Search results for: enzymatic electrode

Authors: Thomas F. Ducey, Kristin M. Trippe, James A. Ippolito, Jeffrey M. Novak, Mark G. Johnson, Gilbert C. Sigua

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The Oronogo-Duenweg mining belt –approximately 20 square miles around the Joplin, Missouri area– is a designated United States Environmental Protection Agency Superfund site due to lead-contaminated soil and groundwater by former mining and smelting operations. Over almost a century of mining (from 1848 to the late 1960’s), an estimated ten million tons of cadmium, lead, and zinc containing material have been deposited on approximately 9,000 acres. Sites that have undergone remediation, in which the O, A, and B horizons have been removed along with the lead contamination, the exposed C horizon remains incalcitrant to revegetation efforts. These sites also suffer from poor soil microbial activity, as measured by soil extracellular enzymatic assays, though 16S ribosomal ribonucleic acid (rRNA) indicates that microbial diversity is equal to sites that have avoided mine-related contamination. Soil analysis reveals low soil organic carbon, along with high levels of bio-available zinc, that reflect the poor soil fertility conditions and low microbial activity. Our study looked at the use of several materials to restore and remediate these sites, with the goal of improving soil health. The following materials, and their purposes for incorporation into the study, were as follows: manure-based biochar for the binding of zinc and other heavy metals responsible for phytotoxicity, locally sourced biosolids and compost to incorporate organic carbon into the depleted soils, effective microorganisms harvested from nearby pristine sites to provide a stable community for nutrient cycling in the newly composited 'soil material'. Our results indicate that all four materials used in conjunction result in the greatest benefit to these mine-impacted soils, based on above ground biomass, microbial biomass, and soil enzymatic activities.

Keywords: locally effective microorganisms, biochar, remediation, reclamation

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Authors: Bahiru Tsegaye, Chandrajit Balomajumder, Partha Roy

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The limited supply and related negative environmental consequence of fossil fuels are driving researcher for finding sustainable sources of energy. Lignocellulose biomass like sorghum straw is considered as among cheap, renewable and abundantly available sources of energy. However, lignocellulose biomass conversion to bioenergy like bioethanol is hindered due to the reluctant nature of lignin in the biomass. Therefore, removal of lignin is a vital step for lignocellulose conversion to renewable energy. The aim of this study is to optimize microwave pretreatment conditions using design expert software to remove lignin and to release maximum possible polysaccharides from sorghum straw for efficient hydrolysis and fermentation process. Sodium hydroxide concentration between 0.5-1.5%, v/v, pretreatment time from 5-25 minutes and pretreatment temperature from 120-2000C were considered to depolymerize sorghum straw. The effect of pretreatment was studied by analyzing the compositional changes before and after pretreatments following renewable energy laboratory procedure. Analysis of variance (ANOVA) was used to test the significance of the model used for optimization. About 32.8%-48.27% of hemicellulose solubilization, 53% -82.62% of cellulose release, and 49.25% to 78.29% lignin solubilization were observed during microwave pretreatment. Pretreatment for 10 minutes with alkali concentration of 1.5% and temperature of 1400C released maximum cellulose and lignin. At this optimal condition, maximum of 82.62% of cellulose release and 78.29% of lignin removal was achieved. Sorghum straw at optimal pretreatment condition was subjected to enzymatic hydrolysis and fermentation. The efficiency of hydrolysis was measured by analyzing reducing sugars by 3, 5 dinitrisylicylic acid method. Reducing sugars of about 619 mg/g of sorghum straw were obtained after enzymatic hydrolysis. This study showed a significant amount of lignin removal and cellulose release at optimal condition. This enhances the yield of reducing sugars as well as ethanol yield. The study demonstrates the potential of microwave pretreatments for enhancing bioethanol yield from sorghum straw.

Keywords: cellulose, hydrolysis, lignocellulose, optimization

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Authors: M. Kowalski, M. Brodowski, K. Dziabowska, E. Czaczyk, W. Bialobrzeska, N. Malinowska, S. Zoledowska, R. Bogdanowicz, D. Nidzworski

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Boron-doped-carbon nanowall (BCNW) electrodes are recently in much interest among scientists. BCNWs are good candidates for biosensor purposes as they possess interesting electrochemical characteristics like a wide potential range and the low difference between redox peaks. Moreover, from technical parameters, they are mechanically resistant and very tough. The production process of the microwave plasma-enhanced chemical vapor deposition (MPECVD) allows boron to build into the structure of the diamond being formed. The effect is the formation of flat, long structures with sharp ends. The potential of these electrodes was checked in the biosensing field. The procedure of simple carbon electrodes modification by antibodies was adopted to BCNW for specific antigen recognition. Surface protein D deriving from H. influenzae pathogenic bacteria was chosen as a target analyte. The electrode was first modified with the aminobenzoic acid diazonium salt by electrografting (electrochemical reduction), next anti-protein D antibodies were linked via 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride/N-hydroxysuccinimide (EDC/NHS) chemistry, and free sites were blocked by BSA. Cyclic voltammetry measurements confirmed the proper electrode modification. Electrochemical impedance spectroscopy records indicated protein detection. The sensor was proven to detect protein D in femtograms. This work was supported by the National Centre for Research and Development (NCBR) TECHMATSTRATEG 1/347324/12/NCBR/ 2017.

Keywords: anti-protein D antibodies, boron-doped carbon nanowall, impedance spectroscopy, Haemophilus influenzae.

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Authors: Angelo Gabriel Buenaventura, Allan Christopher Yago

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

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

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Authors: Siddhant Sethi, Yasuharu Takashima, Shigetaka Nakamura, Kenzo Fujimoto

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Site-directed mutagenesis is a renowned technique to introduce specific mutations in the genome. To achieve site-directed mutagenesis, many chemical and enzymatic approaches have been reported in the past like disulphite induced genome editing, CRISPR-Cas9, TALEN etc. The chemical methods are invasive whereas the enzymatic approaches are time-consuming and expensive. Most of these techniques are unusable in the cellular application due to their toxicity and other limitations. Photo-chemical cytosine deamination, introduced in 2010, is one of the major technique for enzyme-free single-point mutation of cytosine to uracil in DNA and RNA, wherein, 3-cyanovinylcarbazole nucleoside (CNVK) containing oligodeoxyribonucleotide (ODN) having CNVK at -1 position to that of target cytosine is reversibly crosslinked to target DNA strand using 366 nm and then incubated at 90ºC to accommodate deamination. This technique is superior to enzymatic methods of site-directed mutagenesis but has a disadvantage that it requires the use of high temperature for the deamination step which restricts its applicability in the in vivo applications. This study has been focused on improving the technique by reducing the temperature required for deamination. Firstly, the photo-cross-linker, CNVK has been modified by replacing cyano group attached to vinyl group with methyl ester (OMeVK), amide (NH2VK), and carboxylic acid (OHVK) to observe the acceleration in the deamination of target cytosine cross-linked to vinylcarbazole derivative. Among the derivatives, OHVK has shown 2 times acceleration in deamination reaction as compared to CNVK, while the other two derivatives have shown deceleration towards deamination reaction. The trend of rate of deamination reaction follows the same order as that of hydrophilicity of the vinylcarbazole derivatives. OHVK being most hydrophilic has shown highest acceleration while OMeVK is least hydrophilic has proven to be least active for deamination. Secondly, in the related study, the counter-base of the target cytosine, guanine has been replaced by inosine, 2-aminopurine, nebularine, and 5-nitroindole having distinct hydrogen bonding patterns with target cytosine. Among the ODNs with these counter bases, ODN with inosine has shown 12 fold acceleration towards deamination of cytosine cross-linked to CNVK at physiological conditions as compared to guanosine. Whereas, when 2-aminopurine, nebularine, and 5-nitroindole were used, no deamination reaction took place. It can be concluded that inosine has potential to be used as the counter base of target cytosine for the CNVK mediated photo-cross-linking induced deamination of cytosine. The increase in rate of deamination reaction has been attributed to pattern and number of hydrogen bonding between the cytosine and counter base. One of the important factor is presence of hydrogen bond between exo-cyclic amino group of cytosine and the counter base. These results will be useful for development of more efficient technique for site-directed mutagenesis for C → U transformations in the DNA/RNA which might be used in the living system for treatment of various genetic disorders and genome engineering for making designer and non-native proteins.

Keywords: C to U transformation, DNA editing, genome engineering, ultra-fast photo-cross-linking

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Authors: Madalin Enache, Simona Neagu, Roxana Cojoc, Ioana Gomoiu, Delia Ionela Dobre, Ancuta Roxana Trifoi

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Various types of halophilic and halotolerant microorganisms able to be cultivated in laboratory on culture media with a wide range of sodium chloride content are isolated from several salted environments. The extracellular enzymes of these microorganisms showed the enzymatic activity in these spectrums of salinity thus being attractive for several biotechnological processes developed at high ionic strength. In present work, a number of amylase, protease, esterase, lipase, cellulase, pectinase, xilanases and innulinase were identified for more than 50th bacterial strains isolated from water samples and sapropelic mud from four saline and hypersaline lakes located in Romanian plain. On the other hand, the cellulase and pectinase activity were also detected in some halotolerant microorganisms isolated from secondary agricultural flow of grapes processing. The preliminary data revealed that from totally tested strains seven harbor proteases activity, eight amylase activity, four for esterase and another four for lipase, three for pectinase and for one strain were identified either cellulase or pectinase activity. There were no identified enzymes able to hydrolase innulin added to culture media. Several strains isolated from sapropelic mud showed multiple extracellular enzymatic activities, namely three strains harbor three activities and another seven harbor two activities. The data revealed that amylase and protease activities were frequently detected if compare with other tested enzymes. In the case of pectinase were investigated, their ability to be used for increasing resveratrol recovery from material resulted after grapes processing. In this way, the resulted material from grapes processing was treated with microbial supernatant for several times (two, four and 24 hours) and the content of resveratrol was detected by High Performance Liquid Chromatography method (HPLC). The preliminary data revealed some positive results of this treatment.

Keywords: halophilic microorganisms, enzymes, pectinase, salinity

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Authors: D. W. Mohammed, J. Bowen, S. N. Kukureka

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Successful design and fabrication of flexible devices for electrode components requires a low sheet resistance, high optical transmittance, high mechanical reliability. Indium tin oxide (ITO) film is currently the predominant transparent conductive oxide (TCO) film in potential applications such as flexible organic light- emitting diodes, flat-panel displays, solar cells, and thin film transistors (TFTs). However ITO films are too brittle and their resistivity is rather high in some cases compared with ITO/Ag/ ITO, and they cannot completely meet flexible optoelectronic device requirements. Therefore, in this work the mechanical properties of ITO /Ag/ITO multilayer film that deposited on Polyethylene terephthalate (PET) compared with the single layered ITO sample were investigated using bending fatigue, twisting fatigue and thermal cycling experiments. The electrical resistance was monitored during the application of mechanical and thermal loads to see the pattern of relationship between the load and the electrical continuity as a consequent of failure. Scanning electron microscopy and atomic force microscopy were used to provide surface characterization of the mechanically-tested samples. The effective embedment of the Ag layer between upper and lower ITO films led to metallic conductivity and superior flexibility to the single ITO electrode, due to the high failure strain of the ductile Ag layer. These results indicate that flexible ITO/Ag/ITO multilayer electrodes are a promising candidate for use as transparent conductor in flexible displays. They provided significantly reduced sheet resistance compared to ITO, and improved bending and twisting properties both as a function of radius, angle and thermal cycling.

Keywords: ITO/Ag/ITO multilayer, failure strain, mechanical properties, PET

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Authors: Mirko Ante, Şeniz Sörgel, Andreas Bund

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Li-S- (Lithium-Sulfur-) battery systems provide very high specific gravimetric energy (2600 Wh/kg) and volumetric energy density (2800Wh/l). Hence, Li-S batteries are one of the key technologies for both the upcoming electromobility and stationary applications. Furthermore, the Li-S battery system is potentially cheap and environmentally benign. However, the technical implementation suffers from cycling stability, low charge and discharge rates and incomplete understanding of the complex polysulfide reaction mechanism. The aim of this work is to develop an effective electrocatalyst for the polysulfide reactions so that the electrode kinetics of the sulfur half-cell will be improved. Accordingly, the overvoltage will be decreased, and the efficiency of the cell will be increased. An enhanced electroactive surface additionally improves the charge and discharge rates. To reach this goal, functionalized electrocatalytic coatings are investigated to accelerate the kinetics of the polysulfide reactions. In order to determine a suitable electrocatalyst, apparent exchange current densities of a variety of materials (Ni, Co, Pt, Cr, Al, Cu, ITO, stainless steel) have been evaluated in a polysulfide containing electrolyte by potentiodynamic measurements and a Butler-Volmer fit including diffusion limitation. The samples have been examined by Scanning Electron Microscopy (SEM) after the potentiodynamic measurements. Up to now, our work shows that cobalt is a promising material with good electrocatalytic properties for the polysulfide reactions and good chemical stability in the system. Furthermore, an electrodeposition from a modified Watt’s nickel electrolyte with a sulfur source seems to provide an autocatalytic effect, but the electrocatalytic behavior decreases after several cycles of the current-potential-curve.

Keywords: electrocatalyst, energy storage, lithium sulfur battery, sulfur electrode materials

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Authors: Aqsa Kanwal, Min Zhang, Faisal Sharaf, Li Chengtao

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The globe is facing increasing challenges of plastic pollution due to single-use of plastic-based packaging material. The plastic material is continuously being dumped into the natural environment, which causes serious harm to the entire ecosystem. Polymer degradation in nature is very difficult, so the use of biodegradable polymers instead of conventional polymers can mitigate this issue. Due to the good mechanical properties and biodegradability, aliphatic-aromatic polymers are being widely commercialized. Due to the advancement in molecular biology, many studies have reported specific microbes that can effectively degrade PBAT. Aliphatic polyesters undergo hydrolytic cleavage of ester groups, so they can be easily degraded by microorganisms. In this study, we investigated the enzymatic degradation of poly (butylene adipate terephthalate) (PBAT) copolymer using lipase B from Candida Antarctica (CALB). Results of the study displayed approximately 5.16 % loss in PBAT mass after 2 days which significantly increased to approximately 15.7 % at the end of the experiment (12 days) as compared to blank. The pH of the degradation solution also displayed significant reduction and reached the minimum value of 6.85 at the end of the experiment. The structure and morphology of PBAT after degradation were characterized by FTIR, XRD, SEM, and TGA. FTIR analysis showed that after degradation many peaks become weaker and the peak at 2950 cm-1 almost disappeared after 12 days. The XRD results indicated that as the degradation time increases the intensity of diffraction peaks slightly increases as compared to the blank PBAT. TGA analysis also confirmed the successful degradation of PBAT with time. SEM micrographs further confirmed that degradation has occurred. Hence, biodegradable polymers can widely be used. The effect of PBAT biodegradation on plant growth was also studied and it was found that PBAT has no toxic effect on the growth of plants. Hence PBAT can be employed in a wide range of applications.

Keywords: aliphatic-aromatic co-polyesters, polybutylene adipate terephthalate, lipase (CALB), biodegradation, plant growth

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Authors: Sunil Kumar, Vinay Kumar, Mamta Bulla, Rita Dahiya

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Supercapacitors have emerged as a leading energy storage technology, gaining popularity in applications like digital telecommunications, memory backup, and hybrid electric vehicles. Their appeal lies in a long cycle life, high power density, and rapid recharge capabilities. These exceptional traits attract researchers aiming to develop advanced, cost-effective, and high-energy-density electrode materials for next-generation energy storage solutions. Two-dimensional (2D) nanostructures are highly attractive for fabricating nanodevices due to their high surface-to-volume ratio and good compatibility with device design. In the current study, a composite was synthesized by combining MoS2 with reduced graphene oxide (rGO) under optimal conditions and characterized using various techniques, including XRD, FTIR, SEM and XPS. The electrochemical properties of the composite material were assessed through cyclic voltammetry, galvanostatic charging-discharging and electrochemical impedance spectroscopy. The supercapacitor device demonstrated a specific capacitance of 153 F g-1 at a current density of 1 Ag-1, achieving an excellent energy density of 30.5 Wh kg-1 and a power density of 600 W kg-1. Additionally, it maintained excellent cyclic stability over 5000 cycles, establishing it as a promising candidate for efficient and durable energy storage solutions. These findings highlight the dynamic relationship between electrode materials and offer valuable insights for the development and enhancement of high-performance symmetric devices.

Keywords: 2D material, energy density, galvanostatic charge-discharge, hydrothermal reactor, specific capacitance

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Authors: Prasanna Belur, P. R. Ashwini, Sampath Charanyaa, I. Regupathi

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Indian oil sardine (Sardinella longiceps) are one of the richest and cheapest sources of n-3 polyunsaturated fatty acids (n-3 PUFA) such as Eicosapentaenoic acid (EPA) and Docosahexaenoic acid (DHA). The health benefits conferred by n-3 PUFA upon consumption, in the prevention and treatment of coronary, neuromuscular, immunological disorders and allergic conditions are well documented. Natural refined Indian Sardine oil generally contain about 25% (w/w) n-3 PUFA along with various unsaturated and saturated fatty acids in the form of mono, di, and triglycerides. Having high concentration of n-3 PUFA content in the glyceride form is most desirable for human consumption to avail maximum health benefits. Thus, enhancing the n-3 PUFA content while retaining it in the glyceride form with green technology is the need of the hour. In this study, refined Indian Sardine oil was subjected to selective hydrolysis by Candida antartica lipase to enhance n-3 PUFA content. The degree of hydrolysis and enhancement of n-3 PUFA content was estimated by determining acid value, Iodine value, EPA and DHA content (by Gas Chromatographic methods after derivitization) before and after hydrolysis. Various reaction parameters such as pH, temperature, enzyme load, lipid to aqueous phase volume ratio and incubation time were optimized by conducting trials with one parameter at a time approach. Incubating enzyme solution with refined sardine oil with a volume ratio of 1:1, at pH 7.0, for 60 minutes at 50 °C, with an enzyme load of 60 mg/ml was found to be optimum. After enzymatic treatment, the oil was subjected to refining to remove free fatty acids and moisture content using previously optimized refining technology. Enzymatic treatment at the optimal conditions resulted in 12.11 % enhancement in Degree of hydrolysis. Iodine number had increased by 9.7 % and n-3 PUFA content was enhanced by 112 % (w/w). Selective enhancement of n-3 PUFA glycerides, eliminating saturated and unsaturated fatty acids from the oil using enzyme is an interesting preposition as this technique is environment-friendly, cost effective and provide natural source of n-3 PUFA rich oil.

Keywords: Candida antartica, lipase, n-3 polyunsaturated fatty acids, sardine oil

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Authors: Amos Sunday Onikanni, Bashir Lawal, Babatunji Emmanuel Oyinloye, Gomaa Mostafa-Hedeab, Mohammed Alorabi, Simona Cavalu, Augustine O. Olusola, Chih-Hao Wang, Gaber El-Saber Batiha

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The increasing global burden of diabetes mellitus has called for the search for a therapeutic alternative that offers better activities and safety than conventional chemotherapy. Herein, we evaluated the neuroprotective and antioxidant properties of different fractions (ethyl acetate, N-butanol and residual aqueous) of Clompanus pubescens leaves in streptozotocin (STZ)-induced diabetic rats. Our results revealed a significant elevation in the levels of blood glucose, pro-inflammatory cytokines, lipid peroxidation, neuronal activities of acetylcholinesterase, butyrylcholinesterase, nitric oxide, epinephrine, norepinephrine, and Na+/K+-ATPase in diabetic non treated rats. In addition, decreased levels of enzymatic and non-enzymatic antioxidants were observed. Treatment with different fractions of C. pubescens leaves resulted in a significant reversal of the biochemical alteration and improved the neurocognitive deficit in STZ-induced diabetic rats. However, the ethyl-acetate fraction demonstrated higher activities than the other fractions and was characterized for its phytoconstituents, revealing the presence of Gallic acid (713.00 ppm), catechin (0.91 ppm), ferulic acid (0.98 ppm), rutin (59.82 ppm), quercetin (3.22 ppm) and kaempferol (4.07 ppm). Our molecular docking analysis revealed that these compounds exhibited different binding affinities and potentials for targeting BChE/AChE/ IL-1 β/Na+-K+-ATPase. However, only Kampferol and ferulic exhibited good drug-like, ADMET, and permeability properties suitable for use as a neuronal drug target agent. Hence, the ethyl-acetate fraction of C. pubescent leaves could be considered a source of promising bioactive metabolite for the treatment and management of cognitive impairments related to type II diabetes mellitus.

Keywords: diabetes mellitus, neuroprotective, antioxidant, pro-inflammatory cytokines

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Authors: Bulcha Belay Etana, Benny Malengier, Janarthanan Krishnamoorthy, Timothy Kwa, Lieva Vanlangenhove

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Electromyography measures the electrical activity of muscles using surface electrodes or needle electrodes to monitor various disease conditions. Recent developments in the signal acquisition of electromyograms using textile electrodes facilitate wearable devices, enabling patients to monitor and control their health status outside of healthcare facilities. Here, we have developed and tested wearable textile electrodes to acquire electromyography signals from patients suffering from Parkinson’s disease and incorporated a feedback-control system to relieve muscle cramping through thermal stimulus. In brief, the textile electrodes made of stainless steel was knitted into a textile fabric as a sleeve, and their electrical characteristic, such as signal-to-noise ratio, was compared with traditional electrodes. To relieve muscle cramping, a heating element made of stainless-steel conductive yarn sewn onto a cotton fabric, coupled with a vibration system, was developed. The system integrated a microcontroller and a Myoware muscle sensor to activate the heating element as well as the vibration motor when cramping occurred. At the same time, the element gets deactivated when the muscle cramping subsides. An optimum therapeutic temperature of 35.5°C is regulated and maintained continuously by a heating device. The textile electrode exhibited a signal-to-noise ratio of 6.38dB, comparable to that of the traditional electrode’s value of 7.05 dB. For a given 9 V power supply, the rise time for the developed heating element was about 6 minutes to reach an optimum temperature.

Keywords: smart textile system, wearable electronic textile, electromyography, heating textile, vibration therapy, Parkinson’s disease

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Authors: Ansah Iris Baffour, Dong-Ho Kim, Sung-Gyu Park

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The ongoing COVID-19 pandemic, caused by the SARS-CoV-2 virus and is gradually shifting to an endemic phase which implies the outbreak is far from over and will be difficult to eradicate. Global cooperation has led to unified precautions that aim to suppress epidemiological spread (e.g., through travel restrictions) and reach herd immunity (through vaccinations); however, the primary strategy to restrain the spread of the virus in mass populations relies on screening protocols that enable rapid on-site diagnosis of infections. Herein, we employed surface enhanced Raman spectroscopy (SERS) for the rapid detection of SARS-CoV-2 lysate on an Au-modified Au nanodimple(AuND)electrode. Through in situone-pot Au electrodeposition on the AuND electrode, Au-lysate nanocomposites were synthesized, generating3D internal hotspots for large SERS signal enhancements within 30 s of the deposition. The capture of lysate into newly generated plasmonic nanogaps within the nanocomposite structures enhanced metal-spike protein contact in 3D spaces and served as hotspots for sensitive detection. The limit of detection of SARS-CoV-2 lysate was 5 x 10-2 PFU/mL. Interestingly, ultrasensitive detection of the lysates of influenza A/H1N1 and respiratory syncytial virus (RSV) was possible, but the method showed ultimate selectivity for SARS-CoV-2 in lysate solution mixtures. We investigated the practical application of the approach for rapid on-site diagnosis by detecting SARS-CoV-2 lysate spiked in normal human saliva at ultralow concentrations. The results presented demonstrate the reliability and sensitivity of the assay for rapid diagnosis of COVID-19.

Keywords: label-free detection, nanocomposites, SARS-CoV-2, surface-enhanced raman spectroscopy

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Authors: A. K. M. Kafi, S. N. Nina, Mashitah M. Yusoff

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In this work, we have described a new 3-dimensional (3D) network of cross-linked Horseradish Peroxidase/Carbon Nanotube (HRP/CNT) on a thiol-modified Au surface in order to build up the effective electrical wiring of the enzyme units with the electrode. This was achieved by the electropolymerization of aniline-functionalized carbon nanotubes (CNTs) and 4-aminothiophenol -modified-HRP on a 4-aminothiophenol monolayer-modified Au electrode. The synthesized 3D HRP/CNT networks were characterized with cyclic voltammetry and amperometry, resulting the establishment direct electron transfer between the redox active unit of HRP and the Au surface. Electrochemical measurements reveal that the immobilized HRP exhibits high biological activity and stability and a quasi-reversible redox peak of the redox center of HRP was observed at about −0.355 and −0.275 V vs. Ag/AgCl. The electron transfer rate constant, KS and electron transfer co-efficient were found to be 0.57 s-1 and 0.42, respectively. Based on the electrocatalytic process by direct electrochemistry of HRP, a biosensor for detecting H2O2 was developed. The developed biosensor exhibits excellent electrocatalytic activity for the reduction of H2O2. The proposed biosensor modified with HRP/CNT 3D network displays a broader linear range and a lower detection limit for H2O2 determination. The linear range is from 1.0×10−7 to 1.2×10−4M with a detection limit of 2.2.0×10−8M at 3σ. Moreover, this biosensor exhibits very high sensitivity, good reproducibility and long-time stability. In summary, ease of fabrication, a low cost, fast response and high sensitivity are the main advantages of the new biosensor proposed in this study. These obvious advantages would really help for the real analytical applicability of the proposed biosensor.

Keywords: redox enzyme, nanomaterials, biosensors, electrical communication

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Authors: C. Yaddaden, M. Berouaken, L. Talbi, K. Ayouz, M. Ayat, A. Cheriet, F. Boudeffar, A. Manseri, N. Gabouze

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Lithium-ion batteries (LIBs) are widely used in various electronic devices due to their high energy density. However, the performance of the anode material in LIBs is crucial for enhancing the battery's overall efficiency. This research focuses on developing a new anode material by modifying silicon nanostructures, specifically porous silicon nanowires (PSiNWs) and porous silicon nanoparticles (NPSiP), with silver nanoparticles (Ag) to improve the performance of LIBs. The aim of this research is to investigate the potential application of PSiNWs/Ag and NPSiP/Ag as anodes in LIBs and evaluate their performance in terms of specific capacity and Coulombic efficiency. The research methodology involves the preparation of PSiNWs and NPSiP using metal-assisted chemical etching and electrochemical etching techniques, respectively. The Ag nanoparticles are introduced onto the nanostructures through electrodissolution of the porous film and ultrasonic treatment. Galvanostatic charge/discharge measurements are conducted between 1 and 0.01 V to evaluate the specific capacity and Coulombic efficiency of both PSiNWs/Ag and NPSiP/Ag electrodes. The specific capacity of the PSiNWs/Ag electrode is approximately 1800 mA h g-1, with a Coulombic efficiency of 98.8% at the first charge/discharge cycle. On the other hand, the NPSiP/Ag electrode exhibits a specific capacity of 2600 mAh g-1. Both electrodes show a slight increase in capacity retention after 80 cycles, attributed to the high porosity and surface area of the nanostructures and the stabilization of the solid electrolyte interphase (SEI). This research highlights the potential of using modified silicon nanostructures as anodes for LIBs, which can pave the way for the development of more efficient lithium-ion batteries.

Keywords: porous silicon nanowires, silicon nanoparticles, lithium-ion batteries, galvanostatic charge/discharge

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Authors: A. K. M. Kafi, S. N. Nina, Mashitah M. Yusoff

Abstract:

In this work, we have described a new 3-dimensional (3D) network of crosslinked Horseradish Peroxidase/Carbon Nanotube (HRP/CNT) on a thiol-modified Au surface in order to build up the effective electrical wiring of the enzyme units with the electrode. This was achieved by the electropolymerization of aniline-functionalized carbon nanotubes (CNTs) and 4-aminothiophenol -modified-HRP on a 4-aminothiophenol monolayer-modified Au electrode. The synthesized 3D HRP/CNT networks were characterized with cyclic voltammetry and amperometry, resulting the establishment direct electron transfer between the redox active unit of HRP and the Au surface. Electrochemical measurements reveal that the immobilized HRP exhibits high biological activity and stability and a quasi-reversible redox peak of the redox center of HRP was observed at about −0.355 and −0.275 V vs. Ag/AgCl. The electron transfer rate constant, KS and electron transfer co-efficient were found to be 0.57 s-1 and 0.42, respectively. Based on the electrocatalytic process by direct electrochemistry of HRP, a biosensor for detecting H2O2 was developed. The developed biosensor exhibits excellent electrocatalytic activity for the reduction of H2O2. The proposed biosensor modified with HRP/CNT 3D network displays a broader linear range and a lower detection limit for H2O2 determination. The linear range is from 1.0×10−7 to 1.2×10−4M with a detection limit of 2.2.0×10−8M at 3σ. Moreover, this biosensor exhibits very high sensitivity, good reproducibility and long-time stability. In summary, ease of fabrication, a low cost, fast response and high sensitivity are the main advantages of the new biosensor proposed in this study. These obvious advantages would really help for the real analytical applicability of the proposed biosensor.

Keywords: biosensor, nanomaterials, redox enzyme, thiol-modified Au surface

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Authors: Ruolan Zhang, Ryo Imai, Naoko Senda, Tomoyuki Sakai

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Enzymes have attracted increasing attentions in industrial manufacturing for their applicability in catalyzing complex chemical reactions under mild conditions. Directed evolution has become a powerful approach to optimize enzymes and exploit their full potentials under the circumstance of insufficient structure-function knowledge. With the incorporation of cell-free synthetic biotechnology, rapid enzyme synthesis can be realized because no cloning procedure such as transfection is needed. Its open environment also enables direct enzyme measurement. These properties of cell-free biotechnology lead to excellent throughput of enzymes generation. However, the capabilities of current screening methods have limitations. Fluorescence-based assay needs applicable fluorescent label, and the reliability of acquired enzymatic activity is influenced by fluorescent label’s binding affinity and photostability. To acquire the natural activity of an enzyme, another method is to combine pre-screening step and high-performance liquid chromatography (HPLC) measurement. But its throughput is limited by necessary time investment. Hundreds of variants are selected from libraries, and their enzymatic activities are then identified one by one by HPLC. The turn-around-time is 30 minutes for one sample by HPLC, which limits the acquirable enzyme improvement within reasonable time. To achieve the real high-throughput enzyme screening, i.e., obtain reliable enzyme improvement within reasonable time, a widely applicable high-throughput measurement of enzymatic reactions is highly demanded. Here, a high-throughput screening method using broadband coherent anti-Stokes Raman spectroscopy (CARS) was proposed. CARS is one of coherent Raman spectroscopy, which can identify label-free chemical components specifically from their inherent molecular vibration. These characteristic vibrational signals are generated from different vibrational modes of chemical bonds. With the broadband CARS, chemicals in one sample can be identified from their signals in one broadband CARS spectrum. Moreover, it can magnify the signal levels to several orders of magnitude greater than spontaneous Raman systems, and therefore has the potential to evaluate chemical's concentration rapidly. As a demonstration of screening with CARS, alcohol dehydrogenase, which converts ethanol and nicotinamide adenine dinucleotide oxidized form (NAD+) to acetaldehyde and nicotinamide adenine dinucleotide reduced form (NADH), was used. The signal of NADH at 1660 cm⁻¹, which is generated from nicotinamide in NADH, was utilized to measure the concentration of it. The evaluation time for CARS signal of NADH was determined to be as short as 0.33 seconds while having a system sensitivity of 2.5 mM. The time course of alcohol dehydrogenase reaction was successfully measured from increasing signal intensity of NADH. This measurement result of CARS was consistent with the result of a conventional method, UV-Vis. CARS is expected to have application in high-throughput enzyme screening and realize more reliable enzyme improvement within reasonable time.

Keywords: Coherent Anti-Stokes Raman Spectroscopy, CARS, directed evolution, enzyme screening, Raman spectroscopy

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Authors: Vaibhav Budhiraja, Chandra Mouli Pandey

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The ultrasonic synthesis of nanostructured conducting copolymer is an effective technique to synthesize polymer with desired chemical properties. This tailored nanostructure, shows tremendous improvement in sensitivity and stability to detect a variety of analytes. The present work reports ultrasonically synthesized nanostructured conducting poly(o-phenylenediamine)-co-poly(1-naphthylamine) (POPD-co-PNA). The synthesized material has been characterized using Fourier transform infrared spectroscopy (FTIR), ultraviolet-visible spectroscopy, transmission electron microscopy, X-ray diffraction and cyclic voltammetry. FTIR spectroscopy confirmed random copolymerization, while UV-visible studies reveal the variation in polaronic states upon copolymerization. High crystallinity was achieved via ultrasonic synthesis which was confirmed by X-ray diffraction, and the controlled morphology of the nanostructures was confirmed by transmission electron microscopy analysis. Cyclic voltammetry shows that POPD-co-PNA has rather high electrochemical activity. This behavior was explained on the basis of variable orientations adopted by the conducting polymer chains. The synthesized material was electrophoretically deposited at onto indium tin oxide coated glass substrate which is used as cathode and parallel platinum plate as the counter electrode. The fabricated bioelectrode was further used for detection of glucose by crosslinking of glucose oxidase in the PODP-co-PNA film. The bioelectrode shows a surface-controlled electrode reaction with the electron transfer coefficient (α) of 0.72, charge transfer rate constant (ks) of 21.77 s⁻¹ and diffusion coefficient 7.354 × 10⁻¹⁵ cm²s⁻¹.

Keywords: conducting, electrophoretic, glucose, poly (o-phenylenediamine), poly (1-naphthylamine), ultrasonic

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Authors: Bulcha Belay Etana, Benny Malengier, Janarthanan Krishnamoorthy, Timothy Kwa, Lieva VanLangenhove

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Electromyography measures the electrical activity of muscles using surface electrodes or needle electrodes to monitor various disease conditions. Recent developments in the signal acquisition of electromyograms using textile electrodes facilitate wearable devices, enabling patients to monitor and control their health status outside of healthcare facilities. Here, we have developed and tested wearable textile electrodes to acquire electromyography signals from patients suffering from Parkinson’s disease and incorporated a feedback-control system to relieve muscle cramping through thermal stimulus. In brief, the textile electrodes made of stainless steel was knitted into a textile fabric as a sleeve, and their electrical characteristic, such as signal-to-noise ratio, was compared with traditional electrodes. To relieve muscle cramping, a heating element made of stainless-steel conductive yarn sewn onto cotton fabric, coupled with a vibration system, was developed. The system integrated a microcontroller and a Myoware muscle sensor to activate the heating element as well as the vibration motor when cramping occurs, and at the same time, the element gets deactivated when the muscle cramping subsides. An optimum therapeutic temperature of 35.5 °C is regulated by continuous temperature monitoring to deactivate the heating system when this threshold value is reached. The textile electrode exhibited a signal-to-noise ratio of 6.38dB, comparable to that of the traditional electrode’s value of 7.05 dB. For a given 9 V power supply, the rise time was about 6 minutes for the developed heating element to reach an optimum temperature.

Keywords: smart textile system, wearable electronic textile, electromyography, heating textile, vibration therapy, Parkinson’s disease

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Authors: Sudeshna Chandra, Christian Gäbler, Christian Schliebe, Heinrich Lang

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Highly branched dendrimers provide structural homogeneity, controlled composition, comparable size to biomolecules, internal porosity and multiple functional groups for conjugating reactions. Electro-active dendrimers containing multiple redox units have generated great interest in their use as electrode modifiers for development of biosensors. The electron transfer between the redox-active dendrimers and the biomolecules play a key role in developing a biosensor. Ferrocenes have multiple and electrochemically equivalent redox units that can act as electron “pool” in a system. The ferrocenyl-terminated polyamidoamine dendrimer is capable of transferring multiple numbers of electrons under the same applied potential. Therefore, they can be used for dual purposes: one in building a film over the electrode for immunosensors and the other for immobilizing biomolecules for sensing. Electrochemical immunosensor, thus developed, exhibit fast and sensitive analysis, inexpensive and involve no prior sample pre-treatment. Electrochemical amperometric immunosensors are even more promising because they can achieve a very low detection limit with high sensitivity. Detection of the cancer biomarkers at an early stage can provide crucial information for foundational research of life science, clinical diagnosis and prevention of disease. Elevated concentration of biomarkers in body fluid is an early indication of some type of cancerous disease and among all the biomarkers, IgG is the most common and extensively used clinical cancer biomarkers. We present an IgG (=immunoglobulin) electrochemical immunosensor using a newly synthesized redox-active ferrocenyl dendrimer of generation 2 (G2Fc) as glassy carbon electrode material for immobilizing the antibody. The electrochemical performance of the modified electrodes was assessed in both aqueous and non-aqueous media using varying scan rates to elucidate the reaction mechanism. The potential shift was found to be higher in an aqueous electrolyte due to presence of more H-bond which reduced the electrostatic attraction within the amido groups of the dendrimers. The cyclic voltammetric studies of the G2Fc-modified GCE in 0.1 M PBS solution of pH 7.2 showed a pair of well-defined redox peaks. The peak current decreased significantly with the immobilization of the anti-goat IgG. After the immunosensor is blocked with BSA, a further decrease in the peak current was observed due to the attachment of the protein BSA to the immunosensor. A significant decrease in the current signal of the BSA/anti-IgG/G2Fc/GCE was observed upon immobilizing IgG which may be due to the formation of immune-conjugates that blocks the tunneling of mass and electron transfer. The current signal was found to be directly related to the amount of IgG captured on the electrode surface. With increase in the concentration of IgG, there is a formation of an increasing amount of immune-conjugates that decreased the peak current. The incubation time and concentration of the antibody was optimized for better analytical performance of the immunosensor. The developed amperometric immunosensor is sensitive to IgG concentration as low as 2 ng/mL. Tailoring of redox-active dendrimers provides enhanced electroactivity to the system and enlarges the sensor surface for binding the antibodies. It may be assumed that both electron transfer and diffusion contribute to the signal transformation between the dendrimers and the antibody.

Keywords: ferrocenyl dendrimers, electrochemical immunosensors, immunoglobulin, amperometry

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Authors: Faris Tarlochan, Siva Mahesh Tangutooru

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Lateral Geniculate Nucleus (LGN) is the relay center in the visual pathway as it receives most of the input information from retinal ganglion cells (RGC) and sends to visual cortex. Low threshold calcium currents (IT) at the membrane are the unique indicator to characterize this firing functionality of the LGN neurons gained by the RGC input. According to the LGN functional requirements such as functional mapping of RGC to LGN, the morphologies of the LGN neurons were developed. During the neurological disorders like glaucoma, the mapping between RGC and LGN is disconnected and hence stimulating LGN electrically using deep brain electrodes can restore the functionalities of LGN. A computational model was developed for simulating the LGN neurons with three predominant morphologies, each representing different functional mapping of RGC to LGN. The firings of action potentials at LGN neuron due to IT were characterized by varying the stimulation parameters, morphological parameters and orientation. A wide range of stimulation parameters (stimulus amplitude, duration and frequency) represents the various strengths of the electrical stimulation with different morphological parameters (soma size, dendrites size and structure). The orientation (0-1800) of LGN neuron with respect to the stimulating electrode represents the angle at which the extracellular deep brain stimulation towards LGN neuron is performed. A reduced dendrite structure was used in the model using Bush–Sejnowski algorithm to decrease the computational time while conserving its input resistance and total surface area. The major finding is that an input potential of 0.4 V is required to produce the action potential in the LGN neuron which is placed at 100 µm distance from the electrode. From this study, it can be concluded that the neuroprostheses under design would need to consider the capability of inducing at least 0.4V to produce action potentials in LGN.

Keywords: Lateral Geniculate Nucleus, visual cortex, finite element, glaucoma, neuroprostheses

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Authors: Atef Y. Shenouda, Anton A. Momchilov

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Graphene and CdO with different stoichiometric ratios of Cd(CH₃COO)₂ and graphene samples were prepared by hydrothermal reaction. The crystalline phases of pure CdO and 3CdO:1graphene were identified by X-ray diffraction (XRD). The particle morphology was studied with SEM. Furthermore, impedance measurements were applied. Galvanostatic measurements for the cells were carried out using potential limits between 0.01 and 3 V vs. Li/Li⁺. The current cycling intensity was 10⁻⁴ A. The specific discharge capacity of 3CdO-1G cell was about 450 Ah.Kg⁻¹ up to more than 100 cycles.

Keywords: CdO, graphene, negative electrode, lithium battery

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Authors: Sofia G. Meirinho, Luis G. Dias, António M. Peres, Lígia R. Rodrigues

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The emerging development of electrochemical aptasen sors has enabled the easy and fast detection of protein biomarkers in standard and real samples. Biomarkers are produced by body organs or tumours and provide a measure of antigens on cell surfaces. When detected in high amounts in blood, they can be suggestive of tumour activity. These biomarkers are more often used to evaluate treatment effects or to assess the potential for metastatic disease in patients with established disease. Osteopontin (OPN) is a protein found in all body fluids and constitutes a possible biomarker because its overexpression has been related with breast cancer evolution and metastasis. Currently, biomarkers are commonly used for the development of diagnostic methods, allowing the detection of the disease in its initial stages. A previously described RNA aptamer was used in the current work to develop a simple and sensitive electrochemical aptasensor with high affinity for human OPN. The RNA aptamer was biotinylated and immobilized on a gold electrode by avidin-biotin interaction. The electrochemical signal generated from the aptamer–target molecule interaction was monitored electrochemically using cyclic voltammetry in the presence of [Fe (CN) 6]−3/− as a redox probe. The signal observed showed a current decrease due to the binding of OPN. The preliminary results showed that this aptasensor enables the detection of OPN in standard solutions, showing good selectivity towards the target in the presence of others interfering proteins such as bovine OPN and bovine serum albumin. The results gathered in the current work suggest that the proposed electrochemical aptasensor is a simple and sensitive detection tool for human OPN and so, may have future applications in cancer disease monitoring.

Keywords: osteopontin, aptamer, aptasensor, screen-printed electrode, cyclic voltammetry

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Authors: Hosam Abdelhady

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Filming the behaviors of individual DNA molecules in their environment when they interact with individual medicinal nano-polymers in a molecular scale has opened the door to understand the effect of the molecular shape, size, and incubation time with nanocarriers on optimizing the design of robust genetic Nano molecules able to resist the enzymatic degradation, enter the cell, reach to the nucleus and kill individual cancer cells in their environment. To this end, we will show how we applied the 4D AFM as a guide to finetune the design of genetic nanoparticles and to film the effects of these nanoparticles on the nanomechanical and morphological profiles of individual cancer cells.

Keywords: AFM, dendrimers, nanoparticles, DNA, gene therapy, imaging

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Authors: Ludmila A. Gavriliuc, Jerry McLarty, Heather E. Kleiner, J. Michael Mathis

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Abstract -- Background: The citrus coumarine Auraptene (Aur) is an effective chemopreventive agent, as manifested in many models of diseases and cancer. Nuclear factor erythroid 2-related factor (Nrf2) is an important regulator of genes induced by oxidative stress, such as glutathione S-transferases, heme oxygenase-1, and peroxiredoxin 1, by activating the antioxidant response element (ARE). Genetic and biochemical evidence has demonstrated that glutathione (GSH) and glutathione-dependent enzymes, glutathione reductase (GR), glutathione peroxidases (GPs), glutathione S-transferases (GSTs) are responsible for the control of intracellular reduction-oxidation status and participate in cellular adaptation to oxidative stress. The effect of Aur on the activity of GR, GPs (Se-GP and Se-iGP), and content of GSH in the liver, kidney, and spleen is insufficiently explored. Aim: Our goal was the examination of the Aur influence on the redox-system of GSH in Nrf2 wild type and Nrf2 knockout mice via activation of Nrf2 and ARE. Methods: Twenty female mice, 10 Nrf2 wild-type (WT) and 10 Nrf2 (-/-) knockout (KO), were bred and genotyped for our study. The activity of GR, Se-GP, Se-iGP, GST, G6PD, CytP450 reductase, catalase (Cat), and content of GSH were analyzed in the liver, kidney, and spleen using Spectrophotometry methods. The results of the specific activity of enzymes and the amount of GSH were analyzed with ANOVA and Spearman statistical methods. Results: Aur (200 mg/kg) treatment induced hepatic GST, GR, Se-GP activity and inhibited their activity in the spleen of mice, most likely via activation of the ARE through Nrf2. Activation in kidney Se-GP and G6PD by Aur is also controlled, apparently through Nrf2. Results of the non-parametric Spearman correlation analysis indicated the strong positive correlation between GR and G6PD only in the liver in WT control mice (r=+0.972; p < 0.005) and in the kidney KO control mice (r=+0.958; p < 0.005). The observed low content of GSH in the liver of KO mice indicated an increase in its participation in the neutralization of toxic substances with the absence of induction of GSH-dependent enzymes, such as GST, GR, Se-GP, and Se-iGP. Activation of CytP450 in kidney and spleen and Cat in the liver in KO mice probably revealed another regulatory mechanism for these enzymes. Conclusion: Thereby, obtained results testify that Aur can modulate the activity of genes and antioxidant enzymatic redox-system of GSH, responsible for the control of intracellular reduction-oxidation status.

Keywords: auraptene, glutathione, GST, Nrf2

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Authors: Wayde Veldman, Ozlem T. Bishop, Igor Polikarpov

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In bacteria, mono and disaccharides are phosphorylated during uptake into the cell via the widely used phosphoenolpyruvate (PEP)-dependent phosphotransferase transport system. As an initial step in the phosphorylated disaccharide metabolism pathway, certain glycoside hydrolase family 1 (GH1) enzymes play a crucial role in releasing phosphorylated and non-phosphorylated monosaccharides. However, structural determinants for the specificity of these enzymes still need to be clarified. GH1 enzymes are known to have a wide array of functions. According to the CAZy database, there are twenty-one different enzymatic activities in the GH1 family. Here, the structure and substrate specificity of a GH1 enzyme from Bacillus licheniformis, hereafter known as BlBglH, was investigated. The sequence of the enzyme BlBglH was compared to the sequences of other characterized GH1 enzymes using sequence alignment, sequence identity calculations, phylogenetic analysis, and motif discovery. Through these various analyses, BlBglH was found to have sequence features characteristic of the 6-phospho-β-glucosidase activity enzymes. Additionally, motif and structure comparisons of the three most commonly studied GH1 enzyme-activities revealed a shared loop amongst the different structures that consist of different sequence motifs – this loop is thought to guide specific substrates (depending on activity) towards the active-site. To further affirm BlBglH enzyme activity, molecular docking and molecular dynamics simulations were performed. Docking was carried out using 6-phospho-β-glucosidase enzyme-activity positive (p-Nitrophenyl-beta-D-glucoside-6-phosphate) and negative (p-Nitrophenyl-beta-D-galactoside-6-phosphate) control ligands, followed by 400 ns molecular dynamics simulations. The positive-control ligand maintained favourable interactions within the active site until the end of the simulation. The negative-control ligand was observed exiting the enzyme at 287 ns. Binding free energy calculations showed that the positive-control complex had a substantially more favourable binding energy compared to the negative-control complex. Jointly, the findings of this study suggest that the BlBglH enzyme possesses 6-phospho-β-glucosidase enzymatic activity.

Keywords: 6-P-β-glucosidase, glycoside hydrolase 1, molecular dynamics, sequence analysis, substrate specificity

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Authors: Wael Ali Mohammed Hadi

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Pseudomonas fluorescens B29B, which has asparaginase enzymatic activity, was isolated from the surface coastal seawater of Trivandrum, India. We report the complete Pseudomonas fluorescens B29B genome sequenced, identified, and annotated from a marine source. We find the genome at most minuscule a 7,331,508 bp single circular chromosome with a GC content of 62.19% and 6883 protein-coding genes. Three hundred forty subsystems were identified, including two predicted asparaginases from the genome analysis of P. fluorescens B29B for further investigation. This genome data will help further industrial biotechnology applications of proteins in general and asparaginase as a target.

Keywords: pseudomonas, marine, asparaginases, Kerala, whole-genome

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Authors: Celine Bonnaud, Isabelle Billard, Nicolas Papaiconomou, Eric Chainet

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Thanks to their high magnetization and low mass, permanent magnets (NdFeB and SmCo) have quickly became essential for new energies (wind turbines, electrical vehicles…). They contain large quantities of neodymium, samarium and dysprosium, that have been recently classified as critical elements and that therefore need to be recycled. Electrochemical processes including electrodissolution followed by electrodeposition are an elegant and environmentally friendly solution for the recycling of such lanthanides contained in permanent magnets. However, electrochemistry of the lanthanides is a real challenge as their standard potentials are highly negative (around -2.5V vs ENH). Consequently, non-aqueous solvents are required. Ionic liquids (IL) are novel electrolytes exhibiting physico-chemical properties that fulfill many requirements of the sustainable chemistry principles, such as extremely low volatility and non-flammability. Furthermore, their chemical and electrochemical properties (solvation of metallic ions, large electrochemical windows, etc.) render them very attractive media to implement alternative and sustainable processes in view of integrated processes. All experiments that will be presented were carried out using butyl-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide. Linear sweep, cyclic voltammetry and potentiostatic electrochemical techniques were used. The reliability of electrochemical experiments, performed without glove box, for the classic three electrodes cell used in this study has been assessed. Deposits were obtained by chronoamperometry and were characterized by scanning electron microscopy and energy-dispersive X-ray spectroscopy. The IL cathodic behavior under different constraints (argon, nitrogen, oxygen atmosphere or water content) and using several electrode materials (Pt, Au, GC) shows that with argon gas flow and gold as a working electrode, the cathodic potential can reach the maximum value of -3V vs Fc+/Fc; thus allowing a possible reduction of lanthanides. On a gold working electrode, the reduction potential of samarium and neodymium was found to be -1.8V vs Fc+/Fc while that of dysprosium was -2.1V vs Fc+/Fc. The individual deposits obtained were found to be porous and presented some significant amounts of C, N, F, S and O atoms. Selective deposition of neodymium in presence of dysprosium was also studied and will be discussed. Next, metallic Sm, Nd and Dy electrodes were used in replacement of Au, which induced changes in the reduction potential values and the deposit structures of lanthanides. The individual corrosion potentials were also measured in order to determine the parameters influencing the electrodissolution of these metals. Finally, a full recycling process was investigated. Electrodissolution of a real permanent magnet sample was monitored kinetically. Then, the sequential electrodeposition of all lanthanides contained in the IL was investigated. Yields, quality of the deposits and consumption of chemicals will be discussed in depth, in view of the industrial feasibility of this process for real permanent magnets recycling.

Keywords: electrodeposition, electrodissolution, ionic liquids, lanthanides, rcycling

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Authors: Mariana-Dana Damaceanu

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Electrochemical oxidation is one of the most convenient ways to obtain conjugated polymer films as polypyrrole, polyaniline, polythiophene or polycarbazole. The research in the field has been mainly directed to the study of electrical conduction properties of the materials obtained by electropolymerization, often the main reason being their use as electroconducting electrodes, and very little attention has been paid to the morphological and optical quality of the films electrodeposited on flat surfaces. Electropolymerization of the monomer solution was scarcely used in the past to manufacture polymer-based light-emitting diodes (PLED), most probably due to the difficulty of obtaining defectless polymer films with good mechanical and optical properties, or conductive polymers with well controlled molecular weights. Here we report our attempts in using electrochemical deposition as appropriate method for preparing ultrathin films of fluorene-based polymers for PLED applications. The properties of these films were evaluated in terms of structural morphology, optical properties, and electrochemical conduction. Thus, electropolymerization of 4,4'-(9-fluorenylidene)-dianiline was performed in dichloromethane solution, at a concentration of 10-2 M, using 0.1 M tetrabutylammonium tetrafluoroborate as electrolyte salt. The potential was scanned between 0 and 1.3 V on the one hand, and 0 - 2 V on the other hand, when polymer films with different structures and properties were obtained. Indium tin oxide-coated glass substrate of different size was used as working electrode, platinum wire as counter electrode and calomel electrode as reference. For each potential range 100 cycles were recorded at a scan rate of 100 mV/s. The film obtained in the potential range from 0 to 1.3 V, namely poly(FDA-NH), is visible to the naked eye, being light brown, transparent and fluorescent, and displays an amorphous morphology. Instead, the electrogrowth poly(FDA) film in the potential range of 0 - 2 V is yellowish-brown and opaque, presenting a self-assembled structure in aggregates of irregular shape and size. The polymers structure was identified by FTIR spectroscopy, which shows the presence of broad bands specific to a polymer, the band centered at approx. 3443 cm-1 being ascribed to the secondary amine. The two polymer films display two absorption maxima, at 434-436 nm assigned to π-π* transitions of polymers, and another at 832 and 880 nm assigned to polaron transitions. The fluorescence spectra indicated the presence of emission bands in the blue domain, with two peaks at 422 and 488 nm for poly (FDA-NH), and four narrow peaks at 422, 447, 460 and 484 nm for poly(FDA), peaks originating from fluorene-containing segments of varying degrees of conjugation. Poly(FDA-NH) exhibited two oxidation peaks in the anodic region and the HOMO energy value of 5.41 eV, whereas poly(FDA) showed only one oxidation peak and the HOMO level localized at 5.29 eV. The electrochemical data are discussed in close correlation with the proposed chemical structure of the electrogrowth films. Further research will be carried out to study their use and performance in light-emitting devices.

Keywords: electrogrowth polymer films, fluorene, morphology, optical properties

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