile properties exhibited by major ampullate gland silk (MAS) spun by Entelegynae spiders. The α* parameter is calculated from the comparison of the true stress-true strain curve of any MAS fiber after being subjected to maximum supercontraction, with the true stress-true strain curve of the species Argiope aurantia, which is set as a reference curve. This work presents the details of the S3I methodology and, as an example, shows its application to an assemblage of Entelegynae spiders from different families collected at the Pantanos de Villa wetlands (Lima, Peru). The systematic and objective classification of the tensile properties of MAS fibers allowed by the S3I will offer insights into key aspects of the biological evolution of the material, and address questions such as how history and adaptation contributed to shape those properties. In addition, it will surely have far reaching consequences in fields such as Materials Science, and Molecular and Evolutionary Biology, by organizing the range of tensile properties exhibited by spider silk fibers.

Molecular α-relaxation process of exopolysaccharides extracted from Nostoc commune cyanobacteria.

Broadband dielectric spectroscopy was used to investigate the molecular α-relaxation of the exopolysaccharides (EPS) extracted from Nostoc commune cyanobacteria. The EPS were modified in different ways. EPS were carboxymethylated to obtain carboxymethyl-exopolysaccharides (CEPS). EPS and CEPS were doped with ammonium iodide and 1-butyl-3-methylimidazolium chloride. An α relaxation process was observed for all specimens. The temperature dependence of the relaxation times for pure and doped, EPS and CEPS polymers exhibited non-Arrhenius behavior. This relaxation process was associated with the glass transition of the complex heteropolysaccharides produced by the cyanobacteria. The molecular mobility at the glass transition, Tg, was affected by both the carboxymethylation treatment and the doping. The fragility index also decreased for the doped specimens, which may be attributed to an increase in the mobility of the polymer chains due to the plasticizing effect of the doping agents.

Natural Polysaccharide Nanomaterials: An Overview of Their Immunological Properties.

Natural occurring polymers, or biopolymers, represent a huge part of our planet biomass. They are formed by long chains of monomers of the same type or a combination of different ones. Polysaccharides are biopolymers characterized by complex secondary structures performing several roles in plants, animals, and microorganisms. Because of their versatility and biodegradability, some of them are extensively used for packaging, food, pharmaceutical, and biomedical industries as sustainable and renewable materials. In the recent years, their manipulation at the nanometric scale enormously increased the range of potential applications, boosting an interdisciplinary research attempt to exploit all the potential advantages of nanostructured polysaccharides. Biomedical investigation mainly focused on nano-objects aimed at drug delivery, tissue repair, and vaccine adjuvants. The achievement of all these applications requires the deep knowledge of polysaccharide nanomaterials' interactions with the immune system, which orchestrates the biological response to any foreign substance entering the body. In the present manuscript we focused on natural polysaccharides of high commercial importance, namely, starch, cellulose, chitin, and its deacetylated form chitosan, as well as the seaweed-derived carrageenan and alginate. We reviewed the available information on their biocompatibility, highlighting the importance of their physicochemical feature at the nanoscale for the modulation of the immune system.

Ageing and degradation determines failure mode on sea urchin spines.

Sea urchin spines are an example of a hard natural composite with mineral and organic phases. The role of the organic phase in the response to mechanical stress was assessed by promoting the degradation of such spines by exposing them to ageing and ultraviolet (UV) irradiation. Thermal and structural characterization of the irradiated samples show that this UV irradiation treatment promotes degradation of the organic and inorganic phase of spines. Uniaxial compression tests carried out on aged and UV irradiated samples showed that both treatments affected the mechanical properties of the spines. Scanning electron microscopy (SEM) images of failed specimens were used to analyze the failure mechanisms of the compressed spines. The analysis of the fracture surfaces showed that the failure mechanisms of spines were modified as a consequence of UV irradiation, leading in the last case to mostly brittle fracture surfaces. We suggest that the proteins responsible for the formation of calcite also determine the mechanical properties and the failure mode of spines. This system can be used as a model for the study of the failure modes of other natural and synthetic hard composites.

Failure of flight feathers under uniaxial compression.

Flight feathers are light weight engineering structures. They have a central shaft divided in two parts: the calamus and the rachis. The rachis is a thinly walled conical shell filled with foam, while the calamus is a hollow tube-like structure. Due to the fact that bending loads are produced during birds' flight, the resistance to bending of feathers has been reported in different studies. However, the analysis of bent feathers has shown that compression could induce failure by buckling. Here, we have studied the compression of feathers in order to assess the failure mechanisms involved. Axial compression tests were carried out on the rachis and the calamus of dove and pelican feathers. The failure mechanisms and folding structures that resulted from the compression tests were observed from images obtained by scanning electron microscopy (SEM). The rachis and calamus fail due to structural instability. In the case of the calamus, this instability leads to a progressive folding process. In contrast, the rachis undergoes a typical Euler column-type buckling failure. The study of failed specimens showed that delamination buckling, cell collapse and cell densification are the primary failure mechanisms of the rachis structure. The role of the foam is also discussed with regard to the mechanical response of the samples and the energy dissipated during the compression tests. Critical stress values were calculated using delamination buckling models and were found to be in very good agreement with the experimental values measured. Failure analysis and mechanical testing have confirmed that flight feathers are complex thin walled structures with mechanical adaptations that allow them to fulfil their functions.

Hydrazine treatment improves conductivity of bacterial cellulose/graphene nanocomposites obtained by a novel processing method.

A novel method to prepare BC nanocomposites reinforced with reduced graphene oxide (RGO) is reported. A simple hydrazine treatment is shown to in-situ reduce the graphene oxide (GO) incorporated to BC films while increasing their conductivity. Raman spectroscopy was used to confirm the presence of graphene and assess the effect of the hydrazine treatment on its structure. XRD tests revealed no changes on BC structure. We hypothesize that this treatment removes the hydroxyl and epoxy groups present on the reduced graphene and increases the content of nonoxygenated carbon. These changes account for the increase in conductivity of the BC-based films, which behaved as an insulating material before the hydrazine treatment and reach an average conductivity value of 12S/m after such a treatment.