Search results for: thermally activated delayed fluorescence

Authors: Jianuo Sun, Jinghan Wang, Sirui Zhang, Chenhan Xu, Hongxia Hao, Hong Zhou

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In recent years, the diversification and industrialization of drug-related crimes have posed significant threats to public health and safety globally. The widespread and increasingly younger demographics of drug users and the persistence of drug-impaired driving incidents underscore the urgency of this issue. Drug detection, a specialized forensic activity, is pivotal in identifying and analyzing substances involved in drug crimes. It relies on pharmacological and chemical knowledge and employs analytical chemistry and modern detection techniques. However, current drug detection methods are limited by their inability to perform semi-quantitative, real-time field analyses. They require extensive, complex laboratory-based preprocessing, expensive equipment, and specialized personnel and are hindered by long processing times. This study introduces an alternative approach using nucleic acid aptamers and Aggregation-Induced Emission (AIE) technology. Nucleic acid aptamers, selected artificially for their specific binding to target molecules and stable spatial structures, represent a new generation of biosensors following antibodies. Rapid advancements in AIE technology, particularly in tetraphenyl ethene-based luminous, offer simplicity in synthesis and versatility in modifications, making them ideal for fluorescence analysis. This work successfully synthesized, isolated, and purified an AIE molecule and constructed a probe comprising the AIE molecule, nucleic acid aptamers, and exonuclease for cocaine detection. The probe demonstrated significant relative fluorescence intensity changes and selectivity towards cocaine over other drugs. Using 4-Butoxytriethylammonium Bromide Tetraphenylethene (TPE-TTA) as the fluorescent probe, the aptamer as the recognition unit, and Exo I as an auxiliary, the system achieved rapid detection of cocaine within 5 mins in aqueous and urine, with detection limits of 1.0 and 5.0 µmol/L respectively. The probe-maintained stability and interference resistance in urine, enabling quantitative cocaine detection within a certain concentration range. This fluorescent sensor significantly reduces sample preprocessing time, offers a basis for rapid onsite cocaine detection, and promises potential for miniaturized testing setups.

Keywords: drug detection, aggregation-induced emission (AIE), nucleic acid aptamer, exonuclease, cocaine

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Authors: T. Ul Rehman, S. Agnello, F. M. Gelardi, M. M. Calvino, G. Lazzara, G. Buscarino, M. Cannas

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Metal-Organic Frameworks (MOFs) have emerged as promising candidates for detecting metal ions owing to their large surface area, customizable porosity, and diverse functionalities. In recent years, there has been a surge in research focused on MOFs with luminescent properties. These frameworks are constructed through coordinated bonding between metal ions and multi-dentate ligands, resulting in inherent fluorescent structures. Their luminescent behavior is influenced by factors like structural composition, surface morphology, pore volume, and interactions with target analytes, particularly metal ions. MOFs exhibit various sensing mechanisms, including photo-induced electron transfer (PET) and charge transfer processes such as ligand-to-metal (LMCT) and metal-to-ligand (MLCT) transitions. Among these, MIL-53(Al) stands out due to its flexibility, stability, and specific affinity towards certain metal ions, making it a promising platform for selective metal ion sensing. This study investigates the structural, thermal, and luminescent properties of MIL-53(Al) metal-organic framework (MOF) upon Fe3+ cation exchange. Two separate sets of samples were prepared to activate the MOF powder at different temperatures. The first set of samples, referred to as MIL-53(Al), activated (120°C), was prepared by activating the raw powder in a glass tube at 120°C for 12 hours and then sealing it. The second set of samples, referred to as MIL-53(Al), activated (300°C), was prepared by activating the MIL-53(Al) powder in a glass tube at 300°C for 70 hours. Additionally, 25 mg of MIL-53(Al) powder was dispersed in 5 mL of Fe3+ solution at various concentrations (0.1-100 mM) for the cation exchange experiment. The suspension was centrifuged for five minutes at 10,000 rpm to extract MIL-53(Al) powder. After three rounds of washing with ultrapure water, MIL-53(Al) powder was heated at 120°C for 12 hours. For PXRD and TGA analyses, a sample of the obtained MIL-53(Al) was used. We also activated the cation-exchanged samples for time-resolved photoluminescence (TRPL) measurements at two distinct temperatures (120 and 300°C) for comparative analysis. Powder X-ray diffraction patterns reveal amorphization in samples with higher Fe3+ concentrations, attributed to alterations in coordination environments and ion exchange dynamics. Thermal decomposition analysis shows reduced weight loss in Fe3+-exchanged MOFs, indicating enhanced stability due to stronger metal-ligand bonds and altered decomposition pathways. Raman spectroscopy demonstrates intensity decrease, shape disruption, and frequency shifts, indicative of structural perturbations induced by cation exchange. Photoluminescence spectra exhibit ligand-based emission (π-π* or n-π*) and ligand-to-metal charge transfer (LMCT), influenced by activation temperature and Fe3+ incorporation. Quenching of luminescence intensity and shorter lifetimes upon Fe3+ exchange result from structural distortions and Fe3+ binding to organic linkers. In a nutshell, this research underscores the complex interplay between composition, structure, and properties in MOFs, offering insights into their potential for diverse applications in catalysis, gas storage, and luminescent devices.

Keywords: Fe³⁺ cation exchange, luminescent metal-organic frameworks (LMOFs), MIL-53(Al), solid-state analysis

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Authors: Xue Ma, Yang Fu, Dangyuan Lei

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Passive daytime radiative cooling is an emerging technology which has attracted worldwide attention in recent years due to its huge potential in cooling buildings without the use of electricity. Various coating materials with different optical properties have been developed to improve the daytime radiative cooling performance. However, commercial cooling coatings comprising functional fillers with optical bandgaps within the solar spectral range suffers from severe intrinsic absorption, limiting their cooling performance. Fortunately, it has recently been demonstrated that introducing fluorescent materials into polymeric coatings can covert the absorbed sunlight to fluorescent emissions and hence increase the effective solar reflectance and cooling performance. In this paper, we experimentally investigate the key factors for fluorescence-assisted radiative cooling with TiO2-based white coatings. The surrounding TiO2 nanoparticles, which enable spatial and temporal light confinement through multiple Mie scattering, lead to Purcell enhancement of phosphors in the coating. Photoluminescence lifetimes of two phosphors (BaMgAl10O17:Eu2+ and (Sr, Ba)SiO4:Eu2+) exhibit significant reduction of ~61% and ~23%, indicating Purcell factors of 2.6 and 1.3, respectively. Moreover, smaller Stokes shifts of the phosphors are preferred to further diminish solar absorption. Field test of fluorescent cooling coatings demonstrate an improvement of ~4% solar reflectance for the BaMgAl10O17:Eu2+-based fluorescent cooling coating. However, to maximize solar reflectance, a white appearance is introduced based on multiple Mie scattering by the broad size distribution of fillers, which is visually pressurized and aesthetically bored. Besides, most colored pigments absorb visible light significantly and convert it to non-radiative thermal energy, offsetting the cooling effect. Therefore, current colored cooling coatings are facing the compromise between color saturation and cooling effect. To solve this problem, we introduced colored fluorescent materials into white coating based on SiO2 microspheres as a top layer, covering a white cooling coating based on TiO2. Compared with the colored pigments, fluorescent materials could re-emit the absorbed light, reducing the solar absorption introduced by coloration. Our work investigated the scattering properties of SiO2 dielectric spheres with different diameters and detailly discussed their impact on the PL properties of phosphors, paving the way for colored fluorescent-assisted cooling coting to application and industrialization.

Keywords: solar reflection, infrared emissivity, mie scattering, photoluminescent emission, radiative cooling

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Authors: Christi Jackson, Chuka Onaga

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Introduction: We report a case of delayed diagnosis of extra-pulmonary INH-mono-resistant Tuberculosis (TB) in a South African patient with drug-resistant HIV. Case Presentation: A 36-year old male was initiated on 1st line (NNRTI-based) anti-retroviral therapy (ART) in September 2009 and switched to 2nd line (PI-based) ART in 2011, according to local guidelines. He was following up at the outpatient wellness unit of a public hospital, where he was diagnosed with Protease Inhibitor resistant HIV in March 2016. He had an HIV viral load (HIVVL) of 737000 copies/mL, CD4-count of 10 cells/µL and presented with complaints of productive cough, weight loss, chronic diarrhoea and a septic buttock wound. Several investigations were done on sputum, stool and pus samples but all were negative for TB. The patient was treated with antibiotics and the cough and the buttock wound improved. He was subsequently started on a 3rd-line ART regimen of Darunavir, Ritonavir, Etravirine, Raltegravir, Tenofovir and Emtricitabine in May 2016. He continued losing weight, became too weak to stand unsupported and started complaining of abdominal pain. Further investigations were done in September 2016, including a urine specimen for Line Probe Assay (LPA), which showed M. tuberculosis sensitive to Rifampicin but resistant to INH. A lymph node biopsy also showed histological confirmation of TB. Management and outcome: He was started on Rifabutin, Pyrazinamide and Ethambutol in September 2016, and Etravirine was discontinued. After 6 months on ART and 2 months on TB treatment, his HIVVL had dropped to 286 copies/mL, CD4 improved to 179 cells/µL and he showed clinical improvement. Pharmacy supply of his individualised drugs was unreliable and presented some challenges to continuity of treatment. He successfully completed his treatment in June 2017 while still maintaining virological suppression. Discussion: Several laboratory-related factors delayed the diagnosis of TB, including the unavailability of urine-lipoarabinomannan (LAM) and urine-GeneXpert (GXP) tests at this facility. Once the diagnosis was made, it presented a treatment dilemma due to the expected drug-drug interactions between his 3rd-line ART regimen and his INH-resistant TB regimen, and specialist input was required. Conclusion: TB is more difficult to diagnose in patients with severe immunosuppression, therefore additional tests like urine-LAM and urine-GXP can be helpful in expediting the diagnosis in these cases. Patients with non-standard drug regimens should always be discussed with a specialist in order to avoid potentially harmful drug-drug interactions.

Keywords: drug-resistance, HIV, line probe assay, tuberculosis

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Authors: Naomi Sakamoto, Eisuke Fukuma, Mika Nashimoto, Yoshitomo Koshida

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Background: Selective localization of the metastatic lymph node with clip and removal of clipped nodes with sentinel lymph node (SLN), known as targeted axillary dissection (TAD), reduced false-negative rates (FNR) of SLN biopsy (SLNB) after neoadjuvant chemotherapy (NAC). For the patients who achieved nodal pathologic complete response (pCR), accurate staging of axilla by TAD lead to omit axillary lymph node dissection (ALND), decreasing postoperative arm morbidity without a negative effect on overall survival. This study aimed to investigate the ultrasound (US) identification rate and success removal rate of two kinds of ultrasound-visible clips placed in metastatic lymph nodes during TAD procedure. Methods: This prospective study was conducted using patients with clinically T1-3, N1, 2, M0 breast cancer undergoing NAC followed by surgery. A US-visible clip was placed in the suspicious lymph node under US guidance before neoadjuvant chemotherapy. Before surgery, US examination was performed to evaluate the detection rate of clipped node. During the surgery, the clipped node was removed using several localization techniques, including hook-wire localization, dye-injection, or fluorescence technique, followed by a dual-technique SLNB and resection of palpable nodes if present. For the fluorescence technique, after injection of 0.1-0.2 mL of indocyanine green dye (ICG) into the clipped node, ICG fluorescent imaging was performed using the Photodynamic Eye infrared camera (Hamamatsu Photonics k. k., Shizuoka, Japan). For the dye injection method, 0.1-0.2 mL of pyoktanin blue dye was injected into the clipped node. Results: A total of 29 patients were enrolled. Hydromark™ breast biopsy site markers (Hydromark, T3 shape; Devicor Medical Japan, Tokyo, Japan) was used in 15patients, whereas a UltraCor™ Twirl™ breast marker (Twirl; C.R. Bard, Inc, NJ, USA) was placed in 14 patients. US identified the clipped node marked with the UltraCore Twirl in 100% (14/14) and with the Hydromark in 93.3% (14/15, p = ns). Success removal of clipped node marked with the UltraCore Twirl was achieved in 100% (14/14), whereas the node marked with the Hydromark was removed in 80% (12/15) (p = ns). Conclusions: The ultrasound identification rate differed between the two types of ultrasound-visible clips, which also affected the success removal rate of clipped nodes. Labelling the positive node with a US-highly-visible clip allowed successful TAD.

Keywords: breast cancer, neoadjuvant chemotherapy, targeted axillary dissection, breast tissue marker, clip

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Authors: Tânia F. C. V. Silva, Eloísa S. S. Vieira, João Pinto da Costa, Rui A. R. Boaventura, Vitor J. P. Vilar

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Sanitary landfill leachates are characterized as a complex mixture of diverse organic and inorganic contaminants, which are usually removed by combining different treatment processes. Due to its simplicity, reliability, high cost-effectiveness and high nitrogen content (mostly under the ammonium form) inherent in this type of effluent, the activated sludge biological process is almost always applied in leachate treatment plants (LTPs). The purpose of this work is to assess the effect of the main nitrification and denitrification variables on the nitrogen's biological removal, from mature leachates. The leachate samples were collected after an aerated lagoon, at a LTP nearby Porto, presenting a high amount of dissolved organic carbon (1.0-1.3 g DOC/L) and ammonium nitrogen (1.1-1.7 g NH4+-N/L). The experiments were carried out in a 1-L lab-scale batch reactor, equipped with a pH, temperature and dissolved oxygen (DO) control system, in order to determine the reaction kinetic constants at unchanging conditions. The nitrification reaction rate was evaluated while varying the (i) operating temperature (15, 20, 25 and 30ºC), (ii) DO concentration interval (0.5-1.0, 1.0-2.0 and 2.0-4.0 mg/L) and (iii) solution pH (not controlled, 7.5-8.5 and 6.5-7.5). At the beginning of most assays, it was verified that the ammonium stripping occurred simultaneously to the nitrification, reaching up to 37% removal of total dissolved nitrogen. The denitrification kinetic constants and the methanol consumptions were calculated for different values of (i) volatile suspended solids (VSS) content (25, 50 and 100 mL of centrifuged sludge in 1 L solution), (ii) pH interval (6.5-7.0, 7.5-8.0 and 8.5-9.0) and (iii) temperature (15, 20, 25 and 30ºC), using effluent previously nitrified. The maximum nitrification rate obtained was 38±2 mg NH4+-N/h/g VSS (25ºC, 0.5-1.0 mg O2/L, pH not controlled), consuming 4.4±0.3 mg CaCO3/mg NH4+-N. The highest denitrification rate achieved was 19±1 mg (NO2--N+NO3--N)/h/g VSS (30ºC, 50 mL of sludge and pH between 7.5 and 8.0), with a C/N consumption ratio of 1.1±0.1 mg CH3OH/mg (NO2--N+NO3--N) and an overall alkalinity production of 3.7±0.3 mg CaCO3/mg (NO2--N+NO3--N). The denitrification process showed to be sensitive to all studied parameters, while the nitrification reaction did not suffered significant change when DO content was changed.

Keywords: mature sanitary landfill leachate, nitrogen removal, nitrification and denitrification parameters, lab-scale activated sludge biological reactor

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Authors: Elif Gencturk, Ekin Yurdakul, Ahmet Y. Celik, Senol Mutlu, Kutlu O. Ulgen

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Yeast cells are generally used as a model system of eukaryotes due to their complex genetic structure, rapid growth ability in optimum conditions, easy replication and well-defined genetic system properties. Thus, yeast cells increased the knowledge of the principal pathways in humans. During fermentation, carbohydrates (hexoses and pentoses) degrade into some toxic by-products such as 5-hydroxymethylfurfural (5-HMF or HMF) and furfural. HMF influences the ethanol yield, and ethanol productivity; it interferes with microbial growth and is considered as a potent inhibitor of bioethanol production. In this study, yeast single cell behavior under HMF application was monitored by using a continuous flow single phase microfluidic platform. Microfluidic device in operation is fabricated by hot embossing and thermo-compression techniques from cyclo-olefin polymer (COP). COP is biocompatible, transparent and rigid material and it is suitable for observing fluorescence of cells considering its low auto-fluorescence characteristic. The response of yeast cells was recorded through Red Fluorescent Protein (RFP) tagged Nop56 gene product, which is an essential evolutionary-conserved nucleolar protein, and also a member of the box C/D snoRNP complexes. With the application of HMF, yeast cell proliferation continued but HMF slowed down the cell growth, and after HMF treatment the cell proliferation stopped. By the addition of fresh nutrient medium, the yeast cells recovered after 6 hours of HMF exposure. Thus, HMF application suppresses normal functioning of cell cycle but it does not cause cells to die. The monitoring of Nop56 expression phases of the individual cells shed light on the protein and ribosome synthesis cycles along with their link to growth. Further computational study revealed that the mechanisms underlying the inhibitory or inductive effects of HMF on growth are enriched in functional categories of protein degradation, protein processing, DNA repair and multidrug resistance. The present microfluidic device can successfully be used for studying the effects of inhibitory agents on growth by single cell tracking, thus capturing cell to cell variations. By metabolic engineering techniques, engineered strains can be developed, and the metabolic network of the microorganism can thus be manipulated such that chemical overproduction of target metabolite is achieved along with the maximum growth/biomass yield.  

Keywords: COP, HMF, ribosome biogenesis, thermoplastic microbioreactor, yeast

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Authors: Diego Luján Villarreal

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Visual prostheses are designed to repair some eyesight in patients blinded by photoreceptor diseases, such as retinitis pigmentosa (RP) and age-related macular degeneration (AMD). Electrode-to-cell proximity has drawn attention due to its implications on secure single-localized stimulation. Yet, few techniques are available for understanding the relationship between the number of cells activated and the current injection. We propose an answering technique by solving the governing equation for time-dependent electrical currents using finite element discretization to obtain the volume of stimulation.

Keywords: visual prosthetic devices, volume for stimulation, FEM discretization, 3D simulation

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Authors: Pavel Baroch, Jiri Rezek, Michal Prochazka, Tomas Kozak, Jiri Houska

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Transparent semiconducting amorphous IGZO films have attracted great attention due to their excellent electrical properties and possible utilization in thin film transistors or in photovoltaic applications as they show 20-50 times higher mobility than that of amorphous silicon. It is also known that the properties of IGZO films are highly sensitive to process parameters, especially to oxygen partial pressure. In this study we have focused on the comparison of properties of transparent semiconducting amorphous indium gallium zinc oxide (IGZO) thin films prepared by conventional sputtering methods and those prepared by high power impulse magnetron sputtering (HiPIMS) method. Furthermore we tried to optimize electrical and optical properties of the IGZO thin films and to investigate possibility to apply these coatings on thermally sensitive flexible substrates. We employed dc, pulsed dc, mid frequency sine wave and HiPIMS power supplies for magnetron deposition. Magnetrons were equipped with sintered ceramic InGaZnO targets. As oxygen vacancies are considered to be the main source of the carriers in IGZO films, it is expected that with the increase of oxygen partial pressure number of oxygen vacancies decreases which results in the increase of film resistivity. Therefore in all experiments we focused on the effect of oxygen partial pressure, discharge power and pulsed power mode on the electrical, optical and mechanical properties of IGZO thin films and also on the thermal load deposited to the substrate. As expected, we have observed a very fast transition between low- and high-resistivity films depending on oxygen partial pressure when deposition using conventional sputtering methods/power supplies have been utilized. Therefore we established and utilized HiPIMS sputtering system for enlargement of operation window for better control of IGZO thin film properties. It is shown that with this system we are able to effectively eliminate steep transition between low and high resistivity films exhibited by DC mode of sputtering and the electrical resistivity can be effectively controlled in the wide resistivity range of 10-² to 10⁵ Ω.cm. The highest mobility of charge carriers (up to 50 cm2/V.s) was obtained at very low oxygen partial pressures. Utilization of HiPIMS also led to significant decrease in thermal load deposited to the substrate which is beneficial for deposition on the thermally sensitive and flexible polymer substrates. Deposition rate as a function of discharge power and oxygen partial pressure was also systematically investigated and the results from optical, electrical and structure analysis will be discussed in detail. Most important result which we have obtained demonstrates almost linear control of IGZO thin films resistivity with increasing of oxygen partial pressure utilizing HiPIMS mode of sputtering and highly transparent films with low resistivity were prepared already at low pO2. It was also found that utilization of HiPIMS technique resulted in significant improvement of surface smoothness in reactive mode of sputtering (with increasing of oxygen partial pressure).

Keywords: charge carrier mobility, HiPIMS, IGZO, resistivity

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Authors: Hong Dinh Duong, Jong Il Rhee

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In this study, a ratiometric inorganic phosphate sensor was fabricated by a double layer of the rhodamine 6G-doped nanofibers and the CdSe/ZnS QDs-captured polymer. In which, CdSe/ZnS QDs with emission wavelengths of 595nm were synthesized and ligands on their surface were exchanged with mercaptopropionic acid (MPA). The synthesized MPA-QDs were combined with the mixture of sol-gel of 3-glycidoxypropyl trimethoxysilane (GPTMS), 3-aminopropyltrimethoxysilane (APTMS) and polyurethane (PU) to build a layer for sensing inorganic phosphate. Another sensing layer was of nanofibers doped R6G which were produced from poly(styrene-co-acrylonitrile) by electrospining. The ratio of fluorescence intensities between rhodamin 6G (R6G) and CdSe/ZnS QDs exposed at different phosphate concentrations was used for calculating a linear phosphate concentration range of 0-10mM.

Keywords: nanofiber, QDs, ratiometric phosphate sensor, rhodamine 6G, sol-gel

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Authors: Elena S. Belousova, Olga V. Boiprav

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A technique for incorporating particles of allotropic forms of carbon into a fibrous material has been developed. It can be used for the manufacture of composite electromagnetic radiation absorbers. The frequency characteristics of electromagnetic radiation reflection and transmission coefficients in the microwave range of absorbers on the basis of powdered carbon black, activated carbon, shungite, graphite, manufactured in accordance with the developed technique, have been studied.

Keywords: carbon, graphite, electromagnetic radiation absorber, shungite

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Authors: R. Ravisankar, Tholkappian A. Chandrasekaran, Y. Raghu, K. K. Satapathy, M. V. R. Prasad, K. V. Kanagasabapathy

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The coastal areas of Tamilnadu are assuming greater importance owing to increasing human population, urbanization and accelerated industrial activities. sIn the present study, sediment samples are collected along the east coast of Tamilnadu for assessment of heavy metal pollution. The concentration of 13 selected heavy metals such as Mg, Al, Si, K, Ca, Ti, Fe, V, Cr, Mn, Co, Ni and Zn determined by Energy dispersive X-ray fluorescence (EDXRF) technique. In order to describe the pollution status, Contamination factor and pollution load index are calculated and reported. This result suggests that sources of metal contamination were mainly attributed to natural inputs from surrounding environments.

Keywords: sediments, heavy metals, EDXRF, pollution contamination factors

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Authors: D Bhargavi, J. Sharath Kumar Reddy

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The present investigation has been undertaken to assess the effect of viscous dissipation and axial conduction on forced convection heat transfer in the entrance region of a parallel plate channel with the porous insert attached to both walls of the channel. The flow field is unidirectional. Flow in the porous region corresponds to Darcy-Brinkman model and the clear fluid region to that of plane Poiseuille flow. The effects of the parameters Darcy number, Da, Peclet number, Pe, Brinkman number, Br and a porous fraction γ_p on the local heat transfer coefficient are analyzed graphically. Effects of viscous dissipation employing the Darcy model and the clear fluid compatible model have been studied.

Keywords: porous material, channel partially filled with a porous material, axial conduction, viscous dissipation

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Authors: Salem El-Tohami Ashoor

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Here we show that the reduction of [Cr(ArN(CH2)3NAr)2Cl2] (1) where (Ar = 2,6-Pri2C6H3) and in presence of NaCp (2) (Cp= C5H5 = cyclopentadien), with a center coordination η5 interaction between Cp as co-ligand and chromium metal center, this was optimization by using density functional theory (DFT) and then was comparing with experimental data, also other possibility of Cp interacted with ion metal were tested like η1 ,η2 ,η3 and η4 under optimization system. These were carried out under investigation of density functional theory (DFT) calculation, and comparing together. Other methods, explicitly including electron correlation, are necessary for more accurate calculations; MB3LYP ( Becke)( Lee–Yang–Parr ) level of theory often being used to obtain more exact results. These complexes were estimated of electronic energy for molecular system, because it accounts for all electron correlation interactions. The optimised of [Cr(ArN(CH2)3NAr)2(η5-Cp)] (Ar = 2,6-Pri2C6H3 and Cp= C5H5) was found to be thermally more stable than others of chromium cyclopentadienyl. By using Dewar-Chatt-Duncanson model, as a basis of the molecular orbital (MO) analysis and showed the highest occupied molecular orbital (HOMO) and lowest occupied molecular orbital LUMO.

Keywords: Chromium(III) cyclopentadienyl complexes, DFT, MO, HOMO, LUMO

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Authors: Sahar Abbaszadeh, Sharifah Rafidah Wan Alwi, Colin Webb, Nahid Ghasemi, Ida Idayu Muhamad

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Toxic heavy metal discharges into environment due to rapid industrialization is a serious pollution problem that has drawn global attention towards their adverse impacts on both the structure of ecological systems as well as human health. Lead as toxic and bio-accumulating elements through the food chain, is regularly entering to water bodies from discharges of industries such as plating, mining activities, battery manufacture, paint manufacture, etc. The application of conventional methods to degrease and remove Pb(II) ion from wastewater is often restricted due to technical and economic constrains. Therefore, the use of various agro-wastes as low-cost bioadsorbent is found to be attractive since they are abundantly available and cheap. In this study, activated carbon of papaya peel (AC-PP) (as locally available agricultural waste) was employed to evaluate its Pb(II) uptake capacity from single-solute solutions in sets of batch mode experiments. To assess the surface characteristics of the adsorbents, the scanning electron microscope (SEM) coupled with energy disperse X-ray (EDX), and Fourier transform infrared spectroscopy (FT-IR) analysis were utilized. The removal amount of Pb(II) was determined by atomic adsorption spectrometry (AAS). The effects of pH, contact time, the initial concentration of Pb(II) and adsorbent dosage were investigated. The pH value = 5 was observed as optimum solution pH. The optimum initial concentration of Pb(II) in the solution for AC-PP was found to be 200 mg/l where the amount of Pb(II) removed was 36.42 mg/g. At the agitating time of 2 h, the adsorption processes using 100 mg dosage of AC-PP reached equilibrium. The experimental results exhibit high capability and metal affinity of modified papaya peel waste with removal efficiency of 93.22 %. The evaluation results show that the equilibrium adsorption of Pb(II) was best expressed by Freundlich isotherm model (R2 > 0.93). The experimental results confirmed that AC-PP potentially can be employed as an alternative adsorbent for Pb(II) uptake from industrial wastewater for the design of an environmentally friendly yet economical wastewater treatment process.

Keywords: activated carbon, bioadsorption, lead removal, papaya peel, wastewater treatment

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Authors: Mohd Salmi Md Noorani, Ghada Al-Mahbashi, Sakhinah Abu Bakar

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This paper investigates projective lag synchronization (PLS) behavior in drive response dynamical networks (DRDNs) model with identical nodes. A hybrid feedback control method is designed to achieve the PLS with mismatch and without mismatch terms. The stability of the error dynamics is proven theoretically using the Lyapunov stability theory. Finally, analytical results show that the states of the dynamical network with non-delayed coupling can be asymptotically synchronized onto a desired scaling factor under the designed controller. Moreover, the numerical simulations results demonstrate the validity of the proposed method.

Keywords: drive-response dynamical network, projective lag synchronization, hybrid feedback control, stability theory

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Authors: Syed Hassan Raza Shah, Mohammad Mohammad Ali

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The flow over a smoothly profiled airfoil at a low Reynolds number is highly susceptible to separate even at a very low angle of attack. An investigation was made to study the effect of leading-edge and trailing-edge corrugation with the spanwise change in the ridges resulted due to the change in the chord length for an infinite wing. The wind tunnel results using NACA0018 wings revealed that leading and trailing edge corrugation did not have any benefit in terms of aerodynamic efficiency or delayed stall. The leading edge and trailing edge corrugation didn't change the lift curve slope, with the leading edge corrugation wing stalling first in the range of Reynolds number of 50,000 to 125,000.

Keywords: leading and trailing edge corrugations, low reynolds number, wind tunnel testing, NACA0018

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Authors: Jeong-Moh John Yahng, Angelika Na

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Introduction: Increasing numbers of general surgical patients are being prescribed antiplatelet and anticoagulant medications (APAC) for various cardiovascular and cerebrovascular conditions. Surgical patients who are on APAC present a management challenge as bleeding risk needs to be balanced with thromboembolic risk. Although guidelines exist in regards to APAC management in elective surgery, there is a lack of guidelines in the emergency surgery setting. In this study we aim to characterise APAC usage in emergency general surgical patients admitted to a rural hospital. We also assess the impact of APAC usage on clinical management of these patients. Methods: Prospective study of emergency general surgical admissions at Northeast Health Wangaratta (Victoria) from 2 July to 25 Oct 2014. Questionnaire collected demographics data, admission diagnosis, APAC usage, anaesthesia techniques, operation types, transfusion requirement and morbidity / mortality data. Results: During the 4 month study, 118 patients were classified into two groups: non-APAC (n=96, 81%) and APAC (n=22, 19%). Patients in the APAC group were older compared to the non-APAC patients (mean age 72 vs 42 years old). Amongst patients younger than 60 years old, only 1% of them were on APAC. In contrast, 49% of patients older than 60 years old were on APAC (p<0.001). Patients who were admitted with a bleeding problem were more likely to be on APAC (p<0.05). 19% of emergency general surgery patients were on APAC. The majority (91%) of them were on antiplatelet medication, with two patients being on dual antiplatelet agents (aspirin + clopidogrel or ticagrelor). 15% of emergency general surgical patients requiring operations were on APAC. 11% of all laparotomies and 33% of gastroscopy for haematemesis/melaena patients were on APAC. Both of the patients operated for bleeding following surgery at another hospital were in the APAC group. In regards to impact on clinical management, 59% of APAC patients had their medications interrupted or ceased, on average by 3.5 days (range 1-13 days). 2 out of 75 operations were delayed due to APAC usage. There was no difference in the use of central venous or arterial line for increased monitoring (p=0.14) or in the use of warming blanket (Bair Hugger™) (p=0.94). Overall, transfusion rate was higher amongst APAC patients (14% vs 3%) (p 0.04). The recorded morbidity (n=2) and mortality (n=1) in this study were all in the APAC group. Discussion: Nineteen percent of emergency general surgical admissions and fifteen percent of operated patients were on APAC. The prevalence of APAC usage was higher in those aged sixty and above. General surgical patients who were admitted with a bleeding problem were more likely to be on APAC. Two patients who were operated for bleeding following surgery at another hospital were in the APAC group. Note that there was no patient in the non-APAC group who was admitted for post-operative bleeding. We observed two cases in which operation was delayed due to APAC usage. Transfusion, morbidity and mortality rate were higher in the APAC group. Conclusion: In this study, nineteen percent of emergency general surgical admissions were on APAC. The use of APAC is more prevalent in the older age group, particularly those aged sixty and above. Higher proportion of APAC compared to non-APAC patients were admitted and operated for bleeding problems. There is an urgent need for clinical guidelines regarding APAC management in emergency general surgical patients.

Keywords: antiplatelet, anticoagulants, emergency general surgery, rural general surgery, morbidity, mortality

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Authors: Aloke Bapli, Debabrata Seth

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Graphene oxide (GO) is the two-dimensional (2D) nanoscale allotrope of carbon having several physiochemical properties such as high mechanical strength, high surface area, strong thermal and electrical conductivity makes it an important candidate in various modern applications such as drug delivery, supercapacitors, sensors etc. GO has been used in the photothermal treatment of cancers and Alzheimer’s disease etc. The main idea to choose GO in our work is that it is a surface active molecule, it has a large number of hydrophilic functional groups such as carboxylic acid, hydroxyl, epoxide on its surface and in basal plane. So it can easily interact with organic fluorophores through hydrogen bonding or any other kind of interaction and easily modulate the photophysics of the probe molecules. We have used different spectroscopic techniques for our work. The Ground-state absorption spectra and steady-state fluorescence emission spectra were measured by using UV-Vis spectrophotometer from Shimadzu (model-UV-2550) and spectrofluorometer from Horiba Jobin Yvon (model-Fluoromax 4P) respectively. All the fluorescence lifetime and anisotropy decays were collected by using time-correlated single photon counting (TCSPC) setup from Edinburgh instrument (model: LifeSpec-II, U.K.). Herein, we described the photophysics of a hydrophilic molecule 7-(n,n׀-diethylamino) coumarin-3-carboxylic acid (7-DCCA) in the reverse micelles containing GO. It was observed that photophysics of dye is modulated in the presence of GO compared to photophysics of dye in the absence of GO inside the reverse micelles. Here we have reported the solvent relaxation and rotational relaxation time in GO containing reverse micelle and compare our work with normal reverse micelle system by using 7-DCCA molecule. Normal reverse micelle means reverse micelle in the absence of GO. The absorption maxima of 7-DCCA were blue shifted and emission maxima were red shifted in GO containing reverse micelle compared to normal reverse micelle. The rotational relaxation time in GO containing reverse micelle is always faster compare to normal reverse micelle. Solvent relaxation time, at lower w₀ values, is always slower in GO containing reverse micelle compare to normal reverse micelle and at higher w₀ solvent relaxation time of GO containing reverse micelle becomes almost equal to normal reverse micelle. Here emission maximum of 7-DCCA exhibit bathochromic shift in GO containing reverse micelles compared to that in normal reverse micelles because in presence of GO the polarity of the system increases, as polarity increases the emission maxima was red shifted an average decay time of GO containing reverse micelle is less than that of the normal reverse micelle. In GO containing reverse micelle quantum yield, decay time, rotational relaxation time, solvent relaxation time at λₑₓ=375 nm is always higher than λₑₓ=405 nm, shows the excitation wavelength dependent photophysics of 7-DCCA in GO containing reverse micelles.

Keywords: photophysics, reverse micelle, rotational relaxation, solvent relaxation

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Authors: Hiranmoyee Das

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Aim. Due to late presentation and delayed diagnosis mortality rate of retinoblastoma is more than 50% in developing counties. So to facilitate the diagnosis, to decrease the disease and treatment burden and to increase the disease survival rate, an attempt was made for early diagnosis of Retinoblastoma by including fundus examination in routine immunization programs. Methods- A unique immunization card is followed in a tertiary health care center where examination of pupillary reflex is made mandatory in each visit of the child for routine immunization. In case of any abnormality, the child is referred to the ophthalmology department. Conclusion- Early detection is the key in the management of retinoblastoma. Every child is brought to the health care system at least five times before the age of 2 years for routine immunization. We should not miss this golden opportunity for early detection of retinoblastoma.

Keywords: retinoblastoma, immunization, unique, early

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Authors: M. R. S. Nasuha, K. Azman, H. Azhan, S. A. Senawi, A . Mardhiah

Abstract:

Sm3+ doped borotellurite glasses of the system (70-x) TeO2-20B2O3-10ZnO-xSm2O3 (where x = 0.0, 0.5, 1.0, 1.5, 2.0, and 2.5 mol%) have been prepared using melt-quenching method. Their physical properties such as density, molar volume and oxygen packing density as well as the optical measurements by mean of their absorption and emission characteristic have been carried out at room temperature using UV/VIS and photoluminescence spectrophotometer. The result of physical properties is found to vary with respect to Sm3+ ions content. Meanwhile, three strong absorption peaks are observed and are well resolved in the ultraviolet and visible regions due to transitions between the ground state and various excited state of Sm3+ ions. Thus, the photoluminescence spectra exhibit four emission bands from the initial state, which correspond to the 4G5/2 → 6H5/2, 4G5/2 → 6H7/2, 4G5/2 → 6H9/2 and 4G5/2 → 6H11/2 fluorescence transitions at 562 nm, 599 nm, 645 nm, and 706 nm, respectively.

Keywords: absorption, borotellurite, emission, optical, physical

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Authors: Ghandehari-Motlagh, Mohammad

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Purpose: To evaluate of the effect of an ideal fit of RGPs on HOA and keratoconus indices. Methods: In this cohort study, 65 keratoconus eyes with more than 3 lines(Snellen)improvement between BSCVA and BCVA(RGP) were imaged with Pentacam HR and their topometric and Zernike analysis findings without RGP were recorded. After 6 months or later of RGP fitting (Rose-K,Boston XO2), imaging with pentacam was repeated and the above information were recorded. Results: 65 different grades of keratoconus eyes with mean age of 27.32 yrs/old(SD +_5.51)enrolled including M 28(43.1%) and F 37(56.9%). 44(67.7%) with family Hx of Kc and 21(31.25%)without any Kc in their families. 54 (83.1%) with and 11 (16.9%) without any ocular allergy Hx. Maximum percent of age of onset of kc was 15 ys/old(29.2%).This study showed there are meaningful correlations between with and without RGP Pentacam indices and HOA in each grade of Kc.92.3% of patients had foreign body sensation but 96.9% had 11-20 hours/day RGP wear that confirms on psychologic effect of an ideal fit on patient’s motivation. Conclusion: With the three points touch principle of RGP fitting in Kc corneas, the patients will have a decrease in HOA and so delayed need for PK or LK.

Keywords: keratoconus, rigid gas permeable lens, aberration, fitting

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Authors: Jerome G. Chandraseelan, Samuel M. D. Oliveira, Antti Häkkinen, Sofia Startceva, Andre S. Ribeiro

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We used live E. coli containing synthetic genetic oscillators to study how the degree of synchrony between the genetic circuits of sister cells changes with temperature. We found that both the mean and the variability of the degree of synchrony between the fluorescence signals from sister cells are affected by temperature. Also, while most pairs of sister cells were found to be highly synchronous in each condition, the number of asynchronous pairs increased with increasing temperature, which was found to be due to disruptions in the oscillations. Finally we provide evidence that these disruptions tend to affect multiple generations as opposed to individual cells. These findings provide insight in how to design more robust synthetic circuits and in how cell division can affect their dynamics.

Keywords: repressilator, robustness, synchrony, synthetic biology

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Authors: Rasha A.Ibrahim El-Ghazawy, Ashraf M. El-Saeed, Heusin El-Shafey, M. Abdel-Raheim, Maher A. El-Sockary

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Two thermotropic liquid crystalline curing agents based on abietic acid with different mesogens (LCC1 and LCC2) were synthesized for producing thermally stable liquid crystal networks suitable for high performance epoxy coatings. Differential scanning calorimetry (DSC) and polarized optical microscope (POM) was used to identify the liquid crystal phase transformation temperatures and texture, respectively. POM micro graphs for both LCCs revealing cholesteric texture. A multifunctional epoxy resin with two abietic acid moieties was also synthesized. Dynamic mechanical (DMA) and thermogravimetric (TGA) analyses show that the fully bio-based cured epoxies by either LCCs possess high glass transition temperature (Tg), high modulus (G`) and improved thermal stability. The chemical structure of the synthesized LCCs and epoxy resin was investigated through FTIR and 1HNMR spectroscopic techniques.

Keywords: abietic acid, dynamic mechanical analysis, epoxy resin, liquid crystal, thermo gravimetric analysis

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Authors: Ellana Boada, Eric Santos-Clotas, Alba Cabrera-Codony, Maria Martin, Lluis Baneras, Frederic Gich

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Volatile methylsiloxanes (VMS) are a group of manmade silicone compounds widely used in household and industrial applications that end up on the biogas produced through the anaerobic digestion of organic matter in landfills and wastewater treatment plants. The presence of VMS during the biogas energy conversion can cause damage on the engines, reducing the efficiency of this renewable energy source. Non regenerative adsorption onto activated carbon is the most widely used technology to remove siloxanes from biogas, while new trends point out that biotechnology offers a low-cost and environmentally friendly alternative to conventional technologies. The first objective of this research was to enrich, isolate and identify bacterial species able to grow using siloxane molecules as a sole carbon source: anoxic wastewater sludge was used as initial inoculum in liquid anoxic enrichments, adding D4 (as representative siloxane compound) previously adsorbed on activated carbon. After several months of acclimatization, liquid enrichments were plated onto solid media containing D4 and thirty-four bacterial isolates were obtained. 16S rRNA gene sequencing allowed the identification of strains belonging to the following species: Ciceribacter lividus, Alicycliphilus denitrificans, Pseudomonas aeruginosa and Pseudomonas citronellolis which are described to be capable to degrade toxic volatile organic compounds. Kinetic assays with 8 representative strains revealed higher cell growth in the presence of D4 compared to the control. Our second objective was to characterize the community composition and diversity of the microbial community present in the enrichments and to elucidate whether the isolated strains were representative members of the community or not. DNA samples were extracted, the 16S rRNA gene was amplified (515F & 806R primer pair), and the microbiome analyzed from sequences obtained with a MiSeq PE250 platform. Results showed that the retrieved isolates only represented a minor fraction of the microorganisms present in the enrichment samples, which were represented by Alpha, Beta, and Gamma proteobacteria as dominant groups in the category class thus suggesting that other microbial species and/or consortia may be important for D4 biodegradation. These results highlight the need of additional protocols for the isolation of relevant D4 degraders. Currently, we are developing molecular tools targeting key genes involved in siloxane biodegradation to identify and quantify the capacity of the isolates to metabolize D4 in batch cultures supplied with a synthetic gas stream of air containing 60 mg m⁻³ of D4 together with other volatile organic compounds found in the biogas mixture (i.e. toluene, hexane and limonene). The isolates were used as inoculum in a biotrickling filter containing lava rocks and activated carbon to assess their capacity for siloxane removal. Preliminary results of biotrickling filter performance showed 35% of siloxane biodegradation in a contact time of 14 minutes, denoting that biological siloxane removal is a promising technology for biogas upgrading.

Keywords: bacterial cultivation, biogas upgrading, microbiome, siloxanes

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Authors: Egor E. Nuzhin, Nikolay V. Brilliantov

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We propose an approach for addressing Reinforcement Learning (RL) problems. It combines the ideas of umbrella sampling, borrowed from Monte Carlo technique of computational physics and chemistry, with optimal control methods, and is realized on the base of neural networks. This results in a powerful algorithm, designed to solve hard RL problems – the problems, with long-time delayed reward, state-traps sticking and a lack of terminal states. It outperforms the prominent algorithms, such as PPO, RND, iLQR and VI, which are among the most efficient for the hard problems. The new algorithm deals with a continuous ensemble of agents and expected return, that includes the ensemble entropy. This results in a quick and efficient search of the optimal policy in terms of ”exploration-exploitation trade-off” in the state-action space.

Keywords: umbrella sampling, reinforcement learning, policy gradient, dynamic programming

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Authors: Hoda M. Eid, Abir Nachar, Farah Thong, Gary Sweeney, Pierre S. Haddad

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Caffeic acid methyl ester (CAME) and caffeic ethyl esters (CAEE) were previously reported to potently stimulate glucose uptake in cultured C2C12 skeletal muscle cells via insulin-independent mechanisms involving the activation of adenosine monophosphate-activated protein kinase (AMPK). In the present study, we investigated the effect of the two compounds on the translocation of glucose transporter GLUT4 in L6 skeletal muscle cells. The cells were treated with the optimum non-toxic concentration (50 µM) of either CAME or CAEE for 18 h. Levels of GLUT4myc at the cell surface were measured by O-phenylenediamine dihydrochloride (OPD) assay. The effects of CAME and CAEE on GLUT1 and GLUT4 protein content were also measured by western immunoblot. Our results show that CAME and CAEE significantly increased glucose uptake, GLUT4 translocation and GLUT4 protein content. Furthermore, the effect of the two CA esters on two insulin-sensitive cell lines: H4IIE rat hepatoma and 3T3-L1 adipocytes were investigated. CAME and CAEE reduced the enzymatic activity of the key hepatic gluconeogenic enzyme glucose-6-phosphatase in a concentration-dependent manner. In addition, they exerted a concentration-dependent antiadipogenic effect on 3T3-L1 cells. Mitotic clonal expansion (MCE), a prerequisite for adipocytes differentiation was also concentration-dependently inhibited. The two compounds abrogated lipid droplet accumulation, blocked MCE and maintained cells in fibroblast-like state when applied at the maximum non-toxic concentration (100 µM). In addition, the expression of the early key adipogenic transcription factors CCAAT enhancer-binding protein beta (C/EBP-β) and the master regulator of adipogenesis peroxisome-proliferator-activated receptor gamma (PPAR-γ) were inhibited. We, therefore, conclude that CAME and CAEE exert pleiotropic benefits in several insulin-sensitive cell lines through insulin-independent mechanisms involving AMPK, hence they may treat obesity, diabetes and other metabolic diseases.

Keywords: type 2 diabetes mellitus, insulin resistance, GLUT4, Akt, AMPK.

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Authors: Yeimy L. Quintana, Juan G. Zuluaga, Sandra S. Arango

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The comet assay is a method based on electrophoresis that is used to measure DNA damage in cells and has shown important results in the identification of substances with a potential risk to the human population as innumerable physical, chemical and biological agents. With this technique is possible to obtain images like a comet, in which the tail of these refers to damaged fragments of the DNA. One of the main problems is that the image has unequal luminosity caused by the fluorescence microscope and requires different processing to condition it as well as to know how many optimal comets there are per sample and finally to perform the measurements and determine the percentage of DNA damage. In this paper, we propose the design and implementation of software using Image Processing Toolbox-MATLAB that allows the automation of image processing. The software chooses the optimum comets and measuring the necessary parameters to detect the damage.

Keywords: artificial vision, comet assay, DNA damage, image processing

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Authors: Milda Nainyte, Viktoras Masevicius

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Biological methylation is a methyl group transfer from S-adenosyl-L-methionine (AdoMet) onto N-, C-, O- or S-nucleophiles in DNA, RNA, proteins or small biomolecules. The reaction is catalyzed by enzymes called AdoMet-dependent methyltransferases (MTases), which represent more than 3 % of the proteins in the cell. As a general mechanism, the methyl group from AdoMet replaces a hydrogen atom of nucleophilic center producing methylated DNA and S-adenosyl-L-homocysteine (AdoHcy). Recently, DNA methyltransferases have been used for the sequence-specific, covalent labeling of biopolymers. Two types of MTase catalyzed labeling of biopolymers are known, referred as two-step and one-step. During two-step labeling, an alkylating fragment is transferred onto DNA in a sequence-specific manner and then the reporter group, such as biotin, is attached for selective visualization using suitable chemistries of coupling. This approach of labeling is quite difficult and the chemical hitching does not always proceed at 100 %, but in the second step the variety of reporter groups can be selected and that gives the flexibility for this labeling method. In the one-step labeling, AdoMet analog is designed with the reporter group already attached to the functional group. Thus, the one-step labeling method would be more comfortable tool for labeling of biopolymers in order to prevent additional chemical reactions and selection of reaction conditions. Also, time costs would be reduced. However, effective AdoMet analog appropriate for one-step labeling of biopolymers and containing cleavable bond, required for reduction of PCR interferation, is still not known. To expand the practical utility of this important enzymatic reaction, cofactors with activated sulfonium-bound side-chains have been produced and can serve as surrogate cofactors for a variety of wild-type and mutant DNA and RNA MTases enabling covalent attachment of these chains to their target sites in DNA, RNA or proteins (the approach named methyltransferase-directed Transfer of Activated Groups, mTAG). Compounds containing hex-2-yn-1-yl moiety has proved to be efficient alkylating agents for labeling of DNA. Herein we describe synthetic procedures for the preparation of N-biotinoyl-N’-(pent-4-ynoyl)cystamine starting from the coupling of cystamine with pentynoic acid and finally attaching the biotin as a reporter group. The synthesis of the first AdoMet based cofactor containing a cleavable reporter group and appropriate for one-step labeling was developed.

Keywords: adoMet analogs, DNA alkylation, cofactor, methyltransferases

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Authors: Mohamed Abdelmounim Bakkali, Mustapha El Mataouy, Abellatif Aaliti, Mouhamed Khaddor

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In the paper, we study the effects of introducing hafnium oxide on Raman spectra of silica glass planar waveguide activated by 0.3 mol% Er3+ ions. This work compares Raman spectra measured for three thin films deposited on silicon substrate. The films were prepared with different molar ratio of Si/Hf using sol-gel method and deposited by dip coating technique. The effect of hafnium oxide incorporation on the waveguides shows the evolution of the structure of this material. This structural information is useful to understand the luminescence intensity by means of ion–ion interaction mechanisms.

Keywords: optical amplifiers, non-bridging oxygen, erbium, sol-gel, waveguide, silica-hafnia

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