Search results for: porcine circovirus type 2
628 Properties of the CsPbBr₃ Quantum Dots Treated by O₃ Plasma for Integration in the Perovskite Solar Cell
Authors: Sh. Sousani, Z. Shadrokh, M. Hofbauerová, J. Kollár, M. Jergel, P. Nádaždy, M. Omastová, E. Majková
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Perovskite quantum dots (PQDs) have the potential to increase the performance of the perovskite solar cell (PSCs). The integration of PQDs into PSCs can extend the absorption range and enhance photon harvesting and device efficiency. In addition, PQDs can stabilize the device structure by passivating surface defects and traps in the perovskite layer and enhance its stability. The integration of PQDs into PSCs is strongly affected by the type of ligands on the surface of PQDs. The ligands affect the charge transport properties of PQDs, as well as the formation of well-defined interfaces and stability of PSCs. In this work, the CsPbBr₃ QDs were synthesized by the conventional hot-injection method using cesium oleate, PbBr₂ and two different ligands, namely oleic acid (OA) oleylamine (OAm) and didodecyldimethylammonium bromide (DDAB). The STEM confirmed regular shape and relatively monodisperse cubic structure with an average size of about 10-14 nm of the prepared CsPbBr₃ QDs. Further, the photoluminescent (PL) properties of the PQDs/perovskite bilayer with the ligand OA, OAm and DDAB were studied. For this purpose, ITO/PQDs as well as ITO/PQDs/MAPI perovskite structures were prepared by spin coating and the effect of the ligand and oxygen plasma treatment was analyzed. The plasma treatment of the PQDs layer could be beneficial for the deposition of the MAPI perovskite layer and the formation of a well-defined PQDs/MAPI interface. The absorption edge in UV-Vis absorption spectra for OA, OAm CsPbBr₃ QDs is placed around 513 nm (the band gap 2.38 eV); for DDAB CsPbBr₃ QDs, it is located at 490 nm (the band gap 2.33 eV). The photoluminescence (PL) spectra of CsPbBr₃ QDs show two peaks located around 514 nm (503 nm) and 718 nm (708 nm) for OA, OAm (DDAB). The peak around 500 nm corresponds to the PL of PQDs, and the peak close to 710 nm belongs to the surface states of PQDs for both types of ligands. These surface states are strongly affected by the O₃ plasma treatment. For PQDs with DDAB ligand, the O₃ exposure (5, 10, 15 s) results in the blue shift of the PQDs peak and a non-monotonous change of the amplitude of the surface states' peak. For OA, OAm ligand, the O₃ exposition did not cause any shift of the PQDs peak, and the intensity of the PL peak related to the surface states is lower by one order of magnitude in comparison with DDAB, being affected by O₃ plasma treatment. The PL results indicate the possibility of tuning the position of the PL maximum by the ligand of the PQDs. Similar behavior of the PQDs layer was observed for the ITO/QDs/MAPI samples, where an additional strong PL peak at 770 nm coming from the perovskite layer was observed; for the sample with PQDs with DDAB ligands, a small blue shift of the perovskite PL maximum was observed independently of the plasma treatment. These results suggest the possibility of affecting the PL maximum position and the surface states of the PQDs by the combination of a suitable ligand and the O₃ plasma treatment.Keywords: perovskite quantum dots, photoluminescence, O₃ plasma., Perovskite Solar Cells
Procedia PDF Downloads 64627 Properties of the CsPbBr₃ Quantum Dots Treated by O₃ Plasma for Integration in the Perovskite Solar Cell
Authors: Sh. Sousani, Z. Shadrokh, M. Hofbauerová, J. Kollár, M. Jergel, P. Nádaždy, M. Omastová, E. Majková
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Perovskite quantum dots (PQDs) have the potential to increase the performance of the perovskite solar cells (PSCs). The integration of PQDs into PSCs can extend the absorption range and enhance photon harvesting and device efficiency. In addition, PQDs can stabilize the device structure by passivating surface defects and traps in the perovskite layer and enhance its stability. The integration of PQDs into PSCs is strongly affected by the type of ligands on the surface of PQDs. The ligands affect the charge transport properties of PQDs, as well as the formation of well-defined interfaces and stability of PSCs. In this work, the CsPbBr₃ QDs were synthesized by the conventional hot-injection method using cesium oleate, PbBr₂, and two different ligands, namely oleic acid (OA)@oleylamine (OAm) and didodecyldimethylammonium bromide (DDAB). The STEM confirmed regular shape and relatively monodisperse cubic structure with an average size of about 10-14 nm of the prepared CsPbBr₃ QDs. Further, the photoluminescent (PL) properties of the PQDs/perovskite bilayer with the ligand OA@OAm and DDAB were studied. For this purpose, ITO/PQDs, as well as ITO/PQDs/MAPI perovskite structures, were prepared by spin coating, and the effect of the ligand and oxygen plasma treatment was analysed. The plasma treatment of the PQDs layer could be beneficial for the deposition of the MAPI perovskite layer and the formation of a well-defined PQDs/MAPI interface. The absorption edge in UV-Vis absorption spectra for OA@OAm CsPbBr₃ QDs is placed around 513 nm (the band gap 2.38 eV); for DDAB CsPbBr₃ QDs, it is located at 490 nm (the band gap 2.33 eV). The photoluminescence (PL) spectra of CsPbBr₃ QDs show two peaks located around 514 nm (503 nm) and 718 nm (708 nm) for OA@OAm (DDAB). The peak around 500 nm corresponds to the PL of PQDs, and the peak close to 710 nm belongs to the surface states of PQDs for both types of ligands. These surface states are strongly affected by the O₃ plasma treatment. For PQDs with DDAB ligand, the O₃ exposure (5, 10, 15 s) results in the blue shift of the PQDs peak and a non-monotonous change of the amplitude of the surface states' peak. For OA@OAm ligand, the O₃ exposition did not cause any shift of the PQDs peak, and the intensity of the PL peak related to the surface states is lower by one order of magnitude in comparison with DDAB, being affected by O₃ plasma treatment. The PL results indicate the possibility of tuning the position of the PL maximum by the ligand of the PQDs. Similar behaviour of the PQDs layer was observed for the ITO/QDs/MAPI samples, where an additional strong PL peak at 770 nm coming from the perovskite layer was observed; for the sample with PQDs with DDAB ligands, a small blue shift of the perovskite PL maximum was observed independently of the plasma treatment. These results suggest the possibility of affecting the PL maximum position and the surface states of the PQDs by the combination of a suitable ligand and the O₃ plasma treatment.Keywords: perovskite quantum dots, photoluminescence, O₃ plasma., perovskite solar cells
Procedia PDF Downloads 70626 Possibilities and Limits for the Development of Care in Primary Health Care in Brazil
Authors: Ivonete Teresinha Schulter Buss Heidemann, Michelle Kuntz Durand, Aline Megumi Arakawa-Belaunde, Sandra Mara Corrêa, Leandro Martins Costa Do Araujo, Kamila Soares Maciel
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Primary Health Care is defined as the level of a system of services that enables the achievement of answers to health needs. This level of care produces services and actions of attention to the person in the life cycle and in their health conditions or diseases. Primary Health Care refers to a conception of care model and organization of the health system that in Brazil seeks to reorganize the principles of the Unified Health System. This system is based on the principle of health as a citizen's right and duty of the State. Primary health care has family health as a priority strategy for its organization according to the precepts of the Unified Health System, structured in the logic of new sectoral practices, associating clinical work and health promotion. Thus, this study seeks to know the possibilities and limits of the care developed by professionals working in Primary Health Care. It was conducted by a qualitative approach of the participant action type, based on Paulo Freire's Research Itinerary, which corresponds to three moments: Thematic Investigation; Encoding and Decoding; and, Critical Unveiling. The themes were investigated in a health unit with the development of a culture circle with 20 professionals, from a municipality in southern Brazil, in the first half of 2021. The participants revealed as possibilities the involvement, bonding and strengthening of the interpersonal relationships of the professionals who work in the context of primary care. Promoting welcoming in primary care has favoured care and teamwork, as well as improved access. They also highlighted that care planning, the use of technologies in the process of communication and the orientation of the population enhances the levels of problem-solving capacity and the organization of services. As limits, the lack of professional recognition and the scarce material and human resources were revealed, conditions that generate tensions for health care. The reduction in the number of professionals and the low salary are pointed out as elements that boost the motivation of the health team for the development of the work. The participants revealed that due to COVID-19, the flow of care had as a priority the pandemic situation, which affected health care in primary care, and prevention and health promotion actions were canceled. The study demonstrated that empowerment and professional involvement are fundamental to promoting comprehensive and problem-solving care. However, limits of the teams are observed when exercising their activities, these are related to the lack of human and material resources, and the expansion of public health policies is urgent.Keywords: health promotion, primary health care, health professionals, welcoming.
Procedia PDF Downloads 98625 A Review of How COVID-19 Has Created an Insider Fraud Pandemic and How to Stop It
Authors: Claire Norman-Maillet
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Insider fraud, including its various synonyms such as occupational, employee or internal fraud, is a major financial crime threat whereby an employee defrauds (or attempts to defraud) their current, prospective, or past employer. ‘Employee’ covers anyone employed by the company, including contractors, directors, and part time staff; they may be a solo bad actor or working in collusion with others, whether internal or external. Insider fraud is even more of a concern given the impacts of the Coronavirus pandemic, which has generated multiple opportunities to commit insider fraud. Insider fraud is something that is not necessarily thought of as a significant financial crime threat; the focus of most academics and practitioners has historically been on that of ‘external fraud’ against businesses or entities where an individual or group has no professional ties. Without the face-to-face, ‘over the shoulder’ capabilities of staff being able to keep an eye on their employees, there is a heightened reliance on trust and transparency. With this, naturally, comes an increased risk of insider fraud perpetration. The objective of the research is to better understand how companies are impacted by insider fraud, and therefore how to stop it. This research will make both an original contribution and stimulate debate within the financial crime field. The financial crime landscape is never static – criminals are always creating new ways to perpetrate financial crime, and new legislation and regulations are implemented as attempts to strengthen controls, in addition to businesses doing what they can internally to detect and prevent it. By focusing on insider fraud specifically, the research will be more specific and will be of greater use to those in the field. To achieve the aims of the research, semi-structured interviews were conducted with 22 individuals who either work in financial services and deal with insider fraud or work within insider fraud perpetration in a recruitment or advisory capacity. This was to enable the sourcing of information from a wide range of individuals in a setting where they were able to elaborate on their answers. The principal recruitment strategy was engaging with the researcher’s network on LinkedIn. The interviews were then transcribed and analysed thematically. Main findings in the research suggest that insider fraud has been ignored owing to the denial of accepting the possibility that colleagues would defraud their employer. Whilst Coronavirus has led to a significant rise in insider fraud, this type of crime has been a major risk to businesses since their inception, however have never been given the financial or strategic backing required to be mitigated, until it's too late. Furthermore, Coronavirus should have led to companies tightening their access rights, controls and policies to mitigate the insider fraud risk. However, in most cases this has not happened. The research concludes that insider fraud needs to be given a platform upon which to be recognised as a threat to any company and given the same level of weighting and attention by Executive Committees and Boards as other types of economic crime.Keywords: fraud, insider fraud, economic crime, coronavirus, Covid-19
Procedia PDF Downloads 68624 The Negative Impact of Mindfulness on Creativity: An Experimental Test
Authors: Marine Agogue, Beatrice Parguel, Emilie Canet
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Defined as receptive attention to and awareness of present events and experience, mindfulness has grown in popularity over the past 30 years to become a trendy buzzword in business media, which regularly reports on its organizational benefits. Mindfulness would enhance or impede creative thinking depending on the type of meditation. Specifically, focused-attention meditation (focusing attention on one object instead of being open to perceive and observe any sensation or thought) would not be or negatively correlated to creativity. This research explores whether mood, in its two dimensions (i.e., hedonic tone, activation level), could mediate this potentially negative effect. The rationale is that focused-attention meditation is likely to improve hedonic tone but, in the meantime, damage activation level, resulting in opposite effects on creativity through the mediation effect of creative self-efficacy, i.e., the belief that one can perform successfully in an ideation setting. To test this conceptual model, a survey was administered to 97 subjects (53% women, mean age: 25 years), randomly assigned to three conditions (a 10-minute focused-attention meditation session vs. a 10-minute psychometric tests session vs. a control condition) and asked to participate in the egg creative task. Creativity was measured in terms of fluency, expansivity, and originality, the other variables using existing scales: hedonic tone (e.g., joyful, happy), activation level (e.g., passive, sluggish), creative self-efficacy (e.g., ‘I felt confident in my ability to do the task effectively’) and self-perceived creativity (e.g., ‘I have lots of original ideas’). The chains of mediation were tested using PROCESS macro (model 6) and controlled for subjects’ gender, age, and self-perceived creativity. Comparing the mindfulness and the control conditions, no difference appeared in terms of creativity, nor any mediation chain by hedonic tone. However, subjects who participated in the meditation session felt less active than those in the control condition, which decreased their creative self-efficacy, and creativity (whatever the indicator considered). Comparing the mindfulness and the psychometric tests conditions, analyses showed that creativity was higher in the psychometric tests condition. As previously, no mediation chain appeared by hedonic tone. However, subjects who participated in the meditation session felt less active than those in the psychometric tests condition, which decreased their creative self-efficacy, and creativity. These findings confirm that focused-attention meditation does not enhance creativity. They demonstrate an emotional underlying mechanism based on activation level and suggest that both positive and active mood states have the potential to enhance creativity through creative self-efficacy. In the end, they should discourage organizations from trying to nudge creativity using mindfulness ad hoc devices.Keywords: creativity, mindfulness, creative self-efficacy, experiment
Procedia PDF Downloads 132623 The French Ekang Ethnographic Dictionary. The Quantum Approach
Authors: Henda Gnakate Biba, Ndassa Mouafon Issa
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Dictionaries modeled on the Western model [tonic accent languages] are not suitable and do not account for tonal languages phonologically, which is why the [prosodic and phonological] ethnographic dictionary was designed. It is a glossary that expresses the tones and the rhythm of words. It recreates exactly the speaking or singing of a tonal language, and allows the non-speaker of this language to pronounce the words as if they were a native. It is a dictionary adapted to tonal languages. It was built from ethnomusicological theorems and phonological processes, according to Jean. J. Rousseau 1776 hypothesis /To say and to sing were once the same thing/. Each word in the French dictionary finds its corresponding language, ekaη. And each word ekaη is written on a musical staff. This ethnographic dictionary is also an inventive, original and innovative research thesis, but it is also an inventive, original and innovative research thesis. A contribution to the theoretical, musicological, ethno musicological and linguistic conceptualization of languages, giving rise to the practice of interlocution between the social and cognitive sciences, the activities of artistic creation and the question of modeling in the human sciences: mathematics, computer science, translation automation and artificial intelligence. When you apply this theory to any text of a folksong of a world-tone language, you do not only piece together the exact melody, rhythm, and harmonies of that song as if you knew it in advance but also the exact speaking of this language. The author believes that the issue of the disappearance of tonal languages and their preservation has been structurally resolved, as well as one of the greatest cultural equations related to the composition and creation of tonal, polytonal and random music. The experimentation confirming the theorization designed a semi-digital, semi-analog application which translates the tonal languages of Africa (about 2,100 languages) into blues, jazz, world music, polyphonic music, tonal and anatonal music and deterministic and random music). To test this application, I use a music reading and writing software that allows me to collect the data extracted from my mother tongue, which is already modeled in the musical staves saved in the ethnographic (semiotic) dictionary for automatic translation ( volume 2 of the book). Translation is done (from writing to writing, from writing to speech and from writing to music). Mode of operation: you type a text on your computer, a structured song (chorus-verse), and you command the machine a melody of blues, jazz and, world music or, variety etc. The software runs, giving you the option to choose harmonies, and then you select your melody.Keywords: music, language, entenglement, science, research
Procedia PDF Downloads 69622 The Legal Nature of Grading Decisions and the Implications for Handling of Academic Complaints in or out of Court: A Comparative Legal Analysis of Academic Litigation in Europe
Authors: Kurt Willems
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This research examines complaints against grading in higher education institutions in four different European regions: England and Wales, Flanders, the Netherlands, and France. The aim of the research is to examine the correlation between the applicable type of complaint handling on the one hand, and selected qualities of the higher education landscape and of public law on the other hand. All selected regions report a rising number of complaints against grading decisions, not only as to internal complaint handling within the institution but also judicially if the dispute persists. Some regions deem their administrative court system appropriate to deal with grading disputes (France) or have even erected a specialty administrative court to facilitate access (Flanders, the Netherlands). However, at the same time, different types of (governmental) dispute resolution bodies have been established outside of the judicial court system (England and Wales, and to lesser extent France and the Netherlands). Those dispute procedures do not seem coincidental. Public law issues such as the underlying legal nature of the education institution and, eventually, the grading decision itself, have an impact on the way the academic complaint procedures are developed. Indeed, in most of the selected regions, contractual disputes enjoy different legal protection than administrative decisions, making the legal qualification of the relationship between student and higher education institution highly relevant. At the same time, the scope of competence of government over different types of higher education institutions; albeit direct or indirect (o.a. through financing and quality control) is relevant as well to comprehend why certain dispute handling procedures have been established for students. To answer the above questions, the doctrinal and comparative legal method is used. The normative framework is distilled from the relevant national legislative rules and their preparatory texts, the legal literature, the (published) case law of academic complaints and the available governmental reports. The research is mainly theoretical in nature, examining different topics of public law (mainly administrative law) and procedural law in the context of grading decisions. The internal appeal procedure within the education institution is largely left out of the scope of the research, as well as different types of non-governmental-imposed cooperation between education institutions, given the public law angle of the research questions. The research results in the categorization of different academic complaint systems, and an analysis of the possibility to introduce each of those systems in different countries, depending on their public law system and higher education system. By doing so, the research also adds to the debate on the public-private divide in higher education systems, and its effect on academic complaints handling.Keywords: higher education, legal qualification of education institution, legal qualification of grading decisions, legal protection of students, academic litigation
Procedia PDF Downloads 230621 Combination Therapies Targeting Apoptosis Pathways in Pediatric Acute Myeloid Leukemia (AML)
Authors: Ahlam Ali, Katrina Lappin, Jaine Blayney, Ken Mills
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Leukaemia is the most frequently (30%) occurring type of paediatric cancer. Of these, approximately 80% are acute lymphoblastic leukaemia (ALL) with acute myeloid leukaemia (AML) cases making up the remaining 20% alongside other leukaemias. Unfortunately, children with AML do not have promising prognosis with only 60% surviving 5 years or longer. It has been highlighted recently the need for age-specific therapies for AML patients, with paediatric AML cases having a different mutational landscape compared with AML diagnosed in adult patients. Drug Repurposing is a recognized strategy in drug discovery and development where an already approved drug is used for diseases other than originally indicated. We aim to identify novel combination therapies with the promise of providing alternative more effective and less toxic induction therapy options. Our in-silico analysis highlighted ‘cell death and survival’ as an aberrant, potentially targetable pathway in paediatric AML patients. On this basis, 83 apoptotic inducing compounds were screened. A preliminary single agent screen was also performed to eliminate potentially toxic chemicals, then drugs were constructed into a pooled library with 10 drugs per well over 160 wells, with 45 possible pairs and 120 triples in each well. Seven cell lines were used during this study to represent the clonality of AML in paediatric patients (Kasumi-1, CMK, CMS, MV11-14, PL21, THP1, MOLM-13). Cytotoxicity was assessed up to 72 hours using CellTox™ Green reagent. Fluorescence readings were normalized to a DMSO control. Z-Score was assigned to each well based on the mean and standard deviation of all the data. Combinations with a Z-Score <2 were eliminated and the remaining wells were taken forward for further analysis. A well was considered ‘successful’ if each drug individually demonstrated a Z-Score <2, while the combination exhibited a Z-Score >2. Each of the ten compounds in one well (155) had minimal or no effect as single agents on cell viability however, a combination of two or more of the compounds resulted in a substantial increase in cell death, therefore the ten compounds were de-convoluted to identify a possible synergistic pair/triple combinations. The screen identified two possible ‘novel’ drug pairing, with BCL2 inhibitor ABT-737, combined with either a CDK inhibitor Purvalanol A, or AKT/ PI3K inhibitor LY294002. (ABT-737- 100 nM+ Purvalanol A- 1 µM) (ABT-737- 100 nM+ LY294002- 2 µM). Three possible triple combinations were identified (LY2409881+Akti-1/2+Purvalanol A, SU9516+Akti-1/2+Purvalanol A, and ABT-737+LY2409881+Purvalanol A), which will be taken forward for examining their efficacy at varying concentrations and dosing schedules, across multiple paediatric AML cell lines for optimisation of maximum synergy. We believe that our combination screening approach has potential for future use with a larger cohort of drugs including FDA approved compounds and patient material.Keywords: AML, drug repurposing, ABT-737, apoptosis
Procedia PDF Downloads 203620 Modeling and Simulating Productivity Loss Due to Project Changes
Authors: Robert Pellerin, Michel Gamache, Remi Trudeau, Nathalie Perrier
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The context of large engineering projects is particularly favorable to the appearance of engineering changes and contractual modifications. These elements are potential causes for claims. In this paper, we investigate one of the critical components of the claim management process: the calculation of the impacts of changes in terms of losses of productivity due to the need to accelerate some project activities. When project changes are initiated, delays can arise. Indeed, project activities are often executed in fast-tracking in an attempt to respect the completion date. But the acceleration of project execution and the resulting rework can entail important costs as well as induce productivity losses. In the past, numerous methods have been proposed to quantify the duration of delays, the gains achieved by project acceleration, and the loss of productivity. The calculation related to those changes can be divided into two categories: direct cost and indirect cost. The direct cost is easily quantifiable as opposed to indirect costs which are rarely taken into account during the calculation of the cost of an engineering change or contract modification despite several research projects have been made on this subject. However, proposed models have not been accepted by companies yet, nor they have been accepted in court. Those models require extensive data and are often seen as too specific to be used for all projects. These techniques are also ignoring the resource constraints and the interdependencies between the causes of delays and the delays themselves. To resolve this issue, this research proposes a simulation model that mimics how major engineering changes or contract modifications are handled in large construction projects. The model replicates the use of overtime in a reactive scheduling mode in order to simulate the loss of productivity present when a project change occurs. Multiple tests were conducted to compare the results of the proposed simulation model with statistical analysis conducted by other researchers. Different scenarios were also conducted in order to determine the impact the number of activities, the time of occurrence of the change, the availability of resources, and the type of project changes on productivity loss. Our results demonstrate that the number of activities in the project is a critical variable influencing the productivity of a project. When changes occur, the presence of a large number of activities leads to a much lower productivity loss than a small number of activities. The speed of reducing productivity for 30-job projects is about 25 percent faster than the reduction speed for 120-job projects. The moment of occurrence of a change also shows a significant impact on productivity. Indeed, the sooner the change occurs, the lower the productivity of the labor force. The availability of resources also impacts the productivity of a project when a change is implemented. There is a higher loss of productivity when the amount of resources is restricted.Keywords: engineering changes, indirect costs overtime, productivity, scheduling, simulation
Procedia PDF Downloads 238619 Modification of Escherichia coli PtolT Expression Vector via Site-Directed Mutagenesis
Authors: Yakup Ulusu, Numan Eczacıoğlu, İsa Gökçe, Helen Waller, Jeremy H. Lakey
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Besides having the appropriate amino acid sequence to perform the function of proteins, it is important to have correct conformation after this sequence to process. To consist of this conformation depends on the amino acid sequence at the primary structure, hydrophobic interaction, chaperones and enzymes in charge of folding etc. Misfolded proteins are not functional and tend to be aggregated. Cysteine originating disulfide cross-links make stable this conformation of functional proteins. When two of the cysteine amino acids come side by side, disulfide bond is established that forms a cystine bridge. Due to this feature cysteine plays an important role on the formation of three-dimensional structure of many proteins. There are two cysteine amino acids (C44, C69) in the Tol-A-III protein. Unlike protein disulfide bonds from within his own, any non-specific cystine bridge causes a change in the three dimensional structure of the protein. Proteins can be expressed in various host cells as directly or fusion (chimeric). As a result of overproduction of the recombinant proteins, aggregation of insoluble proteins in the host cell can occur by forming a crystal structure called inclusion body. In general fusion proteins are produced for provide affinity tags to make proteins more soluble and production of some toxic proteins via fusion protein expression system like pTolT. Proteins can be modified by using a site-directed mutagenesis. By this way, creation of non-specific disulfide crosslinks can be prevented at fusion protein expression system via the present cysteine replaced by another amino acid such as serine, glycine or etc. To do this, we need; a DNA molecule that contains the gene that encodes for the target protein, required primers for mutation to be designed according to site directed mutagenesis reaction. This study was aimed to be replaced cysteine encoding codon TGT with serine encoding codon AGT. For this sense and reverse primers designed (given below) and used site-directed mutagenesis reaction. Several new copy of the template plasmid DNA has been formed with above mentioned mutagenic primers via polymerase chain reaction (PCR). PCR product consists of both the master template DNA (wild type) and the new DNA sequences containing mutations. Dpn-l endonuclease restriction enzyme which is specific for methylated DNA and cuts them to the elimination of the master template DNA. E. coli cells obtained after transformation were incubated LB medium with antibiotic. After purification of plasmid DNA from E. coli, the presence of the mutation was determined by DNA sequence analysis. Developed this new plasmid is called PtolT-δ.Keywords: site directed mutagenesis, Escherichia coli, pTolT, protein expression
Procedia PDF Downloads 374618 Optimization Principles of Eddy Current Separator for Mixtures with Different Particle Sizes
Authors: Cao Bin, Yuan Yi, Wang Qiang, Amor Abdelkader, Ali Reza Kamali, Diogo Montalvão
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The study of the electrodynamic behavior of non-ferrous particles in time-varying magnetic fields is a promising area of research with wide applications, including recycling of non-ferrous metals, mechanical transmission, and space debris. The key technology for recovering non-ferrous metals is eddy current separation (ECS), which utilizes the eddy current force and torque to separate non-ferrous metals. ECS has several advantages, such as low energy consumption, large processing capacity, and no secondary pollution, making it suitable for processing various mixtures like electronic scrap, auto shredder residue, aluminum scrap, and incineration bottom ash. Improving the separation efficiency of mixtures with different particle sizes in ECS can create significant social and economic benefits. Our previous study investigated the influence of particle size on separation efficiency by combining numerical simulations and separation experiments. Pearson correlation analysis found a strong correlation between the eddy current force in simulations and the repulsion distance in experiments, which confirmed the effectiveness of our simulation model. The interaction effects between particle size and material type, rotational speed, and magnetic pole arrangement were examined. It offer valuable insights for the design and optimization of eddy current separators. The underlying mechanism behind the effect of particle size on separation efficiency was discovered by analyzing eddy current and field gradient. The results showed that the magnitude and distribution heterogeneity of eddy current and magnetic field gradient increased with particle size in eddy current separation. Based on this, we further found that increasing the curvature of magnetic field lines within particles could also increase the eddy current force, providing a optimized method to improving the separation efficiency of fine particles. By combining the results of the studies, a more systematic and comprehensive set of optimization guidelines can be proposed for mixtures with different particle size ranges. The separation efficiency of fine particles could be improved by increasing the rotational speed, curvature of magnetic field lines, and electrical conductivity/density of materials, as well as utilizing the eddy current torque. When designing an ECS, the particle size range of the target mixture should be investigated in advance, and the suitable parameters for separating the mixture can be fixed accordingly. In summary, these results can guide the design and optimization of ECS, and also expand the application areas for ECS.Keywords: eddy current separation, particle size, numerical simulation, metal recovery
Procedia PDF Downloads 89617 Prevalence of Bovine Mastitis and Associated Risk Factors in Selected Dairy Farms in Zoba Anseba, Eritrea
Authors: Redie Kidane Ghebrehawariat, Betiel Habte Hadgu, Filmon Berhane Kahsay, Rim Berhane Fisehaye, Samuel Haile Kahsay, Saron Yemane Yosief, Selemawit Mosazghi Gilazghi
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A cross-sectional study was conducted from 22 February to 9 April 2022 on small, medium, and large holder dairy farms to determine the bovine mastitis prevalence and associated risk factors in the Anseba region, Eritrea. A total of 34 dairy farms and 193 dairy cows were randomly selected. Dairy cows were physically examined for any change on the udder and milk; a California mastitis test was performed to check sub-clinical mastitis; a closed-ended semi-structured questionnaire composed of 28 variables/risk factors (21 management risk factors and 7 animal-level risk factors) was used to determine the risk factors responsible for clinical and sub-clinical mastitis in the dairy cows. The overall cow-level prevalence of mastitis was 147 (76.2%). The animal level prevalence rate of clinical and sub-clinical mastitis was found to be 22 (11.4%) and 125 (64.8%), respectively, while herd level prevalence both for clinical and subclinical mastitis was found to be 14 (41.2%) and 26 (76.5%) respectively. Based on the already set P-value, which is <0.05, a number of risk factors were found to have a significant relationship with the occurrence of clinical and sub-clinical mastitis. Generally, animal risk factors such as animal age, parity, injury on the udder or teat, and previous history of mastitis presence of injury on the udder and lactation stage were risk factors with a significant relationship with the occurrence of clinical and sub-clinical mastitis. On the other hand, management risk factors with a significant relationship to the occurrence of clinical and sub-clinical mastitis were herd size, failure to milk mastitic cow, at last, educational level, floor type, failure to use a towel, using one towel for more than one cow and failure to practice mastitis test. From a total of 772 quarters, 280 (36.3%) were found positive for sub-clinical mastitis using the California mastitis test; of these, 70 (9%) were weakly positive, 90 (11.7%) were distinct positive, and 120 (15.5%) were strongly positive. Furthermore, 13 (1.7%) quarters were blocked. Quarter level prevalence was right front 80 (41.5%), left front 64 (33.3%), right hind 69 (35.8%) and left hind 67 (34.7%). The study has shown that mastitis is a major problem for dairy farms and the findings suggested that mastitis is one of the limiting factors in increasing milk production. Subclinical mastitis was found to be a devastating problem, and it occurred in all three breeds of lactating dairy cattle. Therefore, farmers should work hard to avoid the above-mentioned risk factors to minimize the infection of their dairy cattle by mastitis and thereby increase their profit. On the other hand, the Ministry of Agriculture, through the extension unit, should work in close contact with the farmers to increase awareness of the economic importance of the disease and associated risk factors.Keywords: mastitis, prevalence, dairy cattle, Anseba, Eritrea
Procedia PDF Downloads 128616 An Exploration of Policy-related Documents on District Heating and Cooling in Flanders: A Slow and Bottom-up Process
Authors: Isaura Bonneux
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District heating and cooling (DHC) is increasingly recognized as a viable path towards sustainable heating and cooling. While some countries like Sweden and Denmark have a longstanding tradition of DHC, Belgium is lacking behind. The Northern part of Belgium, Flanders, had only a total of 95 heating networks in July 2023. Nevertheless, it is increasingly exploring its possibilities to enhance the scope of DHC. DHC is a complex energy system, requiring a lot of collaboration between various stakeholders on various levels. Therefore, it is of interest to look closer at policy-related documents at the Flemish (regional) level, as these policies set the scene for DHC development in the Flemish region. This kind of analysis has not been undertaken so far. This paper has the following research question: “Who talks about DHC, and in which way and context is DHC discussed in Flemish policy-related documents?” To answer this question, the Overton policy database was used to search and retrieve relevant policy-related documents. Overton retrieves data from governments, think thanks, NGOs, and IGOs. In total, out of the 244 original results, 117 documents between 2009 and 2023 were analyzed. Every selected document included theme keywords, policymaking department(s), date, and document type. These elements were used for quantitative data description and visualization. Further, qualitative content analysis revealed patterns and main themes regarding DHC in Flanders. Four main conclusions can be drawn: First, it is obvious from the timeframe that DHC is a new topic in Flanders with still limited attention; 2014, 2016 and 2017 were the years with the most documents, yet this number is still only 12 documents. In addition, many documents talked about DHC but not much in depth and painted it as a future scenario with a lot of uncertainty around it. The largest part of the issuing government departments had a link to either energy or climate (e.g. Flemish Environmental Agency) or policy (e.g. Socio-Economic Council of Flanders) Second, DHC is mentioned most within an ‘Environment and Sustainability’ context, followed by ‘General Policy and Regulation’. This is intuitive, as DHC is perceived as a sustainable heating and cooling technique and this analysis compromises policy-related documents. Third, Flanders seems mostly interested in using waste or residual heat as a heating source for DHC. The harbors and waste incineration plants are identified as potential and promising supply sources. This approach tries to conciliate environmental and economic incentives. Last, local councils get assigned a central role and the initiative is mostly taken by them. The policy documents and policy advices demonstrate that Flanders opts for a bottom-up organization. As DHC is very dependent on local conditions, this seems a logic step. Nevertheless, this can impede smaller councils to create DHC networks and slow down systematic and fast implementation of DHC throughout Flanders.Keywords: district heating and cooling, flanders, overton database, policy analysis
Procedia PDF Downloads 44615 Eucalyptus camaldulensis Leaves Attacked by the Gall Wasp Leptocybe invasa: A Phyto-Volatile Constituents Study
Authors: Maged El-Sayed Mohamed
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Eucalyptus camaldulensis is one on the most well-known species of the genus Eucalyptus in the Middle east, its importance relay on the high production of its unique volatile constituents which exhibits many medicinal and pharmacological activities. The gall-forming wasp (Leptocybe invasa) has recently come into sight as the main pest attacking E. camaldulensis and causing severe injury. The wasp lays its eggs in the petiole and midrib of leaves and stems of young shoots of E. camaldulensis, which leads to gall formation. Gall formation by L. invasa damages growing shoot and leaves of Eucalyptus, resulting in abscission of leaves and drying. AIM: This study is an attempt to investigate the effect of the gall wasp (Leptocybe invasa) attack on the volatile constitutes of E. camaldulensis. This could help in the control of this wasp through stimulating plant defenses or production of a new allelochemicals or insecticide. The study of volatile constitutes of Eucalyptus before and after attack by the wasp can help the re-use and recycle of the infected Eucalyptus trees for new pharmacological and medicinal activities. Methodology: The fresh gall wasp-attacked and healthy leaves (100 g each) were cut and immediately subjected to hydrodistillation using Clevenger-type apparatus for 3 hours. The volatile fractions isolated were analyzed using Gas chromatography/mass spectrometry (GC/MS). Kovat’s retention indices (RI) were calculated with respect to a set of co-injected standard hydrocarbons (C10-C28). Compounds were identified by comparing their spectral data and retention indices with Wiley Registry of Mass Spectral Data 10th edition (April 2013), NIST 11 Mass Spectral Library (NIST11/2011/EPA/NIH) and literature data. Results: Fifty-nine components representing 89.13 and 88.60% of the total volatile fraction content respectively were quantitatively analyzed. Twenty-six major compounds at an average concentration greater than 0.1 ± 0.02% have been used for the statistical comparison. From those major components, twenty-one were found in both the attacked and healthy Eucalyptus leaves’ fractions in different concentration and five components, mono terpene p-Mentha-2-4(8) diene and the sesquiterpenes δ-elemene, β-elemene, E-caryophyllene and Bicyclogermacrene, were unique and only produced in the attacked-leaves’ fraction. CONCLUSION: Newly produced components or those commonly found in the volatile fraction and changed in concentration could represent a part of the plant defense mechanisms or might be an element of the plant allelopathic and communication mechanisms. Identification of the components of the gall wasp-damaged leaves can help in their recycling for different physiological, pharmacological and medicinal uses.Keywords: Eucalyptus camaldulensis, eucalyptus recycling, gall wasp, Leptocybe invasa, plant defense mechanisms, Terpene fraction
Procedia PDF Downloads 358614 Oligarchic Transitions within the Tunisian Autocratic Authoritarian System and the Struggle for Democratic Transformation: Before and beyond the 2010 Jasmine Revolution
Authors: M. Moncef Khaddar
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This paper focuses mainly on a contextualized understanding of ‘autocratic authoritarianism’ in Tunisia without approaching its peculiarities in reference to the ideal type of capitalist-liberal democracy but rather analysing it as a Tunisian ‘civilian dictatorship’. This is reminiscent, to some extent, of the French ‘colonial authoritarianism’ in parallel with the legacy of the traditional formal monarchic absolutism. The Tunisian autocratic political system is here construed as a state manufactured nationalist-populist authoritarianism associated with a de facto presidential single party, two successive autocratic presidents and their subservient autocratic elites who ruled with an iron fist the de-colonialized ‘liberated nation’ that came to be subjected to a large scale oppression and domination under the new Tunisian Republic. The diachronic survey of Tunisia’s autocratic authoritarian system covers the early years of autocracy, under the first autocratic president Bourguiba, 1957-1987, as well as the different stages of its consolidation into a police-security state under the second autocratic president, Ben Ali, 1987-2011. Comparing the policies of authoritarian regimes, within what is identified synchronically as a bi-cephalous autocratic system, entails an in-depth study of the two autocrats, who ruled Tunisia for more than half a century, as modern adaptable autocrats. This is further supported by an exploration of the ruling authoritarian autocratic elites who played a decisive role in shaping the undemocratic state-society relations, under the 1st and 2nd President, and left an indelible mark, structurally and ideologically, on Tunisian polity. Emphasis is also put on the members of the governmental and state-party institutions and apparatuses that kept circulating and recycling from one authoritarian regime to another, and from the first ‘founding’ autocrat to his putschist successor who consolidated authoritarian stability, political continuity and autocratic governance. The reconfiguration of Tunisian political life, in the post-autocratic era, since 2011 will be analysed. This will be scrutinized, especially in light of the unexpected return of many high-profile figures and old guards of the autocratic authoritarian apparatchiks. How and why were, these public figures, from an autocratic era, able to return in a supposedly post-revolutionary moment? Finally, while some continue to celebrate the putative exceptional success of ‘democratic transition’ in Tunisia, within a context of ‘unfinished revolution’, others remain perplexed in the face of a creeping ‘oligarchic transition’ to a ‘hybrid regime’, characterized rather by elites’ reformist tradition than a bottom-up genuine democratic ‘change’. This latter is far from answering the 2010 ordinary people’s ‘uprisings’ and ‘aspirations, for ‘Dignity, Liberty and Social Justice’.Keywords: authoritarianism, autocracy, democratization, democracy, populism, transition, Tunisia
Procedia PDF Downloads 147613 Human Creativity through Dooyeweerd's Philosophy: The Case of Creative Diagramming
Authors: Kamaran Fathulla
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Human creativity knows no bounds. More than a millennia ago humans have expressed their knowledge on cave walls and on clay artefacts. Using visuals such as diagrams and paintings have always provided us with a natural and intuitive medium for expressing such creativity. Making sense of human generated visualisation has been influenced by western scientific philosophies which are often reductionist in their nature. Theoretical frameworks such as those delivered by Peirce dominated our views of how to make sense of visualisation where a visual is seen as an emergent property of our thoughts. Others have reduced the richness of human-generated visuals to mere shapes drawn on a piece of paper or on a screen. This paper introduces an alternate framework where the centrality of human functioning is given explicit and richer consideration through the multi aspectual philosophical works of Herman Dooyeweerd. Dooyeweerd's framework of understanding reality was based on fifteen aspects of reality, each having a distinct core meaning. The totality of the aspects formed a ‘rainbow’ like spectrum of meaning. The thesis of this approach is that meaningful human functioning in most cases involves the diversity of all aspects working in synergy and harmony. Illustration of the foundations and applicability of this approach is underpinned in the case of humans use of diagramming for creative purposes, particularly within an educational context. Diagrams play an important role in education. Students and lecturers use diagrams as a powerful tool to aid their thinking. However, research into the role of diagrams used in education continues to reveal difficulties students encounter during both processes of interpretation and construction of diagrams. Their main problems shape up students difficulties with diagrams. The ever-increasing diversity of diagrams' types coupled with the fact that most real-world diagrams often contain a mix of these different types of diagrams such as boxes and lines, bar charts, surfaces, routes, shapes dotted around the drawing area, and so on with each type having its own distinct set of static and dynamic semantics. We argue that the persistence of these problems is grounded in our existing ways of understanding diagrams that are often reductionist in their underpinnings driven by a single perspective or formalism. In this paper, we demonstrate the limitations of these approaches in dealing with the three problems. Consequently, we propose, discuss, and demonstrate the potential of a nonreductionist framework for understanding diagrams based on Symbolic and Spatial Mappings (SySpM) underpinned by Dooyeweerd philosophy. The potential of the framework to account for the meaning of diagrams is demonstrated by applying it to a real-world case study physics diagram.Keywords: SySpM, drawing style, mapping
Procedia PDF Downloads 238612 The Impact of HKUST-1 Metal-Organic Framework Pretreatment on Dynamic Acetaldehyde Adsorption
Authors: M. François, L. Sigot, C. Vallières
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Volatile Organic Compounds (VOCs) are a real health issue, particularly in domestic indoor environments. Among these VOCs, acetaldehyde is frequently monitored in dwellings ‘air, especially due to smoking and spontaneous emissions from the new wall and soil coverings. It is responsible for respiratory complaints and is classified as possibly carcinogenic to humans. Adsorption processes are commonly used to remove VOCs from the air. Metal-Organic Frameworks (MOFs) are a promising type of material for high adsorption performance. These hybrid porous materials composed of metal inorganic clusters and organic ligands are interesting thanks to their high porosity and surface area. The HKUST-1 (also referred to as MOF-199) is a copper-based MOF with the formula [Cu₃(BTC)₂(H₂O)₃]n (BTC = benzene-1,3,5-tricarboxylate) and exhibits unsaturated metal sites that can be attractive sites for adsorption. The objective of this study is to investigate the impact of HKUST-1 pretreatment on acetaldehyde adsorption. Thus, dynamic adsorption experiments were conducted in 1 cm diameter glass column packed with 2 cm MOF bed height. MOF were sieved to 630 µm - 1 mm. The feed gas (Co = 460 ppmv ± 5 ppmv) was obtained by diluting a 1000 ppmv acetaldehyde gas cylinder in air. The gas flow rate was set to 0.7 L/min (to guarantee a suitable linear velocity). Acetaldehyde concentration was monitored online by gas chromatography coupled with a flame ionization detector (GC-FID). Breakthrough curves must allow to understand the interactions between the MOF and the pollutant as well as the impact of the HKUST-1 humidity in the adsorption process. Consequently, different MOF water content conditions were tested, from a dry material with 7 % water content (dark blue color) to water saturated state with approximately 35 % water content (turquoise color). The rough material – without any pretreatment – containing 30 % water serves as a reference. First, conclusions can be drawn from the comparison of the evolution of the ratio of the column outlet concentration (C) on the inlet concentration (Co) as a function of time for different HKUST-1 pretreatments. The shape of the breakthrough curves is significantly different. The saturation of the rough material is slower (20 h to reach saturation) than that of the dried material (2 h). However, the breakthrough time defined for C/Co = 10 % appears earlier in the case of the rough material (0.75 h) compared to the dried HKUST-1 (1.4 h). Another notable difference is the shape of the curve before the breakthrough at 10 %. An abrupt increase of the outlet concentration is observed for the material with the lower humidity in comparison to a smooth increase for the rough material. Thus, the water content plays a significant role on the breakthrough kinetics. This study aims to understand what can explain the shape of the breakthrough curves associated to the pretreatments of HKUST-1 and which mechanisms take place in the adsorption process between the MOF, the pollutant, and the water.Keywords: acetaldehyde, dynamic adsorption, HKUST-1, pretreatment influence
Procedia PDF Downloads 237611 Peculiarities of Snow Cover in Belarus
Authors: Aleh Meshyk, Anastasiya Vouchak
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On the average snow covers Belarus for 75 days in the south-west and 125 days in the north-east. During the cold season snowpack often destroys due to thaws, especially at the beginning and end of winter. Over 50% of thawing days have a positive mean daily temperature, which results in complete snow melting. For instance, in December 10% of thaws occur at 4 С mean daily temperature. Stable snowpack lying for over a month forms in the north-east in the first decade of December but in the south-west in the third decade of December. The cover disappears in March: in the north-east in the last decade but in the south-west in the first decade. This research takes into account that precipitation falling during a cold season could be not only liquid and solid but also a mixed type (about 10-15 % a year). Another important feature of snow cover is its density. In Belarus, the density of freshly fallen snow ranges from 0.08-0.12 g/cm³ in the north-east to 0.12-0.17 g/cm³ in the south-west. Over time, snow settles under its weight and after melting and refreezing. Averaged annual density of snow at the end of January is 0.23-0.28 g/сm³, in February – 0.25-0.30 g/сm³, in March – 0.29-0.36 g/сm³. Sometimes it can be over 0.50 g/сm³ if the snow melts too fast. The density of melting snow saturated with water can reach 0.80 g/сm³. Average maximum of snow depth is 15-33 cm: minimum is in Brest, maximum is in Lyntupy. Maximum registered snow depth ranges within 40-72 cm. The water content in snowpack, as well as its depth and density, reaches its maximum in the second half of February – beginning of March. Spatial distribution of the amount of liquid in snow corresponds to the trend described above, i.e. it increases in the direction from south-west to north-east and on the highlands. Average annual value of maximum water content in snow ranges from 35 mm in the south-west to 80-100 mm in the north-east. The water content in snow is over 80 mm on the central Belarusian highland. In certain years it exceeds 2-3 times the average annual values. Moderate water content in snow (80-95 mm) is characteristic of western highlands. Maximum water content in snow varies over the country from 107 mm (Brest) to 207 mm (Novogrudok). Maximum water content in snow varies significantly in time (in years), which is confirmed by high variation coefficient (Cv). Maximums (0.62-0.69) are in the south and south-west of Belarus. Minimums (0.42-0.46) are in central and north-eastern Belarus where snow cover is more stable. Since 1987 most gauge stations in Belarus have observed a trend to a decrease in water content in snow. It is confirmed by the research. The biggest snow cover forms on the highlands in central and north-eastern Belarus. Novogrudok, Minsk, Volkovysk, and Sventayny highlands are a natural orographic barrier which prevents snow-bringing air masses from penetrating inside the country. The research is based on data from gauge stations in Belarus registered from 1944 to 2014.Keywords: density, depth, snow, water content in snow
Procedia PDF Downloads 161610 Properties Optimization of Keratin Films Produced by Film Casting and Compression Moulding
Authors: Mahamad Yousif, Eoin Cunningham, Beatrice Smyth
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Every year ~6 million tonnes of feathers are produced globally. Due to feathers’ low density and possible contamination with pathogens, their disposal causes health and environmental problems. The extraction of keratin, which represents >90% of feathers’ dry weight, could offer a solution due to its wide range of applications in the food, medical, cosmetics, and biopolymer industries. One of these applications is the production of biofilms which can be used for packaging, edible films, drug delivery, wound healing etc. Several studies in the last two decades investigated keratin film production and its properties. However, the effects of many parameters on the properties of the films remain to be investigated including the extraction method, crosslinker type and concentration, and the film production method. These parameters were investigated in this study. Keratin was extracted from chicken feathers using two methods, alkaline extraction with 0.5 M NaOH at 80 °C or sulphitolysis extraction with 0.5 M sodium sulphite, 8 M urea, and 0.25-1 g sodium dodecyl sulphate (SDS) at 100 °C. The extracted keratin was mixed with different types and concentrations of plasticizers (glycerol and polyethylene glycol) and crosslinkers (formaldehyde (FA), glutaraldehyde, cinnamaldehyde, glyoxal, and 1,4-Butanediol diglycidyl ether (BDE)). The mixtures were either cast in a mould or compression moulded to produce films. For casting, keratin powder was initially dissolved in water to form a 5% keratin solution and the mixture was dried in an oven at 60 °C. For compression moulding, 10% water was added and the compression moulding temperature and pressure were in the range of 60-120 °C and 10-30 bar. Finally, the tensile properties, solubility, and transparency of the films were analysed. The films prepared using the sulphitolysis keratin had superior tensile properties to the alkaline keratin and formed successfully with lower plasticizer concentrations. Lowering the SDS concentration from 1 to 0.25 g/g feathers improved all the tensile properties. All the films prepared without crosslinkers were 100% water soluble but adding crosslinkers reduced solubility to as low as 21%. FA and BDE were found to be the best crosslinkers increasing the tensile strength and elongation at break of the films. Higher compression moulding temperature and pressure lowered the tensile properties of the films; therefore, 80 °C and 10 bar were considered to be the optimal compression moulding temperature and pressure. Nevertheless, the films prepared by casting had higher tensile properties than compression moulding but were less transparent. Two optimal films, prepared by film casting, were identified and their compositions were: (a) Sulphitolysis keratin, 20% glycerol, 10% FA, and 10% BDE. (b) Sulphitolysis keratin, 20% glycerol, and 10% BDE. Their tensile strength, elongation at break, Young’s modulus, solubility, and transparency were: (a) 4.275±0.467 MPa, 86.12±4.24%, 22.227±2.711 MPa, 21.34±1.11%, and 8.57±0.94* respectively. (b) 3.024±0.231 MPa, 113.65±14.61%, 10±1.948 MPa, 25.03±5.3%, and 4.8±0.15 respectively. A higher value indicates that the film is less transparent. The extraction method, film composition, and production method had significant influence on the properties of keratin films and should therefore be tailored to meet the desired properties and applications.Keywords: compression moulding, crosslinker, film casting, keratin, plasticizer, solubility, tensile properties, transparency
Procedia PDF Downloads 34609 Alternate Approaches to Quality Measurement: An Exploratory Study in Differentiation of “Quality” Characteristics in Services and Supports
Authors: Caitlin Bailey, Marian Frattarola Saulino, Beth Steinberg
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Today, virtually all programs offered to people with intellectual and developmental disabilities tout themselves as person-centered, community-based and inclusive, yet there is a vast range in type and quality of services that use these similar descriptors. The issue is exacerbated by the fields’ measurement practices around quality, inclusion, independent living, choice and person-centered outcomes. For instance, community inclusion for people with disabilities is often measured by the number of times person steps into his or her community. These measurement approaches set standards for quality too low so that agencies supporting group home residents to go bowling every week can report the same outcomes as an agency that supports one person to join a book club that includes people based on their literary interests rather than disability labels. Ultimately, lack of delineation in measurement contributes to the confusion between face value “quality” and true quality services and supports for many people with disabilities and their families. This exploratory study adopts alternative approaches to quality measurement including co-production methods and systems theoretical framework in order to identify the factors that 1) lead to high-quality supports and, 2) differentiate high-quality services. Project researchers have partnered with community practitioners who are all committed to providing quality services and supports but vary in the degree to which they are actually able to provide them. The study includes two parts; first, an online survey distributed to more than 500 agencies that have demonstrated commitment to providing high-quality services; and second, four in-depth case studies with agencies in three United States and Israel providing a variety of supports to children and adults with disabilities. Results from both the survey and in-depth case studies were thematically analyzed and coded. Results show that there are specific factors that differentiate service quality; however meaningful quality measurement practices also require that researchers explore the contextual factors that contribute to quality. These not only include direct services and interactions, but also characteristics of service users, their environments as well as organizations providing services, such as management and funding structures, culture and leadership. Findings from this study challenge researchers, policy makers and practitioners to examine existing quality service standards and measurements and to adopt alternate methodologies and solutions to differentiate and scale up evidence-based quality practices so that all people with disabilities have access to services that support them to live, work, and enjoy where and with whom they choose.Keywords: co-production, inclusion, independent living, quality measurement, quality supports
Procedia PDF Downloads 399608 Characterization of New Sources of Maize (Zea mays L.) Resistance to Sitophilus zeamais (Coleoptera: Curculionidae) Infestation in Stored Maize
Authors: L. C. Nwosu, C. O. Adedire, M. O. Ashamo, E. O. Ogunwolu
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The maize weevil, Sitophilus zeamais Motschulsky is a notorious pest of stored maize (Zea mays L.). The development of resistant maize varieties to manage weevils is a major breeding objective. The study investigated the parameters and mechanisms that confer resistance on a maize variety to S. zeamais infestation using twenty elite maize varieties. Detailed morphological, physical and chemical studies were conducted on whole-maize grain and the grain pericarp. Resistance was assessed at 33, 56, and 90 days post infestation using weevil mortality rate, weevil survival rate, percent grain damage, percent grain weight loss, weight of grain powder, oviposition rate and index of susceptibility as indices rated on a scale developed by the present study and on Dobie’s modified scale. Linear regression models that can predict maize grain damage in relation to the duration of storage were developed and applied. The resistant varieties identified particularly 2000 SYNEE-WSTR and TZBRELD3C5 with very high degree of resistance should be used singly or best in an integrated pest management system for the control of S. zeamais infestation in stored maize. Though increases in the physical properties of grain hardness, weight, length, and width increased varietal resistance, it was found that the bases of resistance were increased chemical attributes of phenolic acid, trypsin inhibitor and crude fibre while the bases of susceptibility were increased protein, starch, magnesium, calcium, sodium, phosphorus, manganese, iron, cobalt and zinc, the role of potassium requiring further investigation. Characters that conferred resistance on the test varieties were found distributed in the pericarp and the endosperm of the grains. Increases in grain phenolic acid, crude fibre, and trypsin inhibitor adversely and significantly affected the bionomics of the weevil on further assessment. The flat side of a maize grain at the point of penetration was significantly preferred by the weevil. Why the south area of the flattened side of a maize grain was significantly preferred by the weevil is clearly unknown, even though grain-face-type seemed to be a contributor in the study. The preference shown to the south area of the grain flat side has implications for seed viability. The study identified antibiosis, preference, antixenosis, and host evasion as the mechanisms of maize post harvest resistance to Sitophilus zeamais infestation.Keywords: maize weevil, resistant, parameters, mechanisms, preference
Procedia PDF Downloads 307607 Epididymis in the Agouti (Dasyprocta azarae): Light Microscope Study
Authors: Bruno C. Schimming, Leandro L. Martins, PatríCia F. F. Pinheiro, Raquel F. Domeniconi, FabríCio S. Oliveira
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The agouti is a wildlife rodent that can be used as an alternative source of animal protein and this species has been raised in captivity in Brazil with the aim of providing meat. Thus, the knowledge of their reproductive biology and morphology of the reproductive organs is important. The objective of this study was to describe the morphology of epididymis in the Azara’s agouti, by light microscopy. Samples of epididymis were obtained from five adult Azara’s agouti (Dasyprocta azarae) during castration surgery performed at the Municipal Zoo of Catanduva, Brazil. Fragments of the epididymal regions (initial segment, caput, corpus and cauda) were collected. The biological samples were immediately fixed in paraformaldehyde for 24 hours, followed by histologic procedures comprising embedding in ParaplastTM (Sigma, St. Louis, MO, USA), sections of 5 µm, and staining with HE and Masson’s trichrome. The epididymis was a highly convoluted tubule that links the testis to the vas deferens. The epithelium lining was pseudostratified columnar surrounded by a periductal stroma. The epithelium contains several cell types: principal, basal, apical, clear, and hallo cells. Principal cells were the most abundant cell type. There were observed also migratory cells named halo cells. The caput epididymis was divided into two different regions: initial segment and caput. The initial segment has a very wide lumen, a high epithelium with conspicuous microvilli and the lumen was wide with exfoliated material. The other region of the caput epididymis, showed a lower epithelium when compared with the initial segment, large amounts of spermatozoa in the lumen, and a cytoplasmic vacuolization. This region presented many narrows cells. Many spermatozoa appeared in the lumen of corpus epididymis. The cauda region had a lower epithelium than the other epididymal regions in the agouti. The cauda epithelium presented plicae protruding into the lumen. Large amounts of spermatozoa are also present in the lumen. Small microvilli uniformly arranged so as to form a kind of “brush border” are observed on the apical surface of the cauda epithelium. The pattern of the epithelium lining the duct of the agouti epididymis does not differ greatly from that reported to other mammals, such as domestic and wildlife animals. These findings can cooperate with future investigations especially those related to rational exploration of these animals. All experimental procedures were approved by the institutional ethics committee (CEUA 796/2015). This study was supported by FAPESP (Grants 2015/23822-1).Keywords: wildlife, testis excurrent ducts, epididymis, morphology
Procedia PDF Downloads 236606 Fire Risk Information Harmonization for Transboundary Fire Events between Portugal and Spain
Authors: Domingos Viegas, Miguel Almeida, Carmen Rocha, Ilda Novo, Yolanda Luna
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Forest fires along the more than 1200km of the Spanish-Portuguese border are more and more frequent, currently achieving around 2000 fire events per year. Some of these events develop to large international wildfire requiring concerted operations based on shared information between the two countries. The fire event of Valencia de Alcantara (2003) causing several fatalities and more than 13000ha burnt, is a reference example of these international events. Currently, Portugal and Spain have a specific cross-border cooperation protocol on wildfires response for a strip of about 30km (15 km for each side). It is recognized by public authorities the successfulness of this collaboration however it is also assumed that this cooperation should include more functionalities such as the development of a common risk information system for transboundary fire events. Since Portuguese and Spanish authorities use different approaches to determine the fire risk indexes inputs and different methodologies to assess the fire risk, sometimes the conjoint firefighting operations are jeopardized since the information is not harmonized and the understanding of the situation by the civil protection agents from both countries is not unique. Thus, a methodology aiming the harmonization of the fire risk calculation and perception by Portuguese and Spanish Civil protection authorities is hereby presented. The final results are presented as well. The fire risk index used in this work is the Canadian Fire Weather Index (FWI), which is based on meteorological data. The FWI is limited on its application as it does not take into account other important factors with great effect on the fire appearance and development. The combination of these factors is very complex since, besides the meteorology, it addresses several parameters of different topics, namely: sociology, topography, vegetation and soil cover. Therefore, the meaning of FWI values is different from region to region, according the specific characteristics of each region. In this work, a methodology for FWI calibration based on the number of fire occurrences and on the burnt area in the transboundary regions of Portugal and Spain, in order to assess the fire risk based on calibrated FWI values, is proposed. As previously mentioned, the cooperative firefighting operations require a common perception of the information shared. Therefore, a common classification of the fire risk for the fire events occurred in the transboundary strip is proposed with the objective of harmonizing this type of information. This work is integrated in the ECHO project SpitFire - Spanish-Portuguese Meteorological Information System for Transboundary Operations in Forest Fires, which aims the development of a web platform for the sharing of information and supporting decision tools to be used in international fire events involving Portugal and Spain.Keywords: data harmonization, FWI, international collaboration, transboundary wildfires
Procedia PDF Downloads 252605 The Politics of Foreign Direct Investment for Socio-Economic Development in Nigeria: An Assessment of the Fourth Republic Strategies (1999 - 2014)
Authors: Muritala Babatunde Hassan
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In the contemporary global political economy, foreign direct investment (FDI) is gaining currency on daily basis. Notably, the end of the Cold War has brought about the dominance of neoliberal ideology with its mantra of private-sector-led economy. As such, nation-states now see FDI attraction as an important element in their approach to national development. Governments and policy makers are preoccupying themselves with unraveling the best strategies to not only attract more FDI but also to attain the desired socio-economic development status. In Nigeria, the perceived development potentials of FDI have brought about aggressive hunt for foreign investors, most especially since transition to civilian rule in May 1999. Series of liberal and market oriented strategies are being adopted not only to attract foreign investors but largely to stimulate private sector participation in the economy. It is on this premise that this study interrogates the politics of FDI attraction for domestic development in Nigeria between 1999 and 2014, with the ultimate aim of examining the nexus between regime type and the ability of a state to attract and benefit from FDI. Building its analysis within the framework of institutional utilitarianism, the study posits that the essential FDI strategies for achieving the greatest happiness for the greatest number of Nigerians are political not economic. Both content analysis and descriptive survey methodology were employed in carrying out the study. Content analysis involves desk review of literatures that culminated in the development of the study’s conceptual and theoretical framework of analysis. The study finds no significant relationship between transition to democracy and FDI inflows in Nigeria, as most of the attracted investments during the period of the study were market and resource seeking as was the case during the military regime, thereby contributing minimally to the socio-economic development of the country. It is also found that the country placed much emphasis on liberalization and incentives for FDI attraction at the neglect of improving the domestic investment environment. Consequently, poor state of infrastructure, weak institutional capability and insecurity were identified as the major factors seriously hindering the success of Nigeria in exploiting FDI for domestic development. Given the reality of the currency of FDI as a vector of economic globalization and that Nigeria is trailing the line of private-sector-led approach to development, it is recommended that emphasis should be placed on those measures aimed at improving the infrastructural facilities, building solid institutional framework, enhancing skill and technological transfer and coordinating FDI promotion activities by different agencies and at different levels of government.Keywords: foreign capital, politics, socio-economic development, FDI attraction strategies
Procedia PDF Downloads 164604 New Bio-Strategies for Ochratoxin a Detoxification Using Lactic Acid Bacteria
Authors: José Maria, Vânia Laranjo, Luís Abrunhosa, António Inês
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The occurrence of mycotoxigenic moulds such as Aspergillus, Penicillium and Fusarium in food and feed has an important impact on public health, by the appearance of acute and chronic mycotoxicoses in humans and animals, which is more severe in the developing countries due to lack of food security, poverty and malnutrition. This mould contamination also constitutes a major economic problem due the lost of crop production. A great variety of filamentous fungi is able to produce highly toxic secondary metabolites known as mycotoxins. Most of the mycotoxins are carcinogenic, mutagenic, neurotoxic and immunosuppressive, being ochratoxin A (OTA) one of the most important. OTA is toxic to animals and humans, mainly due to its nephrotoxic properties. Several approaches have been developed for decontamination of mycotoxins in foods, such as, prevention of contamination, biodegradation of mycotoxins-containing food and feed with microorganisms or enzymes and inhibition or absorption of mycotoxin content of consumed food into the digestive tract. Some group of Gram-positive bacteria named lactic acid bacteria (LAB) are able to release some molecules that can influence the mould growth, improving the shelf life of many fermented products and reducing health risks due to exposure to mycotoxins. Some LAB are capable of mycotoxin detoxification. Recently our group was the first to describe the ability of LAB strains to biodegrade OTA, more specifically, Pediococcus parvulus strains isolated from Douro wines. The pathway of this biodegradation was identified previously in other microorganisms. OTA can be degraded through the hydrolysis of the amide bond that links the L-β-phenylalanine molecule to the ochratoxin alpha (OTα) a non toxic compound. It is known that some peptidases from different origins can mediate the hydrolysis reaction like, carboxypeptidase A an enzyme from the bovine pancreas, a commercial lipase and several commercial proteases. So, we wanted to have a better understanding of this OTA degradation process when LAB are involved and identify which molecules where present in this process. For achieving our aim we used some bioinformatics tools (BLAST, CLUSTALX2, CLC Sequence Viewer 7, Finch TV). We also designed specific primers and realized gene specific PCR. The template DNA used came from LAB strains samples of our previous work, and other DNA LAB strains isolated from elderberry fruit, silage, milk and sausages. Through the employment of bioinformatics tools it was possible to identify several proteins belonging to the carboxypeptidase family that participate in the process of OTA degradation, such as serine type D-Ala-D-Ala carboxypeptidase and membrane carboxypeptidase. In conclusions, this work has identified carboxypeptidase proteins being one of the molecules present in the OTA degradation process when LAB are involved.Keywords: carboxypeptidase, lactic acid bacteria, mycotoxins, ochratoxin a.
Procedia PDF Downloads 462603 Gold Nano Particle as a Colorimetric Sensor of HbA0 Glycation Products
Authors: Ranjita Ghoshmoulick, Aswathi Madhavan, Subhavna Juneja, Prasenjit Sen, Jaydeep Bhattacharya
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Type 2 diabetes mellitus (T2DM) is a very complex and multifactorial metabolic disease where the blood sugar level goes up. One of the major consequence of this elevated blood sugar is the formation of AGE (Advance Glycation Endproducts), from a series of chemical or biochemical reactions. AGE are detrimental because it leads to severe pathogenic complications. They are a group of structurally diverse chemical compounds formed from nonenzymatic reactions between the free amino groups (-NH2) of proteins and carbonyl groups (>C=O) of reducing sugars. The reaction is known as Maillard Reaction. It starts with the formation of reversible schiff’s base linkage which after sometime rearranges itself to form Amadori Product along with dicarbonyl compounds. Amadori products are very unstable hence rearrangement goes on until stable products are formed. During the course of the reaction a lot of chemically unknown intermediates and reactive byproducts are formed that can be termed as Early Glycation Products. And when the reaction completes, structurally stable chemical compounds are formed which is termed as Advanced Glycation Endproducts. Though all glycation products have not been characterized well, some fluorescence compounds e.g pentosidine, Malondialdehyde (MDA) or carboxymethyllysine (CML) etc as AGE and α-dicarbonyls or oxoaldehydes such as 3-deoxyglucosone (3-DG) etc as the intermediates have been identified. In this work Gold NanoParticle (GNP) was used as an optical indicator of glycation products. To achieve faster glycation kinetics and high AGE accumulation, fructose was used instead of glucose. Hemoglobin A0 (HbA0) was fructosylated by in-vitro method. AGE formation was measured fluorimetrically by recording emission at 450nm upon excitation at 350nm. Thereafter this fructosylated HbA0 was fractionated by column chromatography. Fractionation separated the proteinaceous substance from the AGEs. Presence of protein part in the fractions was confirmed by measuring the intrinsic protein fluorescence and Bradford reaction. GNPs were synthesized using the templates of chromatographically separated fractions of fructosylated HbA0. Each fractions gave rise to GNPs of varying color, indicating the presence of distinct set of glycation products differing structurally and chemically. Clear solution appeared due to settling down of particles in some vials. The reactive groups of the intermediates kept the GNP formation mechanism on and did not lead to a stable particle formation till Day 10. Whereas SPR of GNP showed monotonous colour for the fractions collected in case of non fructosylated HbA0. Our findings accentuate the use of GNPs as a simple colorimetric sensing platform for the identification of intermediates of glycation reaction which could be implicated in the prognosis of the associated health risk due to T2DM and others.Keywords: advance glycation endproducts, glycation, gold nano particle, sensor
Procedia PDF Downloads 304602 Atypical Retinoid ST1926 Nanoparticle Formulation Development and Therapeutic Potential in Colorectal Cancer
Authors: Sara Assi, Berthe Hayar, Claudio Pisano, Nadine Darwiche, Walid Saad
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Nanomedicine, the application of nanotechnology to medicine, is an emerging discipline that has gained significant attention in recent years. Current breakthroughs in nanomedicine have paved the way to develop effective drug delivery systems that can be used to target cancer. The use of nanotechnology provides effective drug delivery, enhanced stability, bioavailability, and permeability, thereby minimizing drug dosage and toxicity. As such, the use of nanoparticle (NP) formulations in drug delivery has been applied in various cancer models and have shown to improve the ability of drugs to reach specific targeted sites in a controlled manner. Cancer is one of the major causes of death worldwide; in particular, colorectal cancer (CRC) is the third most common type of cancer diagnosed amongst men and women and the second leading cause of cancer related deaths, highlighting the need for novel therapies. Retinoids, consisting of natural and synthetic derivatives, are a class of chemical compounds that have shown promise in preclinical and clinical cancer settings. However, retinoids are limited by their toxicity and resistance to treatment. To overcome this resistance, various synthetic retinoids have been developed, including the adamantyl retinoid ST1926, which is a potent anti-cancer agent. However, due to its limited bioavailability, the development of ST1926 has been restricted in phase I clinical trials. We have previously investigated the preclinical efficacy of ST1926 in CRC models. ST1926 displayed potent inhibitory and apoptotic effects in CRC cell lines by inducing early DNA damage and apoptosis. ST1926 significantly reduced the tumor doubling time and tumor burden in a xenograft CRC model. Therefore, we developed ST1926-NPs and assessed their efficacy in CRC models. ST1926-NPs were produced using Flash NanoPrecipitation with the amphiphilic diblock copolymer polystyrene-b-ethylene oxide and cholesterol as a co-stabilizer. ST1926 was formulated into NPs with a drug to polymer mass ratio of 1:2, providing a stable formulation for one week. The contin ST1926-NP diameter was 100 nm, with a polydispersity index of 0.245. Using the MTT cell viability assay, ST1926-NP exhibited potent anti-growth activities as naked ST1926 in HCT116 cells, at pharmacologically achievable concentrations. Future studies will be performed to study the anti-tumor activities and mechanism of action of ST1926-NPs in a xenograft mouse model and to detect the compound and its glucuroconjugated form in the plasma of mice. Ultimately, our studies will support the use of ST1926-NP formulations in enhancing the stability and bioavailability of ST1926 in CRC.Keywords: nanoparticles, drug delivery, colorectal cancer, retinoids
Procedia PDF Downloads 100601 A Measurement Instrument to Determine Curricula Competency of Licensure Track Graduate Psychotherapy Programs in the United States
Authors: Laith F. Gulli, Nicole M. Mallory
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We developed a novel measurement instrument to assess Knowledge of Educational Programs in Professional Psychotherapy Programs (KEP-PPP or KEP-Triple P) within the United States. The instrument was designed by a Panel of Experts (PoE) that consisted of Licensed Psychotherapists and Medical Care Providers. Licensure track psychotherapy programs are listed in the databases of the Commission on Accreditation for Marriage and Family Therapy Education (COAMFTE); American Psychological Association (APA); Council on Social Work Education (CSWE); and the Council for Accreditation of Counseling & Related Educational Programs (CACREP). A complete list of psychotherapy programs can be obtained from these professional databases, selecting search fields of (All Programs) in (All States). Each program has a Web link that electronically and directly connects to the institutional program, which can be researched using the KEP-Triple P. The 29-item KEP Triple P was designed to consist of six categorical fields; Institutional Type: Degree: Educational Delivery: Accreditation: Coursework Competency: and Special Program Considerations. The KEP-Triple P was designed to determine whether a specific course(s) is offered in licensure track psychotherapy programs. The KEP-Triple P is designed to be modified to assess any part or the entire curriculum of licensure graduate programs. We utilized the KEP-Triple P instrument to study whether a graduate course in Addictions was offered in Marriage and Family Therapy (MFT) programs. Marriage and Family Therapists are likely to commonly encounter patients with Addiction(s) due to the broad treatment scope providing psychotherapy services to individuals, couples and families of all age groups. Our study of 124 MFT programs which concluded at the end of 2016 found that we were able to assess 61 % of programs (N = 76) since 27 % (N = 34) of programs were inaccessible due to broken Web links. From the total of all MFT programs 11 % (N = 14) did not have a published curriculum on their Institutional Web site. From the sample study, we found that 66 % (N = 50) of curricula did not offer a course in Addiction Treatment and that 34 % (N =26) of curricula did require a mandatory course in Addiction Treatment. From our study sample, we determined that 15 % (N = 11) of MFT doctorate programs did not require an Addictions Treatment course and that 1 % (N = 1) did require such a course. We found that 99 % of our study sample offered a Campus based program and 1 % offered a hybrid program with both online and residential components. From the total sample studied, we determined that 84 % of programs would be able to obtain reaccreditation within a five-year period. We recommend that MFT programs initiate procedures to revise curricula to include a required course in Addiction Treatment prior to their next accreditation cycle, to improve the escalating addiction crisis in the United States. This disparity in MFT curricula raises serious ethical and legal consideration for national and Federal stakeholders as well as for patients seeking a competently trained psychotherapist.Keywords: addiction, competency, curriculum, psychotherapy
Procedia PDF Downloads 151600 The Effect of Lead(II) Lone Electron Pair and Non-Covalent Interactions on the Supramolecular Assembly and Fluorescence Properties of Pb(II)-Pyrrole-2-Carboxylato Polymer
Authors: M. Kowalik, J. Masternak, K. Kazimierczuk, O. V. Khavryuchenko, B. Kupcewicz, B. Barszcz
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Recently, the growing interest of chemists in metal-organic coordination polymers (MOCPs) is primarily derived from their intriguing structures and potential applications in catalysis, gas storage, molecular sensing, ion exchanges, nonlinear optics, luminescence, etc. Currently, we are devoting considerable effort to finding the proper method of synthesizing new coordination polymers containing S- or N-heteroaromatic carboxylates as linkers and characterizing the obtained Pb(II) compounds according to their structural diversity, luminescence, and thermal properties. The choice of Pb(II) as the central ion of MOCPs was motivated by several reasons mentioned in the literature: i) a large ionic radius allowing for a wide range of coordination numbers, ii) the stereoactivity of the 6s2 lone electron pair leading to a hemidirected or holodirected geometry, iii) a flexible coordination environment, and iv) the possibility to form secondary bonds and unusual non-covalent interactions, such as classic hydrogen bonds and π···π stacking interactions, as well as nonconventional hydrogen bonds and rarely reported tetrel bonds, Pb(lone pair)···π interactions, C–H···Pb agostic-type interactions or hydrogen bonds, and chelate ring stacking interactions. Moreover, the construction of coordination polymers requires the selection of proper ligands acting as linkers, because we are looking for materials exhibiting different network topologies and fluorescence properties, which point to potential applications. The reaction of Pb(NO₃)₂ with 1H-pyrrole-2-carboxylic acid (2prCOOH) leads to the formation of a new four-nuclear Pb(II) polymer, [Pb4(2prCOO)₈(H₂O)]ₙ, which has been characterized by CHN, FT-IR, TG, PL and single-crystal X-ray diffraction methods. In view of the primary Pb–O bonds, Pb1 and Pb2 show hemidirected pentagonal pyramidal geometries, while Pb2 and Pb4 display hemidirected octahedral geometries. The topology of the strongest Pb–O bonds was determined as the (4·8²) fes topology. Taking the secondary Pb–O bonds into account, the coordination number of Pb centres increased, Pb1 exhibited a hemidirected monocapped pentagonal pyramidal geometry, Pb2 and Pb4 exhibited a holodirected tricapped trigonal prismatic geometry, and Pb3 exhibited a holodirected bicapped trigonal prismatic geometry. Moreover, the Pb(II) lone pair stereoactivity was confirmed by DFT calculations. The 2D structure was expanded into 3D by the existence of non-covalent O/C–H···π and Pb···π interactions, which was confirmed by the Hirshfeld surface analysis. The above mentioned interactions improve the rigidity of the structure and facilitate the charge and energy transfer between metal centres, making the polymer a promising luminescent compound.Keywords: coordination polymers, fluorescence properties, lead(II), lone electron pair stereoactivity, non-covalent interactions
Procedia PDF Downloads 145599 Formation of the Water Assisted Supramolecular Assembly in the Transition Structure of Organocatalytic Asymmetric Aldol Reaction: A DFT Study
Authors: Kuheli Chakrabarty, Animesh Ghosh, Atanu Roy, Gourab Kanti Das
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Aldol reaction is an important class of carbon-carbon bond forming reactions. One of the popular ways to impose asymmetry in aldol reaction is the introduction of chiral auxiliary that binds the approaching reactants and create dissymmetry in the reaction environment, which finally evolves to enantiomeric excess in the aldol products. The last decade witnesses the usage of natural amino acids as chiral auxiliary to control the stereoselectivity in various carbon-carbon bond forming processes. In this context, L-proline was found to be an effective organocatalyst in asymmetric aldol additions. In last few decades the use of water as solvent or co-solvent in asymmetric organocatalytic reaction is increased sharply. Simple amino acids like L-proline does not catalyze asymmetric aldol reaction in aqueous medium not only that, In organic solvent medium high catalytic loading (~30 mol%) is required to achieve moderate to high asymmetric induction. In this context, huge efforts have been made to modify L-proline and 4-hydroxy-L-proline to prepare organocatalyst for aqueous medium asymmetric aldol reaction. Here, we report the result of our DFT calculations on asymmetric aldol reaction of benzaldehyde, p-NO2 benzaldehyde and t-butyraldehyde with a number of ketones using L-proline hydrazide as organocatalyst in wet solvent free condition. Gaussian 09 program package and Gauss View program were used for the present work. Geometry optimizations were performed using B3LYP hybrid functional and 6-31G(d,p) basis set. Transition structures were confirmed by hessian calculation and IRC calculation. As the reactions were carried out in solvent free condition, No solvent effect were studied theoretically. Present study has revealed for the first time, the direct involvement of two water molecules in the aldol transition structures. In the TS, the enamine and the aldehyde is connected through hydrogen bonding by the assistance of two intervening water molecules forming a supramolecular network. Formation of this type of supramolecular assembly is possible due to the presence of protonated -NH2 group in the L-proline hydrazide moiety, which is responsible for the favorable entropy contribution to the aldol reaction. It is also revealed from the present study that, water assisted TS is energetically more favorable than the TS without involving any water molecule. It can be concluded from this study that, insertion of polar group capable of hydrogen bond formation in the L-proline skeleton can lead to a favorable aldol reaction with significantly high enantiomeric excess in wet solvent free condition by reducing the activation barrier of this reaction.Keywords: aldol reaction, DFT, organocatalysis, transition structure
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