The Chemistry of Chelation for Built Heritage Cleaning: The Removal of Copper and Iron Stains.

Chelators are widely used in conservation treatments to remove metal stains from marble, travertine, and limestone surfaces. In the current review the chemical aspects underlying the use of chelators for the removal of copper and iron stains from built heritage are described and clear criteria for the selection of the most efficient stain removal treatment are given. The main chelator structural features are outlined and the operating conditions for effective metal stain removal (pH, time of application, etc.) discussed, with a particular emphasis on the ability to form stable metal complexes, the high selectivity towards the metal that should be removed, and the high sustainability for the environment. Dense matrices often host chelators for higher effectiveness, and further research is required to clarify their role in the cleaning process. Then, relevant case studies of copper and iron stain removal are discussed. On these bases, the most effective chelators for copper and stain removal are indicated, providing chemists and conservation scientists with scientific support for conservation operations on stone works of art and opening the way to the synthesis of new chelators.

PFAS-free superhydrophobic chitosan coating for fabrics.

In view of health and environmental concerns, together with the upcoming restrictive regulations on per- and polyfluoroalkyl substances (PFAS), less impactful materials must be explored for the hydrophobization of surfaces. Polysaccharides, and especially chitosan, are being explored for their desirable properties of film formation and ease of modification. We present a PFAS-free chitosan superhydrophobic coating for textiles deposited through a solvent-free method. By contact angle analysis and drop impact, we observe that the coating imparts hydrophobicity to the fabrics, reaching superhydrophobicty (θA = 151°, θR = 136°) with increased amount of coating (from 1.6 g/cm2). This effect is obtained by the combination of chemical water repellency of the modified chitosan and the nano- and micro-roughness, assessed by SEM analysis. We perform a comprehensive study on the durability of the coatings, showing good results especially for acidic soaking where the hydrophobicity is maintained until the 8th cycle of washing. We assess the degradation of the coating by a TGA-IR investigation to define the compounds released with thermal degradation, and we confirm the coating's biodegradability by biochemical oxygen consumption. Finally, we demonstrate its biocompatibility on keratinocytes (HaCaT cell line) and fibroblasts (HFF-1 cell line), confirming that the coating is safe for human skin cells.

Recent Advances on Porous Siliceous Materials Derived from Waste.

In recent years, significant efforts have been made in view of a transition from a linear to a circular economy, where the value of products, materials, resources, and waste is maintained as long as possible in the economy. The re-utilization of industrial and agricultural waste into value-added products, such as nanostructured siliceous materials, has become a challenging topic as an effective strategy in waste management and a sustainable model aimed to limit the use of landfill, conserve natural resources, and reduce the use of harmful substances. In light of these considerations, nanoporous silica has attracted attention in various applications owing to the tunable pore dimensions, high specific surface areas, tailorable structure, and facile post-functionalization. In this review, recent progress on the synthesis of siliceous materials from different types of waste is presented, analyzing the factors influencing the size and morphology of the final product, alongside different synthetic methods used to impart specific porosity. Applications in the fields of wastewater/gas treatment and catalysis are discussed, focusing on process feasibility in large-scale productions.

Synthesis and Characterization of Alkoxysilane-Bearing Photoreversible Cinnamic Side Groups: A Promising Building-Block for the Design of Multifunctional Silica Nanoparticles.

The present study reports on the synthesis of a new alkoxysilane-bearing light-responsive cinnamyl group and its application as a surface functionalization agent for the development of SiO2 nanoparticles (NPs) with photoreversible tails. In detail, cinnamic acid (CINN) was activated with N-hydroxysuccinimide (NHS) to obtain the corresponding NHS-ester (CINN-NHS). Subsequently, the amine group of 3-aminopropyltriethoxysilane (APTES) was acylated with CINN-NHS leading to the generation of a novel organosilane, CINN-APTES, which was then exploited for decorating SiO2 NPs. The covalent bond to the silica surface was confirmed by solid state NMR, whereas thermogravimetric analysis unveiled a functionalization degree much higher compared to that achieved by a conventional double-step post-grafting procedure. In light of these intriguing results, the strategy was successfully extended to naturally occurring sepiolite fibers, widely employed as fillers in technological applications. Finally, a preliminary proof of concept of the photoreversibility of the obtained SiO2@CINN-APTES system has been carried out through UV diffuse reflectance. The overall outcomes prove the consistency and the versatility of the methodological protocol adopted, which appears promising for the design of hybrid NPs to be employed as building blocks for photoresponsive materials with the ability to change their molecular structure and subsequent properties when exposed to different light stimuli.

Magnetic Composites of Dextrin-Based Carbonate Nanosponges and Iron Oxide Nanoparticles with Potential Application in Targeted Drug Delivery.

Magnetically driven nanosponges with potential application as targeted drug delivery systems were prepared via the addition of magnetite nanoparticles to the synthesis of cyclodextrin and maltodextrin polymers crosslinked with 1,1'-carbonyldiimidazole. The magnetic nanoparticles were obtained separately via a coprecipitation mechanism involving inorganic iron salts in an alkaline environment. Four composite nanosponges were prepared by varying the content of magnetic nanoparticles (5 wt% and 10 wt%) in the cyclodextrin- and maltodextrin-based polymer matrix. The magnetic nanosponges were then characterised by FTIR, TGA, XRD, FESEM, and HRTEM analysis. The magnetic properties of the nanosponges were investigated via magnetisation curves collected at RT. Finally, the magnetic nanosponges were loaded with doxorubicin and tested as a drug delivery system. The nanosponges exhibited a loading capacity of approximately 3 wt%. Doxorubicin was released by the loaded nanosponges with sustained kinetics over a prolonged period of time.

The "Lab4treat" Outreach Experience: Preparation of Sustainable Magnetic Nanomaterials for Remediation of Model Wastewater.

The Lab4treat experience has been developed to demonstrate the use of magnetic materials in environmental applications. It was projected in the frame of the European project Mat4Treat, and it was tested several times in front of different audiences ranging from school students to the general public in training and/or divulgation events. The experience lends itself to discuss several aspects of actuality, physics and chemistry, which can be explained by modulating the discussion depth level, in order to meet the interests of younger or more experienced people and expand their knowledge. The topic is relevant, dealing with the recycling of urban waste and water depollution. The paper is placed within the field of water treatment for contaminant removal; therefore, a rich collection of recent (and less recent) papers dealing with magnetic materials and environmental issues is described in the Introduction section. In addition, the paper contains a detailed description of the experiment and a list of the possible topics which can be developed during the activity. The experimental approach makes the comprehension of scientific phenomena effective, and, from this perspective, the paper can be considered to be an example of interactive teaching.

Waste Cleaning Waste: Combining Alginate with Biowaste-Derived Substances in Hydrogels and Films for Water Cleanup.

Biowaste-derived substances isolated from green compost (BBS-GC) are environmentally friendly reactants similar to humic substances, which contain multiple functionalities, that are suitable for adsorbing different kinds of pollutants in wastewater. Herein, sodium alginate (derived from brown algae) cross-linked with both Ca2+ ions and BBS-GC in the form of hydrogels and dried films are proposed as green, easy-to-form, and handleable materials for tertiary water treatments. The results show that both hydrogels and films are mechanically stable and can effectively remove differently charged dyes through an adsorption mechanism that can be described by the Freundlich model. BBS-GC-containing gels always performed better than samples prepared without BBS-GC, revealing that such unconventional materials can integrate waste valorization and water decontamination, potentially providing social and environmental benefits.

Chitosan-derived biochars obtained at low pyrolysis temperatures for potential application in electrochemical energy storage devices.

N-rich biochars were obtained via pyrolysis treatment of chitosan (a low-cost biopolymer from natural biomasses) at mild conditions (in the 284 °C-540 °C range), thus offering an energy efficient and low carbon footprint synthesis. These low surface area N-doped biochars were morphologically and physicochemically characterized, and tested as hosting material in lithium-sulfur (Li-S) batteries. Sulfur/biochars cathodes thus obtained showed good capacity retention and improved Coulombic efficiency compared to a standard N-rich high surface area carbon and multiwalled carbon nanotubes (MWCNT) reference substrates. Such enhanced electrochemical properties are attributable to the better retention of Li polysulfides by means of the residual functionalities still present in the biochars, thus making the valorization of chitosan potentially appealing even in the industrial sector related to the development of energy storage devices.

Cementitious composite materials for thermal energy storage applications: a preliminary characterization and theoretical analysis.

The lack of robust and low-cost sorbent materials still represents a formidable technological barrier for long-term storage of (renewable) thermal energy and more generally for Adsorptive Heat Transformations-AHT. In this work, we introduce a novel approach for synthesizing cement-based composite sorbent materials. In fact, considering the number of available hygrosopic salts that can be accommodated into a cementitious matrix-whose morphological properties can be also fine-tuned-the new proposed in situ synthesis paves the way to the generation of an entire new class of possible sorbents for AHT. Here, solely focusing on magnesium sulfate in a class G cement matrix, we show preliminary morphological, mechanical and calorimetric characterization of sub-optimal material samples. Our analysis enables us to theoretically estimate one of the most important figures of merit for the considered applications, namely the energy density which was found to range within 0.088-0.2 GJ/m3 (for the best tested sample) under reasonable operating conditions for space heating applications and temperate climate. The above estimates are found to be lower than other composite materials in the literature. Nonetheless, although no special material optimization has been implemented, our samples already compare favourably with most of the known materials in terms of specific cost of stored energy. Finally, an interesting aspect is found in the ageing tests under water sorption-desorption cycling, where a negligible variation in the adsorption capability is demonstrated after over one-hundred cycles.

An Analytical Mini-Review on the Compression Strength of Rubberized Concrete as a Function of the Amount of Recycled Tires Crumb Rubber.

Since waste tires constitute a serious environmental concern, several studies are devoted to the use of finely divided recycled rubber for the production of rubberized concrete by partial substitution of the mineral aggregate fraction. The introduction of rubber into concrete presents several advantages (e.g., improvement of toughness and thermal/electrical/acoustic insulation capacities). Unfortunately, the addition of a high content of rubber into concrete causes an important loss of mechanical resistance of the final composite. In this context, several scientific studies are devoted to investigate the best technical solutions for favoring the interfacial adhesion between rubber and cement paste, but the interpretation of the literature is often misleading. To overcome this issue, the metadata extrapolated from the single scientific works were critically re-analyzed, forming reference diagrams where the variability fields of the different rubber concrete formulations (in terms of mechanical responses as a function of the rubber content) were defined and the best performances discussed. This study evidenced the twofold role of reference diagrams, able in both presenting the data in an unambiguous manner (for a successful comparison) and providing the guidelines for future works in this research field.

The Innovation Comes from the Sea: Chitosan and Alginate Hybrid Gels and Films as Sustainable Materials for Wastewater Remediation.

The growing utilization of renewable and residual biomasses for environmental preservation and remediation are important goals to be pursued to minimize the environmental impact of human activities. In this paper, sodium alginate (derived from brown algae) was crosslinked using chitosan (mainly derived from the exoskeleton of crustaceans) in the presence of biowaste-derived substances isolated from green compost (BBS-GC), to produce hydrogels and dried films. The obtained materials were tested as adsorbents for wastewater remediation. To this purpose, gels were characterized using a multi-analytical approach and used as active substrates for the removal of three differently-charged molecules, chosen as model pollutants: crystal violet, rhodamine B, and orange II. The effectiveness of the gel formulations was demonstrated and attributed to the variety of active functionalities introduced by the different precursors, the structural factors and the peculiar physicochemical properties of the resulting materials.

Sustainable Magnetic Materials (from Chitosan and Municipal Biowaste) for the Removal of Diclofenac from Water.

The photodegradation of an aqueous solution of diclofenac (DCF) has been attempted in the presence of hydrogen peroxide and organic/inorganic hybrid magnetic materials under simulated and real solar light. The hybrid magnetic materials have been prepared via coprecipitation synthesis starting from iron(II) and iron(III) inorganic salts in the presence of bioderived organic products (i.e., chitosan or bio-based substances isolated from commercially available composted urban biowastes) acting as stabilizers of the iron-containing phase. In addition to the as prepared hybrid materials, the corresponding materials obtained after a pyrolytic step at low temperature (550 °C) have been tested. The obtained results evidenced the capability of the materials to activate hydrogen peroxide at mild pH promoting DCF (photo) degradation. All the materials feature also as adsorbents since a decrease of DCF is observed also when working in the dark and in the absence of hydrogen peroxide.

Tips and Tricks for the Surface Engineering of Well-Ordered Morphologically Driven Silver-Based Nanomaterials.

Particularly-shaped silver nanostructures are successfully applied in many scientific fields, such as nanotechnology, catalysis, (nano)engineering, optoelectronics, and sensing. In recent years, the production of shape-controlled silver-based nanostructures and the knowledge around this topic has grown significantly. Hence, on the basis of the most recent results reported in the literature, a critical analysis around the driving forces behind the synthesis of such nanostructures are proposed herein, pointing out the important role of surface-regulating agents in driving crystalline growth by favoring (or opposing) development along specific directions. Additionally, growth mechanisms of the different morphologies considered here are discussed in depth, and critical points highlighted.

The Effects of Conflict on Fertility: Evidence From the Genocide in Rwanda.

Our study analyzes the fertility effects of the 1994 genocide in Rwanda. We study the effects of violence on both the duration time to the first birth in the early post-genocide period and on the total number of post-genocide births per woman up to 15 years following the conflict. We use individual-level data from Demographic and Health Surveys, estimating survival and count data models. This article contributes to the literature on the demographic effects of violent conflict by testing two channels through which conflict influences fertility: (1) the type of violence exposure as measured by the death of a child or sibling, and (2) the conflict-induced change in local demographic conditions as captured by the change in the district-level sex ratio. Results indicate the genocide had heterogeneous effects on fertility, depending on the type of violence experienced by the woman, her age cohort, parity, and the time horizon (5, 10, and 15 years after the genocide). There is strong evidence of a child replacement effect. Having experienced the death of a child during the genocide increases both the hazard of having a child in the five years following the genocide and the total number of post-genocide births. Experiencing sibling death during the genocide significantly lowers post-genocide fertility in both the short-run and the long-run. Finally, a reduction in the local sex ratio negatively impacts the hazard of having a child in the five years following the genocide, especially for older women.

Block copolymers for designing nanostructured porous coatings.

Highly ordered porous coatings find applications in many fields, such as nanotechnology, microfluidics and nanofluidics, membrane separation, and sensing. In recent years, there has been great interest regarding the synthesis of isoporous and well-ordered (in)organic coatings for the production of highly selective functional membranes. Among the different strategies that have been proposed to date for preparing these porous thin coatings, one simple route involves the use of self-assembled amphiphilic block copolymers either as the porogen (acting as sacrificial templating agents for the production of inorganic architectures) or as a source of the porogen (by self-assembly for the production of polymeric substrates). Therefore, an extended discussion around the exploitation of block copolymers is proposed here in this review, using polystyrene-block-polyethylene oxide (PS-b-PEO) as the model substrate, and critical points are highlighted.

New Insights on the Photodegradation of Caffeine in the Presence of Bio-Based Substances-Magnetic Iron Oxide Hybrid Nanomaterials.

The exploitation of organic waste as a source of bio-based substances to be used in environmental applications is gaining increasing interest. In the present research, compost-derived bio-based substances (BBS-Cs) were used to prepare hybrid magnetic nanoparticles (HMNPs) to be tested as an auxiliary in advanced oxidation processes. Hybrid magnetic nanoparticles can be indeed recovered at the end of the treatment and re-used in further water purification cycles. The research aimed to give new insights on the photodegradation of caffeine, chosen as marker of anthropogenic pollution in natural waters, and representative of the contaminants of emerging concern (CECs). Hybrid magnetic nanoparticles were synthetized starting from Fe(II) and Fe(III) salts and BBS-C aqueous solution, in alkali medium, via co-precipitation. Hybrid magnetic nanoparticles were characterized via X-ray diffraction (XRD), thermo-gravimetric analysis (TGA) and Fourier transform infrared (FTIR) spectroscopy. The effect of pH, added hydrogen peroxide, and dissolved oxygen on caffeine photodegradation in the presence of HMNPs was assessed. The results allow for the hypothesis that caffeine abatement can be obtained in the presence of HMNPs and hydrogen peroxide through a heterogeneous photo-Fenton mechanism. The role of hydroxyl radicals in the process was assessed examining the effect of a selective hydroxyl radical scavenger on the caffeine degradation kinetic.

From biowaste to magnet-responsive materials for water remediation from polycyclic aromatic hydrocarbons.

Composted urban biowaste-derived substances (BBS-GC) are used as carbon sources for the preparation of carbon-coated magnet-sensitive nanoparticles obtained via co-precipitation method and the subsequent thermal treatment at 550 °C under nitrogen atmosphere. A multitechnique approach has been applied to investigate the morphology, magnetic properties, phase composition, thermal stability of the obtained magnet-sensitive materials. In particular, pyrolysis-induced modifications affecting the BBS-GC/carbon shell were highlighted. The adsorption capacity of such bio-derivative magnetic materials for the removal of hydrophobic contaminants such as polycyclic aromatic hydrocarbons was evaluated in order to verify their potential application in wastewater remediation process. The promising results suggest their use as a new generation of magnet-responsive easily-recoverable adsorbents for water purification treatments.

Packed hybrid silica nanoparticles as sorbents with thermo-switchable surface chemistry and pore size for fast extraction of environmental pollutants.

Thermoresponsive poly(N-isopropylacrylamide)-grafted silica nanoparticles (SiNPs) have been synthesized and fully characterized by ATR-FTIR, TGA, HRTEM, BET and DLS analysis. Hybrid solid phase extraction (SPE) beds with tuneable pore size and switchable surface chemistry were prepared by packing the polymer-grafted nanoparticles inside SPE cartridges. The cartridges were tested by checking the thermo-regulated elution of model compounds, namely methylene blue, caffeine and amoxicillin. Extraction of the analytes and regeneration of the interaction sites on the sorbent surface was carried out entirely in water solution by changing the external temperature below and above the lower critical solution temperature (LCST) of the polymer. The results demonstrate that the elution of model compounds depends on the temperature-regulated size of the inter-particle voids and on the change of surface properties of the PNIPAM-grafted nanoparticles from hydrophilic to hydrophobic.

Sustainable magnet-responsive nanomaterials for the removal of arsenic from contaminated water.

In this study, chitosan and bio-based substances (BBS) obtained from composted biowaste were used as stabilizers for the synthesis of magnet-sensitive nanoparticles (NPs) via coprecipitation method. A pyrolysis treatment was carried out on both biopolymers at 550°C, and their consequent conversion into a carbon matrix was followed by means of different physicochemical characterization techniques (mainly FTIR spectroscopy and XRD), whereas magnetic properties were evaluated by magnetization curves. The prepared materials were tested in water remediation processes from arsenic (As) species (both inorganic and organic forms). These tests, explained by means of the most common adsorption models, evidenced that the best performances were reached by both materials obtained after pyrolysis treatments, pointing out the promising application of such magnet-sensitive materials as easy-recoverable tools for water purification treatments.

Reactive Hypersaline Route: One-Pot Synthesis of Porous Photoactive Nanocomposites.

Herein, porous photoactive nanocomposites are prepared by a simple one-pot synthesis approach using a salt and aqueous media. Within this reactive hypersaline route, the salt not only serves in the structuring of the composite but also becomes an integral active part of it. Here, the addition of sodium thiocyanate to a titania precursor guides, on the one hand, the formation of needle-shaped nanoparticles and, on the other hand, forms yellow compound isoperthiocyanic acid, which is homogeneously incorporated into the porous nanocomposite. Compared to a pure titania reference, this material reveals a 7-fold-increased photodegradation rate of Rhodamine B as a model compound. This reveals the reactive hypersaline route to be a promising and facile synthesis route toward photoactive porous materials.