Search results for: Mathew Leslie

Authors: N. Mathew, A. Qureshi, D. C. Khakha, R. Sagar

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Adolescents in India, account for one-fifth of the total population and are a significant human resource. Present study was conducted to find out various life stressors of adolescents, coping strategies adopted by them and the impact of stress on adolescent mental health. A descriptive, cross sectional study conducted on schools in the south zone of Delhi, capital city of the country. Data was collected on 360 adolescents between the age group of 13-17 years on socio-demographic profile, Adolescent life event stress scale, brief cope and youth self report for ages 11-18. Adolescents had significantly higher stress on uncontrollable events such as family events, relocation events, accident events and ambiguous events as compared to controllable events such as sexual events, deviance events and autonomy events (p<0.01).Adolescent stress was significantly correlated with various demographic variables in the study. The most frequently used coping strategies by the adolescents were positive reframing, planning, active coping, and instrumental support. It has also been found that the stress has a significant impact on adolescent mental health in the form of either internalizing problems such as anxious, withdrawn and somatic problems or externalizing problems such as rule breaking and aggressive behaviors. Out of the total sample of 360 adolescents 150 were identified as having psycho-social morbidity, including 59 borderline cases and 91 high-risk cases Study pointed out the need for mental health screening among the adolescents and also indicated the need for mental health inputs in educational institutions.

Keywords: adolecents, stress, coping, mental health

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Authors: B. Parchem, M. Watanabe, D. Modrakovic, L. Mathew, A. Franklin, M. Cao, R. E. Broudy

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Objective: Executive functioning (EF) deficits underlie several mental health diagnoses including ADHD, anxiety, and depression. Community mental health clinics face extensive waitlists for services with many referrals involving EF deficits. A pilot trial of a four-week group therapy was developed using key components from Cognitive-Behavioral Therapy (CBT), Dialectical Behavior Therapy (DBT), and mindfulness with an aim to improve EF skills and offer low-fee services. Method: Eight adults (M = 34.5) waiting for services at a community clinic were enrolled in a four-week group therapy at an in-house training clinic for doctoral trainees. Baseline EF, pre-/post-intervention ADHD and distress symptoms, group satisfaction, and curriculum helpfulness were assessed. Results: Downward trends in ADHD and distress symptoms pre/post-intervention were not significant. Favorable responses on group satisfaction and helpfulness suggest clinical utility. Conclusion: Preliminary pilot data from a brief group therapy to improve EF may be an efficacious, acceptable, and feasible intervention for adults waiting for services at community mental health and training clinics where there are high demands and limits to services and staffs.

Keywords: executive functioning, cognitive-behavioral therapy, dialectical behavior therapy, mindfulness, adult group therapy

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Authors: Jiji Jose, R. Narayanacharyulu, Molly Mathew, Jisha Prems

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Introduction: Lercanidipine hydrochloride (LD), an effective calcium channel blocker, widely used for the treatment of chronic stable angina and hypertension seems to be potential transdermal therapeutic system candidate, mainly due to its low oral bio availability, short half life and high first-pass metabolism. Objective: To develop transdermal therapeutic systems for LD and to evaluate its in vivo performance in rabbits. Methodology: Transdermal patches of LD were formulated using the polymer blend of eudragit RL100 (ERL) and polyvinyl pyrolidone (PVP) by casting method Propylene glycol (PG) and tween 80 were used as plasticizer and permeation enhancer respectively. The pharmaco kinetic parameters of LD after the administration of transdermal patches was compared with that of oral administration. The study was carried out in a two way crossover design in male New Zealand albino rabbits. Results: The formulation with ERL: PVP ratio 1:4 with 15% w/w PG as plasticizer and 4% w/w tween 80 as permeation enhancer showed the best drug release results. The pharmacokinetic parameters such as Cmax, tmax, mean residence time (MRT) and area under the curve (AUC 0-∞) were significantly different following transdermal administration compared to oral administration. The terminal half life of transdermally administered LD was found to similar that of oral administration. A sustained drug release over a period of 24 hrs was observed after transdermal administration. Conclusion: The fabricated transdermal delivery system have the potential to provide controlled and extended drug release, better bio availability and thus, this may improve the patient compliance.

Keywords: transdermal therapeutic system, lercanidipine hydrochloride, eudragit, skinpermeation

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Authors: Virender Singh, Mathew Rees, Simon Hampton, Sivaram Annadurai

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Plant identification is a challenging task that aims to identify the family, genus, and species according to plant morphological features. Automated deep learning-based computer vision algorithms are widely used for identifying plants and can help users narrow down the possibilities. However, numerous morphological similarities between and within species render correct classification difficult. In this paper, we tested custom convolution neural network (CNN) and vision transformer (ViT) based models using the PyTorch framework to classify plants. We used a large dataset of 88,000 provided by the Royal Horticultural Society (RHS) and a smaller dataset of 16,000 images from the PlantClef 2015 dataset for classifying plants at genus and species levels, respectively. Our results show that for classifying plants at the genus level, ViT models perform better compared to CNN-based models ResNet50 and ResNet-RS-420 and other state-of-the-art CNN-based models suggested in previous studies on a similar dataset. ViT model achieved top accuracy of 83.3% for classifying plants at the genus level. For classifying plants at the species level, ViT models perform better compared to CNN-based models ResNet50 and ResNet-RS-420, with a top accuracy of 92.5%. We show that the correct set of augmentation techniques plays an important role in classification success. In conclusion, these results could help end users, professionals and the general public alike in identifying plants quicker and with improved accuracy.

Keywords: plant identification, CNN, image processing, vision transformer, classification

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Authors: Ivy Rose Mathew

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The purpose of this study is to outline the efficacy of technology and the opportunities it can bring to implement a successful delivery model in Distance Learning. Distance Learning has proliferated over the past few years across the world. Some of the current challenges faced by current students of distance education include lack of motivation, a sense of isolation and a need for greater and improved communication. Hence the author proposes a creative technology supported model for distance learning exactly mirrored on the traditional face to face learning that can be adopted by distance learning providers. This model suggests the usage of a range of technologies and social networking facilities, with the aim of creating a more engaging and sustaining learning environment to help overcome the isolation often noted by distance learners. While discussing the possibilities, the author also highlights the complexity and practical challenges of implementing such a model. Design/methodology/approach: Theoretical issues from previous research related to successful models for distance learning providers will be considered. And also the analysis of a case study from one of the largest private tertiary institution in Botswana, Botho University will be included. This case study illustrates important aspects of the distance learning delivery model and provides insights on how curriculum development is planned, quality assurance is done, and learner support is assured for successful distance learning experience. Research limitations/implications: While some of the aspects of this study may not be applicable to other contexts, a number of new providers of distance learning can adapt the key principles of this delivery model.

Keywords: distance learning, efficacy, learning experience, technology supported model

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Authors: Rohini Hariharan, Yazhini R., Blessy Maria Mathew

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The task of detecting email spam is a very important one in the era of digital technology that needs effective ways of curbing unwanted messages. This paper presents an approach aimed at making email spam categorization algorithms transparent, reliable and more trustworthy by incorporating Local Interpretable Model-agnostic Explanations (LIME). Our technique assists in providing interpretable explanations for specific classifications of emails to help users understand the decision-making process by the model. In this study, we developed a complete pipeline that incorporates LIME into the spam classification framework and allows creating simplified, interpretable models tailored to individual emails. LIME identifies influential terms, pointing out key elements that drive classification results, thus reducing opacity inherent in conventional machine learning models. Additionally, we suggest a visualization scheme for displaying keywords that will improve understanding of categorization decisions by users. We test our method on a diverse email dataset and compare its performance with various baseline models, such as Gaussian Naive Bayes, Multinomial Naive Bayes, Bernoulli Naive Bayes, Support Vector Classifier, K-Nearest Neighbors, Decision Tree, and Logistic Regression. Our testing results show that our model surpasses all other models, achieving an accuracy of 96.59% and a precision of 99.12%.

Keywords: text classification, LIME (local interpretable model-agnostic explanations), stemming, tokenization, logistic regression.

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Authors: Amrin Moger, Sagar Bhalerao, Martin Mathew

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Advertisements play a vital role in dissemination of information regarding products and services. Advertisements as Mass Media tool is not only a source of entertainment, but also a source of information, education and entertainment. It provides information about the outside world and exposes us to other ways of life and culture. Public service advertisements (PSA) are generally aimed at public well-being. Aim of PSA is not to make profit, but rather to change public opinion and raise awareness in the Society about a social issue.’ Start with the boys’ is one such PSA aims to create awareness about issue of ‘gender bias’ that is taught prevalent in the society. Persons with disabilities (PWDs) are also consumers of PSA in the society. The population of persons with disability in the society also faces gender bias and discrimination. It is a double discrimination. The advertisement selected for the study gives out a strong message on gender bias and therefore must be accessible to everyone including PWDs in the society. Accessibility of PSA in the digital format can be done with the help of Universal Design (UD) in digital media application. Features of UD inclusive in nature, and it focus on eliminating established barriers through initial designs. It considers the needs of diverse people, whether they are persons with or without disability. In this research two aspects of UD in digital media: captioning and Indian sign language (ISL) is used. Hence a short survey study was under taken to know the effects of a multimedia on gender bias, in accessible format on persons with and without disability. The result demonstrated a significant difference in the opinion, on the usage accessible and non-accessible format for persons with and without disability and their understanding of message in the PSA selected for the study.

Keywords: public service advertisements, gender, disability, accessibility

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Authors: Sanaz Mosadeghsedghi, Mathew Hudder, Mohammad Ali Baghbanzadeh, Charbel Atallah, Seyedeh Laleh Dashtban Kenari, Konstantin Volchek

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Lithium has recently been extensively used in lithium-ion batteries (LIBs) for electric vehicles and portable electronic devices. The conventional evaporative approach to recover and concentrate lithium is extremely slow and may take 10-24 months to concentrate lithium from dilute sources, such as geothermal brines. To response to the increasing industrial lithium demand, alternative extraction and concentration technologies should be developed to recover lithium from brines with low concentrations. In this study, a combination of electrocoagulation (EC) and electrodialysis (ED) was evaluated for the recovery of lithium from geothermal brines. The brine samples in this study, collected in Western Canada, had lithium concentrations of 50-75 mg/L on a background of much higher (over 10,000 times) concentrations of sodium. This very high sodium-to-lithium ratio poses challenges to the conventional direct-lithium extraction processes which employ lithium-selective adsorbents. EC was used to co-precipitate lithium using a sacrificial aluminium electrode. The precipitate was then dissolved, and the leachate was treated using ED to separate and concentrate lithium from other ions. The focus of this paper is on the study of ED, including a two-step ED process that included a mono-valent selective stage to separate lithium from multi-valent cations followed by a bipolar ED stage to convert lithium chloride (LiCl) to LiOH product. Eventually, the ED cell was reconfigured using mono-valent cation exchange with the bipolar membranes to combine the two ED steps in one. Using this process at optimum conditions, over 95% of the co-existing cations were removed and the purity of lithium increased to over 90% in the final product.

Keywords: electrochemical separation, electrocoagulation, electrodialysis, lithium extraction

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Authors: Leslie M. Mullins

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In the face of dramatically shifting demographic trends and macroeconomic pressures on affordable housing in high-cost cities, municipalities and developers have been forced to develop new models of sustainable development that integrates elements of substantial rehabilitation and new construction while controlling for relocation and mass displacement. Community development partners in the San Francisco Bay Area of Northern California are starting to prioritize anti-displacement strategies when rehabilitating severely neglected public housing developments. This study explored the community-driven efforts to transform four dilapidated public housing sites (N=2,600 households) into thriving mixed-income housing communities. Eight interviews were conducted with frontline workers (property managers and service providers), who directly worked with residents throughout critical stages of the relocation and leasing process. Interviews were audio-recorded, transcribed, and analyzed by a systematic procedure for qualitative analysis to identify key themes on the topics of interest. Also, an extensive literature analysis was conducted to determine promising practices throughout the industry. This study highlighted that resident’s emotional attachment to their homes (regardless of the deteriorating conditions of their unit) could both a) impede the relocation process and substantially impact the budget and timeline, while b) simultaneously providing a basis for an enhanced sense of belonging and community cohesion. This phenomenon often includes the welcoming of new residents and cultures. Resident centered workshops, healing centered rituals, and extensive 'hands-on' guidance was highlighted as promising practices that resulted in residential retention rates that were two to three times the national average and positively impacted the overall project’s budget and timeline.

Keywords: anti-displacement strategies, community based practices, community cohesion, cultural preservation, healing-centered, public housing, relocation, trauma-informed

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Authors: Abdalla Mansour, Dan Brown, Adel Helmy, Rikin Trivedi, Mathew Guilfoyle

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Introduction: Diagnosing delayed cerebral ischaemia (DCI) following aneurysmal subarachnoid haemorrhage (SAH) can be challenging, particularly in poor-grade patients. Objectives: This study sought to assess the value of routine CTP in identifying (or excluding) DCI and in guiding management. Methods: Eight-year retrospective neuroimaging study at a large UK neurosurgical centre. Subjects included a random sample of adult patients with confirmed aneurysmal SAH that had a CTP scan during their inpatient stay, over a 8-year period (May 2014 - May 2022). Data collected through electronic patient record and PACS. Variables included age, WFNS scale, aneurysm site, treatment, the timing of CTP, radiologist report, and DCI management. Results: Over eight years, 916 patients were treated for aneurysmal SAH; this study focused on 466 patients that were randomly selected. Of this sample, 181 (38.84%) had one or more CTP scans following brain aneurysm treatment (Total 318). The first CTP scan in each patient was performed at 1-20 days following ictus (median 4 days). There was radiological evidence of DCI in 83, and no reversible ischaemia was found in 80. Findings were equivocal in the remaining 18. Of the 103 patients treated with clipping, 49 had DCI radiological evidence, in comparison to 31 of 69 patients treated with endovascular embolization. The remaining 9 patients are either unsecured aneurysms or non-aneurysmal SAH. Of the patients with radiological evidence of DCI, 65 had a treatment change following the CTP directed at improving cerebral perfusion. In contrast, treatment was not changed for (61) patients without radiological evidence of DCI. Conclusion: CTP is a useful adjunct to clinical assessment in the diagnosis of DCI and is helpful in identifying patients that may benefit from intensive therapy and those in whom it is unlikely to be effective.

Keywords: SAH, vasospasm, aneurysm, delayed cerebral ischemia

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Authors: Natalia Fijol, Aji P. Mathew

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We present the processing and characterisation of three-dimensional (3D) monolith filters based on polylactic acid (PLA) reinforced with various nature-derived nanospecies such as hydroxyapatite, modified cellulose fibers and chitin fibers. The nanospecies of choice were dispersed in PLA through Thermally Induced Phase Separation (TIPS) method. The biocomposites were developed via solvent-assisted blending and the obtained pellets were further single-screw extruded into 3D-printing filaments and processed into various geometries using Fused Deposition Modelling (FDM) technique. The printed prototypes included cubic, cylindrical and hour-glass shapes with diverse patterns of printing infill as well as varying pore structure including uniform and multiple level gradual pore structure. The pores and channel structure as well as overall shape of the prototypes were designed in attempt to optimize the flux and maximize the adsorption-active time. FDM is a cost and energy-efficient method, which does not require expensive tools and elaborated post-processing maintenance. Therefore, FDM offers the possibility to produce customized, highly functional water purification filters with tuned porous structures suitable for removal of wide range of common water pollutants. Moreover, as 3D printing becomes more and more available worldwide, it allows producing portable filters at the place and time where they are most needed. The study demonstrates preparation route for the PLA-based, fully biobased composite and their processing via FDM technique into water purification filters, addressing water treatment challenges on an industrial scale.

Keywords: fused deposition modelling, water treatment, biomaterials, 3D printing, nanocellulose, nanochitin, polylactic acid

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Authors: Sajan Antony Mathew, Bhukya Ramdas

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Abstract—The impetus of wind energy deployment over the last few decades has seen potential sites being harvested very actively for wind farm development. Due to the scarce availability of highly potential sites, the turbines are getting more optimized in its location wherein minimum spacing between the turbines are resorted without comprising on the optimization of its energy yield. The optimization of the energy yield from a wind turbine is achieved by effective micrositing techniques. These time-tested techniques which are applied from site to site on terrain conditions that meet the requirements of the International standard for power performance measurements of wind turbines result in the positioning of wind turbines for optimized energy yields. The international standard for Power Curve Measurements has rules of procedure and methodology to evaluate the terrain, obstacles and sector for measurements. There are many challenges at the sites for complying with the requirements for terrain, obstacles and sector for measurements. Studies are being attempted to carry out these measurements within the scope of the international standard as various other procedures specified in alternate standards or the integration of LIDAR for Power Curve Measurements are in the nascent stage. The paper strives to assist in the understanding of the fact that if positioning of a wind turbine at a site is based on an optimized output, then there are no wake effects seen on the power curve of an adjacent wind turbine. The paper also demonstrates that an invalid sector for measurements could be used in the analysis in alteration to the requirement as per the international standard for power performance measurements. Therefore the paper strives firstly to demonstrate that if a wind turbine is optimally positioned, no wake effects are seen and secondly the sector for measurements in such a case could include sectors which otherwise would have to be excluded as per the requirements of International standard for power performance measurements.

Keywords: micrositing, optimization, power performance, wake effects

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Authors: Pratheeba Subramanian, Anjula Gurtoo, Mary Mathew

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Transaction of patents in emerging patent markets is gaining momentum. Pricing patents for a transaction say patent sale remains a challenge. Patents vary in their pricing with some patents fetching higher prices than others. Sale of patents in portfolios further complicates pricing with multiple patents playing a role in pricing a bundle. In this paper, a set of 138 US patents sold individually as single invention lots and 462 US patents sold in bundles of 120 portfolios are investigated to understand the dynamics of selling prices of singletons and portfolios and their determinants. Firstly, price variations when patents are sold individually as singletons and portfolios are studied. Multivariate statistical techniques are used for analysis both at the lot level as well as at the individual patent level. The results show portfolios fetching higher prices than singletons at the lot level. However, at the individual patent level singletons show higher prices than per patent price of individual patent members within the portfolio. Secondly, to understand the price determinants, the effect of patent, seller, and bundling related characteristics on selling prices is studied separately for singletons and portfolios. The results show differences in the set of characteristics determining prices of singletons and portfolios. Selling prices of singletons are found to be dependent on the patent related characteristics, unlike portfolios whose prices are found to be dependent on all three aspects – patent, seller, and bundling. The specific patent, seller and bundling characteristics influencing selling price are discussed along with the implications.

Keywords: auction, patents, portfolio bundling, seller type, selling price, singleton

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Authors: Hamza Javar Magnier, Leslie V. Woodcock

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We report extensive molecular dynamics (MD) computational investigations into the thermodynamic description of supercritical properties for a model fluid that is the simplest realistic representation of atoms or molecules. The pair potential is a hard-sphere repulsion of diameter σ with a very short attraction of length λσ. When λ = 1.005 the range is so short that the model atoms are referred to as “adhesive spheres”. Molecular dimers, trimers …etc. up to large clusters, or droplets, of many adhesive-sphere atoms are unambiguously defined. This then defines percolation transitions at the molecular level that bound the existence of gas and liquid phases at supercritical temperatures, and which define the existence of a supercritical mesophase. Both liquid and gas phases are seen to terminate at the loci of percolation transitions, and below a second characteristic temperature (Tc2) are separated by the supercritical mesophase. An analysis of the distribution of clusters in gas, meso- and liquid phases confirms the colloidal nature of this mesophase. The general phase behaviour is compared with both experimental properties of the water-steam supercritical region and also with formally exact cluster theory of Mayer and Mayer. Both are found to be consistent with the present findings that in this system the supercritical mesophase narrows in density with increasing T > Tc and terminates at a higher Tc2 at a confluence of the primary percolation loci. The expended plot of the MD data points in the mesophase of 7 critical and supercritical isotherms in highlight this narrowing in density of the linear-slope region of the mesophase as temperature is increased above the critical. This linearity in the mesophase implies the existence of a linear combination rule between gas and liquid which is an extension of the Lever rule in the subcritical region, and can be used to obtain critical parameters without resorting to experimental data in the two-phase region. Using this combination rule, the calculated critical parameters Tc = 0.2007 and Pc = 0.0278 are found be agree with the values found by of Largo and coworkers. The properties of this supercritical mesophase are shown to be consistent with an alternative description of the phenomenon of critical opalescence seen in the supercritical region of both molecular and colloidal-protein supercritical fluids.

Keywords: critical opalescence, supercritical, square-well, percolation transition, critical parameters.

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Authors: Mdoe Mwajuma Bakari, Mselle Lilian Teddy, Kibusi Stephen Mathew

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Background: Due to the increase of caesarean section (CS), many women are discharge early to their home. Women should be aware on how to take care of themselves at home after CS. Evidence shows non-uniform health education on home care after CS are provided to post CS mothers because of lack of standard home care guideline on home after CS; as existing guidelines explore only care of women in hospital setting, for health care workers. There is a need to develop post CS home care guide; exploring contents of home based care education after CS provided by nurse midwives will inform the development of the guide. Objective: To explore the content of health education provided by nurse midwives to post CS mother about home care after hospital discharge in Dodoma, Tanzania. Methodology: An exploratory qualitative study using in-depth interview was conducted in this study using triangulation of data collection method; where 14 nurse midwives working in maternity unit and 11 post CS mother attending their post-natal clinic were recruited. Content analysis was used to generate themes that describe health education information provided by nurse midwives to post CS mother about home care after hospital discharge. Results: The study found that, nutrition health education, maternal and newborn hygiene care of caesarean wound at home were the component of health education provided to post CS mothers by nurse midwives. Contradicting instruction were found to be provided to post CS mothers. Conclusion: This study reported non-uniform health education provided by the nurse midwives on home care after CS. Despite of the fact that nurse midwives recognizes the need to provide health education to the post CS mothers, there is a need to develop home care guideline as a reference for their education to ensure uniform package of education is provided to post CS mothers in order to improve recovery of post CS mothers from CS.

Keywords: caesarean section, home care, discharge education, homecare after caesarean section

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Authors: Aneesh Mathew, Arunab K. S., Atul Kumar Sharma

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The uncontrolled rise in population has led to unplanned, swift, and unsustainable urban expansion, causing detrimental environmental impacts on both local and global ecosystems. This research delves into a comprehensive examination of the Urban Heat Island (UHI) phenomenon in Bengaluru and Hyderabad, India. It centers on the spatial and temporal distribution of UHI and its correlation with air pollutants. Conducted across summer and winter seasons from 2001 to 2021 in Bangalore and Hyderabad, this study discovered that UHI intensity varies seasonally, peaking in summer and decreasing in winter. The annual maximum UHI intensities range between 4.65 °C to 6.69 °C in Bengaluru and 5.74 °C to 6.82 °C in Hyderabad. Bengaluru particularly experiences notable fluctuations in average UHI intensity. Introducing the Urban Thermal Field Variance Index (UTFVI), the study indicates a consistent strong UHI effect in both cities, significantly impacting living conditions. Moreover, hotspot analysis demonstrates a rising trend in UHI-affected areas over the years in Bengaluru and Hyderabad. This research underscores the connection between air pollutant concentrations and land surface temperature (LST), highlighting the necessity of comprehending UHI dynamics for urban environmental management and public health. It contributes to a deeper understanding of UHI patterns in swiftly urbanizing areas, providing insights into the intricate relationship between urbanization, climate, and air quality. These findings serve as crucial guidance for policymakers, urban planners, and researchers, facilitating the development of innovative, sustainable strategies to mitigate the adverse impacts of uncontrolled expansion while promoting the well-being of local communities and the global environment.

Keywords: urban heat island effect, land surface temperature, air pollution, urban thermal field variance index

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Authors: Caio E. G. Reis, Sara Wassell, Adriana L. Porto, Angélica A. Amato, Leslie J. C. Bluck, Teresa H. M. da Costa

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Background: Multiple epidemiologic studies have consistently reported association between increased coffee consumption and a lowered risk of Type 2 Diabetes Mellitus. However, the mechanisms behind this finding have not been fully elucidated. Objective: We investigate the effect of coffee (caffeinated and decaffeinated) on glucose effectiveness and insulin sensitivity using the stable isotope minimal model protocol with oral glucose administration in healthy men. Design: Fifteen healthy men underwent 5 arms randomized crossover single-blinding (researchers) clinical trial. They consumed decaffeinated coffee, caffeinated coffee (with and without sugar), and controls – water (with and without sugar) followed 1 hour by an oral glucose tolerance test (75 g of available carbohydrate) with intravenous labeled dosing interpreted by the two compartment minimal model (225 minutes). One-way ANOVA with Bonferroni adjustment were used to compare the effects of the tested beverages on glucose metabolism parameters. Results: Decaffeinated coffee resulted in 29% and 85% higher insulin sensitivity compared with caffeinated coffee and water, respectively, and the caffeinated coffee showed 15% and 60% higher glucose effectiveness compared with decaffeinated coffee and water, respectively. However, these differences were not significant (p > 0.10). In overall analyze (0 – 225 min) there were no significant differences on glucose effectiveness, insulin sensitivity, and glucose and insulin area under the curve between the groups. The beneficial effects of coffee did not seem to act in the short-term (hours) on glucose metabolism parameters mainly on insulin sensitivity indices. The benefits of coffee consumption occur in the long-term (years) as has been shown in the reduction of Type 2 Diabetes Mellitus risk in epidemiological studies. The clinical relevance of the present findings is that there is no need to avoid coffee as the drink choice for healthy people. Conclusions: The findings of this study demonstrate that the consumption of caffeinated and decaffeinated coffee with or without sugar has no acute effects on glucose metabolism in healthy men. Further researches, including long-term interventional studies, are needed to fully elucidate the mechanisms behind the coffee effects on reduced risk for Type 2 Diabetes Mellitus.

Keywords: coffee, diabetes mellitus type 2, glucose, insulin

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Authors: Mathew Wakefield, Matthew Mitchell, Lisa Wise, Christopher McCarthy

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The properties of memory representations in artificial neural networks have cognitive implications. Distributed representations that encode instances as a pattern of activity across layers of nodes afford memory compression and enforce the selection of a single point in instance space. These encoding schemes also appear to distort the representational space, as well as trading off the ability to validate that input information is within the bounds of past experience. In contrast, a localist representation which encodes some meaningful information into individual nodes in a network layer affords less memory compression while retaining the integrity of the representational space. This allows the validity of an input to be determined. The validity (or familiarity) of input along with the capacity of localist representation for multiple instance selections affords a memory sampling approach that dynamically balances the bias-variance trade-off. When the input is familiar, bias may be high by referring only to the most similar instances in memory. When the input is less familiar, variance can be increased by referring to more instances that capture a broader range of features. Using this approach in a localist instance memory network, an experiment demonstrates a relationship between representational conflict, generalization performance, and memorization demand. Relatively small sampling ranges produce the best performance on a classic machine learning dataset of visual objects. Combining memory validity with conflict detection produces a reliable confidence judgement that can separate responses with high and low error rates. Confidence can also be used to signal the need for supervisory input. Using this judgement, the need for supervised learning as well as memory encoding can be substantially reduced with only a trivial detriment to classification performance.

Keywords: artificial neural networks, representation, memory, conflict monitoring, confidence

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Authors: J. J. Mathew

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Pulmonary tuberculosis is highly prevalent in the Indian subcontinent. Most cases of pulmonary tuberculosis are diagnosed with sputum examinations and the vast majority of these are undertaken by the government run establishments. However, mycobacterial cultures are not routinely done, unless drug resistance is detected based on clinical response. Modern diagnostic tests like bronchoscopy and Genexpert are not routinely employed in the government institutions for the diagnosis of pulmonary tuberculosis, but have been accepted widely by good private institutions. The utility of these investigations in the private sector is not yet well recognized. This retrospective study aims to assess the usefulness of bronchoscopy and Genexpert in the diagnosis of pulmonary tuberculosis in quaternary care private hospital in India. 30 patients with respiratory symptoms raising the possibility of tuberculosis based on clinical and radiological features, but without any significant sputum production, were subject to bronchoscopy and BAL samples taken for microbiological studies, including Genexpert. 6 out of the 30 patients were found to be Genexpert positive and none of them showed Rifampicin resistance. All the 6 cases had upper zone predominant disease. One of the 6 cases of tuberculosis had another co-existent bacterial infection according to the routine culture studies. 6 other cases were proven to be due to other bacterial infections alone, 2 had a malignant diagnosis and the remaining cases were thought to be non-infective pathologies. The Genexpert results were made available within 48 hours in the 6 positive cases. All of them were commenced on standard anti-tuberculous regimen with excellent clinical response. The other infective cases were also managed successfully based on the drug susceptibilities. The study has shown the usefulness of these investigations as early intervention enabled diagnosis facilitating treatment and prevention of any clinical deterioration. The study lends support to early bronchoscopy and Genexpert testing in suspected cases of pulmonary tuberculosis without significant sputum production, in a high prevalence country which normally relies on sputum examination for the diagnosis of pulmonary tuberculosis.

Keywords: pulmonary, tuberculosis, bronchoscopy, genexpert

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Authors: Danilo A. F. Fontes, Magaly A. M.Lyra, Maria L. C. Moura, Leslie R. M. Ferraz, Salvana P. M. Costa, Amanda C. Q. M. Vieira, Larissa A. Rolim, Giovanna C. R. M. Schver, Ping I. Lee, Severino Alves-Júnior, José L. Soares-Sobrinho, Pedro J. Rolim-Neto

Abstract:

Efavirenz (EFV) is a first-choice drug in antiretroviral therapy with high efficacy in the treatment of infection by Human Immunodeficiency Virus, which causes Acquired Immune Deficiency Syndrome (AIDS). EFV has low solubility in water resulting in a decrease in the dissolution rate and, consequently, in its bioavailability. Among the technological alternatives to increase solubility, the Lamellar Double Hydroxides (LDH) have been applied in the development of systems with poorly water-soluble drugs. The use of analytical techniques such as X-Ray Diffraction (XRD), Infrared Spectroscopy (IR) and Differential Scanning Calorimetry (DSC) allowed the elucidation of drug interaction with the lamellar compounds. The objective of this work was to characterize and develop the binary systems with EFV and LDH in order to increase the solubility of the drug. The LDH-CaAl was synthesized by the method of co-precipitation from salt solutions of calcium nitrate and aluminum nitrate in basic medium. The systems EFV-LDH and their physical mixtures (PM) were obtained at different concentrations (5-60% of EFV) using the solvent technique described by Takahashi & Yamaguchi (1991). The characterization of the systems and the PM’s was performed by XRD techniques, IR, DSC and dissolution test under non-sink conditions. The results showed improvements in the solubility of EFV when associated with LDH, due to a possible change in its crystal structure and formation of an amorphous material. From the DSC results, one could see that the endothermic peak at 173°C, temperature that correspond to the melting process of EFZ in the crystal form, was present in the PM results. For the EFZ-LDH systems (with 5, 10 and 30% of drug loading), this peak was not observed. XRD profiles of the PM showed well-defined peaks for EFV. Analyzing the XRD patterns of the systems, it was found that the XRD profiles of all the systems showed complete attenuation of the characteristic peaks of the crystalline form of EFZ. The IR technique showed that, in the results of the PM, there was the appearance of one band and overlap of other bands, while the IR results of the systems with 5, 10 and 30% drug loading showed the disappearance of bands and a few others with reduced intensity. The dissolution test under non-sink conditions showed that systems with 5, 10 and 30% drug loading promoted a great increase in the solubility of EFV, but the system with 10% of drug loading was the only one that could keep substantial amount of drug in solution at different pHs.

Keywords: Efavirenz, Lamellar Double Hydroxides, Pharmaceutical Techonology, Solubility

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Authors: Mathew Saxon A, Aneeh Rajan, Sajeev P

Abstract:

Many fluid flow applications employ different types of orifices to control the flow rate or to reduce the pressure. Discharge coefficients generally vary from 0.6 to 0.95 depending on the type of the orifice. The tabulated value of discharge coefficients of various types of orifices available can be used in most common applications. The upstream and downstream flow condition of an orifice is hardly considered while choosing the discharge coefficient of an orifice. But literature shows that the discharge coefficient can be affected by the presence of cross flow. Cross flow is defined as the condition wherein; a fluid is injected nearly perpendicular to a flowing fluid. Most researchers have worked on water being injected into a cross-flow of water. The present work deals with water to gas systems in which water is injected in a normal direction into a flowing stream of gas. The test article used in the current work is called thermal regulator, which is used in a liquid rocket engine to reduce the temperature of hot gas tapped from the gas generator by injecting water into the hot gas so that a cooler gas can be supplied to the turbine. In a thermal regulator, water is injected through an orifice in a normal direction into the hot gas stream. But the injection orifice had been calibrated under backpressure by maintaining a stagnant gas medium at the downstream. The motivation of the present study aroused due to the observation of a lower Cd of the orifice in flight compared to the calibrated Cd. A systematic experimental investigation is carried out in this paper to study the effect of cross-flow on the discharge coefficient of an orifice in water to a gas system. The study reveals that there is an appreciable reduction in the discharge coefficient with cross flow compared to that without cross flow. It is found that the discharge coefficient greatly depends on the ratio of momentum of water injected to the momentum of the gas cross flow. The effective discharge coefficient of different orifices was normalized using the discharge coefficient without cross-flow and it is observed that normalized curves of effective discharge coefficient of different orifices with momentum ratio collapsing into a single curve. Further, an equation is formulated using the test data to predict the effective discharge coefficient with cross flow using the calibrated Cd value without cross flow.

Keywords: cross flow, discharge coefficient, orifice, momentum ratio

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Authors: Anupoju Rajeev, Joanne Mathew, Amit Shelke

Abstract:

In the current study, a new type of Composite Structural Insulated Panels (CSIPs) is developed and investigated its performance against shock loading which can replace the conventional wooden structural materials. The CSIPs is made of Fibre Cement Board (FCB)/aluminum as the facesheet and the expanded polystyrene foam as the core material. As tornadoes are very often in the western countries, it is suggestable to monitor the health of the CSIPs during its lifetime. So, the composite structure is installed with three smart sensors located randomly at definite locations. Each smart sensor is fabricated with an embedded half stainless phononic crystal sensor attached to both ends of the nylon shaft that can resist the shock and impact on facesheet as well as polystyrene foam core and safeguards the system. In addition to the granular crystal sensors, the accelerometers are used in the horizontal spanning and vertical spanning with a definite offset distance. To estimate the health and damage of the CSIP panel using granular crystal sensor, shock wave loading experiments are conducted. During the experiments, the time of flight response from the granular sensors is measured. The main objective of conducting shock wave loading experiments on the CSIP panels is to study the effect and the sustaining capacity of the CSIP panels in the extreme hazardous situations like tornados and hurricanes which are very common in western countries. The effects have been replicated using a shock tube, an instrument that can be used to create the same wind and pressure intensity of tornado for the experimental study. Numerous experiments have been conducted to investigate the flexural strength of the CSIP. Furthermore, the study includes the damage detection using three smart sensors embedded in the CSIPs during the shock wave loading.

Keywords: composite structural insulated panels, damage detection, flexural strength, sandwich structures, shock wave loading

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Authors: S. Reshma Reghu, Shiburaj Sugathan, T. G. Nandu, K. B. Ramesh Kumar, Mathew Dan

Abstract:

Bacterial diseases are considered to be one of the most prevalent health hazards in the developing world and many bacteria are becoming resistant to existing antibiotics making the treatment ineffective. Thus, it is necessary to find novel targets and develop new antibacterial drugs with a novel mechanism of action. The process of bacterial cell division is a novel and attractive target for new antibacterial drug discovery. FtsZ, a homolog of eukaryotic tubulin, is the major protein of the bacterial cell division machinery and is considered as an important antibacterial drug target. Zingiberaceae, the Ginger family consists of aromatic herbs with creeping rhizomes. Many of these plants have antimicrobial properties.This study aimed to determine the anti-bacterial activity of selected Zingiberaceous plants by targeting bacterial cell division protein, FtsZ. Essential oils and methanol extracts of Amomum ghaticum, Alpinia galanga, Kaempferia galanga, K. rotunda, and Zingiber officinale were tested to find its antibacterial efficiency using disc diffusion method against authentic bacterial strains obtained from MTCC (India). Essential oil isolated from A.galanga and Z.officinale were further assayed for FtsZ inhibition assay following non-radioactive malachite green-phosphomolybdate assay using E. coli FtsZ protein obtained from Cytoskelton Inc., USA. Z.officinale essential oil possess FtsZ inhibitory property. A molecular docking study was conducted with the known bioactive compounds of Z. officinale as ligands with the E. coli FtsZ protein homology model. Some of the major constituents of this plant like catechin, epicatechin, and gingerol possess agreeable docking scores. The results of this study revealed that several chemical constituents in Ginger plants can be utilised as potential source of antibacterial activity and it can warrant further investigation through drug discovery studies.

Keywords: antibacterial, FtsZ, zingiberaceae, docking

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Authors: Suleyman Kizil, Tahsin Sogut, Khalid M. Khawar

Abstract:

Genus Allium includes 600 to 750 species and most of these including Allium tuncelianum (Kollman) N. Ozhatay, B. Mathew & Siraneci; Syn; A. macrochaetum Boiss. and Hausskn. subsp. tuncelianum Kollman] or Tunceli garlic is endemic to Eastern Turkish Province of Tunceli and Munzur mountains. They are edible, bear attractive white-to-purple flowers and fertile black seeds with deep seed dormancy. This study aimed to break seed dormancy of Tunceli garlic and determine the conditions for induction of bulblets on these seeds and increase their diameter by culturing them on MS medium supplemented different strengths of KNO3. Tunceli garlic seeds were collected from field grown plants. They were germinated on MS medium with or without 20 g/l sucrose followed by their culture on 1 × 1900 mg/l, 2 × 1900 mg/l, 4 ×1900 mg/l and 6 × 1900 mg/l mg/l KNO3 supplemented with 20 g/l sucrose to increase bulb diameter. Improved seeds germination was noted on MS medium with and without sucrose but with variation compared to previous reports. The bulb development percentage on each of the sprouted seeds was not parallel to the percentage of seed germination. The results showed 34% and 28.5% bulb induction was noted on germinated seeds after 150 and 158 days on MS medium containing 20 g l-1 sucrose and no sucrose respectively showing a delay of 8 days on the latter compared to the former. The results emphatically noted role of cold stratification on agar solidified MS medium supplemented with sucrose to improve seed germination. The best increase in bulb diameter was noted on MS medium containing 1 × 1900 mg/l KNO3 after 178 days with bulblet diameter and bulblet weight of 0.54 cm and 0.048 g, respectively. Consequently, the bulbs induced on sucrose containing MS medium could be transferred to pots earlier. Increased (>1 × 1900 mg/l KNO3) strengths of KNO3 induced negative effect on growth and development of Tunceli garlic bulbs. The strategy of seed germination and bulblet induction reported in this study could be positively used for conservation of this endemic plant species.

Keywords: Tunceli garlic, seed, dormancy, bulblets, bulb growth

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Authors: Joseph L. Mathew, Shourjendra N. Banerjee, R. K. Ratho, Sourabh Dutta, Vanita Suri

Abstract:

Background: In India and many other developing countries, a single dose of measles vaccine is administered to infants at 9 months of age. This is based on the assumption that maternal transplacentally transferred antibodies will protect infants until that age. However, our previous data showed that most infants lose maternal anti-measles antibodies before 6 months of age, making them susceptible to measles before vaccination at 9 months. Objective: This prospective study was designed to compare susceptibility in pre-term vs term infants, at different time points. Material and Methods: Following Institutional Ethics Committee approval and a formal informed consent process, venous blood was drawn from a cohort of 45 consecutive term infants and 45 consecutive pre-term infants (both groups delivered by the vaginal route); at birth, 3 months, 6 months and 9 months (prior to measles vaccination). Serum was separated and anti-measles IgG antibody levels were measured by quantitative ELISA kits (with sensitivity and specificity > 95%). Susceptibility to measles was defined as antibody titre < 200mIU/ml. The mean antibody levels were compared between the two groups at the four time points. Results: The mean gestation of term babies was 38.5±1.2 weeks; and pre-term babies 34.7±2.8 weeks. The respective mean birth weights were 2655±215g and 1985±175g. Reliable maternal vaccination record was available in only 7 of the 90 mothers. Mean anti-measles IgG antibody (±SD) in terms babies was 3165±533 IU/ml at birth, 1074±272 IU/ml at 3 months, 314±153 IU/ml at 6 months, and 68±21 IU/ml at 9 months. The corresponding levels in pre-term babies were 2875±612 IU/ml, 948±377 IU/ml, 265±98 IU/ml, and 72±33 IU/ml at 9 months (p > 0.05 for all inter-group comparisons). The proportion of susceptible term infants at birth, 3months, 6months and 9months was 0%, 16%, 67% and 96%. The corresponding proportions in the pre-term infants were 0%, 29%, 82%, and 100% (p > 0.05 for all inter-group comparisons). Conclusion: Majority of infants are susceptible to measles before 9 months of age suggesting the need to anticipate measles vaccination, but there was no statistically significant difference between the proportion of susceptible term and pre-term infants, at any of the four-time points. A larger study is required to confirm these findings and compare sero-protection if vaccination is anticipated to be administered between 6 and 9 months.

Keywords: measles, preterm, susceptibility, term infant

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Authors: Oladipo Jimoh Ayanda, Fashagba Mathew Olasehinde

Abstract:

Pension is a post retirement benefit paid to employees after retirement to cushion the effects of severance from monthly emoluments. It serves the dual purpose of providing financial succour to retired employees as well as motivating employees currently in service to greater performance on duty. However, the scheme, as operated in Nigeria, is prone to some pitfalls such as delayed and irregular payments, inadequate budgetary provisions, employee sufferings and deaths arising from the rigors of verification exercises, among others. This necessitated the replacement of the old scheme with the contributory pension scheme through an enabling law in 2004. The implementation of the new scheme has its own challenges especially in connection with administration. These challenges pose a fundamental problem of establishing a nexus between pension benefits and work performance which represent the focus of the study. The study objectives were to: determine the effect of contributory pension scheme on employees’ performance. The study population consisted of National Universities Commission recognized public and private universities in the South West Nigeria. Multi-stage sampling method involving stratified sampling and systematic sampling was used in selecting 359 respondents while data were collected through questionnaire administration. The procedure for analyzing the data included descriptive statistic, normal distribution test and cross-tabulation (gamma coefficient). The findings of the study showed that the existence of the scheme positively enhances employees’ performance as indicated by normal distribution test with Z-score (10.169) which is greater than the table value (1.96) at 0.05 level. The study concluded that the scope for enhancing employee current job performance can be quite elastic if future retirement benefits are guaranteed through proper and efficient administration and management of the contributory pension scheme. The study recommended that certain factors such as employers’ commitment which account for different levels of confidence between public and private universities should be looked into in order to improve confidence across board while the provisions of the scheme as they affect the PFAs should be properly monitored to ensure compliance.

Keywords: pension, retirement, performance, employees, benefit

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Authors: Leslie Nobler

Abstract:

African fabrics based specifically on the Dutch Wax Print, or Ankara, popularized during Africa's colonial era, have had an enormous impact on western fashion (especially in the US and UK), in the last half-decade. The trend has had an effect on the world of visual arts as well, which circuitously, also heavily impacts fashion design. In fashion, and notably in celebrity apparel choices, this is in part due to ‘identity’ and taking pride in one's African roots; in the visual arts, artists such as Yinka Shonibare and Njideka Akunyili Crosby are making statements about identity politics, colonialism up through post-colonialism, and racism. The ‘global village’ brought on by the internet has driven this proliferation, as have improvements in the printing technology with which the Ankara print is made, combining wax-resist with roller printing. The newest patterns can now be designed authentically in western African and easily sent electronically to Europe for printing. Examples of Ankara's new reach across the Atlantic abound. They have taken several paths, which the paper will detail. Briefly, the first is its greater utilization in the fashion world, from authentic textile shops in African American neighborhoods to copied (knocked-off) low-end reproductions in discount chains. Secondly, we are seeing far more uses of these textiles/patterns in important works of fine arts from major museums, in Philadelphia to Palm Beach to the Mass MOCA (in the US), all the way to the Israel Museum in Jerusalem, and everywhere in between. And lastly, but quite significantly, we see this trend throughout social media thanks to Instagram, Pinterest and celebrity photos –even at the recent royal wedding. What shall sustain this major new design direction is that Ankara changes with and adapts to the times. Some of it is now printed in West Africa, often in the Nigeria area. And some may be designed in Europe or even at knock-off apparel studios in NY or Asia. But it stays utterly relevant because the motifs are based on objects and scenes in everyday life. In my design studio and university design classes, this idea is first and foremost, from our big spiritual eye motifs to drawings of our art supplies to the ‘politically-loaded’ chain patterns. This first-hand creativity experience becomes part of the research of this paper, along with historic and contemporary sources of inquiry, both through a literature/image search and anecdotal experience into what is behind this exciting and surprising trend.

Keywords: African wax print, Ankara, identity (politics), textile design, surface design

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Authors: Maphuti Georgina Kwata

Abstract:

Coal mining in Mpumalanga Province is known of contributing to the atmospheric pollution from various activities. Gold mining in North-West Province is known of also contributing to the atmospheric pollution especially with the production of radon gas. In this research directional dust deposition gauge was used to measure source of direction and meteorological data was used to determine the wind rose blowing and the influence of the seasonal changes. Fourteen months of dust collection was undertaken in Witbank Area and Carletonville Area. The results shows that the sources of direction for Ericson Dam its East in February 2010 and Tip Area shows that the source of direction its West in October 2010. In the East direction there were mining operations, power stations which contributed to the East to be the sources of direction. In the West direction there were smelters, power stations and agricultural activities which contributed for the source of direction to be the West direction for Driefontein Mine: East Recreational Village Club. The East of Leslie Williams hospital is the source of direction which also indicated that there dust generating activities such as mining operation, agricultural activities. The meteorological results for Emalahleni Area in summer and winter the wind rose blow with wind speed of 5-10 ms-1 from the East sector. Annual average for the wind rose blow its East South eastern sector with 20 ms-1 and day time the wind rose from northwestern sector with excess of 20 ms-1. The night time wind direction East-eastern direction with a maximum wind speed of 20 ms-1. The meteorogical results for Driefontein Mine show that North-western sector and north-eastern sector wind rose is blowing with 5-10 ms-1 win speed. Day time wind blows from the West sector and night time wind blows from the north sector. In summer the wind blows North-east sector with 5-10 ms-1 and winter wind blows from North-west and it’s also predominant. In spring wind blows from north-east. The conclusion is that not only mining operation where the directional dust deposit gauge were installed contributed to the source of direction also the power stations, smelters, and other activities nearby the mining operation contributed. The recommendations are the dust suppressant for unpaved roads should be used on a regular basis and there should be monitoring of the weather conditions (the wind speed and direction prior to blasting to ensure minimal emissions).

Keywords: directional dust deposition gauge, BS part 5 1747 dust deposit gauge, wind rose, wind blowing

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Authors: Luis Guilherme Resende Santos, Ido Nevat, Leslie Norford

Abstract:

The Urban Heat Island (UHI) is characterized by increased air temperatures in urban areas compared to undeveloped rural surrounding environments. With urbanization and densification, the intensity of UHI increases, bringing negative impacts on livability, health and economy. In order to reduce those effects, it is required to take into consideration design factors when planning future developments. Given design constraints such as population size and availability of area for development, non-trivial decisions regarding the buildings’ dimensions and their spatial distribution are required. We develop a framework for optimization of urban design in order to jointly minimize UHI intensity and buildings’ energy consumption. First, the design constraints are defined according to spatial and population limits in order to establish realistic boundaries that would be applicable in real life decisions. Second, the tools Urban Weather Generator (UWG) and EnergyPlus are used to generate outputs of UHI intensity and total buildings’ energy consumption, respectively. Those outputs are changed based on a set of variable inputs related to urban morphology aspects, such as building height, urban canyon width and population density. Lastly, an optimization problem is cast where the utility function quantifies the performance of each design candidate (e.g. minimizing a linear combination of UHI and energy consumption), and a set of constraints to be met is set. Solving this optimization problem is difficult, since there is no simple analytic form which represents the UWG and EnergyPlus models. We therefore cannot use any direct optimization techniques, but instead, develop an indirect “black box” optimization algorithm. To this end we develop a solution that is based on stochastic optimization method, known as the Cross Entropy method (CEM). The CEM translates the deterministic optimization problem into an associated stochastic optimization problem which is simple to solve analytically. We illustrate our model on a typical residential area in Singapore. Due to fast growth in population and built area and land availability generated by land reclamation, urban planning decisions are of the most importance for the country. Furthermore, the hot and humid climate in the country raises the concern for the impact of UHI. The problem presented is highly relevant to early urban design stages and the objective of such framework is to guide decision makers and assist them to include and evaluate urban microclimate and energy aspects in the process of urban planning.

Keywords: building energy consumption, stochastic optimization, urban design, urban heat island, urban weather generator

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Authors: Rehin Sulay, Anandhu Krishna, Jintumol Mathew, Vibin Ipe Thomas

Abstract:

N-Nitrosodimethyl amine, the simplest member of the N-Nitrosoamine family, is a carcinogenic and mutagenic agent that has gained considerable research interest owing to its toxic nature. Ozonation of industrially important hydrazines such as unsymmetrical dimethylhydrazine (UDMH) or monomethylhydrazine (MMH) has been associated with NDMA formation and accumulation in the environment. UDMH/MMH - ozonation also leads to several other transformation products such as acetaldehyde dimethyl hydrazone (ADMH), tetramethyl tetra azene (TMT), diazomethane, methyl diazene, etc, which can be either precursors or competitors for NDMA formation.In this work, we explored the formation mechanism of ADMH and TMT from UDMH-ozonation and their further oxidation to NDMA using the second-order Moller Plesset perturbation theory employing the 6-311G(d) basis set. We have also investigated how MMH selectively forms methyl diazene and diazomethane under normal conditions and NDMA in the presence of excess ozone. Our calculations indicate that the reactions proceed via an initial H abstraction from the hydrazine –NH2 group followed by the oxidation of the generated N-radical species. The formation of ADMH from the UDMH-ozone reaction involves an acetaldehyde intermediate, which then reacts with a second UDMH molecule to generate ADMH. The preferable attack of ozone molecule on N=C bond of ADMH generates DMAN intermediate, which subsequently undergoes oxidation to form NDMA. Unlike other transformation products, TMT formation occurs via the dimerization of DMAN. Though there exist a N=N bonds in the TMT, which are preferable attacking sites for ozone, experimental studies show the lower yields of NDMA formation, which corroborates with the high activation barrier required for the process(42kcal/mol).Overall, our calculated results agree well with the experimental observations and rate constants. Computational calculations bring insights into the electronic nature and kinetics of the elementary reactions of this pathway, enabled by computed energies of structures that are not possible to access experimentally.

Keywords: reaction mechanism, ozonation, substituted hydrazine, transition state

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