Dual-Responsive Hydrogels for Mercury Ion Detection and Removal from Wastewater.

This study describes the development of a fast and cost-effective method for the detection and removal of Hg2+ ions from aqueous media, consisting of hydrogels incorporating chelating agents and a rhodamine derivative (to afford a qualitative evaluation of the heavy metal entrapment inside the 3D polymeric matrix). These hydrogels, designed for the simultaneous detection and entrapment of mercury, were obtained through the photopolymerization of 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPSA) and N-vinyl-2-pyrrolidone (NVP), utilizing N,N'-methylenebisacrylamide (MBA) as crosslinker, in the presence of polyvinyl alcohol (PVA), a rhodamine B derivative, and one of the following chelating agents: phytic acid, 1,3-diamino-2-hydroxypropane-tetraacetic acid, triethylenetetramine-hexaacetic acid, or ethylenediaminetetraacetic acid disodium salt. The rhodamine derivative had a dual purpose in this study: firstly, it was incorporated into the hydrogel to allow the qualitative evaluation of mercury entrapment through its fluorogenic switch-off abilities when sensing Hg2+ ions; secondly, it was used to quantitatively evaluate the level of residual mercury from the decontaminated aqueous solutions, via the UV-Vis technique. The ICP-MS analysis of the hydrogels also confirmed the successful entrapment of mercury inside the hydrogels and a good correlation with the UV-Vis method.

Nanocomposite Hydrogel Films Based on Sequential Interpenetrating Polymeric Networks as Drug Delivery Platforms.

In this study, novel materials have been obtained via a dual covalent and ionic crosslinking strategies, leading to the formation of a fully interpenetrated polymeric network with remarkable mechanical performances as drug delivery platforms for dermal patches. The polymeric network was obtained by the free-radical photopolymerization of N-vinylpyrrolidone using tri(ethylene glycol) divinyl ether as crosslinker in the presence of sodium alginate (1%, weight%). The ionic crosslinking was achieved by the addition of Zn2+, ions which were coordinated by the alginate chains. Bentonite nanoclay was incorporated in hydrogel formulations to capitalize on its mechanical reinforcement and adsorptive capacity. TiO2 and ZnO nanoparticles were also included in two of the samples to evaluate their influence on the morphology, mechanical properties and/or the antimicrobial activity of the hydrogels. The double-crosslinked nanocomposite hydrogels presented a good tensile resistance (1.5 MPa at 70% strain) and compression resistance (12.5 MPa at a strain of 70%). Nafcillin was loaded into nanocomposite hydrogel films with a loading efficiency of up to 30%. The drug release characteristics were evaluated, and the profile was fitted by mathematical models that describe the physical processes taking place during the drug transfer from the polymer to a PBS (phosphate-buffered saline) solution. Depending on the design of the polymeric network and the nanofillers included, it was demonstrated that the nafcillin loaded into the nanocomposite hydrogel films ensured a high to moderate activity against S. aureus and S. pyogenes and no activity against E. coli. Furthermore, it was demonstrated that the presence of zinc ions in these polymeric matrices can be correlated with the inactivation of E. coli.

Nafcillin-Loaded Photocrosslinkable Nanocomposite Hydrogels for Biomedical Applications.

Skin infections are frequently treated via intravenous or oral administration of antibiotics, which can lead to serious adverse effects and may sometimes contribute to the proliferation of resistant bacterial strains. Skin represents a convenient pathway for delivering therapeutic compounds, ensured by the high number of blood vessels and amount of lymphatic fluids in the cutaneous tissues, which are systematically connected to the rest of the body. This study provides a novel, straightforward method to obtain nafcillin-loaded photocrosslinkable nanocomposite hydrogels and demonstrates their performance as drug carriers and antimicrobial efficacy against Gram-positive bacteria. The novel formulations obtained, based on polyvinylpyrrolidone, tri(ethylene glycol) divinyl ether crosslinker, hydrophilic bentonite nanoclay, and/or two types of photoactive (TiO2 and ZnO) nanofillers, were characterized using various analytical methods (transmission electron microscopy (TEM), scanning electron microscopy-energy-dispersive X-ray analysis (SEM-EDX), mechanical tests (tension, compression, and shear), ultraviolet-visible spectroscopy (UV-Vis), swelling investigations, and via specific microbiological assays ("agar disc diffusion method" and "time-kill test"). The results reveal that the nanocomposite hydrogel possessed high mechanical resistance, good swelling abilities, and good antimicrobial activity, demonstrating a decrease in the bacteria growth between 3log10 and 2log10 after one hour of direct contact with S. aureus.

"Green" PBX Formulations Based on High Explosives (RDX and HMX) and Water-Soluble pH-Sensitive Polymeric Binders.

The increasingly harsher and more complex international and European environmental legislation drives the current development of "greener" energetics materials and munitions. The aerospace and defense industries rely on extensive research in the formulation and scale-up production of polymer-bonded explosives (PBX). In this context, this paper aims to present a versatile method for obtaining "green" PBX formulations based on two high explosives (hexogen (RDX) and octogen (HMX)) and acrylic acid-ethyl acrylate copolymeric binders. This study developed an innovative "eco-friendly" technology for coating the RDX and HMX crystals, allowing straightforward and safer manufacture of PBX, avoiding the use of traditional organic solvents. At the same time, these polymeric binders are soluble in water at a slightly alkaline pH and insoluble at acidic or neutral pH, thus ensuring a safer manipulation of the energetic materials during their entire life cycle and a facile recovery of the explosive in its original shape and morphology in demilitarization. The PBX formulations were characterized via specific analytical tools to evaluate the influence of their composition on the safety and performance characteristics: scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FT-IR), alkaline pH solubility tests, differential thermal analysis (DTA), impact sensitivity test (BAM Fall Hammer Test), friction sensitivity test (BAM Friction Test), electrostatic sensitivity test (ESD), vacuum stability test, small scale shock reactivity test (SSRT), detonation velocity test. The "green" PBX formulations obtained through a simple and innovative coating method, based on the polymeric binders' adjustable water solubility, demonstrated remarkable energetic performances and a facile recovery of the explosive crystals by the dissolution of the polymeric binder at pH 11 and 30 °C.

Effect of Aromatic Chain Extenders on Polyurea and Polyurethane Coatings Designed for Defense Applications.

The present work describes the synthesis of new versatile polyurea (PU) and polyurethane (PUR) matrices, including different chain extenders, which facilitate the design of distinct, tunable properties, and high-performance derivatives. These polymers can be used for various defense and security applications, such as coatings for ballistic protection, CBRN protection, binders for energetic formulations, etc. Combining aliphatic and aromatic molecules in PU or PUR structures enables the synthesis of polymers with improved and controllable thermo-mechanical properties. Thus, for polyurea synthesis, we utilized two types of polymeric aliphatic diamines and three types of aromatic chain extenders (1,1'-biphenyl-4,4'-diamine, benzene-1,2-diamine, and 1,2-diphenylhydrazine). An analogous method was used to synthesize polyurethane films by employing one polymeric aliphatic polyol and three types of aromatic chain extenders (benzene-1,3-diol, benzene-1,4-diol, and benzene-1,2,3-triol). Subsequently, various analytic techniques (Fourier transform infrared spectroscopy-attenuated total reflectance (FTIR-ATR), single cantilever dynamic mechanical analysis (DMA), thermogravimetric analysis (TGA), frequency-dependent shear modulus survey, tensile tests, water contact angle measurements, and scanning electron microscopy (SEM) with energy-dispersive X-ray analysis (EDX)) have been utilized to characterize the synthesized materials and to evaluate the influence of each chain extender on their final properties.

The Influence of Potassium Salts Phase Stabilizers and Binder Matrix on the Properties of Novel Composite Rocket Propellants Based on Ammonium Nitrate.

The environmental impact and availability of ingredients are vital for the new generation of rocket propellants. In this context, several novel composite propellants were prepared based on the "greener" oxidizer phase-stabilized ammonium nitrate (PSAN), a micronized aluminum-magnesium alloy fuel, iron oxide powder burn rate modifier, triethylene glycol dinitrate (TEGDN) energetic plasticizer and a polyurethane (PU) binder. The novelty of this study is brought by the innovative procedure of synthesizing and combining the constituents of these heterogeneous compositions to obtain high-performance "eco-friendly" rocket propellants. The polymorphism shortcomings brought by ammonium nitrate in these energetic formulations have been solved by its co-crystallization with potassium salts (potassium nitrate, potassium chromate, potassium dichromate, potassium sulphate, potassium chlorate and potassium perchlorate). Polyester-polyol blends, resulting from recycled post-consumer polyethylene terephthalate (PET) glycolysis, were utilized for the synthesis of the polyurethane binder, especially designed for this type of application. To adjust the energetic output and tailor the mechanical properties of the propellant, the energetic plasticizer TEGDN was also involved. The performance and safety characteristics of the novel composites were evaluated through various analytical techniques (TGA, DTA, XRD) and specific tests (rate of combustion, heat of combustion, specific volume, chemical stability, sensitivity to thermal, impact and friction stimuli), according to NATO standards, providing promising preliminary results for further ballistics investigations.

Peelable Nanocomposite Coatings: "Eco-Friendly" Tools for the Safe Removal of Radiopharmaceutical Spills or Accidental Contamination of Surfaces in General-Purpose Radioisotope Laboratories.

Radioactive materials are potentially harmful due to the radiation emitted by radionuclides and the risk of radioactive contamination. Despite strict compliance with safety protocols, contamination with radioactive materials is still possible. This paper describes innovative and inexpensive formulations that can be employed as 'eco-friendly' tools for the safe decontamination of radiopharmaceuticals spills or other accidental radioactive contamination of the surfaces arising from general-purpose radioisotope handling facilities (radiopharmaceutical laboratories, hospitals, research laboratories, etc.). These new peelable nanocomposite coatings are obtained from water-based, non-toxic, polymeric blends containing readily biodegradable components, which do not damage the substrate on which they are applied while also displaying efficient binding and removal of the contaminants from the targeted surfaces. The properties of the film-forming decontamination solutions were assessed using rheological measurements and evaporation rate tests, while the resulting strippable coatings were subjected to Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and tensile tests. Radionuclide decontamination tests were performed on various types of surfaces encountered in radioisotope workspaces (concrete, painted metal, ceramic tiles, linoleum, epoxy resin cover). Thus, it was shown that they possess remarkable properties (thermal and mechanical resistance which permits facile removal through peeling) and that their capacity to entrap and remove beta and alpha particle emitters depends on the constituents of the decontaminating formulation, but more importantly, on the type of surface tested. Except for the cement surface (which was particularly porous), at which the decontamination level ranged between approximately 44% and 89%, for all the other investigated surfaces, a decontamination efficiency ranging from 80.6% to 96.5% was achieved.

Strippable Polymeric Nanocomposites Comprising "Green" Chelates, for the Removal of Heavy Metals and Radionuclides.

The issue of heavy metal and radionuclide contamination is still causing a great deal of concern worldwide for environmental protection and industrial sites remediation. Various techniques have been developed for surface decontamination aiming for high decontamination factors (DF) and minimal environmental impact, but strippable polymeric nanocomposite coatings are some of the best candidates in this area. In this study, novel strippable coatings for heavy metal and radionuclides decontamination were developed based on the film-forming ability of polyvinyl alcohol, with the remarkable metal retention capacity of bentonite nanoclay, together with the chelating ability of sodium alginate and with "new-generation" "green" complexing agents: iminodisuccinic acid (IDS) and 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC). These environmentally friendly water-based decontamination solutions are capable of generating strippable polymeric films with optimized mechanical and thermal properties while exhibiting high decontamination efficiency (DF ≈ 95-98% for heavy metals tested on glass surface and DF ≈ 91-97% for radionuclides 241Am, 90Sr-Y and 137Cs on metal, painted metal, plastic, and glass surfaces).

Eco-Friendly Peelable Active Nanocomposite Films Designed for Biological and Chemical Warfare Agents Decontamination.

In the context of imminent threats concerning biological and chemical warfare agents, the aim of this study was the development of a new method for biological and chemical decontamination, employing non-toxic, film-forming, water-based biodegradable solutions, using a nano sized reagent together with bentonite as trapping agents for the biological and chemical contaminants. Bentonite-supported nanoparticles of Cu, TiO2, and Ag were successfully synthesized and dispersed in a polyvinyl alcohol (PVA)/glycerol (GLY) aqueous solution. The decontamination effectiveness of the proposed solutions was evaluated by qualitative and quantitative analytical techniques on various micro-organisms, with sulfur mustard (HD) and dimethyl methylphosphonate (DMMP) as contaminants. The results indicate that the peelable active nanocomposite films can be successfully used on contaminated surfaces to neutralize and entrap the hazardous materials and their degradation products. Mechanical and thermal characterization of the polymeric films was also performed to validate the decontamination solution's potential as peelable-film generating materials. The removal efficacy from the contaminated surfaces for the tested micro-organisms varied between 93% and 97%, while for the chemical agent HD, the highest decontamination factor obtained was 90.89%. DMMP was almost completely removed from the contaminated surfaces, and a decontamination factor of 99.97% was obtained.

Novel Polyurethanes Based on Recycled Polyethylene Terephthalate: Synthesis, Characterization, and Formulation of Binders for Environmentally Responsible Rocket Propellants.

Novel polyurethane-based binders, specifically designed for environmentally responsible rocket propellant composites, were obtained by employing the polyester-polyols that resulted from the degradation of polyethylene terephthalate waste. A new class of "greener" rocket propellants, comprising polyurethanes (based on recycled PET) as the binder, phase stabilized ammonium nitrate (PSAN) as the eco-friendly oxidizer, and triethylene glycol dinitrate (TEGDN) as the energetic plasticizer, together with aluminum as fuel and Fe2O3 as the catalyst, is herein reported. The components of the energetic mixtures were investigated (individually and as composite materials) through specific analytical tools: 1H-NMR, FT-IR, SEM-EDX, DTA and TGA, tensile and compression tests, DMA, and micro-CT. Moreover, the feasibility of this innovative solution is sustained by the ballistic performances exhibited by these composite materials in a subscale rocket motor, proving that these new formulations are suitable for rocket propellant applications.

Decontamination of radioactive hazardous materials by using novel biodegradable strippable coatings and new generation complexing agents.

Eight different types of complexing agents were employed for the development of new biodegradable decontamination solutions that are able to form strippable coatings after they are dispersed and allowed to dry on a variety of surfaces contaminated with 60Co, 133Ba, 137Cs and 241Am radioactive isotopes. The new generation of eco-friendly chelators with superior biodegradability, utilized for the first time in such applications, can easily replace the non-biodegradable and carcinogenic complexing agents that are still in use today, due to their decontamination performances. Furthermore, besides the complexing action over the radionuclides, the solutions contain two types of clays, Bentonite (BT) and Saponite (SP), which have the capacity to adsorb specific ions, improving the decontamination efficiency of the solutions. Our research revealed that it is preferable to replace BT with SP, due to its better dispersibility, thermal stability, next to superior ability to gel and better thermal stability (Miles, 2011). The solutions showed a decontamination factor superior to 95% for 137Cs (on all surfaces), over 90% for 60Co and 133Ba, and more than 72% 241Am (on all surfaces), except for galvanized metal plates, where lower decontamination factors were obtained: over 70% for 133Ba, maximum 41.87% for 241Am and 43.19% for 60Co.

Reducing impacts from ammunitions: A comparative life-cycle assessment of four types of 9mm ammunitions.

Increase of environmental awareness of the population has pressured research activities in the defence area to cover environment and toxicity issues, where have been considered appropriate manners to reduce the environmental and toxicological impacts of ammunition. One of the adopted approaches to achieve such goal involves the replacement of lead and other heavy metals by alternative materials. However, the consequences of using alternative materials in ammunitions manufacturing are uncertain for the other life-cycle phases and trade-offs can occur. The present paper describes the potential benefits from the replacement of lead in the primer and in the projectile of a 9mm calibre ammunition. For that purpose, it is assessed and compared the environmental and toxicological impacts associated with the life-cycle of four ammunitions: combination of two types of projectiles (steel jacket and lead core; copper and nylon composite) with two types of primers (lead primer; non-lead primer). In addition, some potential improvements for the environmental performance of small calibre ammunition are also presented. To assess the impacts two Life-Cycle Impact Assessment methods are applied: CML for six environmental categories and USEtox to three toxicity categories. Results showed that the conclusion drawn for environmental and toxicological impact categories are distinct. In fact, ammunition production phase presents higher impacts for the environmental categories, whilst the operation phase has a higher impact to the toxicity categories. The substitution of lead in the primer and in the projectile provides a suitable alternative from a toxicology perspective; however, the composite projectile still presents some environmental concerns. The conclusions drawn are important for the procurement (and design) of environmental responsible ammunitions, in order to avoid (or decrease) the impacts for their manufacture and the effects on human health (e.g. shooters) and ecosystems near shooting ranges or hunting areas.

Novel formulations of ballistic gelatin. 1. Rheological properties.

Ballistic gelatin is the simulant of the human body during field tests in forensics and other related fields, due to its physical and mechanical similarities to human trunk and organs. Since the ballistic gelatin used in present has important issues to overcome, an alternative approach is the use of gelatin-polymer composites, where a key factor is the insertion of biocompatible materials, which replicate accurately the human tissues. In order to be able to obtain an improved material in terms of mechanical performances by an easy industrial-scale technology, before the verification of the ballistic parameters by shooting in agreement with military standards, one of the best and cheapest solutions is to perform a thorough check of their rheological properties, in standard conditions.

Poly(2-hydroxyethyl methacrylate-co-dodecyl methacrylate-co-acrylic acid): synthesis, physico-chemical characterisation and nafcillin carrier.

In the present study polymeric microbeads of poly(2-hydroxyethyl methacrylate-co-dodecyl methacrylate-co-acrylic acid) or p(HEMA-co-dDMA-co-AA) were synthesised and characterized through FT-IR and scanning electron microscopy (SEM); their swelling behavior against saline solution was explored and their in vitro cytotoxicity was evaluated. Further, in order to elucidate kinetic aspects regarding the ternary system p(HEMA-co-dDMA-co-AA), a mathematical model of the reactivity ratios of the comonomers in the terpolymer has been conceived and analyzed. An intensified tendency of AA units accumulation in the copolymer has been noticed, in spite of HEMA units, while dDMA conserves in the copolymer the fraction from the feed. Three compositions have been selected for nafcillin-loading and their in vitro release capacity was evaluated. The compositions of 80:10:10 and 75:10:15 M ratios appear suitable for further in vivo testing, in order to be used as drug delivery systems in the treatment of different osseous diseases.