Search results for: cationic porphyrins

Authors: Dawid Stawski, Silviya Halacheva, Dorota Zielińska

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The surface properties of many materials can be readily and predictably modified by the controlled deposition of thin layers containing appropriate functional groups and this research area is now a subject of widespread interest. The layer-by-layer (lbl) method involves depositing oppositely charged layers of polyelectrolytes onto the substrate material which are stabilized due to strong electrostatic forces between adjacent layers. This type of modification affords products that combine the properties of the original material with the superficial parameters of the new external layers. Through an appropriate selection of the deposited layers, the surface properties can be precisely controlled and readily adjusted in order to meet the requirements of the intended application. In the presented paper a variety of anionic (poly(acrylic acid)) and cationic (linear poly(ethylene imine), polymers were successfully deposited onto the polypropylene nonwoven using the lbl technique. The chemical structure of the surface before and after modification was confirmed by reflectance FTIR spectroscopy, volumetric analysis and selective dyeing tests. As a direct result of this work, new materials with greatly improved properties have been produced. For example, following a modification process significant changes in the electrostatic activity of a range of novel nanocomposite materials were observed. The deposition of polyelectrolyte nanolayers was found to strongly accelerate the loss of electrostatically generated charges and to increase considerably the thermal resistance properties of the modified fabric (the difference in T50% is over 20°C). From our results, a clear relationship between the type of polyelectrolyte layer deposited onto the flat fabric surface and the properties of the modified fabric was identified.

Keywords: layer-by-layer technique, polypropylene nonwoven, surface modification, surface properties

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Authors: Mari Carmen Reyes Angeles, Dalia Michel Reyes Villeda, Ana María Herrera González

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This work reports the design and synthesis of two composite materials based on physically activated carbon and basic polyelectrolytes useful in the adsorption of textile dyes present in aqueous solutions and wastewater. The synthesis of basic polyelectrolytes poly(2-vinylpyridine) (P2VP) and poly(4-vinylpyridine) (P4VP) was made by means of free radical polymerization. The carbon made from prickly pear peel (CarTunaF) was thermally activated in the presence of combustion gases. Composite materials CarTunaF2VP and CarTunaF4VP were obtained from CarTunaF and polybasic polyelectrolytes P2VP and P4VP with a ratio of 67:33 wt. The structure of each polyelectrolyte, P2VP, and P4VP, was elucidated by means of the FTIR and 1H NMR spectrophotometric techniques. Their thermal stability was evaluated using TGA. The characterization of CarTunaF and composite materials CarTunaF2VP and CarTunaF4VP was made by means of FTIR, TGA, SEM, and N2 adsorption. The adsorptive capacities of the polyelectrolytes and the composite materials were evaluated by adsorption of direct dyes present in aqueous solutions. The polyelectrolytes removed between 90 and 100% of the dyes, and the composite materials removed between 68 and 93% of the dyes. Using the four adsorbents P2VP, P4VP, CarTuna2VP, and CarTuna4VP, it was observed that the dyes studied, Direct Blue 80, Direct Turquoise 86, and Direct Orange 26, were adsorbed in the range between 46.1 and 188.7mg∙g-1 by means of electrostatic interactions between the anionic groups in the dyes with the cationic groups in the adsorbents. By using adsorbent materials in the treatment of wastewater from the textile industry, an improvement in the quality of the water was observed by decreasing its pH, COD, conductivity, and color considerably

Keywords: adsorption, anionic dyes, composite, polyelectrolytes

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Authors: Emily Rabe, Stephanie Candelaria, Rachel Malone, Olivia Lenz, Greg Newbloom

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Electrodialysis (ED) is a well-developed technology for ion removal in a variety of applications. However, many industries generate harsh wastewater streams that are incompatible with traditional ion exchange membranes. Membrion® has developed novel ceramic-based ion exchange membranes (IEMs) offering several advantages over traditional polymer membranes: high performance in low pH, chemical resistance to oxidizers, and a rigid structure that minimizes swelling. These membranes are synthesized with our patented silane-based sol-gel techniques. The pore size, shape, and network structure are engineered through a molecular self-assembly process where thermodynamic driving forces are used to direct where and how pores form. Either cationic or anionic groups can be added within the membrane nanopore structure to create cation- and anion-exchange membranes. The ceramic IEMs are produced on a roll-to-roll manufacturing line with low-temperature processing. Membrane performance testing is conducted using in-house permselectivity, area-specific resistance, and ED stack testing setups. Ceramic-based IEMs show comparable performance to traditional IEMs and offer some unique advantages. Long exposure to highly acidic solutions has a negligible impact on ED performance. Additionally, we have observed stable performance in the presence of strong oxidizing agents such as hydrogen peroxide. This stability is expected, as the ceramic backbone of these materials is already in a fully oxidized state. This data suggests ceramic membranes, made using sol-gel chemistry, could be an ideal solution for acidic and/or oxidizing wastewater streams from processes such as semiconductor manufacturing and mining.

Keywords: ion exchange, membrane, silane chemistry, nanostructure, wastewater

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Authors: Mohammed Panthakkal Abdul Muthalif, Shanmugasundaram Kanagaraj, Jumi Park, Hangyu Park, Youngson Choe

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The present study reports the incorporation of calcium ions into the CuS counter electrodes (CEs) in order to modify the photovoltaic performance of quantum dot-sensitized solar cells (QDSSCs). Metal ion-doped CuS thin film was prepared by the chemical bath deposition (CBD) method on FTO substrate and used directly as counter electrodes for TiO₂/CdS/CdSe/ZnS photoanodes based QDSSCs. For the Ca-doped CuS thin films, copper nitrate and thioacetamide were used as anionic and cationic precursors. Calcium nitrate tetrahydrate was used as doping material. The surface morphology of Ca-doped CuS CEs indicates that the fragments are uniformly distributed, and the structure is densely packed with high crystallinity. The changes observed in the diffraction patterns suggest that Ca dopant can introduce increased disorder into CuS material structure. EDX analysis was employed to determine the elemental identification, and the results confirmed the presence of Cu, S, and Ca on the FTO glass substrate. The photovoltaic current density – voltage characteristics of Ca-doped CuS CEs shows the specific improvements in open circuit voltage decay (Voc) and short-circuit current density (Jsc). Electrochemical impedance spectroscopy results display that Ca-doped CuS CEs have greater electrocatalytic activity and charge transport capacity than bare CuS. All the experimental results indicate that 20% Ca-doped CuS CE based QDSSCs exhibit high power conversion efficiency (η) of 4.92%, short circuit current density of 15.47 mA cm⁻², open circuit photovoltage of 0.611 V, and fill factor (FF) of 0.521 under illumination of one sun.

Keywords: Ca-doped CuS counter electrodes, surface morphology, chemical bath deposition method, electrocatalytic activity

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Authors: Nusaiba Al-Nemrawi, Belal Al-Husein

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Methotrexate (MTX) is a stoichiometric inhibitor of dihydrofolate reductase, which is essential for DNA synthesis. MTX is a chemotherapeutic agent used for treating many types of cancer cells. However, cells’ resistant to MTX is very common and its pharmacokinetic behavior is highly problematic. of MTX within tumor cells, we propose encapsulation of antitumor drugs in nanoparticulated systems. Chitosan (CS) is a naturally occurring polymer that is biocompatibe, biodegradable, non-toxic, cationic and bioadhesive. CS nanoparticles (CS-NPs) have been used as drug carrier for targeted delivery. Titanium dioxide (TiO2), a natural mineral oxide, which is used in biomaterials due to its high stability and antimicrobial and anticorrosive properties. TiO2 showed a potential as a tumor suppressor. In this study a new formulation of MTX loaded in CS NPs (CS-MTX NPs) and coated with Titanium oxide (TiO2) was prepared. The mean particle size, zeta potential, polydispersity index were measured. The interaction between CS NPs and TiO2 NPs was confirmed using FTIR and XRD. CS-MTX NPs was studied in vitro using the tumor cell line MCF-7 (human breast cancer). The results showed that CS-MTX has a size around 169 nm and as they were coated with TiO2, the size ranged between and depending on the ratio of CS-MTX to TiO2 ratio used in the preparation. All NPs (uncoated and coated carried positive charges and were monodispersed. The entrapment efficacy was around 65%. Both FTIR and XRD proved that TiO2 interacted with CS-MTX NPs. The drug invitro release was controlled and sustained over days. Finally, the studied in vitro using the tumor cell line MCF-7 suggested that combining nanomaterials with anticancer drugs CS-MTX NPs may be more effective than free MTX for cancer treatment. In conclusion, the combination of CS-MTX NPs and TiO2 NPs showed excellent time-dependent in vitro antitumor behavior, therefore, can be employed as a promising anticancer agent to attain efficient results towards MCF-7 cells.

Keywords: Methotrexate, Titanium dioxide, Chitosan nanoparticles, cancer

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Authors: Florian Billing, Soren Segan, Meike Jakobi, Elsa Arefaine, Aliki Jerch, Xin Xiong, Matthias Becker, Thomas Joos, Burkhard Schlosshauer, Ulrich Rothbauer, Nicole Schneiderhan-Marra, Hanna Hartmann, Christopher Shipp

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The immune response plays a major role in implant biocompatibility, but an understanding of how to design biomaterials for specific immune responses is yet to be achieved. We aimed to better understand how changing certain material properties can drive immune responses. To this end, we tested immune response to experimental implant coatings that vary in specific characteristics. A layer-by-layer approach was employed to vary surface charge and wettability. Human-based in vitro models (THP-1 macrophages and primary peripheral blood mononuclear cells (PBMCS)) were used to assess immune responses using multiplex cytokine analysis, flow cytometry (CD molecule expression) and microscopy (cell morphology). We observed dramatic differences in immune response due to specific alterations in coating properties. For example altering the surface charge of coating A from anionic to cationic resulted in the substantial elevation of the pro-inflammatory molecules IL-1beta, IL-6, TNF-alpha and MIP-1beta, while the pro-wound healing factor VEGF was significantly down-regulated. We also observed changes in cell surface marker expression in relation to altered coating properties, such as CD16 on NK Cells and HLA-DR on monocytes. We furthermore observed changes in the morphology of THP-1 macrophages following cultivation on different coatings. A correlation between these morphological changes and the cytokine expression profile is ongoing. Targeted changes in biomaterial properties can produce vast differences in immune response. The properties of the coatings examined here may, therefore, be a method to direct specific biological responses in order to improve implant biocompatibility.

Keywords: biomaterials, coatings, immune system, implants

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Authors: Meltem Haktaniyan, Eda Cagli, Irem Erel Goktepe

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Polymers that change their properties in response to different stimuli (e.g. light, temperature, pH, ionic strength or magnetic field) are called ‘smart’ or ‘stimuli-responsive polymers’. These polymers have been widely used in biomedical applications such as sensors, gene delivery, drug delivery or tissue engineering. Temperature-responsive polymers have been studied extensively for controlled drug delivery applications. As regard of pseudo-peptides, poly (2-alky-2-oxazoline)s are considered as good candidates for delivery systems due to their stealth behavior and nontoxicity. In order to build responsive multilayer films for controlled drug release applications from surface, Layer by layer technique (LBL) is a powerful technique with an advantage of nanometer scale control over spatial architecture and morphology. Multilayers can be constructed on surface where non-covalent interactions including electrostatic interactions, hydrogen bonding, and charge-transfer or hydrophobic-hydrophobic interactions. In the present study, hydrogen bounded multilayer films of poly (2-alky-2-oxazoline) s with tannic acid were prepared in order to use as a platform to release Doxorubicin (DOX) from surface with pH and thermal triggers. For this purpose, poly (2-isopropyl-2-oxazoline) (PIPOX) and poly (2-ethyl-2-oxazoline) (PETOX) were synthesized via cationic ring opening polymerization (CROP) with hydroxyl end groups. Two polymeric multilayer systems ((PETOX)/(DOX)-(TA) complexes and (PIPOX)/(DOX)-(TA) complexes) were designed to investigate of controlled release of Doxorubicin (DOX) from surface with pH and thermal triggers. The drug release profiles from the multilayer thin films with alterations of pH and temperature will been examined with UV-Vis Spectroscopy and Fluorescence Spectroscopy.

Keywords: temperature responsive polymers, h-bonded multilayer films, drug release, polyoxazoline

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Authors: Hamideh Hamedi, Nima Rezaei, Sohrab Zendehboudi

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Separating emulsified oil contaminations from waste- or produced water is of interest to various industries. Magnetic particles (MPs) application for separating dispersed and emulsified oil from wastewater is becoming more popular. Stabilization of MPs is required through developing a coating layer on their surfaces to prevent their agglomeration and enhance their dispersibility. In this research, we study the effects of coating material, size, and concentration of iron oxide MPs on oil separation efficiency, using oil adsorption capacity measurements. We functionalize both micro-and nanoparticles of Fe3O4 using sodium dodecyl sulfate (SDS) as an anionic surfactant, cetyltrimethylammonium bromide (CTAB) as a cationic surfactant, and stearic acid (SA). The chemical structures and morphologies of these particles are characterized using Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), and Energy Dispersive X-ray (EDX). The oil-water separation results indicate that a low dosage of the coated magnetic nanoparticle with CTAB (0.5 g/L MNP-CTAB) results the highest oil adsorption capacity (nearly 100%) for 1000 ppm dodecane-in-water emulsion, containing ultra-small droplets (250–300 nm). While separation efficiency of the same dosage of bare MNPs is around 57.5%. Demulsification results of magnetic microparticles (MMPs) also reveal that the functionalizing particles with CTAB increase oil removal efficiency from 86.3% for bare MMP to 92% for MMP-CTAB. Comparing the results of different coating materials implies that the major interaction reaction is an electrostatic attraction between negatively charged oil droplets and positively charged MNP-CTAB and MMP-CTAB. Furthermore, the synthesized nanoparticles could be recycled and reused; after ten cycles the oil adsorption capacity slightly decreases to near 95%. In conclusion, functionalized magnetic particles with high oil separation efficiency could be used effectively in treatment of oily wastewater. Finally, optimization of the adsorption process is required by considering the effective system variables, and fluid properties.

Keywords: oily wastewater treatment, emulsions, oil-water separation, adsorption, magnetic nanoparticles

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Authors: Maryam Mohammad Hadi, Heather Nesbitt, Hamzah Masood, Hashim Ahmed, Mark Emberton, John Callan, Alexander MacRobert, Anthony McHale, Nikolitsa Nomikou

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Sonodynamic therapy (SDT) utilises ultrasound in combination with sensitizers, such as porphyrins, for the production of cytotoxic reactive oxygen species (ROS) and the confined ablation of tumours. Ultrasound can be applied locally, and the acoustic waves, at frequencies between 0.5-2 MHz, are transmitted efficiently through tissue. SDT does not require highly toxic agents, and the cytotoxic effect only occurs upon ultrasound exposure at the site of the lesion. Therefore, this approach is not associated with adverse side effects. Further highlighting the benefits of SDT, no cancer cell population has shown resistance to therapy-triggered ROS production or their cytotoxic effects. This is particularly important, given the as yet unresolved issues of radiation and chemo-resistance, to the authors’ best knowledge. Another potential future benefit of this approach – considering its non-thermal mechanism of action – is its possible role as an adjuvant to immunotherapy. Substantial pre-clinical studies have demonstrated the efficacy and targeting capability of this therapeutic approach. However, SDT has yet to be fully characterised and appropriately exploited for the treatment of cancer. In this study, a formulation based on multistimulus-responsive sensitizer-containing nanoparticles that can accumulate in advanced prostate tumours and increase the therapeutic efficacy of SDT has been developed. The formulation is based on a polyglutamate-tyrosine (PGATyr) co-polymer carrying hematoporphyrin. The efficacy of SDT in this study was demonstrated using prostate cancer as the translational exemplar. The formulation was designed to respond to the microenvironment of advanced prostate tumours, such as the overexpression of the proteolytic enzymes, cathepsin-B and prostate-specific membrane antigen (PSMA), that can degrade the nanoparticles, reduce their size, improving both diffusions throughout the tumour mass and cellular uptake. The therapeutic modality was initially tested in vitro using LNCaP and PC3 cells as target cell lines. The SDT efficacy was also examined in vivo, using male SCID mice bearing LNCaP subcutaneous tumours. We have demonstrated that the PGATyr co-polymer is digested by cathepsin B and that digestion of the formulation by cathepsin-B, at tumour-mimicking conditions (acidic pH), leads to decreased nanoparticle size and subsequent increased cellular uptake. Sonodynamic treatment, at both normoxic and hypoxic conditions, demonstrated ultrasound-induced cytotoxic effects only for the nanoparticle-treated prostate cancer cells, while the toxicity of the formulation in the absence of ultrasound was minimal. Our in vivo studies in immunodeficient mice, using the hematoporphyrin-containing PGATyr nanoparticles for SDT, showed a 50% decrease in LNCaP tumour volumes within 24h, following IV administration of a single dose. No adverse effects were recorded, and body weight was stable. The results described in this study clearly demonstrate the promise of SDT to revolutionize cancer treatment. It emphasizes the potential of this therapeutic modality as a fist line treatment or in combination treatment for the elimination or downstaging of difficult to treat cancers, such as prostate, pancreatic, and advanced colorectal cancer.

Keywords: sonodynamic therapy, nanoparticles, tumour ablation, ultrasound

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Authors: Maria Karnachoriti, Ellas Spyratou, Dimitrios Lykidis, Maria Lambropoulou, Yiannis S. Raptis, Ioannis Seimenis, Efstathios P. Efstathopoulos, Athanassios G. Kontos

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Colorectal cancer is the third most common cancer diagnosed in Europe, according to the latest incidence data provided by the World Health Organization (WHO), and early diagnosis has proved to be the key in reducing cancer-related mortality. In cases where surgical interventions are required for cancer treatment, the accurate discrimination between healthy and cancerous tissues is critical for the postoperative care of the patient. The current study focuses on the ex vivo handling of surgically excised colorectal specimens and the acquisition of their spectral fingerprints using Raman spectroscopy. Acquired data were analyzed in an effort to discriminate, in microscopic scale, between healthy and malignant margins. Raman spectroscopy is a spectroscopic technique with high detection sensitivity and spatial resolution of few micrometers. The spectral fingerprint which is produced during laser-tissue interaction is unique and characterizes the biostructure and its inflammatory or cancer state. Numerous published studies have demonstrated the potential of the technique as a tool for the discrimination between healthy and malignant tissues/cells either ex vivo or in vivo. However, the handling of the excised human specimens and the Raman measurement conditions remain challenging, unavoidably affecting measurement reliability and repeatability, as well as the technique’s overall accuracy and sensitivity. Therefore, tissue handling has to be optimized and standardized to ensure preservation of cell integrity and hydration level. Various strategies have been implemented in the past, including the use of balanced salt solutions, small humidifiers or pump-reservoir-pipette systems. In the current study, human colorectal specimens of 10X5 mm were collected from 5 patients up to now who underwent open surgery for colorectal cancer. A novel, non-toxic zinc-based fixative (Z7) was used for tissue preservation. Z7 demonstrates excellent protein preservation and protection against tissue autolysis. Micro-Raman spectra were recorded with a Renishaw Invia spectrometer from successive random 2 micrometers spots upon excitation at 785 nm to decrease fluorescent background and secure avoidance of tissue photodegradation. A temperature-controlled approach was adopted to stabilize the tissue at 2 °C, thus minimizing dehydration effects and consequent focus drift during measurement. A broad spectral range, 500-3200 cm-1,was covered with five consecutive full scans that lasted for 20 minutes in total. The average spectra were used for least square fitting analysis of the Raman modes.Subtle Raman differences were observed between normal and cancerous colorectal tissues mainly in the intensities of the 1556 cm-1 and 1628 cm-1 Raman modes which correspond to v(C=C) vibrations in porphyrins, as well as in the range of 2800-3000 cm-1 due to CH2 stretching of lipids and CH3 stretching of proteins. Raman spectra evaluation was supported by histological findings from twin specimens. This study demonstrates that Raman spectroscopy may constitute a promising tool for real-time verification of clear margins in colorectal cancer open surgery.

Keywords: colorectal cancer, Raman spectroscopy, malignant margins, spectral fingerprints

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Authors: Mohamed dammak

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Great attention has been paid to the design and synthesis of novel organic-inorganic compounds in recent decades because of their structural variety and the large diversity of atomic arrangements. In this work, the structure for the novel dimethyl aminopyridine tetrachlorocobaltate (C₇H₁₁N₂)₂CoCl₄ prepared by the slow evaporation method at room temperature has been successfully discussed. The X-ray diffraction results indicate that the hybrid material has a triclinic structure with a P space group and features a 0D structure containing isolated distorted [CoCl₄]2- tetrahedra interposed between [C7H11N²⁻]+ cations forming planes perpendicular to the c axis at z = 0 and z = ½. The effect of the synthesis conditions and the reactants used, the interactions between the cationic planes, and the isolated [CoCl4]2- tetrahedra are employing N-H...Cl and C-H…Cl hydrogen bonding contacts. The inspection of the Hirshfeld surface analysis helps to discuss the strength of hydrogen bonds and to quantify the inter-contacts. A phase transition was discovered by thermal analysis at 390 K, and comprehensive dielectric research was reported, showing a good agreement with thermal data. Impedance spectroscopy measurements were used to study the electrical and dielectric characteristics over a wide range of frequencies and temperatures, 40 Hz–10 MHz and 313–483 K, respectively. The Nyquist plot (Z" versus Z') from the complex impedance spectrum revealed semicircular arcs described by a Cole-Cole model. An electrical circuit consisting of a link of grain and grain boundary elements is employed. The real and imaginary parts of dielectric permittivity, as well as tg(δ) of (C₇H₁₁N₂)₂CoCl₄ at different frequencies, reveal a distribution of relaxation times. The presence of grain and grain boundaries is confirmed by the modulus investigations. Electric and dielectric analyses highlight the good protonic conduction of this material.

Keywords: organic-inorganic, phase transitions, complex impedance, protonic conduction, dielectric analysis

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Authors: Mhenga Agneta, Li Zhaomin, Zhang Chao

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When velocity is high enough, gas can entrain fluid and carry to the surface, but as time passes by, velocity drops to a critical point where fluids will start to hold up in the tubing and cause liquid loading which prevents gas production and may lead to the death of the well. Foam injection is widely used as one of the methods to unload liquid. Since wells have different characteristics, it is not guaranteed that foam can be applied in all of them and bring successful results. This research presents a technology to optimize the efficiency of foam to unload liquid by air compression. Two methods are used to explain optimization; (i) mathematical formulas are used to solve and explain the myth of how density and critical velocity could be minimized when air is compressed into foaming agents, then the relationship between flow rates and pressure increase which would boost up the bottom hole pressure and increase the velocity to lift liquid to the surface. (ii) Experiments to test foam carryover capacity and stability as a function of time and surfactant concentration whereby three surfactants anionic sodium dodecyl sulfate (SDS), nonionic Triton 100 and cationic hexadecyltrimethylammonium bromide (HDTAB) were probed. The best foaming agents were injected to lift liquid loaded in a created vertical well model of 2.5 cm diameter and 390 cm high steel tubing covered by a transparent glass casing of 5 cm diameter and 450 cm high. The results show that, after injecting foaming agents, liquid unloading was successful by 75%; however, the efficiency of foaming agents to unload liquid increased by 10% with an addition of compressed air at a ratio of 1:1. Measured values and calculated values were compared and brought about ± 3% difference which is a good number. The successful application of the technology indicates that engineers and stakeholders could bring water flooded gas wells back to production with optimized results by firstly paying attention to the type of surfactants (foaming agents) used, concentration of surfactants, flow rates of the injected surfactants then compressing air to the foaming agents at a proper ratio.

Keywords: air compression, foaming agents, gas well, liquid loading

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Authors: K. Sruthi, Sai Snehitha Yadavalli, Swathi Gosh Acharyya

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Water is the most crucial element for sustaining life on earth. Increasing water pollution directly or indirectly leads to harmful effects on human life. Most of the heavy metal ions are harmful in their cationic form. These heavy metal ions are released by various activities like disposing of batteries, industrial wastes, automobile emissions, and soil contamination. Ions like (Pb, Co, Cd) are carcinogenic and show many harmful effects when consumed more than certain limits proposed by WHO. The simultaneous detection of the heavy metal ions (Pb, Co, Cd), which are highly toxic, is reported in this study. There are many analytical methods for quantifying, but electrochemical techniques are given high priority because of their sensitivity and ability to detect and recognize lower concentrations. Square wave voltammetry was preferred in electrochemical methods due to the absence of background currents which is interference. Square wave voltammetry was performed on GCE for the quantitative detection of ions. Three electrode system consisting of a glassy carbon electrode as the working electrode (3 mm diameter), Ag/Agcl electrode as the reference electrode, and a platinum wire as the counter electrode was chosen for experimentation. The mechanism of detection was done by optimizing the experimental parameters, namely pH, scan rate, and temperature. Under the optimized conditions, square wave voltammetry was performed for simultaneous detection. Scan rates were varied from 5 mV/s to 100 mV/s and found that at 25 mV/s all the three ions were detected simultaneously with proper peaks at particular stripping potential. The variation of pH from 3 to 8 was done where the optimized pH was taken as pH 5 which holds good for three ions. There was a decreasing trend at starting because of hydrogen gas evolution, and after pH 5 again there was a decreasing trend that is because of hydroxide formation on the surface of the working electrode (GCE). The temperature variation from 25˚C to 45˚C was done where the optimum temperature concerning three ions was taken as 35˚C. Deposition and stripping potentials were given as +1.5 V and -1.5 V, and the resting time of 150 seconds was given. Three ions were detected at stripping potentials of Cd²⁺ at -0.84 V, Pb²⁺ at -0.54 V, and Co²⁺ at -0.44 V. The parameters of detection were optimized on a glassy carbon electrode for simultaneous detection of the ions at lower concentrations by square wave voltammetry.

Keywords: cadmium, cobalt, lead, glassy carbon electrode, square wave anodic stripping voltammetry

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Authors: Evdokia K. Oikonomou, Nikolay Christov, Galder Cristobal, Graziana Messina, Giovani Marletta, Laurent Heux, Jean-Francois Berret

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Fabric softeners are aqueous formulations that contain ~10 wt. % double tailed cationic surfactants. Here, a formulation in which 50% surfactant was replaced with low quantities of natural guar polymers was developed. Thanks to the reduced surfactant quantity this product has less environmental impact while the guars presence was found to maintain the product’s performance. The objective of this work is to elucidate the effect of the guar polymers on the softener deposition and the adsorption mechanism on the cotton surface. The surfactants in these formulations are assembled into large distributed (0.1 – 1 µm) vesicles that are stable in the presence of guars and upon dilution. The effect of guars on the vesicles adsorption on cotton was first estimated by using cellulose nanocrystals (CNC) as a stand-in for cotton. The dispersion of CNC in water permits to follow the interaction between the vesicles, guars, and CNC in the bulk. It was found that guars enhance the deposition on CNC and that the vesicles are deposited intactly on the fibers driven by electrostatics. The mechanism of the vesicles/guars adsorption on cellulose fibers was identified by quartz crystal microbalance with dissipation monitoring. It was found that the guars increase the surfactant deposited quantity, in agreement with the results in the bulk. Also, the structure of the adsorbed surfactant on the fibers' surfaces (vesicle or bilayer) was influenced by the guars presence. Deposition studies on cotton fabrics were also conducted. Attenuated total reflection and scanning electron microscopy were used to study the effect of the polymers on this deposition. Finally, fluorescent microscopy was used to follow the adsorption of surfactant vesicles, labeled with a fluorescent dye, on cotton fabrics in water. It was found that, in the presence or not of polymers, the surfactant vesicles are adsorbed on fiber maintaining their vesicular structure in water (supported vesicular bilayer structure). The guars influence this process. However, upon drying the vesicles are transformed into bilayers and eventually wrap the fibers (supported lipid bilayer structure). This mechanism is proposed for the adsorption of vesicular conditioner on cotton fiber and can be affected by the presence of polymers.

Keywords: cellulose nanocrystals, cotton fibers, fabric softeners, guar polymers, surfactant vesicles

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Authors: Mohammad Hassan Ramezan zadeh 1 , Majid Seifi 2 , Hoda Hekmat ara 2 1Biomedical Engineering Department, Near East University, Nicosia, Cyprus 2Physics Department, Guilan University , P.O. Box 41335-1914, Rasht, Iran.

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Magnetic nano particles of ferric chloride were synthesised using a co-precipitation technique. For the optimal results, ferric chloride at room temperature was added to different surfactant with different ratio of metal ions/surfactant. The samples were characterised using transmission electron microscopy, X-ray diffraction and Fourier transform infrared spectrum to show the presence of nanoparticles, structure and morphology. Magnetic measurements were also carried out on samples using a Vibrating Sample Magnetometer. To show the effect of surfactant on size distribution and crystalline structure of produced nanoparticles, surfactants with various charge such as anionic cetyl trimethyl ammonium bromide (CTAB), cationic sodium dodecyl sulphate (SDS) and neutral TritonX-100 was employed. By changing the surfactant and ratio of metal ions/surfactant the size and crystalline structure of these nanoparticles were controlled. We also show that using anionic stabilizer leads to smallest size and narrowest size distribution and the most crystalline (polycrystalline) structure. In developing our production technique, many parameters were varied. Efforts at reproducing good yields indicated which of the experimental parameters were the most critical and how carefully they had to be controlled. The conditions reported here were the best that we encountered but the range of possible parameter choice is so large that these probably only represent a local optimum. The samples for our chemical process were prepared by adding 0.675 gr ferric chloride (FeCl3, 6H2O) to three different surfactant in water solution. The solution was sonicated for about 30 min until a transparent solution was achieved. Then 0.5 gr sodium hydroxide (NaOH) as a reduction agent was poured to the reaction drop by drop which resulted to participate reddish brown Fe2O3 nanoparticles. After washing with ethanol the obtained powder was calcinated in 600°C for 2h. Here, the sample 1 contained CTAB as a surfactant with ratio of metal ions/surfactant 1/2, sample 2 with CTAB and ratio 1/1, sample 3 with SDS and ratio 1/2, sample 4 SDS 1/1, sample 5 is triton-X-100 with 1/2 and sample 6 triton-X-100 with 1/1.

Keywords: iron oxide nanoparticles, stabilizer, co-precipitation, surfactant

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Authors: N. Azouaou, H. Mokaddem, D. Senadjki, K. Kedjit, Z. Sadaoui

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Introduction: Water contamination caused by dye industries, including food, leather, textile, plastic, cosmetics, paper-making, printing and dye synthesis, has caused more and more attention, since most dyes are harmful to human being and environments. Untreated coffee grounds were used as a high-efficiency adsorbent for the removal of a cationic dye (methylene blue, MB) from aqueous solution. Characterization of the adsorbent was performed using several techniques such as SEM, surface area (BET), FTIR and pH zero charge. The effects of contact time, adsorbent dose, initial solution pH and initial concentration were systematically investigated. Results showed the adsorption kinetics followed the pseudo-second-order kinetic model. Langmuir isotherm model is in good agreement with the experimental data as compared to Freundlich and D–R models. The maximum adsorption capacity was found equal to 52.63mg/g. In addition, the possible adsorption mechanism was also proposed based on the experimental results. Experimental: The adsorption experiments were carried out in batch at room temperature. A given mass of adsorbent was added to methylene blue (MB) solution and the entirety was agitated during a certain time. The samples were carried out at quite time intervals. The concentrations of MB left in supernatant solutions after different time intervals were determined using a UV–vis spectrophotometer. The amount of MB adsorbed per unit mass of coffee grounds (qt) and the dye removal efficiency (R %) were evaluated. Results and Discussion: Some chemical and physical characteristics of coffee grounds are presented and the morphological analysis of the adsorbent was also studied. Conclusions: The good capacity of untreated coffee grounds to remove MB from aqueous solution was demonstrated in this study, highlighting its potential for effluent treatment processes. The kinetic experiments show that the adsorption is rapid and maximum adsorption capacities qmax= 52.63mg/g achieved in 30min. The adsorption process is a function of the adsorbent concentration, pH and metal ion concentration. The optimal parameters found are adsorbent dose m=5g, pH=5 and ambient temperature. FTIR spectra showed that the principal functional sites taking part in the sorption process included carboxyl and hydroxyl groups.

Keywords: adsorption, methylene blue, coffee grounds, kinetic study

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Authors: Alexandra C. Blaga, Dan Caşcaval, Alexandra Tucaliuc, Madalina Poştaru, Anca I. Galaction

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Amino acids are valuable chemical products used in in human foods, in animal feed additives and in the pharmaceutical field. Recently, there has been a noticeable rise of amino acids utilization throughout the world to include their use as raw materials in the production of various industrial chemicals: oil gelating agents (amino acid-based surfactants) to recover effluent oil in seas and rivers and poly(amino acids), which are attracting attention for biodegradable plastics manufacture. The amino acids can be obtained by biosynthesis or from protein hydrolysis, but their separation from the obtained mixtures can be challenging. In the last decades there has been a continuous interest in developing processes that will improve the selectivity and yield of downstream processing steps. The liquid-liquid extraction of amino acids (dissociated at any pH-value of the aqueous solutions) is possible only by using the reactive extraction technique, mainly with extractants of organophosphoric acid derivatives, high molecular weight amines and crown-ethers. The purpose of this study was to analyse the separation of nine amino acids of acidic character (l-aspartic acid, l-glutamic acid), basic character (l-histidine, l-lysine, l-arginine) and neutral character (l-glycine, l-tryptophan, l-cysteine, l-alanine) by reactive extraction with di-(2-ethylhexyl)phosphoric acid (D2EHPA) dissolved in butyl acetate. The results showed that the separation yield is controlled by the pH value of the aqueous phase: the reactive extraction of amino acids with D2EHPA is possible only if the amino acids exist in aqueous solution in their cationic forms (pH of aqueous phase below the isoeletric point). The studies for individual amino acids indicated the possibility of selectively separate different groups of amino acids with similar acidic properties as a function of aqueous solution pH-value: the maximum yields are reached for a pH domain of 2–3, then strongly decreasing with the pH increase. Thus, for acidic and neutral amino acids, the extraction becomes impossible at the isolelectric point (pHi) and for basic amino acids at a pH value lower than pHi, as a result of the carboxylic group dissociation. From the results obtained for the separation from the mixture of the nine amino acids, at different pH, it can be observed that all amino acids are extracted with different yields, for a pH domain of 1.5–3. Over this interval, the extract contains only the amino acids with neutral and basic character. For pH 5–6, only the neutral amino acids are extracted and for pH > 6 the extraction becomes impossible. Using this technique, the total separation of the following amino acids groups has been performed: neutral amino acids at pH 5–5.5, basic amino acids and l-cysteine at pH 4–4.5, l-histidine at pH 3–3.5 and acidic amino acids at pH 2–2.5.

Keywords: amino acids, di-(2-ethylhexyl) phosphoric acid, reactive extraction, selective extraction

Procedia PDF Downloads 398

Authors: A. Gürses, T. B. Barın, Ç. Doğar

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Bitumen has been widely used as the binder of aggregate in road pavement due to its good viscoelastic properties, as a viscous organic mixture with various chemical compositions. Bitumen is a liquid at high temperature and it becomes brittle at low temperatures, and this temperature-sensitivity can cause the rutting and cracking of the pavement and limit its application. Therefore, the properties of existing asphalt materials need to be enhanced. The pavement with polymer modified bitumen exhibits greater resistance to rutting and thermal cracking, decreased fatigue damage, as well as stripping and temperature susceptibility; however, they are expensive and their applications have disadvantages. Bituminous mixtures are composed of very irregular aggregates bound together with hydrocarbon-based asphalt, with a low volume fraction of voids dispersed within the matrix. Montmorillonite (MMT) is a layered silicate with low cost and abundance, which consists of layers of tetrahedral silicate and octahedral hydroxide sheets. Recently, the layered silicates have been widely used for the modification of polymers, as well as in many different fields. However, there are not too much studies related with the preparation of the modified asphalt with MMT, currently. In this study, organo-clay-modified bitumen, and calcareous aggregate and organo-clay blends were prepared by hot blending method with OMMT, which has been synthesized using a cationic surfactant (Cetyltrymethylammonium bromide, CTAB) and long chain hydrocarbon, and MMT. When the exchangeable cations in the interlayer region of pristine MMT were exchanged with hydrocarbon attached surfactant ions, the MMT becomes organophilic and more compatible with bitumen. The effects of the super hydrophobic OMMT onto the micro structural and mechanic properties (Marshall Stability and volumetric parameters) of the prepared blends were investigated. Stability and volumetric parameters of the blends prepared were measured using Marshall Test. Also, in order to investigate the morphological and micro structural properties of the organo-clay-modified bitumen and calcareous aggregate and organo-clay blends, their SEM and HRTEM images were taken. It was observed that the stability and volumetric parameters of the prepared mixtures improved significantly compared to the conventional hot mixes and even the stone matrix mixture. A micro structural analysis based on SEM images indicates that the organo-clay platelets dispersed in the bitumen have a dominant role in the increase of effectiveness of bitumen - aggregate interactions.

Keywords: hot mix asphalt, stone matrix asphalt, organo clay, Marshall test, calcareous aggregate, modified bitumen

Procedia PDF Downloads 210

Authors: Ahmed S. Fayed, Umima M. Mansour

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Three polyvinyl chloride membrane sensors were developed for the electrochemical evaluation of ferrous, manganese and zinc ions. The sensors were used for assaying metal ions in cervical mucus (CM) of Egyptian river buffalo-cows (Bubalus bubalis) as their levels vary dependent on cyclical hormone variation during different phases of estrus cycle. The presented sensors are based on using ionophores, β-cyclodextrin (β-CD), hydroxypropyl β-cyclodextrin (HP-β-CD) and sulfocalix-4-arene (SCAL) for sensors 1, 2 and 3 for Fe²⁺, Mn²⁺ and Zn²⁺, respectively. Dioctyl phthalate (DOP) was used as the plasticizer in a polymeric matrix of polyvinylchloride (PVC). For increasing the selectivity and sensitivity of the sensors, each sensor was enriched with a suitable complexing agent, which enhanced the sensor’s response. For sensor 1, β-CD was mixed with bathophenanthroline; for sensor 2, porphyrin was incorporated with HP-β-CD; while for sensor 3, oxine was the used complexing agent with SCAL. Linear responses of 10^-7-10^-2 M with cationic slopes of 53.46, 45.01 and 50.96 over pH range 4-8 were obtained using coated graphite sensors for ferrous, manganese and zinc ionic solutions, respectively. The three sensors were validated, according to the IUPAC guidelines. The obtained results by the presented potentiometric procedures were statistically analyzed and compared with those obtained by atomic absorption spectrophotometric method (AAS). No significant differences for either accuracy or precision were observed between the two techniques. Successful application for the determination of the three studied cations in CM, for the purpose to determine the proper time for artificial insemination (AI) was achieved. The results were compared with those obtained upon analyzing the samples by AAS. Proper detection of estrus and correct time of AI was necessary to maximize the production of buffaloes. In this experiment, 30 multi-parous buffalo-cows were in second to third lactation and weighting 415-530 kg, and were synchronized with OVSynch protocol. Samples were taken in three times around ovulation, on day 8 of OVSynch protocol, on day 9 (20 h before AI) and on day 10 (1 h before AI). Beside analysis of trace elements (Fe²⁺, Mn²⁺ and Zn²⁺) in CM using the three sensors, the samples were analyzed for the three cations and also Cu²⁺ by AAS in the CM samples and blood samples. The results obtained were correlated with hormonal analysis of serum samples and ultrasonography for the purpose of determining of the optimum time of AI. The results showed significant differences and powerful correlation with Zn²⁺ composition of CM during heat phase and the ovulation time, indicating that the parameter could be used as a tool to decide optimal time of AI in buffalo-cows.

Keywords: PVC Sensors, buffalo-cows, cyclodextrins, atomic absorption spectrophotometry, artificial insemination, OVSynch protocol

Procedia PDF Downloads 189

Authors: Sima Shakoorjavan, Mahdieh Eskafi, Dawid Stawski, Somaye Akbari

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In this study, poly (amidoamine) dendritic material (PAMAM) and poly (acrylic acid) (PAA) as polycation and polyanion were deposited on surface charged polylactide (PLA) nonwoven to study the relationship of dye absorption capacity of layered-PLA with the number of deposited layers. To produce negatively charged-PLA, acrylic acid (AA) was grafted on the PLA surface (PLA-g-AA) through a chemical redox reaction with the strong oxidizing agent. Spectroscopy analysis, water contact measurement, and FTIR-ATR analysis confirm the successful grafting of AA on the PLA surface through the chemical redox reaction method. In detail, an increase in dye absorption percentage by 19% and immediate absorption of water droplets ensured hydrophilicity of PLA-g-AA surface; and the presence of new carbonyl bond at 1530 cm-¹ and a wide peak of hydroxyl between 3680-3130 cm-¹ confirm AA grafting. In addition, PLA as linear polyester can undergo aminolysis, which is the cleavage of ester bonds and replacement with amid bonds when exposed to an aminolysis agent. Therefore, to produce positively charged PLA, PAMAM as amine-terminated dendritic material was introduced to PLA molecular chains at different conditions; (1) at 60 C for 0.5, 1, 1.5, 2 hours of aminolysis and (2) at room temperature (RT) for 1, 2, 3, and 4 hours of aminolysis. Weight changes and spectrophotometer measurements showed a maximum in weight gain graph and K/S value curve indicating the highest PAMAM attachment at 60 C for 1 hour and RT for 2 hours which is considered as an optimum condition. Also, the emerging new peak around 1650 cm-1 corresponding to N-H bending vibration and double wide peak at around 3670-3170 cm-1 corresponding to N-H stretching vibration confirm PAMAM attachment in selected optimum condition. In the following, regarding the initial surface charge of grafted-PLA, lbl deposition was performed and started with PAA or PAMAM. FTIR-ATR results confirm chemical changes in samples due to deposition of the first layer (PAA or PAMAM). Generally, spectroscopy analysis indicated that an increase in layer number costed dye absorption capacity. It can be due to the partial deposition of a new layer on the previously deposited layer; therefore, the available PAMAM at the first layer is more than the third layer. In detail, in the case of layer-PLA starting lbl with negatively charged, having PAMAM as the first top layer (PLA-g-AA/PAMAM) showed the highest dye absorption of both cationic and anionic model dye.

Keywords: surface modification, layer-by-layer technique, dendritic materials, PAMAM, dye absorption capacity, PLA nonwoven

Procedia PDF Downloads 55

Authors: Elene Zhuravliova, Tamar Barbakadze, Irina Kalandadze, Elnari Zaalishvili, Lali Shanshiashvili, David Mikeladze

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Background: Multiple sclerosis (MS) is an inflammatory, neurodegenerative disease, which is accompanied by demyelination and autoimmune response to myelin proteins. Among post-translational modifications, which mediate the modulation of inflammatory pathways during MS, methylation is the main one. The methylation of DNA, also amino acids lysine and arginine, occurs in the cell. It was found that decreased trans-methylation is associated with neuroinflammatory diseases. Therefore, abnormal regulation of the methyl cycle could induce demyelination through the action on PAD (peptidyl-arginine-deiminase) gene promoter. PAD takes part in protein citrullination and targets myelin basic protein (MBP), which is affected during demyelination. To determine whether MBP charge isomers are changing the methyl cycle, we have estimated the concentrations of methyl cycle metabolites in MBP-activated primary astrocytes and oligodendrocytes. For this purpose, the action of the citrullinated MBP- C8 and the most cationic MBP-C1 isomers on the primary cells were investigated. Methods: Primary oligodendrocyte and astrocyte cell cultures were prepared from whole brains of 2-day-old Wistar rats. The methyl cycle metabolites, including homocysteine, S-adenosylmethionine (SAM), and S-adenosylhomocysteine (SAH), were estimated by HPLC analysis using fluorescence detection and prior derivatization. Results: We found that the action of MBP-C8 and MBP-C1 induces a decrease in the concentration of both methyl cycle metabolites, S-adenosylmethionine (SAM) and S-adenosylhomocysteine (SAH), in astrocytes compared to the control cells. As for oligodendrocytes, the concentration of SAM was increased by the addition of MBP-C1, while MBP-C8 has no significant effect. As for SAH, its concentration was increased compared to the control cells by the action of both MBP-C1 and MBP-C8. A significant increase in homocysteine concentration was observed by the action of the MBP-C8 isomer in both oligodendrocytes and astrocytes. Conclusion: These data suggest that MBP charge isomers change the concentration of methyl cycle metabolites. MBP-C8 citrullinated isomer causes elevation of homocysteine in astrocytes and oligodendrocytes, which may be the reason for decreased astrocyte proliferation and increased oligodendrocyte cell death which takes place in neurodegenerative processes. Elevated homocysteine levels and subsequent abnormal regulation of methyl cycles in oligodendrocytes possibly change the methylation of DNA that activates PAD gene promoter and induces the synthesis of PAD, which in turn provokes the process of citrullination, which is the accompanying process of demyelination. Acknowledgment: This research was supported by the SRNSF Georgia RF17_534 grant.

Keywords: myelin basic protein, astrocytes, methyl cycle metabolites, homocysteine, oligodendrocytes

Procedia PDF Downloads 119

Authors: Kanti Sapkota, Do Hyun Lee, Sung Soo Han

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Nanocomposites have been widely used in various fields such as electronics, catalysis, and in chemical, biological, biomedical and optical fields. They display broad biomedical properties like antidiabetic, anticancer, antioxidant, antimicrobial and antibacterial activities. Moreover, nanomaterials have been used for wastewater treatment. Particularly, bimetallic hybrid nanocomposites exhibit unique features as compared to their monometallic components. Hybrid nanomaterials not only afford the multifunctionality endowed by their constituents but can also show synergistic properties. In addition, these hybrid nanomaterials have noteworthy catalytic and optical properties. Notably, Au−Ag based nanoparticles can be employed in sensor and catalysis due to their characteristic composition-tunable plasmonic properties. Due to their importance and usefulness, various efforts were developed for their preparation. Generally, chemical methods have been described to synthesize such bimetallic nanocomposites. In such chemical synthesis, harmful and hazardous chemicals cause environmental contamination and increase toxicity levels. Therefore, ecologically benevolent processes for the synthesis of nanomaterials are highly desirable to diminish such environmental and safety concerns. In this regard, here we disclose a simple, cost-effective, external additive free and eco-friendly method for the synthesis of Au-Ag@AgCl nanocomposites using Nephrolepis cordifolia root extract. Au-Ag@AgCl NCs were obtained by the simultaneous reduction of cationic Ag and Au into AgCl in the presence of plant extract. The particle size of 10 to 50 nm was observed with the average diameter of 30 nm. The synthesized nanocomposite was characterized by various modern characterization techniques. For example, UV−visible spectroscopy was used to determine the optical activity of the synthesized NCs, and Fourier transform infrared (FT-IR) spectroscopy was employed to investigate the functional groups present in the biomolecules that were responsible for both reducing and capping agents during the formation of nanocomposites. Similarly, powder X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA) and energy-dispersive X-ray (EDX) spectroscopy were used to determine crystallinity, size, oxidation states, thermal stability and weight loss of the synthesized nanocomposites. As a synthetic application, the synthesized nanocomposite exhibited excellent catalytic activity for the multicomponent synthesis of biologically interesting quinoline molecules via domino annulation-aromatization reaction of aniline, arylaldehyde, and phenyl acetylene derivatives. Interestingly, the nanocatalyst was efficiently recycled for five times without substantial loss of catalytic properties.

Keywords: nanoparticles, catalysis, multicomponent, quinoline

Procedia PDF Downloads 97

Authors: Thomas S. Abia II

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Intel Chandler Site has internally developed its first-of-kind (FOK) facility-scale wastewater treatment system to achieve multi-metal ion exchange. The process was carried out using a serial process train of carbon filtration, pH / ORP adjustment, and cationic exchange purification to treat dilute metal wastewater (DMW) discharged from a substrate packaging factory. Spanning a trial period of 10 months, a total of 3,271 samples were collected and statistically analyzed (average baseline + standard deviation) to evaluate the performance of a 95-gpm, multi-reactor continuous copper ion exchange treatment system that was consequently retrofitted for manganese ion exchange to meet environmental regulations. The system is also equipped with an inline acid and hot caustic regeneration system to rejuvenate exhausted IX resins and occasionally remove surface crud. Data generated from lab-scale studies was transferred to system operating modifications following multiple trial-and-error experiments. Despite the DMW treatment system failing to meet internal performance specifications for manganese output, it was observed to remove the cation notwithstanding the prevalence of copper in the waste stream. Accordingly, the average manganese output declined from 6.5 + 5.6 mg¹L⁻¹ at pre-pilot to 1.1 + 1.2 mg¹L⁻¹ post-pilot (83% baseline reduction). This milestone was achieved regardless of the average influent manganese to DMW increasing from 1.0 + 13.7 mg¹L⁻¹ at pre-pilot to 2.1 + 0.2 mg¹L⁻¹ post-pilot (110% baseline uptick). Likewise, the pre-trial and post-trial average influent copper values to DMW were 22.4 + 10.2 mg¹L⁻¹ and 32.1 + 39.1 mg¹L⁻¹, respectively (43% baseline increase). As a result, the pre-trial and post-trial average copper output values were 0.1 + 0.5 mg¹L⁻¹ and 0.4 + 1.2 mg¹L⁻¹, respectively (300% baseline uptick). Conclusively, the operating pH range upstream of treatment (between 3.5 and 5) was shown to be the largest single point of influence for optimizing manganese uptake during multi-metal ion exchange. However, the high variability of the influent copper-to-manganese ratio was observed to adversely impact the system functionality. The journal herein intends to discuss the operating parameters such as pH and oxidation-reduction potential (ORP) that were shown to influence the functional versatility of the ion exchange system significantly. The literature also proposes to discuss limitations of the treatment system such as influent copper-to-manganese ratio variations, operational configuration, waste by-product management, and system recovery requirements to provide a balanced assessment of the multi-metal ion exchange process. The take-away from this literature is intended to analyze the overall feasibility of ion exchange for metals manufacturing facilities that lack the capability to expand hardware due to real estate restrictions, aggressive schedules, or budgetary constraints.

Keywords: copper, industrial wastewater treatment, multi-metal ion exchange, manganese

Procedia PDF Downloads 117

Authors: Nada Verdel, Tomaz Rijavec, Albin Pintar, Ales Lapanje

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Objectives: White water circuits of woodfree paper mills contain suspended, dissolved, and colloidal particles, such as cellulose, starch, paper sizings, and dyes. By closing the white water circuits, these particles start to accumulate and affect the production. Due to high amount of organic matter that scavenge radicals and adsorbs onto catalyst surfaces, treatment of white water with photocatalysis is inappropriate. The most suitable approach should be bioaugmentation-assisted bioremediation. Accordingly, objectives were: - to isolate bacteria capable of degrading organic compounds used for the papermaking process - to select the most active bacteria for bioaugmentation. Status: The state-of-the-art of bioaugmentation of pulp and paper mill effluents is mostly based on biodegradation of lignin. Whereas in white water circuits of woodfree paper mills only papermaking compounds are present. As far as one can tell from the literature, the study on degradation activities of bacteria for all possible compounds of the papermaking process is a novelty. Methodology: The main parameters of the selected white water were systematically analyzed during a period of two months. Bacteria were isolated on selective media with particular carbon source. Organic substances used as carbon source either enter white water circuits as base paper or as recycled broke. The screening of bacterial activities for starch, cellulose, latex, polyvinyl alcohol, alkyl ketene dimers, and resin acids was followed by addition of lugol. Degraders of polycyclic aromatic dyes were selected by cometabolism tests; cometabolism is simultaneous biodegradation of two compounds, in which the degradation of the second compound depends on the presence of the first. The obtained strains were identified by 16S rRNA sequencing. Findings: 335 autochthonous strains were isolated on plates with selected carbon source. The isolated strains were selected according to degradation of the particular carbon source. The ultimate degraders of cationic starch, cellulose, and sizings are Pseudomonas sp. NV-CE12-CF and Aeromonas sp. NV-RES19-BTP. The most active strains capable of degrading azo dyes are Aeromonas sp. NV-RES19-BTP and Sphingomonas sp. NV-B14-CF. Klebsiella sp. NV-Y14A-BTP degrade polycyclic aromatic direct blue 15 and also yellow dye, Agromyces sp. NV-RED15A-BF and Cellulosimicrobium sp. NV-A4-BF are specialists for whitener and Aeromonas sp. NV-RES19-BTP is general degrader of all compounds. To the white water adapted bacteria were isolated and selected according to their degradation activities for particular organic substances. Mostly isolated bacteria are specialized to lower the competition in the microbial community. Degraders of readily-biodegradable compounds do not degrade recalcitrant polycyclic aromatic dyes and vice versa. General degraders are rare.

Keywords: bioaugmentation, biodegradation of azo dyes, cometabolism, smart wastewater treatment technologies

Procedia PDF Downloads 163

Authors: Jeanne Leblond, Warren Viricel, Amira Mbarek

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Although several products have reached the market, gene therapeutics are still in their first stages and require optimization. It is possible to improve their lacking efficiency by the use of carefully engineered vectors, able to carry the genetic material through each of the biological barriers they need to cross. In particular, getting inside the cell is a major challenge, because these hydrophilic nucleic acids have to cross the lipid-rich plasmatic and/or endosomal membrane, before being degraded into lysosomes. It takes less than one hour for newly endocytosed liposomes to reach highly acidic lysosomes, meaning that the degradation of the carried gene occurs rapidly, thus limiting the transfection efficiency. We propose to use a new pH-sensitive lipid able to change its conformation upon protonation at endosomal pH values, leading to the disruption of the lipidic bilayer and thus to the fast release of the nucleic acids into the cytosol. It is expected that this new pH-sensitive mechanism promote endosomal escape of the gene, thereby its transfection efficiency. The main challenge of this work was to design a preparation presenting fast-responding lipidic bilayer destabilization properties at endosomal pH 5 while remaining stable at blood pH value and during storage. A series of pH-sensitive lipids able to perform a conformational switch upon acidification were designed and synthesized. Liposomes containing these switchable lipids, as well as co-lipids were prepared and characterized. The liposomes were stable at 4°C and pH 7.4 for several months. Incubation with siRNA led to the full entrapment of nucleic acids as soon as the positive/negative charge ratio was superior to 2. The best liposomal formulation demonstrated a silencing efficiency up to 10% on HeLa cells, very similar to a commercial agent, with a lowest toxicity than the commercial agent. Using flow cytometry and microscopy assays, we demonstrated that drop of pH was required for the transfection efficiency, since bafilomycin blocked the transfection efficiency. Additional evidence was brought by the synthesis of a negative control lipid, which was unable to switch its conformation, and consequently exhibited no transfection ability. Mechanistic studies revealed that the uptake was mediated through endocytosis, by clathrin and caveolae pathways, as reported for previous lipid nanoparticle systems. This potent system was used for the treatment of hypercholesterolemia. The switchable lipids were able to knockdown PCSK9 expression on human hepatocytes (Huh-7). Its efficiency is currently evaluated on in vivo mice model of PCSK9 KO mice. In summary, we designed and optimized a new cationic pH-sensitive lipid for gene delivery. Its transfection efficiency is similar to the best available commercial agent, without the usually associated toxicity. The promising results lead to its use for the treatment of hypercholesterolemia on a mice model. Anticancer applications and pulmonary chronic disease are also currently investigated.

Keywords: liposomes, siRNA, pH-sensitive, molecular switch

Procedia PDF Downloads 180

Authors: M. A. Rahman, A. T. Ohta, H. V. Trinh, J. Hyvl

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Atmospheric pressure and oxygen (O2) concentration are critical life support parameters for human-occupied aerospace vehicles and habitats. Various medical conditions may require medical O2; for example, the American Medical Association has determined that commercial air travel exposes passengers to altitude-related hypoxia and gas expansion. It may cause some passengers to experience significant symptoms and medical complications during the flight, requiring supplemental medical-grade O2 to maintain adequate tissue oxygenation and prevent hypoxemic complications. Although supplemental medical grade O2 is a successful lifesaver for respiratory and cardiac failure, O2-enriched exhaled air can contain more than 95 % O2, increasing the likelihood of a fire. In an aerospace environment, a localized high concentration O2 bubble forms around a patient being treated for hypoxia, increasing the cabin O2 beyond the safe limit. To address this problem, this work describes a medical O2 delivery system that can reduce the O2 concentration from patient-exhaled O2-rich air to safe levels while maintaining the prescribed O2 administration to the patient. The O2 delivery system is designed to be a part of the medical O2 kit. The system uses cationic multimetallic cobalt complexes to reversibly, selectively, and stoichiometrically chemisorb O2 from the exhaled air. An air-release sub-system monitors the exhaled air, and as soon the O2 percentage falls below 21%, the air is released to the room air. The O2-enriched exhaled air is channeled through a layer of porous, thin-film heaters coated with the cobalt complex. The complex absorbs O2, and when saturated, the complex is heated to 100°C using the thin-film heater. Upon heating, the complex desorbs O2 and is once again ready to absorb or remove the excess O2 from exhaled air. The O2 absorption is a sub-second process, and desorption is a multi-second process. While heating at 0.685 °C/sec, the complex desorbs ~90% O2 in 110 sec. These fast reaction times mean that a simultaneous absorb/desorb process in the O2 delivery system will create a continuous absorption of O2. Moreover, the complex can concentrate O2 by a factor of 160 times that in air and desorb over 90% of the O2 at 100°C. Over 12 cycles of thermogravimetry measurement, less than 0.1% decrease in reversibility in O2 uptake was observed. The 1 kg complex can desorb over 20L of O2, so simultaneous O2 desorption by 0.5 kg of complex and absorption by 0.5 kg of complex can potentially continuously remove 9L/min O2 (~90% desorbed at 100°C) from exhaled air. The complex is synthesized and characterized for reversible O2 absorption and efficacy. The complex changes its color from dark brown to light gray after O2 desorption. In addition to thermogravimetric analysis, the O2 absorption/desorption cycle is characterized using optical imaging, showing stable color changes over ten cycles. The complex was also tested at room temperature in a low O2 environment in its O2 desorbed state, and observed to hold the deoxygenated state under these conditions. The results show the feasibility of using the complex for reversible O2 absorption in the proposed fire safe medical O2 delivery system.

Keywords: fire risk, medical oxygen, oxygen removal, reversible absorption

Procedia PDF Downloads 71

Authors: Saheli Mitra, Ramesh Karri, Praveen K. Mylapalli, Arka. B. Dey, Gourav Bhattacharya, Gouriprasanna Roy, Syed M. Kamil, Surajit Dhara, Sunil K. Sinha, Sajal K. Ghosh

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The most well-known structures of lyotropic liquid crystalline systems are the two dimensional hexagonal phase of cylindrical micelles with a positive interfacial curvature and the lamellar phase of flat bilayers with zero interfacial curvature. In aqueous solution of surfactants, the concentration dependent phase transitions have been investigated extensively. However, instead of changing the surfactant concentrations, the local curvature of an aggregate can be altered by tuning the electrostatic interactions among the constituent molecules. Intermediate phases with non-uniform interfacial curvature are still unexplored steps to understand the route of phase transition from hexagonal to lamellar. Understanding such structural evolution in lyotropic liquid crystalline systems is important as it decides the complex rheological behavior of the system, which is one of the main interests of the soft matter industry. Sodium dodecyl sulfate (SDS) is an anionic surfactant and can be considered as a unique system to tune the electrostatics by cationic additives. In present study, imidazolium-based ionic liquids (ILs) with different number of carbon atoms in their single hydrocarbon chain were used as the additive in the aqueous solution of SDS. At a fixed concentration of total non-aqueous components (SDS and IL), the molar ratio of these components was changed, which effectively altered the electrostatic interactions between the SDS molecules. As a result, the local curvature is observed to modify, and correspondingly, the structure of the hexagonal liquid crystalline phases are transformed into other phases. Polarizing optical microscopy of SDS and imidazole-based-IL systems have exhibited different textures of the liquid crystalline phases as a function of increasing concentration of the ILs. The small angle synchrotron x-ray diffraction (SAXD) study has indicated the hexagonal phase of direct cylindrical micelles to transform to a rectangular phase at the presence of short (two hydrocarbons) chain IL. However, the hexagonal phase is transformed to a lamellar phase at the presence of long (ten hydrocarbons) chain IL. Interestingly, at the presence of a medium (four hydrocarbons) chain IL, the hexagonal phase is transformed to another hexagonal phase of direct cylindrical micelles through the lamellar phase. To the best of our knowledge, such a phase sequence has not been reported earlier. Even though the small angle x-ray diffraction study has revealed the lattice parameters of these phases to be similar to each other, their rheological behavior has been distinctly different. These rheological studies have shed lights on how these phases differ in their viscoelastic behavior. Finally, the packing parameters, calculated for these phases based on the geometry of the aggregates, have explained the formation of the self-assembled aggregates.

Keywords: lyotropic liquid crystals, polarizing optical microscopy, rheology, surfactants, small angle x-ray diffraction

Procedia PDF Downloads 112

Authors: Ghodsieh Isapour Toutizad, Aiyong Wang, Joonsoo Han, Derek Creaser, Louise Olsson, Magnus Skoglundh, Hanna HaRelind

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Nitrous oxide (N2O), which is generally formed as a byproduct of industrial chemical processes and fossil fuel combustion, has attracted considerable attention due to its destructive role in global warming and ozone layer depletion. From various developed technologies used for lean NOx reduction, the selective catalytic reduction (SCR) of NOx with ammonia is presently the most applied method. Therefore, the development of catalysts for efficient lean NOx reduction without forming N2O in the process, or only forming it to a very small extent from the exhaust gases is of crucial significance. One type of catalysts that nowadays are used for this aim are zeolite-based catalysts. It is owing to their remarkable catalytic performance under practical reaction conditions such as high thermal stability and high N2 selectivity. Among all zeolites, copper ion-exchanged zeolites, with CHA, MFI, and BEA framework structure (like SSZ-13, ZSM-5 and Beta, respectively), represent higher hydrothermal stability, high activity and N2 selectivity. This work aims at investigating the effect of the zeolite framework structure on the formation of N2O during NH3-SCR reaction conditions over three Cu-based zeolites ranging from small-pore to large-pore framework structure. In the zeolite framework, Cu exists in two cationic forms, that can catalyze the SCR reaction by activating NO to form NO+ and/or surface nitrate species. The nitrate species can thereafter react with NH3 to form another intermediate, ammonium nitrate, which seems to be one source for N2O formation at low temperatures. The results from in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) indicate that during the NO oxidation step, mainly NO+ and nitrate species are formed on the surface of the catalysts. The intensity of the absorption peak attributed to NO+ species is higher for the Cu-CHA sample compared to the other two samples, indicating a higher stability of this species in small cages. Furthermore, upon the addition of NH3, through the standard SCR reaction conditions, absorption peaks assigned to N-H stretching and bending vibrations are building up. At the same time, negative peaks are evolving in the O-H stretching region, indicating blocking/replacement of surface OH-groups by NH3 and NH4+. By removing NH3 and adding NO2 to the inlet gas composition, the peaks in the N-H stretching and bending vibration regions show a decreasing trend in intensity, with the decrease being more pronounced for increasing pore size. It can probably be owing to the higher accumulation of ammonia species in the small-pore size zeolite compared to the other two samples. Furthermore, it is worth noting that the ammonia surface species are strongly bonded to the CHA zeolite structure, which makes it more difficult to react with NO2. To conclude, the framework structure of the zeolite seems to play an important role in the formation and reactivity of surface species relevant for the SCR process. Here we intend to discuss the connection between the zeolite structure, the surface species, and the formation of N2O during ammonia-SCR.

Keywords: fast SCR, nitrous oxide, NOx, standard SCR, zeolites

Procedia PDF Downloads 202

Authors: Mohammed Sabbah, Prospero Di Pierro, Raffaele Porta

Abstract:

Protein-based edible films and coatings have attracted an increasing interest in recent years since they might be used to protect pharmaceuticals or improve the shelf life of different food products. Among them, several plant proteins represent an abundant, inexpensive and renewable raw source. These natural biopolymers are used as film forming agents, being able to form intermolecular linkages by various interactions. However, without the addition of a plasticizing agent, many biomaterials are brittle and, consequently, very difficult to be manipulated. Plasticizers are generally small and non-volatile organic additives used to increase film extensibility and reduce its crystallinity, brittleness and water vapor permeability. Plasticizers normally act by decreasing the intermolecular forces along the polymer chains, thus reducing the relative number of polymer-polymer contacts, producing a decrease in cohesion and tensile strength and thereby increasing film flexibility allowing its deformation without rupture. The most commonly studied plasticizers are polyols, like glycerol (GLY) and some mono or oligosaccharides. In particular, GLY not only increases film extensibility but also migrates inside the film network often causing the loss of desirable mechanical properties of the material. Therefore, replacing GLY with a different plasticizer might help to improve film characteristics allowing potential industrial applications. To improve film properties, it seemed of interest to test as plasticizers some cationic small molecules like polyamines (PAs). Putrescine, spermidine (SPD), and spermine are PAs widely distributed in nature and of particular interest for their biological activities that may have some beneficial health effects. Since PAs contains amino instead of hydroxyl functional groups, they are able to trigger ionic interactions with negatively charged proteins. Bitter vetch (Vicia ervilia; BV) is an ancient grain legume crop, originated in the Mediterranean region, which can be found today in many countries around the world. This annual Vicia genus shows several favorable features, being their seeds a cheap and abundant protein source. The main objectives of this study were to investigate the effect of different concentrations of SPD on the mechanical and permeability properties of films prepared with native or heat denatured BV proteins in the presence of different concentrations of SPD and/or GLY. Therefore, a BV seed protein concentrate (BVPC), containing about 77% proteins, was used to prepare film forming solutions (FFSs), whereas GLY and SPD were added as film plasticizers, either singly or in combination, at various concentrations. Since a primary plasticizer is generally defined as a molecule that when added to a material makes it softer, more flexible and easier to be processed, our findings lead to consider SPD as a possible primary plasticizer of protein-based films. In fact, the addition of millimolar concentrations of SPD to BVPC FFS allowed obtaining handleable biomaterials with improved properties. Moreover, SPD can be also considered as a secondary plasticizer, namely an 'extender', because of its ability even to enhance the plasticizing performance of GLY. In conclusion, our studies indicate that innovative edible protein-based films and coatings can be obtained by using PAs as new plasticizers.

Keywords: edible films, glycerol, plasticizers, polyamines, spermidine

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Authors: S. A. Krutovertsev, A. E. Tarasova, L. S. Krutovertseva, O. M. Ivanova

Abstract:

The aim of the work was to get stable sensitive films with good sensitivity to ethanolamine (C2H7NO) in air. Ethanolamine is used as adsorbent in different processes of gas purification and separation. Besides it has wide industrial application. Chemical sensors of sorption type are widely used for gas analysis. Their behavior is determined by sensor characteristics of sensitive sorption layer. Forming conditions and characteristics of chemical gas sensors based on nanostructured modified silica films activated by different admixtures have been studied. As additives molybdenum containing polyoxometalates of the eighteen series were incorporated in silica films. The method of hydrolythic polycondensation from tetraethyl orthosilicate solutions was used for forming such films in this work. The method’s advantage is a possibility to introduce active additives directly into an initial solution. This method enables to obtain sensitive thin films with high specific surface at room temperature. Particular properties make polyoxometalates attractive as active additives for forming of gas-sensitive films. As catalyst of different redox processes, they can either accelerate the reaction of the matrix with analyzed gas or interact with it, and it results in changes of matrix’s electrical properties Polyoxometalates based films were deposited on the test structures manufactured by microelectronic planar technology with interdigitated electrodes. Modified silica films were deposited by a casting method from solutions based on tetraethyl orthosilicate and polyoxometalates. Polyoxometalates were directly incorporated into initial solutions. Composite nanostructured films were deposited by drop casting method on test structures with a pair of interdigital metal electrodes formed at their surface. The sensor’s active area was 4.0 x 4.0 mm, and electrode gap was egual 0.08 mm. Morphology of the layers surface were studied with Solver-P47 scanning probe microscope (NT-MDT, Russia), the infrared spectra were investigated by a Bruker EQUINOX 55 (Germany). The conditions of film formation varied during the tests. Electrical parameters of the sensors were measured electronically in real-time mode. Films had highly developed surface with value of 450 m2/g and nanoscale pores. Thickness of them was 0,2-0,3 µm. The study shows that the conditions of the environment affect markedly the sensors characteristics, which can be improved by choosing of the right procedure of forming and processing. Addition of polyoxometalate into silica film resulted in stabilization of film mass and changed markedly of electrophysical characteristics. Availability of Mn3P2Mo18O62 into silica film resulted in good sensitivity and selectivity to ethanolamine. Sensitivity maximum was observed at weight content of doping additive in range of 30–50% in matrix. With ethanolamine concentration changing from 0 to 100 ppm films’ conductivity increased by 10-12 times. The increase of sensor’s sensitivity was received owing to complexing reaction of tested substance with cationic part of polyoxometalate. This fact results in intramolecular redox reaction which sharply change electrophysical properties of polyoxometalate. This process is reversible and takes place at room temperature.

Keywords: ethanolamine, gas analysis, polyoxometalate, silica film

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