Search results for: reversibility

Authors: Joao Teotonio Manzi

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Reversibility, irreversibility, equilibrium and steady-state that play a central role in the thermodynamic analysis of processes arising in the context of reactive systems are discussed in this article. Such concepts have generated substantial doubts, even among the most experienced researchers, and engineers, because from the literature, conclusive or definitive statements cannot be extracted. Concepts such as the time-reversibility of irreversible processes seem paradoxical, requiring further analysis. Equilibrium and reversibility, which appear to be of the same nature, have also been re-examined in the light of maximum entropy. The goal of this paper is to revisit and explore these concepts based on classical thermodynamics in order to have a better understanding them due to their impacts on technological advances, as a result, to generate an optimal procedure for designing, monitoring, and engineering optimization. Furthermore, an effective graphic procedure for dimensioning a Plug Flow Reactor has been provided. Thus, to meet the needs of chemical engineering from a simple conceptual analysis but with significant practical effects, a macroscopic approach is taken so as to integrate the different parts of this paper.

Keywords: reversibility, equilibrium, steady-state, thermodynamics, reactive system

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Authors: Aries Nawel, Bentarzi Mohamed

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This paper deals with the study of some probabilistic and statistical properties of a Periodic Integer-Valued Moving Average Model (PINMA_{S}(q)). The closed forms of the mean, the second moment and the periodic autocovariance function are obtained. Furthermore, the time reversibility of the model is discussed in details. Moreover, the estimation of the underlying parameters are obtained by the Yule-Walker method, the Conditional Least Square method (CLS) and the Weighted Conditional Least Square method (WCLS). A simulation study is carried out to evaluate the performance of the estimation method. Moreover, an application on real data set is provided.

Keywords: periodic integer-valued moving average, periodically correlated process, time reversibility, count data

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Authors: Aicha Laouani, Pascale Calabrese, Sonia Rouatbi, Saad Saguem

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Distances between signals (S d) and between asters (A d) calculated from respiratory inductive plethysmography signals has been used in order to evaluation airways resistances (Raw) during reversibility test among 28 subject with airways obstructions. Correlations studies between these distances and Raw measured by body plethysmography (BP) showed that these RIP variables could be potentially used in airway resistance assessment in patients with airway obstruction. Significant correlation was found between ΔAd and airway resistance changes (ΔRaw) (r= 0.407, p=0.03) and not between ΔSd and ΔRaw. This assumption was supported by the high correlations found when relating the average of ΔS and of ΔA calculated on successive intervals of ΔRaw, with the ΔRaw averages calculated for each interval (r= 0.892, p= 0.006 and r= 0.857, p=0.006 respectively).

Keywords: airways obstruction, distances, respiratory inductive plethysmography, reversibility test

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Authors: Malgorzata Schwab, Ashis Kumer Biswas

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In this concept paper, we explore the topic of Reversibility in Neural Networks leveraged for Network Integrity Verification and crafted the term ''Trusted Neural Network'' (TNN), paired with the API abstraction around it, to embrace the idea formally. This newly proposed high-level generalizable TNN model builds upon the Invertible Neural Network architecture, trained simultaneously in both forward and reverse directions. This allows for the original system inputs to be compared with the ones reconstructed from the outputs in the reversed flow to assess the integrity of the end-to-end inference flow. The outcome of that assessment is captured as an Integrity Score. Concrete implementation reflecting the needs of specific problem domains can be derived from this general approach and is demonstrated in the experiments. The model aspires to become a useful practice in drafting high-level systems architectures which incorporate AI capabilities.

Keywords: trusted, neural, invertible, API

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Authors: Vishal Pareek, Shubham Gupta, Sushil Chandra Jain

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With increasing high-speed computation demand the power consumption, heat dissipation and chip size issues are posing challenges for logic design with conventional technologies. Recovery of bit loss and bit errors is other issues that require reversibility and fault tolerance in the computation. The reversible computing is emerging as an alternative to conventional technologies to overcome the above problems and helpful in a diverse area such as low-power design, nanotechnology, quantum computing. Bit loss issue can be solved through unique input-output mapping which require reversibility and bit error issue require the capability of fault tolerance in design. In order to incorporate reversibility a number of combinational reversible logic based circuits have been developed. However, very few sequential reversible circuits have been reported in the literature. To make the circuit fault tolerant, a number of fault model and test approaches have been proposed for reversible logic. In this paper, we have attempted to incorporate fault tolerance in sequential reversible building blocks such as D flip-flop, T flip-flop, JK flip-flop, R-S flip-flop, Master-Slave D flip-flop, and double edge triggered D flip-flop by making them parity preserving. The importance of this proposed work lies in the fact that it provides the design of reversible sequential circuits completely testable for any stuck-at fault and single bit fault. In our opinion our design of reversible building blocks is superior to existing designs in term of quantum cost, hardware complexity, constant input, garbage output, number of gates and design of online testable D flip-flop have been proposed for the first time. We hope our work can be extended for building complex reversible sequential circuits.

Keywords: parity preserving gate, quantum computing, fault tolerance, flip-flop, sequential reversible logic

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Authors: Ramon Santana

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The use of biometric identifiers in the field of information security, access control to resources, authentication in ATMs and banking among others, are of great concern because of the safety of biometric data. In the general architecture of a biometric system have been detected eight vulnerabilities, six of them allow obtaining minutiae template in plain text. The main consequence of obtaining minutia templates is the loss of biometric identifier for life. To mitigate these vulnerabilities several models to protect minutiae templates have been proposed. Several vulnerabilities in the cryptographic security of these models allow to obtain biometric data in plain text. In order to increase the cryptographic security and ease of reversibility, a minutiae templates protection model is proposed. The model aims to make the cryptographic protection and facilitate the reversibility of data using two levels of security. The first level of security is the data transformation level. In this level generates invariant data to rotation and translation, further transformation is irreversible. The second level of security is the evaluation level, where the encryption key is generated and data is evaluated using a defined evaluation function. The model is aimed at mitigating known vulnerabilities of the proposed models, basing its security on the impossibility of the polynomial reconstruction.

Keywords: fingerprint, template protection, bio-cryptography, minutiae protection

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Authors: Tzan-Chain Lee

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Seeds are non-leaves green tissues. Photosynthesis begins with light absorption by chlorophyll and then the energy transfer between two pigment-protein complexes (PPC). Most studies of photosynthesis and PPC expression were focused on leaves; however, during seeds’ development were rare. Developed seeds from beginning pod (stage R3) to dried seed (stage R8), and the dried seed after sowing for 1-4 day, were analyzed for their chlorophyll contents. Thornber and MARS gel systems analysis compositions of PPC. Chlorophyll fluorescence was used to detect maximal photosynthetic efficiency (Fv/Fm). During soybean and black soybean seeds development (stages R3-R6), Fv/Fm up to 0.8, and then down-regulated after full seed (stage R7). In dried seed (stage R8), the two plant seeds lost photosynthetic activity (Fv/Fm=0), but chlorophyll degradation only occurred in soybean after full seed. After seeds sowing for 4 days, chlorophyll drastically increased in soybean seeds, and Fv/Fm recovered to 0.8 in the two seeds. In PPC, the two soybean seeds contained all PPC during seeds development (stages R3-R6), including CPI, CPII, A1, AB1, AB2, and AB3. However, many proteins A1, AB1, AB2, and CPI were totally missing in the two dried seeds (stage R8). The deficiency of these proteins in dried seeds might be caused by the incomplete photosynthetic activity. After seeds germination and seedling exposed to light for 4 days, all PPC were recovered, suggesting that completed PPC took place in the two soybean seeds. This study showed the reversibility of photosynthetic activity and pigment-protein complexes during soybean and black soybean seeds development.

Keywords: light-harvesting complex, pigment–protein complexes, soybean cotyledon, grana development

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Authors: Nika Botchorishvili, Olgha Giorgishvili

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Many-year investigations of the nature of damping creep of rigid bodies and materials led to the discovery of the fundamental character of this phenomenon. It occurs only when a rigid body comes in contact with a surface-active medium (liquid or gaseous), which brings about a decrease of the free surface energy of a rigid body as a result of adsorption, chemo-sorption or wetting. The reversibility of the process consists of a gradual disappearance of creep deformation when the action of a surface-active medium stops. To clarify the essence of processes, a physical model is constructed by using Griffith’s scheme and the well-known representation formulas of deformation origination and failure processes. The total creep deformation is caused by the formation and opening of microcracks throughout the material volume under the action of load. This supposedly happens in macroscopically homogeneous silicate and organic glasses, while in polycrystals (tuff, gypsum, steel) contacting with a surface-active medium micro crack are formed mainly on the grain boundaries. The creep of rubber is due to its swelling activated by stress. Acknowledgment: All experiments are financially supported by Shota Rustaveli National Science Foundation of Georgia. Study of Properties of Concretes (Both Ordinary and Compacted) Made of Local Building Materials and Containing Admixtures, and Their Further Introduction in Construction Operations and Road Building. DP2016_26. 22.12.2016.

Keywords: process reversibility, surface-active medium, Rebinder’s effect, micro crack, creep

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Authors: Ryan Brisbin, Hassan Harb, Justin Debow, Hrant Hratchian, Ryan Baxter

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Donor-Acceptor (DA) frameworks are crucial parts of any technology requiring charge transport. This type of behavior is ubiquitous across technologies from semi conductors to solar panels. Currently, most DA systems involve metallic components, but progressive research is being pursued to design fully organic DA systems to be used as both organic semi-conductors and light emitting diodes. These systems are currently comprised of conductive polymers and salts. However, little is known about the effect of various physical aspects (size, torsional angle, electron density) have on the act of reversible charge transfer. Herein, the effect of torsional angle on reductive stability in bis(imino)pyridines is analyzed using a combination of single crystal analysis and electro-chemical peak current ratios from cyclic voltammetry. The computed free energies of reduction and electron attachment points were also investigated through density functional theory and natural ionization orbital theory to gain greater understanding of the global effect torsional angles have on electron transfer in bis(imino)pyridines. Findings indicated that torsional angles are a multi-variable parameter affected by both local steric constraints and resonant electronic contributions. Local steric impacted torsional angles demonstrated a negligible effect on electrochemical reversibility, while resonant affected torsional angles were observed to significantly alter the electrochemical reversibility.

Keywords: cyclic voltammetry, bis(imino)pyridines, structure-activity relationship, torsional angles

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Authors: Samira Bensoltane, Smina Ait Hamlet, Samti Meriem, Semmasel Asma

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Living organisms in the soil are subject to regular fluctuations of abiotic parameters, as well as a chemical contamination of the environment due to human activities. They are subject to multiple stressors they face. The aim of our work was to study the effects of insecticide: thiamethoxam (neonicotinoid), and the potential reversibility of the effects by an antioxidant: ginger on a bioindicator species in ecotoxicology, the land snail Helix aspersa. The effects were studied by a targeted cell approach of evaluating the effect of these molecules on tissue and cellular aspect of hepatopancreas through histological study. Treatment with thiamethoxam concentrations 10, 20, and 40 mg/l shows signs of inflammation even at low concentrations and from the 5th day of treatment. Histological examination of the hepatopancreas of snails treated with thiamethoxam showed significant changes from the lowest concentrations tested , note intertubular connective tissue enlargement, necrosis deferent types of cells (cells with calcium , digestive, excretory) , also damage acini, alteration of the apical membrane and lysis of the basement membrane in a dose- dependent manner. After 10 days of treatment and with 40 mg/l, the same changes were observed with a very advanced degeneration of the wall of the member that could be confused with the cell debris. For cons, the histological study of the hepatopancreas in Helix aspersa treated with ginger for a period of 15 days after stopping treatment with thiamethoxam has shown a partial regeneration of hepatopancreatic tissue snails treated with all concentrations of thiamethoxam and especially in the intertubular connective tissue of the wall and hepatopancreatic digestive tubules. Finally, we can conclude that monitoring the effect of the insecticide thiamethoxam showed significant alterations, however, treatment with ginger shows regeneration of damaged cells themselves much sharper at low concentration (10 mg/L).

Keywords: Helix aspersa, insecticides, thiamethoxam, ginger, hepatopancreas

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Authors: Daniel Manaye Kabtamu, Anteneh Wodaje Bayeh

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With the development and utilization of new energy technology, people’s demand for large-scale energy storage system has become increasingly urgent. Vanadium redox flow battery (VRFB) is one of the most promising technologies for grid-scale energy storage applications because of numerous attractive features, such as long cycle life, high safety, and flexible design. However, the relatively low energy efficiency and high production cost of the VRFB still limit its practical implementations. It is of great attention to enhance its energy efficiency and reduce its cost. One of the main components of VRFB that can impressively impact the efficiency and final cost is the electrode materials, which provide the reactions sites for redox couples (V₂₊/V³⁺ and VO²⁺/VO₂⁺). Graphite felt (GF) is a typical carbon-based material commonly employed as electrode for VRFB due to low-cost, good chemical and mechanical stability. However, pristine GF exhibits insufficient wettability, low specific surface area, and poor kinetics reversibility, leading to low energy efficiency of the battery. Therefore, it is crucial to further modify the GF electrode to improve its electrochemical performance towards VRFB by employing active electrocatalysts, such as less expensive metal oxides. This study successfully fabricates low-cost plate-like bismuth vanadate (BiVO₄) material through a simple one-step hydrothermal route, employed as an electrocatalyst to adorn the GF for use as the negative electrode in VRFB. The experimental results show that BiVO₄-3h exhibits the optimal electrocatalytic activity and reversibility for the vanadium redox couples among all samples. The energy efficiency of the VRFB cell assembled with BiVO₄-decorated GF as the negative electrode is found to be 75.42% at 100 mA cm−2, which is about 10.24% more efficient than that of the cell assembled with heat-treated graphite felt (HT-GF) electrode. The possible reasons for the activity enhancement can be ascribed to the existence of oxygen vacancies in the BiVO₄ lattice structure and the relatively high surface area of BiVO₄, which provide more active sites for facilitating the vanadium redox reactions. Furthermore, the BiVO₄-GF electrode obstructs the competitive irreversible hydrogen evolution reaction on the negative side of the cell, and it also has better wettability. Impressively, BiVO₄-GF as the negative electrode shows good stability over 100 cycles. Thus, BiVO₄-GF is a promising negative electrode candidate for practical VRFB applications.

Keywords: BiVO₄ electrocatalyst, electrochemical energy storage, graphite felt, vanadium redox flow battery

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Authors: Michele Aleandri, Matteo Colangeli, Davide Gabrielli

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We study a generalization to a continuous setting of the classical Markov chain tree theorem. In particular, we consider an irreducible diffusion process on a metric graph. The unique invariant measure has an atomic component on the vertices and an absolutely continuous part on the edges. We show that the corresponding density at x can be represented by a normalized superposition of the weights associated to metric arborescences oriented toward the point x. A metric arborescence is a metric tree oriented towards its root. The weight of each oriented metric arborescence is obtained by the product of the exponential of integrals of the form ∫a/b², where b is the drift and σ² is the diffusion coefficient, along the oriented edges, for a weight for each node determined by the local orientation of the arborescence around the node and for the inverse of the diffusion coefficient at x. The metric arborescences are obtained by cutting the original metric graph along some edges.

Keywords: diffusion processes, metric graphs, invariant measure, reversibility

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Authors: Toshanlal Meenpal, Ankita Meenpal

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A very important technique in reversible data hiding field is Difference expansion. Secret message as well as the cover image may be completely recovered without any distortion after data extraction process due to reversibility feature. In general, in any difference expansion scheme embedding is performed by integer transform in the difference image acquired by grouping two neighboring pixel values. This paper proposes an improved reversible difference expansion embedding scheme. We mainly consider edge direction for embedding by modifying the difference of two neighboring pixels values. In general, the larger difference tends to bring a degraded stego image quality than the smaller difference. Image quality in the range of 0.5 to 3.7 dB in average is achieved by the proposed scheme, which is shown through the experimental results. However payload wise it achieves almost similar capacity in comparisons with previous method.

Keywords: information hiding, wedge direction, difference expansion, integer transform

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Authors: Peter O. Osifo, Hein W. J. P. Neomagus

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In this study, a predicted pH model was used to determine adsorption equilibrium properties of copper, lead, zinc and cadmium. Chitosan was prepared from the exoskeleton of Cape rock-lobsters, collected from the surroundings of Cape Town, South Africa. The beads were cross-linked with gluteraldehyde to restore its chemical stability in acid media. The chitosan beads were characterized; the beads water contents and pKa varied in the range of 90-96% and 4.3-6.0 respectively and the degree of crosslinking for the beads was 18%. A pH-model, which described the reversibility of the metal adsorbed onto the beads, was used to predict the equilibrium properties of copper, lead, zinc and cadmium adsorption onto the cross-linked beads. The model accounts for the effect of pH and the important model parameters; the equilibrium adsorption constant (Kads) and to a lesser extent the adsorbent adsorption capacity (qmax). The adsorption equilibrium constant for copper, lead, zinc and cadmium were found to be 2.58×10-3, 2.22×0-3, 9.55×0-3, and 4.79×0-3, respectively. The adsorbent maximum capacity was determined to be 4.2 mmol/g.

Keywords: chitosan beads, adsorption, heavy metals, waste water

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Authors: Osman Adiguzel

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Shape memory alloys take place in a class of smart materials by exhibiting a peculiar property called the shape memory effect. This property is characterized by the recoverability of two certain shapes of material at different temperatures. These materials are often called smart materials due to their functionality and their capacity of responding to changes in the environment. Shape memory materials are used as shape memory devices in many interdisciplinary fields such as medicine, bioengineering, metallurgy, building industry and many engineering fields. The shape memory effect is performed thermally by heating and cooling after first cooling and stressing treatments, and this behavior is called thermoelasticity. This effect is based on martensitic transformations characterized by changes in the crystal structure of the material. The shape memory effect is the result of successive thermally and stress-induced martensitic transformations. Shape memory alloys exhibit thermoelasticity and superelasticity by means of deformation in the low-temperature product phase and high-temperature parent phase region, respectively. Superelasticity is performed by stressing and releasing the material in the parent phase region. Loading and unloading paths are different in the stress-strain diagram, and the cycling loop reveals energy dissipation. The strain energy is stored after releasing, and these alloys are mainly used as deformation absorbent materials in control of civil structures subjected to seismic events, due to the absorbance of strain energy during any disaster or earthquake. Thermal-induced martensitic transformation occurs thermally on cooling, along with lattice twinning with cooperative movements of atoms by means of lattice invariant shears, and ordered parent phase structures turn into twinned martensite structures, and twinned structures turn into the detwinned structures by means of stress-induced martensitic transformation by stressing the material in the martensitic condition. Thermal induced transformation occurs with the cooperative movements of atoms in two opposite directions, <110 > -type directions on the {110} - type planes of austenite matrix which is the basal plane of martensite. Copper-based alloys exhibit this property in the metastable β-phase region, which has bcc-based structures at high-temperature parent phase field. Lattice invariant shear and twinning is not uniform in copper-based ternary alloys and gives rise to the formation of complex layered structures, depending on the stacking sequences on the close-packed planes of the ordered parent phase lattice. In the present contribution, x-ray diffraction and transmission electron microscopy (TEM) studies were carried out on two copper-based CuAlMn and CuZnAl alloys. X-ray diffraction profiles and electron diffraction patterns reveal that both alloys exhibit superlattice reflections inherited from the parent phase due to the displacive character of martensitic transformation. X-ray diffractograms taken in a long time interval show that diffraction angles and intensities of diffraction peaks change with the aging duration at room temperature. In particular, some of the successive peak pairs providing a special relation between Miller indices come close to each other. This result refers to the rearrangement of atoms in a diffusive manner.

Keywords: shape memory effect, martensitic transformation, reversibility, superelasticity, twinning, detwinning

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Authors: Imene Atek, Abed M. Affoune, Hubert Girault, Pekka Peljo

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Due to the need for a rigorous mathematical model that can help to estimate kinetic properties for soluble-insoluble systems, through voltammetric experiments, a Nicholson Semi Analytical Approach was used in this work for modeling and prediction of theoretical linear sweep voltammetry responses for reversible, quasi reversible or irreversible electron transfer reactions. The redox system of interest is a one-step metal electrodeposition process. A rigorous analysis of simulated linear scan voltammetric responses following variation of dimensionless factors, the rate constant and charge transfer coefficients in a broad range was studied and presented in the form of the so called kinetic zones diagrams. These kinetic diagrams were divided into three kinetics zones. Interpreting these zones leads to empirical mathematical models which can allow the experimenter to determine electrodeposition reactions kinetics whatever the degree of reversibility. The validity of the obtained results was tested and an excellent experiment–theory agreement has been showed.

Keywords: electrodeposition, kinetics diagrams, modeling, voltammetry

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Authors: Djamil Guettiche, Ahmed Mekki, Tighilt Fatma-Zohra, Rachid Mahmoud

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The aim of this study was to synthesize and characterize conducting polymer composites of polypyrrole and graphene, including pristine and surface-treated graphene (PPy/GO, PPy/rGO, and PPy/rGO-ArCOOH), for use as sensitive elements in a homemade chemiresistive module for on-line detection of nitrogen oxides vapors. The chemiresistive module was prepared, characterized, and evaluated for performance. Structural and morphological characterizations of the composite were carried out using FTIR, Raman spectroscopy, and XRD analyses. After exposure to NO and NO₂ gases in both static and dynamic modes, the sensitivity, selectivity, limit of detection, and response time of the sensor were determined at ambient temperature. The resulting sensor showed high sensitivity, selectivity, and reversibility, with a low limit of detection of 1 ppm. A composite of polypyrrole and graphene functionalized with aryl 4-carboxy benzene diazonium salt was synthesized and characterized using FTIR, scanning electron microscopy, transmission electron microscopy, UV-visible, and X-ray diffraction. The PPy-rGOArCOOH composite exhibited a good electrical resistance response to NO₂ at room temperature and showed enhanced NO₂-sensing properties compared to PPy-rGO thin films. The selectivity and stability of the NO₂ sensor based on the PPy/rGO-ArCOOH nanocomposite were also investigated.

Keywords: conducting polymers, surface treated graphene, diazonium salt, polypyrrole, Nitrogen oxide sensing

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Authors: Daniela Ribeiro, Silvia Lenyra Meirelles Campos Titotto

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Nature has long served as inspiration for humans, since various technologies present in society are a mirror of the natural world. This is due to the fact that nature has adapted for millions of years to possess the characteristics they have today. In this sense, man takes advantage of this situation and uses it to produce his own objects and solve his problems. This concept, which is known as biomimetics, is something relatively new, once it was only denominated in 1957. Nature, in turn, responds directly and consistently to environmental conditions. For example, plants that have touch sensitivity contract with this stimulus. Such a situation resembles a technology that has been gaining ground in the contemporary world of scientific innovation: 4D printing. 4D printing technology emerged in 2012 as a complement to 3D printing and presents numerous benefits since it provides a deficiency in the second kind of printing mentioned. This type of technology reaches several areas, since it is capable of producing materials that change over time, be it in its composition, form or properties and is such a characteristic that determines the additional dimension of the material. Precisely because of these factors, this type of impression resembles nature and is related to biomimetics. However, only certain types of ‘intelligent’ materials are generally employed in this type of impression, since only they will respond well to such stimuli, one of which is the hydrogel. The hydrogel is a biocompatible polymer that presents several applications, these in turn will be briefly mentioned in this article to exemplify its importance and the reason for choosing this material as object of study. In addition, aspects that configure 4D printing will be treated here, such as the importance of architecture, programming language and the reversibility of printed materials.

Keywords: 4D printing, biomimetic, hydrogel, materials

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Authors: Su Sin Chong, Abdul Aziz Abdul Raman, Sulaiman Wadi Harun, Hamzah Arof

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Chemical Oxygen Demand (COD) plays a vital role determination of an appropriate strategy for wastewater treatment including the control of the quality of an effluent. In this study, a new sensing method was introduced for the first time and developed to investigate chemical oxygen demand (COD) using a Mach-Zehner Interferometer (MZI)-based dye sensor. The sensor is constructed by bridging two single mode fibres (SMF1 and SMF2) with a short section (~20 mm) of multimode fibre (MMF) and was formed by tapering the MMF to generate evanescent field which is sensitive to perturbation of sensing medium. When the COD concentration increase takes effect will induce changes in output intensity and effective refractive index between the microfiber and the sensing medium. The adequacy of decisions based on COD values relies on the quality of the measurements. Therefore, the dual output response can be applied to the analytical procedure enhance measurement quality. This work presents a detailed assessment of the determination of COD values in synthetic wastewaters. Detailed models of the measurement performance, including sensitivity, reversibility, stability, and uncertainty were successfully validated by proficiency tests where supported on sound and objective criteria. Comparison of the standard method with the new proposed method was also conducted. This proposed sensor is compact, reliable and feasible to investigate the COD value.

Keywords: chemical oxygen demand, environmental sensing, Mach-Zehnder interferometer sensor, online monitoring

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Authors: Domenico Chizzoniti, Monica Moscatelli, Letizia Cattani, Luca Preis

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A primary healthcare facility in developing countries should be a multifunctional space able to respond to different requirements: Flexibility, modularity, aggregation and reversibility. These basic features could be better satisfied if applied to an architectural artifact that complies with the typological, figurative and constructive aspects of the context in which it is located. Therefore, the purpose of this paper is to identify a procedure that can define the figurative aspects of the architectural structure of the health prototype for the marginal areas of developing countries through a critical approach. The application context is the rural areas of the Northeast of Bahia in Brazil. The prototype should be located in the rural district of Quingoma, in the municipality of Lauro de Freitas, a particular place where there is still a cultural fusion of black and indigenous populations. Based on the historical analysis of settlement strategies and architectural structures in spaces of public interest or collective use, this paper aims to provide a procedure able to identify the categories and rules underlying typological and figurative aspects, in order to detect significant and generalizable elements, as well as materials and constructive techniques typically adopted in the rural areas of Brazil. The object of this work is therefore not only the recovery of certain constructive approaches but also the development of a procedure that integrates the requirements of the primary healthcare prototype with its surrounding economic, social, cultural, settlement and figurative conditions.

Keywords: architectural typology, developing countries, local construction techniques, primary health care.

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Authors: Eyob Belew Abebe

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Nickel-rich layered oxide cathode materials having a Ni content of ≥ 90% have great potential for use in next-generation lithium-ion batteries (LIBs), due to their high energy densities and relatively low cost. They suffer, however, from poor cycling performance and rate capability, significantly hampering their widespread applicability. In this study we synthesized a Ni-rich precursor through a co-precipitation method and added different amounts of Li-excess on the precursors using a solid-state method to obtain sintered Li1+x(Ni0.9Co0.05Mn0.05)1–xO2 (denoted as L1+x-NCM; x = 0.00, 0.02, 0.04, 0.06, and 0.08) transition metal (TM) oxide cathode materials. The L1+x-NCM cathode having a Li-excess of 4% exhibited a discharge capacity of ca. 216.17 mAh g–1 at 2.7–4.3 V, 0.1C and retained 95.7% of its initial discharge capacity (ca. 181.39 mAh g–1) after 100 cycles of 1C charge/discharge which is the best performance as compared with stoichiometric Li1+x(Ni0.9Co0.05Mn0.05)1-xO2 (i.e. x=0, Li:TM = 1:1). Furthermore, a high-rate capability of ca. 162.92 mAh g–1 at a rate of 10C, led to the 4% Li-excess optimizing the electrochemical performance, relative to the other Li-excess samples. Ex/in-situ X-ray diffraction, scanning electron microscopy, and X-ray photoelectron spectroscopy revealed that the 4% Li-excess in the Ni-rich NCM90 cathode material: (i). decreased the Li+/Ni2+ disorder by increasing the content of Ni3+ in the TM slab, (ii). increased the crystallinity, and (iii). accelerated Li+ ion transport by widening the Li-slab. Furthermore, electrochemical impedance spectroscopy and cyclic voltammetry confirmed that the appropriate Li-excess lowered the electrochemical impedance and improved the reversibility of the electrochemical reaction. Therefore, our results revealed that NCM90 cathode materials featuring an optimal Li-excess are potential candidates for use in next-generation Li-ion batteries.

Keywords: LiNi₀.₉Co₀.₀₉Mn₀.₀₉O₂, li-excess, cation mixing, structure change, cycle stability, electrochemical properties

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Authors: Angelo Gabriel Buenaventura, Allan Christopher Yago

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A carbon paste electrode (CPE) composed of Multiwalled Carbon Nanotube (MWCNT) conducting particle and Polydimethylsiloxane (PDMS) binder was used for simultaneous detection of Dopamine (DA) and Uric Acid (UA) in the presence of Ascorbic Acid (AA) at physiological level. The MWCNT-PDMS CPE was initially activated via potentiodynamic cycling in a basic (NaOH) solution, which resulted in enhanced electrochemical properties. Electrochemical Impedance Spectroscopy measurements revealed a significantly lower charge transfer resistance (Rct) for the OH--activated MWCNT-PDMS CPE (Rct = 5.08kΩ) as compared to buffer (pH 7)-activated MWCNT-PDMS CPE (Rct = 25.9kΩ). Reversibility analysis of Fe(CN)63-/4- redox couple of both Buffer-Activated CPE and OH--Activated CPE showed that the OH—Activated CPE have peak current ratio (Ia/Ic) of 1.11 at 100mV/s while 2.12 for the Buffer-Activated CPE; this showed an electrochemically reversible behavior for Fe(CN)63-/4- redox couple even at relatively fast scan rate using the OH--activated CPE. Enhanced voltammetric signal for DA and significant peak separation between DA and UA was obtained using the OH--activated MWCNT-PDMS CPE in the presence of 50 μM AA via Differential Pulse Voltammetry technique. The anodic peak currents which appeared at 0.263V and 0.414 V were linearly increasing with increasing concentrations of DA and UA, respectively. The linear ranges were obtained at 25 μM – 100 μM for both DA and UA. The detection limit was determined to be 3.86 μM for DA and 5.61 μM for UA. These results indicate a practical approach in the simultaneous detection of important bio-organic molecules using a simple CPE composed of MWCNT and PDMS with base anodization as activation technique.

Keywords: anodization, ascorbic acid, carbon paste electrodes, dopamine, uric acid

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Authors: Ramin Mansouri

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Due to the contrast of rivers discharge regime with water demands, one of the best ways to use water resources is to regulate the natural flow of the rivers and supplying water needs to construct dams. Optimal utilization of reservoirs, consideration of multiple important goals together at the same is of very high importance. To study about analyzing this method, statistical data of Bakhtiari and Roudbar dam over 46 years (1955 until 2001) is used. Initially an appropriate objective function was specified and using DE algorithm, the rule curve was developed. In continue, operation policy using rule curves was compared to standard comparative operation policy. The proposed method distributed the lack to the whole year and lowest damage was inflicted to the system. The standard deviation of monthly shortfall of each year with the proposed algorithm was less deviated than the other two methods. The Results show that median values for the coefficients of F and Cr provide the optimum situation and cause DE algorithm not to be trapped in local optimum. The most optimal answer for coefficients are 0.6 and 0.5 for F and Cr coefficients, respectively. After finding the best combination of coefficients values F and CR, algorithms for solving the independent populations were examined. For this purpose, the population of 4, 25, 50, 100, 500 and 1000 members were studied in two generations (G=50 and 100). result indicates that the generation number 200 is suitable for optimizing. The increase in time per the number of population has almost a linear trend, which indicates the effect of population in the runtime algorithm. Hence specifying suitable population to obtain an optimal results is very important. Standard operation policy had better reversibility percentage, but inflicts severe vulnerability to the system. The results obtained in years of low rainfall had very good results compared to other comparative methods.

Keywords: reservoirs, differential evolution, dam, Optimal operation

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Authors: Adrian Hang Yue Siu, Matthew Holyland, Sharon Carey, Daniel Steffens, Nabila Ansari, Cherry E. Koh

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Introduction: Peritoneal malignancies are challenging cancers to manage. While cytoreductive surgery and hyperthermic intraperitoneal chemotherapy (CRS and HIPEC) may offer a cure, it’s considered radical and morbid. Pre-emptive identification of deconditioned patients for optimization may mitigate the risks of surgery. However, the difficulty lies in the scarcity of validated predictive tools to identify high-risk patients. In recent times, there has been growing interest in sarcopenia, which can occur as a result of malnutrition and malignancies. Therefore, the purpose of this study was to assess the utility of sarcopenia in predicting post-operative outcomes. Methods: A single quaternary-center retrospective study of CRS and HIPEC patients between 2017-2020 was conducted to determine the association between pre-operative sarcopenia and post-operative outcomes. Lumbar CT images were analyzed using Slice-o-matic® to measure sarcopenia. Results : Cohort (n=94) analysis found that 40% had sarcopenia, with a majority being female (53.2%) and a mean age of 55 years. Sarcopenia was statistically associated with decreased weight compared to non-sarcopenia patients, 72.7kg vs. 82.2kg (p=0.014) and shorter overall survival, 1.4 years vs. 2.1 years (p=0.032). Post-operatively, patients with sarcopenia experienced more post-operative complications (p=0.001). Conclusion: Complex procedures often require optimization to prevent complications and improve survival. While patient biomarkers – BMI and weight – are used for optimization, this research advocates for the identification of sarcopenia status for pre-operative planning. Sarcopenia may be an indicator of advanced disease requiring further treatment and is an emerging area of research. Larger studies are required to confirm these findings and to assess the reversibility of sarcopenia after surgery.

Keywords: sarcopaenia, cytoreductive surgery, hyperthermic intraperitoneal chemotherapy, surgical oncology

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Authors: Siddhant Srivastav, Soumyaranjan Mishra, Sumanta Kumar Meher

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Researchers are attempting to develop extremely efficient electrochemical energy storage technologies as a result of the phenomenal advancement of portable electronic devices. Because of their improved electrical conductivity and narrower band gap, transition metal selenide-based nanostructures have piqued the interest of many researchers in this field. Based on this concept, we present a simple anion exchange hydrothermal synthesis method for synthesizing manganese and nickel based selenide (Mn/NiSe2) nanostructure for use in all-solid-state asymmetric supercapacitors. According to the comprehensive physicochemical characterizations, the material has lowly crystalline properties, a distinct porous microstructure, and a significant bonding contact between the metal and the selenium. The electrochemical investigations of the Mn/NiSe2 electrode material revealed supercapacitive charge discharge properties, excellent electro-kinetic reversibility, and minimal charge transfer resistance (Rct). Furthermore, the all-solid-state asymmetric supercapacitor device assembled using Mn/NiSe2 as positive electrode, nitrogen doped reduced graphene oxide (N-rGO) as negative electrode, and PVA-KOH gel as electrolyte/separator exhibit good redox behaviour, excellent charge-discharge properties with negligible voltage (IR) drop, and lower impedance characteristics. The solid state asymmetric supercapacitor device (Mn/NiSe2||N-rGO) demonstrated the power density of ultra-capacitors and the energy density of rechargeable batteries. Conclusively, the Mn/NiSe2 has been proposed as a potential outstanding electrode material for the next generation of all-solid-state asymmetric supercapacitors.

Keywords: anion exchange, asymmetric supercapacitor, supercapacitive charge-discharge, voltage drop

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Authors: Aidan Battison, Neliswa Mama

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Environmental pollution by ionic species has been identified as one of the biggest challenges to the sustainable development of communities. The widespread use of organic and inorganic chemical products and the release of toxic chemical species from industrial waste have resulted in a need for advanced monitoring technologies for environment protection, remediation and restoration. Some of the disadvantages of conventional sensing methods include expensive instrumentation, well-controlled experimental conditions, time-consuming procedures and sometimes complicated sample preparation. On the contrary, the development of fluorescent chemosensors for biological and environmental detection of metal ions has attracted a great deal of attention due to their simplicity, high selectivity, eidetic recognition, rapid response and real-life monitoring. Coumarin derivatives S1 and S2 (Scheme 1) containing 1,2,3-triazole moieties at position -3- have been designed and synthesized from azide and alkyne derivatives by CuAAC “click” reactions for the detection of metal ions. These compounds displayed a strong preference for Fe3+ ions with complexation resulting in fluorescent quenching through photo-induced electron transfer (PET) by the “sphere of action” static quenching model. The tested metal ions included Cd2+, Pb2+, Ag+, Na+, Ca2+, Cr3+, Fe3+, Al3+, Cd2+, Ba2+, Cu2+, Co2+, Hg2+, Zn2+ and Ni2+. The detection limits of S1 and S2 were determined to be 4.1 and 5.1 uM, respectively. Compound S1 displayed the greatest selectivity towards Fe3+ in the presence of competing for metal cations. S1 could also be used for the detection of Fe3+ in a mixture of CH3CN/H¬2¬O. Binding stoichiometry between S1 and Fe3+ was determined by using both Jobs-plot and Benesi-Hildebrand analysis. The binding was shown to occur in a 1:1 ratio between the sensor and a metal cation. Reversibility studies between S1 and Fe3+ were conducted by using EDTA. The binding site of Fe3+ to S1 was determined by using 13 C NMR and Molecular Modelling studies. Complexation was suggested to occur between the lone-pair of electrons from the coumarin-carbonyl and the triazole-carbon double bond.

Keywords: chemosensor, "click" chemistry, coumarin, fluorescence, static quenching, triazole

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Authors: Anteneh Wodaje Bayeh, Daniel Manaye Kabtamu, Chen-Hao Wang

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As one of the most promising electrochemical energy storage systems, vanadium redox flow batteries (VRFBs) have received increasing attention owing to their attractive features for largescale storage applications. However, their high production cost and relatively low energy efficiency still limit their feasibility. For practical implementation, it is of great interest to improve their efficiency and reduce their cost. One of the key components of VRFBs that can greatly influence the efficiency and final cost is the electrode, which provide the reactions sites for redox couples (VO²⁺/VO₂ + and V²⁺/V³⁺). Carbon-based materials are considered to be the most feasible electrode materials in the VRFB because of their excellent potential in terms of operation range, good permeability, large surface area, and reasonable cost. However, owing to limited electrochemical activity and reversibility and poor wettability due to its hydrophobic properties, the performance of the cell employing carbon-based electrodes remained limited. To address the challenges, we synthesized heteroatom-doped bimetallic oxide grown on the surface of carbon through the one-step approach. When applied to VRFBs, the prepared electrode exhibits significant electrocatalytic effect toward the VO²⁺/VO₂ + and V³⁺/V²⁺ redox reaction compared with that of pristine carbon. It is found that the presence of heteroatom on metal oxide promotes the absorption of vanadium ions. The controlled morphology of bimetallic metal oxide also exposes more active sites for the redox reaction of vanadium ions. Hence, the prepared electrode displays the best electrochemical performance with energy and voltage efficiencies of 74.8% and 78.9%, respectively, which is much higher than those of 59.8% and 63.2% obtained from the pristine carbon at high current density. Moreover, the electrode exhibit durability and stability in an acidic electrolyte during long-term operation for 1000 cycles at the higher current density.

Keywords: VRFB, VO²⁺/VO₂ + and V³⁺/V²⁺ redox couples, graphite felt, heteroatom-doping

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Authors: Nidhi Gupta, Omita Nanda, Rakhi Grover, Kanchan Saxena

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Hybrid perovskite is new class of material which has gained much attention due to their different crystal structure and interesting optical and electrical properties. Easy fabrication, high absorption coefficient, and photoluminescence properties make them a strong candidate for various applications such as sensors, photovoltaics, photodetectors, etc. In perovskites, ions arrange themselves in a special type of crystal structure with chemical formula ABX3, where A is organic species like CH3NH3+, B is metal ion (e.g., Pb, Sn, etc.) and X is halide (Cl-, Br-, I-). In crystal structure, A is present at corner position, B at center of the crystal lattice and halide ions at the face centers. High stability and sensitivity of nanostructured perovskite make them suitable for chemical sensors. Researchers have studied sensing properties of perovskites for number of analytes such as 2,4,6-trinitrophenol, ethanol and other hazardous chemical compounds. Ammonia being highly toxic agent makes it a reason of concern for the environment. Thus the detection of ammonia is extremely important. Our present investigation deals with organic inorganic hybrid perovskite based ammonia sensor. Various methods like sol-gel, solid state synthesis, thermal vapor deposition etc can be used to synthesize Different hybrid perovskites. In the present work, a novel hybrid perovskite has been synthesized by a single step method. Ethylenediammnedihalide and lead halide were used as precursor. Formation of hybrid perovskite was confirmed by FT-IR and XRD. Morphological characterization of the synthesized material was performed using scanning electron microscopy (SEM). SEM analysis revealed the formation of one dimensional nanowire perovskite with mean diameter of 200 nm. Measurements for sensing properties of halide perovskite for ammonia vapor were carried out. Perovskite thin films showed a color change from yellow to orange on exposure of ammonia vapor. Electro-optical measurements show that sensor based on lead halide perovskite has high sensitivity towards ammonia with effective selectivity and reversibility. Sensor exhibited rapid response time of less than 20 seconds.

Keywords: hybrid perovskite, ammonia, sensor, nanostructure, thin film

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Authors: Mohamed M. Ibrahim, Gaber A. M. Mersal, Salih Al-Juaid, Samir A. El-Shazly

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A series of mixed ligand complexes, viz., [Cu(BPy)(Gly)X]Y {X = Cl (1), Y = 0; X = 0, Y = ClO4- (2); X = H2O, Y = NO3- (3); X = H2O, Y = CH3COO- (4); and [Cu(BPy)(Gly)-(H2O)]2(SO4) (5) have been synthesized. Their structures and properties were characterized by elemental analysis, thermal analaysis, IR, UV–vis, and ESR spectroscopy, as well as electrochemical measurements including cyclic voltammetry, electrical molar conductivity, and magnetic moment measurements. Complexes 1 and 2 formed slightly distorted square-pyramidal coordination geometries of CuN3OCl and CuN3O2, respectively in which the N,O-donor glycine and N,N-donor bipyridyl bind at the basal plane with chloride ion or water as the axial ligand. Complex 3 shows square planar CuN3O coordination geometry, which exhibits chemically significant hydrogen bonding interactions besides showing coordination polymer formation. The superoxide dismutase and catalase-like activities of all complexes were tested and were found to be promising candidates as durable electron-transfer catalyst being close to the efficiency of the mimicking enzymes displaying either catalase or tyrosinase activity to serve for complete reactive oxygen species (ROS) detoxification, both with respect to superoxide radicals and related peroxides. The DNA binding interaction with super coiled pGEM-T plasmid DNA was investigated by using spectral (absorption and emission) titration and electrochemical techniques. The results revealed that DNA intercalate with complexes 1 and 2 through the groove binding mode. The calculated intrinsic binding constant (Kb) of 1 and 2 were 4.71 and 2.429 × 105 M−1, respectively. Gel electrophoresis study reveals the fact that both complexes cleave super coiled pGEM-T plasmid DNA to nicked and linear forms in the absence of any additives. On the other hand, the interaction of both complexes with DNA, the quasi-reversible CuII/CuI redox couple slightly improves its reversibility with considerable decrease in current intensity. All the experimental results indicate that the bipyridyl mixed copper(II) complex (1) intercalate more effectively into the DNA base pairs.

Keywords: enzyme mimics, mixed ligand complexes, X-ray structures, antioxidant, DNA-binding, DNA cleavage

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Authors: Zeineb Yousse, Fakher Kharrat

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Mosaic is a part of a broad universal cultural heritage; sometimes it represents a rather essential source for the researches on the everyday life of some of the previous civilizations. Tunisia has one of the finest and largest collections of mosaics in the world, which is essentially exhibited in the Museums of Bardo and Sousse. Restored and reconstituted, they bear witnesses to hard work. Our paper deals with the discipline of conservation of Roman mosaics based on the proceedings of the workshop of the Museum of Sousse. Thus, we highlight two main objectives. In the first place, it is a question of revealing the techniques adopted by professionals to handle mosaics and to which school of conservation these techniques belong. In the second place, we are going to interpret the works initiated to preserve the archaeological heritage in order to protect it in present time and transmit it to future generations. To this end, we paid attention to four Roman mosaics currently exhibited in the Museum of Sousse. These Mosaics show different voids or gaps at the level of their surfaces and the method used to fill these gaps seems to be interesting to analyze. These mosaics are known under the names of: Orpheus Charming the Animals, Gladiator and Bears, Stud farm of Sorothus and finally Head of Medusa. The study on the conservation passes through two chained phases. We start with a small historical overview in order to gather information related to the original location, the date of its composition as well as the description of its image. Afterward, the intervention process is analyzed by handling three complementary elements which are: diagnosis of the existing state, the study of the medium processing and the study of the processing of the tesselatum surface which includes the pictorial composition of the mosaic. Furthermore, we have implemented an evaluation matrix with six operating principles allowing the assessment of the appropriateness of the intervention. These principles are the following: minimal intervention, reversibility, compatibility, visibility, durability, authenticity and enhancement. Various accumulated outcomes are pointing out the techniques used to fill the gaps as well as the level of compliance with the principles of conservation. Accordingly, the conservation of mosaics in Tunisia is a practice that combines various techniques without really arguing about the choice of a particular theory.

Keywords: conservation, matrix, museum of Sousse, operating particular theory, principles, Roman mosaics

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