Search

Titanium dioxide (TiO2) nanoparticles are extremely attractive materials for numerous applications, especially in the anatase form. We have made these shaped, ＜10 nm anatase nanoparticles (NPs) via the supercritical (SC) drying of a titania sol, made by a “green” aqueous sol–gel nanosynthesis route. The SC drying was carried out in alcohol at 255–260 °C, and no further heating or processing of the NPs was required. The true phase composition (crystalline and amorphous phases) and the microstructure of the NPs was thoroughly characterised by the advanced X-ray methods, such as Rietveld-reference intensity ratio (RIR) and the whole powder pattern modelling (WPPM) technique, and HR-TEM analysis. Furthermore, the NPs were also characterised by Raman, FT-IR and optical spectroscopy. These anatase NPs showed themselves to exhibit a truncated tetragonal bipyramidal shape, exposing the {101} (side) and {001} (top) faces. They had a euhedral crystal habit, with sharply defined and easily recognised faces, and were very homogeneous and monodisperse in both shape and size. The photocatalytic activity (PCA) of the samples was assessed in gas–solid phase by monitoring the degradation of nitrogen oxides (NOx), a major atmospheric pollutant. Results showed that the particular shape of these anatase NPs played a key role in their photocatalytic behaviour. In fact, these truncated tetragonal bipyramidal nanocrystals exhibited an enhanced photocatalytic activity, double that of spherical anatase NPs of a similar size reported previously by the authors. This was attributed to the exposure of mainly the {101} and, to a lesser extent, {001} crystal faces, which are more reactive under photocatalysis for redox reactions. [ABSTRACT FROM AUTHOR]

Abstract: The production of MgAl2O4 spinel is evaluated using a thermochemical program, THOR, which calculates the equilibrium products resulting from the adiabatic combustion (isobaric and isochoric) or detonation of energetic materials. A classic metalized emulsion was used (ammonium nitrate, fuel oil, aluminium, water and glass microballoons), to which MgO was added. The Al/MgO proportion and the reaction regime were varied, the maximum spinel yield being achieved for the detonation of a fuel-rich emulsion with 5Al:3MgO (mol). In parallel, MgAl2O4 was experimentally synthesized by solution combustion of Al and Mg nitrates with various urea contents. The same reactions were simulated with THOR and the results obtained for products type and amounts were found to be in good agreement. Additionally, THOR simulations provided clear explanations for the experimental observations, which can be of invaluable help in the selection of fuel type and content in solution combustion synthesis of any given mixed oxide. [Copyright &y& Elsevier]

The presence of pharmaceuticals in urban freshwater has been considered an emerging issue. Although rivers are better studied, the streams crossing the cities, which are prone to higher concentrations of pharmaceuticals, and with a higher potential to affect animals, plant and human health, were never specifically addressed in a review. Thus, here we performed a literature review on the existing pharmaceutical contamination and impacts of these compounds in the urban stream ecosystems. To structure the review, 10 questions were designed. From a total of 206 scientific publications, only 51 addressed the issue of pharmaceuticals in urban streams compared to 180 studies in the larger urban rivers. In 49 urban streams located in 13 countries and four continents, 139 pharmaceuticals from ten therapeutic groups were found. Anti-inflammatories and anticonvulsants were detected in the largest number of countries and urban streams, but the latter was more frequent in the streams. Metabolites were also detected, sometimes in higher concentrations than the original pharmaceutical but they were seldom analysed. The pharmaceuticals that caused more effects in the aquatic organisms were 17β-estradiol, estriol, estrone, acetaminophen, caffeine, carbamazepine, diltiazem, diphenhydramine, fluoxetine, norfluoxetine, sertraline, desmethylsertraline, methylphenidate and ciprofloxacin. The effects were varied, from bioaccumulation, endocrine disruption, impaired growth, reproduction inhibition, increased mortality and hatching disorder to morphological alterations, and decreased gross primary production and biomass. Streams had a higher mixture risk compared to the rivers. Important knowledge gaps detected are the low frequency of analysis of metabolites, the inefficient treatment of urban sewage regarding pharmaceuticals and the reduced number of studies on the impacts of pharmaceuticals at the aquatic community/population and functional level., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

Aerogel scaffolds are nanostructured materials with beneficial properties for tissue engineering applications. The tracing of the state of the aerogels after their implantation is challenging due to their variable biodegradation rate and the lack of suitable strategies capable of in vivo monitoring the scaffolds. Upconversion nanoparticles (UCNPs) have emerged as advanced tools for in vitro bioimaging because of their fluorescence properties. In this work, highly fluorescent UCNPs were loaded into aerogels to obtain theranostic implants for tissue engineering and bioimaging applications. 3D-printed alginate-hydroxyapatite aerogels labeled with UCNPs were manufactured by 3D-printing and supercritical CO 2 drying to generate personalize-to-patient aerogels. The physicochemical performance of the resulting structures was evaluated by printing fidelity measurements, nitrogen adsorption-desorption analysis, and different microscopies (confocal, transmission and scanning electron microscopies). Stability of the aerogels in terms of physicochemical properties was also tested after 3 years of storage. Biocompatibility was evaluated in vitro by different cell and hemocompatibility assays, in ovo and in vivo by safety and bioimaging studies using different murine models. Cytokines profile, tissue index and histological evaluations of the main organs unveiled an in vivo downregulation of the inflammation after implantation of the scaffolds. UCNPs-decorated aerogels were first-time manufactured and long-term traceable by fluorescence-based bioimaging until 3 weeks post-implantation, thereby endorsing their suitability as tissue engineering and theranostic nanodevices (i.e. bifunctional implants)., Competing Interests: All authors disclose no actual or potential conflict of interest related with any financial and personal relationships with other people or organizations that could inappropriately influence, or be perceived to influence, this work., (© 2024 The Authors.)

In recent decades, plastic waste management has become one of the main environmental challenges for today's society. The excessive consumption of so-called single-use plastics causes continuous damage to ecosystems, and it is necessary to find alternatives to recycle these products. In this work, a mechanical and hygrothermal characterisation of novel plaster composites incorporating LDPE waste in their interior was carried out. Thus, prefabricated plasterboards have been designed with a partial replacement of the original raw material with recycled LDPE in percentages of 5-10-15% by volume. The results show how these new composites exceeded the 0.18 kN minimum breaking load in panels in all cases, while decreases in density and thermal conductivity of up to 15% and 21%, respectively, were obtained. In addition, an increase of 3.8%in thermal resistance was obtained by incorporating these new gypsum boards in lightweight façade walls through simulations. In this way, a new pathway was explored for the recovery of these wastes and their subsequent application in the construction sector.

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 cm 3 g -1 pore volume), and presented a Brunauer-Emmett-Teller surface area ( S BET ) of 2.05 m 2 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.

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.

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 NaYF 4 :Yb 3+ , Er 3+ -SiO 2 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.

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.

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.

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.

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, R S/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.

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.

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.

Hydrophobic rubber-silica aerogel panels (21.5 × 21.5 × 1.6 cm 3 ) 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.

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.

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.

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/m 3 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).

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.

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., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Background: Dementia due to Alzheimer's disease (AD) is a complex neurodegenerative disorder, which much of heritability remains unexplained. At the clinical level, one of the most common physiological alterations is the slowing of oscillatory brain activity, measurable by electroencephalography (EEG). Relative power (RP) at the conventional frequency bands (i.e., delta, theta, alpha, beta-1, and beta-2) can be considered as AD endophenotypes., Objective: The aim of this work is to analyze the association between sixteen genes previously related with AD: APOE, PICALM, CLU, BCHE, CETP, CR1, SLC6A3, GRIN2 β, SORL1, TOMM40, GSK3 β, UNC5C, OPRD1, NAV2, HOMER2, and IL1RAP, and the slowing of the brain activity, assessed by means of RP at the aforementioned frequency bands., Methods: An Iberian cohort of 45 elderly controls, 45 individuals with mild cognitive impairment, and 109 AD patients in the three stages of the disease was considered. Genomic information and brain activity of each subject were analyzed., Results: The slowing of brain activity was observed in carriers of risk alleles in IL1RAP (rs10212109, rs9823517, rs4687150), UNC5C (rs17024131), and NAV2 (rs1425227, rs862785) genes, regardless of the disease status and situation towards the strongest risk factors: age, sex, and APOE ɛ4 presence., Conclusion: Endophenotypes reduce the complexity of the general phenotype and genetic variants with a major effect on those specific traits may be then identified. The found associations in this work are novel and may contribute to the comprehension of AD pathogenesis, each with a different biological role, and influencing multiple factors involved in brain physiology.