Search results for: block morphology

Authors: P. Dubcek, B. Pivac, J. Dasovic, V. Janicki, S. Bernstorff

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When grown only to nanometric sizes, metallic particles (e.g. Ag, Au and Cu) exhibit specific optical properties caused by the presence of plasmon band. The plasmon band represents collective oscillation of the conduction electrons, and causes a narrow band absorption of light in the visible range. When the nanoparticles are embedded in a dielectric, they also cause modifications of dielectrics optical properties. This can be fine-tuned by tuning the particle size. We investigated Cu nanoparticle growth with and without surrounding dielectric (SiO2 capping layer). The morphology and crystallinity were investigated by GISAXS and GIWAXS, respectively. Samples were produced by high vacuum thermal evaporation of Cu onto monocrystalline silicon substrate held at room temperature, 100°C or 180°C. One series was in situ capped by 10nm SiO2 layer. Additionally, samples were annealed at different temperatures up to 550°C, also in high vacuum. The room temperature deposited samples annealed at lower temperatures exhibit continuous film structure: strong oscillations in the GISAXS intensity are present especially in the capped samples. At higher temperatures enhanced surface dewetting and Cu nanoparticles (nanoislands) formation partially destroy the flatness of the interface. Therefore the particle type of scattering is enhanced, while the film fringes are depleted. However, capping layer hinders particle formation, and continuous film structure is preserved up to higher annealing temperatures (visible as strong and persistent fringes in GISAXS), compared to the non- capped samples. According to GISAXS, lateral particle sizes are reduced at higher temperatures, while particle height is increasing. This is ascribed to close packing of the formed particles at lower temperatures, and GISAXS deduced sizes are partially the result of the particle agglomerate dimensions. Lateral maxima in GISAXS are an indication of good positional correlation, and the particle to particle distance is increased as the particles grow with temperature elevation. This coordination is much stronger in the capped and lower temperature deposited samples. The dewetting is much more vigorous in the non-capped sample, and since nanoparticles are formed in a range of sizes, correlation is receding both with deposition and annealing temperature. Surface topology was checked by atomic force microscopy (AFM). Capped sample's surfaces were smoother and lateral size of the surface features were larger compared to the non-capped samples. Altogether, AFM results suggest somewhat larger particles and wider size distribution, and this can be attributed to the difference in probe size. Finally, the plasmonic effect was monitored by UV-Vis reflectance spectroscopy, and relative weak plasmonic effect could be explained by uncomplete dewetting or partial interconnection of the formed particles.

Keywords: coper, GISAXS, nanoparticles, plasmonics

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Authors: Ali Reza Vaezi, Naser Fakori Ivand, Fereshteh Azarifam

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Interrill erosion is the detachment and transfer of soil particles between the rills due to the impact of raindrops and the shear stress of shallow surface runoff. This erosion can be affected by some soil properties such as texture, amount of organic matter and stability of soil aggregates. Information on the temporal variation of interrill erosion during a rainfall event and the effect soil properties have on it can help in understanding the process of runoff production and soil loss between the rills in hillslopes. The importance of this study is especially grate in semi-arid regions, where the soil is weakly aggregated and vegetation cover is mostly poor. Therefore, this research was conducted to investigate the temporal variation of surface flow and interrill erosion and the effect of soil properties on it in some semi-arid soils. A field experiment was done in eight different soil textures under simulated rainfalls with uniform intensity. A total of twenty four plots were installed for eight study soils with three replicates in the form of a random complete block design along the land. The plots were 1.2 m (length) × 1 m (width) in dimensions which designed with a distance of 3 m from each other across the slope. Then, soil samples were purred into the plots. The plots were surrounded by a galvanized sheet, and runoff and soil erosion equipment were placed at their outlets. Rainfall simulation experiments were done using a designed portable simulator with an intensity of 60 mm per hour for 60 minutes. A plastic cover was used around the rainfall simulator frame to prevent the impact of the wind on the free fall of water drops. Runoff production and soil loss were measured during 1 hour time with 5-min intervals. In order to study soil properties, such as particle size distribution, aggregate stability, bulk density, ESP and Ks were determined in the laboratory. Correlation and regression analysis was done to determine the effect of soil properties on runoff and interrill erosion. Results indicated that the study soils have lower booth organic matter content and aggregate stability. The soils, except for coarse textured textures, are calcareous and with relatively higher exchangeable sodium percentages (ESP). Runoff production and soil loss didn’t occur in sand, which was associated with higher infiltration and drainage rates. In other study soils, interrill erosion occurred simultaneously with the generation of runoff. A strong relationship was found between interrill erosion and surface runoff (R2 = 0.75, p< 0.01). The correlation analysis showed that surface runoff was significantly affected by some soil properties consisting of sand, silt, clay, bulk density, gravel, hydraulic conductivity (Ks), lime (calcium carbonate), and ESP. The soils with lower Ks such as fine-textured soils, produced higher surface runoff and more interrill erosion. In the soils, Surface runoff production temporally increased during rainfall and finally reached a peak after about 25-35 min. Time to peak was very short (30 min) in fine-textured soils, especially clay, which was related to their lower infiltration rate.

Keywords: erosion plot, rainfall simulator, soil properties, surface flow

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Authors: Ines Oliveira, Ana Reis

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Magnetic Pulse Welding (MPW) is a cold solid-state welding process, accomplished by the electromagnetically driven, high-speed and low-angle impact between two metallic surfaces. It has the same working principle of Explosive Welding (EXW), i.e. is based on the collision of two parts at high impact speed, in this case, propelled by electromagnetic force. Under proper conditions, i.e., flyer velocity and collision point angle, a permanent metallurgical bond can be achieved between widely dissimilar metals. MPW has been considered a promising alternative to the conventional welding processes and advantageous when compared to other impact processes. Nevertheless, MPW current applications are mostly academic. Despite the existing knowledge, the lack of consensus regarding several aspects of the process calls for further investigation. As a result, the mechanical resistance, morphology and structure of the weld interface in MPW of Al/Cu dissimilar pair were investigated. The effect of process parameters, namely gap, standoff distance and energy, were studied. It was shown that welding only takes place if the process parameters are within an optimal range. Additionally, the formation of intermetallic phases cannot be completely avoided in the weld of Al/Cu dissimilar pair by MPW. Depending on the process parameters, the intermetallic compounds can appear as continuous layer or small pockets. The thickness and the composition of the intermetallic layer depend on the processing parameters. Different intermetallic phases can be identified, meaning that different temperature-time regimes can occur during the process. It is also found that lower pulse energies are preferred. The relationship between energy increase and melting is possibly related to multiple sources of heating. Higher values of pulse energy are associated with higher induced currents in the part, meaning that more Joule heating will be generated. In addition, more energy means higher flyer velocity, the air existing in the gap between the parts to be welded is expelled, and this aerodynamic drag (fluid friction) is proportional to the square of the velocity, further contributing to the generation of heat. As the kinetic energy also increases with the square of velocity, the dissipation of this energy through plastic work and jet generation will also contribute to an increase in temperature. To reduce intermetallic phases, porosity, and melt pockets, pulse energy should be minimized. The bond formation is affected not only by the gap, standoff distance, and energy but also by the mandrel’s surface conditions. No correlation was clearly identified between surface roughness/scratch orientation and joint strength. Nevertheless, the aspect of the interface (thickness of the intermetallic layer, porosity, presence of macro/microcracks) is clearly affected by the surface topology. Welding was not established on oil contaminated surfaces, meaning that the jet action is not enough to completely clean the surface.

Keywords: bonding mechanisms, impact welding, intermetallic compounds, magnetic pulse welding, wave formation

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Authors: R. S. Giraddi, B. Thirupam Reddy, D. N. Kambrekar

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Chilli (Capsicum annum L.) an important commercial vegetable crop is ravaged by a number of insect-pests during both vegetative and reproductive phase resulting into significant crop loss.Thrips, Scirtothripsdorsalis, mite, Polyphagotarsonemuslatus and whitefly, Bemisiatabaci are the key sap feeding insects, their infestation leads to leaf curl, stunted growth and yield loss.During flowering and fruit formation stage, gall midge fly, Asphondyliacapparis (Rubsaaman) infesting flower buds and young fruits andHelicoverpaarmigera (Hubner) feeding on matured green fruits are the important insect pests causing significant crop loss.The pest is known to infest both flower buds and young fruits resulting into malformation of flower buds and twisting of fruits.In order to manage these insect-pests a combi product consisting of imidacloprid and betacyfluthrin (Soloman 300 OD) was evaluated for its bio-efficacy, phytotoxicity and effect on predator activity.Imidacloprid, a systemic insecticide belonging to neo-nicotinoid group, is effective against insect pests such as aphids, whiteflies (sap feeders) and other insectsviz., termites and soil insects.Beta-Cyfluthrin is an insecticide of synthetic pyrethroid group which acts by contact action and ingestion. It acts on the insects' nervous system as sodium channel blocker consequently a disorder of the nervous system occurs leading finally to the death. The field experiments were taken up during 2015 and 2016 at the Main Agricultural Research Station of University of Agricultural Sciences, Dharwad, Karnataka, India.The trials were laid out in a Randomized Block Design (RBD) with three replications using popular land race of Byadagi crop variety.Results indicated that the product at 21.6 + 50.4% gai/ha (240 ml/ha) and 27.9 + 65% gai/ha (310 ml/ha) was found quite effective in controlling thrips (0.00 to 0.66 thrips per six leaves) as against the standard check insecticide recommended for thrips by the University of Agricultural Sciences, Dharwad wherein the density of thrips recorded was significantly higher (1.00 to 2.00 Nos./6 leaves). Similarly, the test insecticide was quite effective against other target insects, whiteflies, fruit borer and gall midge fly as indicated by lower insect population observed in the treatments as compared to standard insecticidal control. The predatory beetle activity was found to be normal in all experimental plots. Highest green fruit yield of 5100-5500 kg/ha was recorded in Soloman 300 OD applied crop at 310 ml/ha rate as compared to 4750 to 5050 kg/ha recorded in check. At present 6-8 sprays of insecticides are recommended for management of these insect-pests on the crop. If combi-products are used in pest management programmes, it is possible to reduce insecticide usages in crop ecosystem.

Keywords: Imidacloprid, Betacyfluthrin, gallmidge fly, thrips, chilli

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Authors: Monika Patel, Kazuaki Matsumura

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Synthetic hydrogels, with their unique properties such as porosity, strength, and swelling in aqueous environment, are being used in many fields from food additives to regenerative medicines, from diagnostic and pharmaceuticals to drug delivery systems (DDS). But, hydrogels also have some limitations in terms of homogeneity of drug distribution and quantity of loaded drugs. As an alternate, polymeric micelles are extensively used as DDS. With the ease of self-assembly, and distinct stability they remarkably improve the solubility of hydrophobic drugs. However, presently, combinational therapy is the need of time and so are systems which are capable of releasing more than one drug. And it is one of the major challenges towards DDS to control the release of each drug independently, which simple DDS cannot meet. In this work, we present an amphiphilic polypeptide based micelle hydrogel composite to study the dual drug release for wound healing purposes using Amphotericin B (AmpB) and Curcumin as model drugs. Firstly, two differently charged amphiphilic polypeptide chains were prepared namely, poly L-Lysine-b-poly phenyl alanine (PLL-PPA) and poly Glutamic acid-b-poly phenyl alanine (PGA-PPA) through ring opening polymerization of amino acid N-carboxyanhydride. These polymers readily self-assemble to form micelles with hydrophobic PPA block as core and hydrophilic PLL/PGA as shell with an average diameter of about 280nm. The thus formed micelles were loaded with the model drugs. The PLL-PPA micelle was loaded with curcumin and PGA-PPA was loaded with AmpB by dialysis method. Drug loaded micelles showed a slight increase in the mean diameter and were fairly stable in solution and lyophilized forms. For forming the micelles hydrogel composite, the drug loaded micelles were dissolved and were cross linked using genipin. Genipin uses the free –NH2 groups in the PLL-PPA micelles to form a hydrogel network with free PGA-PPA micelles trapped in between the 3D scaffold formed. Different composites were tested by changing the weight ratios of the both micelles and were seen to alter its resulting surface charge from positive to negative with increase in PGA-PPA ratio. The composites with high surface charge showed a burst release of drug in initial phase, were as the composites with relatively low net charge showed a sustained release. Thus the resultant surface charge of the composite can be tuned to tune its drug release profile. Also, while studying the degree of cross linking among the PLL-PPA particles for effect on dual drug release, it was seen that as the degree of crosslinking increases, an increase in the tendency to burst release the drug (AmpB) is seen in PGA-PPA particle, were as on the contrary the PLL-PPA particles showed a slower release of Curcumin with increasing the cross linking density. Thus, two different pharmacokinetic profile of drugs were seen by changing the cross linking degree. In conclusion, a unique charged amphiphilic polypeptide based micelle hydrogel composite for dual drug delivery. This composite can be finely tuned on the basis of need of drug release profiles by changing simple parameters such as composition, cross linking and pH.

Keywords: amphiphilic polypeptide, dual drug release, micelle hydrogel composite, tunable DDS

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Authors: Monica Sanchez

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What responsibility does urban planning have on climate changes? How does the territory give us answers of resilience? Historically, urban plans have civilized territories: waters are channeled, grounds are sealed, foreign species are incorporated, native ones are extinguished, and/or enclosed spaces are heated or cooled. Socially this facilitates coexistence, but in turn brings negative environmental consequences. The past fifty years, mankind has tried to redirect these consequences through different strategies. Research studies produced strategies designed to alleviate climate change. Exploring the nature of territories has been incorporated in urban planning to discover natures response. The case to be studied is Santiago, Chile: for its combined impacts of climate change and the significant response by this city on climate governance in the last decades. Warmer areas in Santiago are seen in the areas of high-density buildings such as the commune of Recoleta, while the coldest are characterized by the predominance of low residential densities as the commune of Providencia. These two communes are separated and complemented by an undulating body that comes from the Andes mountains called San Cristobal Hill. What if the hill were taken into account when making roads, zoning and buildings? Was it difficult to prolong in the urban plans the hill characteristics to the city solving the intersection with other natural areas? Apparently it was, because the projected-profile informs us that the planned strategies used correspond to the same operations used in the flat areas of Santiago. This research focuses on: explaining the geographic relationships between city-hill; explaining the planning process around the hill with a morphological analysis; evaluating how the hill has been considered the in the city in the plans that intended to cushion the environmental impacts and studying what is missing on the hill and city to strengthen their integration. Therefore, the research will have different scales of understanding: addressing territorial scale -understanding the vegetation, topography and hydrology; a city scale -analyzing urban plans that Santiago has dealt with the environment and city; and a local scale -studying the integration and public spaces and coverage- norms of the adjacent communes. The expected outcome is to decipher possible deficits and capabilities of the current urban plans for climate change. It is anticipated that the hill and valley is now trying to reconcile after such a long separation. Yet it seems that never will prevail all the Rules of Nature, but the Urban Rules. The plans will require pruning, irrigation, control of invasive alien species and public safety standards, but will be rejoining a dose of nature with the building environment -this will protect us better from it from the time that we feared from it and knew little about it. Today we know a little more, enough to adapt to the process. Although nature is not perceived and we ignore it, it has a remarkable ability to respond.

Keywords: resilience, climate change, urban plans, land use, hills and cities, heat islands, morphology

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Authors: Aymen Arfaoui, Abdelkader Soumaya, Noureddine Ben Ayed

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The study region is located in the Tunisian Dorsal Backland (Central Mediterranean), which is the easternmost part of the Saharan Atlas mountain range, trending southwest-northeast. Based on our fieldwork, seismic tomography images, seismicity, and previous studies, we propose an interpretation of the relationship between the surface deformation and fault kinematics in the study area and the internal dynamic processes acting in the Central Mediterranean from the Cenozoic to the present. The subduction and dynamics of internal forces beneath the complicated Maghrebides mobile belt have an impact on the Tertiary and Quaternary tectonic regimes in the Pelagian and Atlassic foreland that is part of our study region. The left lateral reactivation of the major "Tunisian N-S Axis fault" and the development of a compressional relay between the Hammamet Korbous and Messella-Ressas faults are possibly a result of tectonic stresses due to the slab roll-back following the Africa/Eurasia convergence. After the slab segmentation and its eastward migration (5–4 Ma) and the formation of the Strait of Sicily "rift zone" further east, a transtensional tectonic regime has been installed in this area. According to seismic tomography images, the STEP fault of the "North-South Axis" at Hammamet-Korbous coincides with the western edge of the "Slab windows" of the Sicilian Channel and the eastern boundary of the positive anomalies attributed to the residual Slab of Tunisia. On the other hand, significant E-W Plio-Quaternary tectonic activity may be observed along the eastern portion of this STEP fault system in the Grombalia zone as a result of recent vertical lithospheric motion in response to the lateral slab migration eastward to Sicily Channel. According to SKS fast splitting directions, the upper mantle flow pattern beneath Tunisian Dorsal is parallel to the NE-SW to E-W orientation of the Shmin identified in the study area, similar to the Plio-Quaternary extensional orientation in the Central Mediterranean. Additionally, the removal of the lithosphere and the subsequent uplift of the sub-lithospheric mantle beneath the topographic highs of the Dorsal and its surroundings may be the cause of the dominant extensional to transtensional Quaternary regime. The occurrence of strike-slip and extensional seismic events in the Pelagian block reveals that the regional transtensional tectonic regime persists today. Finally, we believe that the geodynamic history of the study area since the Cenozoic is primarily influenced by the preexisting weak zones, the African slab detachment, and the upper mantle flow pattern in the central Mediterranean.

Keywords: Tunisia, lithospheric discontinuity (STEP fault), geodynamic evolution, Tunisian dorsal backland, strike-slip fault, seismic tomography, seismicity, central Mediterranean

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Authors: Emma Worley, Mhairi De Sainte Croix, Savneet Lochab, Christopher Roberts, Mark Stroud, Mo Salehan, Kevin Jones

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Awareness about the importance of teaching about diversity at medical school is growing. In the realm of diversity includes discussion around the LGBTQ+ community. At Bristol, diversity is taught in first or second year. However, echoing and expanding that teaching throughout the curriculum is needed. This feeds into the spiral curriculum but also highlights the relevance of the topic. It is well known that some people in the LGBTQ+ community struggle the access healthcare due to previous negative experiences. In 2019, 1 in 7 LGBTQ+ people avoided seeking medical care due to fears about discrimination. If people have fears about seeking medical help, then seeking help from Palliative care when they are at their most vulnerable situation can be even harder. To improve positive healthcare situations for people who identify as LGBTQ+ needs to start with talking. Along with some of our CTAs (clinical teaching assistants) we created a teaching session to explore the barriers faced by LGBTQ+ and incorporated communication stations into this. Our plan is to run this session as a three-hour session first discussing different topics: ethnical diversity, ‘coming out’, LGBTQ+ in the older generation, transgender. This will be followed by looking more closely at the barriers to accessing the hospice. The next part of the session will encompass two or three communication scenarios hopefully prompting further discussion and reflection on ways to improve our communication. The first scenario outline is a gay man/lesbian woman with lung cancer discussing options around the hospice. The second scenario is a transgender person with female genitalia who now has cervical cancer (as was not followed up on pap smears after the change of name). The third scenario is a HIV homosexual male patient who has been admitted with dementia. He has a partner but is not married. His next of kin is down as his parents but his parents do not know about his sexuality and HIV status. It allows discussion around confidentiality as well as broaching the meaning of ‘family’ in the LGBTQ+ community. We have chosen to pitch this teaching session to Bristol Year 4 students. They will be currently doing their 6-week Palliative care block, which fits in well. Each session will have four students attend. We have been lucky enough to have two CTAs (clinical teaching assistants) who identify as LGBTQ+ offer their experiences and help. They have been able to help us with the preparation and delivery of the session. Given anecdotal evidence and stories helps to highlight the importance and relevance of this session. The aim is to increase awareness of some factors that may contribute to people who identify as LGBTQ+ having a negative healthcare experience. By starting to talk about it allows awareness and only then will we be able to start to change and improve. Our aim, if the sessions run well, is to expand these sessions to different academy hospitals. Therefore, all Bristol 4th year students would have the opportunity to take part in the teaching session. We would like to expand our portfolio of case scenarios, to address so tricker topics such as a transgender person with dementia who reverts back to a different gender. We would also like to recruit a diverse range of actors, ideally people who identify as the patient in the scenario does. For example, a transgender person acts the transgender scenario. This would give authenticity and enhance the student’s learning experience.

Keywords: communication skills, healthcare barriers, LGBTQ+, palliative care

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Authors: Beverly Wang

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Background: Rosai-Dorfman disease (RDD), aka sinus histiocytosis with massive lymphadenopathy, is a rare, idiopathic histiocytic proliferative disorder. Although RDD can be seen involving the head and neck lymph nodes, rarely it can affect other extranodal sites. It present 3 unique cases of RDD affecting the nasal cavity, paranasal sinuses, and ear canal. The initial clinical presentation on two cases mimicked a malignant neoplasm. The 3rd case of RDD co-existed with a cholesteatoma of the ear canal. The clinical presentation, histology and immunohistochemical stains, and radiographic findings are discussed. Design: An overview of 3 cases of RDD affected sinonasal cavity and ear canal from UCI Medical Center was conducted. Case 1: A 61 year old male complaining of breathing difficulty presented with bilateral polypoid sinonasal masses and severe nasal obstruction. The masses elevated the nasal floor, and involved the anterior nasal septum to lateral wall. It was endoscopically excised. At intraoperative consultation, frozen section reported a pleomorphic spindle cell neoplasm with scattered large atypical spindle cells, resembling a high grade sarcoma. Case 2: A 46 year old male presented with recurrent bilateral maxillary chronic sinusitis with mass formation, clinically suspicious for malignant lymphoma. Excisional tissue sample showed large irregular spindled histiocytes with abundant granular and vacuolated cytoplasm. Case 3: A 36 year old female with a history of asthma initially presented with left-sided chronic otalgia, occasional nausea, vertigo, and fluctuating pain exacerbated by head movement and temperature changes. CT scan revealed an external auditory canal mass extending to the middle ear, coexisting with a small cholesteatoma. Results: The morphology of all cases revealed large atypical spindled histiocytes resembling fibrohistiocytic or myofibroblastic proliferative neoplasms. Scattered emperipolesis was seen. All 3 cases were confirmed as extranodal sinus RDD, confirmed by immunohistochemistry. The large atypical cells were positive for S100, CD68, and CD163. No evidence for malignancy was identified. Case 3 showed concurrent RDD co-existing with a cholesteatoma. Conclusion: Due to its rarity and variable clinical presentations, the diagnosis of RDD is seldom clinically considered. Extranodal sinus RDD morphologically can be pitfall as mimicker of spindly neoplasm, especially at intraoperative consultation. It can create diagnostic and therapeutic challenges. Correlation of radiological findings with histologic features will help to reach the diagnosis.

Keywords: head and neck, extranodal, rosai-dorfman disease, mimicker, immunohistochemistry

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Authors: Harriet Koshie Lamptey, Richard Boateng

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Mobile learning (m-learning) is a novel approach to knowledge acquisition and dissemination and is gaining global attention. Steady progress in wireless technologies and the portability of communication devices continue to broaden the scope and use of mobiles. With the convergence of Web functionality onto mobile platforms and the affordability and availability of mobile technology, m-learning has the potential of being the next prevalent channel of education in both formal and informal settings. There is substantive literature on developed countries but the state in developing countries (DCs) however appears vague. This paper is a synthesis of extant literature on mobile learning in DCs. The research interest is based on the fact that in DCs, mobile communication and internet connectivity are popular. However, its use in education is under explored. There are some reviews on the state, conceptualizations, trends and teacher education, but to the authors’ knowledge, no study has focused on mobile learning adoption and integration issues. This study examines issues and gaps associated with its adoption and integration in DCs higher education institutions. A qualitative build-up of literature was conducted using articles pooled from electronic databases (Google Scholar and ERIC). To enable criteria for inclusion and incorporate diverse study perspectives, search terms used were m-learning, DCs, higher education institutions, challenges, benefits, impact, gaps and issues. The synthesis revealed that though mobile technology has diffused globally, its pedagogical pursuit in DCs remains quite low. The absence of a mobile Web and the difficulty of resource conversion into mobile format due to lack of funding and technical competence is a stumbling block. Again, the lack of established design and implementation rules to guide the development of m-learning platforms in DCs is a hindrance. The absence of access restrictions on devices poses security threats to institutional systems. Negative perceptions that devices are taking over faculty roles lead to resistance in some situations. Resistance to change can be a hindrance to the acceptance and success of new systems. Lack of interest for m-learning is also attributed to lower technological literacy levels of the underprivileged masses. Scholarly works on m-learning in DCs is yet to mature. Most technological innovations are handed down from developed countries, and this constantly creates a lag for DCs. Lack of theoretical grounding was also identified which reduces the objectivity of study reports. The socio-cultural terrain of DCs results in societies with different views and needs that have been identified as a hindrance to research. Institutional commitment decisions, adequate funding for the necessary infrastructural development as well as multiple stakeholder participation is important for project success. Evidence suggests that while adoption decisions are readily made, successful integration of the concept for its full benefits to be realized is often neglected. Recommendations to findings were made to provide possible remedies to identified issues.

Keywords: developing countries, higher education institutions, mobile learning, literature review

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Authors: B. K. Kanungo, Monika Thakur, Minati Baral

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8-hydroxyquinoline, (8HQ), experiences a renaissance due to its utility as a building block in metallosupramolecular chemistry and its versatile use of its derivatives in various fields of analytical chemistry, materials science, and pharmaceutics. It forms stable complexes with a variety of metal ions. Assembly of more than one such unit to form a polydentate chelator enhances its coordinating ability and the related properties due to the chelate effect resulting in high stability constant. Keeping in view the above, a nonadentate chelator N-[3,5-bis(8-hydroxyquinoline-2-amido)cyclohexyl]-8-hydroxyquinoline-2-carboxamide, (TACH2OX), containing a central cis,cis-1,3,5-triaminocyclohexane appended to three 8-hydroxyquinoline at 2-position through amide linkage is developed, and its solution thermodynamics, photophysical and Density Functional Theory (DFT) studies were undertaken. The synthesis of TACH2OX was carried out by condensation of cis,cis-1,3,5-triaminocyclohexane, (TACH) with 8‐hydroxyquinoline‐2‐carboxylic acid. The brown colored solid has been fully characterized through melting point, infrared, nuclear magnetic resonance, electrospray ionization mass and electronic spectroscopy. In solution, TACH2OX forms protonated complexes below pH 3.4, which consecutively deprotonates to generate trinegative ion with the rise of pH. Nine protonation constants for the ligand were obtained that ranges between 2.26 to 7.28. The interaction of the chelator with two trivalent metal ion Fe3+ and Al3+ were studied in aqueous solution at 298 K. The metal-ligand formation constants (ML) obtained by potentiometric and spectrophotometric method agree with each other. The protonated and hydrolyzed species were also detected in the system. The in-silico studies of the ligand, as well as the complexes including their protonated and deprotonated species assessed by density functional theory technique, gave an accurate correlation with each observed properties such as the protonation constants, stability constants, infra-red, nmr, electronic absorption and emission spectral bands. The nature of electronic and emission spectral bands in terms of number and type were ascertained from time-dependent density functional theory study and the natural transition orbitals (NTO). The global reactivity indices parameters were used for comparison of the reactivity of the ligand and the complex molecules. The natural bonding orbital (NBO) analysis could successfully describe the structure and bonding of the metal-ligand complexes specifying the percentage of contribution in atomic orbitals in the creation of molecular orbitals. The obtained high value of metal-ligand formation constants indicates that the newly synthesized chelator is a very powerful synthetic chelator. The minimum energy molecular modeling structure of the ligand suggests that the ligand, TACH2OX, in a tripodal fashion firmly coordinates to the metal ion as hexa-coordinated chelate displaying distorted octahedral geometry by binding through three sets of N, O- donor atoms, present in each pendant arm of the central tris-cyclohexaneamine tripod.

Keywords: complexes, DFT, formation constant, TACH2OX

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Authors: Javed Iqbal

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The growing need for energy by the human society and depletion of conventional energy sources demands a renewable, safe, infinite, low-cost and omnipresent energy source. One of the most suitable ways to solve the foreseeable world’s energy crisis is to use the power of the sun. Photovoltaic devices are especially of wide interest as they can convert solar energy to electricity. Recently the best performing solar cells are silicon-based cells. However, silicon cells are expensive, rigid in structure and have a large timeline for the payback of cost and electricity. Organic photovoltaic cells are cheap, flexible and can be manufactured in a continuous process. Therefore, organic photovoltaic cells are an extremely favorable replacement. Organic photovoltaic cells utilize sunlight as energy and convert it into electricity through the use of conductive polymers/ small molecules to separate electrons and electron holes. A major challenge for these new organic photovoltaic cells is the efficiency, which is low compared with the traditional silicon solar cells. To overcome this challenge, usually two straightforward strategies have been considered: (1) reducing the band-gap of molecular donors to broaden the absorption range, which results in higher short circuit current density (JSC) of devices, and (2) lowering the highest occupied molecular orbital (HOMO) energy of molecular donors so as to increase the open-circuit voltage (VOC) of applications devices.8 Keeping in mind the cost of chemicals it is hard to try many materials on test basis. The best way is to find the suitable material in the bulk. For this purpose, we use computational approach to design molecules based on our organic chemistry knowledge and determine their physical and electronic properties. In this study, we did DFT calculations with different options to get high open circuit voltage and after getting suitable data from calculation we finally did synthesis of a novel D–π–A–π–D type low band-gap small molecular donor material (ZOPTAN-TPA). The Aarylene vinylene based bis(arylhalide) unit containing a cyanostilbene unit acts as a low-band- gap electron-accepting block, and is coupled with triphenylamine as electron-donating blocks groups. The motivation for choosing triphenylamine (TPA) as capped donor was attributed to its important role in stabilizing the separated hole from an exciton and thus improving the hole-transporting properties of the hole carrier.3 A π-bridge (thiophene) is inserted between the donor and acceptor unit to reduce the steric hindrance between the donor and acceptor units and to improve the planarity of the molecule. The ZOPTAN-TPA molecule features a low HOMO level of 5.2 eV and an optical energy gap of 2.1 eV. Champion OSCs based on a solution-processed and non-annealed active-material blend of [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) and ZOPTAN-TPA in a mass ratio of 2:1 exhibits a power conversion efficiency of 1.9 % and a high open-circuit voltage of over 1.0 V.

Keywords: high open circuit voltage, donor, triphenylamine, organic solar cells

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Authors: Jie Lin, Yiwen Pan, Li Zhang, Zhangyong Xia

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Atherosclerosis is a chronic inflammatory disease characterized by the accumulation of lipids, immune cells, and extracellular matrix in the arterial walls. This pathological process can lead to the formation of plaques that can obstruct blood flow and trigger various cardiovascular diseases such as heart attack and stroke. The underlying molecular mechanisms still remain unclear, although many studies revealed the dysfunction of endothelial cells, recruitment and activation of monocytes and macrophages, and the production of pro-inflammatory cytokines and chemokines in atherosclerosis. This study aimed to identify hub genes involved in the progression of atherosclerosis and to analyze their biological function in silico, thereby enhancing our understanding of the disease’s molecular mechanisms. Through the analysis of microarray data, we examined the gene expression in media and neo-intima from plaques, as well as distant macroscopically intact tissue, across a cohort of 32 hypertensive patients. Initially, 112 differentially expressed genes (DEGs) were identified. Subsequent immune infiltration analysis indicated a predominant presence of 27 immune cell types in the atherosclerosis group, particularly noting an increase in monocytes and macrophages. In the Weighted gene co-expression network analysis (WGCNA), 10 modules with a minimum of 30 genes were defined as key modules, with blue, dark, Oliver green and sky-blue modules being the most significant. These modules corresponded respectively to monocyte, activated B cell, and activated CD4 T cell gene patterns, revealing a strong morphological-genetic correlation. From these three gene patterns (modules morphology), a total of 2509 key genes (Gene Significance >0.2, module membership>0.8) were extracted. Six hub genes (CD36, DPP4, HMOX1, PLA2G7, PLN2, and ACADL) were then identified by intersecting 2509 key genes, 102 DEGs with lipid-related genes from the Genecard database. The bio-functional analysis of six hub genes was estimated by a robust classifier with an area under the curve (AUC) of 0.873 in the ROC plot, indicating excellent efficacy in differentiating between the disease and control group. Moreover, PCA visualization demonstrated clear separation between the groups based on these six hub genes, suggesting their potential utility as classification features in predictive models. Protein-protein interaction (PPI) analysis highlighted DPP4 as the most interconnected gene. Within the constructed key gene-drug network, 462 drugs were predicted, with ursodeoxycholic acid (UDCA) being identified as a potential therapeutic agent for modulating DPP4 expression. In summary, our study identified critical hub genes implicated in the progression of atherosclerosis through comprehensive bioinformatic analyses. These findings not only advance our understanding of the disease but also pave the way for applying similar analytical frameworks and predictive models to other diseases, thereby broadening the potential for clinical applications and therapeutic discoveries.

Keywords: atherosclerosis, hub genes, drug prediction, bioinformatics

Procedia PDF Downloads 65

Authors: Mogale T. E., Ayisi K. K., Munjonji L., Kifle Y. G.

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Grain sorghum and cowpea are important staple crops in many areas of South Africa, particularly the Limpopo Province. The two crops are produced under a wide range of unsustainable conventional methods, which reduces productivity in the long run. Climate-smart traditional methods such as intercropping can be adopted to ensure sustainable production of these important two crops in the province. A no-tillage field experiment was laid out in a randomised complete block design (RCBD) with four replications over two seasons in two distinct agro-ecological zones, Syferkuil and Ofcolacoin, the province to assess the productivity of sorghum-cowpea intercropped under two cowpea densities.LCi Ultra compact photosynthesis machine was used to collect photosynthetic rate data biweekly between 11h00 and 13h00 until physiological maturity. Biomass and grain yield of the component crops in binary and sole cultures were determined at harvest maturity from middle rows of 2.7 m2 area. The biomass was oven dried in the laboratory at 65oC till constant weight. To obtain grain yield, harvested sorghum heads and cowpea pods were threshed, cleaned, and weighed. Harvest index (HI) and land equivalent ratio (LER) of the two crops were calculated to assess intercrop productivity relative to sole cultures. Data was analysed using the statistical analysis software system (SAS) 9.4 version, followed by mean separation using the least significant difference method. The photosyntheticrate of sorghum-cowpea intercrop was influenced by cowpea density and sorghum cultivar. Photosynthetic rate under low density was higher compared to high density, but this was dependent on the growing conditions. Dry biomass accumulation, grain yield, and harvest index differed among the sorghum cultivars and cowpea in both binary and sole cultures at the two test locations during the 2018/19 and 2020/21 growing seasons. Cowpea grain and dry biomass yields werein excess of 60% under high density compared to low density in both binary and sole cultures. The results revealed that grain yield accumulation of sorghum cultivars was influenced by the density of the companion cowpea crop as well as the production season. For instant, at Syferkuil, Enforcer and Ns5511 accumulated high yield under low density, whereas, at Ofcolaco, the higher yield was recorded under high density. Generally, under low cowpea density, cultivar Enforcer produced relatively higher grain yield whereas, under higher density, Titan yield was superior. The partial and total LER varied with growing season and the treatments studied. The total LERs exceeded 1.0 at the two locations across seasons, ranging from 1.3 to 1.8. From the results, it can be concluded that resources were used more efficiently in sorghum-cowpea intercrop at both Syferkuil and Ofcolaco. Furthermore, intercropping system improved photosynthetic rate, grain yield, and dry matter accumulation of sorghum and cowpea depending on growing conditions and density of cowpea. Hence, the sorghum-cowpea intercropping system can be adopted as a climate-smart practice for sustainable production in the Limpopo province.

Keywords: cowpea, climate-smart, grain sorghum, intercropping

Procedia PDF Downloads 219

Authors: Eiji Nakamachi, Ryota Sakiyama, Koji Yamamoto, Yusuke Morita, Hidetoshi Sakamoto

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The regeneration of injured central nerve network caused by the cerebrovascular accidents is difficult, because of poor regeneration capability of central nerve system composed of the brain and the spinal cord. Recently, new regeneration methods such as transplant of nerve cells and supply of nerve nutritional factor were proposed and examined. However, there still remain many problems with the canceration of engrafted cells and so on and it is strongly required to establish an efficacious treating method of a central nerve system. Blackman proposed the electromagnetic stimulation method to enhance the axonal nerve extension. In this study, we try to design and fabricate a new three-dimensional (3D) bio-reactor, which can load a uniform AC magnetic field stimulation on PC12 cells in the extracellular environment for enhancement of an axonal nerve extension and 3D nerve network generation. Simultaneously, we measure the morphology of PC12 cell bodies, axons, and dendrites by the multiphoton excitation fluorescence microscope (MPM) and evaluate the effectiveness of the uniform AC magnetic stimulation to enhance the axonal nerve extension. Firstly, we designed and fabricated the uniform AC magnetic field stimulation bio-reactor. For the AC magnetic stimulation system, we used the laminated silicon steel sheets for a yoke structure of 3D chamber, which had a high magnetic permeability. Next, we adopted the pole piece structure and installed similar specification coils on both sides of the yoke. We searched an optimum pole piece structure using the magnetic field finite element (FE) analyses and the response surface methodology. We confirmed that the optimum 3D chamber structure showed a uniform magnetic flux density in the PC12 cell culture area by using FE analysis. Then, we fabricated the uniform AC magnetic field stimulation bio-reactor by adopting analytically determined specifications, such as the size of chamber and electromagnetic conditions. We confirmed that measurement results of magnetic field in the chamber showed a good agreement with FE results. Secondly, we fabricated a dish, which set inside the uniform AC magnetic field stimulation of bio-reactor. PC12 cells were disseminated with collagen gel and could be 3D cultured in the dish. The collagen gel were poured in the dish. The collagen gel, which had a disk shape of 6 mm diameter and 3mm height, was set on the membrane filter, which was located at 4 mm height from the bottom of dish. The disk was full filled with the culture medium inside the dish. Finally, we evaluated the effectiveness of the uniform AC magnetic field stimulation to enhance the nurve axonal extension. We confirmed that a 6.8 increase in the average axonal extension length of PC12 under the uniform AC magnetic field stimulation at 7 days culture in our bio-reactor, and a 24.7 increase in the maximum axonal extension length. Further, we confirmed that a 60 increase in the number of dendrites of PC12 under the uniform AC magnetic field stimulation. Finally, we confirm the availability of our uniform AC magnetic stimulation bio-reactor for the nerve axonal extension and the nerve network generation.

Keywords: nerve regeneration, axonal extension , PC12 cell, magnetic field, three-dimensional bio-reactor

Procedia PDF Downloads 166

Authors: Zatovska T. V., Nesterova N. V., Baranova G. V., Zagorodnya S. D.

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In recent years, biosensor technologies based on the phenomenon of surface plasmon resonance (SPR) are becoming increasingly used in biology and medicine. Their application facilitates exploration in real time progress of binding of biomolecules and identification of agents that specifically interact with biologically active substances immobilized on the biosensor surface (biochips). Special attention is paid to the use of Biosensor analysis in determining the antibody-antigen interaction in the diagnostics of diseases caused by viruses and bacteria. According to WHO, the diseases that are caused by the herpes simplex virus (HSV), take second place (15.8%) after influenza as a cause of death from viral infections. Current diagnostics of HSV infection include PCR and ELISA assays. The latter allows determination the degree of immune response to viral infection and respective stages of its progress. In this regard, the searches for new and available diagnostic methods are very important. This work was aimed to develop Biosensor chip for detection of specific antibodies to HSV-1 in the human blood serum. The proteins of HSV1 (strain US) were used as antigens. The viral particles were accumulated in cell culture MDBK and purified by differential centrifugation in cesium chloride density gradient. Analysis of the HSV1 proteins was performed by polyacrylamide gel electrophoresis and ELISA. The protein concentration was measured using De Novix DS-11 spectrophotometer. The device for detection of antigen-antibody interactions was an optoelectronic two-channel spectrometer ‘Plasmon-6’, using the SPR phenomenon in the Krechman optical configuration. It was developed at the Lashkarev Institute of Semiconductor Physics of NASU. The used carrier was a glass plate covered with 45 nm gold film. Screening of human blood serums was performed using the test system ‘HSV-1 IgG ELISA’ (GenWay, USA). Development of Biosensor chip included optimization of conditions of viral antigen sorption and analysis steps. For immobilization of viral proteins 0.2% solution of Dextran 17, 200 (Sigma, USA) was used. Sorption of antigen took place at 4-8°C within 18-24 hours. After washing of chip, three times with citrate buffer (pH 5,0) 1% solution of BSA was applied to block the sites not occupied by viral antigen. It was found direct dependence between the amount of immobilized HSV1 antigen and SPR response. Using obtained biochips, panels of 25 positive and 10 negative for the content of antibodies to HSV-1 human sera were analyzed. The average value of SPR response was 185 a.s. for negative sera and from 312 to. 1264 a.s. for positive sera. It was shown that SPR data were agreed with ELISA results in 96% of samples proving the great potential of SPR in such researches. It was investigated the possibility of biochip regeneration and it was shown that application of 10 mM NaOH solution leads to rupture of intermolecular bonds. This allows reuse the chip several times. Thus, in this study biosensor chip for detection of specific antibodies to HSV1 was successfully developed expanding a range of diagnostic methods for this pathogen.

Keywords: biochip, herpes virus, SPR

Procedia PDF Downloads 416

Authors: Mohamed Habireche, Nacer E. Bacha, Mohamed Djeghdjough

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In the brick industry, smooth double roll crusher is used for medium and fine crushing of soft to medium hard material. Due to opposite inward rotation of the rolls, the feed material is nipped between the rolls and crushed by compression. They are subject to intense wear, known as three-body abrasion, due to the action of abrasive products. The production downtime affecting productivity stems from two sources: the bi-monthly rectification of the roll crushers and their replacement when they are completely worn out. Choosing the right material for the roll crushers should result in longer machine cycles, and reduced repair and maintenance costs. All roll crushers are imported from outside Algeria. This results in sometimes very long delivery times which handicap the brickyards, in particular in respecting delivery times and honored the orders made by customers. The aim of this work is to investigate the effect of alloying additions on microstructure and wear behavior of grey lamellar cast iron for smooth roll crushers in brick industry. The base gray iron was melted in an induction furnace with low frequency at a temperature of 1500 °C, in which return cast iron scrap, new cast iron ingot, and steel scrap were added to the melt to generate the desired composition. The chemical analysis of the bar samples was carried out using Emission Spectrometer Systems PV 8050 Series (Philips) except for the carbon, for which a carbon/sulphur analyser Elementrac CS-i was used. Unetched microstructure was used to evaluate the graphite flake morphology using the image comparison measurement method. At least five different fields were selected for quantitative estimation of phase constituents. The samples were observed under X100 magnification with a Zeiss Axiover T40 MAT optical microscope equipped with a digital camera. SEM microscope equipped with EDS was used to characterize the phases present in the microstructure. The hardness (750 kg load, 5mm diameter ball) was measured with a Brinell testing machine for both treated and as-solidified condition test pieces. The test bars were used for tensile strength and metallographic evaluations. Mechanical properties were evaluated using tensile specimens made as per ASTM E8 standards. Two specimens were tested for each alloy. From each rod, a test piece was made for the tensile test. The results showed that the quenched and tempered alloys had best wear resistance at 400 °C for alloyed grey cast iron (containing 0.62%Mn, 0.68%Cr, and 1.09% Cu) due to fine carbides in the tempered matrix. In quenched and tempered condition, increasing Cu content in cast irons improved its wear resistance moderately. Combined addition of Cu and Cr increases hardness and wear resistance for a quenched and tempered hypoeutectic grey cast iron.

Keywords: casting, cast iron, microstructure, heat treating

Procedia PDF Downloads 104

Authors: Gondrexon, Gonon, Mendil-Jakani, Mareau

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Proton Exchange Membrane Fuel Cells (PEMFCs) seems to be a promising device used for converting hydrogen into electricity. PEMFC is made of a Membrane Electrode Assembly (MEA) composed of a Proton Exchange Membrane (PEM) sandwiched by two catalytic layers. Nowadays, specific performances are targeted in order to ensure the long-term expansion of this technology. Current polymers used (perfluorinated as Nafion®) are unsuitable (loss of mechanical properties) for the high-temperature range. To overcome this issue, sulfonated polyaromatic polymers appear to be a good alternative since it has very good thermomechanical properties. However, their proton conductivity and chemical stability (oxidative resistance to H2O2 formed during fuel cell (FC) operating) are very low. In our team, we patented an original concept of hybrid membranes able to fulfill the specific requirements for PEMFC. This idea is based on the improvement of commercialized polymer membrane via an easy and processable stabilization thanks to sol-gel (SG) chemistry with judicious embeded chemical functions. This strategy is thus breaking up with traditional approaches (design of new copolymers, use of inorganic charges/additives). In 2020, we presented the elaboration and functional properties of a 1st generation of hybrid membranes with promising performances and durability. The latter was made by self-condensing a SG phase with 3(mercaptopropyl)trimethoxysilane (MPTMS) inside a commercial sPEEK host membrane. The successful in-situ condensation reactions of the MPTMS was demonstrated by measures of mass uptakes, FTIR spectroscopy (presence of C-Haliphatics) and solid state NMR 29Si (T2 & T3 signals of self-condensation products). The ability of the SG phase to prevent the oxidative degradation of the sPEEK phase (thanks to thiol chemical functions) was then proved with H2O2 accelerating tests and FC operating tests. A 2nd generation made of thiourea functionalized SG precursors (named HTU & TTU) was made after. By analysing in depth the morphologies of these different hybrids by direct space analysis (AFM/SEM/TEM) and reciprocal space analysis (SANS/SAXS/WAXS), we highlighted that both SG phase morphology and its localisation into the host has a huge impact on the PEM functional properties observed. This relationship is also dependent on the chemical function embedded. The hybrids obtained have shown very good chemical resistance during aging test (exposed to H2O2) compared to the commercial sPEEK. But the chemical function used is considered as “sacrificial” and cannot react indefinitely with H2O2. Thus, we are now working on a 3rd generation made of both sacrificial/regenerative chemical functions which are expected to inhibit the chemical aging of sPEEK more efficiently. With this work, we are confident to reach a predictive approach of the key parameters governing the final properties.

Keywords: fuel cells, ionomers, membranes, sPEEK, chemical stability

Procedia PDF Downloads 70

Authors: K. Yu Vlasova, M. A. Abakumov, H. Wishwarsao, M. Sokolsky, N. V. Nukolova, A. G. Majouga, Y. I. Golovin, N. L. Klyachko, A. V. Kabanov

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Introduction:Nowadays pharmaceutical medicine is aimed to create systems for combined therapy, diagnostic, drug delivery and controlled release of active molecules to target cells. Magnetic nanoparticles (MNPs) are used to achieve this aim. MNPs can be applied in molecular diagnostics, magnetic resonance imaging (T1/T2 contrast agents), drug delivery, hyperthermia and could improve therapeutic effect of drugs. The most common drug containers, containing MNPs, are liposomes, micelles and polymeric molecules bonded to the MNPs surface. Usually superparamagnetic nanoparticles are used (the general diameter is about 5-6 nm) and all effects of high frequency magnetic field (MF) application are based on Neel relaxation resulting in heating of surrounded media. In this work we try to develop a new method to improve drug release from MNPs under super low frequency MF. We suppose that under low frequency MF exposures the Brown’s relaxation dominates and MNPs rotation could occur leading to conformation changes and release of bioactive molecules immobilized on MNPs surface.The aim of this work was to synthesize different systems with active drug (biopolymers coated MNPs nanoclusters with immobilized enzymes and doxorubicin (Dox) loaded magnetic liposomes/micelles) and investigate the effect of super low frequency MF on these drug containers. Methods: We have synthesized MNPs of magnetite with magnetic core diameter 7-12 nm . The MNPs were coated with block-copolymer of polylysine and polyethylene glycol. Superoxide dismutase 1 (SOD1) was electrostatically adsorbed on the surface of the clusters. Liposomes were prepared as follow: MNPs, phosphatidylcholine and cholesterol were dispersed in chloroform, dried to get film and then dispersed in distillated water, sonicated. Dox was added to the solution, pH was adjusted to 7.4 and excess of drug was removed by centrifugation through 3 kDa filters. Results: Polylysine coated MNPs formed nanosized clusters (as observed by TEM) with intensity average diameter of 112±5 nm and zeta potential 12±3 mV. After low frequency AC MF exposure we observed change of immobilized enzyme activity and hydrodynamic size of clusters. We suppose that the biomolecules (enzymes) are released from the MNPs surface followed with additional aggregation of complexes at the MF in medium. Centrifugation of the nanosuspension after AC MF exposures resulted in increase of positive charge of clusters and change in enzyme concentration in comparison with control sample without MF, thus confirming desorption of negatively charged enzyme from the positively charged surface of MNPs. Dox loaded magnetic liposomes had average diameter of 160±8 nm and polydispersity index (PDI) 0.25±0.07. Liposomes were stable in DW and PBS at pH=7.4 at 370C during a week. After MF application (10 min of exposure, 50 Hz, 230 mT) diameter of liposomes raised to 190±10 nm and PDI was 0.38±0.05. We explain this by destroying and/or reorganization of lipid bilayer, that leads to changes in release of drug in comparison with control without MF exposure. Conclusion: A new application of low frequency AC MF for drug delivery and controlled drug release was shown. Investigation was supported by RSF-14-13-00731 grant, K1-2014-022 grant.

Keywords: magnetic nanoparticles, low frequency magnetic field, drug delivery, controlled drug release

Procedia PDF Downloads 479

Authors: Jiujie Cai, Fengxia LI, Haibo Wang

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After years of research, offshore oil and gas development now are shifted to unconventional reservoirs, where multi-stage hydraulic fracturing technology has been widely used. However, the simulation of complex hydraulic fractures in tight reservoirs is faced with geological and engineering difficulties, such as large burial depths, sand-shale interbeds, and complex stress barriers. The objective of this work is to simulate the hydraulic fracture propagation in the tight sandstone matrix of the marine-continental transitional reservoirs, where the Shanxi Formation in Tianhuan syncline of the Dongsheng gas field was used as the research target. The characteristic parameters of the vertical rock samples with rich beddings were clarified through rock mechanics experiments. The influence of rock mechanical parameters, vertical stress difference of pay-zone and bedding layer, and fracturing parameters (such as injection rates, fracturing fluid viscosity, and number of perforation clusters within single stage) on fracture initiation and propagation were investigated. In this paper, a 3-D fracture propagation model was built to investigate the complex fracture propagation morphology by boundary element method, considering the strength of bonding surface between layers, vertical stress difference and fracturing parameters (such as injection rates, fluid volume and viscosity). The research results indicate that on the condition of vertical stress difference (3 MPa), the fracture height can break through and enter the upper interlayer when the thickness of the overlying bedding layer is 6-9 m, considering effect of the weak bonding surface between layers. The fracture propagates within the pay zone when overlying interlayer is greater than 13 m. Difference in fluid volume distribution between clusters could be more than 20% when the stress difference of each cluster in the segment exceeds 2MPa. Fracture cluster in high stress zones cannot initiate when the stress difference in the segment exceeds 5MPa. The simulation results of fracture height are much higher if the effect of weak bonding surface between layers is not involved. By increasing the injection rates, increasing fracturing fluid viscosity, and reducing the number of clusters within single stage can promote the fracture height propagation through layers. Optimizing the perforation position and reducing the number of perforations can promote the uniform expansion of fractures. Typical curves of fracture height estimation were established for the tight sandstone of the Lower Permian Shanxi Formation. The model results have good consistency with micro-seismic monitoring results of hydraulic fracturing in Well 1HF.

Keywords: fracture propagation, boundary element method, fracture height, offshore oil and gas, marine-continental transitional reservoirs, rock mechanics experiment

Procedia PDF Downloads 125

Authors: O. Gsib, U. Peirera, C. Egles, S. A. Bencherif

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In skin regenerative medicine, one of the critical issues is to produce a three-dimensional scaffold with optimized porosity for dermal fibroblast infiltration and neovascularization, which exhibits high mechanical properties and displays sufficient wound healing characteristics. In this study, we report on the synthesis and characterization of macroporous sequential interpenetrating polymer networks (IPNs) combining skin wound healing properties of fibrin with the excellent physical properties of polyethylene glycol (PEG). Fibrin fibers serve as a provisional biologically active network to promote cell adhesion and proliferation while PEG provides the mechanical stability to maintain the entire 3D construct. After having modified both PEG and Serum Albumin (used for promoting enzymatic degradability) by adding methacrylate residues (PEGDM and SAM, respectively), Fibrin/PEGDM-SAM sequential IPNs were synthesized as follows: Macroporous sponges were first produced from PEGDM-SAM hydrogels by a freeze-drying technique and then rehydrated by adding the fibrin precursors. Environmental Scanning Electron Microscopy (ESEM) and Confocal Laser Scanning Microscopy (CLSM) were used to characterize their microstructure. Human dermal fibroblasts were cultivated during one week in the constructs and different cell culture parameters (viability, morphology, proliferation) were evaluated. Subcutaneous implantations of the scaffolds were conducted on five-week old male nude mice to investigate their biocompatibility in vivo. We successfully synthesized interconnected and macroporous Fibrin/PEGDM-SAM sequential IPNs. The viability of primary dermal fibroblasts was well maintained (above 90%) after 2 days of culture. Cells were able to adhere, spread and proliferate in the scaffolds suggesting the suitable porosity and intrinsic biologic properties of the constructs. The fibrin network adopted a spider web shape that covered partially the pores allowing easier cell infiltration into the macroporous structure. To further characterize the in vitro cell behavior, cell proliferation (EdU incorporation, MTS assay) is being studied. Preliminary histological analysis of animal studies indicated the persistence of hydrogels even after one-month post implantation and confirmed the absence of inflammation response, good biocompatibility and biointegration of our scaffolds within the surrounding tissues. These results suggest that our Fibrin/PEGDM-SAM IPNs could be considered as potential candidates for dermis regenerative medicine. Histological analysis will be completed to further assess scaffold remodeling including de novo extracellular matrix protein synthesis and early stage angiogenesis analysis. Compression measurements will be conducted to investigate the mechanical properties.

Keywords: fibrin, hydrogels for dermal reconstruction, polyethylene glycol, semi-interpenetrating polymer network

Procedia PDF Downloads 236

Authors: Godfrey Omulo, Regina Birner, Karlheinz Koller, Thomas Daum

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Conservation agriculture (CA) as a climate-resilient and sustainable practice have been carried out for over three decades in Zambia. However, its continued promotion and adoption has been predominantly on a small-scale basis. Despite the plethora of scholarship pointing to the positive benefits of CA in regard to enhanced yield, profitability, carbon sequestration and minimal environmental degradation, these have not stimulated commensurate agricultural extensification desired for Zambia. The objective of this study was to investigate the potential differences between mechanized conventional and conservation tillage practices on operation time, fuel consumption, labor costs, soil moisture retention, soil temperature and crop yield. An on-farm mechanized conservation agriculture (MCA) experiment arranged in a randomized complete block design with four replications was used. The research was conducted on a 15 ha of sandy loam rainfed land: soybeans on 7ha with plot dimensions of 24 m by 210 m and maize on 8ha with plot dimensions of 24 m by 250 m. The three tillage treatments were: residue burning followed by disc harrowing, ripping tillage and no-till. The crops were rotated in two subsequent seasons. All operations were done using a 60hp 2-wheel tractor, a disc harrow, a two-tine ripper and a two-row planter. Soil measurements and the agro-economic factors were recorded for two farming seasons. The season results showed that the yield of maize and soybeans under no-till and ripping tillage practices were not significantly different from the conventional burning and discing. But, there was a significant difference in soil moisture content between no-till (25.31SFU±2.77) and disced (11.91SFU±0.59) plots at depths from 10-60 cm. Soil temperature in no-till plots (24.59°C±0.91) was significantly lower compared to the disced plots (26.20°C±1.75) at the depths 15 cm and 45 cm. For maize, there was a significant difference in operation time between disc-harrowed (3.68hr/ha±1.27) and no-till (1.85hr/ha±0.04) plots, and a significant difference in cost of labor between disc-harrowed (45.45$/ha±19.56) and no-till (21.76$/ha) plots. There was no significant difference in fuel consumption between ripping and disc-harrowing and direct seeding. For soybeans, there was a significant difference in operation time between no-tillage (1.96hr/ha±0.31) and ripping (3.34hr/ha±0.53) and disc harrowing (3.30hr/ha±0.16). Further, fuel consumption and labor on no-till plots were significantly different from both the ripped and disc-harrowed plots. The high seed emergence percentage on maize disc-harrowed plot (93.75%±5.87) was not significantly different from ripping and no-till plots. Again, the high seed emergence percentage for the soybean ripped plot (93.75%±13.03) had no significant difference with discing and ripping. The results show that it is economically sound and timesaving to practice MCA and get viable yields compared to conventional farming. This research fills the gap on the potential of MCA in the context of Zambia and its profitability in incentivizing policymakers to invest in appropriate and sustainable machinery and implements for extensive agricultural production.

Keywords: climate-smart agriculture, labor cost, mechanized conservation agriculture, soil moisture, Zambia

Procedia PDF Downloads 147

Authors: Elena Filova, Ondrej Kaplan, Marie Markova, Helena Dragounova, Roman Matejka, Eduard Brynda, Lucie Bacakova

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Decellularized vessels have been evaluated as small-diameter vascular prostheses. Reseeding autologous cells onto decellularized tissue prior implantation should prolong prostheses function and make them living tissues. Suitable cell types for reseeding are both endothelial cells and bone marrow-derived stem cells, with a capacity for differentiation into smooth muscle cells upon mechanical loading. Endothelial cells assure antithrombogenicity of the vessels and MSCs produce growth factors and, after their differentiation into smooth muscle cells, they are contractile and produce extracellular matrix proteins as well. Fibrin is a natural scaffold, which allows direct cell adhesion based on integrin receptors. It can be prepared autologous. Fibrin can be modified with bound growth factors, such as basic fibroblast growth factor (FGF-2) and vascular endothelial growth factor (VEGF). These modifications in turn make the scaffold more attractive for cells ingrowth into the biological scaffold. The aim of the study was to prepare thin surface-attached fibrin assemblies with bound FGF-2 and VEGF, and to evaluate growth and differentiation of bone marrow-derived mesenchymal stem cells on the fibrin (Fb) assemblies. Following thin surface-attached fibrin assemblies were prepared: Fb, Fb+VEGF, Fb+FGF2, Fb+heparin, Fb+heparin+VEGF, Fb+heparin+FGF2, Fb+heparin+FGF2+VEGF. Cell culture poly-styrene and glass coverslips were used as controls. Human MSCs (passage 3) were seeded at the density of 8800 cells/1.5 mL alpha-MEM medium with 2.5% FS and 200 U/mL aprotinin per well of a 24-well cell culture. The cells have been cultured on the samples for 6 days. Cell densities on day 1, 3, and 6 were analyzed after staining with LIVE/DEAD cytotoxicity/viability assay kit. The differentiation of MSCs is being analyzed using qPCR. On day 1, the highest density of MSCs was observed on Fb+VEGF and Fb+FGF2. On days 3 and 6, there were similar densities on all samples. On day 1, cell morphology was polygonal and spread on all sample. On day 3 and 6, MSCs growing on Fb assemblies with FGF2 became apparently elongated. The evaluation of expression of genes for von Willebrand factor and CD31 (endothelial cells), for alpha-actin (smooth muscle cells), and for alkaline phosphatase (osteoblasts) is in progress. We prepared fibrin assemblies with bound VEGF and FGF-2 that supported attachment and growth of mesenchymal stem cells. The layers are promising for improving the ingrowth of MSCs into the biological scaffold. Supported by the Technology Agency of the Czech Republic TA04011345, and Ministry of Health NT11270-4/2010, and BIOCEV – Biotechnology and Biomedicine Centre of the Academy of Sciences and Charles University” project (CZ.1.05/1.1.00/02.0109), funded by the European Regional Development Fund for their financial supports.

Keywords: fibrin assemblies, FGF-2, mesenchymal stem cells, VEGF

Procedia PDF Downloads 324

Authors: Mohammed Makha, Jakob Heier, Frank Nüesch, Roland Hany

Abstract:

Organic solar cells (OSCs) have made rapid progress and currently achieve power conversion efficiencies (PCE) of over 10%. OSCs have several merits over other direct light-to-electricity generating cells and can be processed at low cost from solution on flexible substrates over large areas. Moreover, combining organic semiconductors with transparent and conductive electrodes allows for the fabrication of semitransparent OSCs (SM-OSCs). For SM-OSCs the challenge is to achieve a high average visible transmission (AVT) while maintaining a high short circuit current (Jsc). Typically, Jsc of SM-OSCs is smaller than when using an opaque metal top electrode. This is because the non-absorbed light during the first transit through the active layer and the transparent electrode is forward-transmitted out of the device. Recently, OSCs using a ternary blend of organic materials have received attention. This strategy was pursued to extend the light harvesting over the visible range. However, it is a general challenge to manipulate the performance of ternary OSCs in a predictable way, because many key factors affect the charge generation and extraction in ternary solar cells. Consequently, the device performance is affected by the compatibility between the blend components and the resulting film morphology, the energy levels and bandgaps, the concentration of the guest material and its location in the active layer. In this work, we report on a solvent-free lamination process for the fabrication of efficient and semitransparent ternary blend OSCs. The ternary blend was composed of PC70BM and the electron donors PBDTTT-C and an NIR cyanine absorbing dye (Cy7T). Using an opaque metal top electrode, a PCE of 6% was achieved for the optimized binary polymer: fullerene blend (AVT = 56%). However, the PCE dropped to ~2% when decreasing (to 30 nm) the active film thickness to increase the AVT value (75%). Therefore we resorted to the ternary blend and measured for non-transparent cells a PCE of 5.5% when using an active polymer: dye: fullerene (0.7: 0.3: 1.5 wt:wt:wt) film of 95 nm thickness (AVT = 65% when omitting the top electrode). In a second step, the optimized ternary blend was used of the fabrication of SM-OSCs. We used a plastic/metal substrate with a light transmission of over 90% as a transparent electrode that was applied via a lamination process. The interfacial layer between the active layer and the top electrode was optimized in order to improve the charge collection and the contact with the laminated top electrode. We demonstrated a PCE of 3% with AVT of 51%. The parameter space for ternary OSCs is large and it is difficult to find the best concentration ratios by trial and error. A rational approach for device optimization is the construction of a ternary blend phase diagram. We discuss our attempts to construct such a phase diagram for the PBDTTT-C: Cy7T: PC70BM system via a combination of using selective Cy7T selective solvents and atomic force microscopy. From the ternary diagram suitable morphologies for efficient light-to-current conversion can be identified. We compare experimental OSC data with these predictions.

Keywords: organic photovoltaics, ternary phase diagram, ternary organic solar cells, transparent solar cell, lamination

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Authors: Farzan Gity, Lida Ansari, Ian M. Povey, Roger E. Nagle, James C. Greer

Abstract:

Titanium nitride (TiN) films have been widely used in variety of fields, due to its unique electrical, chemical, physical and mechanical properties, including low electrical resistivity, chemical stability, and high thermal conductivity. In microelectronic devices, thin continuous TiN films are commonly used as diffusion barrier and metal gate material. However, as the film thickness decreases below a few nanometers, electrical properties of the film alter considerably. In this study, the physical and electrical characteristics of 1.5nm to 22nm thin films deposited by Plasma-Enhanced Atomic Layer Deposition (PE-ALD) using Tetrakis(dimethylamino)titanium(IV), (TDMAT) chemistry and Ar/N2 plasma on 80nm SiO2 capped in-situ by 2nm Al2O3 are investigated. ALD technique allows uniformly-thick films at monolayer level in a highly controlled manner. The chemistry incorporates low level of oxygen into the TiN films forming titanium oxynitride (TiON). Thickness of the films is characterized by Transmission Electron Microscopy (TEM) which confirms the uniformity of the films. Surface morphology of the films is investigated by Atomic Force Microscopy (AFM) indicating sub-nanometer surface roughness. Hall measurements are performed to determine the parameters such as carrier mobility, type and concentration, as well as resistivity. The >5nm-thick films exhibit metallic behavior; however, we have observed that thin film resistivity is modulated significantly by film thickness such that there are more than 5 orders of magnitude increment in the sheet resistance at room temperature when comparing 5nm and 1.5nm films. Scattering effects at interfaces and grain boundaries could play a role in thickness-dependent resistivity in addition to quantum confinement effect that could occur at ultra-thin films: based on our measurements the carrier concentration is decreased from 1.5E22 1/cm3 to 5.5E17 1/cm3, while the mobility is increased from < 0.1 cm2/V.s to ~4 cm2/V.s for the 5nm and 1.5nm films, respectively. Also, measurements at different temperatures indicate that the resistivity is relatively constant for the 5nm film, while for the 1.5nm film more than 2 orders of magnitude reduction has been observed over the range of 220K to 400K. The activation energy of the 2.5nm and 1.5nm films is 30meV and 125meV, respectively, indicating that the TiON ultra-thin films are exhibiting semiconducting behaviour attributing this effect to a metal-semiconductor transition. By the same token, the contact is no longer Ohmic for the thinnest film (i.e., 1.5nm-thick film); hence, a modified lift-off process was developed to selectively deposit thicker films allowing us to perform electrical measurements with low contact resistance on the raised contact regions. Our atomic scale simulations based on molecular dynamic-generated amorphous TiON structures with low oxygen content confirm our experimental observations indicating highly n-type thin films.

Keywords: activation energy, ALD, metal-semiconductor transition, resistivity, titanium oxynitride, ultra-thin film

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Authors: Zuhal Eltayeb Awad

Abstract:

Alryad neighborhood is located in Khartoum town– the administrative center of the Capital of Sudan. The neighborhood is one of the high-income residential areas with villa type development of low-density. It was planned and developed in 1972 with large plots (600-875m²), wide crossing roads and balanced environment. Recently the area transformed into more compact urban form of high density, mixed-use integrated development with more intensive use of land; multi-storied apartments. The most important socio-economic process in the neighborhood has been the commercialization and deinitialization of the area in connect with the displacement of the residential function. This transformation affected the quality of the neighborhood and the inter-related features of the built environment. A case study approach was chosen to gather the necessary qualitative and quantitative data. A detailed survey on existing development pattern was carried out over the whole area of Alryad. Data on the built and social environment of the neighborhoods were collected through observations, interviews and secondary data sources. The paper reflected a theoretical and empirical interest in the particular characteristics of compact neighborhood with high density, and mixed land uses and their effect on social wellbeing of the residents all in the context of the sustainable development. The research problem is focused on the challenges of transformation that associated with compact neighborhood that created multiple urban problems, e.g., stress of essential services (water supply, electricity, and drainage), congestion of streets and demand for parking. The main objective of the study is to analyze the transformation of this area from residential use to commercial and administrative use. The study analyzed the current situation of the neighborhood compared to the five principles of sustainable neighborhood prepared by UN Habitat. The study found that the neighborhood is experienced changes that occur to inner-city residential areas and the process of change of the neighborhood was originated by external forces due to the declining economic situation of the whole country. It is evident that non-residential uses have taken place uncontrolled, unregulated and haphazardly that led to damage the residential environment and deficiency in infrastructure. The quality of urban life and in particular on levels of privacy was reduced, the neighborhood changed gradually to be a central business district that provides services to the whole Khartoum town. The change of house type may be attributed to a demand-led housing market and absence of policy. The results showed that Alryad is not fully sustainable and self-contained, street network characteristics and mixed land-uses development are compatible with the principles of sustainability. The area of streets represents 27.4% of the total area of the neighborhood. Residential density is 4,620 people/ km², that is lower than the recommendations, and the limited block land-use specialization is higher than 10% of the blocks. Most inhabitants have a high income so that there is no social mix in the neighborhood. The study recommended revision of the current zoning regulations in order to control and regulate undesirable development in the neighborhood and provide new solutions which allow promoting the neighborhood sustainable development.

Keywords: compact neighborhood, land uses, mixed use, residential area, transformation

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Authors: Valentina V. Goftman, Vladislav A. Pankratov, Alexey V. Markin, Tangi Aubert, Zeger Hens, Sarah De Saeger, Irina Yu. Goryacheva

Abstract:

The most important requirements for biochemical applicability of quantum dots (QDs) are: 1) the surface cap should render intact or improved optical properties; 2) mono-dispersion and good stability in aqueous phase in a wide range of pH and ionic strength values; 3) presence of functional groups, available for bioconjugation; 4) minimal impact from the environment on the QDs’ properties and, vice versa, minimal influence of the QDs’ components on the environment; and 5) stability against chemical/biochemical/physical influence. The latter is especially important for in vitro and in vivo applications. For example, some physical intracellular delivery strategies (e.g., electroporation) imply a rapid high-voltage electric field impulse in order to temporarily generate hydrophilic pores in the cell plasma membrane, necessary for the passive transportation of QDs into the cell. In this regard, it is interesting to investigate how different capping layers, which can provide high stability and sufficient fluorescent properties of QDs in a water solution, behave under these abnormal conditions. In this contribution, hydrophobic core-shell CdSe/CdS/CdZnS/ZnS QDs (λem=600 nm), produced by means of the Successive Ion Layer Adsorption and Reaction (SILAR) technique, were transferred to a water solution using two of the most commonly used methods: (i) encapsulation in an amphiphilic brush polymer based on poly(maleic anhydride-alt-1-octadecene) (PMAO) modified with polyethylene glycol (PEG) chains and (ii) silica covering. Polymer encapsulation preserves the initial ligands on the QDs’ surface owing to the hydrophobic attraction between the hydrophobic groups of the amphiphilic molecules and the surface hydrophobic groups of the QDs. This covering process allows maintaining the initial fluorescent properties, but it leads to a considerable increase of the QDs’ size. However, covering with a silica shell, by means of the reverse microemulsion method, allows maintaining both size and fluorescent properties of the initial QDs. The obtained water solutions of polymer covered and silica-coated QDs in three different concentrations were exposed to a low-voltage electric field for a short time and the fluorescent properties were investigated. It is shown that the PMAO-PEG polymer acquires some additional charges in the presence of the electric field, which causes repulsion between the polymer and the QDs’ surface. This process destroys the homogeneity of the whole amphiphilic shell and it dramatically decreases the fluorescent properties (dropping to 10% from its initial value) because of the direct contact of the QDs with the strongly oxidative environment (water). In contrast, a silica shell possesses dielectric properties which allow retaining 90% of its initial fluorescence intensity, even after a longer electric impact. Thus, silica shells are clearly a preferable covering for bio-application of QDs, because – besides the high uniform morphology, controlled size and biocompatibility – it allows protecting QDs from oxidation, even under the influence of an electric field.

Keywords: electric field, polymer coating, quantum dots, silica covering, stability

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Authors: Leslie Raphael de M. Ferraz, Salvana Priscylla M. Costa, Tarcyla de A. Gomes, Giovanna Christinne R. M. Schver, Cristóvão R. da Silva, Magaly Andreza M. de Lyra, Danilo Augusto F. Fontes, Larissa A. Rolim, Amanda Carla Q. M. Vieira, Miracy M. de Albuquerque, Pedro J. Rolim-Neto

Abstract:

Efavirenz (EFV) is a drug used as first-line treatment of AIDS. However, it has poor aqueous solubility and wettability, presenting problems in the gastrointestinal tract absorption and bioavailability. One of the most promising strategies to improve the solubility is the use of solid dispersions (SD). Therefore, this study aimed to characterize SD EFZ with the polymers: PVP-K30, PVPVA 64 and SOLUPLUS in order to find an optimal formulation to compose a future pharmaceutical product for AIDS therapy. Initially, Physical Mixtures (PM) and SD with the polymers were obtained containing 10, 20, 50 and 80% of drug (w/w) by the solvent method. The best formulation obtained between the SD was selected by in vitro dissolution test. Finally, the drug-carrier system chosen, in all ratios obtained, were analyzed by the following techniques: Differential Scanning Calorimetry (DSC), polarization microscopy, Scanning Electron Microscopy (SEM) and spectrophotometry of absorption in the region of infrared (IR). From the dissolution profiles of EFV, PM and SD, the values of area Under The Curve (AUC) were calculated. The data showed that the AUC of all PM is greater than the isolated EFV, this result is derived from the hydrophilic properties of the polymers thus favoring a decrease in surface tension between the drug and the dissolution medium. In adittion, this ensures an increasing of wettability of the drug. In parallel, it was found that SD whom had higher AUC values, were those who have the greatest amount of polymer (with only 10% drug). As the amount of drug increases, it was noticed that these results either decrease or are statistically similar. The AUC values of the SD using the three different polymers, followed this decreasing order: SD PVPVA 64-EFV 10% > SD PVP-K30-EFV 10% > SD Soluplus®-EFV 10%. The DSC curves of SD’s did not show the characteristic endothermic event of drug melt process, suggesting that the EFV was converted to its amorphous state. The analysis of polarized light microscopy showed significant birefringence of the PM’s, but this was not observed in films of SD’s, thus suggesting the conversion of the drug from the crystalline to the amorphous state. In electron micrographs of all PM, independently of the percentage of the drug, the crystal structure of EFV was clearly detectable. Moreover, electron micrographs of the SD with the two polymers in different ratios investigated, we observed the presence of particles with irregular size and morphology, also occurring an extensive change in the appearance of the polymer, not being possible to differentiate the two components. IR spectra of PM corresponds to the overlapping of polymer and EFV bands indicating thereby that there is no interaction between them, unlike the spectra of all SD that showed complete disappearance of the band related to the axial deformation of the NH group of EFV. Therefore, this study was able to obtain a suitable formulation to overcome the solubility limitations of the EFV, since SD PVPVA 64-EFZ 10% was chosen as the best system in delay crystallization of the prototype, reaching higher levels of super saturation.

Keywords: characterization, dissolution, Efavirenz, solid dispersions

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Authors: E. Poupelloz, S. Gauffinet

Abstract:

Ettringite Ca₆Al₂(SO₄)₃(OH)₁₂26H₂O is one of the major hydrates formed during cement hydration. Ettringite forms in Portland cement from the reaction between tricalcium aluminate Ca₃Al₂O₆ and calcium sulfate. Ettringite is also present in calcium sulfoaluminate cement in which it is the major hydrate, formed by the reaction between yeelimite Ca₄(AlO₂)₆SO₄ and calcium sulfate. About the formation of ettringite, numerous results are available in the literature even if some issues are still under discussion. However, almost all published work about ettringite was done on cementitious systems. Yet in cement, hydration reactions are very complex, the result of dissolution-precipitation processes and are submitted to various interactions. Understanding the formation process of a phase alone, here ettringite, is the first step to later understand the much more complex reactions happening in cement. This study is crucial for the comprehension of early cement hydration and physical behavior. Indeed formation of hydrates, in particular, ettringite, will have an influence on the rheological properties of the cement paste and on the need for admixtures. To make progress toward the understanding of existing phenomena, a specific study of nucleation and growth processes of ettringite was conducted. First ettringite nucleation was studied in ionic aqueous solutions, with controlled but different experimental conditions, as different supersaturation degrees (β), different pH or presence of exogenous ions. Through induction time measurements, interfacial ettringite crystals solution energies (γ) were determined. Growth of ettringite in supersaturated solutions was also studied through chain crystallization reactions. Specific BET surface area measurements and Scanning Electron Microscopy observations seemed to prove that growth process is favored over the nucleation process when ettringite crystals are initially present in a solution with a low supersaturation degree. The influence of stirring on ettringite formation was also investigated. Observation was made that intensity and nature of stirring have a high influence on the size of ettringite needles formed. Needle sizes vary from less than 10µm long depending on the stirring to almost 100µm long without any stirring. During all previously mentioned experiments, initially present ions are consumed to form ettringite in such a way that the supersaturation degree with regard to ettringite is decreasing over time. To avoid this phenomenon a device compensating the drop of ion concentrations by adding some more solutions, and therefore always have constant ionic concentrations, was used. This constant β recreates the conditions of the beginning of cement paste hydration, when the dissolution of solid reagents compensates the consumption of ions to form hydrates. This device allowed the determination of the ettringite precipitation rate as a function of the supersaturation degree β. Taking samples at different time during ettringite precipitation and doing BET measurements allowed the determination of the interfacial growth rate of ettringite in m²/s. This work will lead to a better understanding and control of ettringite formation alone and thus during cements hydration. This study will also ultimately define the impact of ettringite formation process on the rheology of cement pastes at early age, which is a crucial parameter from a practical point of view.

Keywords: cement hydration, ettringite, morphology of crystals, nucleation-growth process

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Authors: Edite Kulmane, Mara Pilmane, Romans Lacis

Abstract:

Introduction: Acquired heart diseases remain one of the leading health care problems in the world. Changes in myocardium of the diseased hearts are complex and pathogenesis is still not fully clear. The aim of this study was to identify appearance and distribution of apoptosis, homeostasis regulating factors, and innervation and ischemia markers in right atrial tissue in different acquired heart diseases. Methods: During elective open heart surgery were taken right atrial tissue fragments from 12 patients. All patients were operated because of acquired heart diseases- aortic valve stenosis (5 patients), coronary heart disease (5 patients), coronary heart disease and secondary mitral insufficiency (1 patient) and mitral disease (1 patient). The mean age was (mean±SD) 70,2±7,0 years (range 58-83 years). The tissues were stained with haematoxylin and eosin methods for routine light-microscopical examination and for immunohistochemical detection of protein gene peptide 9.5 (PGP 9.5), human atrial natriuretic peptide (hANUP), vascular endothelial growth factor (VEGF), chromogranin A and endothelin. Apoptosis was detected by TUNEL method. Results: All specimens showed degeneration of cardiomyocytes with lysis of myofibrils, diffuse vacuolization especially in perinuclear region, different size of cells and their nuclei. The severe invasion of connective tissue was observed in main part of all fragments. The apoptotic index ranged from 24 to 91%. One specimen showed region of newly performed microvessels with cube shaped endotheliocytes that were positive for PGP 9.5, endothelin, chromogranin A and VEGF. From all fragments, taken from patients with coronary heart disease, there were observed numerous PGP 9.5-containing nerve fibres, except in patient with secondary mitral insufficiency, who showed just few PGP 9.5 positive nerves. In majority of specimens there were regions observed with cube shaped mixed -VEGF immunoreactive endocardial and epicardial cells. Only VEGF positive endothelial cells were observed just in few specimens. There was no significant difference of hANUP secreting cells among all specimens. All patients operated due to the coronary heart disease moderate to numerous number of chromogranin A positive cells were seen while in patients with aortic valve stenosis tissue demonstrated just few factor positive cells. Conclusions: Complex detection of different factors may indicate selectively disordered morphopathogenetical event of heart disease: decrease of PGP 9.5 nerves suggests the decreased innervation of organ; increased apoptosis indicates the cell death without ingrowth of connective tissue; persistent presence of hANUP proves the unchanged homeostasis of cardiomyocytes probably supported by expression of chromogranins. Finally, decrease of VEGF detects the regions of affected blood vessels in heart affected by acquired heart disease.

Keywords: heart, apoptosis, protein-gene peptide 9.5, atrial natriuretic peptide, vascular endothelial growth factor, chromogranin A, endothelin

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