Next-generation of smart dressings: Integrating multiplexed sensors and theranostic functions.

Non-healing wounds represent a significant burden for healthcare systems and society, giving rise to severe economic and human issues. Currently, the use of dressings and visual assessment represent the primary and standard care for wounds. Conventional dressings, like cotton gauze, provide only passive physical protection. Besides, they end up paradoxically hampering the wound-healing process by producing tissue damage and pain when removed during routine check-ups. In response to these limitations, researchers, engineers, and technologists are developing innovative dressings that incorporate advanced diagnostic and therapeutic functionalities, coined as "smart dressings". Now, the maturation of smart dressing is bringing them closer to real-life applications, leading to an exciting new generation of these devices. The next generation of smart dressings is capable of monitoring in real-time multiple biomarkers while including pro-healing capabilities in a single platform. Such multiplexed and theranostic smart dressings are expected to offer a timely biomarker-directed diagnosis of non-healing wounds while enabling rapid, automated, and personalized treatments of infection and chronicity. Herein, we provide an insightful overview of these advantageous devices, delving into the diverse spectrum of possible engineering strategies. This encompasses the use of electrochemical and optical platforms with diverse multiplexing architectures, such as multi-zone sensing arrays and multi-layered devices. Open or closed-loop theranostic mechanisms using various stimuli-responsive materials that could be internally or externally controlled are also included. Finally, a critical discussion on the main challenges and future directions of smart dressings is also offered.

Porous Structural Properties of K or Na-Co Hexacyanoferrates as Efficient Materials for CO2 Capture.

The stoichiometry of the components of hexacyanoferrate materials affecting their final porosity properties and applications in CO2 capture is an issue that is rarely studied. In this work, the effect that stoichiometry of all element components and oxidation states of transition metals has on the structures of mesoporous K or Na-cobalt hexacyanoferrates (CoHCFs) and CO2 removal is reported. A series of CoHCFs model systems are synthesized using the co-precipitation method with varying amounts of Co ions. CoHCFs are characterized by N2 adsorption, TGA, FTIR-ATR, XRD, and XPS. N2 adsorption results reveal a more developed external surface area (72.69-172.18 m2/g) generated in samples containing mixtures of K+/Fe2+/Fe3+ ions (system III) compared to samples with Na+/Fe2+ ions (systems I, II). TGA results show that the porous structure of CoHCFs is affected by Fe and Co ions oxidation states, the number of water molecules, and alkali ions. The formation of two crystalline cells (FCC and triclinic) is confirmed by XRD results. Fe and Co oxidation states are authenticated by XPS and allow for the confirmation of charges involved in the stabilization of CoCHFs. CO2 removal capacities (3.04 mmol/g) are comparable with other materials reported. CO2 adsorption kinetics is fast (3-6 s), making CoHCFs attractive for continuous operations. Qst (24.3 kJ/mol) reveals a physical adsorption process. Regeneration effectiveness for adsorption/desorption cycles indicates ~1.6% loss and selectivity (~47) for gas mixtures (CO2:N2 = 15:85). The results of this study demonstrate that the CoHCFs have practical implications in the potential use of CO2 capture and flue gas separations.

Deep Eutectic Solvent-Enabled Plasmonic Nanocellulose Aerogel: On-Demand Three-Dimensional (3D) SERS Hotspot Based on Collapsing Mechanism.

Exceptional surface enhanced Raman scattering (SERS) can be achieved by on-demand mechanisms mediated by the formation of three-dimensional (3D) network supporting hotspots. Herein, a deep eutectic solvent (DES) is used to fabricate plasmonic aerogels as sustainable SERS substrates consisting of different gold nanoparticle (AuNP) heterostructures synthesized in the presence of cellulose nanocrystals (CNCs). This analytical approach is based on the AuNPs 3D arrangement within the CNC matrix, where the transient inter-CNCs interactions collapse after loading with the analyte aqueous solution, forming hotspots on demand. Theoretical calculations support the on-demand SERS mechanism, which consists of the hotspot formation by bringing the AuNPs closer upon activation with the liquid sample loading. To evaluate the plasmonic aerogel performance as a sensing platform, the organophosphorus pesticides edifenphos and parathion were tested in rice and tea extracts. Also, the detection of Methylene Blue in fish muscle extract resulted in a detection limit of 9.8 nM. The results demonstrate that the 3D plasmonic aerogel exhibits significantly higher SERS enhancement and sensitivity when compared to conventional 2D SERS substrates. The use of a green designer solvent, biobased ingredients, and the introduction of on-demand SERS-based sensing pave the way for further developments in the analysis of liquid samples within a sustainable framework.

Polystyrene Macroporous Magnetic Nanocomposites Synthesized through Deep Eutectic Solvent-in-Oil High Internal Phase Emulsions and Fe3O4 Nanoparticles for Oil Sorption.

In this work, we report a nonaqueous one-step method to synthesize polystyrene macroporous magnetic nanocomposites through high internal phase emulsions (HIPEs) formulated with the deep eutectic solvent (DES) composed of urea:choline chloride (U:ChCl, in a 2:1 molar ratio) as the internal phase and co-stabilized with mixtures of Span 60 surfactant and non-functionalized magnetite nanoparticles (Fe3O4 NPs). The porous structure and the magnetic and lipophilic properties of the nanocomposite materials were easily tailored by varying the amount of Fe3O4 NPs (0, 2, 5 and 10 wt %) and the surfactant Span 60 (0, 5, 10, and 20 wt %) used in the precursor emulsion. The resultant nanocomposite polyHIPEs exhibit high sorption capacity toward different oils (hexane, gasoline, and vegetable oil) due to their high porosity, interconnectivity, and hydrophobic surface. It was observed that the oil sorption capacity was improved when the amount of surfactant decreased and Fe3O4 NPs increased in HIPE formulation. Therefore, polyHIPE formulated with 5 and 10 wt % Span 60 and Fe3O4 NPs, respectively, showed the highest oil sorption capacities of 4.151, 3.556, and 3.266 g g-1 for gasoline, hexane, and vegetable oil, respectively. In addition, the magnetic monoliths were reused for more than ten sorption/desorption cycles without losing their oil sorption capacity.

Boosting cell proliferation in three-dimensional polyacrylates/nanohydroxyapatite scaffolds synthesized by deep eutectic solvent-based emulsion templating.

Among three-dimensional (3D) scaffold fabrication methods, porous polymers templated using high internal phase emulsions (HIPEs) have emerged as an attractive method due to the facile generation of interconnected porosity through a variety of synthetic routes. These include a bottom-up approach to selectively incorporate nanomaterials onto the inner walls in a nonaqueous environment. In this work, novel nonaqueous HIPEs made of different (meth)acrylate monomers and a deep eutectic solvent (DES) were formulated with nonfunctionalized nanohydroxyapatite (NHA), which also played the role of cosurfactant. Free radical polymerization of HIPEs yielded free-standing nanocomposites with 3D interconnected macroporosity and nonfunctionalized NHA selectively decorating the scaffolds' inner surface. The influence of different polymer functionalities, acrylate or methacrylate, their alkyl tail length, and the presence of NHA on MC3T3-E1 preosteoblast cell proliferation in vitro, reactive oxygen species (ROS) production and alkaline phosphatase (ALP) activity were evaluated. All materials presented promising biocompatibility, non-hemolytic activity, negligible inflammatory response along to remarkably enhanced cell proliferation (e.g., up to 160-fold cell proliferation increase compared with polystyrene plate) in vitro, which open the path for the development of scaffolds in regenerative medicine. It is noteworthy that polyHIPEs studied here were obtained using a green synthetic protocol where nonfunctionalized nanoparticles can be selectively incorporated into a scaffolds' inner walls. This versatile technique allows for the simple construction of 3D bioactive nanocomposite scaffolds with varied compositions for cell culture.

Deep eutectic solvent-assisted phase separation in chitosan solutions for the production of 3D monoliths and films with tailored porosities.

A facile and greener methodology to obtain pure chitosan-based 3D porous structures in the form of monoliths and films is proposed. It is based on a modified evaporation-induced phase separation process in a chitosan solution precursor. In this approach, a deep eutectic solvent (DES) is used as the nonsolvent system and an ecofriendly, cost effective, simple and versatile alternative for the production of highly structured chitosan materials. The porous heterogeneous structure can be fine-tuned by varying the chitosan content in the precursor solution and chitosan/DES ratio, and enabled the structured polymer to absorb large amounts of water to form hydrogels. This is a versatile and unexplored approach to design porous chitosan with tailored morphology in the absence of crosslinkers, which, based on preliminary studies on V. cholerae biofilm formation, is expected to open new avenues for various applications in biomedical, catalysis, water purification, filtration and other areas where the control of bacterial biofilm formation is critical.

Oil-in-eutectic mixture HIPEs co-stabilized with surfactant and nanohydroxyapatite: ring-opening polymerization for nanocomposite scaffold synthesis.

Mixtures of a nonionic surfactant and non-functionalized nanohydroxyapatite (NHA) enhanced the stability of oil-in-eutectic mixture high internal phase emulsions (HIPEs). Upon ring opening polymerization of the eutectic mixture composed of l-lactide and ε-caprolactone, biodegradable polyHIPEs with specific cavity sizes and selective interfacial functionalization with NHA are produced.

Choline chloride-zinc chloride deep eutectic solvent mediated preparation of partial O-acetylation of chitin nanocrystal in one step reaction.

An efficient and one step production of acetylated and esterified chitin nanocrystals (CNCs) was successfully achieved using choline chloride-zinc chloride deep-eutectic solvent (ChCl-ZnCl2 DES). In this method, ChCl-ZnCl2 DES with a mole ratio of 1:2, was used for the esterification and O-acetylation of chitin at 90 °C for 3 h and 6 h. This strategy consisted in using ChCl-ZnCl2 DES as a green and non-volatile solvent for chitin under heterogeneous condition that, upon addition of acetic anhydride or acetic acid, simultaneous acetylation or esterification and hydrolysis occurred. The DES act as an efficient catalysis of the functional reaction. The acetylation and hydrolysis proceeded efficiently and the yield of partial acetylated CNCs was ca. 61.6% with DS (degree of substitution) of 0.23 under the optimized conditions. Acetic acid was used to substituted acid anhydride to produce CNCs. The yield of acetic acid induced CNCs was ca. 62.0% with higher DS of 0.34. A thorough investigation of the physicochemical characteristics changes of chitin pointed out that the main skeletal structure of obtained CNCs was intact. The thermal stability of CNCs decreased after treated by ChCl/ZnCl2. In addition, thermal stability of CNCs functionalized with acetic acid is lower than the ones functionalized with acetic anhydride. DES showed low expenditure and toxicity. This approach provides a novel method for production of functional chitin nanocrystals.

Toxicity of silver nanoparticles in biological systems: Does the complexity of biological systems matter?

Currently, nanomaterials are more frequently in our daily life, specifically in biomedicine, electronics, food, textiles and catalysis just to name a few. Although nanomaterials provide many benefits, recently their toxicity profiles have begun to be explored. In this work, the toxic effects of silver nanoparticles (35nm-average diameter and Polyvinyl-Pyrrolidone-coated) on biological systems of different levels of complexity was assessed in a comprehensive and comparatively way, through a variety of viability and toxicological assays. The studied organisms included viruses, bacteria, microalgae, fungi, animal and human cells (including cancer cell lines). It was found that biological systems of different taxonomical groups are inhibited at concentrations of silver nanoparticles within the same order of magnitude. Thus, the toxicity of nanomaterials on biological/living systems, constrained by their complexity, e.g. taxonomic groups, resulted contrary to the expected. The fact that cells and virus are inhibited with a concentration of silver nanoparticles within the same order of magnitude could be explained considering that silver nanoparticles affects very primitive cellular mechanisms by interacting with fundamental structures for cells and virus alike.

Effect of silver nanoparticles on the metabolic rate, hematological response, and survival of juvenile white shrimp Litopenaeus vannamei.

White spot syndrome virus (WSSV) is highly lethal and contagious in shrimps; its outbreaks causes an economic crisis for aquaculture. Several attempts have been made to treat this disease; however, to date, there is no effective cure. Because of their antimicrobial activities, silver nanoparticles (AgNPs) are the most studied nanomaterial. Although the antiviral properties of AgNPs have been studied, their antiviral effect against viral infection in aquaculture has not been reported. The AgNPs tested herein are coated with polyvinylpyrrolidone (PVP) and possess multiple international certifications for their use in veterinary and human applications. The aim of this work was to evaluate the survival rate of juvenile white shrimps (Litopenaeus vannamei) after the intramuscular administration of AgNPs. For this, different concentrations of metallic AgNPs and PVP alone were injected into the organisms. After 96 h of administration, shrimp survival was more than 90% for all treatments. The oxygen consumption routine rate and total hemocyte count remained unaltered after AgNP injection, reflecting no stress caused. We evaluated whether AgNPs had an antiviral effect in shrimps infected with WSSV. The results revealed that the survival rate of WSSV-infected shrimps after AgNP administration was 80%, whereas the survival rate of untreated organisms was only 10% 96 h after infection. These results open up the possibility to explore the potential use of AgNPs as antiviral agents for the treatment of diseases in aquaculture organisms, particularly the WSSV in shrimp culture.

Deep-Eutectic Solvents as MWCNT Delivery Vehicles in the Synthesis of Functional Poly(HIPE) Nanocomposites for Applications as Selective Sorbents.

We report an alternative green strategy based on deep-eutectic solvents (DES) to deliver multiwalled carbon nanotubes (MWCNTs) for a bottom-up approach that allows for the selective interfacial functionalization of nonaqueous poly(high internal phase emulsions), poly(HIPEs). The formation and polymerization of methacrylic and styrenic HIPEs were possible through stabilization with nitrogen doped carbon nanotube (CNX) and surfactant mixtures using a urea-choline chloride DES as a delivering phase. Subtle changes in CNX concentration (less than 0.2 wt % to the internal phase) produced important changes in the macroporous monolith functionalization, which in turn led to increased monolith hydrophobicity and pore openness. These materials displayed great oleophilicity with water contact angles as high as 140° making them apt for biodiesel, diesel, and gasoline fuel sorption applications. Overall, styrene divinylbenzene (StDvB) based poly(HIPEs) showed hydrophobicity and fuel sorption capacities as high as 4.8 (g/g). Pore hierarchy, namely pore openness, regulated sorption capacity, and sorption times where greater openness resulted in faster sorption and increased sorption capacity. Monoliths were subject to 20 sorption-desorption cycles demonstrating recyclability and stable sorption capacity. Finally, CNX/surfactant hybrids made it possible to reduce surfactant requirements for successful HIPE formation and stabilization during polymerization. All poly(HIPEs) retained acceptable conversion as a function of CNX loading nearing 90% or better with thermal stability as high as 283 °C.

Synthesis of Biodegradable Macroporous Poly(l-lactide)/Poly(ε-caprolactone) Blend Using Oil-in-Eutectic-Mixture High-Internal-Phase Emulsions as Template.

We have demonstrated that l-lactide (LLA) forms a eutectic mixture with ε-caprolactone (CL) in a 30:70 mol ratio with a melting point of -19 °C. Taking advantage of the liquid nature and polarity at the LLA-CL eutectic mixture, we have formulated oil-in-eutectic-mixture high-internal-phase emulsions (HIPEs) by stepwise addition of the oil phase (tetradecane) into the continuous phase (mixture of surfactant and LLA-CL eutectic mixture) at room temperature and under stirring. The oil-in-LLA-CL-eutectic-mixture HIPEs were polymerized in the presence of both the organocatalysts 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and methanesulfonic acid (MSA) and the initiator benzyl alcohol (BnOH) at 37 °C and without the addition of any extra reagent or solvent in one single pot. The catalytic selectivities of DBU and MSA for the ring-opening polymerizations of LLA and CL, respectively, allowed the synthesis of macroporous poly(l-lactide)/poly(ε-caprolactone) blend materials. The resulting materials exhibited a macroporous morphology that resembled that of the HIPE internal-phase droplets used as templates. These materials proved effective as oil absorbents for oil/water separation with not only a noticeable performance, similar to that of conventional sorbents in terms of both selectivity and recyclability, but also unprecedented safe disposability, certainly of interest for applications in the cleanup of industrial oily wastewaters and oil spills, thanks to the biodegradable features of both poly(ε-caprolactone) and poly(l-lactide).

On the High Sensitivity of the Electronic States of 1 nm Gold Particles to Pretreatments and Modifiers.

In this paper, the effect of modifiers and pretreatments on the electronic states of 1 nm gold nanoparticles (AuNPs) supported on silica was systematically studied. AuNPs deposited on silica (particle size of 2-4 nm) modified with Ce, La and Fe oxides, were studied by FTIR of adsorbed CO after different redox treatments at 100, 300 and 500 °C. This study was conducted at room temperature to allow detecting the electronic states of gold, which is more likely involved in CO oxidation at the same temperature. AuNP size distribution was measured by HRTEM. It is shown that the electronic state of gold species (Aun(δ-), Au°, Aun(δ+), Au⁺) in 1 nm AuNPs is sensitive to the modifier as well as to the temperatures of redox pretreatments. Supports modified with the same additives but containing larger AuNPs (~3, 4, 5, and 7 nm) were also studied. They showed that Au° remains stable irrespective of additives and redox pretreatments, indicating no significant effect of such treatments on the electronic properties of larger AuNPs. Samples with a predominant AuNP size of 2 nm are an intermediate case between these two groups of materials.

Identification of Subnanometric Ag Species, Their Interaction with Supports and Role in Catalytic CO Oxidation.

The nature and size of the real active species of nanoparticulated metal supported catalysts is still an unresolved question. The technique of choice to measure particle sizes at the nanoscale, HRTEM, has a practical limit of 1 nm. This work is aimed to identify the catalytic role of subnanometer species and methods to detect and characterize them. In this frame, we investigated the sensitivity to redox pretreatments of Ag/Fe/TiO2, Ag/Mg/TiO2 and Ag/Ce/TiO2 catalysts in CO oxidation. The joint application of HRTEM, SR-XRD, DRS, XPS, EXAFS and XANES methods indicated that most of the silver in all samples is in the form of Ag species with size <1 nm. The differences in catalytic properties and sensitivity to pretreatments, observed for the studied Ag catalysts, could not be explained taking into account only the Ag particles whose size distribution is measured by HRTEM, but may be explained by the presence of the subnanometer Ag species, undetectable by HRTEM, and their interaction with supports. This result highlights their role as active species and the need to take them into account to understand integrally the catalysis by supported nanometals.

Potential application of silver nanoparticles to control the infectivity of Rift Valley fever virus in vitro and in vivo.

In this work we have tested the potential antiviral activity of silver nanoparticles formulated as Argovit™ against Rift Valley fever virus (RVFV). The antiviral activity of Argovit was tested on Vero cell cultures and in type-I interferon receptor deficient mice (IFNAR (-/-) mice) by two different approaches: (i) different dilutions of Argovit were added to previously infected cells or administrated to animals infected with a lethal dose of virus; (ii) virus was pre-incubated with different dilutions of Argovit before inoculation in mice or cells. Though the ability of silver nanoparticles to control an ongoing RVFV infection in the conditions tested was limited, the incubation of virus with Argovit before the infection led to a reduction of the infectivity titers both in vitro and in vivo. These results reveal the potential application of silver nanoparticles to control the infectivity of RVFV, which is an important zoonotic pathogen.

Effect of doping in carbon nanotubes on the viability of biomimetic chitosan-carbon nanotubes-hydroxyapatite scaffolds.

This work describes the preparation and characterization of biomimetic chitosan/multiwall carbon nanotubes/nano-hydroxyapatite (CTS/MWCNT/nHAp) scaffolds and their viability for bone tissue engineering applications. The cryogenic process ice segregation-induced self-assembly (ISISA) was used to fabricate 3D biomimetic CTS scaffolds. Proper combination of cryogenics, freeze-drying, nature and molecular ratio of solutes give rise to 3D porous interconnected scaffolds with clusters of nHAp distributed along the scaffold surface. The effect of doping in CNT (e.g. with oxygen and nitrogen atoms) on cell viability was tested. Under the same processing conditions, pore size was in the range of 20-150 µm and irrespective on the type of CNT. Studies on cell viability with scaffolds were carried out using human cells from periosteum biopsy. Prior to cell seeding, the immunophenotype of mesenchymal periosteum or periosteum-derived stem cells (MSCs-PCs) was characterized by flow cytometric analysis using fluorescence-activated and characteristic cell surface markers for MSCs-PCs. The characterized MSCs-PCs maintained their periosteal potential in cell cultures until the 2nd passage from primary cell culture. Thus, the biomimetic CTS/MWCNT/nHAp scaffolds demonstrated good biocompatibility and cell viability in all cases such that it can be considered as promising biomaterials for bone tissue engineering.

New insights into the bactericidal activity of chitosan-Ag bionanocomposite: the role of the electrical conductivity.

The relationship between electrical conductivity, structure and antibacterial properties of chitosan-silver nanoparticles (CS/AgnP) biocomposites has been analyzed. To test the film's antimicrobial activity, Gram-positive and Gram-negative bacteria were studied. The interactions between silver nanoparticles with chitosan suggest the formation of silver ions which plays a major role in nanocomposite's bactericidal potency. In CS/AgnP biocomposites, the bactericide effectiveness increases by increasing AgnP concentrations up to 3 wt%, which is close to the electrical percolation threshold of ca. 3 wt%. As the AgnP concentration increases above this threshold, the bactericidal potency is greatly diminished. The elucidated correlation between electrical conductivity and antibacterial activity could be useful in the design of other nanocomposites that involve polymeric-based matrices.

Frontal polymerizations carried out in Deep-Eutectic mixtures providing both the monomers and the polymerization medium.

Deep Eutectic Solvents (DESs) based upon mixtures of Acrylic Acid (AA) or Methacrylic Acid (MAA) and Choline Chloride (CCl) demonstrated superior performance than regular organic solvents and even ionic liquids for frontal polymerizations (FPs). Full recovering of CCl after FP provided an interesting green character to the process.