Search results for: tunable%20decoder
Commenced in January 2007
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Edition: International
Paper Count: 129

Search results for: tunable%20decoder

9 Charged Amphiphilic Polypeptide Based Micelle Hydrogel Composite for Dual Drug Release

Authors: Monika Patel, Kazuaki Matsumura

Abstract:

Synthetic hydrogels, with their unique properties such as porosity, strength, and swelling in aqueous environment, are being used in many fields from food additives to regenerative medicines, from diagnostic and pharmaceuticals to drug delivery systems (DDS). But, hydrogels also have some limitations in terms of homogeneity of drug distribution and quantity of loaded drugs. As an alternate, polymeric micelles are extensively used as DDS. With the ease of self-assembly, and distinct stability they remarkably improve the solubility of hydrophobic drugs. However, presently, combinational therapy is the need of time and so are systems which are capable of releasing more than one drug. And it is one of the major challenges towards DDS to control the release of each drug independently, which simple DDS cannot meet. In this work, we present an amphiphilic polypeptide based micelle hydrogel composite to study the dual drug release for wound healing purposes using Amphotericin B (AmpB) and Curcumin as model drugs. Firstly, two differently charged amphiphilic polypeptide chains were prepared namely, poly L-Lysine-b-poly phenyl alanine (PLL-PPA) and poly Glutamic acid-b-poly phenyl alanine (PGA-PPA) through ring opening polymerization of amino acid N-carboxyanhydride. These polymers readily self-assemble to form micelles with hydrophobic PPA block as core and hydrophilic PLL/PGA as shell with an average diameter of about 280nm. The thus formed micelles were loaded with the model drugs. The PLL-PPA micelle was loaded with curcumin and PGA-PPA was loaded with AmpB by dialysis method. Drug loaded micelles showed a slight increase in the mean diameter and were fairly stable in solution and lyophilized forms. For forming the micelles hydrogel composite, the drug loaded micelles were dissolved and were cross linked using genipin. Genipin uses the free –NH2 groups in the PLL-PPA micelles to form a hydrogel network with free PGA-PPA micelles trapped in between the 3D scaffold formed. Different composites were tested by changing the weight ratios of the both micelles and were seen to alter its resulting surface charge from positive to negative with increase in PGA-PPA ratio. The composites with high surface charge showed a burst release of drug in initial phase, were as the composites with relatively low net charge showed a sustained release. Thus the resultant surface charge of the composite can be tuned to tune its drug release profile. Also, while studying the degree of cross linking among the PLL-PPA particles for effect on dual drug release, it was seen that as the degree of crosslinking increases, an increase in the tendency to burst release the drug (AmpB) is seen in PGA-PPA particle, were as on the contrary the PLL-PPA particles showed a slower release of Curcumin with increasing the cross linking density. Thus, two different pharmacokinetic profile of drugs were seen by changing the cross linking degree. In conclusion, a unique charged amphiphilic polypeptide based micelle hydrogel composite for dual drug delivery. This composite can be finely tuned on the basis of need of drug release profiles by changing simple parameters such as composition, cross linking and pH.

Keywords: amphiphilic polypeptide, dual drug release, micelle hydrogel composite, tunable DDS

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8 Functionalizing Gold Nanostars with Ninhydrin as Vehicle Molecule for Biomedical Applications

Authors: Swati Mishra

Abstract:

In recent years, there has been an explosion in Gold NanoParticle (GNP) research, with a rapid increase in publications in diverse fields, including imaging, bioengineering, and molecular biology. GNPs exhibit unique physicochemical properties, including surface plasmon resonance (SPR) and bind amine and thiol groups, allowing surface modification and use in biomedical applications. Nanoparticle functionalization is the subject of intense research at present, with rapid progress being made towards developing biocompatible, multi-functional particles. In the present study, the photochemical method has been done to functionalize various-shaped GNPs like nanostars by the molecules like ninhydrin. Ninhydrin is bactericidal, virucidal, fungicidal, antigen-antibody reactive, and used in fingerprint technology in forensics. The GNPs functionalized with ninhydrin efficiently will bind to the amino acids on the target protein, which is of eminent importance during the pandemic, especially where long-term treatments of COVID- 19 bring many side effects of the drugs. The photochemical method is adopted as it provides low thermal load, selective reactivity, selective activation, and controlled radiation in time, space, and energy. The GNPs exhibit their characteristic spectrum, but a distinctly blue or redshift in the peak will be observed after UV irradiation, ensuring efficient ninhydrin binding. Now, the bound ninhydrin in the GNP carrier, upon chemically reacting with any amino acid, will lead to the formation of Rhumann purple. A common method of GNP production includes citrate reduction of Au [III] derivatives such as aurochloric acid (HAuCl4) in water to Au [0] through a one-step synthesis of size-tunable GNPs. The following reagents are prepared to validate the approach. Reagent A solution 1 is0.0175 grams ninhydrin in 5 ml Millipore water Reagent B 30 µl of HAuCl₄.3H₂O in 3 ml of solution 1 Reagent C 1 µl of gold nanostars in 3 ml of solution 1 Reagent D 6 µl of cetrimonium bromide (CTAB) in 3 ml of solution1 ReagentE 1 µl of gold nanostars in 3 ml of ethanol ReagentF 30 µl of HAuCl₄.₃H₂O in 3 ml of ethanol ReagentG 30 µl of HAuCl₄.₃H₂O in 3 ml of solution 2 ReagentH solution 2 is0.0087 grams ninhydrin in 5 ml Millipore water ReagentI 30 µl of HAuCl₄.₃H₂O in 3 ml of water The reagents were irradiated at 254 nm for 15 minutes, followed by their UV Visible spectroscopy. The wavelength was selected based on the one reported for excitation of a similar molecule Pthalimide. It was observed that the solution B and G deviate around 600 nm, while C peaks distinctively at 567.25 nm and 983.9 nm. Though it is tough to say about the chemical reaction happening, butATR-FTIR of reagents will ensure that ninhydrin is not forming Rhumann purple in the absence of amino acids. Therefore, these experiments, we achieved the functionalization of gold nanostars with ninhydrin corroborated by the deviation in the spectrum obtained in a mixture of GNPs and ninhydrin irradiated with UV light. It prepares them as a carrier molecule totake up amino acids for targeted delivery or germicidal action.

Keywords: gold nanostars, ninhydrin, photochemical method, UV visible specgtroscopy

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7 A Hybrid of BioWin and Computational Fluid Dynamics Based Modeling of Biological Wastewater Treatment Plants for Model-Based Control

Authors: Komal Rathore, Kiesha Pierre, Kyle Cogswell, Aaron Driscoll, Andres Tejada Martinez, Gita Iranipour, Luke Mulford, Aydin Sunol

Abstract:

Modeling of Biological Wastewater Treatment Plants requires several parameters for kinetic rate expressions, thermo-physical properties, and hydrodynamic behavior. The kinetics and associated mechanisms become complex due to several biological processes taking place in wastewater treatment plants at varying times and spatial scales. A dynamic process model that incorporated the complex model for activated sludge kinetics was developed using the BioWin software platform for an Advanced Wastewater Treatment Plant in Valrico, Florida. Due to the extensive number of tunable parameters, an experimental design was employed for judicious selection of the most influential parameter sets and their bounds. The model was tuned using both the influent and effluent plant data to reconcile and rectify the forecasted results from the BioWin Model. Amount of mixed liquor suspended solids in the oxidation ditch, aeration rates and recycle rates were adjusted accordingly. The experimental analysis and plant SCADA data were used to predict influent wastewater rates and composition profiles as a function of time for extended periods. The lumped dynamic model development process was coupled with Computational Fluid Dynamics (CFD) modeling of the key units such as oxidation ditches in the plant. Several CFD models that incorporate the nitrification-denitrification kinetics, as well as, hydrodynamics was developed and being tested using ANSYS Fluent software platform. These realistic and verified models developed using BioWin and ANSYS were used to plan beforehand the operating policies and control strategies for the biological wastewater plant accordingly that further allows regulatory compliance at minimum operational cost. These models, with a little bit of tuning, can be used for other biological wastewater treatment plants as well. The BioWin model mimics the existing performance of the Valrico Plant which allowed the operators and engineers to predict effluent behavior and take control actions to meet the discharge limits of the plant. Also, with the help of this model, we were able to find out the key kinetic and stoichiometric parameters which are significantly more important for modeling of biological wastewater treatment plants. One of the other important findings from this model were the effects of mixed liquor suspended solids and recycle ratios on the effluent concentration of various parameters such as total nitrogen, ammonia, nitrate, nitrite, etc. The ANSYS model allowed the abstraction of information such as the formation of dead zones increases through the length of the oxidation ditches as compared to near the aerators. These profiles were also very useful in studying the behavior of mixing patterns, effect of aerator speed, and use of baffles which in turn helps in optimizing the plant performance.

Keywords: computational fluid dynamics, flow-sheet simulation, kinetic modeling, process dynamics

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6 Wetting Characterization of High Aspect Ratio Nanostructures by Gigahertz Acoustic Reflectometry

Authors: C. Virgilio, J. Carlier, P. Campistron, M. Toubal, P. Garnier, L. Broussous, V. Thomy, B. Nongaillard

Abstract:

Wetting efficiency of microstructures or nanostructures patterned on Si wafers is a real challenge in integrated circuits manufacturing. In fact, bad or non-uniform wetting during wet processes limits chemical reactions and can lead to non-complete etching or cleaning inside the patterns and device defectivity. This issue is more and more important with the transistors size shrinkage and concerns mainly high aspect ratio structures. Deep Trench Isolation (DTI) structures enabling pixels’ isolation in imaging devices are subject to this phenomenon. While low-frequency acoustic reflectometry principle is a well-known method for Non Destructive Test applications, we have recently shown that it is also well suited for nanostructures wetting characterization in a higher frequency range. In this paper, we present a high-frequency acoustic reflectometry characterization of DTI wetting through a confrontation of both experimental and modeling results. The acoustic method proposed is based on the evaluation of the reflection of a longitudinal acoustic wave generated by a 100 µm diameter ZnO piezoelectric transducer sputtered on the silicon wafer backside using MEMS technologies. The transducers have been fabricated to work at 5 GHz corresponding to a wavelength of 1.7 µm in silicon. The DTI studied structures, manufactured on the wafer frontside, are crossing trenches of 200 nm wide and 4 µm deep (aspect ratio of 20) etched into a Si wafer frontside. In that case, the acoustic signal reflection occurs at the bottom and at the top of the DTI enabling its characterization by monitoring the electrical reflection coefficient of the transducer. A Finite Difference Time Domain (FDTD) model has been developed to predict the behavior of the emitted wave. The model shows that the separation of the reflected echoes (top and bottom of the DTI) from different acoustic modes is possible at 5 Ghz. A good correspondence between experimental and theoretical signals is observed. The model enables the identification of the different acoustic modes. The evaluation of DTI wetting is then performed by focusing on the first reflected echo obtained through the reflection at Si bottom interface, where wetting efficiency is crucial. The reflection coefficient is measured with different water / ethanol mixtures (tunable surface tension) deposited on the wafer frontside. Two cases are studied: with and without PFTS hydrophobic treatment. In the untreated surface case, acoustic reflection coefficient values with water show that liquid imbibition is partial. In the treated surface case, the acoustic reflection is total with water (no liquid in DTI). The impalement of the liquid occurs for a specific surface tension but it is still partial for pure ethanol. DTI bottom shape and local pattern collapse of the trenches can explain these incomplete wetting phenomena. This high-frequency acoustic method sensitivity coupled with a FDTD propagative model thus enables the local determination of the wetting state of a liquid on real structures. Partial wetting states for non-hydrophobic surfaces or low surface tension liquids are then detectable with this method.

Keywords: wetting, acoustic reflectometry, gigahertz, semiconductor

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5 3D Printing of Polycaprolactone Scaffold with Multiscale Porosity Via Incorporation of Sacrificial Sucrose Particles

Authors: Mikaela Kutrolli, Noah S. Pereira, Vanessa Scanlon, Mohamadmahdi Samandari, Ali Tamayol

Abstract:

Bone tissue engineering has drawn significant attention and various biomaterials have been tested. Polymers such as polycaprolactone (PCL) offer excellent biocompatibility, reasonable mechanical properties, and biodegradability. However, PCL scaffolds suffer a critical drawback: a lack of micro/mesoporosity, affecting cell attachment, tissue integration, and mineralization. It also results in a slow degradation rate. While 3D-printing has addressed the issue of macroporosity through CAD-guided fabrication, PCL scaffolds still exhibit poor smaller-scale porosity. To overcome this, we generated composites of PCL, hydroxyapatite (HA), and powdered sucrose (PS). The latter serves as a sacrificial material to generate porous particles after sucrose dissolution. Additionally, we have incorporated dexamethasone (DEX) to boost the PCL osteogenic properties. The resulting scaffolds maintain controlled macroporosity from the lattice print structure but also develop micro/mesoporosity within PCL fibers when exposed to aqueous environments. The study involved mixing PS into solvent-dissolved PCL in different weight ratios of PS to PCL (70:30, 50:50, and 30:70 wt%). The resulting composite was used for 3D printing of scaffolds at room temperature. Printability was optimized by adjusting pressure, speed, and layer height through filament collapse and fusion test. Enzymatic degradation, porogen leaching, and DEX release profiles were characterized. Physical properties were assessed using wettability, SEM, and micro-CT to quantify the porosity (percentage, pore size, and interconnectivity). Raman spectroscopy was used to verify the absence of sugar after leaching. Mechanical characteristics were evaluated via compression testing before and after porogen leaching. Bone marrow stromal cells (BMSCs) behavior in the printed scaffolds was studied by assessing viability, metabolic activity, osteo-differentiation, and mineralization. The scaffolds with a 70% sugar concentration exhibited superior printability and reached the highest porosity of 80%, but performed poorly during mechanical testing. A 50% PS concentration demonstrated a 70% porosity, with an average pore size of 25 µm, favoring cell attachment. No trace of sucrose was found in Raman after leaching the sugar for 8 hours. Water contact angle results show improved hydrophilicity as the sugar concentration increased, making the scaffolds more conductive to cell adhesion. The behavior of bone marrow stromal cells (BMSCs) showed positive viability and proliferation results with an increasing trend of mineralization and osteo-differentiation as the sucrose concentration increased. The addition of HA and DEX also promoted mineralization and osteo-differentiation in the cultures. The integration of PS as porogen at a concentration of 50%wt within PCL scaffolds presents a promising approach to address the poor cell attachment and tissue integration issues of PCL in bone tissue engineering. The method allows for the fabrication of scaffolds with tunable porosity and mechanical properties, suitable for various applications. The addition of HA and DEX further enhanced the scaffolds. Future studies will apply the scaffolds in an in-vivo model to thoroughly investigate their performance.

Keywords: bone, PCL, 3D printing, tissue engineering

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4 Multifunctional Epoxy/Carbon Laminates Containing Carbon Nanotubes-Confined Paraffin for Thermal Energy Storage

Authors: Giulia Fredi, Andrea Dorigato, Luca Fambri, Alessandro Pegoretti

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Thermal energy storage (TES) is the storage of heat for later use, thus filling the gap between energy request and supply. The most widely used materials for TES are the organic solid-liquid phase change materials (PCMs), such as paraffin. These materials store/release a high amount of latent heat thanks to their high specific melting enthalpy, operate in a narrow temperature range and have a tunable working temperature. However, they suffer from a low thermal conductivity and need to be confined to prevent leakage. These two issues can be tackled by confining PCMs with carbon nanotubes (CNTs). TES applications include the buildings industry, solar thermal energy collection and thermal management of electronics. In most cases, TES systems are an additional component to be added to the main structure, but if weight and volume savings are key issues, it would be advantageous to embed the TES functionality directly in the structure. Such multifunctional materials could be employed in the automotive industry, where the diffusion of lightweight structures could complicate the thermal management of the cockpit environment or of other temperature sensitive components. This work aims to produce epoxy/carbon structural laminates containing CNT-stabilized paraffin. CNTs were added to molten paraffin in a fraction of 10 wt%, as this was the minimum amount at which no leakage was detected above the melting temperature (45°C). The paraffin/CNT blend was cryogenically milled to obtain particles with an average size of 50 µm. They were added in various percentages (20, 30 and 40 wt%) to an epoxy/hardener formulation, which was used as a matrix to produce laminates through a wet layup technique, by stacking five plies of a plain carbon fiber fabric. The samples were characterized microstructurally, thermally and mechanically. Differential scanning calorimetry (DSC) tests showed that the paraffin kept its ability to melt and crystallize also in the laminates, and the melting enthalpy was almost proportional to the paraffin weight fraction. These thermal properties were retained after fifty heating/cooling cycles. Laser flash analysis showed that the thermal conductivity through the thickness increased with an increase of the PCM, due to the presence of CNTs. The ability of the developed laminates to contribute to the thermal management was also assessed by monitoring their cooling rates through a thermal camera. Three-point bending tests showed that the flexural modulus was only slightly impaired by the presence of the paraffin/CNT particles, while a more sensible decrease of the stress and strain at break and the interlaminar shear strength was detected. Optical and scanning electron microscope images revealed that these could be attributed to the preferential location of the PCM in the interlaminar region. These results demonstrated the feasibility of multifunctional structural TES composites and highlighted that the PCM size and distribution affect the mechanical properties. In this perspective, this group is working on the encapsulation of paraffin in a sol-gel derived organosilica shell. Submicron spheres have been produced, and the current activity focuses on the optimization of the synthesis parameters to increase the emulsion efficiency.

Keywords: carbon fibers, carbon nanotubes, lightweight materials, multifunctional composites, thermal energy storage

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3 Expanded Polyurethane Foams and Waterborne-Polyurethanes from Vegetable Oils

Authors: A.Cifarelli, L. Boggioni, F. Bertini, L. Magon, M. Pitalieri, S. Losio

Abstract:

Nowadays, the growing environmental awareness and the dwindling of fossil resources stimulate the polyurethane (PU) industry towards renewable polymers with low carbon footprint to replace the feed stocks from petroleum sources. The main challenge in this field consists in replacing high-performance products from fossil-fuel with novel synthetic polymers derived from 'green monomers'. The bio-polyols from plant oils have attracted significant industrial interest and major attention in scientific research due to their availability and biodegradability. Triglycerides rich in unsaturated fatty acids, such as soybean oil (SBO) and linseed oil (ELO), are particularly interesting because their structures and functionalities are tunable by chemical modification in order to obtain polymeric materials with expected final properties. Unfortunately, their use is still limited for processing or performance problems because a high functionality, as well as OH number of the polyols will result in an increase in cross-linking densities of the resulting PUs. The main aim of this study is to evaluate soy and linseed-based polyols as precursors to prepare prepolymers for the production of polyurethane foams (PUFs) or waterborne-polyurethanes (WPU) used as coatings. An effective reaction route is employed for its simplicity and economic impact. Indeed, bio-polyols were synthesized by a two-step method: epoxidation of the double bonds in vegetable oils and solvent-free ring-opening reaction of the oxirane with organic acids. No organic solvents have been used. Acids with different moieties (aliphatic or aromatics) and different length of hydrocarbon backbones can be used to customize polyols with different functionalities. The ring-opening reaction requires a fine tuning of the experimental conditions (time, temperature, molar ratio of carboxylic acid and epoxy group) to control the acidity value of end-product as well as the amount of residual starting materials. Besides, a Lewis base catalyst is used to favor the ring opening reaction of internal epoxy groups of the epoxidized oil and minimize the formation of cross-linked structures in order to achieve less viscous and more processable polyols with narrower polydispersity indices (molecular weight lower than 2000 g/mol⁻¹). The functionality of optimized polyols is tuned from 2 to 4 per molecule. The obtained polyols are characterized by means of GPC, NMR (¹H, ¹³C) and FT-IR spectroscopy to evaluate molecular masses, molecular mass distributions, microstructures and linkage pathways. Several polyurethane foams have been prepared by prepolymer method blending conventional synthetic polyols with new bio-polyols from soybean and linseed oils without using organic solvents. The compatibility of such bio-polyols with commercial polyols and diisocyanates is demonstrated. The influence of the bio-polyols on the foam morphology (cellular structure, interconnectivity), density, mechanical and thermal properties has been studied. Moreover, bio-based WPUs have been synthesized by well-established processing technology. In this synthesis, a portion of commercial polyols is substituted by the new bio-polyols and the properties of the coatings on leather substrates have been evaluated to determine coating hardness, abrasion resistance, impact resistance, gloss, chemical resistance, flammability, durability, and adhesive strength.

Keywords: bio-polyols, polyurethane foams, solvent free synthesis, waterborne-polyurethanes

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2 Biocellulose as Platform for the Development of Multifunctional Materials

Authors: Junkal Gutierrez, Hernane S. Barud, Sidney J. L. Ribeiro, Agnieszka Tercjak

Abstract:

Nowadays the interest on green nanocomposites and on the development of more environmental friendly products has been increased. Bacterial cellulose has been recently investigated as an attractive environmentally friendly material for the preparation of low-cost nanocomposites. The formation of cellulose by laboratory bacterial cultures is an interesting and attractive biomimetic access to obtain pure cellulose with excellent properties. Additionally, properties as molar mass, molar mass distribution, and the supramolecular structure could be control using different bacterial strain, culture mediums and conditions, including the incorporation of different additives. This kind of cellulose is a natural nanomaterial, and therefore, it has a high surface-to-volume ratio which is highly advantageous in composites production. Such property combined with good biocompatibility, high tensile strength, and high crystallinity makes bacterial cellulose a potential material for applications in different fields. The aim of this investigation work was the fabrication of novel hybrid inorganic-organic composites based on bacterial cellulose, cultivated in our laboratory, as a template. This kind of biohybrid nanocomposites gathers together excellent properties of bacterial cellulose with the ones displayed by typical inorganic nanoparticles like optical, magnetic and electrical properties, luminescence, ionic conductivity and selectivity, as well as chemical or biochemical activity. In addition, the functionalization of cellulose with inorganic materials opens new pathways for the fabrication of novel multifunctional hybrid materials with promising properties for a wide range of applications namely electronic paper, flexible displays, solar cells, sensors, among others. In this work, different pathways for fabrication of multifunctional biohybrid nanopapers with tunable properties based on BC modified with amphiphilic poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) (EPE) block copolymer, sol-gel synthesized nanoparticles (titanium, vanadium and a mixture of both oxides) and functionalized iron oxide nanoparticles will be presented. In situ (biosynthesized) and ex situ (at post-production level) approaches were successfully used to modify BC membranes. Bacterial cellulose based biocomposites modified with different EPE block copolymer contents were developed by in situ technique. Thus, BC growth conditions were manipulated to fabricate EPE/BC nanocomposite during the biosynthesis. Additionally, hybrid inorganic/organic nanocomposites based on BC membranes and inorganic nanoparticles were designed via ex-situ method, by immersion of never-dried BC membranes into different nanoparticle solutions. On the one hand, sol-gel synthesized nanoparticles (titanium, vanadium and a mixture of both oxides) and on the other hand superparamagnetic iron oxide nanoparticles (SPION), Fe2O3-PEO solution. The morphology of designed novel bionanocomposites hybrid materials was investigated by atomic force microscopy (AFM) and scanning electron microscopy (SEM). In order to characterized obtained materials from the point of view of future applications different techniques were employed. On the one hand, optical properties were analyzed by UV-vis spectroscopy and spectrofluorimetry and on the other hand electrical properties were studied at nano and macroscale using electric force microscopy (EFM), tunneling atomic force microscopy (TUNA) and Keithley semiconductor analyzer, respectively. Magnetic properties were measured by means of magnetic force microscopy (MFM). Additionally, mechanical properties were also analyzed.

Keywords: bacterial cellulose, block copolymer, advanced characterization techniques, nanoparticles

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1 Metal-Organic Frameworks-Based Materials for Volatile Organic Compounds Sensing Applications: Strategies to Improve Sensing Performances

Authors: Claudio Clemente, Valentina Gargiulo, Alessio Occhicone, Giovanni Piero Pepe, Giovanni Ausanio, Michela Alfè

Abstract:

Volatile organic compound (VOC) emissions represent a serious risk to human health and the integrity of the ecosystems, especially at high concentrations. For this reason, it is very important to continuously monitor environmental quality and develop fast and reliable portable sensors to allow analysis on site. Chemiresistors have become promising candidates for VOC sensing as their ease of fabrication, variety of suitable sensitive materials, and simple sensing data. A chemoresistive gas sensor is a transducer that allows to measure the concentration of an analyte in the gas phase because the changes in resistance are proportional to the amount of the analyte present. The selection of the sensitive material, which interacts with the target analyte, is very important for the sensor performance. The most used VOC detection materials are metal oxides (MOx) for their rapid recovery, high sensitivity to various gas molecules, easy fabrication. Their sensing performance can be improved in terms of operating temperature, selectivity, and detection limit. Metal-organic frameworks (MOFs) have attracted a lot of attention also in the field of gas sensing due to their high porosity, high surface area, tunable morphologies, structural variety. MOFs are generated by the self-assembly of multidentate organic ligands connecting with adjacent multivalent metal nodes via strong coordination interactions, producing stable and highly ordered crystalline porous materials with well-designed structures. However, most MOFs intrinsically exhibit low electrical conductivity. To improve this property, MOFs can be combined with organic and inorganic materials in a hybrid fashion to produce composite materials or can be transformed into more stable structures. MOFs, indeed, can be employed as the precursors of metal oxides with well-designed architectures via the calcination method. The MOF-derived MOx partially preserved the original structure with high surface area and intrinsic open pores, which act as trapping centers for gas molecules, and showed a higher electrical conductivity. Core-shell heterostructures, in which the surface of a metal oxide core is completely coated by a MOF shell, forming a junction at the core-shell heterointerface, can also be synthesized. Also, nanocomposite in which MOF structures are intercalated with graphene related materials can also be produced, and the conductivity increases thanks to the high mobility of electrons of carbon materials. As MOF structures, zinc-based MOFs belonging to the ZIF family were selected in this work. Several Zn-based materials based and/or derived from MOFs were produced, structurally characterized, and arranged in a chemo resistive architecture, also exploring the potentiality of different approaches of sensing layer deposition based on PLD (pulsed laser deposition) and, in case of thermally labile materials, MAPLE (Matrix Assisted Pulsed Laser Evaporation) to enhance the adhesion to the support. The sensors were tested in a controlled humidity chamber, allowing for the possibility of varying the concentration of ethanol, a typical analyte chosen among the VOCs for a first survey. The effect of heating the chemiresistor to improve sensing performances was also explored. Future research will focus on exploring new manufacturing processes for MOF-based gas sensors with the aim to improve sensitivity, selectivity and reduce operating temperatures.

Keywords: chemiresistors, gas sensors, graphene related materials, laser deposition, MAPLE, metal-organic frameworks, metal oxides, nanocomposites, sensing performance, transduction mechanism, volatile organic compounds

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