Search results for: Michelann Parr

Authors: Ameur Soukaina, Zeroual Abdellah, Mazoir Noureddine

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Molecular Electron Density Theory (MEDT) elucidates the regioselectivity of the [4+2] cycloaddition reaction between 3-aroylpyrrolo[1,2-α]quinoxaline-1,2,4(5H)-trione and butyl vinyl ether Regioselectivity and stereoselectivity. The regioselectivity mechanisms of these reactions were investigated by evaluating potential energy surfaces calculated for cycloaddition processes and DFT density-based reactivity indices. These methods have been successfully applied to predict preferred regioisomers for different method alternatives. Reactions were monitored by performing transition state optimizations, calculations of intrinsic reaction coordinates, and activation energies. The observed regioselectivity was rationalized using DFT-based reactivity descriptors such as the Parr function. Solvent effects were also investigated in 1,4-dioxane solvent using a field model for self-consistent reactions. The results were compared with experimental data to find good agreement.

Keywords: cycloaddition, DFT, ELF, MEDT, parr, stereoselectivité

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Authors: Imad Eddine Charif, Wafaa Benchouk, Sidi Mohamed Mekelleche

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The regioselectivity of a series of 16 1,3-dipolar cycloaddition reactions of nitrile oxides with 2(5H)-furanones has been analysed by means of global and local electrophilic and nucleophilic reactivity indices using density functional theory at the B3LYP level together with the 6-31G(d) basis set. The local electrophilicity and nucleophilicity indices, based on Fukui and Parr functions, have been calculated for the terminal sites, namely the C1 and O3 atoms of the 1,3-dipole and the C4 and C5 atoms of the dipolarophile. These local indices were calculated using both Mulliken and natural charges and spin densities. The results obtained show that the C5 atom of the 2(5H)-furanones is the most electrophilic site whereas the O3 atom of the nitrile oxides is the most nucleophilic centre. It turns out that the experimental regioselectivity is correctly reproduced, indicating that both Fukui- and Parr-based indices are efficient tools for the prediction of the regiochemistry of the studied reactions and could be used for the prediction of newly designed reactions of the same kind.

Keywords: 1, 3-dipolar cycloaddition, density functional theory, nitrile oxides, regioselectivity, reactivity indices

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Authors: Michelann Parr

Abstract:

Family-school-community engagement enhances family-school-community well-being, collective confidence, and school climate. While it is often referred to as a positive thing in the literature for families, schools, and communities, it does not come without its struggles. While there are numerous things families, schools, and communities do each and every day to enhance engagement, it is often difficult to find our way to true belonging and engagement. Working our way surface level barriers is easy; we can provide childcare, transportation, resources, and refreshments. We can even change the environment so that families will feel welcome, valued, and respected. But there are often mindsets and perpsectives buried deep below the surface, most often grounded in societal, familial, and political norms, expectations, pressures, and narratives. This work requires ongoing energy, commitment, and engagement of all stakeholders, including families, schools, and communities. Each and every day, we need to take a reflective and introspective stance at what is said and done and how it supports the overall goal of family-school-community engagement. And whatever we must occur within a paradigm of care in additional to one of critical thinking and social justice. Families, and those working with families, must not simply accept all that is given, but should instead ask these types of questions: a) How, and by whom, are the current philosophies and practices of family-school engagement interrogated? b) How might digging below surface level meanings support understanding of what is being said and done? c) How can we move toward meaningful and authentic engagement that balances knowledge and power between family, school, district, community (local and global), and government? This type of work requires conscious attention and intentional decision-making at all levels bringing us one step closer to authentic and meaningful partnerships. Strategies useful to building a growth mindset include: a) interrogating and exploring consistencies and inconsistencies by looking at what is done and what is not done through multiple perspectives; b) recognizing that enhancing family-engagement and changing mindsets take place at the micro-level (e.g., family and school), but also require active engagement and awareness at the macro-level (e.g., community agencies, district school boards, government); c) taking action as an advocate or activist. Negative narratives about families, schools, and communities should not be maintained, but instead critical and courageous conversations in and out of school should be initiated and sustained; and d) maintaining consistency, simplicity, and steady progress. All involved in engagement need to be aware of the struggles, but keep them in check with the many successes. Change may not be observed on a day-to-day basis or even immediately, but stepping back and looking from the outside in, might change the view. Working toward a growth mindset will produce better results than a fixed mindset, and this takes time.

Keywords: family engagment, family-school-community engagement, parent engagement, parent involvment

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Authors: Catalina Iticescu, Lucian Georgescu, Mihaela Timofti, Dumitru Dima, Gabriel Murariu

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The amounts of sludge resulting from the treatment of domestic and industrial wastewater can create serious environmental problems if no solutions are found to eliminate them. At present, the predominant method of sewage sludge disposal is to store and use them in agricultural applications. The sewage sludge has fertilizer properties and can be used to enrich agricultural soils due to the nutrient content. In addition to plant growth (nitrogen and phosphorus), the sludge also contains heavy metals in varying amounts. An increasingly used method is the incineration of sludge. Thermal processes can be used to convert large amounts of sludge into useful energy. The sewage sludge analyzed for the present paper was extracted from the Wastewater Treatment Station (WWTP) Galati, Romania. The physico-chemical parameters determined were: pH (upH), nutrients and heavy metals. The determination methods were electrochemical, spectrophotometric and energy dispersive X–ray analyses (EDX). The results of the tests made on the content of nutrients in the sewage sludge have shown that existing nutrients can be used to increase the fertility of agricultural soils. The conclusion reached was that these sludge can be safely used on agricultural land and with good agricultural productivity results. To be able to use sewage sludge as a fuel, we need to know its calorific values. For wet sludge, the caloric power is low, while for dry sludge it is high. Higher calorific value and lower calorific value are determined only for dry solids. The apparatus used to determine the calorific power was a Parr 6755 Solution Calorimeter Calorimeter (Parr Instrument Company USA 2010 model). The calorific capacities for the studied sludge indicate that they can be used successfully in incinerators. Mixed with coal, they can also be used to produce electricity. The advantages are: it reduces the cost of obtaining electricity and considerably reduces the amount of sewage sludge.

Keywords: agriculture, incinerators, properties, sewage sludge

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Authors: Esmat Mohammadinasab

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The aim of this paper is to investigate theoretically and establish a predictive model for determination LogP of armchair polyhex BN nanotubes by using simple descriptors. The relationship between the octanol-water partition coefficient (LogP) and quantum chemical descriptors, electric moments, and topological indices of some armchair polyhex BN nanotubes with various lengths and fixed circumference are represented. Based on density functional theory (DFT) electric moments and physico-chemical properties of those nanotubes are calculated. The DFT method performed based on the Becke’s 3-parameter formulation with the Lee-Yang-Parr functional (B3LYP) method and 3-21G standard basis sets. For the first time, the relationship between partition coefficient and different properties of polyhex BN nanotubes is investigated.

Keywords: topological indices, quantum descriptors, DFT method, nanotubes

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Authors: Salem El-Tohami Ashoor

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A novel new vanadium (IV) complexes incorporating the chelating diamido cyclopentadienyl {ArN(CH2)3NAr)}2-((ηn-Cp)Cp)} (Ar = 2,6-Pri2C6H3)(Cp = C5H5 and n = 1,2,3,4 and 5) have been studied with calculation of the properties of species involved in various of cyclopentadienyl reaction. These were carried out under investigation of density functional theory (DFT) calculation, and comparing together. Other methods, explicitly including electron correlation, are necessary for more accurate calculations; MB3LYP (Becke) (Lee–Yang–Parr) level of theory often being used to obtain more exact results. These complexes were estimated of electronic energy for molecular system, because it accounts for all electron correlation interactions. The optimised of [V(ArN(CH2)3NAr)2Cl(η5-Cp)] (Ar = 2,6-Pri2C6H3 and Cp= C5H5) was found to be thermally more stable than others of vanadium cyclopentadienyl. In the meantime the complex [V(ArN(CH2)3NAr)2Cl(η1-Cp)] (Ar = 2,6-Pri2C6H3 and Cp= C5H5) which is showed a low thermal stability in case of the just one carbon of cyclopentadienyl can be insertion with vanadium metal centre. By using Dewar-Chatt-Duncanson model, as a basis of the molecular orbital (MO) analysis and showed the highest occupied molecular orbital (HOMO) and lowest occupied molecular orbital LUMO.

Keywords: vanadium (IV) cyclopentadienyl complexes, DFT, MO, HOMO, LUMO

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Authors: Salem El-Tohami Ashoor

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

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

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Authors: Imad Eddine Charif, Sidi Mohamed Mekelleche, Didier Villemin

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The solvent effects on the keto-enol tautomeric equilibriums of acetylacetone and dimedone are theoretically investigated at the correlated Becke-3-parameter-Lee-Yang-Parr (B3LYP) and second-order Møller-Plesset (MP2) computational levels. The present study shows that the most stable keto tautomer of acetylacetone corresponds to the trans-diketo, E,Z form; while the most stable enol tautomer corresponds to the closed cis-enol,Z,Z form. The keto tautomer of dimedone prefers the trans diketo, E, E form; while the most stable enol tautomer corresponds to trans-enol form. The calculated free Gibbs enthalpies indicate that, in polar solvents, the keto-enol equilibrium of acetylacetone is shifted toward the keto tautomer; whereas the keto-enol equilibrium of dimedone is shifted towards the enol tautomer. The experimental trends of the change of equilibrium constants with respect to the change of solvent polarity are well reproduced by both B3LYP and MP2 calculations.

Keywords: acetylacetone, dimedone, solvent effects, keto-enol equilibrium, theoretical calculations

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Authors: Nirmala Deenadayalu, Kwanele B. Mazibuko, Lethiwe D. Mthembu

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Sugarcane bagasse is the residue obtained after the extraction of sugar from the sugarcane. The main aim of this work was to produce catechol from sugarcane bagasse. The optimization of catechol production was investigated using a Box-Behnken design of experiments. The sugarcane bagasse was heated in a Parr reactor at a set temperature. The reactions were carried out at different temperatures (100-250) °C, catalyst loading (1% -10% KOH (m/v)) and reaction times (60 – 240 min) at 17 bar pressure. The solid and liquid fractions were then separated by vacuum filtration. The liquid fraction was analyzed for catechol using high-pressure liquid chromatography (HPLC) and characterized for the functional groups using Fourier transform infrared spectroscopy (FTIR). The optimized condition for catechol production was 175 oC, 240 min, and 10 % KOH with a catechol yield of 79.11 ppm. Since the maximum time was 240 min and 10 % KOH, a further series of experiments were conducted at 175 oC, 260 min, and 20 % KOH and yielded 2.46 ppm catechol, which was a large reduction in catechol produced. The HPLC peak for catechol was obtained at 2.5 min for the standards and the samples. The FTIR peak at 1750 cm⁻¹ was due to the C=C vibration band of the aromatic ring in the catechol present for both the standard and the samples. The peak at 3325 cm⁻¹ was due to the hydrogen-bonded phenolic OH vibration bands for the catechol. The ANOVA analysis was also performed on the set of experimental data to obtain the factors that most affected the amount of catechol produced.

Keywords: catechol, sugarcane bagasse, lignin, hydrothermal liquefaction

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Authors: O. Mowla, E. Kennedy, M. Stockenhuber

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Finding alternative renewable resources of energy has attracted the attentions in consequence of limitation of the traditional fossil fuel resources, increasing of crude oil price and environmental concern over greenhouse gas emissions. Biodiesel (or Fatty Acid Methyl Esters (FAME)), an alternative energy source, is synthesised from renewable sources such as vegetable oils and animal fats and can be produced from waste oils. FAME can be produced via hydroesterification of oils. The process involves two stages. In the first stage of this process, fatty acids and glycerol are being obtained by hydrolysis of the feed stock oil. In the second stage, the recovered fatty acids are then esterified with an alcohol to methyl esters. The presence of a catalyst accelerates the rate of the hydroesterification reaction of oils. The overarching aim of this study is to find the effect of using zeolite as a catalyst in the heterogeneous hydroesterification of soybean oil. Both stages of the catalytic hydroesterification of soybean oil had been conducted at atmospheric and high-pressure conditions using reflux glass reactor and Parr reactor, respectively. The effect of operating parameters such as temperature and reaction time on the overall yield of biodiesel formation was also investigated.

Keywords: biodiesel, heterogeneous catalytic hydroesterification, soybean oil, zeolite

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Authors: Julius K. Gane, Mohamad N. Nahil, Paul T. Williams

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In today’s world of rapid population growth and a changing climate, one way to mitigate various negative effects is via renewable energy solutions. Energy and power as basic requirements in almost all human endeavours are also the banes of the changing climate and the impacts thereof. Thus it is crucial to develop innovative and environmentally friendly energy options to ameliorate various negative repercussions. Upgrading of fast pyrolysis bio-oil via hydro-treatment offers such opportunities, as quality renewable liquid transportation fuels can be produced. The process, however, is typically accompanied by bio-char formation as a by-product. The goal of this work was to study the yield and some properties of bio-chars formed from a hydrotreatment process, with an overall aim to promote the valuable utilization of wastes or by-products from renewable energy technologies. It is assumed that bio-chars that have comparable energy contents with coals will be more desirable as solid energy materials due to renewability and environmental friendliness. Therefore, the analytical work in this study focused mainly on determining the higher heating value (HHV) of the chars. The method involved the reaction of bio-oil in an autoclave supplied by the Parr Instrument Company, IL, USA. Two main parameters (different temperatures and resident times) were investigated. The chars were characterized using a Thermo EA2000 CHNS analyser, then oxygen contents and HHVs computed based on the literature. From the results, these bio-chars can readily serve as feedstocks for the production of renewable solid fuels. Their HHVs ranged between 29.26-39.18 MJ/kg, affected by different temperatures and retention times. There was an inverse relationship between the oxygen content and the HHVs of the chars. It can, therefore, be concluded that it is possible to optimize the process efficiency of the hydrotreatment process used through the production of renewable energy materials from the 'waste’ char by-products. Future work should consider developing a suitable balance between the primary objective of bio-oil upgrading processes (which is to improve the quality of the liquid fuels) and the conversion of its solid wastes into value-added products such as smokeless briquettes.

Keywords: bio-char, renewable solid biofuels, valorisation, waste-to-energy

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Authors: Natalie Tyldesley-Marshall, Janette Parr, Anna Brown, Yen-Fu Chen, Amy Grove

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It is widely recognised in policy and research that the provision of services for children and young people (CYP) with Special Educational Needs and Disabilities (SEND) is enhanced when health and social care, and education services collaborate and interact effectively. In the UK, there have been significant changes to policy and provisions which support and improve collaboration. However, professionals responsible for implementing these changes face multiple challenges, including a lack of specific implementation guidance or framework to illustrate how effective multi-agency working could or should work. This systematic review will identify the key components of effective multi-agency working in services for CYP with SEND; and the most effective forms of partnership working in this setting. The review highlights interventions that lead to service improvements; and the conditions in the local area that support and encourage success. A protocol was written and registered with PROSPERO registration: CRD42022352194. Searches were conducted on several health, care, education, and applied social science databases from the year 2012 onwards. Citation chaining has been undertaken, as well as broader grey literature searching to enrich the findings. Qualitative, quantitative, mixed methods studies and systematic reviews were included, assessed independently, and critically appraised or assessed for risk of bias using appropriate tools based on study design. Data were extracted in NVivo software and checked by a more experienced researcher. A convergent segregated approach to synthesis and integration was used in which the quantitative and qualitative data were synthesised independently and then integrated using a joint display integration matrix. Findings demonstrate the key ingredients for effective partnership working for services delivering SEND. Interventions deemed effective are described, and lessons learned across interventions are summarised. Results will be of interest to educators and health and social care professionals that provide services to those with SEND. These will also be used to develop policy recommendations for how UK healthcare, social care, and education services for CYP with SEND aged 0-25 can most effectively collaborate and achieve service improvement. The review will also identify any gaps in the literature to recommend areas for future research. Funding for this review was provided by the Department for Education.

Keywords: collaboration, joint commissioning, service delivery, service improvement

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Authors: Katerina Koliou, Scott Parr, Evangelos Kaisar

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The surface transportation of freight is particularly vulnerable to storm and hurricane disasters, while at the same time, it is the primary transportation mode for delivering medical supplies, fuel, water, and other essential goods. To better plan for commercial vehicles during an evacuation, it is necessary to understand how these vehicles travel during an evacuation and determine if this travel is different from the general public. The research investigation used Florida's statewide continuous-count station traffic volumes, where then compared between years, to identify locations where traffic was moving differently during the evacuation. The data was then used to identify days on which traffic was significantly different between years. While the literature on auto-based evacuations is extensive, the consideration of freight travel is lacking. To better plan for commercial vehicles during an evacuation, it is necessary to understand how these vehicles travel during an evacuation and determine if this travel is different from the general public. The goal of this research was to investigate the movement of vehicles by classification, with an emphasis on freight during two major evacuation events: hurricanes Irma (2017) and Michael (2018). The methodology of the research was divided into three phases: data collection and management, spatial analysis, and temporal comparisons. Data collection and management obtained continuous-co station data from the state of Florida for both 2017 and 2018 by vehicle classification. The data was then processed into a manageable format. The second phase used geographic information systems (GIS) to display where and when traffic varied across the state. The third and final phase was a quantitative investigation into which vehicle classifications were statistically different and on which dates statewide. This phase used a two-sample, two-tailed t-test to compare sensor volume by classification on similar days between years. Overall, increases in freight movement between years prevented a more precise paired analysis. This research sought to identify where and when different classes of vehicles were traveling leading up to hurricane landfall and post-storm reentry. Of the more significant findings, the research results showed that commercial-use vehicles may have underutilized rest areas during the evacuation, or perhaps these rest areas were closed. This may suggest that truckers are driving longer distances and possibly longer hours before hurricanes. Another significant finding of this research was that changes in traffic patterns for commercial-use vehicles occurred earlier and lasted longer than changes for personal-use vehicles. This finding suggests that commercial vehicles are perhaps evacuating in a fashion different from personal use vehicles. This paper may serve as the foundation for future research into commercial travel during evacuations and explore additional factors that may influence freight movements during evacuations.

Keywords: evacuation, freight, travel time, evacuation

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Authors: Sam Derakhshan Deilami, Iain N. Kings, Lynne E. Macaskie, Brajendra K. Sharma, Anthony V. Bridgwater, Joseph Wood

Abstract:

This paper reports the application of a bacteria-supported palladium catalyst to the hydrodeoxygenation (HDO) of pyrolysis bio-oil, towards producing an upgraded transport fuel. Biofuels are key to the timely replacement of fossil fuels in order to mitigate the emissions of greenhouse gases and depletion of non-renewable resources. The process is an essential step in the upgrading of bio-oils derived from industrial by-products such as agricultural and forestry wastes, the crude oil from pyrolysis containing a large amount of oxygen that requires to be removed in order to create a fuel resembling fossil-derived hydrocarbons. The bacteria supported catalyst manufacture is a means of utilizing recycled metals and second life bacteria, and the metal can also be easily recovered from the spent catalysts after use. Comparisons are made between bio-Pd, and a conventional activated carbon supported Pd/C catalyst. Bio-oil was produced by fast pyrolysis of beechwood at 500 C at a residence time below 2 seconds, provided by Aston University. 5 wt % BioPd/C was prepared under reducing conditions, exposing cells of E. coli MC4100 to a solution of sodium tetrachloropalladate (Na2PdCl4), followed by rinsing, drying and grinding to form a powder. Pd/C was procured from Sigma-Aldrich. The HDO experiments were carried out in a 100 mL Parr batch autoclave using ~20g bio-crude oil and 0.6 g bio-Pd/C catalyst. Experimental variables investigated for optimization included temperature (160-350C) and reaction times (up to 5 h) at a hydrogen pressure of 100 bar. Most of the experiments resulted in an aqueous phase (~40%) and an organic phase (~50-60%) as well as gas phase (<5%) and coke (<2%). Study of the temperature and time upon the process showed that the degree of deoxygenation increased (from ~20 % up to 60 %) at higher temperatures in the region of 350 C and longer residence times up to 5 h. However minimum viscosity (~0.035 Pa.s) occurred at 250 C and 3 h residence time, indicating that some polymerization of the oil product occurs at the higher temperatures. Bio-Pd showed a similar degree of deoxygenation (~20 %) to Pd/C at lower temperatures of 160 C, but did not rise as steeply with temperature. More coke was formed over bio-Pd/C than Pd/C at temperatures above 250 C, suggesting that bio-Pd/C may be more susceptible to coke formation than Pd/C. Reactions occurring during bio-oil upgrading include catalytic cracking, decarbonylation, decarboxylation, hydrocracking, hydrodeoxygenation and hydrogenation. In conclusion, it was shown that bio-Pd/C displays an acceptable rate of HDO, which increases with residence time and temperature. However some undesirable reactions also occur, leading to a deleterious increase in viscosity at higher temperatures. Comparisons are also drawn with earlier work on the HDO of Chlorella derived bio-oil manufactured from micro-algae via hydrothermal liquefaction. Future work will analyze the kinetics of the reaction and investigate the effect of bi-metallic catalysts.

Keywords: bio-oil, catalyst, palladium, upgrading

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