Search results for: spectra
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 718

Search results for: spectra

88 Freshwater Cyanobacterial Bioactive Insights: Planktothricoides raciorskii Compounds vs. Green Synthesized Silver Nanoparticles: Characterization, in vitro Cytotoxicity, and Antibacterial Exploration

Authors: Sujatha Edla

Abstract:

Introduction: New compounds and possible uses for the bioactive substances produced by freshwater cyanobacteria are constantly being discovered through research. Certain molecules are hazardous to the environment and human health, but others have potential applications in industry, biotechnology, and pharmaceuticals. These discoveries advance our knowledge of the varied functions these microbes perform in different ecosystems. Cyanobacterial silver nanoparticles (AgNPs) have special qualities and possible therapeutic advantages, which make them very promising for a range of medicinal uses. Aim: In our study; the attention was focused on the analysis and characterization of bioactive compounds extracted from freshwater cyanobacteria Planktothricoides raciorskii and its comparative study on Cyanobacteria-mediated silver nanoparticles synthesized by cell-free extract of Planktothricoides raciorskii. Material and Methods: A variety of bioactive secondary metabolites have been extracted, purified, and identified from cyanobacterial species using column chromatography, FTIR, and GC-MS/MS chromatography techniques and evaluated for antibacterial and cytotoxic studies, where the Cyanobacterial silver nanoparticles (CSNPs) were characterized by UV-Vis spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Fourier transform infrared (FTIR) analysis and were further tested for antibacterial and cytotoxic efficiency. Results: The synthesis of CSNPs was confirmed through visible color change and shift of peaks at 430–445 nm by UV-Vis spectroscopy. The size of CSNPs was between 22 and 34 nm and oval-shaped which were confirmed by SEM and TEM analyses. The FTIR spectra showed a new peak at the range of 3,400–3,460 cm−1 compared to the control, confirming the reduction of silver nitrate. The antibacterial activity of both crude bioactive compound extract and CSNPs showed remarkable activity with Zone of inhibition against E. coli with 9.5mm and 10.2mm, 13mm and 14.5mm against S. paratyphi, 9.2mm and 9.8mm zone of inhibition against K. pneumonia by both crude extract and CSNPs, respectively. The cytotoxicity as evaluated by extracts of Planktothricoides raciorskii against MCF7-Human Breast Adenocarcinoma cell line and HepG2- Human Hepatocellular Carcinoma cell line employing MTT assay gave IC50 value of 47.18ug/ml, 110.81ug/ml against MCF7cell line and HepG2 cell line, respectively. The cytotoxic evaluation of Planktothricoides raciorskii CSNPs against the MCF7cell line was 43.37 ug/ml and 20.88 ug/ml against the HepG2 cell line. Our ongoing research in this field aims to uncover the full therapeutic potential of cyanobacterial silver nanoparticles and address any associated challenges.

Keywords: cyanobacteria, silvernanoparticles, pharmaceuticals, bioactive compounds, cytotoxic

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87 Synthesized Doped TiO2 Photocatalysts for Mineralization of Quinalphos from Aqueous Streams

Authors: Nidhi Sharotri, Dhiraj Sud

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Water pollution by pesticides constitutes a serious ecological problem due to their potential toxicity and bioaccumulation. The widespread use of pesticides in industry and agriculture along with their resistance to natural decomposition, biodegradation, chemical and photochemical degradation under typical environmental conditions has resulted in the emergence of these chemicals and their transformed products in natural water. Among AOP’s, heterogeneous photocatalysis using TiO2 as photocatalyst appears as the most emerging destructive technology for mineralization of the pollutant in aquatic streams. Among the various semiconductors (TiO2, ZnO, CdS, FeTiO3, MnTiO3, SrTiO2 and SnO2), TiO2 has proven to be the most efficient photocatalyst for environmental applications due to its biological and chemical inertness, high photo reactivity, non-toxicity, and photo stability. Semiconductor photocatalysts are characterized by an electronic band structure in which valence band and conduction band are separated by a band gap, i.e. a region of forbidden energy. Semiconductor based photocatalysts produces e-/h+ pairs which have been employed for degradation of organic pollutants. The present paper focuses on modification of TiO2 photocatalyst in order to shift its absorption edge towards longer wavelength to make it active under natural light. Semiconductor TiO2 photocatalysts was prepared by doping with anion (N), cation (Mn) and double doped (Mn, N) using greener approach. Titanium isopropoxide is used as titania precursor and ethanedithiol, hydroxyl amine hydrochloride, manganous chloride as sulphur, nitrogen and manganese precursors respectively. Synthesized doped TiO2 nanomaterials are characterized for surface morphology (SEM, TEM), crystallinity (XRD) and optical properties (absorption spectra and band gap). EPR data confirms the substitutional incorporation of Mn2+ in TiO2 lattice. The doping influences the phase transformation of rutile and anatase phase crystal and thereby the absorption spectrum changes were observed. The effect of variation of reaction parameters such as solvent, reaction time and calcination temperature on the yield, surface morphology and optical properties was also investigated. The TEM studies show the particle size of nanomaterials varies from 10-50 nm. The calculated band gap of nanomaterials varies from 2.30-2.60 eV. The photocatalytic degradation of organic pollutant organophosphate pesticide (Quinalphos) has been investigated by studying the changes in UV absorption spectrum and the promising results were obtained under visible light. The complete mineralization of quinalphos has occurred as no intermediates were recorded after 8 hrs of degradation confirmed from the HPLC studies.

Keywords: quinalphos, doped-TiO2, mineralization, EPR

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86 Sterilization Effects of Low Concentration of Hydrogen Peroxide Solution on 3D Printed Biodegradable Polyurethane Nanocomposite Scaffold for Heart Valve Regeneration

Authors: S. E. Mohmad-Saberi, W. Song, N. Oliver, M. Adrian, T.C. Hsu, A. Darbyshire

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Biodegradable polyurethane (PU) has emerged as a potential material to promote repair and regeneration of damaged/diseased tissues in heart valve regeneration due to its excellent biomechanical profile. Understanding the effects of sterilization on their properties is vital since they are more sensitive and more critical of porous structures compared to bulk ones. In this study, the effects of low concentration of hydrogen peroxide (H₂O₂) solution sterilization has been investigated to determine whether the procedure would be efficient and non-destructive to porous three-dimensional (3D) elastomeric nanocomposite, polyhedral oligomeric silsesquioxane-terminated poly (ethylene-diethylene glycol succinate-sebacate) urea-urethane (POSS-EDSS-PU) scaffold. All the samples were tested for sterility following sterilization using phosphate buffer saline (PBS) as control and 5 % v/v H₂O₂ solution. The samples were incubated in tryptic soy broth for the cultivation of microorganisms under agitation at 37˚C for 72 hours. The effects of the 5 % v/v H₂O₂ solution sterilization were evaluated in terms of morphology, chemical and mechanical properties using scanning electron microscopy (SEM), Fourier transform infrared (FTIR) and tensile tester apparatus. Toxicity effects of the 5 % v/v H₂O₂ solution decontamination were studied by in vitro cytotoxicity test, where the cellular responses of human dermal fibroblast (HDF) were examined. A clear, uncontaminated broth using 5 % v/v H₂O₂ solution method indicated efficient sterilization after 3 days, while the non-sterilized control shows clouding broth indicated contamination. The morphology of 3D POSS-EDSS-PU scaffold appeared to have similar morphology after sterilization with 5 % v/v H₂O₂ solution regarding of pore size and surface. FTIR results show that the sterilized samples and non-sterilized control share the same spectra pattern, confirming no significant alterations over the surface chemistry. For the mechanical properties of the H₂O₂ solution-treated scaffolds, the tensile strain was not significantly decreased, however, become significantly stiffer after the sterilization. No cytotoxic effects were observed after the 5 % v/v H₂O₂ solution sterilization as confirmed by cell viability assessed by Alamar Blue assay. The results suggest that low concentration of 5 % v/v hydrogen peroxide solution can be used as an alternative method for sterilizing biodegradable 3D porous scaffold with micro/nano-architecture without structural deformation. This study provides the understanding of the sterilization effects on biomechanical profile and cell proliferation of 3D POSS-EDSS-PU scaffolds.

Keywords: biodegradable, hydrogen peroxide solution, POSS-EDSS-PU, sterilization

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85 Investigation of the Carbon Dots Optical Properties Using Laser Scanning Confocal Microscopy and TimE-resolved Fluorescence Microscopy

Authors: M. S. Stepanova, V. V. Zakharov, P. D. Khavlyuk, I. D. Skurlov, A. Y. Dubovik, A. L. Rogach

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Carbon dots are small carbon-based spherical nanoparticles, which are typically less than 10 nm in size that can be modified with surface passivation and heteroatoms doping. The light-absorbing ability of carbon dots has attracted a significant amount of attention in photoluminescence for bioimaging and fluorescence sensing applications owing to their advantages, such as tunable fluorescence emission, photo- and thermostability and low toxicity. In this study, carbon dots were synthesized by the solvothermal method from citric acid and ethylenediamine dissolved in water. The solution was heated for 5 hours at 200°C and then cooled down to room temperature. The carbon dots films were obtained by evaporation from a high-concentration aqueous solution. The increase of both luminescence intensity and light transmission was obtained as a result of a 405 nm laser exposure to a part of the carbon dots film, which was detected using a confocal laser scanning microscope (LSM 710, Zeiss). Blueshift up to 35 nm of the luminescence spectrum is observed as luminescence intensity, which is increased more than twofold. The exact value of the shift depends on the time of the laser exposure. This shift can be caused by the modification of surface groups at the carbon dots, which are responsible for long-wavelength luminescence. In addition, a shift of the absorption peak by 10 nm and a decrease in the optical density at the wavelength of 350 nm is detected, which is responsible for the absorption of surface groups. The obtained sample was also studied with time-resolved confocal fluorescence microscope (MicroTime 100, PicoQuant), which made it possible to receive a time-resolved photoluminescence image and construct emission decays of the laser-exposed and non-exposed areas. 5 MHz pulse rate impulse laser has been used as a photoluminescence excitation source. Photoluminescence decay was approximated by two exhibitors. The laser-exposed area has the amplitude of the first-lifetime component (A1) twice as much as before, with increasing τ1. At the same time, the second-lifetime component (A2) decreases. These changes evidence a modification of the surface groups of carbon dots. The detected effect can be used to create thermostable fluorescent marks, the physical size of which is bounded by the diffraction limit of the optics (~ 200-300 nm) used for exposure and to improve the optical properties of carbon dots or in the field of optical encryption. Acknowledgements: This work was supported by the Ministry of Science and Higher Education of Russian Federation, goszadanie no. 2019-1080 and financially supported by Government of Russian Federation, Grant 08-08.

Keywords: carbon dots, photoactivation, optical properties, photoluminescence and absorption spectra

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84 Assessing the Material Determinants of Cavity Polariton Relaxation using Angle-Resolved Photoluminescence Excitation Spectroscopy

Authors: Elizabeth O. Odewale, Sachithra T. Wanasinghe, Aaron S. Rury

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Cavity polaritons form when molecular excitons strongly couple to photons in carefully constructed optical cavities. These polaritons, which are hybrid light-matter states possessing a unique combination of photonic and excitonic properties, present the opportunity to manipulate the properties of various semiconductor materials. The systematic manipulation of materials through polariton formation could potentially improve the functionalities of many optoelectronic devices such as lasers, light-emitting diodes, photon-based quantum computers, and solar cells. However, the prospects of leveraging polariton formation for novel devices and device operation depend on more complete connections between the properties of molecular chromophores, and the hybrid light-matter states they form, which remains an outstanding scientific goal. Specifically, for most optoelectronic applications, it is paramount to understand how polariton formation affects the spectra of light absorbed by molecules coupled strongly to cavity photons. An essential feature of a polariton state is its dispersive energy, which occurs due to the enhanced spatial delocalization of the polaritons relative to bare molecules. To leverage the spatial delocalization of cavity polaritons, angle-resolved photoluminescence excitation spectroscopy was employed in characterizing light emission from the polaritonic states. Using lasers of appropriate energies, the polariton branches were resonantly excited to understand how molecular light absorption changes under different strong light-matter coupling conditions. Since an excited state has a finite lifetime, the photon absorbed by the polariton decays non-radiatively into lower-lying molecular states, from which radiative relaxation to the ground state occurs. The resulting fluorescence is collected across several angles of excitation incidence. By modeling the behavior of the light emission observed from the lower-lying molecular state and combining this result with the output of angle-resolved transmission measurements, inferences are drawn about how the behavior of molecules changes when they form polaritons. These results show how the intrinsic properties of molecules, such as the excitonic lifetime, affect the rate at which the polaritonic states relax. While it is true that the lifetime of the photon mediates the rate of relaxation in a cavity, the results from this study provide evidence that the lifetime of the molecular exciton also limits the rate of polariton relaxation.

Keywords: flourescece, molecules in cavityies, optical cavity, photoluminescence excitation, spectroscopy, strong coupling

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83 Mesoporous BiVO4 Thin Films as Efficient Visible Light Driven Photocatalyst

Authors: Karolina Ordon, Sandrine Coste, Malgorzata Makowska-Janusik, Abdelhadi Kassiba

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Photocatalytic processes play key role in the production of a new source of energy (as hydrogen), design of self-cleaning surfaces or for the environment preservation. The most challenging task deals with the purification of water distinguished by high efficiency. In the mentioned process, organic pollutants in solutions are decomposed to the simple, non-toxic compounds as H2O and CO2. The most known photocatalytic materials are ZnO, CdS and TiO2 semiconductors with a particular involvement of TiO2 as an efficient photocatalysts even with a high band gap equal to 3.2 eV which exploit only UV radiation from solar emitted spectrum. However, promising material with visible light induced photoactivity was searched through the monoclinic polytype of BiVO4 which has energy gap about 2.4 eV. As required in heterogeneous photocatalysis, the high contact surface is required. Also, BiVO4 as photocatalyst can be optimized by increasing its surface area by achieving the mesoporous structure synthesize. The main goal of the present work consists in the synthesis and characterization of BiVO4 mesoporous thin film. The synthesis method based on sol-gel was carried out using a standard surfactants such as P123 and F127. The thin film was deposited by spin and dip coating method. Then, the structural analysis of the obtained material was performed thanks to X-ray diffraction (XRD) and Raman spectroscopy. The surface of resulting structure was investigated using a scanning electron microscopy (SEM). The computer simulations based on modeling the optical and electronic properties of bulk BiVO4 by using DFT (density functional theory) methodology were carried out. The semiempirical parameterized method PM6 was used to compute the physical properties of BiVO4 nanostructures. The Raman and IR absorption spectra were also measured for synthesized mesoporous material, and the results were compared with the theoretical predictions. The simulations of nanostructured BiVO4 have pointed out the occurrence of quantum confinement for nanosized clusters leading to widening of the band gap. This result overcame the relevance of nanosized objects to harvest wide part of the solar spectrum. Also, a balance was searched experimentally through the mesoporous nature of the films devoted to enhancing the contact surface as required for heterogeneous catalysis without to lower the nanocrystallite size under some critical sizes inducing an increased band gap. The present contribution will discuss the relevant features of the mesoporous films with respect to their photocatalytic responses.

Keywords: bismuth vanadate, photocatalysis, thin film, quantum-chemical calculations

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82 The Direct Deconvolutional Model in the Large-Eddy Simulation of Turbulence

Authors: Ning Chang, Zelong Yuan, Yunpeng Wang, Jianchun Wang

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The utilization of Large Eddy Simulation (LES) has been extensive in turbulence research. LES concentrates on resolving the significant grid-scale motions while representing smaller scales through subfilter-scale (SFS) models. The deconvolution model, among the available SFS models, has proven successful in LES of engineering and geophysical flows. Nevertheless, the thorough investigation of how sub-filter scale dynamics and filter anisotropy affect SFS modeling accuracy remains lacking. The outcomes of LES are significantly influenced by filter selection and grid anisotropy, factors that have not been adequately addressed in earlier studies. This study examines two crucial aspects of LES: Firstly, the accuracy of direct deconvolution models (DDM) is evaluated concerning sub-filter scale (SFS) dynamics across varying filter-to-grid ratios (FGR) in isotropic turbulence. Various invertible filters are employed, including Gaussian, Helmholtz I and II, Butterworth, Chebyshev I and II, Cauchy, Pao, and rapidly decaying filters. The importance of FGR becomes evident as it plays a critical role in controlling errors for precise SFS stress prediction. When FGR is set to 1, the DDM models struggle to faithfully reconstruct SFS stress due to inadequate resolution of SFS dynamics. Notably, prediction accuracy improves when FGR is set to 2, leading to accurate reconstruction of SFS stress, except for cases involving Helmholtz I and II filters. Remarkably high precision, nearly 100%, is achieved at an FGR of 4 for all DDM models. Furthermore, the study extends to filter anisotropy and its impact on SFS dynamics and LES accuracy. By utilizing the dynamic Smagorinsky model (DSM), dynamic mixed model (DMM), and direct deconvolution model (DDM) with anisotropic filters, aspect ratios (AR) ranging from 1 to 16 are examined in LES filters. The results emphasize the DDM’s proficiency in accurately predicting SFS stresses under highly anisotropic filtering conditions. Notably high correlation coefficients exceeding 90% are observed in the a priori study for the DDM’s reconstructed SFS stresses, surpassing those of the DSM and DMM models. However, these correlations tend to decrease as filter anisotropy increases. In the a posteriori analysis, the DDM model consistently outperforms the DSM and DMM models across various turbulence statistics, including velocity spectra, probability density functions related to vorticity, SFS energy flux, velocity increments, strainrate tensors, and SFS stress. It is evident that as filter anisotropy intensifies, the results of DSM and DMM deteriorate, while the DDM consistently delivers satisfactory outcomes across all filter-anisotropy scenarios. These findings underscore the potential of the DDM framework as a valuable tool for advancing the development of sophisticated SFS models for LES in turbulence research.

Keywords: deconvolution model, large eddy simulation, subfilter scale modeling, turbulence

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81 Effects of Drying and Extraction Techniques on the Profile of Volatile Compounds in Banana Pseudostem

Authors: Pantea Salehizadeh, Martin P. Bucknall, Robert Driscoll, Jayashree Arcot, George Srzednicki

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Banana is one of the most important crops produced in large quantities in tropical and sub-tropical countries. Of the total plant material grown, approximately 40% is considered waste and left in the field to decay. This practice allows fungal diseases such as Sigatoka Leaf Spot to develop, limiting plant growth and spreading spores in the air that can cause respiratory problems in the surrounding population. The pseudostem is considered a waste residue of production (60 to 80 tonnes/ha/year), although it is a good source of dietary fiber and volatile organic compounds (VOC’s). Strategies to process banana pseudostem into palatable, nutritious and marketable food materials could provide significant social and economic benefits. Extraction of VOC’s with desirable odor from dried and fresh pseudostem could improve the smell of products from the confectionary and bakery industries. Incorporation of banana pseudostem flour into bakery products could provide cost savings and improve nutritional value. The aim of this study was to determine the effects of drying methods and different banana species on the profile of volatile aroma compounds in dried banana pseudostem. The banana species analyzed were Musa acuminata and Musa balbisiana. Fresh banana pseudostem samples were processed by either freeze-drying (FD) or heat pump drying (HPD). The extraction of VOC’s was performed at ambient temperature using vacuum distillation and the resulting, mostly aqueous, distillates were analyzed using headspace solid phase microextraction (SPME) gas chromatography – mass spectrometry (GC-MS). Optimal SPME adsorption conditions were 50 °C for 60 min using a Supelco 65 μm PDMS/DVB Stableflex fiber1. Compounds were identified by comparison of their electron impact mass spectra with those from the Wiley 9 / NIST 2011 combined mass spectral library. The results showed that the two species have notably different VOC profiles. Both species contained VOC’s that have been established in literature to have pleasant appetizing aromas. These included l-Menthone, D-Limonene, trans-linlool oxide, 1-Nonanol, CIS 6 Nonen-1ol, 2,6 Nonadien-1-ol, Benzenemethanol, 4-methyl, 1-Butanol, 3-methyl, hexanal, 1-Propanol, 2-methyl- acid، 2-Methyl-2-butanol. Results show banana pseudostem VOC’s are better preserved by FD than by HPD. This study is still in progress and should lead to the optimization of processing techniques that would promote the utilization of banana pseudostem in the food industry.

Keywords: heat pump drying, freeze drying, SPME, vacuum distillation, VOC analysis

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80 Development of High-Efficiency Down-Conversion Fluoride Phosphors to Increase the Efficiency of Solar Panels

Authors: S. V. Kuznetsov, M. N. Mayakova, V. Yu. Proydakova, V. V. Pavlov, A. S. Nizamutdinov, O. A. Morozov, V. V. Voronov, P. P. Fedorov

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Increase in the share of electricity received by conversion of solar energy results in the reduction of the industrial impact on the environment from the use of the hydrocarbon energy sources. One way to increase said share is to improve the efficiency of solar energy conversion in silicon-based solar panels. Such efficiency increase can be achieved by transferring energy from sunlight-insensitive areas of work of silicon solar panels to the area of their photoresistivity. To achieve this goal, a transition to new luminescent materials with the high quantum yield of luminescence is necessary. Improvement in the quantum yield can be achieved by quantum cutting, which allows obtaining a quantum yield of down conversion of more than 150% due to the splitting of high-energy photons of the UV spectral range into lower-energy photons of the visible and near infrared spectral ranges. The goal of present work is to test approach of excitation through sensibilization of 4f-4f fluorescence of Yb3+ by various RE ions absorbing in UV and Vis spectral ranges. One of promising materials for quantum cutting luminophores are fluorides. In our investigation we have developed synthesis of nano- and submicron powders of calcium fluoride and strontium doped with rare-earth elements (Yb: Ce, Yb: Pr, Yb: Eu) of controlled dimensions and shape by co-precipitation from water solution technique. We have used Ca(NO3)2*4H2O, Sr(NO3)2, HF, NH4F as precursors. After initial solutions of nitrates were prepared they have been mixed with fluorine containing solution by dropwise manner. According to XRD data, the synthesis resulted in single phase samples with fluorite structure. By means of SEM measurements, we have confirmed spherical morphology and have determined sizes of particles (50-100 nm after synthesis and 150-300 nm after calcination). Temperature of calcination appeared to be 600°C. We have investigated the spectral-kinetic characteristics of above mentioned compounds. Here the diffuse reflection and laser induced fluorescence spectra of Yb3+ ions excited at around 4f-4f and 4f-5d transitions of Pr3+, Eu3+ and Ce3+ ions in the synthesized powders are reported. The investigation of down conversion luminescence capability of synthesized compounds included measurements of fluorescence decays and quantum yield of 2F5/2-2F7/2 fluorescence of Yb3+ ions as function of Yb3+ and sensitizer contents. An optimal chemical composition of CaF2-YbF3- LnF3 (Ln=Ce, Eu, Pr), SrF2-YbF3-LnF3 (Ln=Ce, Eu, Pr) micro- and nano- powders according to criteria of maximal IR fluorescence yield is proposed. We suppose that investigated materials are prospective in solar panels improvement applications. Work was supported by Russian Science Foundation grant #17-73- 20352.

Keywords: solar cell, fluorides, down-conversion luminescence, maximum quantum yield

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79 Metalorganic Chemical Vapor Deposition Overgrowth on the Bragg Grating for Gallium Nitride Based Distributed Feedback Laser

Authors: Junze Li, M. Li

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Laser diodes fabricated from the III-nitride material system are emerging solutions for the next generation telecommunication systems and optical clocks based on Ca at 397nm, Rb at 420.2nm and Yb at 398.9nm combined 556 nm. Most of the applications require single longitudinal optical mode lasers, with very narrow linewidth and compact size, such as communication systems and laser cooling. In this case, the GaN based distributed feedback (DFB) laser diode is one of the most effective candidates with gratings are known to operate with narrow spectra as well as high power and efficiency. Given the wavelength range, the period of the first-order diffraction grating is under 100 nm, and the realization of such gratings is technically difficult due to the narrow line width and the high quality nitride overgrowth based on the Bragg grating. Some groups have reported GaN DFB lasers with high order distributed feedback surface gratings, which avoids the overgrowth. However, generally the strength of coupling is lower than that with Bragg grating embedded into the waveguide within the GaN laser structure by two-step-epitaxy. Therefore, the overgrowth on the grating technology need to be studied and optimized. Here we propose to fabricate the fine step shape structure of first-order grating by the nanoimprint combined inductively coupled plasma (ICP) dry etching, then carry out overgrowth high quality AlGaN film by metalorganic chemical vapor deposition (MOCVD). Then a series of gratings with different period, depths and duty ratios are designed and fabricated to study the influence of grating structure to the nano-heteroepitaxy. Moreover, we observe the nucleation and growth process by step-by-step growth to study the growth mode for nitride overgrowth on grating, under the condition that the grating period is larger than the mental migration length on the surface. The AFM images demonstrate that a smooth surface of AlGaN film is achieved with an average roughness of 0.20 nm over 3 × 3 μm2. The full width at half maximums (FWHMs) of the (002) reflections in the XRD rocking curves are 278 arcsec for the AlGaN film, and the component of the Al within the film is 8% according to the XRD mapping measurement, which is in accordance with design values. By observing the samples with growth time changing from 200s, 400s to 600s, the growth model is summarized as the follow steps: initially, the nucleation is evenly distributed on the grating structure, as the migration length of Al atoms is low; then, AlGaN growth alone with the grating top surface; finally, the AlGaN film formed by lateral growth. This work contributed to carrying out GaN DFB laser by fabricating grating and overgrowth on the nano-grating patterned substrate by wafer scale, moreover, growth dynamics had been analyzed as well.

Keywords: DFB laser, MOCVD, nanoepitaxy, III-niitride

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78 A Laser Instrument Rapid-E+ for Real-Time Measurements of Airborne Bioaerosols Such as Bacteria, Fungi, and Pollen

Authors: Minghui Zhang, Sirine Fkaier, Sabri Fernana, Svetlana Kiseleva, Denis Kiselev

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The real-time identification of bacteria and fungi is difficult because they emit much weaker signals than pollen. In 2020, Plair developed Rapid-E+, which extends abilities of Rapid-E to detect smaller bioaerosols such as bacteria and fungal spores with diameters down to 0.3 µm, while keeping the similar or even better capability for measurements of large bioaerosols like pollen. Rapid-E+ enables simultaneous measurements of (1) time-resolved, polarization and angle dependent Mie scattering patterns, (2) fluorescence spectra resolved in 16 channels, and (3) fluorescence lifetime of individual particles. Moreover, (4) it provides 2D Mie scattering images which give the full information on particle morphology. The parameters of every single bioaerosol aspired into the instrument are subsequently analysed by machine learning. Firstly, pure species of microbes, e.g., Bacillus subtilis (a species of bacteria), and Penicillium chrysogenum (a species of fungal spores), were aerosolized in a bioaerosol chamber for Rapid-E+ training. Afterwards, we tested microbes under different concentrations. We used several steps of data analysis to classify and identify microbes. All single particles were analysed by the parameters of light scattering and fluorescence in the following steps. (1) They were treated with a smart filter block to get rid of non-microbes. (2) By classification algorithm, we verified the filtered particles were microbes based on the calibration data. (3) The probability threshold (defined by the user) step provides the probability of being microbes ranging from 0 to 100%. We demonstrate how Rapid-E+ identified simultaneously microbes based on the results of Bacillus subtilis (bacteria) and Penicillium chrysogenum (fungal spores). By using machine learning, Rapid-E+ achieved identification precision of 99% against the background. The further classification suggests the precision of 87% and 89% for Bacillus subtilis and Penicillium chrysogenum, respectively. The developed algorithm was subsequently used to evaluate the performance of microbe classification and quantification in real-time. The bacteria and fungi were aerosolized again in the chamber with different concentrations. Rapid-E+ can classify different types of microbes and then quantify them in real-time. Rapid-E+ enables classifying different types of microbes and quantifying them in real-time. Rapid-E+ can identify pollen down to species with similar or even better performance than the previous version (Rapid-E). Therefore, Rapid-E+ is an all-in-one instrument which classifies and quantifies not only pollen, but also bacteria and fungi. Based on the machine learning platform, the user can further develop proprietary algorithms for specific microbes (e.g., virus aerosols) and other aerosols (e.g., combustion-related particles that contain polycyclic aromatic hydrocarbons).

Keywords: bioaerosols, laser-induced fluorescence, Mie-scattering, microorganisms

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77 Loss of the Skin Barrier after Dermal Application of the Low Molecular Methyl Siloxanes: Volatile Methyl Siloxanes, VMS Silicones

Authors: D. Glamowska, K. Szymkowska, K. Mojsiewicz- Pieńkowska, K. Cal, Z. Jankowski

Abstract:

Introduction: The integrity of the outermost layer of skin (stratum corneum) is vital to the penetration of various compounds, including toxic substances. Barrier function of skin depends of its structure. The barrier function of the stratum corneum is provided by patterned lipid lamellae (binlayer). However, a lot of substances, including the low molecular methyl siloxanes (volatile methyl siloxanes, VMS) have an impact on alteration the skin barrier due to damage of stratum corneum structure. VMS belong to silicones. They are widely used in the pharmaceutical as well as cosmetic industry. Silicones fulfill the role of ingredient or excipient in medicinal products and the excipient in personal care products. Due to the significant human exposure to this group of compounds, an important aspect is toxicology of the compounds and safety assessment of products. Silicones in general opinion are considered as a non-toxic substances, but there are some data about their negative effect on living organisms through the inhaled or oral application. However, the transdermal route has not been described in the literature as a possible alternative route of penetration. The aim of the study was to verify the possibility of penetration of the stratum corneum, further permeation into the deeper layers of the skin (epidermis and dermis) as well as to the fluid acceptor by VMS. Methods: Research methodology was developed based on the OECD and WHO guidelines. In ex-vivo study, the fluorescence microscope and ATR FT-IR spectroscopy was used. The Franz- type diffusion cells were used to application of the VMS on the sample of human skin (A=0.65 cm) for 24h. The stratum corneum at the application site was tape-stripped. After separation of epidermis, relevant dyes: fluorescein, sulforhodamine B, rhodamine B hexyl ester were put on and observations were carried in the microscope. To confirm the penetration and permeation of the cyclic or linear VMS and thus the presence of silicone in the individual layers of the skin, spectra ATR FT-IR of the sample after application of silicone and H2O (control sample) were recorded. The research included comparison of the intesity of bands in characteristic positions for silicones (1263 cm-1, 1052 cm-1 and 800 cm-1). Results: and Conclusions The results present that cyclic and linear VMS are able to overcome the barrier of the skin. Influence of them on damage of corneocytes of the stratum corneum was observed. This phenomenon was due to distinct disturbances in the lipid structure of the stratum corneum. The presence of cyclic and linear VMS were identified in the stratum corneum, epidermis as well as in the dermis by both fluorescence microscope and ATR FT-IR spectroscopy. This confirms that the cyclic and linear VMS can penetrate to stratum corneum and permeate through the human skin layers. Apart from this they cause changes in the structure of the skin. Results show to possible absorption into the blood and lymphathic vessels by the VMS with linear and cyclic structure.

Keywords: low molecular methyl siloxanes, volatile methyl siloxanes, linear and cyclic siloxanes, skin penetration, skin permeation

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76 Polymer Nanocomposite Containing Silver Nanoparticles for Wound Healing

Authors: Patrícia Severino, Luciana Nalone, Daniele Martins, Marco Chaud, Classius Ferreira, Cristiane Bani, Ricardo Albuquerque

Abstract:

Hydrogels produced with polymers have been used in the development of dressings for wound treatment and tissue revitalization. Our study on polymer nanocomposites containing silver nanoparticles shows antimicrobial activity and applications in wound healing. The effects are linked with the slow oxidation and Ag⁺ liberation to the biological environment. Furthermore, bacterial cell membrane penetration and metabolic disruption through cell cycle disarrangement also contribute to microbial cell death. The silver antimicrobial activity has been known for many years, and previous reports show that low silver concentrations are safe for human use. This work aims to develop a hydrogel using natural polymers (sodium alginate and gelatin) combined with silver nanoparticles for wound healing and with antimicrobial properties in cutaneous lesions. The hydrogel development utilized different sodium alginate and gelatin proportions (20:80, 50:50 and 80:20). The silver nanoparticles incorporation was evaluated at the concentrations of 1.0, 2.0 and 4.0 mM. The physico-chemical properties of the formulation were evaluated using ultraviolet-visible (UV-Vis) absorption spectroscopy, Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), and thermogravimetric (TG) analysis. The morphological characterization was made using transmission electron microscopy (TEM). Human fibroblast (L2929) viability assay was performed with a minimum inhibitory concentration (MIC) assessment as well as an in vivo cicatrizant test. The results suggested that sodium alginate and gelatin in the (80:20) proportion with 4 mM of AgNO₃ in the (UV-Vis) exhibited a better hydrogel formulation. The nanoparticle absorption spectra of this analysis showed a maximum band around 430 - 450 nm, which suggests a spheroidal form. The TG curve exhibited two weight loss events. DSC indicated one endothermic peak at 230-250 °C, due to sample fusion. The polymers acted as stabilizers of a nanoparticle, defining their size and shape. Human fibroblast viability assay L929 gave 105 % cell viability with a negative control, while gelatin presented 96% viability, alginate: gelatin (80:20) 96.66 %, and alginate 100.33 % viability. The sodium alginate:gelatin (80:20) exhibited significant antimicrobial activity, with minimal bacterial growth at a ratio of 1.06 mg.mL⁻¹ in Pseudomonas aeruginosa and 0.53 mg.mL⁻¹ in Staphylococcus aureus. The in vivo results showed a significant reduction in wound surface area. On the seventh day, the hydrogel-nanoparticle formulation reduced the total area of injury by 81.14 %, while control reached a 45.66 % reduction. The results suggest that silver-hydrogel nanoformulation exhibits potential for wound dressing therapeutics.

Keywords: nanocomposite, wound healing, hydrogel, silver nanoparticle

Procedia PDF Downloads 78
75 Graphic Procession Unit-Based Parallel Processing for Inverse Computation of Full-Field Material Properties Based on Quantitative Laser Ultrasound Visualization

Authors: Sheng-Po Tseng, Che-Hua Yang

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Motivation and Objective: Ultrasonic guided waves become an important tool for nondestructive evaluation of structures and components. Guided waves are used for the purpose of identifying defects or evaluating material properties in a nondestructive way. While guided waves are applied for evaluating material properties, instead of knowing the properties directly, preliminary signals such as time domain signals or frequency domain spectra are first revealed. With the measured ultrasound data, inversion calculation can be further employed to obtain the desired mechanical properties. Methods: This research is development of high speed inversion calculation technique for obtaining full-field mechanical properties from the quantitative laser ultrasound visualization system (QLUVS). The quantitative laser ultrasound visualization system (QLUVS) employs a mirror-controlled scanning pulsed laser to generate guided acoustic waves traveling in a two-dimensional target. Guided waves are detected with a piezoelectric transducer located at a fixed location. With a gyro-scanning of the generation source, the QLUVS has the advantage of fast, full-field, and quantitative inspection. Results and Discussions: This research introduces two important tools to improve the computation efficiency. Firstly, graphic procession unit (GPU) with large amount of cores are introduced. Furthermore, combining the CPU and GPU cores, parallel procession scheme is developed for the inversion of full-field mechanical properties based on the QLUVS data. The newly developed inversion scheme is applied to investigate the computation efficiency for single-layered and double-layered plate-like samples. The computation efficiency is shown to be 80 times faster than unparalleled computation scheme. Conclusions: This research demonstrates a high-speed inversion technique for the characterization of full-field material properties based on quantitative laser ultrasound visualization system. Significant computation efficiency is shown, however not reaching the limit yet. Further improvement can be reached by improving the parallel computation. Utilizing the development of the full-field mechanical property inspection technology, full-field mechanical property measured by non-destructive, high-speed and high-precision measurements can be obtained in qualitative and quantitative results. The developed high speed computation scheme is ready for applications where full-field mechanical properties are needed in a nondestructive and nearly real-time way.

Keywords: guided waves, material characterization, nondestructive evaluation, parallel processing

Procedia PDF Downloads 174
74 Evolution of Microstructure through Phase Separation via Spinodal Decomposition in Spinel Ferrite Thin Films

Authors: Nipa Debnath, Harinarayan Das, Takahiko Kawaguchi, Naonori Sakamoto, Kazuo Shinozaki, Hisao Suzuki, Naoki Wakiya

Abstract:

Nowadays spinel ferrite magnetic thin films have drawn considerable attention due to their interesting magnetic and electrical properties with enhanced chemical and thermal stability. Spinel ferrite magnetic films can be implemented in magnetic data storage, sensors, and spin filters or microwave devices. It is well established that the structural, magnetic and transport properties of the magnetic thin films are dependent on microstructure. Spinodal decomposition (SD) is a phase separation process, whereby a material system is spontaneously separated into two phases with distinct compositions. The periodic microstructure is the characteristic feature of SD. Thus, SD can be exploited to control the microstructure at the nanoscale level. In bulk spinel ferrites having general formula, MₓFe₃₋ₓ O₄ (M= Co, Mn, Ni, Zn), phase separation via SD has been reported only for cobalt ferrite (CFO); however, long time post-annealing is required to occur the spinodal decomposition. We have found that SD occurs in CoF thin film without using any post-deposition annealing process if we apply magnetic field during thin film growth. Dynamic Aurora pulsed laser deposition (PLD) is a specially designed PLD system through which in-situ magnetic field (up to 2000 G) can be applied during thin film growth. The in-situ magnetic field suppresses the recombination of ions in the plume. In addition, the peak’s intensity of the ions in the spectra of the plume also increases when magnetic field is applied to the plume. As a result, ions with high kinetic energy strike into the substrate. Thus, ion-impingement occurred under magnetic field during thin film growth. The driving force of SD is the ion-impingement towards the substrates that is induced by in-situ magnetic field. In this study, we report about the occurrence of phase separation through SD and evolution of microstructure after phase separation in spinel ferrite thin films. The surface morphology of the phase separated films show checkerboard like domain structure. The cross-sectional microstructure of the phase separated films reveal columnar type phase separation. Herein, the decomposition wave propagates in lateral direction which has been confirmed from the lateral composition modulations in spinodally decomposed films. Large magnetic anisotropy has been found in spinodally decomposed nickel ferrite (NFO) thin films. This approach approves that magnetic field is also an important thermodynamic parameter to induce phase separation by the enhancement of up-hill diffusion in thin films. This thin film deposition technique could be a more efficient alternative for the fabrication of self-organized phase separated thin films and employed in controlling of the microstructure at nanoscale level.

Keywords: Dynamic Aurora PLD, magnetic anisotropy, spinodal decomposition, spinel ferrite thin film

Procedia PDF Downloads 339
73 Growth and Characterization of Cuprous Oxide (Cu2O) Nanorods by Reactive Ion Beam Sputter Deposition (Ibsd) Method

Authors: Assamen Ayalew Ejigu, Liang-Chiun Chao

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In recent semiconductor and nanotechnology, quality material synthesis, proper characterizations, and productions are the big challenges. As cuprous oxide (Cu2O) is a promising semiconductor material for photovoltaic (PV) and other optoelectronic applications, this study was aimed at to grow and characterize high quality Cu2O nanorods for the improvement of the efficiencies of thin film solar cells and other potential applications. In this study, well-structured cuprous oxide (Cu2O) nanorods were successfully fabricated using IBSD method in which the Cu2O samples were grown on silicon substrates with a substrate temperature of 400°C in an IBSD chamber of pressure of 4.5 x 10-5 torr using copper as a target material. Argon, and oxygen gases were used as a sputter and reactive gases, respectively. The characterization of the Cu2O nanorods (NRs) were done in comparison with Cu2O thin film (TF) deposited with the same method but with different Ar:O2 flow rates. With Ar:O2 ratio of 9:1 single phase pure polycrystalline Cu2O NRs with diameter of ~500 nm and length of ~4.5 µm were grow. Increasing the oxygen flow rates, pure single phase polycrystalline Cu2O thin film (TF) was found at Ar:O2 ratio of 6:1. The field emission electron microscope (FE-SEM) measurements showed that both samples have smooth morphologies. X-ray diffraction and Rama scattering measurements reveals the presence of single phase Cu2O in both samples. The differences in Raman scattering and photoluminescence (PL) bands of the two samples were also investigated and the results showed us there are differences in intensities, in number of bands and in band positions. Raman characterization shows that the Cu2O NRs sample has pronounced Raman band intensities, higher numbers of Raman bands than the Cu2O TF which has only one second overtone Raman signal at 2 (217 cm-1). The temperature dependent photoluminescence (PL) spectra measurements, showed that the defect luminescent band centered at 720 nm (1.72 eV) is the dominant one for the Cu2O NRs and the 640 nm (1.937 eV) band was the only PL band observed from the Cu2O TF. The difference in optical and structural properties of the samples comes from the oxygen flow rate change in the process window of the samples deposition. This gave us a roadmap for further investigation of the electrical and other optical properties for the tunable fabrication of the Cu2O nano/micro structured sample for the improvement of the efficiencies of thin film solar cells in addition to other potential applications. Finally, the novel morphologies, excellent structural and optical properties seen exhibits the grown Cu2O NRs sample has enough quality to be used in further research of the nano/micro structured semiconductor materials.

Keywords: defect levels, nanorods, photoluminescence, Raman modes

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72 MXene Mediated Layered 2D-3D-2D g-C3N4@WO3@Ti3C2 Multijunctional Heterostructure with Enhanced Photoelectrochemical and Photocatalytic Properties

Authors: Lekgowa Collen Makola, Cecil Naphtaly Moro Ouma, Sharon Moeno, Langelihle Dlamini

Abstract:

In recent years, advancement in the field of nanotechnology has evolved new strategies to address energy and environmental issues. Amongst the developing technologies, visible-light-driven photocatalysis is regarded as a sustainable approach for energy production and environmental detoxifications, where transition metal oxides (TMOs) and metal-free carbon-based semiconductors such as graphitic carbon nitride (CN) evidenced notable potential in this matter. Herein, g-C₃N₄@WO₃@Ti₃C₂Tx three-component multijunction photocatalyst was fabricated via facile ultrasonic-assisted self-assembly, followed by calcination to facilitate extensive integrations of the materials. A series of different Ti₃C₂ wt% loading in the g-C₃N4@WO₃@Ti₃C₂Tx were prepared and represented as 1-CWT, 3-CWT, 5-CWT, and 7-CWT corresponding to 1, 3, 5, and 7wt%, respectively. Systematic characterization using spectroscopic and microscopic techniques were employed to validate the successful preparation of the photocatalysts. Enhanced optoelectronic and photoelectrochemical properties were observed for the WO₃@Ti₃C2@g-C₃N4 heterostructure with respect to the individual materials. Photoluminescence spectra and Nyquist plots show restrained recombination rates and improved photocarrier conductivities, respectively, and this was credited to the synergistic coupling effect and the presence of highly conductive Ti₃C2 MXene. The strong interfacial contact surfaces upon the formation of the composite were confirmed using XPS. Multiple charge transfer mechanisms were proposed for the WO3@Ti3C₂@g-C3N4, which couples Z-scheme and Schottky-junction mediated with Ti3C2 MXene. Bode phase plots show improved charge carrier life-times upon the formation of the multijunctional photocatalyst. Moreover, transient photocurrent density of 7-CWT is 40 and seven (7) times higher compared to that of g-C₃N4 and WO3, correspondingly. Unlike in the traditional Z-Scheme, the formed ternary heterostructure possesses interfaces through the metallic 2D Ti₃C₂ MXene, which provided charge transfer channels for efficient photocarrier transfers with carrier concentrations (ND) of 17.49×1021 cm-3 and 4.86% photo-to-chemical conversion efficiency. The as-prepared ternary g-C₃N₄@WO₃@Ti₃C₂Tx exhibited excellent photoelectrochemical properties with reserved redox band potential potencies to facilitate efficient photo-oxidation and -reduction reactions. The fabricated multijunction photocatalyst exhibits potentials to be used in an extensive range of photocatalytic process vis., production of valuable hydrocarbons from CO₂, production of H₂, and degradation of a plethora of pollutants from wastewater.

Keywords: photocatalysis, Z-scheme, multijunction heterostructure, Ti₃C₂ MXene, g-C₃N₄

Procedia PDF Downloads 78
71 The Direct Deconvolution Model for the Large Eddy Simulation of Turbulence

Authors: Ning Chang, Zelong Yuan, Yunpeng Wang, Jianchun Wang

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Large eddy simulation (LES) has been extensively used in the investigation of turbulence. LES calculates the grid-resolved large-scale motions and leaves small scales modeled by sub lfilterscale (SFS) models. Among the existing SFS models, the deconvolution model has been used successfully in the LES of the engineering flows and geophysical flows. Despite the wide application of deconvolution models, the effects of subfilter scale dynamics and filter anisotropy on the accuracy of SFS modeling have not been investigated in depth. The results of LES are highly sensitive to the selection of fi lters and the anisotropy of the grid, which has been overlooked in previous research. In the current study, two critical aspects of LES are investigated. Firstly, we analyze the influence of sub-fi lter scale (SFS) dynamics on the accuracy of direct deconvolution models (DDM) at varying fi lter-to-grid ratios (FGR) in isotropic turbulence. An array of invertible filters are employed, encompassing Gaussian, Helmholtz I and II, Butterworth, Chebyshev I and II, Cauchy, Pao, and rapidly decaying filters. The signi ficance of FGR becomes evident, as it acts as a pivotal factor in error control for precise SFS stress prediction. When FGR is set to 1, the DDM models cannot accurately reconstruct the SFS stress due to the insufficient resolution of SFS dynamics. Notably, prediction capabilities are enhanced at an FGR of 2, resulting in accurate SFS stress reconstruction, except for cases involving Helmholtz I and II fi lters. A remarkable precision close to 100% is achieved at an FGR of 4 for all DDM models. Additionally, the further exploration extends to the fi lter anisotropy to address its impact on the SFS dynamics and LES accuracy. By employing dynamic Smagorinsky model (DSM), dynamic mixed model (DMM), and direct deconvolution model (DDM) with the anisotropic fi lter, aspect ratios (AR) ranging from 1 to 16 in LES fi lters are evaluated. The findings highlight the DDM's pro ficiency in accurately predicting SFS stresses under highly anisotropic filtering conditions. High correlation coefficients exceeding 90% are observed in the a priori study for the DDM's reconstructed SFS stresses, surpassing those of the DSM and DMM models. However, these correlations tend to decrease as lter anisotropy increases. In the a posteriori studies, the DDM model consistently outperforms the DSM and DMM models across various turbulence statistics, encompassing velocity spectra, probability density functions related to vorticity, SFS energy flux, velocity increments, strain-rate tensors, and SFS stress. It is observed that as fi lter anisotropy intensify , the results of DSM and DMM become worse, while the DDM continues to deliver satisfactory results across all fi lter-anisotropy scenarios. The fi ndings emphasize the DDM framework's potential as a valuable tool for advancing the development of sophisticated SFS models for LES of turbulence.

Keywords: deconvolution model, large eddy simulation, subfilter scale modeling, turbulence

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70 Study of Chemical State Analysis of Rubidium Compounds in Lα, Lβ₁, Lβ₃,₄ and Lγ₂,₃ X-Ray Emission Lines with Wavelength Dispersive X-Ray Fluorescence Spectrometer

Authors: Harpreet Singh Kainth

Abstract:

Rubidium salts have been commonly used as an electrolyte to improve the efficiency cycle of Li-ion batteries. In recent years, it has been implemented into the large scale for further technological advances to improve the performance rate and better cyclability in the batteries. X-ray absorption spectroscopy (XAS) is a powerful tool for obtaining the information in the electronic structure which involves the chemical state analysis in the active materials used in the batteries. However, this technique is not well suited for the industrial applications because it needs a synchrotron X-ray source and special sample file for in-situ measurements. In contrast to this, conventional wavelength dispersive X-ray fluorescence (WDXRF) spectrometer is nondestructive technique used to study the chemical shift in all transitions (K, L, M, …) and does not require any special pre-preparation planning. In the present work, the fluorescent Lα, Lβ₁ , Lβ₃,₄ and Lγ₂,₃ X-ray spectra of rubidium in different chemical forms (Rb₂CO₃ , RbCl, RbBr, and RbI) have been measured first time with high resolution wavelength dispersive X-ray fluorescence (WDXRF) spectrometer (Model: S8 TIGER, Bruker, Germany), equipped with an Rh anode X-ray tube (4-kW, 60 kV and 170 mA). In ₃₇Rb compounds, the measured energy shifts are in the range (-0.45 to - 1.71) eV for Lα X-ray peak, (0.02 to 0.21) eV for Lβ₁ , (0.04 to 0.21) eV for Lβ₃ , (0.15 to 0.43) eV for Lβ₄ and (0.22 to 0.75) eV for Lγ₂,₃ X-ray emission lines. The chemical shifts in rubidium compounds have been measured by considering Rb₂CO₃ compounds taking as a standard reference. A Voigt function is used to determine the central peak position of all compounds. Both positive and negative shifts have been observed in L shell emission lines. In Lα X-ray emission lines, all compounds show negative shift while in Lβ₁, Lβ₃,₄, and Lγ₂,₃ X-ray emission lines, all compounds show a positive shift. These positive and negative shifts result increase or decrease in X-ray energy shifts. It looks like that ligands attached with central metal atom attract or repel the electrons towards or away from the parent nucleus. This pulling and pushing character of rubidium affects the central peak position of the compounds which causes a chemical shift. To understand the chemical effect more briefly, factors like electro-negativity, line intensity ratio, effective charge and bond length are responsible for the chemical state analysis in rubidium compounds. The effective charge has been calculated from Suchet and Pauling method while the line intensity ratio has been calculated by calculating the area under the relevant emission peak. In the present work, it has been observed that electro-negativity, effective charge and intensity ratio (Lβ₁/Lα, Lβ₃,₄/Lα and Lγ₂,₃/Lα) are inversely proportional to the chemical shift (RbCl > RbBr > RbI), while bond length has been found directly proportional to the chemical shift (RbI > RbBr > RbCl).

Keywords: chemical shift in L emission lines, bond length, electro-negativity, effective charge, intensity ratio, Rubidium compounds, WDXRF spectrometer

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69 Tailoring Quantum Oscillations of Excitonic Schrodinger’s Cats as Qubits

Authors: Amit Bhunia, Mohit Kumar Singh, Maryam Al Huwayz, Mohamed Henini, Shouvik Datta

Abstract:

We report [https://arxiv.org/abs/2107.13518] experimental detection and control of Schrodinger’s Cat like macroscopically large, quantum coherent state of a two-component Bose-Einstein condensate of spatially indirect electron-hole pairs or excitons using a resonant tunneling diode of III-V Semiconductors. This provides access to millions of excitons as qubits to allow efficient, fault-tolerant quantum computation. In this work, we measure phase-coherent periodic oscillations in photo-generated capacitance as a function of an applied voltage bias and light intensity over a macroscopically large area. Periodic presence and absence of splitting of excitonic peaks in the optical spectra measured by photocapacitance point towards tunneling induced variations in capacitive coupling between the quantum well and quantum dots. Observation of negative ‘quantum capacitance’ due to a screening of charge carriers by the quantum well indicates Coulomb correlations of interacting excitons in the plane of the sample. We also establish that coherent resonant tunneling in this well-dot heterostructure restricts the available momentum space of the charge carriers within this quantum well. Consequently, the electric polarization vector of the associated indirect excitons collective orients along the direction of applied bias and these excitons undergo Bose-Einstein condensation below ~100 K. Generation of interference beats in photocapacitance oscillation even with incoherent white light further confirm the presence of stable, long-range spatial correlation among these indirect excitons. We finally demonstrate collective Rabi oscillations of these macroscopically large, ‘multipartite’, two-level, coupled and uncoupled quantum states of excitonic condensate as qubits. Therefore, our study not only brings the physics and technology of Bose-Einstein condensation within the reaches of semiconductor chips but also opens up experimental investigations of the fundamentals of quantum physics using similar techniques. Operational temperatures of such two-component excitonic BEC can be raised further with a more densely packed, ordered array of QDs and/or using materials having larger excitonic binding energies. However, fabrications of single crystals of 0D-2D heterostructures using 2D materials (e.g. transition metal di-chalcogenides, oxides, perovskites etc.) having higher excitonic binding energies are still an open challenge for semiconductor optoelectronics. As of now, these 0D-2D heterostructures can already be scaled up for mass production of miniaturized, portable quantum optoelectronic devices using the existing III-V and/or Nitride based semiconductor fabrication technologies.

Keywords: exciton, Bose-Einstein condensation, quantum computation, heterostructures, semiconductor Physics, quantum fluids, Schrodinger's Cat

Procedia PDF Downloads 156
68 An Automated Magnetic Dispersive Solid-Phase Extraction Method for Detection of Cocaine in Human Urine

Authors: Feiyu Yang, Chunfang Ni, Rong Wang, Yun Zou, Wenbin Liu, Chenggong Zhang, Fenjin Sun, Chun Wang

Abstract:

Cocaine is the most frequently used illegal drug globally, with the global annual prevalence of cocaine used ranging from 0.3% to 0.4 % of the adult population aged 15–64 years. Growing consumption trend of abused cocaine and drug crimes are a great concern, therefore urine sample testing has become an important noninvasive sampling whereas cocaine and its metabolites (COCs) are usually present in high concentrations and relatively long detection windows. However, direct analysis of urine samples is not feasible because urine complex medium often causes low sensitivity and selectivity of the determination. On the other hand, presence of low doses of analytes in urine makes an extraction and pretreatment step important before determination. Especially, in gathered taking drug cases, the pretreatment step becomes more tedious and time-consuming. So developing a sensitive, rapid and high-throughput method for detection of COCs in human body is indispensable for law enforcement officers, treatment specialists and health officials. In this work, a new automated magnetic dispersive solid-phase extraction (MDSPE) sampling method followed by high performance liquid chromatography-mass spectrometry (HPLC-MS) was developed for quantitative enrichment of COCs from human urine, using prepared magnetic nanoparticles as absorbants. The nanoparticles were prepared by silanizing magnetic Fe3O4 nanoparticles and modifying them with divinyl benzene and vinyl pyrrolidone, which possesses the ability for specific adsorption of COCs. And this kind of magnetic particle facilitated the pretreatment steps by electromagnetically controlled extraction to achieve full automation. The proposed device significantly improved the sampling preparation efficiency with 32 samples in one batch within 40mins. Optimization of the preparation procedure for the magnetic nanoparticles was explored and the performances of magnetic nanoparticles were characterized by scanning electron microscopy, vibrating sample magnetometer and infrared spectra measurements. Several analytical experimental parameters were studied, including amount of particles, adsorption time, elution solvent, extraction and desorption kinetics, and the verification of the proposed method was accomplished. The limits of detection for the cocaine and cocaine metabolites were 0.09-1.1 ng·mL-1 with recoveries ranging from 75.1 to 105.7%. Compared to traditional sampling method, this method is time-saving and environmentally friendly. It was confirmed that the proposed automated method was a kind of highly effective way for the trace cocaine and cocaine metabolites analyses in human urine.

Keywords: automatic magnetic dispersive solid-phase extraction, cocaine detection, magnetic nanoparticles, urine sample testing

Procedia PDF Downloads 171
67 Comparison of Equivalent Linear and Non-Linear Site Response Model Performance in Kathmandu Valley

Authors: Sajana Suwal, Ganesh R. Nhemafuki

Abstract:

Evaluation of ground response under earthquake shaking is crucial in geotechnical earthquake engineering. Damage due to seismic excitation is mainly correlated to local geological and geotechnical conditions. It is evident from the past earthquakes (e.g. 1906 San Francisco, USA, 1923 Kanto, Japan) that the local geology has strong influence on amplitude and duration of ground motions. Since then significant studies has been conducted on ground motion amplification revealing the importance of influence of local geology on ground. Observations from the damaging earthquakes (e.g. Nigata and San Francisco, 1964; Irpinia, 1980; Mexico, 1985; Kobe, 1995; L’Aquila, 2009) divulged that non-uniform damage pattern, particularly in soft fluvio-lacustrine deposit is due to the local amplification of seismic ground motion. Non-uniform damage patterns are also observed in Kathmandu Valley during 1934 Bihar Nepal earthquake and recent 2015 Gorkha earthquake seemingly due to the modification of earthquake ground motion parameters. In this study, site effects resulting from amplification of soft soil in Kathmandu are presented. A large amount of subsoil data was collected and used for defining the appropriate subsoil model for the Kathamandu valley. A comparative study of one-dimensional total-stress equivalent linear and non-linear site response is performed using four strong ground motions for six sites of Kathmandu valley. In general, one-dimensional (1D) site-response analysis involves the excitation of a soil profile using the horizontal component and calculating the response at individual soil layers. In the present study, both equivalent linear and non-linear site response analyses were conducted using the computer program DEEPSOIL. The results show that there is no significant deviation between equivalent linear and non-linear site response models until the maximum strain reaches to 0.06-0.1%. Overall, it is clearly observed from the results that non-linear site response model perform better as compared to equivalent linear model. However, the significant deviation between two models is resulted from other influencing factors such as assumptions made in 1D site response, lack of accurate values of shear wave velocity and nonlinear properties of the soil deposit. The results are also presented in terms of amplification factors which are predicted to be around four times more in case of non-linear analysis as compared to equivalent linear analysis. Hence, the nonlinear behavior of soil prevails the urgent need of study of dynamic characteristics of the soft soil deposit that can specifically represent the site-specific design spectra for the Kathmandu valley for building resilient structures from future damaging earthquakes.

Keywords: deep soil, equivalent linear analysis, non-linear analysis, site response

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66 Iron Doping Enhanced Photocatalytic Nitrogen Fixation Performance of WO₃ with Three-Dimensionally Orderd Macroporous Structure

Authors: Xiaoling Ren, Guidong Yang

Abstract:

Ammonia, as one of the largest-volume industrial chemicals, is mostly produced by century-old Haber-Bosch process with extreme conditionsand high-cost. Under the circumstance, researchersarededicated in finding new ways to replace the Haber-Bosch process. Photocatalytic nitrogen fixation is a promising sustainable, clear and green strategy for ammonia synthesis, butit is still a big challenge due to the high activation energy for nitrogen. It is essential to develop an efficient photocatalyst for making this approach industrial application. Constructing chemisorption active sites through defect engineering can be defined as an effective and reliable means to improve nitrogen activation by forming the extraordinary coordination environment and electronic structure. Besides, the construction of three-dimensionally orderdmacroporous (3DOM) structured photocatalyst is considered to be one of effectivestrategiesto improve the activity due to it canincrease the diffusion rate of reactants in the interior, which isbeneficial to the mass transfer process of nitrogen molecules in photocatalytic nitrogen reduction. Herein, Fe doped 3DOM WO₃(Fe-3DOM WO₃) without noble metal cocatalysts is synthesized by a polystyrene-template strategy, which is firstly used for photocatalytic nitrogen fixation. To elucidate the chemical nature of the dopant, the X-ray diffraction (XRD) analysiswas conducted. The pure 3DOM WO₃ has a monoclinic type crystal structure. And no additional peak is observed in Fe doped 3DOM WO₃, indicating that the incorporation of Fe atoms did not result in a secondary phase formation. In order to confirm the morphologies of Fe-3DOM WO₃and 3DOM WO₃, scanning electron microscopy (SEM) was employed. The synthesized Fe-3DOM WO₃and 3DOM WO₃ both exhibit a highly ordered three dimensional inverse opal structure with interconnected pores. From high-resolution TEM image of Fe-3DOM WO₃, the ordered lattice fringes with a spacing of 3.84 Å can be assigned to the (001) plane of WO₃, which is consistent with the XRD results. Finally, the photocatalytic nitrogen reduction performance of 3DOM WO₃ and Fe doped 3DOM WO₃with various Fe contents were examined. As a result, both Fe-3DOM WO₃ samples achieve higher ammonia production rate than that of pure 3DOM WO₃, indicating that the doped Fe plays a critical role in the photocatalytic nitrogen fixation performance. To verify the reaction process upon N2 reduction on the Fe-3DOM WO₃, in-situ diffuse reflectance infrared Fourier-transform spectroscopy was employed to monitor the intermediates. The in-situ DRIFTS spectra of Fe-3DOM WO₃ exhibit the increased signals with the irradiation time from 0–60min in the N2 atmosphere. The above results prove that nitrogen is gradually hydrogenated to produce ammonia over Fe-3DOM WO₃. Thiswork would enrich our knowledge in designing efficient photocatalystsfor photocatalytic nitrogen reduction.

Keywords: ammonia, photocatalytic, nitrogen fixation, Fe doped 3DOM WO₃

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65 Preparation, Solid State Characterization of Etraverine Co-Crystals with Improved Solubility for the Treatment of Human Immunodeficiency Virus

Authors: B. S. Muddukrishna, Karthik Aithal, Aravind Pai

Abstract:

Introduction: Preparation of binary cocrystals of Etraverine (ETR) by using Tartaric Acid (TAR) as a conformer was the main focus of this study. Etravirine is a Class IV drug, as per the BCS classification system. Methods: Cocrystals were prepared by slow evaporation technique. A mixture of total 500mg of ETR: TAR was weighed in molar ratios of 1:1 (371.72mg of ETR and 128.27mg of TAR). Saturated solution of Etravirine was prepared in Acetone: Methanol (50:50) mixture in which tartaric acid is dissolved by sonication and then this solution was stirred using a magnetic stirrer until the solvent got evaporated. Shimadzu FTIR – 8300 system was used to acquire the FTIR spectra of the cocrystals prepared. Shimadzu thermal analyzer was used to achieve DSC measurements. X-ray diffractometer was used to obtain the X-ray powder diffraction pattern. Shake flask method was used to determine the equilibrium dynamic solubility of pure, physical mixture and cocrystals of ETR. USP buffer (pH 6.8) containing 1% of Tween 80 was used as the medium. The pure, physical mixture and the optimized cocrystal of ETR were accurately weighed sufficient to maintain the sink condition and were filled in hard gelatine capsules (size 4). Electrolab-Tablet Dissolution tester using basket apparatus at a rotational speed of 50 rpm and USP phosphate buffer (900 mL, pH = 6.8, 37 ˚C) + 1% Tween80 as a media, was used to carry out dissolution. Shimadzu LC-10 series chromatographic system was used to perform the analysis with PDA detector. An Hypersil BDS C18 (150mm ×4.6 mm ×5 µm) column was used for separation with mobile phase comprising of a mixture of ace¬tonitrile and phosphate buffer 20mM, pH 3.2 in the ratio 60:40 v/v. The flow rate was 1.0mL/min and column temperature was set to 30°C. The detection was carried out at 304 nm for ETR. Results and discussions: The cocrystals were subjected to various solid state characterization and the results confirmed the formation of cocrystals. The C=O stretching vibration (1741cm-1) in tartaric acid was disappeared in the cocrystal and the peak broadening of primary amine indicates hydrogen bond formation. The difference in the melting point of cocrystals when compared to pure Etravirine (265 °C) indicates interaction between the drug and the coformer which proves that first ordered transformation i.e. melting endotherm has disappeared. The difference in 2θ values of pure drug and cocrystals indicates the interaction between the drug and the coformer. Dynamic solubility and dissolution studies were also conducted by shake flask method and USP apparatus one respectively and 3.6 fold increase in the dynamic solubility were observed and in-vitro dissolution study shows four fold increase in the solubility for the ETR: TAR (1:1) cocrystals. The ETR: TAR (1:1) cocrystals shows improved solubility and dissolution as compared to the pure drug which was clearly showed by solid state characterization and dissolution studies.

Keywords: dynamic solubility, Etraverine, in vitro dissolution, slurry method

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64 Characteristics of Bio-hybrid Hydrogel Materials with Prolonged Release of the Model Active Substance as Potential Wound Dressings

Authors: Katarzyna Bialik-Wąs, Klaudia Pluta, Dagmara Malina, Małgorzata Miastkowska

Abstract:

In recent years, biocompatible hydrogels have been used more and more in medical applications, especially as modern dressings and drug delivery systems. The main goal of this research was the characteristics of bio-hybrid hydrogel materials incorporated with the nanocarrier-drug system, which enable the release in a gradual and prolonged manner, up to 7 days. Therefore, the use of such a combination will provide protection against mechanical damage and adequate hydration. The proposed bio-hybrid hydrogels are characterized by: transparency, biocompatibility, good mechanical strength, and the dual release system, which allows for gradual delivery of the active substance, even up to 7 days. Bio-hybrid hydrogels based on sodium alginate (SA), poly(vinyl alcohol) (PVA), glycerine, and Aloe vera solution (AV) were obtained through the chemical crosslinking method using poly(ethylene glycol) diacrylate as a crosslinking agent. Additionally, a nanocarrier-drug system was incorporated into SA/PVA/AV hydrogel matrix. Here, studies were focused on the release profiles of active substances from bio-hybrid hydrogels using the USP4 method (DZF II Flow-Through System, Erweka GmbH, Langen, Germany). The equipment incorporated seven in-line flow-through diffusion cells. The membrane was placed over support with an orifice of 1,5 cm in diameter (diffusional area, 1.766 cm²). All the cells were placed in a cell warmer connected with the Erweka heater DH 2000i and the Erweka piston pump HKP 720. The piston pump transports the receptor fluid via seven channels to the flow-through cells and automatically adapts the setting of the flow rate. All volumes were measured by gravimetric methods by filling the chambers with Milli-Q water and assuming a density of 1 g/ml. All the determinations were made in triplicate for each cell. The release study of the model active substance was carried out using a regenerated cellulose membrane Spectra/Por®Dialysis Membrane MWCO 6-8,000 Carl Roth® Company. These tests were conducted in buffer solutions – PBS at pH 7.4. A flow rate of receptor fluid of about 4 ml /1 min was selected. The experiments were carried out for 7 days at a temperature of 37°C. The released concentration of the model drug in the receptor solution was analyzed using UV-Vis spectroscopy (Perkin Elmer Company). Additionally, the following properties of the modified materials were studied: physicochemical, structural (FT-IR analysis), morphological (SEM analysis). Finally, the cytotoxicity tests using in vitro method were conducted. The obtained results exhibited that the dual release system allows for the gradual and prolonged delivery of the active substances, even up to 7 days.

Keywords: wound dressings, SA/PVA hydrogels, nanocarrier-drug system, USP4 method

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63 Irradion: Portable Small Animal Imaging and Irradiation Unit

Authors: Josef Uher, Jana Boháčová, Richard Kadeřábek

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In this paper, we present a multi-robot imaging and irradiation research platform referred to as Irradion, with full capabilities of portable arbitrary path computed tomography (CT). Irradion is an imaging and irradiation unit entirely based on robotic arms for research on cancer treatment with ion beams on small animals (mice or rats). The platform comprises two subsystems that combine several imaging modalities, such as 2D X-ray imaging, CT, and particle tracking, with precise positioning of a small animal for imaging and irradiation. Computed Tomography: The CT subsystem of the Irradion platform is equipped with two 6-joint robotic arms that position a photon counting detector and an X-ray tube independently and freely around the scanned specimen and allow image acquisition utilizing computed tomography. Irradiation measures nearly all conventional 2D and 3D trajectories of X-ray imaging with precisely calibrated and repeatable geometrical accuracy leading to a spatial resolution of up to 50 µm. In addition, the photon counting detectors allow X-ray photon energy discrimination, which can suppress scattered radiation, thus improving image contrast. It can also measure absorption spectra and recognize different materials (tissue) types. X-ray video recording and real-time imaging options can be applied for studies of dynamic processes, including in vivo specimens. Moreover, Irradion opens the door to exploring new 2D and 3D X-ray imaging approaches. We demonstrate in this publication various novel scan trajectories and their benefits. Proton Imaging and Particle Tracking: The Irradion platform allows combining several imaging modules with any required number of robots. The proton tracking module comprises another two robots, each holding particle tracking detectors with position, energy, and time-sensitive sensors Timepix3. Timepix3 detectors can track particles entering and exiting the specimen and allow accurate guiding of photon/ion beams for irradiation. In addition, quantifying the energy losses before and after the specimen brings essential information for precise irradiation planning and verification. Work on the small animal research platform Irradion involved advanced software and hardware development that will offer researchers a novel way to investigate new approaches in (i) radiotherapy, (ii) spectral CT, (iii) arbitrary path CT, (iv) particle tracking. The robotic platform for imaging and radiation research developed for the project is an entirely new product on the market. Preclinical research systems with precision robotic irradiation with photon/ion beams combined with multimodality high-resolution imaging do not exist currently. The researched technology can potentially cause a significant leap forward compared to the current, first-generation primary devices.

Keywords: arbitrary path CT, robotic CT, modular, multi-robot, small animal imaging

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62 2,7-Diazaindole as a Photophysical Probe for Excited State Hydrogen/Proton Transfer

Authors: Simran Baweja, Bhavika Kalal, Surajit Maity

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Photoinduced tautomerization reactions have been the centre of attention among the scientific community over the past several decades because of their significance in various biological systems. 7-azaindole (7AI) is considered a model system for DNA base pairing and to understand the role of such tautomerization reactions in mutations. To the best of our knowledge, extensive studies have been carried out on 7-azaindole and its solvent clusters exhibiting proton/ hydrogen transfer in both solution as well as gas phases. Derivatives of the above molecule, like 2,7- and 2,6-diazaindoles are proposed to have even better photophysical properties due to the presence of -aza group on the 2nd position. However, there are studies in the solution phase that suggest the relevance of these molecules, but there are no experimental studies reported in the gas phase yet. In our current investigation, we present the first gas phase spectroscopic data of 2,7-diazaindole (2,7-DAI) and its solvent cluster (2,7-DAI-H2O). In this, we have employed state-of-the-art laser spectroscopic methods such as fluorescence excitation (LIF), dispersed fluorescence (DF), resonant two-photon ionization-time of flight mass spectrometry (2C-R2PI), photoionization efficiency spectroscopy (PIE), IR-UV double resonance spectroscopy, i.e., fluorescence-dip infrared spectroscopy (FDIR) and resonant ion-dip infrared spectroscopy (IDIR) to understand the electronic structure of the molecule. The origin band corresponding to the S1 ← S0 transition of the bare 2,7-DAI is found to be positioned at 33910 cm-1, whereas the origin band corresponding to S1 ← S0 transition of the 2,7-DAI-H2O is positioned at 33074 cm-1. The red-shifted transition in the case of solvent cluster suggests the enhanced feasibility of excited state hydrogen/ proton transfer. The ionization potential for the 2,7-DAI molecule is found to be 8.92 eV which is significantly higher than the previously reported 7AI (8.11 eV) molecule, making it a comparatively complex molecule to study. The ionization potential is reduced by 0.14 eV in the case of 2,7-DAI-H2O (8.78 eV) cluster compared to that of 2,7-DAI. Moreover, on comparison with the available literature values of 7AI, we found the origin band of 2,7-DAI and 2,7-DAI-H2O to be red-shifted by -729 and -280 cm-1 respectively. The ground and excited state N-H stretching frequencies of the 27DAI molecule were determined using fluorescence-dip infrared spectra (FDIR) and resonant ion dip infrared spectroscopy (IDIR), obtained at 3523 and 3467 cm-1, respectively. The lower value of vNH in the electronically excited state of 27DAI implies the higher acidity of the group compared to the ground state. Moreover, we have done extensive computational analysis, which suggests that the energy barrier in the excited state reduces significantly as we increase the number of catalytic solvent molecules (S= H2O, NH3) as well as the polarity of solvent molecules. We found that the ammonia molecule is a better candidate for hydrogen transfer compared to water because of its higher gas-phase basicity. Further studies are underway to understand the excited state dynamics and photochemistry of such N-rich chromophores.

Keywords: excited state hydrogen transfer, supersonic expansion, gas phase spectroscopy, IR-UV double resonance spectroscopy, laser induced fluorescence, photoionization efficiency spectroscopy

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61 Primary-Color Emitting Photon Energy Storage Nanophosphors for Developing High Contrast Latent Fingerprints

Authors: G. Swati, D. Haranath

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Commercially available long afterglow /persistent phosphors are proprietary materials and hence the exact composition and phase responsible for their luminescent characteristics such as initial intensity and afterglow luminescence time are not known. Further to generate various emission colors, commercially available persistence phosphors are physically blended with fluorescent organic dyes such as rodhamine, kiton and methylene blue etc. Blending phosphors with organic dyes results into complete color coverage in visible spectra, however with time, such phosphors undergo thermal and photo-bleaching. This results in the loss of their true emission color. Hence, the current work is dedicated studies on inorganic based thermally and chemically stable primary color emitting nanophosphors namely SrAl2O4:Eu2+, Dy3+, (CaZn)TiO3:Pr3+, and Sr2MgSi2O7:Eu2+, Dy3+. SrAl2O4: Eu2+, Dy3+ phosphor exhibits a strong excitation in UV and visible region (280-470 nm) with a broad emission peak centered at 514 nm is the characteristic emission of parity allowed 4f65d1→4f7 transitions of Eu2+ (8S7/2→2D5/2). Sunlight excitable Sr2MgSi2O7:Eu2+,Dy3+ nanophosphors emits blue color (464 nm) with Commercial international de I’Eclairage (CIE) coordinates to be (0.15, 0.13) with a color purity of 74 % with afterglow time of > 5 hours for dark adapted human eyes. (CaZn)TiO3:Pr3+ phosphor system possess high color purity (98%) which emits intense, stable and narrow red emission at 612 nm due intra 4f transitions (1D2 → 3H4) with afterglow time of 0.5 hour. Unusual property of persistence luminescence of these nanophoshphors supersedes background effects without losing sensitive information these nanophosphors offer several advantages of visible light excitation, negligible substrate interference, high contrast bifurcation of ridge pattern, non-toxic nature revealing finger ridge details of the fingerprints. Both level 1 and level 2 features from a fingerprint can be studied which are useful for used classification, indexing, comparison and personal identification. facile methodology to extract high contrast fingerprints on non-porous and porous substrates using a chemically inert, visible light excitable, and nanosized phosphorescent label in the dark has been presented. The chemistry of non-covalent physisorption interaction between the long afterglow phosphor powder and sweat residue in fingerprints has been discussed in detail. Real-time fingerprint development on porous and non-porous substrates has also been performed. To conclude, apart from conventional dark vision applications, as prepared primary color emitting afterglow phosphors are potentional candidate for developing high contrast latent fingerprints.

Keywords: fingerprints, luminescence, persistent phosphors, rare earth

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60 Electroactive Fluorene-Based Polymer Films Obtained by Electropolymerization

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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59 Composition and Catalytic Behaviour of Biogenic Iron Containing Materials Obtained by Leptothrix Bacteria Cultivation in Different Growth Media

Authors: M. Shopska, D. Paneva, G. Kadinov, Z. Cherkezova-Zheleva, I. Mitov

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The iron containing materials are used as catalysts in different processes. The chemical methods of their synthesis use toxic and expensive chemicals; sophisticated devices; energy consumption processes that raise their cost. Besides, dangerous waste products are formed. At present time such syntheses are out of date and wasteless technologies are indispensable. The bioinspired technologies are consistent with the ecological requirements. Different microorganisms participate in the biomineralization of the iron and some phytochemicals are involved, too. The methods for biogenic production of iron containing materials are clean, simple, nontoxic, realized at ambient temperature and pressure, cheaper. The biogenic iron materials embrace different iron compounds. Due to their origin these substances are nanosized, amorphous or poorly crystalline, porous and have number of useful properties like SPM, high magnetism, low toxicity, biocompatibility, absorption of microwaves, high surface area/volume ratio, active sites on the surface with unusual coordination that distinguish them from the bulk materials. The biogenic iron materials are applied in the heterogeneous catalysis in different roles - precursor, active component, support, immobilizer. The application of biogenic iron oxide materials gives rise to increased catalytic activity in comparison with those of abiotic origin. In our study we investigated the catalytic behavior of biomasses obtained by cultivation of Leptothrix bacteria in three nutrition media – Adler, Fedorov, and Lieske. The biomass composition was studied by Moessbauer spectroscopy and transmission IRS. Catalytic experiments on CO oxidation were carried out using in situ DRIFTS. Our results showed that: i) the used biomasses contain α-FeOOH, γ-FeOOH, γ-Fe2O3 in different ratios; ii) the biomass formed in Adler medium contains γ-FeOOH as main phase. The CO conversion was about 50% as evaluated by decreased integrated band intensity in the gas mixture spectra during the reaction. The main phase in the spent sample is γ-Fe2O3; iii) the biomass formed in Lieske medium contains α-FeOOH. The CO conversion was about 20%. The main phase in the spent sample is α-Fe2O3; iv) the biomass formed in Fedorov medium contains γ-Fe2O3 as main phase. CO conversion in the test reaction was about 19%. The results showed that the catalytic activity up to 200°C resulted predominantly from α-FeOOH and γ-FeOOH. The catalytic activity at temperatures higher than 200°C was due to the formation of γ-Fe2O3. The oxyhydroxides, which are the principal compounds in the biomass, have low catalytic activity in the used reaction; the maghemite has relatively good catalytic activity; the hematite has activity commensurate with that of the oxyhydroxides. Moreover it can be affirmed that catalytic activity is inherent in maghemite, which is obtained by transformation of the biogenic lepidocrocite, i.e. it has biogenic precursor.

Keywords: nanosized biogenic iron compounds, catalytic behavior in reaction of CO oxidation, in situ DRIFTS, Moessbauer spectroscopy

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