Search results for: raman spectra

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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Authors: Anitha Kandasamy, Thirumurugan Ramaiah

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Interestingly, organic materials exhibit large optical nonlinearity with quick responses and having the flexibility of molecular tailoring using computational modelling and favourable synthetic methodologies. Pyridine based organic compounds and carboxylic acid contained aromatic compounds play a crucial role in crystal engineering of NCS complexes that displays admirable optical nonlinearity with fast response and favourable physicochemical properties such as low dielectric constant, wide optical transparency and large laser damage threshold value requires for optoelectronics device applications. Based on these facts, it was projected to form an acentric molecule of π-conjugated system interaction with appropriately replaced electron donor and acceptor groups for achieving higher SHG activity in which quinoline-2-carboyxlic acid is chosen as an electron acceptor and capable of acting as an acid as well as a base molecule, while 2-amino-4-methylpyridine is used as an electron donor and previously employed in numerous proton transfer complexes for synthesis of NLO materials for optoelectronic applications. 2-amino-4-mehtylpyridinium quinoline-2-carboxylate molecular complex (2AQ) is having π-donor-acceptor groups in which 2-amino-4-methylpyridine donates one of its electron to quinoline -2-carboxylic acid thereby forming a protonated 2-amino-4-methyl pyridinium moiety and mono ionized quinoline-2-carboxylate moiety which are connected via N-H…O intermolecular interactions with non-centrosymmetric crystal packing arrangement at microscopic scale is accountable to the enhancement of macroscopic second order NLO activity. The 2AQ crystal was successfully grown by a slow evaporation solution growth technique and its structure was determined in orthorhombic crystal system with acentric, P212121, space group. Hirshfeld surface analysis reveals that O…H intermolecular interactions primarily contributed with 31.0 % to the structural stabilization of 2AQ. The molecular structure of title compound has been confirmed by 1H and 13C NMR spectral studies. The vibrational modes of functional groups present in 2AQ have been assigned by using FTIR and FT-Raman spectroscopy. The grown 2AQ crystal exhibits high optical transparency with lower cut-off wavelength (275 nm) within the region of 275-1500 nm. The laser study confirmed that 2AQ exhibits high SHG efficiency of 12.6 times greater than that of KDP. TGA-DTA analysis revealed that 2AQ crystal had a thermal stability of 223 °C. The low dielectric constant and low dielectric loss at higher frequencies confirmed good crystalline nature with fewer defects of grown 2AQ crystal. The grown crystal exhibits soft material and positive photoconduction behaviour. Mulliken atomic distribution and FMOs analysis suggested that the strong intermolecular hydrogen bonding which lead to the enhancement of NLO activity. These properties suggest that 2AQ crystal is a suitable material for optoelectronic and laser frequency conversion applications.

Keywords: crystal growth, NLO activity, proton transfer complex, quantum chemical investigation

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

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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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Authors: Rewati Raman, Uttam K. Roy

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One of the main adversaries of city planning in present times is the ever-expanding problem of urbanization and the antagonistic issues accompanying it. The prevalent challenges in urbanization such as population growth, urban sprawl, poverty, inequality, pollution, congestion, etc. call for reforms in the urban fabric as well as in planning theory and practice. One of the various paradigms of city planning, land use planning, has been the major instruments for spatial planning of cities and regions in India. Zoning regulation based land use planning in the form of land use and development control plans (LUDCP) and development control regulations (DCR) have been considered mainstream guiding principles in land use planning for decades. In spite of many advantages of such zoning based regulations, over a period of time, it has been critiqued by scholars for its own limitations of isolation and lack of vitality, inconvenience in business in terms of proximity to residence and low operating cost, unsuitable environment for small investments, higher travel distance for facilities, amenities and thereby higher expenditure, safety issues etc. Mixed land use has been advocated as a tool to avoid such limitations in city planning by researchers. In addition, mixed land use can offer many advantages like housing variety and density, the creation of an economic blend of compatible land use, compact development, stronger neighborhood character, walkability, and generation of jobs, etc. Alternatively, the mixed land use beyond a suitable balance of use can also bring disadvantages like traffic congestion, encroachments, very high-density housing leading to a slum like condition, parking spill out, non-residential uses operating on residential premises paying less tax, chaos hampering residential privacy, pressure on existing infrastructure facilities, etc. This research aims at studying and outlining the various challenges and potentials of mixed land use zoning, through modeling tools, as a competent instrument for city planning in lieu of the present urban scenario. The methodology of research adopted in this paper involves the study of a mixed land use neighborhood in India, identification of indicators and parameters related to its extent and spatial pattern and the subsequent use of system dynamics as a modeling tool for simulation. The findings from this analysis helped in identifying the various advantages and challenges associated with the dynamic nature of a mixed use urban settlement. The results also confirmed the hypothesis that mixed use neighborhoods are catalysts for employment generation, socioeconomic gains while improving vibrancy, health, safety, and security. It is also seen that certain challenges related to chaos, lack of privacy and pollution prevail in mixed use neighborhoods, which can be mitigated by varying the percentage of mixing as per need, ensuring compatibility of adjoining use, institutional interventions in the form of policies, neighborhood micro-climatic interventions, etc. Therefore this paper gives a consolidated and holistic framework and quantified outcome pertaining to the extent and spatial pattern of mixed land use that should be adopted to ensure sustainable urban planning.

Keywords: mixed land use, sustainable development, system dynamics analysis, urban dynamics modelling

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

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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

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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

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

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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

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Authors: Dimitra Das, Anuradha Mitra, Kalyan Kumar Chattopadhyay

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Organic polymers, constructed from light elements like carbon, hydrogen, nitrogen, oxygen, sulphur, and boron atoms, are the emergent class of non-toxic, metal-free, environmental benign advanced materials. Covalent triazine-based polymers with a functional triazine group are significant class of organic materials due to their remarkable stability arising out of strong covalent bonds. They can conventionally form hydrogen bonds, favour π–π contacts, and they were recently revealed to be involved in interesting anion–π interactions. The present work mainly focuses upon the development of a single-crystalline, highly cross-linked triazine-based nitrogen-rich organic polymer with nanodendritic morphology and significant thermal stability. The polymer has been synthesized through hydrothermal treatment of melamine and ethylene glycol resulting in cross-polymerization via condensation-polymerization reaction. The crystal structure of the polymer has been evaluated by employing Rietveld whole profile fitting method. The polymer has been found to be composed of monoclinic melamine having space group P21/a. A detailed insight into the chemical structure of the as synthesized polymer has been elucidated by Fourier Transform Infrared Spectroscopy (FTIR) and Raman spectroscopic analysis. X-Ray Photoelectron Spectroscopic (XPS) analysis has also been carried out for further understanding of the different types of linkages required to create the backbone of the polymer. The unique rod-like morphology of the triazine based polymer has been revealed from the images obtained from Field Emission Scanning Electron Microscopy (FESEM) and Transmission Electron Microscopy (TEM). Interestingly, this polymer has been found to selectively detect mercury (Hg²⁺) ions at an extremely low concentration through fluorescent quenching with detection limit as low as 0.03 ppb. The high toxicity of mercury ions (Hg²⁺) arise from its strong affinity towards the sulphur atoms of biological building blocks. Even a trace quantity of this metal is dangerous for human health. Furthermore, owing to its small ionic radius and high solvation energy, Hg²⁺ ions remain encapsulated by water molecules making its detection a challenging task. There are some existing reports on fluorescent-based heavy metal ion sensors using covalent organic frameworks (COFs) but reports on mercury sensing using triazine based polymers are rather undeveloped. Thus, the importance of ultra-trace detection of Hg²⁺ ions with high level of selectivity and sensitivity has contemporary significance. A plausible sensing phenomenon by the polymer has been proposed to understand the applicability of the material as a potential sensor. The impressive sensitivity of the polymer sample towards Hg²⁺ is the very first report in the field of highly crystalline triazine based polymers (without the introduction of any sulphur groups or functionalization) towards mercury ion detection through photoluminescence quenching technique. This crystalline metal-free organic polymer being cheap, non-toxic and scalable has current relevance and could be a promising candidate for Hg²⁺ ion sensing at commercial level.

Keywords: fluorescence quenching , mercury ion sensing, single-crystalline, triazine-based polymer

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

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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

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Authors: Chris Miskelly, Eoin Cunningham, Beatrice Smyth, John. D. Holbrey, Gosia Swadzba-Kwasny, Emily L. Byrne, Yoan Delavoux, Mantian Li.

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Recently, the use of ionic liquids (ILs) for the preparation of lignocellulose derived cellulosic materials as alternatives to petrochemical feedstocks has been the focus of considerable research interest. While the technical viability of IL-based lignocellulose treatment methodologies has been well established, the high cost of reagents inhibits commercial feasibility. This work aimed to assess the technoeconomic viability of the preparation of cellulose rich materials (CRMs) using protic ionic liquids (PILs) synthesized from low cost alkylamines and sulphuric acid. For this purpose, the tertiary alkylamines, triethylamine, and dimethylbutylamine were selected. Bulk scale production cost of the synthesized PILs, triethylammonium hydrogen sulphate and dimetheylbutylammonium hydrogen sulphate, was reported as $0.78 kg-1 to $1.24 kg-1. CRMs were prepared through the treatment of common wheat (Triticum aestivum) straw with these PILs. By controlling treatment parameters, CRMs with a cellulose content of ≥ 80 wt% were prepared. This was achieved using a T. aestivum straw to PIL loading ratio of 1:15 w/w, a treatment duration of 180 minutes, and ethanol as a cellulose antisolvent. Infrared spectra data and decreased onset degradation temperature of CRMs (ΔTONSET ~ 70 °C) suggested the formation of cellulose sulphate esters during treatment. Chemical derivatisation can aid the dispersion of prepared CRMs in non-polar polymer/ composite matrices, but act as a barrier to thermal processing at temperatures above 150 °C. It was also shown that treatment increased the crystallinity of CRMs (ΔCrI ~ 40 %) without altering the native crystalline structure or crystallite size (~ 2.6 nm) of cellulose; peaks associated with the cellulose I crystalline planes (110), (200), and (004) were observed at Bragg angles 16.0 °, 22.5 ° and 35.0 ° respectively. This highlighted the inability of assessed PILs to dissolve crystalline cellulose and was attributed to the high acidity (pKa ~ - 1.92 to - 6.42) of sulphuric acid derived anions. Electron micrographs revealed that the stratified multilayer tissue structure of untreated T. aestivum straw was significantly modified during treatment. T. aestivum straw particles were disassembled during treatment, with prepared CRMs adopting a golden-brown film-like appearance. This work demonstrated the degradation of non-cellulosic fractions of lignocellulose without dissolution of cellulose. It is the first to report on the derivatisation of cellulose during treatment with protic hydrogen sulphate ionic liquids, and the potential implications of this with reference to biopolymer feedstock preparation.

Keywords: cellulose, extraction, protic ionic liquids, esterification, thermal stability, waste valorisation, biopolymer feedstock

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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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Authors: Harpreet Singh Kainth

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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

Procedia PDF Downloads 506

Authors: Piotr Jablonski, Krzysztof Mars, Wiktor Niemiec, Agnieszka Kyziol, Marek Hebda, Halina Krawiec, Karol Kyziol

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NiTi alloys, possessing unique mechanical properties such as pseudoelasticity and shape memory effect (SME), are suitable for many applications, including implanthology and biomedical devices. Additionally, these alloys have similar values of elastic modulus to those of human bones, what is very important in orthopedics. Unfortunately, the environment of physiological fluids in vivo causes unfavorable release of Ni ions, which in turn may lead to metalosis as well as allergic reactions and toxic effects in the body. For these reasons, the surface properties of NiTi alloys should be improved to increase corrosion resistance, taking into account biological properties, i.e. excellent biocompatibility. The prospective in this respect are layers based on DLC (Diamond-Like Carbon) structures, which are an attractive solution for many applications in implanthology. These coatings (DLC), usually obtained by PVD (Physical Vapour Deposition) and PA CVD (Plasma Activated Chemical Vapour Deposition) methods, can be also modified by doping with other elements like silicon, nitrogen, oxygen, fluorine, titanium and silver. These methods, in combination with a suitably designed structure of the layers, allow the possibility co-decide about physicochemical and biological properties of modified surfaces. Mentioned techniques provide specific physicochemical properties of substrates surface in a single technological process. In this work, the following types of layers based on DLC structures (incl. Si-DLC or Si/N-DLC) were proposed as prospective and attractive approach in surface functionalization of shape memory alloy. Nitinol substrates were modified in plasma conditions, using RF CVD (Radio Frequency Chemical Vapour Deposition). The influence of plasma treatment on the useful properties of modified substrates after deposition DLC layers doped with silica and/or nitrogen atoms, as well as only pre-treated in O2 NH3 plasma atmosphere in a RF reactor was determined. The microstructure and topography of the modified surfaces were characterized using scanning electron microscopy (SEM) and atomic force microscopy (AFM). Furthermore, the atomic structure of coatings was characterized by IR and Raman spectroscopy. The research also included the evaluation of surface wettability, surface energy as well as the characteristics of selected mechanical and biological properties of the layers. In addition, the corrosion properties of alloys after and before modification in the physiological saline were also investigated. In order to determine the corrosion resistance of NiTi in the Ringer solution, the potentiodynamic polarization curves (LSV – Linear Sweep Voltamperometry) were plotted. Furthermore, the evolution of corrosion potential versus immersion time of TiNi alloy in Ringer solution was performed. Based on all carried out research, the usefullness of proposed modifications of nitinol for medical applications was assessed. It was shown, inter alia, that the obtained Si-DLC layers on the surface of NiTi alloy exhibit a characteristic complex microstructure, increased surface development, which is an important aspect in improving the osteointegration of an implant. Furthermore, the modified alloy exhibits biocompatibility, the transfer of the metal (Ni, Ti) to Ringer’s solution is clearly limited.

Keywords: bioactive coatings, corrosion resistance, doped DLC structure, NiTi alloy, RF CVD

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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

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

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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 204

Authors: Satam Alotibi, Osama A. Hussein, Aziz H. Al-Shaibani, Nawaf A. Al-Aqeel, Abdellah Kaiba, Fatehia S. Alhakami, Mohammed Alyami, Talal F. Qahtan

Abstract:

The demand for sustainable and efficient energy conversion using solar energy has grown rapidly in recent years. In this pursuit, solar-to-chemical conversion has emerged as a promising approach, with oxygen vacancies-rich tungsten trioxide (WO₃) playing a crucial role. This study presents a method for synthesizing oxygen vacancies-rich WO3, resulting in a significant enhancement of its photocatalytic activity, representing a significant step towards sustainable energy solutions. Experimental results underscore the importance of oxygen vacancies in modifying the properties of WO₃. These vacancies introduce additional energy states within the material, leading to a reduction in the bandgap, increased light absorption, and acting as electron traps, thereby reducing emissions. Our focus lies in developing oxygen vacancies-rich WO₃, which demonstrates unparalleled potential for improved photocatalytic applications. The effectiveness of oxygen vacancies-rich WO₃ in solar-to-chemical conversion was showcased through rigorous assessments of its photocatalytic degradation performance. Sunlight irradiation was employed to evaluate the material's effectiveness in degrading organic pollutants in wastewater. The results unequivocally demonstrate the superior photocatalytic performance of oxygen vacancies-rich WO₃ compared to conventional WO₃ nanomaterials, establishing its efficacy in sustainable and efficient energy conversion. Furthermore, the synthesized material is utilized to fabricate films, which are subsequently employed in immobilized WO₃ and oxygen vacancies-rich WO₃ reactors for water purification under natural sunlight irradiation. This application offers a sustainable and efficient solution for water treatment, harnessing solar energy for effective decontamination. In addition to investigating the photocatalytic capabilities, we extensively analyze the structural and chemical properties of the synthesized material. The synthesis process involves in situ thermal reduction of WO₃ nano-powder in a nitrogen environment, meticulously monitored using thermogravimetric analysis (TGA) to ensure precise control over the synthesis of oxygen vacancies-rich WO₃. Comprehensive characterization techniques such as UV-Vis spectroscopy, X-ray photoelectron spectroscopy (XPS), FTIR, Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and selected area electron diffraction (SAED) provide deep insights into the material's optical properties, chemical composition, elemental states, structure, surface properties, and crystalline structure. This study represents a significant advancement in sustainable energy conversion through solar-to-chemical processes and water purification. By harnessing the unique properties of oxygen vacancies-rich WO₃, we not only enhance our understanding of energy conversion mechanisms but also pave the way for the development of highly efficient and environmentally friendly photocatalytic materials. The application of this material in water purification demonstrates its versatility and potential to address critical environmental challenges. These findings bring us closer to a sustainable energy future and cleaner water resources, laying a solid foundation for a more sustainable planet.

Keywords: sustainable energy conversion, solar-to-chemical conversion, oxygen vacancies-rich tungsten trioxide (WO₃), photocatalytic activity enhancement, water purification

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Authors: Sajana Suwal, Ganesh R. Nhemafuki

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

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

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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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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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Authors: Simran Baweja, Bhavika Kalal, Surajit Maity

Abstract:

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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Authors: G. Swati, D. Haranath

Abstract:

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

Abstract:

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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Authors: Vishal Kumar, Soumitra Satapathi

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Föster Resonance Energy Transfer (FRET) is a powerful technique used to probe close-range molecular interactions. Physically, the FRET phenomenon manifests as a dipole–dipole interaction between closely juxtaposed fluorescent molecules (10–100 Å). Our effort is to employ this FRET technique to make a prototype device for highly sensitive detection of environment pollutant. Among the most common environmental pollutants, nitroaromatic compounds (NACs) are of particular interest because of their durability and toxicity. That’s why, sensitive and selective detection of small amounts of nitroaromatic explosives, in particular, 2,4,6-trinitrophenol (TNP), 2,4-dinitrotoluene (DNT) and 2,4,6-trinitrotoluene (TNT) has been a critical challenge due to the increasing threat of explosive-based terrorism and the need of environmental monitoring of drinking and waste water. In addition, the excessive utilization of TNP in several other areas such as burn ointment, pesticides, glass and the leather industry resulted in environmental accumulation, and is eventually contaminating the soil and aquatic systems. To the date, high number of elegant methods, including fluorimetry, gas chromatography, mass, ion-mobility and Raman spectrometry have been successfully applied for explosive detection. Among these efforts, fluorescence-quenching methods based on the mechanism of FRET show good assembly flexibility, high selectivity and sensitivity. Here, we report a FRET-based sensor system for the highly selective detection of NACs, such as TNP, DNT and TNT. The sensor system is composed of a copolymer Poly [(N,N-dimethylacrylamide)-co-(Boc-Trp-EMA)] (RP) bearing tryptophan derivative in the side chain as donor and dansyl tagged copolymer P(MMA-co-Dansyl-Ala-HEMA) (DCP) as an acceptor. Initially, the inherent fluorescence of RP copolymer is quenched by non-radiative energy transfer to DCP which only happens once the two molecules are within Förster critical distance (R0). The excellent spectral overlap (Jλ= 6.08×10¹⁴ nm⁴M⁻¹cm⁻¹) between donors’ (RP) emission profile and acceptors’ (DCP) absorption profile makes them an exciting and efficient FRET pair i.e. further confirmed by the high rate of energy transfer from RP to DCP i.e. 0.87 ns⁻¹ and lifetime measurement by time correlated single photon counting (TCSPC) to validate the 64% FRET efficiency. This FRET pair exhibited a specific fluorescence response to NACs such as DNT, TNT and TNP with 5.4, 2.3 and 0.4 µM LODs, respectively. The detection of NACs occurs with high sensitivity by photoluminescence quenching of FRET signal induced by photo-induced electron transfer (PET) from electron-rich FRET pair to electron-deficient NAC molecules. The estimated stern-volmer constant (KSV) values for DNT, TNT and TNP are 6.9 × 10³, 7.0 × 10³ and 1.6 × 104 M⁻¹, respectively. The mechanistic details of molecular interactions are established by time-resolved fluorescence, steady-state fluorescence and absorption spectroscopy confirmed that the sensing process is of mixed type, i.e. both dynamic and static quenching as lifetime of FRET system (0.73 ns) is reduced to 0.55, 0.57 and 0.61 ns DNT, TNT and TNP, respectively. In summary, the simplicity and sensitivity of this novel FRET sensor opens up the possibility of designing optical sensor of various NACs in one single platform for developing multimodal sensor for environmental monitoring and future field based study.

Keywords: FRET, nitroaromatic, stern-Volmer constant, tryptophan and dansyl tagged copolymer

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Authors: Hugo Lefeuvre, Jerôme Donnard, Michael Descostes, Sophie Billon, Samuel Duval, Tugdual Oger, Herve Toubon, Paul Sardini

Abstract:

Spectroscopic autoradiography is a method of interest for geological sample analysis. Indeed, researchers may face different issues such as radioelement identification and quantification in the field of environmental studies. Imaging gaseous ionization detectors find their place in geosciences for conducting specific measurements of radioactivity to improve the monitoring of natural processes using naturally-occurring radioactive tracers, but also for the nuclear industry linked to the mining sector. In geological samples, the location and identification of the radioactive-bearing minerals at the thin-section scale remains a major challenge as the detection limit of the usual elementary microprobe techniques is far higher than the concentration of most of the natural radioactive decay products. The spatial distribution of each decay product in the case of uranium in a geomaterial is interesting for relating radionuclides concentration to the mineralogy. The present study aims to provide spectroscopic autoradiography analysis method for measuring the initial energy of alpha particles with a parallel ionization multiplier gaseous detector. The analysis method has been developed thanks to Geant4 modelling of the detector. The track of alpha particles recorded in the gas detector allow the simultaneous measurement of the initial point of emission and the reconstruction of the initial particle energy by a selection based on the linear energy distribution. This spectroscopic autoradiography method was successfully used to reproduce the alpha spectra from a 238U decay chain on a geological sample at the thin-section scale. The characteristics of this measurement are an energy spectrum resolution of 17.2% (FWHM) at 4647 keV and a spatial resolution of at least 50 µm. Even if the efficiency of energy spectrum reconstruction is low (4.4%) compared to the efficiency of a simple autoradiograph (50%), this novel measurement approach offers the opportunity to select areas on an autoradiograph to perform an energy spectrum analysis within that area. This opens up possibilities for the detailed analysis of heterogeneous geological samples containing natural alpha emitters such as uranium-238 and radium-226. This measurement will allow the study of the spatial distribution of uranium and its descendants in geo-materials by coupling scanning electron microscope characterizations. The direct application of this dual modality (energy-position) of analysis will be the subject of future developments. The measurement of the radioactive equilibrium state of heterogeneous geological structures, and the quantitative mapping of 226Ra radioactivity are now being actively studied.

Keywords: alpha spectroscopy, digital autoradiography, mining activities, natural decay products

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Authors: Antonina Semakova, Karim Mynbaev, Nikolai Bazhenov, Anton Chernyaev, Sergei Kizhaev, Nikolai Stoyanov

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At present, heterostructures are used for fabrication of almost all types of optoelectronic devices. Our research focuses on the optoelectronic properties of InAs(Sb) solid solutions that are widely used in fabrication of light emitting diodes (LEDs) operating in middle wavelength infrared range (MWIR). This spectral range (2-6 μm) is relevant for laser diode spectroscopy of gases and molecules, for systems for the detection of explosive substances, medical applications, and for environmental monitoring. The fabrication of MWIR LEDs that operate efficiently at room temperature is mainly hindered by the predominance of non-radiative Auger recombination of charge carriers over the process of radiative recombination, which makes practical application of LEDs difficult. However, non-radiative recombination can be partly suppressed in quantum-well structures. In this regard, studies of such structures are quite topical. In this work, electroluminescence (EL) of LED heterostructures based on InAs(Sb) epitaxial films with the molar fraction of InSb ranging from 0 to 0.09 and multi quantum-well (MQW) structures was studied in the temperature range 4.2-300 K. The growth of the heterostructures was performed by metal-organic chemical vapour deposition on InAs substrates. On top of the active layer, a wide-bandgap InAsSb(Ga,P) barrier was formed. At low temperatures (4.2-100 K) stimulated emission was observed. As the temperature increased, the emission became spontaneous. The transition from stimulated emission to spontaneous one occurred at different temperatures for structures with different InSb contents in the active region. The temperature-dependent carrier lifetime, limited by radiative recombination and the most probable Auger processes (for the materials under consideration, CHHS and CHCC), were calculated within the framework of the Kane model. The effect of various recombination processes on the carrier lifetime was studied, and the dominant role of Auger processes was established. For MQW structures quantization energies for electrons, light and heavy holes were calculated. A characteristic feature of the experimental EL spectra of these structures was the presence of peaks with energy different from that of calculated optical transitions between the first quantization levels for electrons and heavy holes. The obtained results showed strong effect of the specific electronic structure of InAsSb on the energy and intensity of optical transitions in nanostructures based on this material. For the structure with MQWs in the active layer, a very weak temperature dependence of EL peak was observed at high temperatures (>150 K), which makes it attractive for fabricating temperature-resistant gas sensors operating in the middle-infrared range.

Keywords: Electroluminescence, InAsSb, light emitting diode, quantum wells

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