Chitosan-Based Beads Incorporating Inorganic-Organic Composites for Copper Ion Retention in Aqueous Solutions.

In recent years, there has been a challenging interest in developing low-cost biopolymeric materials for wastewater treatment. In the present work, new adsorbents, based on different types of chitosan (commercial, commercial chitin-derived chitosan and chitosan synthesized from shrimp shell waste) and inorganic-organic composites have been evaluated for copper ions removal. The efficacy of the synthesis of chitosan-based composite beads has been determined by studying various characteristics using several techniques, including FTIR spectroscopy, X-ray diffraction, porosimetry (N2 adsorption), and scanning electron microscopy (SEM). Adsorption kinetics was performed using different adsorption models to determine the adsorption behavior of the materials in the aqueous media. For all composite beads, regardless of the type of chitosan used, good capacity to remove copper ions from simulated waters was observed (up to 17 mg/g), which proves that the new materials hold potential for heavy metal retention. However, the adsorption efficiency was influenced by the type of chitosan used. Thus, for the series where commercial chitosan (CC) was used, the removal efficiency was approximately 29%; for the series with chitosan obtained from commercial chitin (SC), the removal efficiency was approximately 34%; for the series with chitosan enriched with CaCO3 (SH), the removal efficiency was approximately 52%.

Luminescent Papers with Asymmetric Complexes of Eu(III) and Tb(III) in Polymeric Matrices and Suggested Combinations for Color Tuning.

Complexes of lanthanide ions, such as Eu(III) (red light emission) and Tb(III) (green light emission), with proper ligands can be highly luminescent and color-tunable, also attaining yellow and orange emission under UV radiation. The ligands employed in this work were poly(sodium acrylate), working as polymeric matrix, and 1,10-phenanthroline, taking advantage of its antenna effect. Possibilities of color display were further enhanced by incorporating a cationic polyfluorene with blue emission. This strategy allowed for obtaining cyan and magenta, besides the aforementioned colors. Uncoated cellulose paper was impregnated with the resulting luminescent inks, observing a strong hypsochromic shift in excitation wavelength upon drying. Hence, while a cheap UV-A lamp sufficed to reveal the polyfluorene's blue emission, shorter wavelengths were necessary to visualize the emission due to lanthanide ions as well. The capacity to reveal, with UV-C radiation, a full-color image that remains invisible under natural light is undoubtedly useful for anti-counterfeiting applications. Furthermore, both lanthanide ion complexes and polyfluorenes were shown to have their luminescence quenched by Cu(II) ions and nitroarenes, respectively.

Reduced Chitosan as a Strategy for Removing Copper Ions from Water.

Toxic heavy metals are priority pollutants in wastewater, commonly present in dangerous concentrations in many places across the globe. Although in trace quantities copper is a heavy metal essential to human life, in excess it causes various diseases, whereby its removal from wastewater is a necessity. Among several reported materials, chitosan is a highly abundant, non-toxic, low-cost, biodegradable polymer, comprising free hydroxyl and amino groups, that has been directly applied as an adsorbent or chemically modified to increase its performance. Taking this into account, reduced chitosan derivatives (RCDs 1-4) were synthesised by chitosan modification with salicylaldehyde, followed by imine reduction, characterised by RMN, FTIR-ATR, TGA and SEM, and used to adsorb Cu(II) from water. A reduced chitosan (RCD3), with a moderate modification percentage (43%) and a high imine reduction percentage (98%), proved to be more efficient than the remainder RCDs and even chitosan, especially at low concentrations under the best adsorption conditions (pH 4, RS/L = 2.5 mg mL-1). RCD3 adsorption data were better described by the Langmuir-Freundlich isotherm and the pseudo-second-order kinetic models. The interaction mechanism was assessed by molecular dynamics simulations, showing that RCDs favour Cu(II) capture from water compared to chitosan, due to a greater Cu(II) interaction with the oxygen of the glucosamine ring and the neighbouring hydroxyl groups.

Triantennary GalNAc-Functionalized Multi-Responsive Mesoporous Silica Nanoparticles for Drug Delivery Targeted at Asialoglycoprotein Receptor.

In recent years, mesoporous silica particles have been revealed as promising drug delivery systems combining high drug loading capacity, excellent biocompatibility, and easy and affordable synthetic and post-synthetic procedures. In fact, the straightforward functionalization approaches of these particles allow their conjugation with targeting moieties in order to surpass one of the major challenges in drug administration, the absence of targeting ability of free drugs that reduces their therapeutic efficacy and causes undesired side effects. In this context, the main goal of this work was to develop a new targeted mesoporous silica nanoparticle formulation with the capability to specifically and efficiently deliver an anticancer drug to hepatocellular carcinoma (HCC) cells. To this purpose, and as proof of concept, we developed redox-responsive mesoporous silica nanoparticles functionalized with the targeting ligand triantennary N-acetylgalactosamine (GalNAc) cluster, which has high affinity to asialoglycoprotein receptors overexpressed in HCC cells, and loaded them with epirubicin, an anthracycline drug. The produced nanocarrier exhibits suitable physicochemical properties for drug delivery, high drug loading capacity, high biocompatibility, and targeting ability to HCC cells, revealing its biopharmaceutical potential as a targeted drug carrier for therapeutic applications in liver diseases.

Silica Aerogels/Xerogels Modified with Nitrogen-Containing Groups for Heavy Metal Adsorption.

Heavy metals are common inorganic pollutants found in the environment that have to be removed from wastewaters and drinking waters. In this work, silica-derived aerogels and xerogels were modified via a co-precursor method to obtain functional adsorbents for metal cations. A total of six formulations based upon four different functional precursors were prepared. The materials' structural characterization revealed a decreased porosity and surface area on modified samples, more prominent in xerogel counterparts. Preliminary tests were conducted, and the prepared samples were also compared to activated carbon. Three samples were selected for in-depth studies. Isotherm studies revealed that the pre-selected samples remove well copper, lead, cadmium and nickel, and with similar types of interactions, following a Langmuir trend. The adsorption kinetics starts very fast and either equilibrium is reached quickly or slowly, in a two-stage process attributed to the existence of different types of active sites. Based on the previous tests, the best sample, prepared by mixing different functional co-precursors, was selected and its behavior was studied under different temperatures. For this material, the adsorption performance at 20 °C is dependent on the cation, ranging from 56 mg·g-1 for copper to 172 mg·g-1 for lead.

Assessment of heavy metal pollution from anthropogenic activities and remediation strategies: A review.

Heavy metal pollution is a nefarious issue with implications for life. Heavy metals are natural occurring elements, having both natural and anthropogenic sources. The latter are however the most significant, releasing greater amounts of these pollutants in more toxic and mobile forms. Their chemistry and dynamics in the ecosystems are presented, and the relation to the pollution problematic thereof is discussed. The concentration of heavy metals in several sites, assessed in water, soil and sediment samples, affected by different pollution sources are reviewed. These evidence how human activities impact natural media and how the pollution spreads. The pollution in each media is assessed by the concentration relative to drinking and irrigation water guidelines, and by the geoaccumulation index of soils and sediments. It is found that ore extraction and processing and metallurgical industries stand atop the most polluting sources. Given the dynamics of heavy metal cations and that, most of these are released in liquid effluents, wastewater treatment techniques for the removal of heavy metals are also surveyed and critically discussed. Economic viability at a large municipal scale and the ability to comply with strict regulations are the determining factors in the selection of these techniques. A critical discussion on the viability of such techniques is made, reviewing some literature studies and commenting on their applicability on the previously found polluted media.

Amine Modification of Silica Aerogels/Xerogels for Removal of Relevant Environmental Pollutants.

Serious environmental and health problems arise from the everyday release of industrial wastewater effluents. A wide range of pollutants, such as volatile organic compounds, heavy metals or textile dyes, may be efficiently removed by silica materials advanced solutions such as aerogels. This option is related to their exceptional characteristics that favors the adsorption of different contaminants. The aerogels performance can be selectively tuned by an appropriate chemical or physical modification of the aerogel's surface. Therefore, the introduction of amine groups enhances the affinity between different organic and inorganic contaminants and the silica aerogels. In this work, different case studies are reported to investigate and better understand the role of these functional groups in the adsorption process, since the properties of the synthesized aerogels were significantly affected, regarding their microstructure and surface area. In general, an improvement of the removal efficiency after functionalization of aerogels with amine groups was found, with removal efficiencies higher than 90% for lead and Rubi Levafix CA. To explain the adsorption mechanism, both Langmuir and Freundlich models were applied; chemisorption is most likely the sorption type taking place in the studied cases.

An Opinion Paper on Aerogels for Biomedical and Environmental Applications.

Aerogels are a special class of nanostructured materials with very high porosity and tunable physicochemical properties. Although a few types of aerogels have already reached the market in construction materials, textiles and aerospace engineering, the full potential of aerogels is still to be assessed for other technology sectors. Based on current efforts to address the material supply chain by a circular economy approach and longevity as well as quality of life with biotechnological methods, environmental and life science applications are two emerging market opportunities where the use of aerogels needs to be further explored and evaluated in a multidisciplinary approach. In this opinion paper, the relevance of the topic is put into context and the corresponding current research efforts on aerogel technology are outlined. Furthermore, key challenges to be solved in order to create materials by design, reproducible process technology and society-centered solutions specifically for the two abovementioned technology sectors are analyzed. Overall, advances in aerogel technology can yield innovative and integrated solutions for environmental and life sciences which in turn can help improve both the welfare of population and to move towards cleaner and smarter supply chain solutions.

Chitosan-Silica Composite Aerogel for the Adsorption of Cupric Ions.

A chitosan-silica hybrid aerogel was synthesized and presented as a potential adsorbent for the purification of cupric ion-contaminated media. The combination of the organic polymer (chitosan), which can be obtained from fishery wastes, with silica produced a mostly macroporous material with an average pore diameter of 33 µm. The obtained aerogel was extremely light (56 kg m-3), porous (96% porosity, 17 cm3 g-1 pore volume), and presented a Brunauer-Emmett-Teller surface area (SBET) of 2.05 m2 g-1. The effects of solution pH, aerogel and Cu(II) concentration, contact time, and counterion on cupric removal with the aerogel were studied. Results showed that the initial pH of the cation-containing aqueous solution had very little influence on the removal performance of this aerogel. According to Langmuir isotherm, this material can remove a maximum amount of ca. 40 mg of cupric ions per gram and the kinetic data showed that the surface reaction was the rate-limiting step and equilibrium was quickly reached (in less than one hour). Thus, the approach developed in this study enabled the recovery of waste for the preparation of a novel material, which can be efficiently reused in a new application, namely water remediation.

Retention of Ciprofloxacin and Carbamazepine from Aqueous Solutions Using Chitosan-Based Cryostructured Composites.

Water pollution is becoming a great concern at the global level due to highly polluted effluents, which are charged year by year with increasing amounts of organic residues, dyes, pharmaceuticals and heavy metals. For some of these pollutants, the industrial treatment of wastewater is still relevant. Yet, in some cases, such as pharmaceuticals, specific treatment schemes are urgently required. Therefore, the present study describes the synthesis and evaluation of promising cryostructured composite adsorbents based on chitosan containing native minerals and two types of reinforcement materials (functionalized kaolin and synthetic silicate microparticles). The targeted pharmaceuticals refer to the ciprofloxacin (CIP) antibiotic and the carbamazepine (CBZ) drug, for which the current water treatment process seem to be less efficient, making them appear in exceedingly high concentrations, even in tap water. The study reveals first the progress made for improving the mechanical stability and resilience to water disintegration, as a function of pH, of chitosan-based cryostructures. Further on, a retention study shows that both pharmaceuticals are retained with high efficiency (up to 85.94% CIP and 86.38% CBZ) from diluted aqueous solutions.

A Comparative Thermoacoustic Insulation Study of Silica Aerogels Reinforced with Reclaimed Textile Fibres: Cotton, Polyester and Wool.

Silica aerogels are highly porous materials with exceptional thermal insulation performance. They become even more attractive if combined thermal and acoustic insulation is achieved. Silica aerogel composites reinforced with fibres are an ingenious way to surpass the fragility stemmed from the aerogel's intrinsic porosity, and textile fibres are good sound absorption materials. Reclaimed fibres are a relatively low-cost feedstock and were obtained in this work exclusively through mechanical processes from textile wastes, thus promoting the concept of circular economy, namely for cotton, polyester and wool fibres. These reclaimed fibres were used as reinforcement matrices for silica aerogel composites obtained from sol-gel transformation of tetraethyl orthosilicate and isobutyltriethoxysilane/or vinyltrimethoxysilane precursors and dried at ambient pressure after silylation. Silica aerogel composites reinforced with reclaimed cotton fibres had the best sound absorption coefficient (a peak value of 0.89), while the polyester-reinforced composite exhibited the lowest thermal conductivity (k = ~24 mW m-1 K-1, Hot Disk). The better combined results on thermal and acoustic insulation were achieved by the wool-reinforced composites. The thermal conductivity values were less than 27 mW m-1 K-1, and the sound absorption coefficient achieved a peak value of 0.85. Therefore, the aerogel composites developed here can be selected for thermal or/and acoustic barriers by choosing a suitable type of fibre. Their design and preparation protocol followed environmental-friendly and cost-effective approaches.

Thermomechanical Performance Assessment of Sustainable Buildings' Insulating Materials under Accelerated Ageing Conditions.

The reliable characterization of insulation materials in relevant environmental conditions is crucial, since it strongly influences the performance (e.g., thermal) of building elements. In fact, their properties may vary with the moisture content, temperature, ageing degradation, etc. Therefore, in this work, the thermomechanical behaviour of different materials was compared when subjected to accelerated ageing. Insulation materials that use recycled rubber in their composition were studied, along with others for comparison: heat-pressed rubber, rubber_cork composites, aerogel_rubber composite (developed by the authors), silica aerogel, and extruded polystyrene. The ageing cycles comprised dry-heat, humid-heat, and cold conditions as the stages, during cycles of 3 and 6 weeks. The materials' properties after ageing were compared with the initial values. Aerogel-based materials showed superinsulation behaviour and good flexibility due to their very high porosity and reinforcement with fibres. Extruded polystyrene also had a low thermal conductivity but exhibited permanent deformation under compression. In general, the ageing conditions led to a very slight increase in the thermal conductivity, which vanished after drying of the samples in an oven, and to a decrease in Young's moduli.

Improvement of the Mechanical Properties of Silica Aerogels for Thermal Insulation Applications through a Combination of Aramid Nanofibres and Microfibres.

Reinforcement of silica aerogels, remarkable lightweight mesoporous materials with outstanding insulation performance, is still a challenging research topic. Among the strategies used to overcome their brittleness, one of the most effective is the manufacturing of aerogel composites with embedded fibres. In this work, the incorporation of nanofibres together with microfibres in a tetraethoxysilane-vinyltrimethoxysilane matrix is investigated for the first time for the development of novel aerogel nanocomposites. The nanofibres, synthesized from different aramid fibres, including Kevlar® pulp, Technora®, Teijinconex® and Twaron® fibres, were used in different combinations with microaramids and the resulting nanocomposites were thoroughly investigated for their physicochemical and thermomechanical features. The properties depended on the type and amount of the nano/microfibre used. While the microfibres exhibited low interaction with the silica matrix, the higher surface of the nanofibres ensured increased contact with the gel matrix. A low bulk density of 161 kg m-3 and thermal conductivity of 38.3 mW m-1 K-1 (Hot Disk®) was achieved when combining the nanofibres obtained from Kevlar® pulp with the Technora® or Teijinconex® long fibres. The nanofibres showed higher dispersion and random orientation and in combination with microfibres led to the improvement by a factor of three regarding the mechanical properties of the aerogel nanocomposites reinforced only with microfibres. The scale-up process of the samples and simulated tests of thermal cycling and vacuum outgassing successfully conducted indicate good compliance with space applications.

Carbon Nanostructures-Silica Aerogel Composites for Adsorption of Organic Pollutants.

Silica aerogels are a class of materials that can be tailored in terms of their final properties and surface chemistry. They can be synthesized with specific features to be used as adsorbents, resulting in improved performance for wastewater pollutants' removal. The purpose of this research was to investigate the effect of amino functionalization and the addition of carbon nanostructures to silica aerogels made from methyltrimethoxysilane (MTMS) on their removal capacities for various contaminants in aqueous solutions. The MTMS-based aerogels successfully removed various organic compounds and drugs, achieving adsorption capacities of 170 mg⋅g-1 for toluene and 200 mg⋅g-1 for xylene. For initial concentrations up to 50 mg⋅L-1, removals greater than 71% were obtained for amoxicillin, and superior to 96% for naproxen. The addition of a co-precursor containing amine groups and/or carbon nanomaterials was proven to be a valuable tool in the development of new adsorbents by altering the aerogels' properties and enhancing their adsorption capacities. Therefore, this work demonstrates the potential of these materials as an alternative to industrial sorbents due to their high and fast removal efficiency, less than 60 min for the organic compounds, towards different types of pollutants.

Synthesis of Highly Luminescent Silica-Coated Upconversion Nanoparticles from Lanthanide Oxides or Nitrates Using Co-Precipitation and Sol-Gel Methods.

Upconversion nanoparticles (UCNPs) are under consideration for their use as bioimaging probes with enhanced optical performance for real time follow-up under non-invasive conditions. Photostable and core-shell NaYF4:Yb3+, Er3+-SiO2 UCNPs obtained by a novel and simple co-precipitation method from lanthanide nitrates or oxides were herein synthesized for the first time. The sol-gel Stöber method followed by oven or supercritical gel drying was used to confer biocompatible surface properties to UCNPs by the formation of an ultrathin silica coating. Upconversion (UC) spectra were studied to evaluate the fluorescence of UCNPs upon red/near infrared (NIR) irradiation. ζ-potential measurements, TEM analyses, XRD patterns and long-term physicochemical stability were also assessed and confirmed that the UCNPs co-precipitation synthesis is a shape- and phase-controlling approach. The bio- and hemocompatibility of the UCNPs formulation with the highest fluorescence intensity was evaluated with murine fibroblasts and human blood, respectively, and provided excellent results that endorse the efficacy of the silica gel coating. The herein synthesized UCNPs can be regarded as efficient fluorescent probes for bioimaging purposes with the high luminescence, physicochemical stability and biocompatibility required for biomedical applications.

Aerogel Composites Produced from Silica and Recycled Rubber Sols for Thermal Insulation.

Hydrophobic rubber-silica aerogel panels (21.5 × 21.5 × 1.6 cm3) were fabricated from silica and rubber sols and reinforced with several fiber types (recycled tire textile fibers, polyester blanket, silica felt, glass wool). A recycled rubber sol was prepared using peracetic acid and incorporated for the first time in TEOS-based sol-gel chemistry. The composites exhibited good thermal stability up to 400 °C and very low thermal conductivity, in the superinsulation range when using polyester fibers (16.4 ± 1.0 mW·m-1·K-1), and of 20-30 mW·m-1·K-1 for the remaining fibers. They could also endure cyclic compression loads with near full recovery, thus showing very promising properties for insulation of buildings.

Silica-Based Aerogel Composites Reinforced with Reticulated Polyurethane Foams: Thermal and Mechanical Properties.

In this work, silica aerogel composites reinforced with reticulated polyurethane (PU) foams have been manufactured having densities in the range from 117 to 266 kg/m3 and porosities between 85.7 and 92.3%. Two different drying processes were employed (ambient pressure drying and supercritical drying) and a surface modification step was applied to some of the silica formulations. These composites, together with the reference PU foam and the monolithic silica aerogels, were fully characterized in terms of their textural properties, mechanical properties and thermal conductivities. The surface modification with hexamethyldisilazane (HMDZ) proved to improve the cohesion between the reticulated foam and the silica aerogels, giving rise to a continuous network of aerogel reinforced by a polyurethane porous structure. The samples dried under supercritical conditions showed the best interaction between matrixes as well as mechanical and insulating properties. These samples present better mechanical properties than the monolithic aerogels having a higher elastic modulus (from 130 to 450 kPa), a really exceptional flexibility and resilience, and the capacity of being deformed without breaking. Moreover, these silica aerogel-polyurethane foam (Sil-PU) composites showed an excellent insulating capacity, reaching thermal conductivities as low as 14 mW/(m·K).

Thermal Conductivity of Nanoporous Materials: Where Is the Limit?

Nowadays, our society is facing problems related to energy availability. Owing to the energy savings that insulators provide, the search for effective insulating materials is a focus of interest. Since the current insulators do not meet the increasingly strict requirements, developing materials with a greater insulating capacity is needed. Until now, several nanoporous materials have been considered as superinsulators achieving thermal conductivities below that of the air 26 mW/(m K), like nanocellular PMMA/TPU, silica aerogels, and polyurethane aerogels reaching 24.8, 10, and 12 mW/(m K), respectively. In the search for the minimum thermal conductivity, still undiscovered, the first step is understanding heat transfer in nanoporous materials. The main features leading to superinsulation are low density, nanopores, and solid interruptions hindering the phonon transfer. The second crucial condition is obtaining reliable thermal conductivity measurement techniques. This review summarizes these techniques, and data in the literature regarding the structure and thermal conductivity of two nanoporous materials, nanocellular polymers and aerogels. The key conclusion of this analysis specifies that only steady-state methods provide a reliable value for thermal conductivity of superinsulators. Finally, a theoretical discussion is performed providing a detailed background to further explore the lower limit of superinsulation to develop more efficient materials.

Biological Thermal Performance of Organic and Inorganic Aerogels as Patches for Photothermal Therapy.

Aerogels are materials with unique properties, among which are low density and thermal conductivity. They are also known for their exquisite biocompatibility and biodegradability. All these features make them attractive for biomedical applications, such as their potential use in photothermal therapy (PTT). This technique is, yet, still associated with undesirable effects on surrounding tissues which emphasizes the need to minimize the exposure of healthy regions. One way to do so relies on the use of materials able to block the radiation and the heat generated. Aerogels might be potentially useful for this purpose by acting as insulators. Silica- and pectin-based aerogels are reported as the best inorganic and organic thermal insulators, respectively; thus, the aim of this work relies on assessing the possibility of using these materials as light and thermal insulators and delimiters for PTT. Silica- and pectin-based aerogels were prepared and fully characterized. The thermal protection efficacy of the aerogels when irradiated with a near-infrared laser was assessed using phantoms and ex vivo grafts. Lastly, safety was assessed in human volunteers. Both types presented good textural properties and safe profiles. Moreover, thermal activation unveils the better performance of silica-based aerogels, confirming the potential of this material for PTT.

Ligands as copper and nickel ionophores: Applications and implications on wastewater treatment.

Modern society depends on many finite natural resources, from which metals are of great importance. Copper and nickel's relevance is due to their vast applications, resulting in high market value and demand. As such, their polluting emissions are also significant and their removal from wastewaters is imperative. Moreover, effluent treatment techniques can be used to recover the metallic cations, via selective processes. In this review, copper and nickel selective ligands in the literature are surveyed. These are most commonly Schiff bases, along with crown ethers and porphyrins. They are usually employed in ion sensing (colorimetric chemosensors or electrodes) with great success - the disruption in response of colorimetric sensors is up to 7% and binding constants are usually at least one order of magnitude greater with the desired cation than with interferents. However, modified adsorbents are also reported. The possibilities of using ionophores in wastewater cleaning, allowing the treatment of effluents and the selective recovery of valuable materials, and their implications on new green policies is discussed.