Search results for: phase space

Authors: Zarabizan Zakaria, Hayati Zainal

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The construction industry is one of the most important sectors that contribute to the nation’s economy and catalyze towards the growth of other industries. However, some construction projects have not been completed on its stipulated time and duration, scope and budget due to several factors. This problem arises due to the weaknesses of human factors, especially from ineffective leadership quality practiced by project managers and contractors in managing project teams. Therefore, a construction project should impose the element of Project Team. The project team is formed in the implementation of the project which includes the project brief, project scope, customer requirements and provided designs. Many organizations in the construction sector use teams to meet today's global competition and customer expectations, however, team effectiveness evaluation is required. In insuring the construction team is successful and effectiveness, the construction department must encourage, measure, set up, and evaluate or review the effectiveness of project team that was formed. In order to produce a better outcome for a high-end project, an effective and efficient project team is required which also help in increasing overall productivity. The purpose of this study is to determine the role of team effectiveness in the construction project team based on the overall construction project performance. It examines several different factors which related to team effectiveness. It also examines the relationship between team effectiveness factor and project performance aspect. Team Effect Review and Project Performance Review are developed to be used for data collection. Data collected were analyzed using several statistical tests. Results obtained from data analysis are validated using semi-structured interviews. Besides that, a comprehensive survey were developed to assess the way construction project teams in order to maintain its effectiveness throughout the project phase. In order to determine a project successful it has been found that Project Team Leadership is the most important factor. In addition, the definition of team effectiveness in the construction project team is developed based on the perspective of project clients and project team members. The results of this study are expected to provide an idea on the factors that are needed to be focused on improving the team's effectiveness towards project performance aspects. At the same time, the definition of team effectiveness from team members and owner views has been developed in order to provide a better understanding of the word team's effectiveness in construction projects.

Keywords: project team, leadership, construction project, project successful

Procedia PDF Downloads 147

Authors: Peiming Li

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This paper presents an innovative blockchain-based approach to enhance the reliability and efficiency of federated learning systems. By integrating a decentralized oracle consensus mechanism into the federated learning framework, we address key challenges of data and model integrity. Our approach utilizes a network of redundant oracles, functioning as independent validators within an epoch-based training system in the federated learning model. In federated learning, data is decentralized, residing on various participants' devices. This scenario often leads to concerns about data integrity and model quality. Our solution employs blockchain technology to establish a transparent and tamper-proof environment, ensuring secure data sharing and aggregation. The decentralized oracles, a concept borrowed from blockchain systems, act as unbiased validators. They assess the contributions of each participant using a Hidden Markov Model (HMM), which is crucial for evaluating the consistency of participant inputs and safeguarding against model poisoning and malicious activities. Our methodology's distinct feature is its epoch-based training. An epoch here refers to a specific training phase where data is updated and assessed for quality and relevance. The redundant oracles work in concert to validate data updates during these epochs, enhancing the system's resilience to security threats and data corruption. The effectiveness of this system was tested using the Mnist dataset, a standard in machine learning for benchmarking. Results demonstrate that our blockchain-oriented federated learning approach significantly boosts system resilience, addressing the common challenges of federated environments. This paper aims to make these advanced concepts accessible, even to those with a limited background in blockchain or federated learning. We provide a foundational understanding of how blockchain technology can revolutionize data integrity in decentralized systems and explain the role of oracles in maintaining model accuracy and reliability.

Keywords: federated learning system, block chain, decentralized oracles, hidden markov model

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Authors: Dmitry Aron

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Major radiation accidents carry not only the potential risks of negative consequences for public health due to exposure but also because of large-scale emergency measures were taken by authorities to protect the population, which can lead to unreasonable social and economic damage. It is technically difficult, as a rule, to assess the possible costs and damages from decisions on evacuation or resettlement of residents in the shortest possible time, since it requires specially prepared information systems containing relevant information on demographic, economic parameters and incoming data on radiation conditions. Foreign observers also face the difficulties in assessing the consequences of an accident in a foreign territory, since they usually do not have official and detailed statistical data on the territory of foreign state beforehand. Also, they can suppose the application of unofficial data from open Internet sources is an unreliable and overly labor-consuming procedure. This paper describes an approach to prompt creation of relational database that contains detailed actual data on economics, demographics and radiation situation at the Fukushima Prefecture during the Fukushima Daiichi NPP accident, received by the author from open Internet sources. This database was developed and used to assess the number of evacuated population, radiation doses, expected financial losses and other parameters of the affected areas. The costs for the areas with temporarily evacuated and long-term resettled population were investigated, and the radiological and economic effectiveness of the measures taken to protect the population was estimated. Some of the results are presented in the article. The study showed that such a tool for analyzing the consequences of radiation accidents can be prepared in a short space of time for the entire territory of Japan, and it can serve for the modeling of social and economic consequences for hypothetical accidents for any nuclear power plant in its territory.

Keywords: Fukushima, radiation accident, emergency measures, database

Procedia PDF Downloads 166

Authors: Boor Singh Lalia, Yarjan Abdul Samad, Raed Hashaikeh

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Three different kinds of solid polymer electrolytes were prepared using polyethylene oxide (PEO) as a base polymer, networked cellulose (NC) as a physical support and LiClO4 as a conductive salt for the electrolytes. Networked cellulose, a modified form of cellulose, is a biodegradable and environmentally friendly additive which provides a strong fibrous networked support for structural stability of the electrolytes. Although the PEO/NC/LiClO4 electrolyte retains its structural integrity and mechanical properties at 100oC as compared to pristine PEO-based polymer electrolytes, it suffers from poor ionic conductivity. To improve the room temperature conductivity of the electrolyte, PEO is replaced by the polyethylene glycol (PEG) which is a liquid phase that provides high mobility for Li+ ions transport in the electrolyte. PEG/NC/LiClO4 shows improvement in ionic conductivity compared to PEO/NC/LiClO4 at room temperature, but it is brittle and tends to form cracks during processing. An advanced solid polymer electrolyte with optimum ionic conductivity and mechanical properties is developed by using a ternary system: TEGDME/PEO/NC+LiClO4. At room temperature, this electrolyte exhibits an ionic conductivity to the order of 10-5 S/cm, which is very high compared to that of the PEO/LiClO4 electrolyte. Pristine PEO electrolytes start melting at 65 °C and completely lose its mechanical strength. Dynamic mechanical analysis of TEGDME: PEO: NC (70:20:10 wt%) showed an improvement of storage modulus as compared to the pristine PEO in the 60–120 °C temperature range. Also, with an addition of NC, the electrolyte retains its mechanical integrity at 100 oC which is beneficial for Li-ion battery operation at high temperatures. Differential scanning calorimetry (DSC) and thermal gravimetry analysis (TGA) studies revealed that the ternary polymer electrolyte is thermally stable in the lithium ion battery operational temperature range. As-prepared polymer electrolyte was used to assemble LiFePO4/ TEGDME/PEO/NC+LiClO4/Li half cells and their electrochemical performance was studied via cyclic voltammetry and charge-discharge cycling.

Keywords: solid polymer electrolyte, ionic conductivity, mechanical properties, lithium ion batteries, cyclic voltammetry

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Authors: Sercan Altundemir, Pinar Eribol, A. Kerem Uguz

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Microfluidics systems allow many-large scale laboratory applications to be miniaturized on a single device in order to reduce cost and advance fluid control. Moreover, such systems enable to generate and control droplets which have a significant role on improved analysis for many chemical and biological applications. For example, they can be employed as the model for cells in microfluidic systems. In this work, the interfacial instability of two immiscible Newtonian liquids flowing in a microchannel is investigated. When two immiscible liquids are in laminar regime, a flat interface is formed between them. If a direct current electric field is applied, the interface may deform, i.e. may become unstable and it may be ruptured and form micro-droplets. First, the effect of thickness ratio, total flow rate, viscosity ratio of the silicone oil and ethylene glycol liquid couple on the critical voltage at which the interface starts to destabilize is investigated. Then the droplet sizes are measured under the effect of these parameters at various voltages. Moreover, the effect of total flow rate on the time elapsed for the interface to be ruptured to form droplets by hitting the wall of the channel is analyzed. It is observed that an increase in the viscosity or the thickness ratio of the silicone oil to the ethylene glycol has a stabilizing effect, i.e. a higher voltage is needed while the total flow rate has no effect on it. However, it is observed that an increase in the total flow rate results in shortening of the elapsed time for the interface to hit the wall. Moreover, the droplet size decreases down to 0.1 μL with an increase in the applied voltage, the viscosity ratio or the total flow rate or a decrease in the thickness ratio. In addition to these observations, two empirical models for determining the critical electric number, i.e., the dimensionless voltage and the droplet size and another model which is a combination of both models, for determining the droplet size at the critical voltage are established.

Keywords: droplet formation, electrohydrodynamics, microfluidics, two-phase flow

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Authors: Mai Hussein

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'Littoral' is an original voice in Québécois theatre, spanning the cultural gaps that can exist between the playwrights’ native Lebanon, North America, Quebec, and Europe. Littoral is a 'crossroad' of cultures and themes, a 'bridge' connecting cultures and languages. It represents a new form of theatrical writing that combines the verbal, the vocal and the pantomimic, calling upon the stage to question the real, to engage characters in a quest, in a journey of mourning, of reconstructing identity and a collective memory despite ruins and wars. A theatre of witness, a theatre denouncing irrationality of racism and war, a theatre 'performing' the symptoms of the stress disorders of characters passing from resistance and anger to reconciliation and giving voice to the silenced victims, these are some of the pillars that this play has to offer. In this corrida between life and death, the identity seems like a work-in-progress that is shaped in the presence of the Self and the Other. This trajectory will lead to re-open widely the door to questions, interrogations, and reflections to show how this play is at the nexus of contemporary preoccupations of the 21st century: the importance of memory, the search for meaning, the pursuit of the infinite. It also shows how a play can create bridges between languages, cultures, societies, and movements. To what extent does it mediate between the words and the silence, and how does it burn the bridges or the gaps between the textual and the performative while investigating the power of intermediality to confront racism and segregation. It also underlines the centrality of confrontation between cultures, languages, writing and representation techniques to challenge the characters in their quest to restructure their shattered, but yet intertwined identities. The goal of this theatre would then be to invite everyone involved in the process of a journey of self-discovery away from their comfort zone. Everyone will have to explore the liminal space, to read in between the lines of the written text as well as in between the text and the performance to explore the gaps and the tensions that exist between what is said, and what is played, between the 'parole' and the performative body.

Keywords: identity, memory, performance, testimony, trauma

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Authors: Debabrata Adhikari, Mikhail Matveev, Louise Brown, Jan Kočí, Andy Long

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Resin transfer molding (RTM) is increasingly used for manufacturing high-quality composite structures due to its additional advantages over prepregs of low-cost out-of-autoclave processing. However, to retain the advantages, it is critical to reduce the void content during the injection. Reinforcements commonly used in RTM, such as woven fabrics, have dual-scale porosity with mesoscale pores between the yarns and the micro-scale pores within the yarns. Due to the fabric geometry and the nature of the dual-scale flow, the flow front during injection creates a complicated fingering formation which leads to void formation. Analytical modeling of void formation for woven fabrics has been widely studied elsewhere. However, there is scope for improvement to the reduction in void formation in 3D fabrics wherein the in-plane yarn layers are confined by additional through-thickness binder yarns. In the present study, the structural morphology of the tortuous pore spaces in the 3D fabric has been studied and implemented using open-source software TexGen. An analytical model for the void and the fingering formation has been implemented based on an idealized unit cell model of the 3D fabric. Since the pore spaces between the yarns are free domains, the region is treated as flow-through connected channels, whereas intra-yarn flow has been modeled using Darcy’s law with an additional term to account for capillary pressure. Later the void fraction has been characterised using the criterion of void formation by comparing the fill time for inter and intra yarn flow. Moreover, the dual-scale two-phase flow of resin with air has been simulated in the commercial CFD solver OpenFOAM/ANSYS to predict the probable location of voids and validate the analytical model. The use of an idealised unit cell model will give the insight to optimise the mesoscale geometry of the reinforcement and injection parameters to minimise the void content during the LCM process.

Keywords: 3D fiber, void formation, RTM, process modelling

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Authors: Mohammed Alasel, Michael Keusgen

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Gold is a noble metal; in its nano-scale level (e.g. spherical nanoparticles), the conduction electrons are triggered to collectively oscillate with a resonant frequency when certain wavelengths of electromagnetic radiation interact with its surface; this phenomenon is known as surface plasmon resonance (SPR). SPR is responsible for giving the gold nanoparticles its intense red color depending mainly on its size, shape and distance between nanoparticles. A decreased distance between gold nanoparticles results in aggregation of them causing a change in color from red to blue. This aggregation enables gold nanoparticles to serve as a sensitive biosensoric indicator. In the proposed work, gold nanoparticles were modified with two proteins: i) Borrelia antigen, variable lipoprotein surface-exposed protein (VlsE), and ii) protein A. VlsE antigen induces a strong antibody response against Lyme disease and can be detected from early to late phase during the disease in humans infected with Borrelia. In addition, it shows low cross-reaction with the other non-pathogenic Borrelia strains. The high specificity of VlsE antigen to anti-Borrelia antibodies, combined simultaneously with the high specificity of protein A to the Fc region of all IgG human antibodies, was utilized to develop a rapid test for serological point of care diagnosis of borreliosis in human serum. Only in the presence of anti-Borrelia antibodies in the serum probe, an aggregation of gold nanoparticles can be observed, which is visible by a concentration-dependent colour shift from red (low IgG) to blue (high IgG). Experiments showed it is clearly possible to distinguish between positive and negative sera samples using a simple suspension of the two-protein modified gold nanoparticles in a very short time (30 minutes). The proposed work showed the potential of using such modified gold nanoparticles generally for serological diagnosis. Improved specificity and reduced assay time can be archived in applying increased salt concentrations combined with decreased pH values (pH 5).

Keywords: gold nanoparticles, gold aggregation, serological diagnosis, protein A, lyme borreliosis

Procedia PDF Downloads 364

Authors: Karen Fang

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Investigative genetic genealogy has attracted much interest in both the field of ethics and the public eye due to its global application in criminal cases. Arguments have been made regarding privacy and informed consent, especially with law enforcement using consumer genetic testing results to convict individuals. In the case of public interest, DNA databases have the strong potential to significantly reduce crime, which in turn leads to safer communities and better futures. With the advancement of genetic technologies, the integration of a universal forensic DNA database in violent crimes, crimes against children, and missing person cases is expected to deter crime while protecting one’s privacy. Rather than collecting whole genomes from the whole population, STR profiles can be used to identify unrelated individuals without compromising personal information such as physical appearance, disease risk, and geographical origin, and additionally, reduce cost and storage space. STR DNA profiling is already used in the forensic science field and going a step further benefits several areas, including the reduction in recidivism, improved criminal court case turnaround time, and just punishment. Furthermore, adding individuals to the database as early as possible prevents young offenders and first-time offenders from participating in criminal activity. It is important to highlight that DNA databases should be inclusive and tightly governed, and the misconception on the use of DNA based on crime television series and other media sources should be addressed. Nonetheless, deterrent effects have been observed in countries like the US and Denmark with DNA databases that consist of serious violent offenders. Fewer crimes were reported, and fewer people were convicted of those crimes- a favorable outcome, not even the death penalty could provide. Currently, there is no better alternative than a universal forensic DNA database made up of STR profiles. It can open doors for investigative genetic genealogy and fostering better communities. Expanding the appropriate use of DNA databases is ethically acceptable and positively impacts the public.

Keywords: bioethics, deterrent effects, DNA database, investigative genetic genealogy, privacy, public interest

Procedia PDF Downloads 130

Authors: Kalpana Goel

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Australian social work schools are finding it difficult to find appropriate placements for the increasing number of international students enrolled in their Master of Social Work qualifying (MSWQ) programs. Anecdotally, it has been noticed that fewer social work students are ready to work with older people whose numbers are rising globally. An innovative and unique placement for international students enrolled in the MSWQ at one Australian university was organised in partnership with a community-based service working with older clients to meet two objectives: increasing the number of suitable placements for international students and preparing social work students to work with older people. Creative activities and projects were designed to provide meaningful engagement and experience in working with older people in the community. Students participated in a number of projects that were matched with their interest and capability in a 500-hour placement. The students were asked to complete an online survey after all work for the placement had been completed. The areas of assessment were: self-perceived change in perception towards age and older people, valued field placement experiences including reflective practice, knowledge and skill development, and constraints and challenges experienced in the placement. Findings revealed students’ increased level of confidence in applying social work theory to practice, developing effective communication and interpersonal skills, and use of innovation and creativity in preparing well-being plans with older adults. Challenges and constraints related to their limited English language ability and lack of cultural knowledge of the host society. It was recognised that extra support for these students and more planning in the beginning phase of placement are vital to placement success. Caution in matching students with clients of similar cultural background must be exercised to ensure that there is equity in task allocation and opportunities for wider experiences.

Keywords: field placement, international students, older people, social work

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Authors: Aamna Lawrence, Ashutosh Mishra

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Tremors occur in 60% of the patients who have Multiple Sclerosis (MS), the most common demyelinating disease that affects the central and peripheral nervous system, and are the primary cause of disability in young adults. While pharmacological agents provide minimal benefits, surgical interventions like Deep Brain Stimulation and Thalamotomy are riddled with dangerous complications which make non-invasive electrical stimulation an appealing treatment of choice for dealing with tremors. Hence, we hypothesized that if the non-invasive electrical stimulation parameters (mainly frequency) can be computed by mathematically modeling the nerve fibre to take into consideration the minutest details of the axon morphologies, tremors due to demyelination can be optimally alleviated. In this computational study, we have modeled the random demyelination pattern in a nerve fibre that typically manifests in MS using the High-Density Hodgkin-Huxley model with suitable modifications to account for the myelin. The internode of the nerve fibre in our model could have up to ten demyelinated regions each having random length and myelin thickness. The arrival time of action potentials traveling the demyelinated and the normally myelinated nerve fibre between two fixed points in space was noted, and its relationship with the nerve fibre radius ranging from 5µm to 12µm was analyzed. It was interesting to note that there were no overlaps between the arrival time for action potentials traversing the demyelinated and normally myelinated nerve fibres even when a single internode of the nerve fibre was demyelinated. The study gave us an opportunity to design DC pulses whose frequency of application would be a function of the random demyelination pattern to block only the delayed tremor-causing action potentials. The DC pulses could be delivered to the peripheral nervous system non-invasively by an electrode bracelet that would suppress any shakiness beyond it thus paving the way for wearable neuro-rehabilitative technologies.

Keywords: demyelination, Hodgkin-Huxley model, non-invasive electrical stimulation, tremor

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Authors: Cristian Cazacu, Bela Kobulniczky

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Even though nowadays the median area of the Bucharest’s Sector 1 owns one of the best reputations in terms of quality of life level, the problems in urban planning from the last twenty years, as well as those related to the urban environment, became more and more obvious and shrill. And all this happened as long as non-compliance with urban and spatial planning laws, corroborated with uncontrolled territorial expansion on certain areas and faulty management of public and private spaces were more acute. The action of all these factors has been felt more and more strongly in the territory in the last twenty years, generating the degradation of the quality of the urban environment and affecting in parallel the general level of the inhabitants¬’ quality of life. Our methodology is based on analyzing a wide range of environmental parameters and it is also based on using advanced resources and skills for mapping planning and environmental dysfunctions as well as the possibility of integrating information into GIS programs, all data sets corroborated with problems related to spatial planning management and inaccuracies of the urbanistic sector. In the end, we managed to obtain a calculated and realistic image of the dysfunctions and a quantitative view of their magnitude in the territory. We also succeeded to create a full general map of the degree of degradation of the urban environment by typologies of urban tissues. Moreover, the methods applied by us can also be used globally to calculate and create realistic images and intelligent maps over the quality of the environment in areas larger than this one. Our study shows that environmental degradation occurred differently in the urban tissues from our study area, depending on several factors, reviewing the faulty way in which the processes of recovery / urban regeneration of the gap in recent years have led to the creation of new territorial dysfunctions. The general, centralized results show that the analyzed space has a much wider range of problems than initially thought, although notoriety and social etiquette place them far above other spaces from the same city of study.

Keywords: environment, GIS, planning, urban tissues

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Authors: Adriano Losso, Birgit Dämon, Stefan Mayr

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In vascular plants, water flows from roots to leaves in a metastable state, and even a small perturbation of the system can lead a sudden transition from the liquid to the vapor phase, resulting in xylem embolism (cavitation). Xylem embolism, induced by drought stress and/or freezing stress is caused by the aspiration of gaseous bubbles into xylem conduits from adjacent gas-filled compartments through pit membrane pores (‘air seeding’). At water potentials less negative than the threshold for air seeding, the surface tension (γ) stabilizes the air-water interface and thus prevents air from passing the pit pores. This hold is probably also true for conifers, where this effect occurs at the edge of the sealed torus. Accordingly, it was experimentally demonstrated that γ influences air seeding, but information on the relevance of this effect under field conditions is missing. In this study, we analyzed seasonal changes in γ of the xylem sap in two conifers growing at the alpine timberline (Picea abies and Pinus mugo). In addition, cut branches were perfused (40 min perfusion at 0.004 MPa) with different γ solutions (i.e. distilled and degassed water, 2, 5 and 15% (v/v) ethanol-water solution corresponding to a γ of 74, 65, 55 and 45 mN m-1, respectively) and their vulnerability to drought-induced embolism analyzed via the centrifuge technique (Cavitron). In both species, xylem sap γ changed considerably (ca. 53-67 and ca. 50-68 mN m-1 in P. abies and P. cembra, respectively) over the season. Branches perfused with low γ solutions showed reduced resistance against drought-induced embolism in both species. A significant linear relationship (P < 0.001) between P12, P50 and P88 (i.e. water potential at 12, 50 and 88% of the loss of conductivity) and xylem sap γ was found. Based on this correlation, a variation in P50 between -3.10 and -3.83 MPa (P. abies) and between -3.21 and -4.11 MPa (P. mugo) over the season could be estimated. Results demonstrate that changes in γ of the xylem sap can considerably influence a tree´s resistance to drought-induced embolism. They indicate that vulnerability analyses, normally conducted at a γ near that of pure water, might often underestimate vulnerabilities under field conditions. For studied timberline conifers, seasonal changes in γ might be especially relevant in winter, when frost drought and freezing stress can lead to an excessive embolism.

Keywords: conifers, Picea abies, Pinus mugo, timberline

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Authors: Pierre van Tonder, Dinesh Muthoo, Kim twiname

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Many existing and newly built structures are constructed on the design basis of the engineer and the workmanship of the construction company. However, when considering larger structures where more people are exposed to the building, its structural integrity is of great importance considering the safety of its occupants (Raghu, 2013). But how can the structural integrity of a building be monitored efficiently and effectively. This is where the fourth industrial revolution step in, and with minimal human interaction, data can be collected, analysed, and stored, which could also give an indication of any inconsistencies found in the data collected, this is where the Fibre Bragg Grating (FBG) monitoring system is introduced. This paper illustrates how data can be collected and converted to develop stress – strain behaviour and to produce bending moment diagrams for the utilisation and prediction of the structure’s integrity. Embedded fibre optic sensors were used in this study– fibre Bragg grating sensors in particular. The procedure entailed making use of the shift in wavelength demodulation technique and an inscription process of the phase mask technique. The fibre optic sensors considered in this report were photosensitive and embedded in the slab and beams for data collection and analysis. Two sets of fibre cables have been inserted, one purposely to collect temperature recordings and the other to collect strain and temperature. The data was collected over a time period and analysed used to produce bending moment diagrams to make predictions of the structure’s integrity. The data indicated the fibre Bragg grating sensing system proved to be useful and can be used for structural health monitoring in any environment. From the experimental data for the slab and beams, the moments were found to be64.33 kN.m, 64.35 kN.m and 45.20 kN.m (from the experimental bending moment diagram), and as per the idealistic (Ultimate Limit State), the data of 133 kN.m and 226.2 kN.m were obtained. The difference in values gave room for an early warning system, in other words, a reserve capacity of approximately 50% to failure.

Keywords: fibre bragg grating, structural health monitoring, fibre optic sensors, beams

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Authors: Miao Li, Mengyuan Xu

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As a low-carbon travel mode, bicycling has drawn increasing political interest in the contemporary Chinese urban context, and the public sharing bikes have become the most popular ways of bike usage in China now. This research aims to explore the spatial-temporal relationship between sharing bike usage and different characteristics of the urban street built environment. In the research, street segments were used as the analytic unit of the street built environment defined by street intersections. The sharing bike usage data in the research include a total of 2.64 million samples that are the entire sharing bike distribution data recorded in two days in 2018 within a neighborhood of 185.4 hectares in the city of Wuhan, China. And these data are assigned to the 97 urban street segments in this area based on their geographic location. The built environment variables used in this research are categorized into three sections: 1) street design characteristics, such as street width, street greenery, types of bicycle lanes; 2) condition of other public transportation, such as the availability of metro station; 3) Street function characteristics that are described by the categories and density of the point of interest (POI) along the segments. Spatial Lag Models (SLM) were used in order to reveal the relationships of specific urban streets built environment characteristics and the likelihood of sharing bicycling usage in whole and different periods a day. The results show: 1) there is spatial autocorrelation among sharing bicycling usage of urban streets in case area in general, non-working day, working day and each period of a day, which presents a clustering pattern in the street space; 2) a statistically strong association between bike sharing usage and several different built environment characteristics such as POI density, types of bicycle lanes and street width; 3) the pattern that bike sharing usage is influenced by built environment characteristics depends on the period within a day. These findings could be useful for policymakers and urban designers to better understand the factors affecting bike sharing system and thus propose guidance and strategy for urban street planning and design in order to promote the use of sharing bikes.

Keywords: big data, sharing bike usage, spatial statistics, urban street built environment

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Authors: Samar Swaid

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Today, corporates are moving toward the adoption of Design-Thinking techniques to develop products and services, putting their consumer as the heart of the development process. One of the leading companies in Design-Thinking, IDEO (Innovation, Design, Engineering Organization), defines Design-Thinking as an approach to problem-solving that relies on a set of multi-layered skills, processes, and mindsets that help people generate novel solutions to problems. Design thinking may result in new ideas, narratives, objects or systems. It is about redesigning systems, organizations, infrastructures, processes, and solutions in an innovative fashion based on the users' feedback. Tim Brown, president and CEO of IDEO, sees design thinking as a human-centered approach that draws from the designer's toolkit to integrate people's needs, innovative technologies, and business requirements. The application of design thinking has been witnessed to be the road to developing innovative applications, interactive systems, scientific software, healthcare application, and even to utilizing Design-Thinking to re-think business operations, as in the case of Airbnb. Recently, there has been a movement to apply design thinking to machine learning and artificial intelligence to ensure creating the "wow" effect on consumers. The Association of Computing Machinery task force on Data Science program states that" Data scientists should be able to implement and understand algorithms for data collection and analysis. They should understand the time and space considerations of algorithms. They should follow good design principles developing software, understanding the importance of those principles for testability and maintainability" However, this definition hides the user behind the machine who works on data preparation, algorithm selection and model interpretation. Thus, the Data Science program includes design thinking to ensure meeting the user demands, generating more usable machine learning tools, and developing ways of framing computational thinking. Here, describe the fundamentals of Design-Thinking and teaching modules for data science programs.

Keywords: data science, design thinking, AI, currculum, transformation

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Authors: Ritwik Saha, Anindita Chaudhuri

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The psychological dimension of work-based mobility of the contemporary time in the context of the ever-changing socio-economic process mounting the interest to address the consequential issues of quality of life and well-being of the migrant section of society. The negotiation with the fluidity of the job market and the changing psychosocial dimensions within and between psychosocial relations may disentangle the resilience as well as the mechanism of diligence toward migrant (marginal) life. The work-based mobility and its associated phenomena have highly impacted the migrant’s quality of life especially the marginalized (socioeconomically weak) ones along with their family members staying away from them. The subjective experiences of the journey of their migrant life and reconstruction of the psychosocial being in terms of existence and well-being at the host place are the minimal addressed issues in migrant literature. Hence this gap instigates to bring forth the issue with the present study exploring the phenomenal aspects of lived experiences, resilience, and sense-making of the well-being of migrant living by the marginalized migrant people engaging in unorganized space. In doing so qualitative research method was followed, and semi-structured interviews were used for data collection from the four selected migrant groups (Fuchkawala, Bhunjawala, Bhari - drinking water supplier, Construction worker) as they migrated to Kolkata and its metropolis area from different states of India, Five participants from each group (20 participants in total) age range between 20 to 45 were interviewed physically and participants’ observatory notes were taken to capture their lived experiences, audio recordings were transcribed and analyzed systematically following Charmaz’s three-layer coding of grounded theory. Being truthful to daily industry, the strong desire to build children’s future, the mastering mechanism to dual existence, use of traditional social network these four themes emerges after analysis of the data. However, incorporating fate as their usual way of life and making sense of well-being through their assertion is another evolving aspect of migrant life.

Keywords: lived experiences, marginal living, resilience, sense-making process, well-being

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Authors: Jason Clarke, Michaela Porubanova, Angela Mazzoli, Gulsah Kut

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What accounts for our perception that time inexorably passes in one direction, from the past to the future, the so-called arrow of time, given that the laws of physics permit motion in one temporal direction to also happen in the reverse temporal direction? Modern physics says that the reason for time’s unidirectional physical arrow is the relationship between time and entropy, the degree of disorder in the universe, which is evolving from low entropy (high order; thermal disequilibrium) toward high entropy (high disorder; thermal equilibrium), the second law of thermodynamics. Accordingly, our perception of the direction of time, from past to future, is believed to emanate as a result of the natural evolution of entropy from low to high, with low entropy defining our notion of ‘before’ and high entropy defining our notion of ‘after’. Here we explored this proposed relationship between entropy and the perception of time’s arrow. We predicted that if the brain has some mechanism for detecting entropy, whose output feeds into processes involved in constructing our perception of the direction of time, presentation of violations to the expectation that low entropy defines ‘before’ and high entropy defines ‘after’ would alert this mechanism, leading to measurable behavioral effects, namely a disruption in duration perception. To test this hypothesis, participants were shown briefly-presented (1000 ms or 500 ms) computer-generated visual dynamic events: novel 3D shapes that were seen either to evolve from whole figures into parts (low to high entropy condition) or were seen in the reverse direction: parts that coalesced into whole figures (high to low entropy condition). On each trial, participants were instructed to reproduce the duration of their visual experience of the stimulus by pressing and releasing the space bar. To ensure that attention was being deployed to the stimuli, a secondary task was to report the direction of the visual event (forward or reverse motion). Participants completed 60 trials. As predicted, we found that duration reproduction was significantly longer for the high to low entropy condition compared to the low to high entropy condition (p=.03). This preliminary data suggests the presence of a neural mechanism that detects entropy, which is used by other processes to construct our perception of the direction of time or time’s arrow.

Keywords: time perception, entropy, temporal illusions, duration perception

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Authors: Chinwe Susan Oguejiofor, Daniel Osamwonyi Iyioha

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Over the last two decades, Nigeria has witnessed an upsurge in graduate unemployment occasioned by the lack of industries and proliferation of tertiary institutions churning out thousands of graduates every year to compete for the few available job space. The astronomical rise in the unemployment rate amongst Nigerian graduates however, is principally assumed to be the defective curricula of the universities and other tertiary institutions whose focus is on training for white-collar jobs. Although graduate unemployment has become a global scourge, its adverse economic impact is believed to be more in developing economies like Nigeria with a huge young population within the working age who cannot seem to find gainful employment to make out a respectable livelihood. Thus, higher institutions especially Universities found itself under pressure and intense competition to produce graduates who can think outside the box and create jobs; hence there was the need to focus on instilling hands-on practical job skills into their students that will make them job creators rather than job seekers on graduation. In the same vein stakeholders in education have continued to lend their voices to the philosophy that the undergraduate curricula should be completely overhauled to accomodate the development of hand-on practical skills and innovative capacity relevant to creating solutions to societal problems. In a bid to correct this anomaly, the Federal Government of Nigeria in conjunction with the Ministry of Commerce, Industry and Investment inaugurated a programme tagged “University Entrepreneurship Development Programme” (UNEDEP) whose objective was basically to promote self-employment among the youth right from the institutions of higher learning. But the question is whether the objectives of the programme have actually been achieved. Despite the inclusion in Nigerian educational curriculum close to two decades now,, one wonder if the essence has been aborted. Thus, the paper focused on the concept of entrepreneurship education, objectives of entrepreneurship education, Graduates unemployment, rethinking entrepreneurship education programme in tertiary institution for employment generation , role of entrepreneurship in job creation, challenges of entrepreneurship education in tertiary institution in Nigeria, conclusion and recommendations were drawn accordingly.

Keywords: rethinking, entrepreneurship education, remedy, unemployment, job creation

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Authors: Ime R. Udotong, Justina I. R. Udotong, Ofonime U. M. John

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Brass terminal, one of the several crude oil and petroleum products storage/handling facilities in the Niger Delta was built in the 1980s. Activities at this site, over the years, released crude oil into this 3 m-deep, 1500 m-long canal lying adjacent to the terminal with oil floating on it and its sediment heavily polluted. To ensure effective clean-up, three major activities were planned: Site characterization, bioremediation pilot plant construction and testing and full-scale bioremediation of contaminated sediment/bank soil by land farming. The canal was delineated into 12 lots and each characterized, with reference to the floating oily phase, contaminated sediment and canal bank soil. As a result of site characterization, a pilot plant for on-site bioremediation was designed and a treatment basin constructed for carrying out pilot bioremediation test. Following a designed sampling protocol, samples from this pilot plant were collected for analysis at two laboratories as a quality assurance/quality control check. Results showed that Brass Canal upstream is contaminated with dark, thick and viscous oily film with characteristic hydrocarbon smell while downstream, thin oily film interspersed with water were observed. Sediments were observed to be dark with mixture of brownish sandy soil with TPH ranging from 17,800 mg/kg in Lot 1 to 88,500 mg/kg in Lot 12 samples. Brass Canal bank soil was observed to be sandy from ground surface to 3m, below ground surface (bgs) it was silty-sandy and brownish while subsurface soil (4-10m bgs) was sandy-clayey and whitish/grayish with typical hydrocarbon smell. Preliminary results obtained so far have been very promising but were proprietary. This project is considered, to the best of technical literature knowledge, the first large-scale on-site bioremediation project in the Niger Delta region, Nigeria.

Keywords: bioremediation, contaminated sediment, land farming, oily sludge, oil terminal

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Authors: Mona Alharbi

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Melioidosis has emerged as a lethal disease. Unfortunately, the molecular mechanisms of virulence and pathogenicity of Burkholderia pseudomallei remain unknown. However, proteomics research has selected putative targets in B. pseudomallei that might play roles in the B. pseudomallei virulence. BPSL 2418 putative protein has been predicted as a free methionine sulfoxide reductase and interestingly there is a link between the level of the methionine sulfoxide in pathogen tissues and its virulence. Therefore in this work, we describe the cloning expression, purification, and crystallization of BPSL 2418 and the solution of its 3D structure using X-ray crystallography. Also, we aimed to identify the substrate binding and reduced forms of the enzyme to understand the role of BPSL 2418. The gene encoding BPSL2418 from B. pseudomallei was amplified by PCR and reclone in pETBlue-1 vector and transformed into E. coli Tuner DE3 pLacI. BPSL2418 was overexpressed using E. coli Tuner DE3 pLacI and induced by 300μM IPTG for 4h at 37°C. Then BPS2418 purified to better than 95% purity. The pure BPSL2418 was crystallized with PEG 4000 and PEG 6000 as precipitants in several conditions. Diffraction data were collected to 1.2Å resolution. The crystals belonged to space group P2 21 21 with unit-cell parameters a = 42.24Å, b = 53.48Å, c = 60.54Å, α=γ=β= 90Å. The BPSL2418 binding MES was solved by molecular replacement with the known structure 3ksf using PHASER program. The structure is composed of six antiparallel β-strands and four α-helices and two loops. BPSL2418 shows high homology with the GAF domain fRMsrs enzymes which suggest that BPSL2418 might act as methionine sulfoxide reductase. The amino acids alignment between the fRmsrs including BPSL 2418 shows that the three cysteines that thought to catalyze the reduction are fully conserved. BPSL 2418 contains the three conserved cysteines (Cys⁷⁵, Cys⁸⁵ and Cys¹⁰⁹). The active site contains the six antiparallel β-strands and two loops where the disulfide bond formed between Cys⁷⁵ and Cys¹⁰⁹. X-ray structure of free methionine sulfoxide binding and native forms of BPSL2418 were solved to increase the understanding of the BPSL2418 catalytic mechanism.

Keywords: X-Ray Crystallography, BPSL2418, Burkholderia pseudomallei, Melioidosis

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Authors: Tarek Duzan

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Fractures are a fundamental property of most reservoirs. Despite their abundance, they remain difficult to detect and quantify. The most effective characterization of fractured reservoirs is accomplished by integrating geological, geophysical, and engineering data. Detection of fractures and defines their relative contribution is crucial in the early stages of exploration and later in the production of any field. Because fractures could completely change our thoughts, efforts, and planning to produce a specific field properly. From the structural point of view, all reservoirs are fractured to some point of extent. North Gialo field is thought to be a naturally fractured reservoir to some extent. Historically, natural fractured reservoirs are more complicated in terms of their exploration and production efforts, and most geologists tend to deny the presence of fractures as an effective variable. Our aim in this paper is to determine the degree of fracturing, and consequently, our evaluation and planning can be done properly and efficiently from day one. The challenging part in this field is that there is no enough data and straightforward well testing that can let us completely comfortable with the idea of fracturing; however, we cannot ignore the fractures completely. Logging images, available well testing, and limited core studies are our tools in this stage to evaluate, model, and predict possible fracture effects in this reservoir. The aims of this study are both fundamental and practical—to improve the prediction and diagnosis of natural-fracture attributes in N. Gialo hydrocarbon reservoirs and accurately simulate their influence on production. Moreover, the production of this field comes from 2-phase plan; a self depletion of oil and then gas injection period for pressure maintenance and increasing ultimate recovery factor. Therefore, well understanding of fracturing network is essential before proceeding with the targeted plan. New analytical methods will lead to more realistic characterization of fractured and faulted reservoir rocks. These methods will produce data that can enhance well test and seismic interpretations, and that can readily be used in reservoir simulators.

Keywords: natural fracture, sandstone reservoir, geological, geophysical, and engineering data

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Authors: Samiyah Tasleem, Muhammad Abdul Haq, Syed Baqir Shyum Naqvi, Muhammad Abid Husnain, Sajjad Haider Naqvi

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The objective of the present study was: a) to investigate the antimicrobial activity of honey samples of different floral sources of Pakistan, b) to recover the phenolic acids in them as a possible contributing factor of antimicrobial activity. Six honey samples from different floral sources, namely: Trachysperm copticum, Acacia species, Helianthus annuus, Carissa opaca, Zizyphus and Magnifera indica were used. The antimicrobial activity was investigated by the disc diffusion method against eight freshly isolated clinical isolates (Staphylococci aureus, Staphylococci epidermidis, Streptococcus faecalis, Pseudomonas aeruginosa, Klebsiella pneumonia, Escherichia coli, Proteus vulgaris and Candida albicans). Antimicrobial activity of honey was compared with five commercial antibiotics, namely: doxycycline (DO-30ug/mL), oxytetracycline (OT-30ug/mL), clarithromycin (CLR–15ug/mL), moxifloxacin (MXF-5ug/mL) and nystatin (NT – 100 UT). The fractions responsible for antimicrobial activity were extracted using ethyl acetate. Solid phase extraction (SPE) was used to recover the phenolic acids of honey samples. Identification was carried out via High-Performance Liquid Chromatography (HPLC). The results indicated that antimicrobial activity was present in all honey samples and found comparable to the antibiotics used in the study. In the microbiological assay, the ethyl acetate honey extract was found to exhibit a very promising antimicrobial activity against all the microorganisms tested, indicating the existence of phenolic compounds. Six phenolic acids, namely: gallic, caffeic, ferulic, vanillic, benzoic and cinnamic acids were identified besides some unknown substance by HPLC. In conclusion, Pakistani honey samples showed a broad spectrum antibacterial and promising antifungal activity. Identification of six different phenolic acids showed that Pakistani honey samples are rich sources of phenolic compounds that could be the contributing factor of antimicrobial activity.

Keywords: Pakistani honey, antimicrobial activity, Phenolic acids eg.gallic, caffeic, ferulic, vanillic, benzoic and cinnamic acids

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Authors: Alessandro Suardi, Rodolfo Picchio, Domenico Coaloa, Maria Bonaventura Forleo, Nadia Palmieri, Luigi Pari

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The reconversion process of the Italian sugar supply chain to bio-energy supply chains, as a result of the 2006 Sugar CMO reform, have involved research to define the best logistics, the most adapted energy crops for the Italian territory and their sustainability. Rapeseed (Brassica napus L.), Giant reed (Arundo donax L.) and Poplar (Poplar ssp.) are energy crops considered strategic for the development of Italian energy supply-chains. This study analyzed the environmental and the economic impacts on the farm level of these three energy crops. The environmental assessment included six farming units, two per crop, which were extracted from a sample of 251 rapeseed farm units (2751 ha), 7 giant reed farm units (7.8 ha), and 91 poplar farm units (440 ha) using a statistical multivariate analysis. Life Cycle Assessment (LCA) research method has been used to evaluate and compare the sustainability of the agricultural phases of the crops studied. The impact analyses have been performed at mid-point and end-point levels. The results of the analysis shown that the fertilization, is the major source of environmental impact of the agricultural phase due to the production of the fertilizers and the soil emissions of GHG following the treatment. The perennial energy crops studied (Arundo donax L., Poplar ssp.) were environmentally more sustainable if compared with the annual crop (Brassica napus L.) for all the impact categories at mid-point and end-point levels analyzed. The most relevant impact category influenced by the agricultural process result the fossil depletion, mainly due to the fossil fuels consumed during the mineral fertilizers production (urea). Human health was the most affected damage category at the end point level. Poplar result the energy crop with the best environmental performance for the Italian territory, in the distribution areas most suitable for its cultivation.

Keywords: LCA, energy crops, rapeseed, giant reed, poplar

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Authors: Xuewei Li, Jingfeng Yuan, Jianliang Zhou

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The 21st century has been called the century of human exploitation of underground space. Due to the characteristics of large quantity, tight schedule, low safety reserve and high uncertainty of deep foundation pit engineering, accidents frequently occur in deep foundation pit engineering, causing huge economic losses and casualties. With the successful application of information technology in the construction industry, building information modeling has become a research hotspot in the field of architectural engineering. Therefore, the application of building information modeling (BIM) and other information communication technologies (ICTs) in construction safety management is of great significance to improve the level of safety management. This research summed up the mechanism of the deep foundation pit engineering accident through the fault tree analysis to find the control factors of deep foundation pit engineering safety management, the deficiency existing in the traditional deep foundation pit construction site safety management. According to the accident cause mechanism and the specific process of deep foundation pit construction, the hazard information of deep foundation pit engineering construction site was identified, and the hazard list was obtained, including early warning information. After that, the system framework was constructed by analyzing the early warning information demand and early warning function demand of the safety management system of deep foundation pit. Finally, the safety management system of deep foundation pit construction site based on BIM through combing the database and Web-BIM technology was developed, so as to realize the three functions of real-time positioning of construction site personnel, automatic warning of entering a dangerous area, real-time monitoring of deep foundation pit structure deformation and automatic warning. This study can initially improve the current situation of safety management in the construction site of deep foundation pit. Additionally, the active control before the occurrence of deep foundation pit accidents and the whole process dynamic control in the construction process can be realized so as to prevent and control the occurrence of safety accidents in the construction of deep foundation pit engineering.

Keywords: Web-BIM, safety management, deep foundation pit, construction

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Authors: Victoria I. Michailova, Denitsa B. Momekova, Hristiana A. Velichkova, Evgeni H. Ivanov

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The aim of this work is to design and develop thermo-responsive nanosized drug delivery systems based on poly(N-isopropylacrylamide)-g-poly(ethylene oxide) (PNIPAM-g-PEO) double hydrophilic graft copolymers. The PNIPAM-g-PEO copolymers are able to self-assemble in water into nanoparticles above the LCST of the thermo-responsive PNIPAM backbone and to disassemble and rapidly release the entrapped drugs upon cooling. However, their drug delivery applications are often hindered by their low loading capacity as the drugs to be encapsulated do not dissolve in water. In order to overcome this limitation, here we applied a low-temperature procedure with ethanol as an alternative route to the formation and loading a model hydrophobic drug, Indomethacin (IMC), into PNIPAM-g-PEO nanoparticles. The rationale for this approach was that ethanol dissolves both IMC and the copolymer and its mixing with water may induce micellization of PNIPAM-g-PEO at temperatures lower than the LCST. The influence of the volume fraction of ethanol and the temperature on the aggregation characteristics of PNIPAM-g-PEO copolymers (2.7 mol% PEO) was investigated by means of DLS, TEM and rheological dynamic oscillatory tests. The studies showed rich phase behavior at T < LCST, incl. the formation of highly solvated 500-1000 nm complex structures, 30-70 nm micelles and polymersomes as well as giant polymersomes, as the fraction of added ethanol increased. We believe that the PNIPAM-g-PEO self-assembly is favored due to the different solvation of its constituting blocks in ethanol-water mixtures. The incorporation of IMC led to alteration of the physicochemical and morphological characteristics of the blank nanoparticles. In this case, only monodisperse polymersomes and micelles were observed in the solutions with an average diameter less than 65 nm and substantial drug loading (DLC ~117 – 146 wt%). Indomethacin release from the nanoparticles was responsive to temperature changes, being much faster at a temperature of 42oC compared to that of 37oC under otherwise the same conditions. The results obtained suggest that these PNIPAM-g-PEO nanoparticles could be potential in mild hyper-thermic delivery of nonsteroidal anti-inflammatory drugs.

Keywords: drug delivery, nanoparticles, poly(N-isopropylacryl amide)-g-poly(ethylene oxide), thermo-responsive

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Authors: Ravi Verma

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Cryosorption pump is the best solution to achieve clean, vibration free ultra-high vacuum. Furthermore, the operation of cryosorption pump is free from the influence of electric and magnetic fields. Due to these attributes, this pump is used in the space simulation chamber to create the ultra-high vacuum. The cryosorption pump comprises of three parts (a) panel which is cooled with the help of cryogen or cryocooler, (b) an adsorbent which is used to adsorb the gas molecules, (c) an epoxy which holds the adsorbent and the panel together thereby aiding in heat transfer from adsorbent to the panel. The performance of cryosorption pump depends on the temperature of the adsorbent and hence, on the thermal conductivity of the epoxy. Therefore we have made an attempt to increase the thermal conductivity of epoxy adhesive by mixing nano-sized graphene filler particles. The thermal conductivity of epoxy-graphene composite adhesive is measured with the help of indigenously developed experimental setup in the temperature range from 4.5 K to 7 K, which is generally the operating temperature range of cryosorption pump for efficiently pumping of hydrogen and helium gas. In this article, we have presented the experimental results of epoxy-graphene composite adhesive in the temperature range from 4.5 K to 7 K. We have also proposed an analytical heat conduction model to find the thermal conductivity of the composite. In this case, the filler particles, such as graphene, are randomly distributed in a base matrix of epoxy. The developed model considers the complete spatial random distribution of filler particles and this distribution is explained by Binomial distribution. The results obtained by the model have been compared with the experimental results as well as with the other established models. The developed model is able to predict the thermal conductivity in both isotropic regions as well as in anisotropic region over the required temperature range from 4.5 K to 7 K. Due to the non-empirical nature of the proposed model, it will be useful for the prediction of other properties of composite materials involving the filler in a base matrix. The present studies will aid in the understanding of low temperature heat transfer which in turn will be useful towards the development of high performance cryosorption pump.

Keywords: composite adhesive, computational modelling, cryosorption pump, thermal conductivity

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Authors: David Lynch Steinicke, Citlali Aguilera Lira, Andrea León García

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The proposal posed in this work comes from a researching-action approach. In Mexico, a dialogue of knowledge may function as a link between traditional, local, pragmatic knowledge, and technological, scientific knowledge. The advantage of generating this nexus lies on the positive impact in the environment, in society and economy. This work attempts to combine, on the one hand the traditional Mexican knowledge such as the usage of medicinal herb and the agroecosystem milpa; and on the other hand make use of a newly created agricultural ecotechnology which main function is to take advantage of the urban space and to save water. This ecotechnology is the wicking bed. In a globalized world, is relevant to have a proposal where the most important aspect is to revalorize the culture through the acquisition of traditional knowledge but at the same time adapting them to the new social and urbanized structures without threatening the environment. The methodology used in this work comes from a researching-action approach combined with a practical dimension where an experimental model made of three wickingbeds was implemented. In this model, there were cultivated medicinal herb and milpa components. The water efficiency and the social acceptance were compared with a traditional ground crop, all this practice was made in an urban social context. The implementation of agricultural ecotechnology has had great social acceptance as its irrigation involves minimal effort and it is economically feasible for low-income people. The wicking bed system raised in this project is attainable to be implemented in schools, urban and peri-urban environments, homemade gardens and public areas. The proposal managed to carry out an innovative and sustainable knowledge-based traditional Mexican agricultural technology, allowing regain Milpa agroecosystem in urban environments to strengthen food security in favour of nutritional and protein benefits for the Mexican fare.

Keywords: milpa, traditional medicine, urban agriculture, wicking bed

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Authors: Shalini Arora, Sri Sivakumar

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The deep removal of high molecular weight sulphur compounds (e.g., 4,6, dimethyl dibenzothiophene) is challenging due to their steric hindrance. Hydrogenation desulfurization (HYD) pathway is the main pathway to remove these sulfur compounds, and it is mainly governed by the number of type 2 sites. The formation of type 2 sites can be enhanced by modulating the pore structure and the interaction between the active metal and support. To this end, we report the enhanced HDS catalytic activity of ultrasmall NiMo supported on amorphous alumina (A-Al₂O₃) catalysts by one pot colloidal synthesis method followed by calcination and sulfidation. The amorphous alumina (A-Al₂O₃) was chosen as the support due to its lower surface energy, better physicochemical properties, and enhanced acidic sites (due to the dominance of tetra and penta coordinated [Al] sites) than crystalline alumina phase. At 20% metal oxide composition, NiMo supported on A-Al₂O₃ catalyst showed 1.4 and 1.2 times more reaction rate constant and turn over frequency (TOF) respectively than the conventional catalyst (wet impregnated NiMo catalysts) for HDS reaction of dibenzothiophene reactant molecule. A-Al₂O₃ supported catalysts represented enhanced type 2 sites formation (because this catalystpossesses higher sulfidation degree (80%) and NiMoS sites (19.3 x 10¹⁷ sites/mg) with desired optimum stacking degree (2.5) than wet impregnated catalyst at same metal oxide composition 20%) along with higher active metal dispersion, Mo edge site fraction. The experimental observations were also supported by DFT simulations. Lower heat of adsorption (< 4.2 ev for MoS2 interaction and < 3.15 ev for Ni doped MoS2 interaction) values for A-Al₂O₃ confirmed the presence of weaker metal-support interaction in A-Al₂O₃ in contrast to crystalline ℽ-Al₂O3. The weak metal-support interaction for prepared catalysts clearly suggests the higher formation of type 2 sites which leads to higher catalytic activity for HDS reaction.

Keywords: amorphous alumina, colloidal, desulfurization, metal-support interaction

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Authors: Krasimira N. Zhilkova, Mariya K. Kyulavska, Roza P. Mateva

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The anionic polymerization of -caprolactam (CL) with bifunctional activators has been extensively studied as an effective and beneficial method of improving chemical and impact resistances, elasticity and other mechanical properties of polyamide (PA6). In presence of activators or macroactivators (MAs) also called polymeric activators (PACs) the anionic polymerization of lactams proceeds rapidly at a temperature range of 130-180C, well below the melting point of PA-6 (220C) permitting thus the direct manufacturing of copolymer product together with desired modifications of polyamide properties. Copolymers of PA6 with an elastic polypropylene glycol (PPG) middle block into main chain were successfully synthesized via activated anionic ring opening polymerization (ROP) of CL. Using novel PACs based on PPG polyols (with differ molecular weight) the anionic ROP of CL was realized and investigated in the presence of a basic initiator sodium salt of CL (NaCL). The PACs were synthesized as N-carbamoyllactam derivatives of hydroxyl terminated PPG functionalized with isophorone diisocyanate [IPh, 5-Isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane] and blocked then with CL units via an addition reaction. The block copolymers were analyzed and proved with 1H-NMR and FT-IR spectroscopy. The influence of the CL/PACs ratio in feed, the length of the PPG segments and polymerization conditions on the kinetics of anionic ROP, on average molecular weight, and on the structure of the obtained block copolymers were investigated. The structure and phase behaviour of the copolymers were explored with differential scanning calorimetry, wide-angle X-ray diffraction, thermogravimetric analysis and dynamic mechanical thermal analysis. The crystallinity dependence of PPG content incorporated into copolymers main backbone was estimate. Additionally, the mechanical properties of the obtained copolymers were studied by notched impact test. From the performed investigation in this study could be concluded that using PPG based PACs at the chosen ROP conditions leads to obtaining well-defined PA6-b-PPG-b-PA6 copolymers with improved impact resistance.

Keywords: anionic ring opening polymerization, caprolactam, polyamide copolymers, polypropylene glycol

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