Search results for: attractive smile
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 769

Search results for: attractive smile

19 The Impact of the Media in the Implementation of Qatar’s Foreign Policy on the Public Opinion of the People of the Middle East (2011-2023)

Authors: Negar Vkilbashi, Hassan Kabiri

Abstract:

Modern diplomacy, in its general form, refers to the people and not the governments, and diplomacy tactics are more addressed to the people than to the governments. Media diplomacy and cyber diplomacy are also one of the sub-branches of public diplomacy and, in fact, the role of media in the process of influencing public opinion and directing foreign policy. Mass media, including written, radio and television, theater, satellite, internet, and news agencies, transmit information and demands. What the Qatari government tried to implement in the countries of the region during the Arab Spring and after was through its important media, Al Jazeera. The embargo on Qatar began in 2017, when Saudi Arabia, the United Arab Emirates, Bahrain, and Egypt imposed a land, sea, and air blockade against the country. The media tool constitutes the cornerstone of soft power in the field of foreign policy, which Qatari leaders have consistently resorted to over the past two decades. Undoubtedly, the role it played in covering the events of the Arab Spring has created geopolitical tensions. The United Arab Emirates and other neighboring countries sometimes criticize Al Jazeera for providing a platform for the Muslim Brotherhood, Hamas, and other Islamists to promote their ideology. In 2011, at the same time as the Arab Spring, Al Jazeera reached the peak of its popularity. Al Jazeera's live coverage of protests in Tunisia, Egypt, Yemen, Libya, and Syria helped create a unified narrative of the Arab Spring, with audiences tuning in every Friday to watch simultaneous protests across the Middle East. Al Jazeera operates in three groups: First, it is a powerful base in the hands of the government so that it can direct and influence Arab public opinion. Therefore, this network has been able to benefit from the unlimited financial support of the Qatar government to promote its desired policies and culture. Second, it has provided an attractive platform for politicians and scientific and intellectual elites, thus attracting their support and defense from the government and its rulers. Third, during the last years of Prince Hamad's reign, the Al Jazeera network formed a deterrent weapon to counter the media and political struggle campaigns. The importance of the research is that this network covers a wide range of people in the Middle East and, therefore, has a high influence on the decision-making of countries. On the other hand, Al Jazeera is influential as a tool of public diplomacy and soft power in Qatar's foreign policy, and by studying it, the results of its effectiveness in the past years can be examined. Using a qualitative method, this research analyzes the impact of the media on the implementation of Qatar's foreign policy on the public opinion of the people of the Middle East. Data collection has been done by the secondary method, that is, reading related books, magazine articles, newspaper reports and articles, and analytical reports of think tanks. The most important findings of the research are that Al Jazeera plays an important role in Qatar's foreign policy in Qatar's public diplomacy. So that, in 2011, 2017 and 2023, it played an important role in Qatar's foreign policy in various crises. Also, the people of Arab countries use Al-Jazeera as their first reference.

Keywords: Al Jazeera, Qatar, media, diplomacy

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18 Gas-Phase Noncovalent Functionalization of Pristine Single-Walled Carbon Nanotubes with 3D Metal(II) Phthalocyanines

Authors: Vladimir A. Basiuk, Laura J. Flores-Sanchez, Victor Meza-Laguna, Jose O. Flores-Flores, Lauro Bucio-Galindo, Elena V. Basiuk

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Noncovalent nanohybrid materials combining carbon nanotubes (CNTs) with phthalocyanines (Pcs) is a subject of increasing research effort, with a particular emphasis on the design of new heterogeneous catalysts, efficient organic photovoltaic cells, lithium batteries, gas sensors, field effect transistors, among other possible applications. The possibility of using unsubstituted Pcs for CNT functionalization is very attractive due to their very moderate cost and easy commercial availability. However, unfortunately, the deposition of unsubstituted Pcs onto nanotube sidewalls through the traditional liquid-phase protocols turns to be very problematic due to extremely poor solubility of Pcs. On the other hand, unsubstituted free-base H₂Pc phthalocyanine ligand, as well as many of its transition metal complexes, exhibit very high thermal stability and considerable volatility under reduced pressure, which opens the possibility for their physical vapor deposition onto solid surfaces, including nanotube sidewalls. In the present work, we show the possibility of simple, fast and efficient noncovalent functionalization of single-walled carbon nanotubes (SWNTs) with a series of 3d metal(II) phthalocyanines Me(II)Pc, where Me= Co, Ni, Cu, and Zn. The functionalization can be performed in a temperature range of 400-500 °C under moderate vacuum and requires about 2-3 h only. The functionalized materials obtained were characterized by means of Fourier-transform infrared (FTIR), Raman, UV-visible and energy-dispersive X-ray spectroscopy (EDS), scanning and transmission electron microscopy (SEM and TEM, respectively) and thermogravimetric analysis (TGA). TGA suggested that Me(II)Pc weight content is 30%, 17% and 35% for NiPc, CuPc, and ZnPc, respectively (CoPc exhibited anomalous thermal decomposition behavior). The above values are consistent with those estimated from EDS spectra, namely, of 24-39%, 27-36% and 27-44% for CoPc, CuPc, and ZnPc, respectively. A strong increase in intensity of D band in the Raman spectra of SWNT‒Me(II)Pc hybrids, as compared to that of pristine nanotubes, implies very strong interactions between Pc molecules and SWNT sidewalls. Very high absolute values of binding energies of 32.46-37.12 kcal/mol and the highest occupied and lowest unoccupied molecular orbital (HOMO and LUMO, respectively) distribution patterns, calculated with density functional theory by using Perdew-Burke-Ernzerhof general gradient approximation correlation functional in combination with the Grimme’s empirical dispersion correction (PBE-D) and the double numerical basis set (DNP), also suggested that the interactions between Me(II) phthalocyanines and nanotube sidewalls are very strong. The authors thank the National Autonomous University of Mexico (grant DGAPA-IN200516) and the National Council of Science and Technology of Mexico (CONACYT, grant 250655) for financial support. The authors are also grateful to Dr. Natalia Alzate-Carvajal (CCADET of UNAM), Eréndira Martínez (IF of UNAM) and Iván Puente-Lee (Faculty of Chemistry of UNAM) for technical assistance with FTIR, TGA measurements, and TEM imaging, respectively.

Keywords: carbon nanotubes, functionalization, gas-phase, metal(II) phthalocyanines

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17 Effectiveness of Essential Oils as Inhibitors of Quorum Sensing Activity Using Biomonitor Strain Chromobacterium Violaceum

Authors: Ivana Cabarkapa, Zorica Tomicic, Olivera Duragic

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Antimicrobial resistance represents one of the major challenges facing humanity in the last decades. Increasing antibiotic-resistant pathogens indicates the need for the development of alternative antibacterial drugs and new treatment strategies. One of the innovative emerging treatments in overcoming multidrug-resistant pathogens certainly represents the inhibition anti-quorum sensing system. For most of the food-borne pathogens, the expression of the virulence depends on their capability communication with other members of the population by means of quorum sensing (QS). QS represents a specific way of bacterial intercellular communication, which enabled owing to their ability to detect and to respond to cell population density by gene regulation. QS mechanisms are responsible for controls the pathogenesis, virulence luminescence, motility, sporulation and biofilm formation of many organisms by regulating gene expression. Therefore, research in this field is being an attractive target for the development of new natural antibacterial agents. Anti-QS compounds are known to have the ability to prohibit bacterial pathogenicity. Considering the importance of quorum sensing during bacterial pathogenesis, this research has been focused on evaluation anti - QS properties of four essential oils (EOs) Origanum heracleoticum, Origanum vulgare, Thymus vulgare, and Thymus serpyllum, using biomonitor strain of Chromobacterium violaceum CV026. Tests conducted on Luria Bertani agar supplemented with N hexanol DL homoserine lacton (HHL) 10µl/50ml of agar. The anti-QS potential of the EOs was assayed in a range of concentrations of 200 – 0.39 µl/ml using the disc diffusion method. EOs of Th. vulgaris and T. serpyllum were exhibited anti-QS activity indicated by a non- pigmented ring with a dilution-dependent manner. The lowest dilution of EOs T. vulgaris and T. serpyllum in which they exhibited visually detectable inhibition of violacein synthesis was 6.25 µl/ml for both tested EOs. EOs of O. heracleoticum and O. vulgare were displayed different active principles, i.e., antimicrobial activity indicated by the inner clear ring and anti-QS activity indicated by the outer non-pigmented ring, in a concentration-dependent manner. The lowest dilution of EOs of O. heracleoticum and O. vulgare in which exhibited visually detectable inhibition of violacein synthesis was 1.56 and 3.25 µl/ml, respectively. Considering that, the main constituents of the tested EOs represented by monoterpenes (carvacrol, thymol, γ-terpinene, and p-cymene), anti - QS properties of tested EOs can be mainly attributed to their activity. In particular, from the scientific literature, carvacrol and thymol show a sub-inhibitory effect against foodborne pathogens. Previous studies indicated that sub-lethal concentrations of carvacrol reduced the mobility of bacteria due to the ability of interference using QS mechanism between the bacterial cells, and thereby reducing the ability of biofilm formation The precise mechanism by which carvacrol inhibits biofilm formation is still not fully understood. Our results indicated that EOs displayed different active principles, i.e., antimicrobial activity indicated by the inner clear ring and anti-QS activity indicated by an outer non- pigmented ring with visually detectable inhibition of violacein. Preliminary results suggest that EOs represent a promising alternative for effective control of the emergence and spread of resistant pathogens.

Keywords: anti-quorum sensing activity, Chromobacterium violaceum, essential oils, violacein

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16 Pivoting to Fortify our Digital Self: Revealing the Need for Personal Cyber Insurance

Authors: Richard McGregor, Carmen Reaiche, Stephen Boyle

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Cyber threats are a relatively recent phenomenon and offer cyber insurers a dynamic and intelligent peril. As individuals en mass become increasingly digitally dependent, Personal Cyber Insurance (PCI) offers an attractive option to mitigate cyber risk at a personal level. This abstract proposes a literature review that conceptualises a framework for siting Personal Cyber Insurance (PCI) within the context of cyberspace. The lack of empirical research within this domain demonstrates an immediate need to define the scope of PCI to allow cyber insurers to understand personal cyber risk threats and vectors, customer awareness, capabilities, and their associated needs. Additionally, this will allow cyber insurers to conceptualise appropriate frameworks allowing effective management and distribution of PCI products and services within a landscape often in-congruent with risk attributes commonly associated with traditional personal line insurance products. Cyberspace has provided significant improvement to the quality of social connectivity and productivity during past decades and allowed enormous capability uplift of information sharing and communication between people and communities. Conversely, personal digital dependency furnish ample opportunities for adverse cyber events such as data breaches and cyber-attacksthus introducing a continuous and insidious threat of omnipresent cyber risk–particularly since the advent of the COVID-19 pandemic and wide-spread adoption of ‘work-from-home’ practices. Recognition of escalating inter-dependencies, vulnerabilities and inadequate personal cyber behaviours have prompted efforts by businesses and individuals alike to investigate strategies and tactics to mitigate cyber risk – of which cyber insurance is a viable, cost-effective option. It is argued that, ceteris parabus, the nature of cyberspace intrinsically provides characteristic peculiarities that pose significant and bespoke challenges to cyber insurers, often in-congruent with risk attributes commonly associated with traditional personal line insurance products. These challenges include (inter alia) a paucity of historical claim/loss data for underwriting and pricing purposes, interdependencies of cyber architecture promoting high correlation of cyber risk, difficulties in evaluating cyber risk, intangibility of risk assets (such as data, reputation), lack of standardisation across the industry, high and undetermined tail risks, and moral hazard among others. This study proposes a thematic overview of the literature deemed necessary to conceptualise the challenges to issuing personal cyber coverage. There is an evident absence of empirical research appertaining to PCI and the design of operational business models for this business domain, especially qualitative initiatives that (1) attempt to define the scope of the peril, (2) secure an understanding of the needs of both cyber insurer and customer, and (3) to identify elements pivotal to effective management and profitable distribution of PCI - leading to an argument proposed by the author that postulates that the traditional general insurance customer journey and business model are ill-suited for the lineaments of cyberspace. The findings of the review confirm significant gaps in contemporary research within the domain of personal cyber insurance.

Keywords: cyberspace, personal cyber risk, personal cyber insurance, customer journey, business model

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15 Investigation of Different Electrolyte Salts Effect on ZnO/MWCNT Anode Capacity in LIBs

Authors: Şeyma Dombaycıoğlu, Hilal Köse, Ali Osman Aydın, Hatem Akbulut

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Rechargeable lithium ion batteries (LIBs) have been considered as one of the most attractive energy storage choices for laptop computers, electric vehicles and cellular phones owing to their high energy and power density. Compared with conventional carbonaceous materials, transition metal oxides (TMOs) have attracted great interests and stand out among versatile novel anode materials due to their high theoretical specific capacity, wide availability and good safety performance. ZnO, as an anode material for LIBs, has a high theoretical capacity of 978 mAh g-1, much higher than that of the conventional graphite anode (∼370 mAhg-1). However, several major problems such as poor cycleability, resulting from the severe volume expansion and contraction during the alloying-dealloying cycles with Li+ ions and the associated charge transfer process, the pulverization and the agglomeration of individual particles, which drastically reduces the total entrance/exit sites available for Li+ ions still hinder the practical use of ZnO powders as an anode material for LIBs. Therefore, a great deal of effort has been devoted to overcome these problems, and many methods have been developed. In most of these methods, it is claimed that carbon nanotubes (CNTs) will radically improve the performance of batteries, because their unique structure may especially enhance the kinetic properties of the electrodes and result in an extremely high specific charge compared with the theoretical limits of graphitic carbon. Due to outstanding properties of CNTs, MWCNT buckypaper substrate is considered a buffer material to prevent mechanical disintegration of anode material during the battery applications. As the bridge connecting the positive and negative electrodes, the electrolyte plays a critical role affecting the overall electrochemical performance of the cell including rate, capacity, durability and safety. Commercial electrolytes for Li-ion batteries normally consist of certain lithium salts and mixed organic linear and cyclic carbonate solvents. Most commonly, LiPF6 is attributed to its remarkable features including high solubility, good ionic conductivity, high dissociation constant and satisfactory electrochemical stability for commercial fabrication. Besides LiPF6, LiBF4 is well known as a conducting salt for LIBs. LiBF4 shows a better temperature stability in organic carbonate based solutions and less moisture sensitivity compared to LiPF6. In this work, free standing zinc oxide (ZnO) and multiwalled carbon nanotube (MWCNT) nanocomposite materials were prepared by a sol gel technique giving a high capacity anode material for lithium ion batteries. Electrolyte solutions (including 1 m Li+ ion) were prepared with different Li salts in glove box. For this purpose, LiPF6 and LiBF4 salts and also mixed of these salts were solved in EC:DMC solvents (1:1, w/w). CR2016 cells were assembled by using these prepared electrolyte solutions, the ZnO/MWCNT buckypaper nanocomposites as working electrodes, metallic lithium as cathode and polypropylene (PP) as separator. For investigating the effect of different Li salts on the electrochemical performance of ZnO/MWCNT nanocomposite anode material electrochemical tests were performed at room temperature.

Keywords: anode, electrolyte, Li-ion battery, ZnO/MWCNT

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14 Evaluation of the Biological Activity of New Antimicrobial and Biodegradable Textile Materials for Protective Equipment

Authors: Safa Ladhari, Alireza Saidi, Phuong Nguyen-Tri

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During health crises, such as COVID-19, using disposable protective equipment (PEs) (masks, gowns, etc.) causes long-term problems, increasing the volume of hazardous waste that must be handled safely and expensively. Therefore, producing textiles for antimicrobial and reusable materials is highly desirable to decrease the use of disposable PEs that should be treated as hazardous waste. In addition, if these items are used regularly in the workplace or for daily activities by the public, they will most likely end up in household waste. Furthermore, they may pose a high risk of contagion to waste collection workers if contaminated. Therefore, to protect the whole population in times of sanitary crisis, it is necessary to equip these materials with tools that make them resilient to the challenges of carrying out daily activities without compromising public health and the environment and without depending on them external technologies and producers. In addition, the materials frequently used for EPs are plastics of petrochemical origin. The subject of the present work is replacing petroplastics with bioplastic since it offers better biodegradability. The chosen polymer is polyhydroxybutyrate (PHB), a family of polyhydroxyalkanoates synthesized by different bacteria. It has similar properties to conventional plastics. However, it is renewable, biocompatible, and has attractive barrier properties compared to other polyesters. These characteristics make it ideal for EP protection applications. The current research topic focuses on the preparation and rapid evaluation of the biological activity of nanotechnology-based antimicrobial agents to treat textile surfaces used for PE. This work will be carried out to provide antibacterial solutions that can be transferred to a workplace application in the fight against short-term biological risks. Three main objectives are proposed during this research topic: 1) the development of suitable methods for the deposition of antibacterial agents on the surface of textiles; 2) the development of a method for measuring the antibacterial activity of the prepared textiles and 3) the study of the biodegradability of the prepared textiles. The studied textile is a non-woven fabric based on a biodegradable polymer manufactured by the electrospinning method. Indeed, nanofibers are increasingly studied due to their unique characteristics, such as high surface-to-volume ratio, improved thermal, mechanical, and electrical properties, and confinement effects. The electrospun film will be surface modified by plasma treatment and then loaded with hybrid antibacterial silver and titanium dioxide nanoparticles by the dip-coating method. This work uses simple methods with emerging technologies to fabricate nanofibers with suitable size and morphology to be used as components for protective equipment. The antibacterial agents generally used are based on silver, zinc, copper, etc. However, to our knowledge, few researchers have used hybrid nanoparticles to ensure antibacterial activity with biodegradable polymers. Also, we will exploit visible light to improve the antibacterial effectiveness of the fabric, which differs from the traditional contact mode of killing bacteria and presents an innovation of active protective equipment. Finally, this work will allow for the innovation of new antibacterial textile materials through a simple and ecological method.

Keywords: protective equipment, antibacterial textile materials, biodegradable polymer, electrospinning, hybrid antibacterial nanoparticles

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13 Integrated Approach Towards Safe Wastewater Reuse in Moroccan Agriculture

Authors: Zakia Hbellaq

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The Mediterranean region is considered a hotbed for climate change. Morocco is a semi-arid Mediterranean country facing water shortages and poor water quality. Its limited water resources limit the activities of various economic sectors. Most of Morocco's territory is in arid and desert areas. The potential water resources are estimated at 22 billion m3, which is equivalent to about 700 m3/inhabitant/year, and Morocco is in a state of structural water stress. Strictly speaking, the Kingdom of Morocco is one of the “very riskiest” countries, according to the World Resources Institute (WRI), which oversees the calculation of water stress risk in 167 countries. The surprising results of the Institute (WRI) rank Morocco as one of the riskiest countries in terms of water scarcity, ranking 3.89 out of 5, thus occupying the 23rd place out of a total of 167 countries, which indicates that the demand for water exceeds the available resources. Agriculture with a score of 3.89 is most affected by water stress from irrigation and places a heavy burden on the water table. Irrigation is an unavoidable technical need and has undeniable economic and social benefits given the available resources and climatic conditions. Irrigation, and therefore the agricultural sector, currently uses 86% of its water resources, while industry uses 5.5%. Although its development has undeniable economic and social benefits, it also contributes to the overfishing of most groundwater resources and the surprising decline in levels and deterioration of water quality in some aquifers. In this context, REUSE is one of the proposed solutions to reduce the water footprint of the agricultural sector and alleviate the shortage of water resources. Indeed, wastewater reuse, also known as REUSE (reuse of treated wastewater), is a step forward not only for the circular economy but also for the future, especially in the context of climate change. In particular, water reuse provides an alternative to existing water supplies and can be used to improve water security, sustainability, and resilience. However, given the introduction of organic trace pollutants or, organic micro-pollutants, the absorption of emerging contaminants, and decreasing salinity, it is possible to tackle innovative capabilities to overcome these problems and ensure food and health safety. To this end, attention will be paid to the adoption of an integrated and attractive approach, based on the reinforcement and optimization of the treatments proposed for the elimination of the organic load with particular attention to the elimination of emerging pollutants, to achieve this goal. , membrane bioreactors (MBR) as stand-alone technologies are not able to meet the requirements of WHO guidelines. They will be combined with heterogeneous Fenton processes using persulfate or hydrogen peroxide oxidants. Similarly, adsorption and filtration are applied as tertiary treatment In addition, the evaluation of crop performance in terms of yield, productivity, quality, and safety, through the optimization of Trichoderma sp strains that will be used to increase crop resistance to abiotic stresses, as well as the use of modern omics tools such as transcriptomic analysis using RNA sequencing and methylation to identify adaptive traits and associated genetic diversity that is tolerant/resistant/resilient to biotic and abiotic stresses. Hence, ensuring this approach will undoubtedly alleviate water scarcity and, likewise, increase the negative and harmful impact of wastewater irrigation on the condition of crops and the health of their consumers.

Keywords: water scarcity, food security, irrigation, agricultural water footprint, reuse, emerging contaminants

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12 Antibacterial Nanofibrous Film Encapsulated with 4-terpineol/β-cyclodextrin Inclusion Complexes: Relative Humidity-Triggered Release and Shrimp Preservation Application

Authors: Chuanxiang Cheng, Tiantian Min, Jin Yue

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Antimicrobial active packaging enables extensive biological effects to improve food safety. However, the efficacy of antimicrobial packaging hinges on factors including the diffusion rate of the active agent toward the food surface, the initial content in the antimicrobial agent, and the targeted food shelf life. Among the possibilities of antimicrobial packaging design, an interesting approach involves the incorporation of volatile antimicrobial agents into the packaging material. In this case, the necessity for direct contact between the active packaging material and the food surface is mitigated, as the antimicrobial agent exerts its action through the packaging headspace atmosphere towards the food surface. However, it still remains difficult to achieve controlled and precise release of bioactive compounds to the specific target location with required quantity in food packaging applications. Remarkably, the development of stimuli-responsive materials for electrospinning has introduced the possibility of achieving controlled release of active agents under specific conditions, thereby yielding enduring biological effects. Relative humidity (RH) for the storage of food categories such as meat and aquatic products typically exceeds 90%. Consequently, high RH can be used as an abiotic trigger for the release of active agents to prevent microbial growth. Hence, a novel RH - responsive polyvinyl alcohol/chitosan (PVA/CS) composite nanofibrous film incorporated with 4-terpineol/β-cyclodextrin inclusion complexes (4-TA@β-CD ICs) was engineered by electrospinning that can be deposited as a functional packaging materials. The characterization results showed the thermal stability of the films was enhanced after the incorporation due to the hydrogen bonds between ICs and polymers. Remarkably, the 4 wt% 4-TA@β-CD ICs/PVA/CS film exhibited enhanced crystallinity, moderate hydrophilic (Water contact angle of 81.53°), light barrier property (Transparency of 1.96%) and water resistance (Water vapor permeability of 3.17 g mm/m2 h kPa). Moreover, this film also showed optimized mechanical performance with a Young’s modulus of 11.33 MPa, a tensile strength of 19.99 MPa and an elongation at break of 4.44 %. Notably, the antioxidant and antibacterial properties of this packaging material were significantly improved. The film demonstrated the half-inhibitory concentrations (IC50) values of 87.74% and 85.11% for scavenging 2,2-diphenyl-1-picrylhydrazyl (DPPH) and 2, 2′-azinobis (3-ethylbenzothiazoline-6-sulfonic) (ABTS) free radicals, respectively, in addition to an inhibition efficiency of 65% against Shewanella putrefaciens, the characteristic bacteria in aquatic products. Most importantly, the film achieved controlled release of 4-TA under high 98% RH by inducing the plasticization of polymers caused by water molecules, swelling of polymer chains, and destruction of hydrogen bonds within the cyclodextrin inclusion complex. Consequently, low relative humidity is suitable for the preservation of nanofibrous film, while high humidity conditions typical in fresh food packaging environments effectively stimulated the release of active compounds in the film. This film with a long-term antimicrobial effect successfully extended the shelf life of Litopenaeus vannamei shrimp to 7 days at 4 °C. This attractive design could pave the way for the development of new food packaging materials.

Keywords: controlled release, electrospinning, nanofibrous film, relative humidity–responsive, shrimp preservation

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11 Date Palm Wastes Turning into Biochars for Phosphorus Recovery from Aqueous Solutions: Static and Dynamic Investigations

Authors: Salah Jellali, Nusiba Suliman, Yassine Charabi, Jamal Al-Sabahi, Ahmed Al Raeesi, Malik Al-Wardy, Mejdi Jeguirim

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Huge amounts of agricultural biomasses are worldwide produced. At the same time, large quantities of phosphorus are annually discharged into water bodies with possible serious effects onto the environment quality. The main objective of this work is to turn a local Omani biomass (date palm fronds wastes: DPFW) into an effective material for phosphorus recovery from aqueous and the reuse of this P-loaded material in agriculture as ecofriendly amendment. For this aim, the raw DPFW were firstly impregnated with 1 M salt separated solutions of CaCl₂, MgCl₂, FeCl₃, AlCl₃, and a mixture of MgCl₂/AlCl₃ for 24 h, and then pyrolyzed under N2 flow at 500 °C for 2 hours by using an adapted tubular furnace (Carbolite, UK). The synthetized biochars were deeply characterized through specific analyses concerning their morphology, structure, texture, and surface chemistry. These analyses included the use of a scanning electron microscope (SEM) coupled with an energy-dispersive X-Ray spectrometer (EDS), X-Ray diffraction (XRD), Fourier Transform Infrared (FTIR), sorption micrometrics, and X-ray Fluorescence (XRF) apparatus. Then, their efficiency in recovering phosphorus was investigated in batch mode for various contact times (1 min to 3 h), aqueous pH values (from 3 to 11), initial phosphorus concentrations (10-100 mg/L), presence of anions (nitrates, sulfates, and chlorides). In a second step, dynamic assays, by using laboratory columns (height of 30 cm and diameter of 3 cm), were performed in order to investigate the recovery of phosphorus by the modified biochar with a mixture of Mg/Al. The effect of the initial P concentration (25-100 mg/L), the bed depth height (3 to 8 g), and the flow rate (10-30 mL/min) was assessed. Experimental results showed that the biochars physico-chemical properties were very dependent on the type of the used modifying salt. The main affected parameters concerned the specific surface area, microporosity area, and the surface chemistry (pH of zero-point charge and available functional groups). These characteristics have significantly affected the phosphorus recovery efficiency from aqueous solutions. Indeed, the P removal efficiency in batch mode varies from about 5 mg/g for the Fe-modified biochar to more than 13 mg/g for the biochar functionalized with Mg/Al layered double hydroxides. Moreover, the P recovery seems to be a time dependent process and significantly affected by the pH of the aqueous media and the presence of foreign anions due to competition phenomenon. The laboratory column study of phosphorus recovery by the biochar functionalized with Mg/Al layered double hydroxides showed that this process is affected by the used phosphorus concentration, the flow rate, and especially the column bed depth height. Indeed, the phosphorus recovered amount increased from about 4.9 to more than 9.3 mg/g used biochar mass of 3 and 8 g, respectively. This work proved that salt-modified palm fronds-derived biochars could be considered as attractive and promising materials for phosphorus recovery from aqueous solutions even under dynamic conditions. The valorization of these P-loaded-modified biochars as eco-friendly amendment for agricultural soils is necessary will promote sustainability and circular economy concepts in the management of both liquid and solid wastes.

Keywords: date palm wastes, Mg/Al double-layered hydroxides functionalized biochars, phosphorus, recovery, sustainability, circular economy

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10 High Purity Lignin for Asphalt Applications: Using the Dawn Technology™ Wood Fractionation Process

Authors: Ed de Jong

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Avantium is a leading technology development company and a frontrunner in renewable chemistry. Avantium develops disruptive technologies that enable the production of sustainable high value products from renewable materials and actively seek out collaborations and partnerships with like-minded companies and academic institutions globally, to speed up introductions of chemical innovations in the marketplace. In addition, Avantium helps companies to accelerate their catalysis R&D to improve efficiencies and deliver increased sustainability, growth, and profits, by providing proprietary systems and services to this regard. Many chemical building blocks and materials can be produced from biomass, nowadays mainly from 1st generation based carbohydrates, but potential for competition with the human food chain leads brand-owners to look for strategies to transition from 1st to 2nd generation feedstock. The use of non-edible lignocellulosic feedstock is an equally attractive source to produce chemical intermediates and an important part of the solution addressing these global issues (Paris targets). Avantium’s Dawn Technology™ separates the glucose, mixed sugars, and lignin available in non-food agricultural and forestry residues such as wood chips, wheat straw, bagasse, empty fruit bunches or corn stover. The resulting very pure lignin is dense in energy and can be used for energy generation. However, such a material might preferably be deployed in higher added value applications. Bitumen, which is fossil based, are mostly used for paving applications. Traditional hot mix asphalt emits large quantities of the GHG’s CO₂, CH₄, and N₂O, which is unfavorable for obvious environmental reasons. Another challenge for the bitumen industry is that the petrochemical industry is becoming more and more efficient in breaking down higher chain hydrocarbons to lower chain hydrocarbons with higher added value than bitumen. This has a negative effect on the availability of bitumen. The asphalt market, as well as governments, are looking for alternatives with higher sustainability in terms of GHG emission. The usage of alternative sustainable binders, which can (partly) replace the bitumen, contributes to reduce GHG emissions and at the same time broadens the availability of binders. As lignin is a major component (around 25-30%) of lignocellulosic material, which includes terrestrial plants (e.g., trees, bushes, and grass) and agricultural residues (e.g., empty fruit bunches, corn stover, sugarcane bagasse, straw, etc.), it is globally highly available. The chemical structure shows resemblance with the structure of bitumen and could, therefore, be used as an alternative for bitumen in applications like roofing or asphalt. Applications such as the use of lignin in asphalt need both fundamental research as well as practical proof under relevant use conditions. From a fundamental point of view, rheological aspects, as well as mixing, are key criteria. From a practical point of view, behavior in real road conditions is key (how easy can the asphalt be prepared, how easy can it be applied on the road, what is the durability, etc.). The paper will discuss the fundamentals of the use of lignin as bitumen replacement as well as the status of the different demonstration projects in Europe using lignin as a partial bitumen replacement in asphalts and will especially present the results of using Dawn Technology™ lignin as partial replacement of bitumen.

Keywords: biorefinery, wood fractionation, lignin, asphalt, bitumen, sustainability

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9 The Optimization of Topical Antineoplastic Therapy Using Controlled Release Systems Based on Amino-functionalized Mesoporous Silica

Authors: Lacramioara Ochiuz, Aurelia Vasile, Iulian Stoleriu, Cristina Ghiciuc, Maria Ignat

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Topical administration of chemotherapeutic agents (eg. carmustine, bexarotene, mechlorethamine etc.) in local treatment of cutaneous T-cell lymphoma (CTCL) is accompanied by multiple side effects, such as contact hypersensitivity, pruritus, skin atrophy or even secondary malignancies. A known method of reducing the side effects of anticancer agent is the development of modified drug release systems using drug incapsulation in biocompatible nanoporous inorganic matrices, such as mesoporous MCM-41 silica. Mesoporous MCM-41 silica is characterized by large specific surface, high pore volume, uniform porosity, and stable dispersion in aqueous medium, excellent biocompatibility, in vivo biodegradability and capacity to be functionalized with different organic groups. Therefore, MCM-41 is an attractive candidate for a wide range of biomedical applications, such as controlled drug release, bone regeneration, protein immobilization, enzymes, etc. The main advantage of this material lies in its ability to host a large amount of the active substance in uniform pore system with adjustable size in a mesoscopic range. Silanol groups allow surface controlled functionalization leading to control of drug loading and release. This study shows (I) the amino-grafting optimization of mesoporous MCM-41 silica matrix by means of co-condensation during synthesis and post-synthesis using APTES (3-aminopropyltriethoxysilane); (ii) loading the therapeutic agent (carmustine) obtaining a modified drug release systems; (iii) determining the profile of in vitro carmustine release from these systems; (iv) assessment of carmustine release kinetics by fitting on four mathematical models. Obtained powders have been described in terms of structure, texture, morphology thermogravimetric analysis. The concentration of the therapeutic agent in the dissolution medium has been determined by HPLC method. In vitro dissolution tests have been done using cell Enhancer in a 12 hours interval. Analysis of carmustine release kinetics from mesoporous systems was made by fitting to zero-order model, first-order model Higuchi model and Korsmeyer-Peppas model, respectively. Results showed that both types of highly ordered mesoporous silica (amino grafted by co-condensation process or post-synthesis) are thermally stable in aqueous medium. In what regards the degree of loading and efficiency of loading with the therapeutic agent, there has been noticed an increase of around 10% in case of co-condensation method application. This result shows that direct co-condensation leads to even distribution of amino groups on the pore walls while in case of post-synthesis grafting many amino groups are concentrated near the pore opening and/or on external surface. In vitro dissolution tests showed an extended carmustine release (more than 86% m/m) both from systems based on silica functionalized directly by co-condensation and after synthesis. Assessment of carmustine release kinetics revealed a release through diffusion from all studied systems as a result of fitting to Higuchi model. The results of this study proved that amino-functionalized mesoporous silica may be used as a matrix for optimizing the anti-cancer topical therapy by loading carmustine and developing prolonged-release systems.

Keywords: carmustine, silica, controlled, release

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8 Development of Peptide Inhibitors against Dengue Virus Infection by in Silico Design

Authors: Aussara Panya, Nunghathai Sawasdee, Mutita Junking, Chatchawan Srisawat, Kiattawee Choowongkomon, Pa-Thai Yenchitsomanus

Abstract:

Dengue virus (DENV) infection is a global public health problem with approximately 100 million infected cases a year. Presently, there is no approved vaccine or effective drug available; therefore, the development of anti-DENV drug is urgently needed. The clinical reports revealing the positive association between the disease severity and viral titer has been reported previously suggesting that the anti-DENV drug therapy can possibly ameliorate the disease severity. Although several anti-DENV agents showed inhibitory activities against DENV infection, to date none of them accomplishes clinical use in the patients. The surface envelope (E) protein of DENV is critical for the viral entry step, which includes attachment and membrane fusion; thus, the blocking of envelope protein is an attractive strategy for anti-DENV drug development. To search the safe anti-DENV agent, this study aimed to search for novel peptide inhibitors to counter DENV infection through the targeting of E protein using a structure-based in silico design. Two selected strategies has been used including to identify the peptide inhibitor which interfere the membrane fusion process whereby the hydrophobic pocket on the E protein was the target, the destabilization of virion structure organization through the disruption of the interaction between the envelope and membrane proteins, respectively. The molecular docking technique has been used in the first strategy to search for the peptide inhibitors that specifically bind to the hydrophobic pocket. The second strategy, the peptide inhibitor has been designed to mimic the ectodomain portion of membrane protein to disrupt the protein-protein interaction. The designed peptides were tested for the effects on cell viability to measure the toxic to peptide to the cells and their inhibitory assay to inhibit the DENV infection in Vero cells. Furthermore, their antiviral effects on viral replication, intracellular protein level and viral production have been observed by using the qPCR, cell-based flavivirus immunodetection and immunofluorescence assay. None of tested peptides showed the significant effect on cell viability. The small peptide inhibitors achieved from molecular docking, Glu-Phe (EF), effectively inhibited DENV infection in cell culture system. Its most potential effect was observed for DENV2 with a half maximal inhibition concentration (IC50) of 96 μM, but it partially inhibited other serotypes. Treatment of EF at 200 µM on infected cells also significantly reduced the viral genome and protein to 83.47% and 84.15%, respectively, corresponding to the reduction of infected cell numbers. An additional approach was carried out by using peptide mimicking membrane (M) protein, namely MLH40. Treatment of MLH40 caused the reduction of foci formation in four individual DENV serotype (DENV1-4) with IC50 of 24-31 μM. Further characterization suggested that the MLH40 specifically blocked viral attachment to host membrane, and treatment with 100 μM could diminish 80% of viral attachment. In summary, targeting the hydrophobic pocket and M-binding site on the E protein by using the peptide inhibitors could inhibit DENV infection. The results provide proof of-concept for the development of antiviral therapeutic peptide inhibitors to counter DENV infection through the use of a structure-based design targeting conserved viral protein.

Keywords: dengue virus, dengue virus infection, drug design, peptide inhibitor

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7 La0.80Ag0.15MnO3 Magnetic Nanoparticles for Self-Controlled Magnetic Fluid Hyperthermia

Authors: Marian Mihalik, Kornel Csach, Martin Kovalik, Matúš Mihalik, Martina Kubovčíková, Maria Zentková, Martin Vavra, Vladimír Girman, Jaroslav Briančin, Marija Perovic, Marija Boškovic, Magdalena Fitta, Robert Pelka

Abstract:

Current nanomaterials for use in biomedicine are based mainly on iron oxides and on present knowledge on magnetic nanostructures. Manganites can represent another material which can be used optionally. Manganites and their unique electronic properties have been extensively studied in the last decades not only due to fundamental interest but to possible applications of colossal magnetoresistance, magnetocaloric effect, and ferroelectric properties. It was found that the oxygen-reduction reaction on perovskite oxide is intimately connected with metal ion e.g., orbital occupation. The effect of oxygen deviation from the stoichiometric composition on crystal structure was studied very carefully by many authors on LaMnO₃. Depending on oxygen content, the crystal structure changes from orthorhombic one to rhombohedric for oxygen content 3.1. In the case of hole-doped manganites, the change from the orthorhombic crystal structure, which is typical for La1-xCaxMnO3 based manganites, to the rhombohedric crystal structure (La1-xMxMnO₃ where M = K, Ag, and Sr based materials) results in an enormous increase of the Curie temperature. In our paper, we study the effect of oxygen content on crystal structure, thermal, and magnetic properties (including magnetocaloric effect) of La1-xAgxMnO₃nano particle system. The content of oxygen in samples was tuned by heat treatment in different thermal regimes and in various environment (air, oxygen, argon). Water nanosuspensions based on La0.80Ag0.15MnO₃ magnetic particles with the Curie temperature of about 43oC were prepared by two different approaches. First, by using a laboratory circulation mill for milling of powder in the presence of sodium dodecyl sulphate (SDS) and subsequent centrifugation. Second nanosuspension was prepared using an agate bowl, etching in citric acid and HNO3, ultrasound homogeniser, centrifugation, and dextran 40 kDA or 15 kDA as surfactant. Electrostatic stabilisation obtained by the first approach did not offer long term kinetic and aggregation colloidal stability and was unable to compensate for attractive forces between particles under a magnetic field. By the second approach, we prepared suspension oversaturated by dextran 40 kDA for steric stabilisation, with evidence of the presence of superparamagnetic behaviour. Low concentration of nanoparticles and not ideal coverage of nanoparticles impacting the stability of ferrofluids was the disadvantage of this approach. Strong steric stabilisation was observable at alcaic conditions under pH = ~10. Application of dextran 15 kDA leads to relatively stable ferrofluid with pH around physiological conditions, but desegregation of powder by HNO₃ was not effective enough, and the average size of fragments was to large of about 150 nm, and we did not see any signature of superparamagnetic behaviour. The prepared ferrofluids were characterised by scanning and transition microscope method, thermogravimetry, magnetization, and AC susceptibility measurements. Specific Absorption Rate measurements were undertaken on powder as well on ferrofluids in order to estimate the potential application of La₀.₈₀Ag₀.₁₅MnO₃ magnetic particles based ferrofluid for hyperthermia. Our complex study contains an investigation of biocompatibility and potential biohazard of this material.

Keywords: manganites, magnetic nanoparticles, oxygen content, magnetic phase transition, magnetocaloric effect, ferrofluid, hyperthermia

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6 The Impact of β Nucleating Agents and Carbon-Based Nanomaterials on Water Vapor Permeability of Polypropylene Composite Films

Authors: Glykeria A. Visvini, George Ν. Mathioudakis, Amaia Soto Beobide, George A. Voyiatzis

Abstract:

Polymer nanocomposites are materials in which a polymer matrix is reinforced with nanoscale inclusions, such as nanoparticles, nanoplates, or nanofibers. These nanoscale inclusions can significantly enhance the mechanical, thermal, electrical, and other properties of the polymer matrix, making them attractive for a wide range of industrial applications. These properties can be tailored by adjusting the type and the concentration of the nanoinclusions, which provides a high degree of flexibility in their design and development. An important property that polymeric membranes can exhibit is water vapor permeability (WVP). This can be accomplished by various methods, including the incorporation of micro/nano-fillers into the polymer matrix. In this way, a micro/nano-pore network can be formed, allowing water vapor to permeate through the membrane. At the same time, the membrane can be stretched uni- or bi-axially, creating aligned or cross-linked micropores in the composite, respectively, which can also increase the WVP. Nowadays, in industry, stretched films reinforced with CaCO3 develop micro-porosity sufficient to give them breathability characteristics. Carbon-based nanomaterials, such as graphene oxide (GO), are tentatively expected to be able to effectively improve the WVP of corresponding composite polymer films. The presence in the GO structure of various functional oxidizing groups enhances its ability to attract and channel water molecules, exploiting the unique large surface area of graphene that allows the rapid transport of water molecules. Polypropylene (PP) is widely used in various industrial applications due to its desirable properties, including good chemical resistance, excellent thermal stability, low cost, and easy processability. The specific properties of PP are highly influenced by its crystalline behavior, which is determined by its processing conditions. The development of the β-crystalline phase in PP, in combination with stretching, is anticipating improving the microporosity of the polymer matrix, thereby enhancing its WVP. The aim of present study is to create breathable PP composite membranes using carbon-based nanomaterials, such as graphene oxide (GO), reduced graphene oxide (rGO), and graphene nanoplatelets (GNPs). Unlike traditional methods that rely on the drawing process to enhance the WVP of PP, this study intents to develop a low-cost approach using melt mixing with β-nucleating agents and carbon fillers to create highly breathable PP composite membranes. The study aims to investigate how the concentration of these additives affects the water vapor transport properties of the resulting PP films/membranes. The presence of β-nucleating agents and carbon fillers is expected to enhance β-phase growth in PP, while an alternation between β- and α-phase is expected to lead to improved microporosity and WVP. Our ambition is to develop highly breathable PP composite films with superior performance and at a lower cost compared to the benchmark. Acknowledgment: This research has been co‐financed by the European Union and Greek national funds through the Operational Program Competitiveness, Entrepreneurship and Innovation, under the call «Special Actions "AQUACULTURE"-"INDUSTRIAL MATERIALS"-"OPEN INNOVATION IN CULTURE"» (project code: Τ6YBP-00337)

Keywords: carbon based nanomaterials, nanocomposites, nucleating agent, polypropylene, water vapor permeability

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5 Deciphering Tumor Stroma Interactions in Retinoblastoma

Authors: Rajeswari Raguraman, Sowmya Parameswaran, Krishnakumar Subramanian, Jagat Kanwar, Rupinder Kanwar

Abstract:

Background: Tumor microenvironment has been implicated in several cancers to regulate cell growth, invasion and metastasis culminating in outcome of therapy. Tumor stroma consists of multiple cell types that are in constant cross-talk with the tumor cells to favour a pro-tumorigenic environment. Not much is known about the existence of tumor microenvironment in the pediatric intraocular malignancy, Retinoblastoma (RB). In the present study, we aim to understand the multiple stromal cellular subtypes and tumor stromal interactions expressed in RB tumors. Materials and Methods: Immunohistochemistry for stromal cell markers CD31, CD68, alpha-smooth muscle (α-SMA), vimentin and glial fibrillary acidic protein (GFAP) was performed on formalin fixed paraffin embedded tissues sections of RB (n=12). The differential expression of stromal target molecules; fibroblast activation protein (FAP), tenascin-C (TNC), osteopontin (SPP1), bone marrow stromal antigen 2 (BST2), stromal derived factor 2 and 4 (SDF2 and SDF4) in primary RB tumors (n=20) and normal retina (n=5) was studied by quantitative reverse transcriptase polymerase chain reaction (qRT-PCR) and Western blotting. The differential expression was correlated with the histopathological features of RB. The interaction between RB cell lines (Weri-Rb-1, NCC-RbC-51) and Bone marrow stromal cells (BMSC) was also studied using direct co-culture and indirect co-culture methods. The functional effect of the co-culture methods on the RB cells was evaluated by invasion and proliferation assays. Global gene expression was studied by using Affymetrix 3’ IVT microarray. Pathway prediction was performed using KEGG and the key molecules were validated using qRT-PCR. Results: The immunohistochemistry revealed the presence of several stromal cell types such as endothelial cells (CD31+;Vim+/-); macrophages (CD68+;Vim+/-); Fibroblasts (Vim+; CD31-;CD68- );myofibroblasts (α-SMA+/ Vim+) and invading retinal astrocytes/ differentiated retinal glia (GFAP+; Vim+). A characteristic distribution of these stromal cell types was observed in the tumor microenvironment, with endothelial cells predominantly seen in blood vessels and macrophages near actively proliferating tumor or necrotic areas. Retinal astrocytes and glia were predominant near the optic nerve regions in invasive tumors with sparse distribution in tumor foci. Fibroblasts were widely distributed with rare evidence of myofibroblasts in the tumor. Both gene and protein expression revealed statistically significant (P<0.05) up-regulation of FAP, TNC and BST2 in primary RB tumors compared to the normal retina. Co-culture of BMSC with RB cells promoted invasion and proliferation of RB cells in direct and indirect contact methods respectively. Direct co-culture of RB cell lines with BMSC resulted in gene expression changes in ECM-receptor interaction, focal adhesion, IL-8 and TGF-β signaling pathways associated with cancer. In contrast, various metabolic pathways such a glucose, fructose and amino acid metabolism were significantly altered under the indirect co-culture condition. Conclusion: The study suggests that the close interaction between RB cells and the stroma might be involved in RB tumor invasion and progression which is likely to be mediated by ECM-receptor interactions and secretory factors. Targeting the tumor stroma would be an attractive option for redesigning treatment strategies for RB.

Keywords: gene expression profiles, retinoblastoma, stromal cells, tumor microenvironment

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4 Fe Modified Tin Oxide Thin Film Based Matrix for Reagentless Uric Acid Biosensing

Authors: Kashima Arora, Monika Tomar, Vinay Gupta

Abstract:

Biosensors have found potential applications ranging from environmental testing and biowarfare agent detection to clinical testing, health care, and cell analysis. This is driven in part by the desire to decrease the cost of health care and to obtain precise information more quickly about the health status of patient by the development of various biosensors, which has become increasingly prevalent in clinical testing and point of care testing for a wide range of biological elements. Uric acid is an important byproduct in human body and a number of pathological disorders are related to its high concentration in human body. In past few years, rapid growth in the development of new materials and improvements in sensing techniques have led to the evolution of advanced biosensors. In this context, metal oxide thin film based matrices due to their bio compatible nature, strong adsorption ability, high isoelectric point (IEP) and abundance in nature have become the materials of choice for recent technological advances in biotechnology. In the past few years, wide band-gap metal oxide semiconductors including ZnO, SnO₂ and CeO₂ have gained much attention as a matrix for immobilization of various biomolecules. Tin oxide (SnO₂), wide band gap semiconductor (Eg =3.87 eV), despite having multifunctional properties for broad range of applications including transparent electronics, gas sensors, acoustic devices, UV photodetectors, etc., it has not been explored much for biosensing purpose. To realize a high performance miniaturized biomolecular electronic device, rf sputtering technique is considered to be the most promising for the reproducible growth of good quality thin films, controlled surface morphology and desired film crystallization with improved electron transfer property. Recently, iron oxide and its composites have been widely used as matrix for biosensing application which exploits the electron communication feature of Fe, for the detection of various analytes using urea, hemoglobin, glucose, phenol, L-lactate, H₂O₂, etc. However, to the authors’ knowledge, no work is being reported on modifying the electronic properties of SnO₂ by implanting with suitable metal (Fe) to induce the redox couple in it and utilizing it for reagentless detection of uric acid. In present study, Fe implanted SnO₂ based matrix has been utilized for reagentless uric acid biosensor. Implantation of Fe into SnO₂ matrix is confirmed by energy-dispersive X-Ray spectroscopy (EDX) analysis. Electrochemical techniques have been used to study the response characteristics of Fe modified SnO₂ matrix before and after uricase immobilization. The developed uric acid biosensor exhibits a high sensitivity to about 0.21 mA/mM and a linear variation in current response over concentration range from 0.05 to 1.0 mM of uric acid besides high shelf life (~20 weeks). The Michaelis-Menten kinetic parameter (Km) is found to be relatively very low (0.23 mM), which indicates high affinity of the fabricated bioelectrode towards uric acid (analyte). Also, the presence of other interferents present in human serum has negligible effect on the performance of biosensor. Hence, obtained results highlight the importance of implanted Fe:SnO₂ thin film as an attractive matrix for realization of reagentless biosensors towards uric acid.

Keywords: Fe implanted tin oxide, reagentless uric acid biosensor, rf sputtering, thin film

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3 Simulation of Multistage Extraction Process of Co-Ni Separation Using Ionic Liquids

Authors: Hongyan Chen, Megan Jobson, Andrew J. Masters, Maria Gonzalez-Miquel, Simon Halstead, Mayri Diaz de Rienzo

Abstract:

Ionic liquids offer excellent advantages over conventional solvents for industrial extraction of metals from aqueous solutions, where such extraction processes bring opportunities for recovery, reuse, and recycling of valuable resources and more sustainable production pathways. Recent research on the use of ionic liquids for extraction confirms their high selectivity and low volatility, but there is relatively little focus on how their properties can be best exploited in practice. This work addresses gaps in research on process modelling and simulation, to support development, design, and optimisation of these processes, focusing on the separation of the highly similar transition metals, cobalt, and nickel. The study exploits published experimental results, as well as new experimental results, relating to the separation of Co and Ni using trihexyl (tetradecyl) phosphonium chloride. This extraction agent is attractive because it is cheaper, more stable and less toxic than fluorinated hydrophobic ionic liquids. This process modelling work concerns selection and/or development of suitable models for the physical properties, distribution coefficients, for mass transfer phenomena, of the extractor unit and of the multi-stage extraction flowsheet. The distribution coefficient model for cobalt and HCl represents an anion exchange mechanism, supported by the literature and COSMO-RS calculations. Parameters of the distribution coefficient models are estimated by fitting the model to published experimental extraction equilibrium results. The mass transfer model applies Newman’s hard sphere model. Diffusion coefficients in the aqueous phase are obtained from the literature, while diffusion coefficients in the ionic liquid phase are fitted to dynamic experimental results. The mass transfer area is calculated from the surface to mean diameter of liquid droplets of the dispersed phase, estimated from the Weber number inside the extractor. New experiments measure the interfacial tension between the aqueous and ionic phases. The empirical models for predicting the density and viscosity of solutions under different metal loadings are also fitted to new experimental data. The extractor is modelled as a continuous stirred tank reactor with mass transfer between the two phases and perfect phase separation of the outlet flows. A multistage separation flowsheet simulation is set up to replicate a published experiment and compare model predictions with the experimental results. This simulation model is implemented in gPROMS software for dynamic process simulation. The results of single stage and multi-stage flowsheet simulations are shown to be in good agreement with the published experimental results. The estimated diffusion coefficient of cobalt in the ionic liquid phase is in reasonable agreement with published data for the diffusion coefficients of various metals in this ionic liquid. A sensitivity study with this simulation model demonstrates the usefulness of the models for process design. The simulation approach has potential to be extended to account for other metals, acids, and solvents for process development, design, and optimisation of extraction processes applying ionic liquids for metals separations, although a lack of experimental data is currently limiting the accuracy of models within the whole framework. Future work will focus on process development more generally and on extractive separation of rare earths using ionic liquids.

Keywords: distribution coefficient, mass transfer, COSMO-RS, flowsheet simulation, phosphonium

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2 The Prospects of Optimized KOH/Cellulose 'Papers' as Hierarchically Porous Electrode Materials for Supercapacitor Devices

Authors: Dina Ibrahim Abouelamaiem, Ana Jorge Sobrido, Magdalena Titirici, Paul R. Shearing, Daniel J. L. Brett

Abstract:

Global warming and scarcity of fossil fuels have had a radical impact on the world economy and ecosystem. The urgent need for alternative energy sources has hence elicited an extensive research for exploiting efficient and sustainable means of energy conversion and storage. Among various electrochemical systems, supercapacitors attracted significant attention in the last decade due to their high power supply, long cycle life compared to batteries and simple mechanism. Recently, the performance of these devices has drastically improved, as tuning of nanomaterials provided efficient charge and storage mechanisms. Carbon materials, in various forms, are believed to pioneer the next generation of supercapacitors due to their attractive properties that include high electronic conductivities, high surface areas and easy processing and functionalization. Cellulose has eco-friendly attributes that are feasible to replace man-made fibers. The carbonization of cellulose yields carbons, including activated carbon and graphite fibers. Activated carbons successively are the most exploited candidates for supercapacitor electrode materials that can be complemented with pseudocapacitive materials to achieve high energy and power densities. In this work, the optimum functionalization conditions of cellulose have been investigated for supercapacitor electrode materials. The precursor was treated with potassium hydroxide (KOH) at different KOH/cellulose ratios prior to the carbonization process in an inert nitrogen atmosphere at 850 °C. The chalky products were washed, dried and characterized with different techniques including transmission electron microscopy (TEM), x-ray tomography and nitrogen adsorption-desorption isotherms. The morphological characteristics and their effect on the electrochemical performances were investigated in two and three-electrode systems. The KOH/cellulose ratios of 0.5:1 and 1:1 exhibited the highest performances with their unique hierarchal porous network structure, high surface areas and low cell resistances. Both samples acquired the best results in three-electrode systems and coin cells with specific gravimetric capacitances as high as 187 F g-1 and 20 F g-1 at a current density of 1 A g-1 and retention rates of 72% and 70%, respectively. This is attributed to the morphology of the samples that constituted of a well-balanced micro-, meso- and macro-porosity network structure. This study reveals that the electrochemical performance doesn’t solely depend on high surface areas but also an optimum pore size distribution, specifically at low current densities. The micro- and meso-pore contribution to the final pore structure was found to dominate at low KOH loadings, reaching ‘equilibrium’ with macropores at the optimum KOH loading, after which macropores dictate the porous network. The wide range of pore sizes is detrimental for the mobility and penetration of electrolyte ions in the porous structures. These findings highlight the influence of various morphological factors on the double-layer capacitances and high performance rates. In addition, they open a platform for the investigation of the optimized conditions for double-layer capacitance that can be coupled with pseudocapacitive materials to yield higher energy densities and capacities.

Keywords: carbon, electrochemical performance, electrodes, KOH/cellulose optimized ratio, morphology, supercapacitor

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1 Human Bone Marrow Stem Cell Behavior on 3D Printed Scaffolds as Trabecular Bone Grafts

Authors: Zeynep Busra Velioglu, Deniz Pulat, Beril Demirbakan, Burak Ozcan, Ece Bayrak, Cevat Erisken

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Bone tissue has the ability to perform a wide array of functions including providing posture, load-bearing capacity, protection for the internal organs, initiating hematopoiesis, and maintaining the homeostasis of key electrolytes via calcium/phosphate ion storage. The most common cause for bone defects is extensive trauma and subsequent infection. Bone tissue has the self-healing capability without a scar tissue formation for the majority of the injuries. However, some may result with delayed union or fracture non-union. Such cases include reconstruction of large bone defects or cases of compromised regenerative process as a result of avascular necrosis and osteoporosis. Several surgical methods exist to treat bone defects, including Ilizarov method, Masquelete technique, growth factor stimulation, and bone replacement. Unfortunately, these are technically demanding and come with noteworthy disadvantages such as lengthy treatment duration, adverse effects on the patient’s psychology, repeated surgical procedures, and often long hospitalization times. These limitations associated with surgical techniques make bone substitutes an attractive alternative. Here, it was hypothesized that a 3D printed scaffold will mimic trabecular bone in terms of biomechanical properties and that such scaffolds will support cell attachment and survival. To test this hypothesis, this study aimed at fabricating poly(lactic acid), PLA, structures using 3D printing technology for trabecular bone defects, characterizing the scaffolds and comparing with bovine trabecular bone. Capacity of scaffolds on human bone marrow stem cell (hBMSC) attachment and survival was also evaluated. Cubes with a volume of 1 cm³ having pore sizes of 0.50, 1.00 and 1.25 mm were printed. The scaffolds/grafts were characterized in terms of porosity, contact angle, compressive mechanical properties as well cell response. Porosities of the 3D printed scaffolds were calculated based on apparent densities. For contact angles, 50 µl distilled water was dropped over the surface of scaffolds, and contact angles were measured using ‘Image J’ software. Mechanical characterization under compression was performed on scaffolds and native trabecular bone (bovine, 15 months) specimens using a universal testing machine at a rate of 0.5mm/min. hBMSCs were seeded onto the 3D printed scaffolds. After 3 days of incubation with fully supplemented Dulbecco’s modified Eagle’s medium, the cells were fixed using 2% formaldehyde and glutaraldehyde mixture. The specimens were then imaged under scanning electron microscopy. Cell proliferation was determined by using EZQuant dsDNA Quantitation kit. Fluorescence was measured using microplate reader Spectramax M2 at the excitation and emission wavelengths of 485nm and 535nm, respectively. Findings suggested that porosity of scaffolds with pore dimensions of 0.5mm, 1.0mm and 1.25mm were not affected by pore size, while contact angle and compressive modulus decreased with increasing pore size. Biomechanical characterization of trabecular bone yielded higher modulus values as compared to scaffolds with all pore sizes studied. Cells attached and survived in all surfaces, demonstrating higher proliferation on scaffolds with 1.25mm pores as compared with those of 1mm. Collectively, given lower mechanical properties of scaffolds as compared to native bone, and biocompatibility of the scaffolds, the 3D printed PLA scaffolds of this study appear as candidate substitutes for bone repair and regeneration.

Keywords: 3D printing, biomechanics, bone repair, stem cell

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