Publications

Abstract The thermodynamic characterization of dihydroxylammonium 5,5 '-bitetrazole-1,1 '-dioxide (TKX-50) was reinvestigated. Although TKX-50 is one of the most promising new-generation energetic materials, contradictory reports are found in the literature with regard to its solid enthalpy of formation. The standard (p degrees=10(5) Pa) molar enthalpy of formation of crystalline TKX-50, (175.3 +/- 1.9) kJ center dot mol(-1), was determined experimentally based on the measured standard massic energy of combustion, determined through static-bomb combustion calorimetry. Additionally, the standard molar enthalpy of sublimation of TKX-50, at T=298.15 K, (165.0 +/- 2.4) kJ center dot mol(-1), was derived from vapor pressure measurements determined by a Knudsen mass-loss effusion technique. Finally, different approaches were used in attempts to calculate the standard enthalpy of formation of TKX-50 in the solid state. A critical overview and assessment of the data on the enthalpy of formation of TKX-50 is also presented.

Abstract This experimental and computational study on the energetic properties of 2-methyl-, 3-methyl-, 4-methoxy- and 5-methoxy-indanones has been carried out using mostly calorimetric techniques and a suitable computational approach. The combustion and sublimation/vaporization enthalpies were determined via combustion calorimetry and Calvet microcalorimetry, respectively, allowing for the calculation of the standard molar enthalpies of formation in the gaseous phase. The enthalpy of sublimation of 5-methoxy-indanone was also derived via Knudsen effusion. Additionally, the gas-phase standard molar enthalpies of formation of these compounds were determined from high-level ab initio calculations at the G3(MP2)//B3LYP level of theory. The results obtained experimentally and through the computational approach are in good agreement. Thus, the gas-phase enthalpy of formation of 2-methylcyclopentanone was estimated with this approach. Moreover, the energetic effects associated with the presence of a methyl and methoxy group on the indanone core were analyzed, using the experimental values reported in this work. The presence of a methoxy group contributes to a decrease in the gas-phase enthalpy of formation, of about 153 kJ center dot mol(-1), whereas in the case of a methyl group, the corresponding value is c.a. 35 kJ center dot mol(-1). Finally, a quantitative analysis of the effects of delocalization of the electron density on the methyl-indanones was performed, using NBO calculations at the B3LYP/6-311+G(2df,2p) wave function.

Abstract A plasmonic nanostructure was constructed as a biorecognition element coupled to an optical sensing platform in sandwich format, targeting the hazelnut Cor a 14 allergen-encoding gene. The analytical performance of the genosensor presented a linear dynamic range between 100 amol L-1 and 1 nmol L-1 , a limit of detection (LOD) < 19.9 amol L-1 , and a sensitivity of 13.4 +/- 0.6 m.. The genosensor was successfully hybridized with hazelnut PCR products, tested with model foods, and further validated by real-time PCR. It reached a LOD <0.001% (10 mg kg(-1) ) of hazelnut in wheat material (corresponding to 1.6 mg kg(-1) of protein) and a sensitivity of 17.2 +/- 0.5 m. for a linear range of 0.001%-1%. Herein, a new genosensing approach is proposed as a highly sensitive and specific alternative tool with potential application in monitoring hazelnut as an allergenic food, protecting the health of sensitized/allergic individuals.

Abstract Waste, in particular, biowaste, can be a valuable sourceof novelcarbon materials. Renewable carbon materials, such as biomass-derivedcarbons, have gained significant attention recently as potential electrodematerials for various electrochemical devices, including batteriesand supercapacitors. The importance of renewable carbon materialsas electrodes can be attributed to their sustainability, low cost,high purity, high surface area, and tailored properties. Fish wasterecovered from the fish processing industry can be used for energyapplications and prioritizing the circular economy principles. Herein,a method is proposed to prepare a high surface area biocarbon fromglycogen extracted from mussel cooking wastewater. The biocarbon materialswere characterized using a Brunauer-Emmett-Teller surfacearea analyzer to determine the specific surface area and pore sizeand by scanning electron microscopy coupled with energy-dispersiveX-ray analysis, Raman analysis, attenuated total reflectance Fouriertransform infrared spectroscopy, X-ray diffraction, X-ray photoelectronspectroscopy, and transmission electron microscopy. The electrochemicalcharacterization was performed using a three-electrode system, utilizinga choline chloride-based deep eutectic solvent (DES) as an eco-friendlyand sustainable electrolyte. Optimal time and temperature allowedthe preparation of glycogen-based carbon materials, with a specificsurface area of 1526 m(2) g(-1), a pore volumeof 0.38 cm(3) g(-1), and an associated specificcapacitance of 657 F g(-1) at a current density of1 A g(-1), at 30 degrees C. The optimal material wasscaled up to a two-electrode supercapacitor using a DES-based solid-stateelectrolyte (SSE@DES). This prototype delivered a maximum capacitanceof 703 F g(-1) at a 1 A g(-1) of currentdensity, showing 75% capacitance retention over 1000 cycles, deliveringthe highest energy density of 0.335 W h kg(-1) andpower density of 1341 W kg(-1). Marine waste can bea sustainable source for producing nanoporous carbon materials tobe incorporated as electrode materials in energy storage devices.

Abstract Many theoretical and experimental studies have been focused on the physicochemical properties of dense ionic fluids such as ionic liquids (ILs). However, less attention has been given to interfacial properties involving deep eutectic solvents (DES). The impact of the DES composition, hydrogen bond donor (HBD) structure, temperature, and electrode nature material on the DES-electrode vertical interactions remain vague. The lack of knowledge imposes significant constraints in proposing a suitable Electrical Double Layer model (EDL) to describe the DES at electrified interfaces. Measuring differential capacitance-potential curves is a strategy to assess the EDL structure and understand how ions interact with the electrode surface, which knowledge is fundamental to designing and optimizing electrochemical systems for various applications (e.g., energy storage devices). Accordingly, a set of choline chloride-based DESs was assessed containing distinct HBD at their eutectic composition (the poly-alcohol's 1,2-ethanediol, 1,2-propylene glycol, 1,3-propylene glycol, and the amide urea) against glassy carbon (GC), gold (Au), and the platinum (Pt) electrode at different temperatures. The differential capacitance-potential curves were found to vary significantly in shape in the three different electrode surfaces studied, ranging from camel shape (Au electrode), U-shape (GC), and asymmetric bell shape (polycrystalline Pt). The carboxylic malonic and oxalic acids were also assessed for a proper comparison to understand better the role of the HBD's functional group in shaping the electrode-electrolyte structure against the trend found with diol isomers. A suitable EDL model must inevitably accommodate interfacial properties assessed at the capacitive region, namely the influence of the surface chemistry, potential dependence, DES structure molecules, and temperature in shaping the electrified interfacial anatomy.

Abstract Over the past decade, molecular imprinting (MI) technologyhasmade tremendous progress, and the advancements in nanotechnology havebeen the major driving force behind the improvement of MI technology.The preparation of nanoscale imprinted materials, i.e., molecularlyimprinted polymer nanoparticles (MIP NPs, also commonly called nanoMIPs),opened new horizons in terms of practical applications, includingin the field of sensors. Currently, hydrogels are very promising forapplications in bioanalytical assays and sensors due to their highbiocompatibility and possibility to tune chemical composition, size(microgels, nanogels, etc.), and format (nanostructures, MIP film,fibers, etc.) to prepare optimized analyte-responsive imprinted materials.This review aims to highlight the recent progress on the use of hydrogelMIP NPs for biosensing purposes over the past decade, mainly focusingon their incorporation on sensing devices for detection of a fundamentalclass of biomolecules, the peptides and proteins. The review beginsby directing its focus on the ability of MIPs to replace biologicalantibodies in (bio)analytical assays and highlight their great potentialto face the current demands of chemical sensing in several fields,such as disease diagnosis, food safety, environmental monitoring,among others. After that, we address the general advantages of nanosizedMIPs over macro/micro-MIP materials, such as higher affinity towardtarget analytes and improved binding kinetics. Then, we provide ageneral overview on hydrogel properties and their great advantagesfor applications in the field of Sensors, followed by a brief descriptionon current popular routes for synthesis of imprinted hydrogel nanospherestargeting large biomolecules, namely precipitation polymerizationand solid-phase synthesis, along with fruitful combination with epitopeimprinting as reliable approaches for developing optimized protein-imprintedmaterials. In the second part of the review, we have provided thestate of the art on the application of MIP nanogels for screeningmacromolecules with sensors having different transduction modes (optical,electrochemical, thermal, etc.) and design formats for single use,reusable, continuous monitoring, and even multiple analyte detectionin specialized laboratories or in situ using mobiletechnology. Finally, we explore aspects about the development of thistechnology and its applications and discuss areas of future growth.

Abstract <jats:p>In this work, an optical fiber flowmeter based on a Michelson interferometer is presented. The Michelson interferometer uses a long period fiber grating (LPFG) to couple light to the cladding modes followed by a section of a GO-coated single mode fiber (SMF). By radiating the GO thin film, it will increase its temperature changing the effective refractive index of the optical cavity of the Michelson interferometer. By placing the sensor on a gas flow, its temperature surface will decrease in a proportional manner to the flow rate. The sensor was studied in both static and dynamic dry nitrogen flow, attaining an absolute sensitivity of 17.4 ± 0.8 pm/(L.min<jats:sup>-1</jats:sup>) and a maximum response time of 1.1 ± 0.4 s.</jats:p>

Abstract The scientific community's interest in developing sustainable carbon materials from biomass waste is increasing steadily, responding to the need to reduce dependence on fossil fuels. Every day, different biomass sources are suggested for obtaining porous carbon materials with characteristics for application in different areas. Porous carbon materials with a high specific surface area are a subject of interest for application in energy storage devices. This work reports the use of blue shark chondroitin sulfate and gelatine as precursors for developing porous carbon materials for energy storage devices. Commercial chondroitin sulfate was used for comparison. The porous carbons obtained in this study underwent various characterization techniques to assess their properties. A BET surface area analyzer measured the specific surface area and pore size. Additionally, scanning electron microscopy (SEM) coupled with energy dispersive X-ray analysis (EDX), a high resolution-scanning transmission electron microscope (HR-STEM), Raman spectroscopy, attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) were employed to examine the morphology, composition, and structure of the carbons. A modified glassy carbon (GC) electrode was used as the working electrode for the electrochemical characterization. Cyclic voltammetry and galvanostatic charge/discharge techniques were employed with ethaline, an environmentally friendly and sustainable electrolyte based on choline chloride, to assess the electrochemical performance. Furthermore, the most promising samples were subjected to ball-milling to investigate the impact of this process on surface area and capacitance. Blue shark chondroitin sulfate-based carbon presented a specific surface area of 135.2 m(2) g(-1), compared to 76.11 m(2) g(-1) of commercial chondroitin sulfate, both carbonized for 1 h at 1000 & DEG;C. Blue shark gelatine presented a specific surface area of 30.32 m(2) g(-1). The associated specific capacitance of these three samples is 40 F g(-1), 25 F g(-1), and 7 F g(-1). Ball-milling on these samples increased the specific surface area and capacitance of the three studied samples with different optimal milling times. This study presents the novel utilization of carbon materials derived from blue shark (with and without ball-milling) through a one-step carbonization process. These carbon materials were combined with an environmentally friendly DES electrolyte. The aim was to explore their potential application in energy storage devices, representing the first instance of employing blue shark-based carbon materials in this manner.

Abstract Long-term stability and high scalability are significant issues in plasmonic optical fiber sensors. This work presents a highly scalable and low-cost all-chemical approach for production of gold-coated silver thin-films, ensuring high performance and chemical stability. © Optica Publishing Group 2023, © 2023 The Authors.