Search results for: magnetic attraction and repulsion

Authors: Mostafa Shahriari, Sergio Rojas, David Pardo, Angel Rodriguez- Rozas, Shaaban A. Bakr, Victor M. Calo, Ignacio Muga

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Logging-While Drilling (LWD) is a technique to record down-hole logging measurements while drilling the well. Nowadays, LWD devices (e.g., nuclear, sonic, resistivity) are mostly used commercially for geo-steering applications. Modern borehole resistivity tools are able to measure all components of the magnetic field by incorporating tilted coils. The depth of investigation of LWD tools is limited compared to the thickness of the geological layers. Thus, it is a common practice to approximate the Earth’s subsurface with a sequence of 1D models. For a 1D model, we can reduce the dimensionality of the problem using a Hankel transform. We can solve the resulting system of ordinary differential equations (ODEs) either (a) analytically, which results in a so-called semi-analytic method after performing a numerical inverse Hankel transform, or (b) numerically. Semi-analytic methods are used by the industry due to their high performance. However, they have major limitations, namely: -The analytical solution of the aforementioned system of ODEs exists only for piecewise constant resistivity distributions. For arbitrary resistivity distributions, the solution of the system of ODEs is unknown by today’s knowledge. -In geo-steering, we need to solve inverse problems with respect to the inversion variables (e.g., the constant resistivity value of each layer and bed boundary positions) using a gradient-based inversion method. Thus, we need to compute the corresponding derivatives. However, the analytical derivatives of cross-bedded formation and the analytical derivatives with respect to the bed boundary positions have not been published to the best of our knowledge. The main contribution of this work is to overcome the aforementioned limitations of semi-analytic methods by solving each 1D model (associated with each Hankel mode) using an efficient multi-scale finite element method. The main idea is to divide our computations into two parts: (a) offline computations, which are independent of the tool positions and we precompute only once and use them for all logging positions, and (b) online computations, which depend upon the logging position. With the above method, (a) we can consider arbitrary resistivity distributions along the 1D model, and (b) we can easily and rapidly compute the derivatives with respect to any inversion variable at a negligible additional cost by using an adjoint state formulation. Although the proposed method is slower than semi-analytic methods, its computational efficiency is still high. In the presentation, we shall derive the mathematical variational formulation, describe the proposed multi-scale finite element method, and verify the accuracy and efficiency of our method by performing a wide range of numerical experiments and comparing the numerical solutions to semi-analytic ones when the latest are available.

Keywords: logging-While-Drilling, resistivity measurements, multi-scale finite elements, Hankel transform

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Authors: Chris Cadman, Marcel Strauss

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Background: In 2020, the University Hospital Wishaw in the United Kingdom became the centre for trauma and orthopaedics within its health board. This resulted in the majority of patients with suspected cauda equina syndrome (CES) being assessed and imaged at this site, putting an increased demand on MR imaging and displacing other previous activity. Following this transition, imaging requests for CES did not always follow national guidelines and would often be missing important clinical and safety information. There also appeared to be a very low positive scan rate compared with previously reported studies. In an attempt to improve patient selection and reduce the burden of CES imaging at this site clinical audit was performed. Methods: A total of 250 consecutive patients imaged to assess for CES were evaluated. Patients had to have presented to either the emergency or orthopaedic department acutely with a presenting complaint of suspected CES. Patients were excluded if they were not admitted acutely or were assessed by other clinical specialities. In total, 233 patients were included. Requests were assessed for appropriate clinical history, accurate and complete clinical assessment and MRI safety information. Clinical assessment was allocated a score of 1-6 based on information relating to history of pain, level of pain, dermatomes/myotomes affected, peri-anal paraesthesia/anaesthesia, anal tone and post-void bladder volume with each element scoring one point. Images were assessed for positive findings of CES, acquired spinal stenosis or nerve root compression. Results: Overall, 73% of requests had a clear clinical history of CES. The urgency of the request for imaging was given in 23% of cases. The mean clinical assessment score was 3.7 out of a total of 6. Overall, 2% of scans were positive for CES, 29% had acquired spinal stenosis and 30% had nerve root compression. For patients with CES, 75% had acute neurological signs compared with 68% of the study population. CES patients had a mean clinical history score of 5.3 compared with 3.7 for the study population. Overall, 95% of requests had appropriate MRI safety information. Discussion: it study included 233 patients who underwent specialist assessment and referral for MR imaging for suspected CES. Despite the serious nature of this condition, a large proportion of imaging requests did not have a clear clinical query of CES and the level of urgency was not given, which could potentially lead to a delay in imaging and treatment. Clinical examination was often also incomplete, which can make triaging of patients presenting with similar symptoms challenging. The positive rate for CES was only 2%, much below other studies which had positive rates of 6–40% with a large meta-analysis finding a mean positive rate of 19%. These findings demonstrate an opportunity to improve the quality of imaging requests for suspected CES. This may help to improve patient selection for imaging and result in a positive rate for CES imaging that is more in line with other centres.

Keywords: cauda equina syndrome, acute back pain, MRI, spine

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Authors: Natalia Politaeva, Iuliia Smiatskaia, Iuliia Bazarnova, Iryna Atamaniuk, Kerstin Kuchta

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Nowadays, the progressive decrease of primary natural resources and ongoing upward trend in terms of energy demand, have resulted in development of new generation technological processes which are focused on step-wise production and residues utilization. Thus, microalgae-based 3^rd generation bioeconomy is considered one of the most promising approaches that allow production of value-added products and sophisticated utilization of residues biomass. In comparison to conventional biomass, microalgae can be cultivated in wide range of conditions without compromising food and feed production, and thus, addressing issues associated with negative social and environmental impacts. However, one of the most challenging tasks is to undergo seasonal variations and to achieve optimal growing conditions for indoor closed systems that can cover further demand for material and energetic utilization of microalgae. For instance, outdoor cultivation in St. Petersburg (Russia) is only suitable within rather narrow time frame (from mid-May to mid-September). At earlier and later periods, insufficient sunlight and heat for the growth of microalgae were detected. On the other hand, without additional physical effects, the biomass increment in summer is 3-5 times per week, depending on the solar radiation and the ambient temperature. In order to increase biomass production, scientists from all over the world have proposed various technical solutions for cultivators and have been studying the influence of various physical factors affecting biomass growth namely: magnetic field, radiation impact, and electric field, etc. In this paper, the influence of infrared radiation (IR) and fluorescent light on the growth rate of microalgae Chlorella sorokiniana has been studied. The cultivation of Chlorella sorokiniana was carried out in 500 ml cylindrical glass vessels, which were constantly aerated. To accelerate the cultivation process, the mixture was stirred for 15 minutes at 500 rpm following 120 minutes of rest time. At the same time, the metabolic needs in nutrients were provided by the addition of micro- and macro-nutrients in the microalgae growing medium. Lighting was provided by fluorescent lamps with the intensity of 2500 ± 300 lx. The influence of IR was determined using IR lamps with a voltage of 220 V, power of 250 W, in order to achieve the intensity of 13 600 ± 500 lx. The obtained results show that under the influence of fluorescent lamps along with the combined effect of active aeration and variable mixing, the biomass increment on the 2^nd day was three times, and on the 7^th day, it was eight-fold. The growth rate of microalgae under the influence of IR radiation was lower and has reached 22.6·10⁶ cells·mL^-1. However, application of IR lamps for the biomass growth allows maintaining the optimal temperature of microalgae suspension at approximately 25-28°C, which might especially be beneficial during the cold season in extreme climate zones.

Keywords: biomass, fluorescent lamp, infrared radiation, microalgae

Procedia PDF Downloads 187

Authors: Daniel Dahis, Haim Azhari

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Noninvasive image-guided intracranial treatments using high intensity focused ultrasound (HIFU) are on the course of translation into clinical applications. They include, among others, tumor ablation, hyperthermia, and blood-brain-barrier (BBB) penetration. Since many of these procedures are associated with local temperature elevation, thermal monitoring is essential. MRI constitutes an imaging method with high spatial resolution and thermal mapping capacity. It is the currently leading modality for temperature guidance, commonly under the name MRgHIFU (magnetic-resonance guided HIFU). Nevertheless, MRI is a very expensive non-portable modality which jeopardizes its accessibility. Ultrasonic thermal monitoring, on the other hand, could provide a modular, cost-effective alternative with higher temporal resolution and accessibility. In order to assess the feasibility of ultrasonic brain thermal monitoring, this study investigated the usage of brain tissue attenuation coefficient (AC) temporal changes as potential estimators of thermal changes. Newton's law of cooling describes a temporal exponential decay behavior for the temperature of a heated object immersed in a relatively cold surrounding. Similarly, in the case of cerebral HIFU treatments, the temperature in the region of interest, i.e., focal zone, is suggested to follow the same law. Thus, it was hypothesized that the AC of the irradiated tissue may follow a temporal exponential behavior during cool down regime. Three ex-vivo bovine brain tissue specimens were inserted into plastic containers along with four thermocouple probes in each sample. The containers were placed inside a specially built ultrasonic tomograph and scanned at room temperature. The corresponding pixel-averaged AC was acquired for each specimen and used as a reference. Subsequently, the containers were placed in a beaker containing hot water and gradually heated to about 45ᵒC. They were then repeatedly rescanned during cool down using ultrasonic through-transmission raster trajectory until reaching about 30ᵒC. From the obtained images, the normalized AC and its temporal derivative as a function of temperature and time were registered. The results have demonstrated high correlation (R² > 0.92) between both the brain AC and its temporal derivative to temperature. This indicates the validity of the hypothesis and the possibility of obtaining brain tissue temperature estimation from the temporal AC thermal changes. It is important to note that each brain yielded different AC values and slopes. This implies that a calibration step is required for each specimen. Thus, for a practical acoustic monitoring of the brain, two steps are suggested. The first step consists of simply measuring the AC at normal body temperature. The second step entails measuring the AC after small temperature elevation. In face of the urging need for a more accessible thermal monitoring technique for brain treatments, the proposed methodology enables a cost-effective high temporal resolution acoustical temperature estimation during HIFU treatments.

Keywords: attenuation coefficient, brain, HIFU, image-guidance, temperature

Procedia PDF Downloads 161

Authors: Shiyi He, Yan Xia, Xiaoping Ouyang, Liang Chen, Zhongbing Zhang, Jinlu Ruan

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As the key system of the spacecraft, various propelling system have been developing rapidly, including ion thrust, laser thrust, solar sail and other micro-thrusters. However, there still are some shortages in these systems. The ion thruster requires the high-voltage or magnetic field to accelerate, resulting in extra system, heavy quantity and large volume. The laser thrust now is mostly ground-based and providing pulse thrust, restraint by the station distribution and the capacity of laser. The thrust direction of solar sail is limited to its relative position with the Sun, so it is hard to propel toward the Sun or adjust in the shadow.In this paper, a novel nuclear thruster based on alpha decay and spontaneous fission is proposed and the principle of this radiation-thrust with alpha particle has been expounded. Radioactive materials with different released energy, such as 210Po with 5.4MeV and 238Pu with 5.29MeV, attached to a metal film will provides various thrust among 0.02-5uN/cm2. With this repulsive force, radiation is able to be a power source. With the advantages of low system quantity, high accuracy and long active time, the radiation thrust is promising in the field of space debris removal, orbit control of nano-satellite array and deep space exploration. To do further study, a formula lead to the amplitude and direction of thrust by the released energy and decay coefficient is set up. With the initial formula, the alpha radiation elements with the half life period longer than a hundred days are calculated and listed. As the alpha particles emit continuously, the residual charge in metal film grows and affects the emitting energy distribution of alpha particles. With the residual charge or extra electromagnetic field, the emitting of alpha particles performs differently and is analyzed in this paper. Furthermore, three more complex situations are discussed. Radiation element generating alpha particles with several energies in different intensity, mixture of various radiation elements, and cascaded alpha decay are studied respectively. In combined way, it is more efficient and flexible to adjust the thrust amplitude. The propelling model of the spontaneous fission is similar with the one of alpha decay, which has a more complex angular distribution. A new quasi-sphere space propelling system based on the radiation-thrust has been introduced, as well as the collecting and processing system of excess charge and reaction heat. The energy and spatial angular distribution of emitting alpha particles on unit area and certain propelling system have been studied. As the alpha particles are easily losing energy and self-absorb, the distribution is not the simple stacking of each nuclide. With the change of the amplitude and angel of radiation-thrust, orbital variation strategy on space debris removal is shown and optimized.

Keywords: alpha decay, angular distribution, emitting energy, orbital variation, radiation-thruster

Procedia PDF Downloads 207

Authors: Xiaoyong He

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The manipulation of THz waves is still a challenging task due to lack of natural materials interacted with it strongly. Designed by tailoring the characters of unit cells (meta-molecules), the advance of metamaterials (MMs) may solve this problem. However, because of Ohmic and radiation losses, the performance of MMs devices is subjected to the dissipation and low quality factor (Q-factor). This dilemma may be circumvented by Fano resonance, which arises from the destructive interference between a bright continuum mode and dark discrete mode (or a narrow resonance). Different from symmetric Lorentz spectral curve, Fano resonance indicates a distinct asymmetric line-shape, ultrahigh quality factor, steep variations in spectrum curves. Fano resonance is usually realized through symmetry breaking. However, if concentric double rings (DR) are placed closely to each other, the near-field coupling between them gives rise to two hybridized modes (bright and narrowband dark modes) because of the local asymmetry, resulting into the characteristic Fano line shape. Furthermore, from the practical viewpoint, it is highly desirable requirement that to achieve the modulation of Fano spectral curves conveniently, which is an important and interesting research topics. For current Fano systems, the tunable spectral curves can be realized by adjusting the geometrical structural parameters or magnetic fields biased the ferrite-based structure. But due to limited dispersion properties of active materials, it is still a tough work to tailor Fano resonance conveniently with the fixed structural parameters. With the favorable properties of extreme confinement and high tunability, graphene is a strong candidate to achieve this goal. The DR-structure possesses the excitation of so-called “trapped modes,” with the merits of simple structure and high quality of resonances in thin structures. By depositing graphene circular DR on the SiO2/Si/ polymer substrate, the tunable Fano resonance has been theoretically investigated in the terahertz regime, including the effects of graphene Fermi level, structural parameters and operation frequency. The results manifest that the obvious Fano peak can be efficiently modulated because of the strong coupling between incident waves and graphene ribbons. As Fermi level increases, the peak amplitude of Fano curve increases, and the resonant peak position shifts to high frequency. The amplitude modulation depth of Fano curves is about 30% if Fermi level changes in the scope of 0.1-1.0 eV. The optimum gap distance between DR is about 8-12 μm, where the value of figure of merit shows a peak. As the graphene ribbon width increases, the Fano spectral curves become broad, and the resonant peak denotes blue shift. The results are very helpful to develop novel graphene plasmonic devices, e.g. sensors and modulators.

Keywords: graphene, metamaterials, terahertz, tunable

Procedia PDF Downloads 344

Authors: Eashwar V. Somasundaram, Raoul R. Wadhwa, Jacob G. Scott

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The use of radiomics in measuring geometric properties of tumor images such as size, surface area, and volume has been invaluable in assessing cancer diagnosis, treatment, and prognosis. In addition to analyzing geometric properties, radiomics would benefit from measuring topological properties using persistent homology. Intuitively, features uncovered by persistent homology may correlate to tumor structural features. One example is necrotic cavities (corresponding to 2D topological features), which are markers of very aggressive tumors. We develop a data pipeline in R that clusters tumors images based on persistent homology is used to identify meaningful clinical distinctions between tumors and possibly new relationships not captured by established clinical categorizations. A preliminary analysis was performed on 16 Magnetic Resonance Imaging (MRI) breast tissue segments downloaded from the 'Investigation of Serial Studies to Predict Your Therapeutic Response with Imaging and Molecular Analysis' (I-SPY TRIAL or ISPY1) collection in The Cancer Imaging Archive. Each segment represents a patient’s breast tumor prior to treatment. The ISPY1 dataset also provided the estrogen receptor (ER), progesterone receptor (PR), and human epidermal growth factor receptor 2 (HER2) status data. A persistent homology matrix up to 2-dimensional features was calculated for each of the MRI segmentation. Wasserstein distances were then calculated between all pairwise tumor image persistent homology matrices to create a distance matrix for each feature dimension. Since Wasserstein distances were calculated for 0, 1, and 2-dimensional features, three hierarchal clusters were constructed. The adjusted Rand Index was used to see how well the clusters corresponded to the ER/PR/HER2 status of the tumors. Triple-negative cancers (negative status for all three receptors) significantly clustered together in the 2-dimensional features dendrogram (Adjusted Rand Index of .35, p = .031). It is known that having a triple-negative breast tumor is associated with aggressive tumor growth and poor prognosis when compared to non-triple negative breast tumors. The aggressive tumor growth associated with triple-negative tumors may have a unique structure in an MRI segmentation, which persistent homology is able to identify. This preliminary analysis shows promising results in the use of persistent homology on tumor imaging to assess the severity of breast tumors. The next step is to apply this pipeline to other tumor segment images from The Cancer Imaging Archive at different sites such as the lung, kidney, and brain. In addition, whether other clinical parameters, such as overall survival, tumor stage, and tumor genotype data are captured well in persistent homology clusters will be assessed. If analyzing tumor MRI segments using persistent homology consistently identifies clinical relationships, this could enable clinicians to use persistent homology data as a noninvasive way to inform clinical decision making in oncology.

Keywords: cancer biology, oncology, persistent homology, radiomics, topological data analysis, tumor imaging

Procedia PDF Downloads 135

Authors: Laura C. Loaiza, Elodie Salager, Nicolas Louvain, Athmane Boulaoued, Antonella Iadecola, Patrik Johansson, Lorenzo Stievano, Vincent Seznec, Laure Monconduit

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Lithium-ion batteries (LIBs) have an important place among energy storage devices due to their high capacity and good cyclability. However, the advancements in portable and transportation applications have extended the research towards new horizons, and today the development is hampered, e.g., by the capacity of the electrodes employed. Silicon and germanium are among the considered modern anode materials as they can undergo alloying reactions with lithium while delivering high capacities. It has been demonstrated that silicon in its highest lithiated state can deliver up to ten times more capacity than graphite (372 mAh/g): 4200 mAh/g for Li₂₂Si₅ and 3579 mAh/g for Li₁₅Si₄, respectively. On the other hand, germanium presents a capacity of 1384 mAh/g for Li₁₅Ge₄, and a better electronic conductivity and Li ion diffusivity as compared to Si. Nonetheless, the commercialization potential of Ge is limited by its cost. The synergetic effect of Si₁₋ₓGeₓ alloys has been proven, the capacity is increased compared to Ge-rich electrodes and the capacity retention is increased compared to Si-rich electrodes, but the exact performance of this type of electrodes will depend on factors like specific capacity, C-rates, cost, etc. There are several reports on various formulations of Si₁₋ₓGeₓ alloys with promising LIB anode performance with most work performed on complex nanostructures resulting from synthesis efforts implying high cost. In the present work, we studied the electrochemical mechanism of the Si₀.₅Ge₀.₅ alloy as a realistic micron-sized electrode formulation using carboxymethyl cellulose (CMC) as the binder. A combination of a large set of in situ and operando techniques were employed to investigate the structural evolution of Si₀.₅Ge₀.₅ during lithiation and delithiation processes: powder X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), Raman spectroscopy, and 7Li solid state nuclear magnetic resonance spectroscopy (NMR). The results have presented a whole view of the structural modifications induced by the lithiation/delithiation processes. The Si₀.₅Ge₀.₅ amorphization was observed at the beginning of discharge. Further lithiation induces the formation of a-Liₓ(Si/Ge) intermediates and the crystallization of Li₁₅(Si₀.₅Ge₀.₅)₄ at the end of the discharge. At really low voltages a reversible process of overlithiation and formation of Li₁₅₊δ(Si₀.₅Ge₀.₅)₄ was identified and related with a structural evolution of Li₁₅(Si₀.₅Ge₀.₅)₄. Upon charge, the c-Li₁₅(Si₀.₅Ge₀.₅)₄ was transformed into a-Liₓ(Si/Ge) intermediates. At the end of the process an amorphous phase assigned to a-SiₓGey was recovered. Thereby, it was demonstrated that Si and Ge are collectively active along the cycling process, upon discharge with the formation of a ternary Li₁₅(Si₀.₅Ge₀.₅)₄ phase (with a step of overlithiation) and upon charge with the rebuilding of the a-Si-Ge phase. This process is undoubtedly behind the enhanced performance of Si₀.₅Ge₀.₅ compared to a physical mixture of Si and Ge.

Keywords: lithium ion battery, silicon germanium anode, in situ characterization, X-Ray diffraction

Procedia PDF Downloads 285

Authors: Lina Paola Orozco Marin, Yuliet Montoya Osorio, John Bustamante Osorno

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Ischemic events can culminate in acute myocardial infarction by irreversible cardiac lesions that cannot be restored due to the limited regenerative capacity of the heart. Cell therapy seeks to replace these injured or necrotic cells by transplanting healthy and functional cells. The therapeutic alternatives proposed by tissue engineering and cardiovascular regenerative medicine are the use of biomaterials to mimic the native extracellular medium, which is full of proteins, proteoglycans, and glycoproteins. The selected biomaterials must provide structural support to the encapsulated cells to avoid their migration and death in the host tissue. In this context, the present research work focused on developing a natural thermosensitive hydrogel, its physical and chemical characterization, and the determination of its biocompatibility in vitro. The hydrogel was developed by mixing hydrolyzed bovine and porcine collagen at 2% w/v, chitosan at 2.5% w/v, and beta-glycerolphosphate at 8.5% w/w and 10.5% w/w in magnetic stirring at 4°C. Once obtained, the thermosensitivity and gelation time were determined, incubating the samples at 37°C and evaluating them through the inverted tube method. The morphological characterization of the hydrogels was carried out through scanning electron microscopy. Chemical characterization was carried out employing infrared spectroscopy. The biocompatibility was determined using the MTT cytotoxicity test according to the ISO 10993-5 standard for the hydrogel’s precursors using the fetal human ventricular cardiomyocytes cell line RL-14. The RL-14 cells were also seeded on the top of the hydrogels, and the supernatants were subculture at different periods to their observation under a bright field microscope. Four types of thermosensitive hydrogels were obtained, which differ in their composition and concentration, called A1 (chitosan/bovine collagen/beta-glycerolphosphate 8.5%w/w), A2 (chitosan/porcine collagen/beta-glycerolphosphate 8.5%), B1 (chitosan/bovine collagen/beta-glycerolphosphate 10.5%) and B2 (chitosan/porcine collagen/beta-glycerolphosphate 10.5%). A1 and A2 had a gelation time of 40 minutes, and B1 and B2 had a gelation time of 30 minutes at 37°C. Electron micrographs revealed a three-dimensional internal structure with interconnected pores for the four types of hydrogels. This facilitates the exchange of nutrients, oxygen, and the exit of metabolites, allowing to preserve a microenvironment suitable for cell proliferation. In the infrared spectra, it was possible to observe the interaction that occurs between the amides of polymeric compounds with the phosphate groups of beta-glycerolphosphate. Finally, the biocompatibility tests indicated that cells in contact with the hydrogel or with each of its precursors are not affected in their proliferation capacity for a period of 16 days. These results show the potential of the hydrogel to increase the cell survival rate in the cardiac cell therapies under investigation. Moreover, the results lay the foundations for its characterization and biological evaluation in both in vitro and in vivo models.

Keywords: cardiac cell therapy, cardiac ischemia, natural polymers, thermosensitive hydrogel

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Authors: Ines Raies, Eric Kohler, Marc Fleury, Béatrice Ledésert

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In this work, the impact of clay minerals on the formation damage of sandstone reservoirs is studied to provide a better understanding of the problem of deep geothermal reservoir permeability reduction due to fine particle dispersion and migration. In some situations, despite the presence of filters in the geothermal loop at the surface, particles smaller than the filter size (<1 µm) may surprisingly generate significant permeability reduction affecting in the long term the overall performance of the geothermal system. Our study is carried out on cores from a Triassic reservoir in the Paris Basin (Feigneux, 60 km Northeast of Paris). Our goal is to first identify the clays responsible for clogging, a mineralogical characterization of these natural samples was carried out by coupling X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectroscopy (EDS). The results show that the studied stratigraphic interval contains mostly illite and chlorite particles. Moreover, the spatial arrangement of the clays in the rocks as well as the morphology and size of the particles, suggest that illite is more easily mobilized than chlorite by the flow in the pore network. Thus, based on these results, illite particles were prepared and used in core flooding in order to better understand the factors leading to the aggregation and deposition of this type of clay particles in geothermal reservoirs under various physicochemical and hydrodynamic conditions. First, the stability of illite suspensions under geothermal conditions has been investigated using different characterization techniques, including Dynamic Light Scattering (DLS) and Scanning Transmission Electron Microscopy (STEM). Various parameters such as the hydrodynamic radius (around 100 nm), the morphology and surface area of aggregates were measured. Then, core-flooding experiments were carried out using sand columns to mimic the permeability decline due to the injection of illite-containing fluids in sandstone reservoirs. In particular, the effects of ionic strength, temperature, particle concentration and flow rate of the injected fluid were investigated. When the ionic strength increases, a permeability decline of more than a factor of 2 could be observed for pore velocities representative of in-situ conditions. Further details of the retention of particles in the columns were obtained from Magnetic Resonance Imaging and X-ray Tomography techniques, showing that the particle deposition is nonuniform along the column. It is clearly shown that very fine particles as small as 100 nm can generate significant permeability reduction under specific conditions in high permeability porous media representative of the Triassic reservoirs of the Paris basin. These retention mechanisms are explained in the general framework of the DLVO theory

Keywords: geothermal energy, reinjection, clays, colloids, retention, porosity, permeability decline, clogging, characterization, XRD, SEM-EDS, STEM, DLS, NMR, core flooding experiments

Procedia PDF Downloads 176

Authors: Shreya Saxena

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Background: Choledocholithiasis is a common complication of gallstone disease. Risk scoring systems exist to guide the need for further imaging or endoscopy in managing choledocholithiasis. We completed an audit to review the American Society for Gastrointestinal Endoscopy (ASGE) scoring system for prediction and management of choledocholithiasis against the current practice at a tertiary hospital to assess its utility in resource optimisation. We have now conducted a cost focused sub-analysis on patients categorized high-risk for choledocholithiasis according to the guidelines to determine any associated cost benefits. Method: Data collection from our prior audit was used to retrospectively identify thirteen patients considered high-risk for choledocholithiasis. Their ongoing management was mapped against the guidelines. Individual costs for the key investigations were obtained from our hospital financial data. Total cost for the different management pathways identified in clinical practice were calculated and compared against predicted costs associated with recommendations in the guidelines. We excluded the cost of laparoscopic cholecystectomy and considered a set figure for per day hospital admission related expenses. Results: Based on our previous audit data, we identified a77% positive predictive value for the ASGE risk stratification tool to determine patients at high-risk of choledocholithiasis. 47% (6/13) had an magnetic resonance cholangiopancreatography (MRCP) prior to endoscopic retrograde cholangiopancreatography (ERCP), whilst 53% (7/13) went straight for ERCP. The average length of stay in the hospital was 7 days, with an additional day and cost of £328.00 (£117 for ERCP) for patients awaiting an MRCP prior to ERCP. Per day hospital admission was valued at £838.69. When calculating total cost, we assumed all patients had admission bloods and ultrasound done as the gold standard. In doing an MRCP prior to ERCP, there was a 130% increase in cost incurred (£580.04 vs £252.04) per patient. When also considering hospital admission and the average length of stay, it was an additional £1166.69 per patient. We then calculated the exact costs incurred by the department, over a three-month period, for all patients, for key investigations or procedures done in the management of choledocholithiasis. This was compared to an estimate cost derived from the recommended pathways in the ASGE guidelines. Overall, 81% (£2048.45) saving was associated with following the guidelines compared to clinical practice. Conclusion: MRCP is the most expensive test associated with the diagnosis and management of choledocholithiasis. The ASGE guidelines recommend endoscopy without an MRCP in patients stratified as high-risk for choledocholithiasis. Our audit that focused on assessing the utility of the ASGE risk scoring system showed it to be relatively reliable for identifying high-risk patients. Our cost analysis has shown significant cost savings per patient and when considering the average length of stay associated with direct endoscopy rather than an additional MRCP. Part of this is also because of an increased average length of stay associated with waiting for an MRCP. The above data supports the ASGE guidelines for the management of high-risk for choledocholithiasis patients from a cost perspective. The only caveat is our small data set that may impact the validity of our average length of hospital stay figures and hence total cost calculations.

Keywords: cost-analysis, choledocholithiasis, risk stratification tool, general surgery

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Authors: Iordana Neamtu, Aurica P. Chiriac, Loredana E. Nita, Mihai Asandulesa, Elena Butnaru, Nita Tudorachi, Alina Diaconu

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In the last decade, the attention of many researchers is focused on the synthesis of innovative “intelligent” copolymer structures with great potential for different uses. This considerable scientific interest is stimulated by possibility of the significant improvements in physical, mechanical, thermal and other important specific properties of these materials. Functionalization of polymer in synthesis by designing a suitable composition with the desired properties and applications is recognized as a valuable tool. In this work is presented a comparative study of the properties of the new copolymers poly(maleic anhydride maleic-co-3,9-divinyl-2,4,8,10-tetraoxaspiro[5.5]undecane) and poly(itaconic-anhydride-co-3,9-divinyl-2,4,8,10-tetraoxaspiro[5.5]undecane) obtained by radical polymerization in dioxane, using 2,2′-azobis(2-methylpropionitrile) as free-radical initiator. The comonomers are able for generating special effects as for example network formation, biodegradability and biocompatibility, gel formation capacity, binding properties, amphiphilicity, good oxidative and thermal stability, good film formers, and temperature and pH sensitivity. Maleic anhydride (MA) and also the isostructural analog itaconic anhydride (ITA) as polyfunctional monomers are widely used in the synthesis of reactive macromolecules with linear, hyperbranched and self & assembled structures to prepare high performance engineering, bioengineering and nano engineering materials. The incorporation of spiroacetal groups in polymer structures improves the solubility and the adhesive properties, induce good oxidative and thermal stability, are formers of good fiber or films with good flexibility and tensile strength. Also, the spiroacetal rings induce interactions on ether oxygen such as hydrogen bonds or coordinate bonds with other functional groups determining bulkiness and stiffness. The synthesized copolymers are analyzed by DSC, oscillatory and rotational rheological measurements and dielectric spectroscopy with the aim of underlying the heating behavior, solution viscosity as a function of shear rate and temperature and to investigate the relaxation processes and the motion of functional groups present in side chain around the main chain or bonds of the side chain. Acknowledgments This work was financially supported by the grant of the Romanian National Authority for Scientific Research, CNCS-UEFISCDI, project number PN-II-132/2014 “Magnetic biomimetic supports as alternative strategy for bone tissue engineering and repair’’ (MAGBIOTISS).

Keywords: Poly(maleic anhydride-co-3, 9-divinyl-2, 4, 8, 10-tetraoxaspiro (5.5)undecane); Poly(itaconic anhydride-co-3, 9-divinyl-2, 4, 8, 10-tetraoxaspiro (5.5)undecane); DSC; oscillatory and rotational rheological analysis; dielectric spectroscopy

Procedia PDF Downloads 227

Authors: Frederick Huie, Lauren Fusfeld, William Burchenal, Scott Howell, Alyssa McVey, Thomas F. Goss

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Alzheimer’s Disease (AD) is a degenerative brain disease characterized by memory loss and cognitive decline that presents a substantial economic burden for patients and health insurers in the US. This study evaluates the payer budget impact of the DISCERN™ test in the diagnosis and management of patients with symptoms of dementia evaluated for AD. DISCERN™ comprises three assays that assess critical factors related to AD that regulate memory, formation of synaptic connections among neurons, and levels of amyloid plaques and neurofibrillary tangles in the brain and can provide a quicker, more accurate diagnosis than tests in the current diagnostic pathway (CDP). An Excel-based model with a three-year horizon was developed to assess the budget impact of DISCERN™ compared with CDP in a Medicare Advantage plan with 1M beneficiaries. Model parameters were identified through a literature review and were verified through consultation with clinicians experienced in diagnosis and management of AD. The model assesses direct medical costs/savings for patients based on the following categories: •Diagnosis: costs of diagnosis using DISCERN™ and CDP. •False Negative (FN) diagnosis: incremental cost of care avoidable with a correct AD diagnosis and appropriately directed medication. •True Positive (TP) diagnosis: AD medication costs; cost from a later TP diagnosis with the CDP versus DISCERN™ in the year of diagnosis, and savings from the delay in AD progression due to appropriate AD medication in patients who are correctly diagnosed after a FN diagnosis.•False Positive (FP) diagnosis: cost of AD medication for patients who do not have AD. A one-way sensitivity analysis was conducted to assess the effect of varying key clinical and cost parameters ±10%. An additional scenario analysis was developed to evaluate the impact of individual inputs. In the base scenario, DISCERN™ is estimated to decrease costs by $4.75M over three years, equating to approximately $63.11 saved per test per year for a cohort followed over three years. While the diagnosis cost is higher with DISCERN™ than with CDP modalities, this cost is offset by the higher overall costs associated with CDP due to the longer time needed to receive a TP diagnosis and the larger number of patients who receive a FN diagnosis and progress more rapidly than if they had received appropriate AD medication. The sensitivity analysis shows that the three parameters with the greatest impact on savings are: reduced sensitivity of DISCERN™, improved sensitivity of the CDP, and a reduction in the percentage of disease progression that is avoided with appropriate AD medication. A scenario analysis in which DISCERN™ reduces the utilization for patients of computed tomography from 21% in the base case to 16%, magnetic resonance imaging from 37% to 27% and cerebrospinal fluid biomarker testing, positive emission tomography, electroencephalograms, and polysomnography testing from 4%, 5%, 10%, and 8%, respectively, in the base case to 0%, results in an overall three-year net savings of $14.5M. DISCERN™ improves the rate of accurate, definitive diagnosis of AD earlier in the disease and may generate savings for Medicare Advantage plans.

Keywords: Alzheimer’s disease, budget, dementia, diagnosis.

Procedia PDF Downloads 138

Authors: Kantha Siddhanth Gujjari, Shaani Singhal, Robert Andrew Danks, Adrian Praeger

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Background: Trigeminal neuralgia (TN) is a heterogenous pain syndrome characterised by short paroxysms of lancinating facial pain in the distribution of the trigeminal nerve, often triggered by usually innocuous stimuli. TN has a low prevalence of less than 0.1%, of which 80% to 90% is caused by compression of the trigeminal nerve from an adjacent artery or vein. The root entry zone of the trigeminal nerve is most sensitive to neurovascular conflict (NVC), causing dysmyelination. Whilst microvascular decompression (MVD) is an effective treatment for TN with NVC, all patients do not achieve long-term pain relief. Pre-operative scoring systems by Panczykowski and Hardaway have been proposed but have not been externally validated. These pre-operative scoring systems are composite scores calculated according to a subtype of TN, presence and degree of neurovascular conflict, and response to medical treatments. There is discordance in the assessment of NVC identified on pre-operative magnetic resonance imaging (MRI) between neurosurgeons and radiologists. To our best knowledge, the prognostic impact for MVD of this difference of interpretation has not previously been investigated in the form of a composite scoring system such as those suggested by Panczykowski and Hardaway. Aims: This study aims to identify prognostic factors and externally validate the proposed scoring systems by Panczykowski and Hardaway for TN. A secondary aim is to investigate the prognostic difference between a neurosurgeon's interpretation of NVC on MRI compared with a radiologist’s. Methods: This retrospective cohort study included 95 patients who underwent de novo MVD in a single neurosurgical unit in Melbourne. Data was recorded from patients’ hospital records and neurosurgeon’s correspondence from perioperative clinic reviews. Patient demographics, type of TN, distribution of TN, response to carbamazepine, neurosurgeon, and radiologist interpretation of NVC on MRI, were clearly described prospectively and preoperatively in the correspondence. Scoring systems published by Panczykowski et al. and Hardaway et al. were used to determine composite scores, which were compared with the recurrence of TN recorded during follow-up over 1-year. Categorical data analysed using Pearson chi-square testing. Independent numerical and nominal data analysed with logistical regression. Results: Logistical regression showed that a Panczykowski composite score of greater than 3 points was associated with a higher likelihood of pain-free outcome 1-year post-MVD with an OR 1.81 (95%CI 1.41-2.61, p=0.032). The composite score using neurosurgeon’s impression of NVC had an OR 2.96 (95%CI 2.28-3.31, p=0.048). A Hardaway composite score of greater than 2 points was associated with a higher likelihood of pain-free outcome 1 year post-MVD with an OR 3.41 (95%CI 2.58-4.37, p=0.028). The composite score using neurosurgeon’s impression of NVC had an OR 3.96 (95%CI 3.01-4.65, p=0.042). Conclusion: Composite scores developed by Panczykowski and Hardaway were validated for the prediction of response to MVD in TN. A composite score based on the neurosurgeon’s interpretation of NVC on MRI, when compared with the radiologist’s had a greater correlation with pain-free outcomes 1 year post-MVD.

Keywords: de novo microvascular decompression, neurovascular conflict, prognosis, trigeminal neuralgia

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Authors: Anupalli Roja Rani, Pavithra Dasari

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Background: Among several, breast cancer has emerged as the most common female cancer in developing countries. It is the most common cause of cancer-related deaths worldwide among women. It is a molecularly and clinically heterogeneous disease. Moreover, it is a hormone–dependent tumor in which estrogens can regulate the growth of breast cells by binding with estrogen receptors (ERs). Moreover, the use of natural products in cancer therapeutics is due to their properties of biocompatibility and less toxicity. Plants are the vast reservoirs for various bioactive compounds. Coleus barbatus (Lamiaceae) contains anticancer properties against several cancer cell lines. Method: In the present study, an attempt is being made to enrich the knowledge of the anticancer activity of pure compounds extracted from Coleus barbatus (Andrew). On human breast cancer cell lines MCF-7. Here in, we are assessing the antiproliferative activity of Coleus barbatus (Andrew) plant extracts against MCF 7 and also evaluating their toxicity in normal human mammary cell lines such as Human Mammary Epithelial Cells (HMEC). The active fraction of plant extract was further purified with the help of Flash chromatography, Medium Pressure Liquid Chromatography (MPLC) and preparative High-Performance Liquid Chromatography (HPLC). The structure of pure compounds will be elucidated by using modern spectroscopic methods like Nuclear magnetic resonance (NMR), Electrospray Ionisation Mass Spectrometry (ESI-MS) methods. Later, the growth inhibition morphological assessment of cancer cells and cell cycle analysis of purified compounds were assessed using FACS. The growth and progression of signaling molecules HER2, GRP78 was studied by secretion assay using ELISA and expression analysis by flow cytometry. Result: Cytotoxic effect against MCF-7 with IC50 values were derived from dose response curves, using six concentrations of twofold serially diluted samples, by SOFTMax Pro software (Molecular device) and respectively Ellipticine and 0.5% DMSO were used as a positive and negative control. Conclusion: The present study shows the significance of various bioactive compounds extracted from Coleus barbatus (Andrew) root material. It acts as an anti-proliferative and shows cytotoxic effects on human breast cancer cell lines MCF7. The plant extracts play an important role pharmacologically. The whole plant has been used in traditional medicine for decades and the studies done have authenticated the practice. Earlier, as described, the plant has been used in the ayurveda and homeopathy medicine. However, more clinical and pathological studies must be conducted to investigate the unexploited potential of the plant. These studies will be very useful for drug designing in the future.

Keywords: coleus barbatus, HPLC, MPLC, NMR, MCF7, flash chromatograph, ESI-MS, FACS, ELISA.

Procedia PDF Downloads 113

Authors: Emma Castiglioni, Nigel Scrutton, Derren Heyes, Alistair Fielding

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By using light as trigger, it is possible to study many biological processes, such as the activity of genes, proteins, and other molecules, with precise spatiotemporal control. Caged compounds, where biologically active molecules are generated from an inert precursor upon laser photolysis, offer the potential to initiate such biological reactions with high temporal resolution. As light acts as the trigger for cleaving the protecting group, the ‘caging’ technique provides a number of advantages as it can be intracellular, rapid and controlled in a quantitative manner. We are developing caging strategies to study the catalytic cycle of a number of enzyme systems, such as nitric oxide synthase and ethanolamine ammonia lyase. These include the use of caged substrates, caged electrons and the possibility of caging the enzyme itself. In addition, we are developing a novel freeze-quench instrument to study these reactions, which combines rapid mixing and flashing capabilities. Reaction intermediates will be trapped at low temperatures and will be analysed by using electron paramagnetic resonance (EPR) spectroscopy to identify the involvement of any radical species during catalysis. EPR techniques typically require relatively long measurement times and very often, low temperatures to fully characterise these short-lived species. Therefore, common rapid mixing techniques, such as stopped-flow or quench-flow are not directly suitable. However, the combination of rapid freeze-quench (RFQ) followed by EPR analysis provides the ideal approach to kinetically trap and spectroscopically characterise these transient radical species. In a typical RFQ experiment, two reagent solutions are delivered to the mixer via two syringes driven by a pneumatic actuator or stepper motor. The new mixed solution is then sprayed into a cryogenic liquid or surface, and the frozen sample is then collected and packed into an EPR tube for analysis. The earliest RFQ instrument consisted of a hydraulic ram unit as a drive unit with direct spraying of the sample into a cryogenic liquid (nitrogen, isopentane or petroleum). Improvements to the RFQ technique have arisen from the design of new mixers in order to reduce both the volume and the mixing time. In addition, the cryogenic isopentane bath has been coupled to a filtering system or replaced by spraying the solution onto a surface that is frozen via thermal conductivity with a cryogenic liquid. In our work, we are developing a novel RFQ instrument which combines the freeze-quench technology with flashing capabilities to enable the studies of both thermally-activated and light-activated biological reactions. This instrument also uses a new rotating plate design based on magnetic couplings and removes the need for mechanical motorised rotation, which can otherwise be problematic at cryogenic temperatures.

Keywords: caged compounds, freeze-quench apparatus, photolysis, radicals

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Authors: Darren A. Whitaker, Dan Palmer, Jens Wesholowski, James Flaherty, John Mack, Ahmad B. Albadarin, Gavin Walker

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Traditional mechanosynthesis has been performed by either ball milling or manual grinding. However, neither of these techniques allow the easy application of process control. The temperature may change unpredictably due to friction in the process. Hence the amount of energy transferred to the reactants is intrinsically non-uniform. Recently, it has been shown that the use of Twin-Screw extrusion (TSE) can overcome these limitations. Additionally, TSE enables a platform for continuous synthesis or manufacturing as it is an open-ended process, with feedstocks at one end and product at the other. Several materials including metal-organic frameworks (MOFs), co-crystals and small organic molecules have been produced mechanochemically using TSE. The described advantages of TSE are offset by drawbacks such as increased process complexity (a large number of process parameters) and variation in feedstock flow impacting on product quality. To handle the above-mentioned drawbacks, this study utilizes UV-Vis spectrophotometry (InSpectroX, ColVisTec) as an online tool to gain real-time information about the quality of the product. Additionally, this is combined with real-time process information in an Advanced Process Control system (PharmaMV, Perceptive Engineering) allowing full supervision and control of the TSE process. Further, by characterizing the dynamic behavior of the TSE, a model predictive controller (MPC) can be employed to ensure the process remains under control when perturbed by external disturbances. Two reactions were studied; a Knoevenagel condensation reaction of barbituric acid and vanillin and, the direct amidation of hydroquinone by ammonium acetate to form N-Acetyl-para-aminophenol (APAP) commonly known as paracetamol. Both reactions could be carried out continuously using TSE, nuclear magnetic resonance (NMR) spectroscopy was used to confirm the percentage conversion of starting materials to product. This information was used to construct partial least squares (PLS) calibration models within the PharmaMV development system, which relates the percent conversion to product to the acquired UV-Vis spectrum. Once this was complete, the model was deployed within the PharmaMV Real-Time System to carry out automated optimization experiments to maximize the percentage conversion based on a set of process parameters in a design of experiments (DoE) style methodology. With the optimum set of process parameters established, a series of PRBS process response tests (i.e. Pseudo-Random Binary Sequences) around the optimum were conducted. The resultant dataset was used to build a statistical model and associated MPC. The controller maximizes product quality whilst ensuring the process remains at the optimum even as disturbances such as raw material variability are introduced into the system. To summarize, a combination of online spectral monitoring and advanced process control was used to develop a robust system for optimization and control of two TSE based mechanosynthetic processes.

Keywords: continuous synthesis, pharmaceutical, spectroscopy, advanced process control

Procedia PDF Downloads 177

Authors: K. Mohon Singh

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Cambro-Ordovician (512.5 ± 8.7 Ma) felsic magmatism in the Kyrdem region of Meghalaya plateau, herewith referred to as Kyrdem granitoids (KG), intrudes the low-grade Shillong Group of metasediments and Precambrian Basement Gneissic complex forming an oval-shaped plutonic body with longer axis almost trending N-S. Thermal aureole is poorly developed or covered under the alluvium. KG exhibit very coarse grained porphyritic texture with abundant K-feldspar megacrysts (up to 9cm long) and subordinate amount of amphibole, biotite, plagioclase, and quartz. The size of K-feldspar megacrysts increases from margin (Dwarksuid) to the interior (Kyrdem) of the KG pluton. Late felsic pulses as fine grained granite, leucocratic (aplite), and pegmatite veins intrude the KG at several places. Grey and pink varieties of KG can be recognized, but pink colour of KG is the result of post-magmatic fluids, which have not affected the magnetic properties of KG. Modal composition of KG corresponds to quartz monzonite, monzogranite, and granodiorite. KG has been geochemically characterized as metaluminous (I-type) to peraluminous (S-type) granitoids. The KG is characterized by development of variable attitude of primary foliations mostly marked along the margin of the pluton and is located at the proximity of Tyrsad-Barapani lineament. The KG contains country rock xenoliths (amphibolite, gneiss, schist, etc.) which are mostly confined to the margin of the pluton, and microgranular enclaves (ME) are hosted in the porphyritic variety of KG. Microgranular Enclaves (ME) in Kyrdem Granitoids are fine- to medium grained, mesocratic to melanocratic, phenocryst bearing or phenocryst-free, rounded to ellipsoidal showing typical magmatic textures. Mafic-felsic phenocrysts in ME are partially corroded and dissolved because of their involvement in magma-mixing event, and thus represent xenocrysts. Sharp to diffused contacts of ME with host Kyrdem Granitoids, fine grained nature and presence of acicular apatite in ME suggest comingling and undercooling of coeval, semi-solidified ME magma within partly crystalline felsic host magma. Geochemical features recognize the nature of ME (molar A/CNK=0.76-1.42) and KG (molar A/CNK =0.41-1.75) similar to hybrid-type formed by mixing of mantle-derived mafic and crustal-derived felsic magmas. Major and trace including rare earth elements variations of ME suggest the involvement of combined processes such as magma mixing, mingling and crystallization differentiation in the evolution of ME but KG variations appear primarily controlled by fractionation of plagioclase, hornblende biotite, and accessory phases. Most ME are partially to nearly re-equilibrate chemically with felsic host KG during magma mixing and mingling processes.

Keywords: geochemistry, Kyrdem Granitoids, microgranular enclaves, Northeast India

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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: Bruno RamaëL, GwenaëL Page, Catherine Knopf-Lenoir, Olivier Baledent, Anne-Virginie Salsac

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No routine technique currently exists for clinicians to measure the mechanical properties of vascular walls non-invasively. Most of the data available in the literature come from traction or dilatation tests conducted ex vivo on native blood vessels. The objective of the study is to develop a non-invasive characterization technique based on Magnetic Resonance Imaging (MRI) measurements of the deformation of vascular walls under pulsating blood flow conditions. The goal is to determine the mechanical properties of the vessels by inverse analysis, coupling imaging measurements and numerical simulations of the fluid-structure interactions. The hyperelastic properties are identified using Solidworks and Ansys workbench (ANSYS Inc.) solving an optimization technique. The vessel of interest targeted in the study is the common carotid artery. In vivo MRI measurements of the vessel anatomy and inlet velocity profiles was acquired along the facial vascular network on a cohort of 30 healthy volunteers: - The time-evolution of the blood vessel contours and, thus, of the cross-section surface area was measured by 3D imaging angiography sequences of phase-contrast MRI. - The blood flow velocity was measured using a 2D CINE MRI phase contrast (PC-MRI) method. Reference arterial pressure waveforms were simultaneously measured in the brachial artery using a sphygmomanometer. The three-dimensional (3D) geometry of the arterial network was reconstructed by first creating an STL file from the raw MRI data using the open source imaging software ITK-SNAP. The resulting geometry was then transformed with Solidworks into volumes that are compatible with Ansys softwares. Tetrahedral meshes of the wall and fluid domains were built using the ANSYS Meshing software, with a near-wall mesh refinement method in the case of the fluid domain to improve the accuracy of the fluid flow calculations. Ansys Structural was used for the numerical simulation of the vessel deformation and Ansys CFX for the simulation of the blood flow. The fluid structure interaction simulations showed that the systolic and diastolic blood pressures of the common carotid artery could be taken as reference pressures to identify the mechanical properties of the different arteries of the network. The coefficients of the hyperelastic law were identified using Ansys Design model for the common carotid. Under large deformations, a stiffness of 800 kPa is measured, which is of the same order of magnitude as the Young modulus of collagen fibers. Areas of maximum deformations were highlighted near bifurcations. This study is a first step towards patient-specific characterization of the mechanical properties of the facial vessels. The method is currently applied on patients suffering from facial vascular malformations and on patients scheduled for facial reconstruction. Information on the blood flow velocity as well as on the vessel anatomy and deformability will be key to improve surgical planning in the case of such vascular pathologies.

Keywords: identification, mechanical properties, arterial walls, MRI measurements, numerical simulations

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Authors: Marta Malo, Carlota Soto, Carmen García-Rosales, Teresa Hernández

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SiC based composites are candidates for possible use as structural and functional materials in the future fusion reactors, the main role is intended for the blanket modules. In the blanket, the neutrons produced in the fusion reaction slow down and their energy is transformed into heat in order to finally generate electrical power. In the blanket design named Dual Coolant Lead Lithium (DCLL), a PbLi alloy for power conversion and tritium breeding circulates inside hollow channels called Flow Channel Inserts (FCIs). These FCI must protect the steel structures against the highly corrosive PbLi liquid and the high temperatures, but also provide electrical insulation in order to minimize magnetohydrodynamic interactions of the flowing liquid metal with the high magnetic field present in a magnetically confined fusion environment. Due to their nominally high temperature and radiation stability as well as corrosion resistance, SiC is the main choice for the flow channel inserts. The significantly lower manufacturing cost presents porous SiC (dense coating is required in order to assure protection against corrosion and as a tritium barrier) as a firm alternative to SiC/SiC composites for this purpose. This application requires the materials to be exposed to high radiation levels and extreme temperatures, conditions for which previous studies have shown noticeable changes in both the microstructure and the electrical properties of different types of silicon carbide. Both initial properties and radiation/temperature induced damage strongly depend on the crystal structure, polytype, impurities/additives that are determined by the fabrication process, so the development of a suitable material requires full control of these variables. For this work, several SiC samples with different percentage of porosity and sintering additives have been manufactured by the so-called sacrificial template method at the Ceit-IK4 Technology Center (San Sebastián, Spain), and characterized at Ciemat (Madrid, Spain). Electrical conductivity was measured as a function of temperature before and after irradiation with 1.8 MeV electrons in the Ciemat HVEC Van de Graaff accelerator up to 140 MGy (~ 2·10 -5 dpa). Radiation-induced conductivity (RIC) was also examined during irradiation at 550 ºC for different dose rates (from 0.5 to 5 kGy/s). Although no significant RIC was found in general for any of the samples, electrical conductivity increase with irradiation dose was observed to occur for some compositions with a linear tendency. However, first results indicate enhanced radiation resistance for coated samples. Preliminary thermogravimetric tests of selected samples, together with posterior XRD analysis allowed interpret radiation-induced modification of the electrical conductivity in terms of changes in the SiC crystalline structure. Further analysis is needed in order to confirm this.

Keywords: DCLL blanket, electrical conductivity, flow channel insert, porous SiC, radiation damage, thermal stability

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Authors: Elizaveta S. Prokofyeva, Svetlana V. Maltseva, Roman D. Zaitsev

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Rapidly evolving modern data analysis technologies in healthcare play a large role in understanding the operation of the system and its characteristics. Nowadays, one of the key tasks in urban healthcare is to optimize the resource allocation. Thus, the application of data analysis in medical institutions to solve optimization problems determines the significance of this study. The purpose of this research was to establish the dependence between the indicators of the effectiveness of the medical institution and its resources. Hospital discharges by diagnosis; hospital days of in-patients and in-patient average length of stay were selected as the performance indicators and the demand of the medical facility. The hospital beds by type of care, medical technology (magnetic resonance tomography, gamma cameras, angiographic complexes and lithotripters) and physicians characterized the resource provision of medical institutions for the developed models. The data source for the research was an open database of the statistical service Eurostat. The choice of the source is due to the fact that the databases contain complete and open information necessary for research tasks in the field of public health. In addition, the statistical database has a user-friendly interface that allows you to quickly build analytical reports. The study provides information on 28 European for the period from 2007 to 2016. For all countries included in the study, with the most accurate and complete data for the period under review, predictive models were developed based on historical panel data. An attempt to improve the quality and the interpretation of the models was made by cluster analysis of the investigated set of countries. The main idea was to assess the similarity of the joint behavior of the variables throughout the time period under consideration to identify groups of similar countries and to construct the separate regression models for them. Therefore, the original time series were used as the objects of clustering. The hierarchical agglomerate algorithm k-medoids was used. The sampled objects were used as the centers of the clusters obtained, since determining the centroid when working with time series involves additional difficulties. The number of clusters used the silhouette coefficient. After the cluster analysis it was possible to significantly improve the predictive power of the models: for example, in the one of the clusters, MAPE error was only 0,82%, which makes it possible to conclude that this forecast is highly reliable in the short term. The obtained predicted values of the developed models have a relatively low level of error and can be used to make decisions on the resource provision of the hospital by medical personnel. The research displays the strong dependencies between the demand for the medical services and the modern medical equipment variable, which highlights the importance of the technological component for the successful development of the medical facility. Currently, data analysis has a huge potential, which allows to significantly improving health services. Medical institutions that are the first to introduce these technologies will certainly have a competitive advantage.

Keywords: data analysis, demand modeling, healthcare, medical facilities

Procedia PDF Downloads 144

Authors: D. Ficai, A. Ficai, D. Gudovan, I. A. Gudovan, I. Ardelean, R. Trusca, E. Andronescu, V. Mitran, A. Cimpean

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In the last years, scientists struggled hardly to mimic bone structures to develop implants and biostructures which present higher biocompatibility and reduced rejection rate. One way to obtain this goal is to use similar materials as that of bone, namely collagen/hydroxyapatite composite materials. However, it is very important to tailor both compositions but also the microstructure of the bone that would ensure both the optimal osteointegartion and the mechanical properties required by the application. In this study, new collagen/hydroxyapatites composite materials doped with Cu, Li, Mn, Zn were successfully prepared. The synthesis method is described below: weight the Ca(OH)₂ mass, i.e., 7,3067g, and ZnCl₂ (0.134g), CuSO₄ (0.159g), LiCO₃ (0.133g), MnCl₂.4H₂O (0.1971g), and suspend in 100ml distilled water under magnetic stirring. The solution thus obtained is added a solution of NaH₂PO₄*H2O (8.247g dissolved in 50ml distilled water) under slow dropping of 1 ml/min followed by adjusting the pH to 9.5 with HCl and finally filter and wash until neutral pH. The as-obtained slurry was dried in the oven at 80°C and then calcined at 600°C in order to ensure a proper purification of the final product of organic phases, also inducing a proper sterilization of the mixture before insertion into the collagen matrix. The collagen/hydroxyapatite composite materials are tailored from morphological point of view to optimize their biocompatibility and bio-integration against mechanical properties whereas the addition of the dopants is aimed to improve the biological activity of the samples. The addition of transitional metals can improve the biocompatibility and especially the osteoblasts adhesion (Mn²⁺) or to induce slightly better osteoblast differentiation of the osteoblast, Zn²⁺ being a cofactor for many enzymes including those responsible for cell differentiation. If the amount is too high, the final material can become toxic and lose all of its biocompatibility. In order to achieve a good biocompatibility and not reach the cytotoxic effect, the amount of transitional metals added has to be maintained at low levels (0.5% molar). The amount of transitional metals entering into the elemental cell of HA will be verified using inductively-coupled plasma mass spectrometric system. This highly sensitive technique is necessary, because, at such low levels of transitional metals, the difference between biocompatible and cytotoxic is a very thin line, thus requiring proper and thorough investigation using a precise technique. In order to determine the structure and morphology of the obtained composite materials, IR spectroscopy, X-Ray diffraction (XRD), scanning electron microscopy (SEM), and Energy Dispersive X-Ray Spectrometry (EDS) were used. Acknowledgment: The present work was possible due to the EU-funding grant POSCCE-A2O2.2.1-2013-1, Project No. 638/12.03.2014, code SMIS-CSNR 48652. The financial contribution received from the national project “Biomimetic porous structures obtained by 3D printing developed for bone tissue engineering (BIOGRAFTPRINT), No. 127PED/2017 is also highly acknowledged.

Keywords: collagen, composite materials, hydroxyapatite, bone tissue engineering

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Authors: Lesly Y Carmona-Sarabia, Luisa Barraza-Vergara, Vilmalí López-Mejías, Wandaliz Torres-García, Maribella Domenech-Garcia, Madeline Torres-Lugo

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Biosensors are used in many applications providing real-time monitoring to treat long-term conditions. Thus, understanding the physicochemical properties and biological side effects on the skin of polymers (e. g., poly(methyl methacrylate), PMMA) employed in the fabrication of wearable biosensors is crucial for the selection of manufacturing materials within this field. The PMMA (hydrophobic and thermoplastic polymer) is commonly employed as a coating material or substrate in the fabrication of wearable devices. The cytotoxicityof PMMA (including residual monomers or degradation products) on the skin, in terms of cells and tissue, is required to prevent possible adverse effects (cell death, skin reactions, sensitization) on human health. Within this work, accelerated aging of PMMA (Mw ~ 15000) through thermal and photochemical degradation was under-taken. The accelerated aging of PMMA was carried out by thermal (200°C, 1h) and photochemical degradation (UV-Vis, 8-15d) adapted employing ISO protocols (ISO-10993-12, ISO-4892-1:2016, ISO-877-1:2009, ISO-188: 2011). In addition, in vitro cytotoxicity evaluation of PMMA degradation products was performed using NIH3T3 fibroblast cells to assess the response of skin tissues (in terms of cell viability) exposed with polymers utilized to manufacture wearable biosensors, such as PMMA. The PMMA (Mw ~ 15000) before and after accelerated aging experiments was characterized by thermal gravimetric analysis (TGA), differential scanning calorimetric (DSC), powder X-ray diffractogram (PXRD), and scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) to determine and verify the successful degradation of this polymer under the specific conditions previously mention. The degradation products were characterized through nuclear magnetic resonance (NMR) to identify possible byproducts generated after the accelerated aging. Results demonstrated a percentage (%) weight loss between 1.5-2.2% (TGA thermographs) for PMMA after accelerated aging. The EDS elemental analysis reveals a 1.32 wt.% loss of carbon for PMMA after thermal degradation. These results might be associated with the amount (%) of PMMA degrade after the accelerated aging experiments. Furthermore, from the thermal degradation products was detected the presence of the monomer and methyl formate (low concentrations) and a low molecular weight radical (·COOCH3) in higher concentrations by NMR. In the photodegradation products, methyl formate was detected in higher concentrations. These results agree with the proposed thermal or photochemical degradation mechanisms found in the literature.1,2 Finally, significant cytotoxicity on the NIH3T3 cells was obtained for the thermal and photochemical degradation products. A decrease in cell viability by > 90% (stock solutions) was observed. It is proposed that the presence of byproducts (e.g. methyl formate or radicals such as ·COOCH₃) from the PMMA degradation might be responsible for the cytotoxicity observed in the NIH3T3 fibroblast cells. Additionally, experiments using skin models will be employed to compare with the NIH3T3 fibroblast cells model.

Keywords: biosensors, polymer, skin irritation, degradation products, cell viability

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Authors: Scott M. Black, Craig Maclean, Pauline Hall Barrientos, Konstantinos Ritos, Asimina Kazakidi

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Aortic aneurysms and dissections are leading causes of death in cardiovascular disease. Both inevitably lead to hemodynamic instability without surgical intervention in the form of vascular stent-graft deployment. An accurate description of the aortic geometry and blood flow in patient-specific cases is vital for treatment planning and long-term success of such grafts, as they must generate physiological branch perfusion and in-stent hemodynamics. The aim of this study was to create patient-specific computational fluid dynamics (CFD) models through a multi-modality, multi-dimensional approach with boundary condition optimization to predict branch flow rates and in-stent hemodynamics in custom stent-graft configurations. Three-dimensional (3D) thoracoabdominal aortae were reconstructed from four-dimensional flow-magnetic resonance imaging (4D Flow-MRI) and computed tomography (CT) medical images. The former employed a novel approach to generate and enhance vessel lumen contrast via through-plane velocity at discrete, user defined cardiac time steps post-hoc. To produce patient-specific boundary conditions (BCs), the aortic geometry was reduced to a one-dimensional (1D) model. Thereafter, a zero-dimensional (0D) 3-Element Windkessel model (3EWM) was coupled to each terminal branch to represent the distal vasculature. In this coupled 0D-1D model, the 3EWM parameters were optimized to yield branch flow waveforms which are representative of the 4D Flow-MRI-derived in-vivo data. Thereafter, a 0D-3D CFD model was created, utilizing the optimized 3EWM BCs and a 4D Flow-MRI-obtained inlet velocity profile. A sensitivity analysis on the effects of stent-graft configuration and BC parameters was then undertaken using multiple stent-graft configurations and a range of distal vasculature conditions. 4D Flow-MRI granted unparalleled visualization of blood flow throughout the cardiac cycle in both the pre- and postsurgical states. Segmentation and reconstruction of healthy and stented regions from retrospective 4D Flow-MRI images also generated 3D models with geometries which were successfully validated against their CT-derived counterparts. 0D-1D coupling efficiently captured branch flow and pressure waveforms, while 0D-3D models also enabled 3D flow visualization and quantification of clinically relevant hemodynamic parameters for in-stent thrombosis and graft limb occlusion. It was apparent that changes in 3EWM BC parameters had a pronounced effect on perfusion distribution and near-wall hemodynamics. Results show that the 3EWM parameters could be iteratively changed to simulate a range of graft limb diameters and distal vasculature conditions for a given stent-graft to determine the optimal configuration prior to surgery. To conclude, this study outlined a methodology to aid in the prediction post-surgical branch perfusion and in-stent hemodynamics in patient specific cases for the implementation of custom stent-grafts.

Keywords: 4D flow-MRI, computational fluid dynamics, vascular stent-grafts, windkessel

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Authors: Sonia Boscenco, Zihan Wang, Euclides José de Mendoça Filho, João Paulo Hoppe, Irina Pokhvisneva, Geoffrey B.C. Hall, Michael J. Meaney, Patricia Pelufo Silveira

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Entropy can be described as a measure of the number of states of a system, and when used in the context of physiological time-based signals, it serves as a measure of complexity. In functional connectivity data, entropy can account for the moment-to-moment variability that is neglected in traditional functional magnetic resonance imaging (fMRI) analyses. While brain fMRI resting state entropy has been associated with some pathological conditions like schizophrenia, no investigations have explored the association between brain entropy measures and individual differences in child behavior in healthy children. We describe a novel exploratory approach to evaluate brain fMRI resting state data in two child cohorts, and MAVAN (N=54, 4.5 years, 48% males) and GUSTO (N = 206, 4.5 years, 48% males) and its associations to child behavior, that can be used in future research in the context of child exposures and long-term health. Following rs-fMRI data pre-processing and Shannon entropy calculation across 32 network regions of interest to acquire 496 unique functional connections, partial correlation coefficient analysis adjusted for sex was performed to identify associations between entropy data and Strengths and Difficulties questionnaire in MAVAN and Child Behavior Checklist domains in GUSTO. Significance was set at p < 0.01, and we found eight significant associations in GUSTO. Negative associations were found between two frontoparietal regions and cerebellar posterior and oppositional defiant problems, (r = -0.212, p = 0.006) and (r = -0.200, p = 0.009). Positive associations were identified between somatic complaints and four default mode connections: salience insula (r = 0.202, p < 0.01), dorsal attention intraparietal sulcus (r = 0.231, p = 0.003), language inferior frontal gyrus (r = 0.207, p = 0.008) and language posterior superior temporal gyrus (r = 0.210, p = 0.008). Positive associations were also found between insula and frontoparietal connection and attention deficit / hyperactivity problems (r = 0.200, p < 0.01), and insula – default mode connection and pervasive developmental problems (r = 0.210, p = 0.007). In MAVAN, ten significant associations were identified. Two positive associations were found = with prosocial scores: the salience prefrontal cortex and dorsal attention connection (r = 0.474, p = 0.005) and the salience supramarginal gyrus and dorsal attention intraparietal sulcus (r = 0.447, p = 0.008). The insula and prefrontal connection were negatively associated with peer problems (r = -0.437, p < 0.01). Conduct problems were negatively associated with six separate connections, the left salience insula and right salience insula (r = -0.449, p = 0.008), left salience insula and right salience supramarginal gyrus (r = -0.512, p = 0.002), the default mode and visual network (r = -0.444, p = 0.009), dorsal attention and language network (r = -0.490, p = 0.003), and default mode and posterior parietal cortex (r = -0.546, p = 0.001). Entropy measures of resting state functional connectivity can be used to identify individual differences in brain function that are correlated with variation in behavioral problems in healthy children. Further studies applying this marker into the context of environmental exposures are warranted.

Keywords: child behaviour, functional connectivity, imaging, Shannon entropy

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Authors: Kyoungrean Kim

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Importance of deep-sea mineral resources is dramatically increasing due to the depletion of land mineral resources corresponding to increasing human’s economic activities. Korea has acquired exclusive exploration licenses at four areas which are the Clarion-Clipperton Fracture Zone in the Pacific Ocean (2002), Tonga (2008), Fiji (2011) and Indian Ocean (2014). The preparation for commercial mining of Nautilus minerals (Canada) and Lockheed martin minerals (USA) is expected by 2020. The London Protocol 1996 (LP) under International Maritime Organization (IMO) and International Seabed Authority (ISA) will set environmental guidelines for deep-sea mining until 2020, to protect marine environment. In this research, the applicability of washing/extraction treatment for the remediation of deep-sea mining tailings was mainly evaluated in order to present preliminary data to develop practical remediation technology in near future. Polymetallic nodule samples were collected at the Clarion-Clipperton Fracture Zone in the Pacific Ocean, then stored at room temperature. Samples were pulverized by using jaw crusher and ball mill then, classified into 3 particle sizes (> 63 µm, 63-20 µm, < 20 µm) by using vibratory sieve shakers (Analysette 3 Pro, Fritsch, Germany) with 63 µm and 20 µm sieve. Only the particle size 63-20 µm was used as the samples for investigation considering the lower limit of ore dressing process which is tens to 100 µm. Rhamnolipid and sodium alginate as biosurfactant and aluminum sulfate which are mainly used as flocculant were used as environmentally friendly additives. Samples were adjusted to 2% liquid with deionized water then mixed with various concentrations of additives. The mixture was stirred with a magnetic bar during specific reaction times and then the liquid phase was separated by a centrifugal separator (Thermo Fisher Scientific, USA) under 4,000 rpm for 1 h. The separated liquid was filtered with a syringe and acrylic-based filter (0.45 µm). The extracted heavy metals in the filtered liquid were then determined using a UV-Vis spectrometer (DR-5000, Hach, USA) and a heat block (DBR 200, Hach, USA) followed by US EPA methods (8506, 8009, 10217 and 10220). Polymetallic nodule was mainly composed of manganese (27%), iron (8%), nickel (1.4%), cupper (1.3 %), cobalt (1.3%) and molybdenum (0.04%). Based on remediation standards of various countries, Nickel (Ni), Copper (Cu), Cadmium (Cd) and Zinc (Zn) were selected as primary target materials. Throughout this research, the use of rhamnolipid was shown to be an effective approach for removing heavy metals in samples originated from manganese nodules. Sodium alginate might also be one of the effective additives for the remediation of deep-sea mining tailings such as polymetallic nodules. Compare to the use of rhamnolipid and sodium alginate, aluminum sulfate was more effective additive at short reaction time within 4 h. Based on these results, sequencing particle separation, selective extraction/washing, advanced filtration of liquid phase, water treatment without dewatering and solidification/stabilization may be considered as candidate technologies for the remediation of deep-sea mining tailings.

Keywords: deep-sea mining tailings, heavy metals, remediation, extraction, additives

Procedia PDF Downloads 155

Authors: Miroslava Cuperlovic-Culf, Lipu Wang, Ketty Boyle, Nadine Makley, Ian Burton, Anissa Belkaid, Mohamed Touaibia, Marc E. Surrette

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Metabolic changes are one of the major factors in the development of a variety of diseases in various species. Metabolism of agricultural plants is altered the following infection with pathogens sometimes contributing to resistance. At the same time, pathogens use metabolites for infection and progression. In humans, metabolism is a hallmark of cancer development for example. Quantified metabolomics data combined with other omics or clinical data and analyzed using various unsupervised and supervised methods can lead to better diagnosis and prognosis. It can also provide information about resistance as well as contribute knowledge of compounds significant for disease progression or prevention. In this work, different methods for metabolomics quantification and analysis from Nuclear Magnetic Resonance (NMR) measurements that are used for investigation of disease development in wheat and human cells will be presented. One-dimensional 1H NMR spectra are used extensively for metabolic profiling due to their high reliability, wide range of applicability, speed, trivial sample preparation and low cost. This presentation will describe a new method for metabolite quantification from NMR data that combines alignment of spectra of standards to sample spectra followed by multivariate linear regression optimization of spectra of assigned metabolites to samples’ spectra. Several different alignment methods were tested and multivariate linear regression result has been compared with other quantification methods. Quantified metabolomics data can be analyzed in the variety of ways and we will present different clustering methods used for phenotype determination, network analysis providing knowledge about the relationships between metabolites through metabolic network as well as biomarker selection providing novel markers. These analysis methods have been utilized for the investigation of fusarium head blight resistance in wheat cultivars as well as analysis of the effect of estrogen receptor and carbonic anhydrase activation and inhibition on breast cancer cell metabolism. Metabolic changes in spikelet’s of wheat cultivars FL62R1, Stettler, MuchMore and Sumai3 following fusarium graminearum infection were explored. Extensive 1D 1H and 2D NMR measurements provided information for detailed metabolite assignment and quantification leading to possible metabolic markers discriminating resistance level in wheat subtypes. Quantification data is compared to results obtained using other published methods. Fusarium infection induced metabolic changes in different wheat varieties are discussed in the context of metabolic network and resistance. Quantitative metabolomics has been used for the investigation of the effect of targeted enzyme inhibition in cancer. In this work, the effect of 17 β -estradiol and ferulic acid on metabolism of ER+ breast cancer cells has been compared to their effect on ER- control cells. The effect of the inhibitors of carbonic anhydrase on the observed metabolic changes resulting from ER activation has also been determined. Metabolic profiles were studied using 1D and 2D metabolomic NMR experiments, combined with the identification and quantification of metabolites, and the annotation of the results is provided in the context of biochemical pathways.

Keywords: metabolic biomarkers, metabolic network, metabolomics, multivariate linear regression, NMR quantification, quantified metabolomics, spectral alignment

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Authors: Igor B. Sivaev

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Design of molecular machines is an extraordinary growing and very important area of research that it was recognized by awarding Sauvage, Stoddart and Feringa the Nobel Prize in Chemistry in 2016 'for the design and synthesis of molecular machines'. Based on the type of motion being performed, molecular machines can be divided into two main types: molecular motors and molecular switches. Molecular switches are molecules or supramolecular complexes having bistability, i.e., the ability to exist in two or more stable forms, among which may be reversible transitions under external influence (heating, lighting, changing the medium acidity, the action of chemicals, exposure to magnetic or electric field). Molecular switches are the main structural element of any molecular electronics devices. Therefore, the design and the study of molecules and supramolecular systems capable of performing mechanical movement is an important and urgent problem of modern chemistry. There is growing interest in molecular switches and other devices of molecular electronics based on transition metal complexes; therefore choice of suitable stable organometallic unit is of great importance. An example of such unit is bis(dicarbollide) complexes of transition metals [3,3’-M(1,2-C₂B₉H₁₁)₂]ⁿ⁻. The control on the ligand rotation in such complexes can be reached by introducing substituents which could provide stabilization of certain rotamers due to specific interactions between the ligands, on the one hand, and which can participate as Lewis bases in complex formation with external metals resulting in a change in the rotation angle of the ligands, on the other hand. A series of isomeric methyl sulfide derivatives of cobalt bis(dicarbollide) complexes containing methyl sulfide substituents at boron atoms in different positions of the pentagonal face of the dicarbollide ligands [8,8’-(MeS)₂-3,3’-Co(1,2-C₂B₉H₁₀)₂]⁻, rac-[4,4’-(MeS)₂-3,3’-Co(1,2-C₂B₉H₁₀)₂]⁻ and meso-[4,7’-(MeS)₂-3,3’-Co(1,2-C₂B₉H₁₀)₂]⁻ were synthesized by the reaction of CoCl₂ with the corresponding methyl sulfide carborane derivatives [10-MeS-7,8-C₂B₉H₁₁)₂]⁻ and [10-MeS-7,8-C₂B₉H₁₁)₂]⁻. In the case of asymmetrically substituted cobalt bis(dicarbollide) complexes the corresponding rac- and meso-isomers were successfully separated by column chromatography as the tetrabutylammonium salts. The compounds obtained were studied by the methods of ¹H, ¹³C, and ¹¹B NMR spectroscopy, single crystal X-ray diffraction, cyclic voltammetry, controlled potential coulometry and quantum chemical calculations. It was found that in the solid state, the transoid- and gauche-conformations of the 8,8’- and 4,4’-isomers are stabilized by four intramolecular CH···S(Me)B hydrogen bonds each one (2.683-2.712 Å and 2.709-2.752 Å, respectively), whereas gauche-conformation of the 4,7’-isomer is stabilized by two intramolecular CH···S hydrogen bonds (2.699-2.711 Å). The existence of the intramolecular CH·S(Me)B hydrogen bonding in solutions was supported by the 1H NMR spectroscopy. These data are in a good agreement with results of the quantum chemical calculations. The corresponding iron and nickel complexes were synthesized as well. The reaction of the methyl sulfide derivatives of cobalt bis(dicarbollide) with various labile transition metal complexes results in rupture of intramolecular hydrogen bonds and complexation of the methyl sulfide groups with external metal. This results in stabilization of other rotational conformation of cobalt bis(dicarbollide) and can be used in design of molecular switches. This work was supported by the Russian Science Foundation (16-13-10331).

Keywords: molecular switches, NMR spectroscopy, single crystal X-ray diffraction, transition metal bis(dicarbollide) complexes, quantum chemical calculations

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Authors: komal verma, V. S. Moholkar

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In this current study, the challenge of effectively treating and mineralizing industrial wastewater prior to its discharge into natural water bodies, such as rivers and lakes, is being addressed. Particularly, the focus is on the wastewater produced by chemical process industries, including refineries, petrochemicals, fertilizer, pharmaceuticals, pesticides, and dyestuff industries. These wastewaters often contain stubborn organic pollutants that conventional techniques, such as microbial processes cannot efficiently degrade. To tackle this issue, a ternary hybrid technique comprising of adsorption, heterogeneous Fenton process, and sonication has been employed. The study aims to evaluate the effectiveness of this approach for treating and mineralizing wastewater from a fertilizer industry located in Northeast India. The study comprises several key components, starting with the synthesis of the Fe3O4@AC nanocomposite using the co-precipitation method. The nanocomposite is then subjected to comprehensive characterization through various standard techniques, including FTIR, FE-SEM, EDX, TEM, BET surface area analysis, XRD, and magnetic property determination using VSM. Next, the process parameters of wastewater treatment are statistically optimized, focusing on achieving a high level of COD (Chemical Oxygen Demand) removal as the response variable. The Fe3O4@AC nanocomposite's adsorption characteristics and kinetics are also assessed in detail. The remarkable outcome of this study is the successful application of the ternary hybrid technique, combining adsorption, Fenton process, and sonication. This approach proves highly effective, leading to nearly complete mineralization (or TOC removal) of the fertilizer industry wastewater. The results highlight the potential of the Fe3O4@AC nanocomposite and the ternary hybrid technique as a promising solution for tackling challenging wastewater pollutants from various chemical process industries. This paper reports investigations in the mineralization of industrial wastewater (COD = 3246 mg/L, TOC = 2500 mg/L) using a ternary (ultrasound + Fenton + adsorption) hybrid advanced oxidation process. Fe3O4 decorated activated charcoal (Fe3O4@AC) nanocomposites (surface area = 538.88 m2/g; adsorption capacity = 294.31 mg/g) were synthesized using co-precipitation. The wastewater treatment process was optimized using central composite statistical design. At optimum conditions, viz. pH = 4.2, H2O2 loading = 0.71 M, adsorbent dose = 0.34 g/L, reduction in COD and TOC of wastewater were 94.75% and 89%, respectively. This result results from synergistic interactions among the adsorption of pollutants onto activated charcoal and surface Fenton reactions induced due to the leaching of Fe2+/Fe3+ ions from the Fe3O4 nanoparticles. Micro-convection generated due to sonication assisted faster mass transport (adsorption/desorption) of pollutants between Fe3O4@AC nanocomposite and the solution. The net result of this synergism was high interactions and reactions among and radicals and pollutants that resulted in the effective mineralization of wastewater. The Fe3O4@AC showed excellent recovery (> 90 wt%) and reusability (> 90% COD removal) in 5 successive cycles of treatment. LC-MS analysis revealed effective (> 50%) degradation of more than 25 significant contaminants (in the form of herbicides and pesticides) after the treatment with ternary hybrid AOP. Similarly, the toxicity analysis test using the seed germination technique revealed ~ 60% reduction in the toxicity of the wastewater after treatment.

Keywords: chemical oxygen demand (cod), fe3o4@ac nanocomposite, kinetics, lc-ms, rsm, toxicity

Procedia PDF Downloads 72