Search results for: differential magnetic susceptibility

Authors: S. R. Dehghani, Y. S. Muzychka, G. F. Naterer

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The ice accretion of salt water on cold substrates creates brine-spongy ice. This type of ice is a mixture of pure ice and liquid brine. A real case of creation of this type of ice is superstructure icing which occurs on marine vessels and offshore structures in cold and harsh conditions. Transient heat transfer through this medium causes phase changes between brine pockets and pure ice. Salt rejection during the process of transient heat conduction increases the salinity of brine pockets to reach a local equilibrium state. In this process the only effect of passing heat through the medium is not changing the sensible heat of the ice and brine pockets; latent heat plays an important role and affects the mechanism of heat transfer. In this study, a new analytical model for evaluating heat transfer through brine-spongy ice is suggested. This model considers heat transfer and partial solidification and melting together. Properties of brine-spongy ice are obtained using properties of liquid brine and pure ice. A numerical solution using Method of Lines discretizes the medium to reach a set of ordinary differential equations. Boundary conditions are chosen using one of the applicable cases of this type of ice; one side is considered as a thermally isolated surface, and the other side is assumed to be suddenly affected by a constant temperature boundary. All cases are evaluated in temperatures between -20 C and the freezing point of brine-spongy ice. Solutions are conducted using different salinities from 5 to 60 ppt. Time steps and space intervals are chosen properly to maintain the most stable and fast solution. Variation of temperature, volume fraction of brine and brine salinity versus time are the most important outputs of this study. Results show that transient heat conduction through brine-spongy ice can create a various range of salinity of brine pockets from the initial salinity to that of 180 ppt. The rate of variation of temperature is found to be slower for high salinity cases. The maximum rate of heat transfer occurs at the start of the simulation. This rate decreases as time passes. Brine pockets are smaller at portions closer to the colder side than that of the warmer side. A the start of the solution, the numerical solution tends to increase instabilities. This is because of sharp variation of temperature at the start of the process. Changing the intervals improves the unstable situation. The analytical model using a numerical scheme is capable of predicting thermal behavior of brine spongy ice. This model and numerical solutions are important for modeling the process of freezing of salt water and ice accretion on cold structures.

Keywords: method of lines, brine-spongy ice, heat conduction, salt water

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Authors: Eileen Y. Wong, Katherine Jin, Anat Talmon

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Background: Help seeking behaviors are highly contingent on socio-cultural factors such as ethnicity. Both Latino and Asian Americans underutilize mental health services compared to their White American counterparts. This difference may be related to the composite of one’s social support system, which includes family cohesion and social networks. Previous studies have found that Latino families are characterized by higher levels of family cohesion and social support, and Asian American families with greater family cohesion exhibit lower levels of help seeking behaviors. While both are broadly considered collectivist communities, within-culture variability is also significant. Therefore, this study aims to investigate the relationship between help seeking behaviors in the two cultures with levels of family cohesion and strength of social network. We also consider such relationships in light of previous traumatic events and diagnoses, particularly post-traumatic stress disorder (PTSD), to understand whether clinically diagnosed individuals differ in their strength of network and help seeking behaviors. Method: An adult sample (N = 2,990) from the National Latino and Asian American Study (NLAAS) provided data on participants’ social network, family cohesion, likelihood of seeking professional help, and DSM-IV diagnoses. T-tests compared Latino American (n = 1,576) and Asian American respondents (n = 1,414) in strength of social network, level of family cohesion, and likelihood of seeking professional help. Linear regression models were used to identify the probability of help-seeking behavior based on ethnicity, PTSD diagnosis, and strength of social network. Results: Help-seeking behavior was significantly associated with family cohesion and strength of social network. It was found that higher frequency of expressing one’s feelings with family significantly predicted lower levels of help-seeking behaviors (β = [-.072], p = .017), while higher frequency of spending free time with family significantly predicted higher levels of help-seeking behaviors (β = [.129], p = .002) in the Asian American sample. Subjective importance of family relations compared to that of one’s peers also significantly predict higher levels of help-seeking behaviors (β = [.095], p = .011) in the Asian American sample. Frequency of sharing one’s problems with relatives significantly predicted higher levels of help-seeking behaviors (β = [.113], p < .01) in the Latino American sample. A PTSD diagnosis did not have any significant moderating effect. Conclusion: Considering the underutilization of mental health services in Latino and Asian American minority groups, it is crucial to understand ways in which help seeking behavior can be encouraged. Our findings suggest that different dimensions within family cohesion and social networks have differential impacts on help-seeking behavior. Given the multifaceted nature of family cohesion and cultural relevance, the implications of our findings for theory and practice will be discussed.

Keywords: family cohesion, social networks, Asian American, Latino American, help-seeking behavior

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Authors: Soad Abubakr Abdelgalil, Gaber Attia Abo-Zaid, Mohamed Mohamed Yousri Kaddah

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Background: The Environmental Protection Agency has listed eggshell waste as the 15th most significant food industry pollution hazard. The utilization of eggshell waste as a source of renewable energy has been a hot topic in recent years. Therefore, finding a sustainable solution for the recycling and valorization of eggshell waste by investigating its potential to produce acid phosphatase (ACP) and organic acids by the newly-discovered B. sonorensis was the target of the current investigation. Results: The most potent ACP-producing B. sonorensis strain ACP2 was identified as a local bacterial strain obtained from the effluent of paper and pulp industries on basis of molecular and morphological characterization. The use of consecutive statistical experimental approaches of Plackett-Burman Design (PBD), and Orthogonal Central Composite Design (OCCD), followed by pH-uncontrolled cultivation conditions in a 7 L bench-top bioreactor, revealed an innovative medium formulation that substantially improved ACP production, reaching 216 U L⁻¹ with ACP yield coefficient Yp/x of 18.2 and a specific growth rate (µ) of 0.1 h⁻¹. The metals Ag+, Sn+, and Cr+ were the most efficiently released from eggshells during the solubilization process by B. sonorensis. The uncontrolled pH culture condition is the most suited and favored setting for improving the ACP and organic acids production simultaneously. Quantitative and qualitative analyses of produced organic acids were carried out using liquid chromatography-tandem mass spectrometry (LC-MS/MS). Lactic acid, citric acid, and hydroxybenzoic acid isomer were the most common organic acids produced throughout the cultivation process. The findings of thermogravimetric analysis (TGA), differential scan calorimeter (DSC), scanning electron microscope (SEM), energy-dispersive spectroscopy (EDS), Fourier-Transform Infrared Spectroscopy (FTIR), and X-Ray Diffraction (XRD) analysis emphasize the significant influence of organic acids and ACP activity on the solubilization of eggshells particles. Conclusions: This study emphasized robust microbial engineering approaches for the large-scale production of a newly discovered acid phosphatase accompanied by organic acids production from B. sonorensis. The biovalorization of the eggshell waste and the production of cost-effective ACP and organic acids were integrated into the current study, and this was done through the implementation of a unique and innovative medium formulation design for eggshell waste management, as well as scaling up ACP production on a bench-top scale.

Keywords: chicken eggshells waste, bioremediation, statistical experimental design, batch fermentation

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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

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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

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Authors: Mustafa M. Donma, Orkide Donma

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The number of indices developed for the evaluation of obesity both in adults and pediatric population is ever increasing. These indices are also used in cases with metabolic syndrome (MetS), mostly the ultimate form of morbid obesity. Aside from anthropometric measurements, formulas constituted using these parameters also find clinical use. These formulas can be listed as two groups; being weight-dependent and –independent. Some are extremely sophisticated equations and their clinical utility is questionable in routine clinical practice. The aim of this study is to compare presently available obesity indices and find the most practical one. Their associations with MetS components were also investigated to determine their capacities in differential diagnosis of morbid obesity with and without MetS. Children with normal body mass index (N-BMI) and morbid obesity were recruited for this study. Three groups were constituted. Age- and sex- dependent BMI percentiles for morbid obese (MO) children were above 99 according to World Health Organization tables. Of them, those with MetS findings were evaluated as MetS group. Children, whose values were between 85 and 15 were included in N-BMI group. The study protocol was approved by the Ethics Committee of the Institution. Parents filled out informed consent forms to participate in the study. Anthropometric measurements and blood pressure values were recorded. Body mass index, hip index (HI), conicity index (CI), triponderal mass index (TPMI), body adiposity index (BAI), body shape index (ABSI), body roundness index (BRI), abdominal volume index (AVI), waist-to-hip ratio (WHR) and waist circumference+hip circumference/2 ((WC+HC)/2) were the formulas examined within the scope of this study. Routine biochemical tests including fasting blood glucose (FBG), insulin (INS), triglycerides (TRG), high density lipoprotein-cholesterol (HDL-C) were performed. Statistical package program SPSS was used for the evaluation of study data. p<0.05 was accepted as the statistical significance degree. Hip index did not differ among the groups. A statistically significant difference was noted between N-BMI and MetS groups in terms of ABSI. All the other indices were capable of making discrimination between N-BMI-MO, N-BMI- MetS and MO-MetS groups. No correlation was found between FBG and any obesity indices in any groups. The same was true for INS in N-BMI group. Insulin was correlated with BAI, TPMI, CI, BRI, AVI and (WC+HC)/2 in MO group without MetS findings. In MetS group, the only index, which was correlated with INS was (WC+HC)/2. These findings have pointed out that complicated formulas may not be required for the evaluation of the alterations among N-BMI and various obesity groups including MetS. The simple easily computable weight-independent index, (WC+HC)/2, was unique, because it was the only index, which exhibits a valuable association with INS in MetS group. It did not exhibit any correlation with other obesity indices showing associations with INS in MO group. It was concluded that (WC+HC)/2 was pretty valuable practicable index for the discrimination of MO children with and without MetS findings.

Keywords: children, insulin, metabolic syndrome, obesity indices

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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: Catariny C. Aleman, Flavio B. Campos, Matheus A. Caliman, Everardo C. Mantovani

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The seedling production stage is a critical point in the vegetable production system. Obtaining high-quality seedlings is a prerequisite for subsequent cropping to occur well and productivity optimization is required. The water management is an important step in agriculture production. The adequate water requirement in horticulture seedlings can provide higher quality and increase field production. The practice of irrigation is indispensable and requires a duly adjusted quality irrigation system, together with a specific water management plan to meet the water demand of the crop. Irrigation management in seedling management requires a great deal of specific information, especially when it involves the use of inputs such as hydrorentering polymers and automation technologies of the data acquisition and irrigation system. The experiment was conducted in a greenhouse at the Federal University of Viçosa, Viçosa - MG. Tomato seedlings (Lycopersicon esculentum Mill) were produced in plastic trays of 128 cells, suspended at 1.25 m from the ground. The seedlings were irrigated by 4 micro sprinklers of fixed jet 360º per tray, duly isolated by sideboards, following the methodology developed for this work. During Phase 1, in January / February 2017 (duration of 24 days), the cultivation coefficient (Kc) of seedlings cultured in the presence and absence of hydrogel was evaluated by weighing lysimeter. In Phase 2, September 2017 (duration of 25 days), the seedlings were submitted to 4 irrigation managements (Kc, timer, 0.50 ETo, and 1.00 ETo), in the presence and absence of hydrogel and then evaluated in relation to quality parameters. The microclimate inside the greenhouse was monitored with the use of air temperature, relative humidity and global radiation sensors connected to a microcontroller that performed hourly calculations of reference evapotranspiration by Penman-Monteith standard method FAO56 modified for the balance of long waves according to Walker, Aldrich, Short (1983), and conducted water balance and irrigation decision making for each experimental treatment. Kc of seedlings cultured on a substrate with hydrogel (1.55) was higher than Kc on a pure substrate (1.39). The use of the hydrogel was a differential for the production of earlier tomato seedlings, with higher final height, the larger diameter of the colon, greater accumulation of a dry mass of shoot, a larger area of crown projection and greater the rate of relative growth. The handling 1.00 ETo promoted higher relative growth rate.

Keywords: automatic system; efficiency of water use; precision irrigation, micro sprinkler.

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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

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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.

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Authors: Marina Chavleishvili

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Introduction: Today, the study of monopolies, including natural monopolies, is topical. In real life, pure monopolies are natural monopolies. Natural monopolies are used widely and are regulated by the state. In particular, the prices and rates are regulated. The paper considers the problems associated with the operation of natural monopolies in Georgia, in particular, their microeconomic analysis, pricing mechanisms, and legal mechanisms of their operation. The analysis was carried out on the example of the power industry. The rates of natural monopolies in Georgia are controlled by the Georgian National Energy and Water Supply Regulation Commission. The paper analyzes the positive role and importance of the regulatory body and the issues of improving the legislative base that will support the efficient operation of the branch. Methodology: In order to highlight natural monopolies market tendencies, the domestic and international markets are studied. An analysis of monopolies is carried out based on the endogenous and exogenous factors that determine the condition of companies, as well as the strategies chosen by firms to increase the market share. According to the productivity-based competitiveness assessment scheme, the segmentation opportunities, business environment, resources, and geographical location of monopolist companies are revealed. Main Findings: As a result of the analysis, certain assessments and conclusions were made. Natural monopolies are quite a complex and versatile economic element, and it is important to specify and duly control their frame conditions. It is important to determine the pricing policy of natural monopolies. The rates should be transparent, should show the level of life in the country, and should correspond to the incomes. The analysis confirmed the significance of the role of the Antimonopoly Service in the efficient management of natural monopolies. The law should adapt to reality and should be applied only to regulate the market. The present-day differential electricity tariffs varying depending on the consumed electrical power need revision. The effects of the electricity price discrimination are important, segmentation in different seasons in particular. Consumers use more electricity in winter than in summer, which is associated with extra capacities and maintenance costs. If the price of electricity in winter is higher than in summer, the electricity consumption will decrease in winter. The consumers will start to consume the electricity more economically, what will allow reducing extra capacities. Conclusion: Thus, the practical realization of the views given in the paper will contribute to the efficient operation of natural monopolies. Consequently, their activity will be oriented not on the reduction but on the increase of increments of the consumers or producers. Overall, the optimal management of the given fields will allow for improving the well-being throughout the country. In the article, conclusions are made, and the recommendations are developed to deliver effective policies and regulations toward the natural monopolies in Georgia.

Keywords: monopolies, natural monopolies, regulation, antimonopoly service

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Authors: Shashi Bhushan, Sucharita Sen

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In India, forest and people are inextricably linked since millions of people live adjacent to or within protected areas and harvest forest products. Indian forest has their own legacy to sustain by its own climatic nature with several social, economic and cultural activities. People surrounding forest areas are not only dependent on this resource for their livelihoods but also for the other source, like religious ceremonies, social customs and herbal medicines, which are determined by the forest like agricultural land, groundwater level, and soil fertility. The assumption that fuelwood and fodder extraction, which is the part of local livelihood leads to deforestation, has so far been the dominant mainstream views in deforestation discourses. Given the occupational division across social groups in Kaimur reserve forest, the differential nature of dependence of forest resources is important to understand. This paper attempts to assess the nature of dependence and impact of forest degradation on rural households across various social groups. Also, an additional element that is added to the enquiry is the way degradation of forests leading to scarcity of forest-based resources impacts the patterns of dependence across various social groups. Change in forest area calculated through land use land cover analysis using remote sensing technique and examination of different economic activities carried out by the households that are forest-based was collected by primary survey in Kaimur reserve forest of state of Bihar in India. The general finding indicates that the Scheduled Tribe and Scheduled Caste communities, the most socially and economically deprived sections of the rural society are involved in a significant way in collection of fuelwood, fodder, and fruits, both for self-consumption and sale in the market while other groups of society uses fuelwood, fruit, and fodder for self-use only. Depending on the local forest resources for fuelwood consumption was the primary need for all social groups due to easy accessibility and lack of alternative energy source. In last four decades, degradation of forest made a direct impact on rural community mediated through the socio-economic structure, resulting in a shift from forest-based occupations to cultivation and manual labour in agricultural and non-agricultural activities. Thus there is a need to review the policies with respect to the ‘community forest management’ since this study clearly throws up the fact that engagement with and dependence on forest resources is socially differentiated. Thus tying the degree of dependence and forest management becomes extremely important from the view of ‘sustainable’ forest resource management. The statization of forest resources also has to keep in view the intrinsic way in which the forest-dependent population interacts with the forest.

Keywords: forest degradation, livelihood, social groups, tribal community

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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: Sudhir Kumar, V. R. Sinha

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Background: The topical and systemic toxicity associated with present nonmelanoma skin cancer (NMSC) treatment therapy using 5-Fluorouracil (5-FU) make it necessary to develop a novel delivery system having lesser toxicity and better control over drug release. Solid lipid nanoparticles offer many advantages like: controlled and localized release of entrapped actives, nontoxicity, and better tolerance. Aim:-To investigate safety and efficacy of 5-FU loaded solid lipid nanoparticles as a topical delivery system for the treatment of nonmelanoma skin cancer. Method: Topical solid lipid nanoparticles of 5-FU were prepared using Compritol 888 ATO (Glyceryl behenate) as lipid component and pluronic F68 (Poloxamer 188), Tween 80 (Polysorbate 80), Tyloxapol (4-(1,1,3,3-Tetramethylbutyl) phenol polymer with formaldehyde and oxirane) as surfactants. The SLNs were prepared with emulsification method. Different formulation parameters viz. type and ratio of surfactant, ratio of lipid and ratio of surfactant:lipid were investigated on particle size and drug entrapment efficiency. Results: Characterization of SLNs like–Transmission Electron Microscopy (TEM), Differential Scannig calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), Particle size determination, Polydispersity index, Entrapment efficiency, Drug loading, ex vivo skin permeation and skin retention studies, skin irritation and histopathology studies were performed. TEM results showed that shape of SLNs was spherical with size range 200-500nm. Higher encapsulation efficiency was obtained for batches having higher concentration of surfactant and lipid. It was found maximum 64.3% for SLN-6 batch with size of 400.1±9.22 nm and PDI 0.221±0.031. Optimized SLN batches and marketed 5-FU cream were compared for flux across rat skin and skin drug retention. The lesser flux and higher skin retention was obtained for SLN formulation in comparison to topical 5-FU cream, which ensures less systemic toxicity and better control of drug release across skin. Chronic skin irritation studies lacks serious erythema or inflammation and histopathology studies showed no significant change in physiology of epidermal layers of rat skin. So, these studies suggest that the optimized SLN formulation is efficient then marketed cream and safer for long term NMSC treatment regimens. Conclusion: Topical and systemic toxicity associated with long-term use of 5-FU, in the treatment of NMSC, can be minimized with its controlled release with significant drug retention with minimal flux across skin. The study may provide a better alternate for effective NMSC treatment.

Keywords: 5-FU, topical formulation, solid lipid nanoparticles, non melanoma skin cancer

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Authors: Qian Sun, Dannie Dai, Vivian Lou

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Background: Changes in population structure and modernization have left traditional channels of achieving intergenerational solidarity in crisis. Policies and projects purposefully structuring intergenerational interaction are regarded as effective ways to enhance positive attitude changes between generations. However, few inter-generational interaction program has put equal emphasis on promoting positive changes on both attitude and behavior across generational groups. Objective: This study evaluated the effectiveness of an intergenerational interaction program which aims to facilitate positive attitude and behavioral interaction between both young and old individuals in Hong Kong. Method: A quasi-experimental design was adopted with the sample of 150 older participants and 161 young participants. Among 73 older and 78 young participants belong to experiment groups while 77 older participants and 84 young participants belong to control groups. The Age Group Evaluation and Description scale (AGED) was adopted to measure attitude toward young people by older participants and the Chinese version of Kogan’s Attitude towards Older People (KAOP) as well as Polizzi’s refined version of the Ageing Semantic Differential Scale (ASD) were used to measure attitude toward older people by the younger generation. The interpersonal behaviour of participants was assessed using Beglgrave’s behavioural observation tool. Six primary verbal or non-verbal interpersonal behaviours including smiles, looks, touches, encourages, initiated conversations and assists were identified and observed. Findings Effectiveness of attitude and behavior changes on both younger and older participants was confirmed in results. Compared with participants from the control group, experimental participants of elderly showed significant positive changes of attitudes toward the younger generation as assessed by AGED (F=138.34, p < .001). Moreover, older participants showed significant positive changes on three out of six behaviours (visual attention: t=2.26, p<0.05; initiate conversation: t=3.42, p<0.01; and touch: t=2.28, p<0.05). For younger participants, participants from experimental group showed significant positive changes in attitude toward older people (with F-score of 47.22 for KAOP and 72.75 for ASD, p<.001). Young participants also showed significant positive changes in two out of six behaviours (visual attention: t=3.70, p<0.01; initiate conversation: t=2.04, p<0.001). There is no significant relationship between attitude change and behaviour change in both older (p=0.86) and younger (p=0.22) groups. Conclusion: This study has brought practical implications for social work. The effective model of this program could assist social workers and allied professionals to design relevant projects for nurture intergenerational solidarity. Furthermore, insignificant results between attitude and behavior changes revealed that attitude change was not a strong predictor for behavior change, hence, intergenerational programs against age-stereotype should put equal emphasis on both attitudinal and behavioral aspects.

Keywords: attitude and behaviour changes, intergenerational interaction, intergenerational solidarity, program design

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Authors: Mustafa M. Donma, Orkide Donma

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Metabolic syndrome (MetS) is a severe health problem which is common among obese individuals. The components of MetS are rather stable in adults compared to the components discussed for children. Due to the ambiguity in this group of the population, how to diagnose MetS in morbid obese (MO) children still constitutes a matter of discussion. For this purpose, a formula, which facilitates the diagnosis of MetS in MO children, was investigated. The aim of this study was to develop a formula which was capable of discriminating MO children with and without MetS findings. Study population comprised MO children. Age and sex-dependent body mass index (BMI) percentiles of the children were above 99. Metabolic syndrome components were also determined. Elevated systolic and diastolic blood pressures (SBP and DBP), elevated fasting blood glucose (FBG), elevated triglycerides (TRG), and/or depressed high density lipoprotein cholesterol (HDL-C) in addition to central obesity were listed as MetS components for each child. Presence of at least two of these components confirmed that the case was MetS. Two groups were constituted. In the first group, there were forty-two MO children without MetS components. Second group was composed of forty-four MO children with at least two MetS components. Anthropometric measurements, including weight, height, waist, and hip circumferences, were performed following physical examination. Body mass index and homeostatic model assessment of insulin resistance values were calculated. Informed consent forms were obtained from the parents of the children. Institutional Non-Interventional Ethics Committee approved the study design. Blood pressure values were recorded. Routine biochemical analysis, including FBG, insulin (INS), TRG, HDL-C were performed. The performance and the clinical utility of the Diagnostic Obesity Notation Model Assessment Metabolic Syndrome Index (DONMA MetS index) [(INS/FBG)/(HDL-C/TRG)*100] was tested. Appropriate statistical tests were applied to the study data. p value smaller than 0.05 was defined as significant. Metabolic syndrome index values were 41.6±5.1 in MO group and 104.4±12.8 in MetS group. Corresponding values for HDL-C values were 54.5±13.2 mg/dl and 44.2±11.5 mg/dl. There were statistically significant differences between the groups (p<0.001). Upon evaluation of the correlations between MetS index and HDL-C values, a much stronger negative correlation was found in MetS group (r=-0.515; p=0.001) in comparison with the correlation detected in MO group (r=-0.371; p=0.016). From these findings, it was concluded that the statistical significance degree of the difference between MO and MetS groups was highly acceptable for this recently introduced MetS index as expected. This was due to the involvement of all of the biochemically defined MetS components into the index. This is particularly important because each of these four parameters used in the formula is cardiac risk factor. Aside from discriminating MO children with and without MetS findings, MetS index introduced in this study is important from the cardiovascular risk point of view in MetS group of children.

Keywords: children, fasting blood glucose, high density lipoprotein cholesterol, index, insulin, metabolic syndrome, morbid obesity, triglycerides.

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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.

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Authors: Xincheng Jiang, Yanyan An, Yaoyao Huang, Wei Ding, Manli Sun, Hong Li, Huaili Zheng

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The residual antibiotics in the environment will pose a threat to the environment and human health. Thus, efficient removal and rapid detection of norfloxacin (NOR) in wastewater is very important. The main sources of NOR pollution are the agricultural, pharmaceutical industry and hospital wastewater. The total consumption of NOR in China can reach 5440 tons per year. It is found that neither animals nor humans can totally absorb and metabolize NOR, resulting in the excretion of NOR into the environment. Therefore, residual NOR has been detected in water bodies. The hazards of NOR in wastewater lie in three aspects: (1) the removal capacity of the wastewater treatment plant for NOR is limited (it is reported that the average removal efficiency of NOR in the wastewater treatment plant is only 68%); (2) NOR entering the environment will lead to the emergence of drug-resistant strains; (3) NOR is toxic to many aquatic species. At present, the removal and detection technologies of NOR are applied separately, which leads to a cumbersome operation process. The development of simultaneous adsorption-flocculation removal and FTIR detection of pollutants has three advantages: (1) Adsorption-flocculation technology promotes the detection technology (the enrichment effect on the material surface improves the detection ability); (2) The integration of adsorption-flocculation technology and detection technology reduces the material cost and makes the operation easier; (3) FTIR detection technology endows the water treatment agent with the ability of molecular recognition and semi-quantitative detection for pollutants. Thus, it is of great significance to develop a smart water treatment material with high removal capacity and detection ability for pollutants. This study explored the feasibility of combining NOR removal method with the semi-quantitative detection method. A magnetic Cu-Ni-S/Ni foam was synthesized by in-situ loading Cu-Ni-S nanostructures on the surface of Ni foam. The novelty of this material is the combination of adsorption-flocculation technology and semi-quantitative detection technology. Batch experiments showed that Cu-Ni-S/Ni foam has a high removal rate of NOR (96.92%), wide pH adaptability (pH=4.0-10.0) and strong ion interference resistance (0.1-100 mmol/L). According to the Langmuir fitting model, the removal capacity can reach 417.4 mg/g at 25 °C, which is much higher than that of other water treatment agents reported in most studies. Characterization analysis indicated that the main removal mechanisms are surface complexation, cation bridging, electrostatic attraction, precipitation and flocculation. Transmission FTIR detection experiments showed that NOR on Cu-Ni-S/Ni foam has easily recognizable FTIR fingerprints; the intensity of characteristic peaks roughly reflects the concentration information to some extent. This semi-quantitative detection method has a wide linear range (5-100 mg/L) and a low limit of detection (4.6 mg/L). These results show that Cu-Ni-S/Ni foam has excellent removal performance and semi-quantitative detection ability of NOR molecules. This paper provides a new idea for designing and preparing multi-functional water treatment materials to achieve simultaneous removal and semi-quantitative detection of organic pollutants in water.

Keywords: adsorption-flocculation, antibiotics detection, Cu-Ni-S/Ni foam, norfloxacin

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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: Karolina Rutkowska, Hubert Pausch, Jolanta Oprzadek, Krzysztof Flisikowski

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The placenta is one of the most important organs that plays a crucial role in the fetal growth and development. Placenta dysfunction is one of the primary cause of the intrauterine growth restriction (IUGR). Cattle have the cotyledonary placenta which consists of two anatomical parts: fetal and maternal. In the case of cattle during the first months of pregnancy, it is very easy to separate maternal caruncle from fetal cotyledon tissue, easier in fact than removing an ordinary glove from one's hand. Which in fact make easier to conduct tissue-specific molecular studies. Typically, animal models for the study of IUGR are created using surgical methods and malnutrition of the pregnant mother or in the case of mice by genetic modifications. However, proposed cattle model with MIMT1Del/WT deletion is unique because it was created without any surgical methods what significantly distinguish it from the other animal models. The primary objective of the study was to identify differential expression of selected miRNAs in the placenta from normal and intrauterine growth restricted fetuses. There was examined the expression of miRNA in the fetal and maternal part of the placenta from 24 fetuses (12 samples from the fetal part of the placenta and 12 samples from maternal part of the placenta). In the study, there was done miRNAs sequencing in the placenta of MIMT1Del/WT fetuses and MIMT1WT/WT fetuses. Then, there were selected miRNAs that are involved in fetal growth and development. Analysis of miRNAs expression was conducted on ABI7500 machine. miRNAs expression was analyzed by reverse-transcription polymerase chain reaction (RT-PCR). As the reference gene was used SNORD47. The results were expressed as 2ΔΔCt: ΔΔCt = (Ctij − CtSNORD47j) − (Cti1 − CtSNORD471). Where Ctij and CtSNORD47j are the Ct values for gene i and for SNORD47 in a sample (named j); Cti1 and CtSNORD471 are the Ct values in sample 1. Differences between groups were evaluated with analysis of variance by using One-Way ANOVA. Bonferroni’s tests were used for interpretation of the data. All normalised miRNA expression values are expressed on a value of natural logarithm. The data were expressed as least squares mean with standard errors. Significance was declared when P < 0.05. The study shows that miRNAs expression depends on the part of the placenta where they origin (fetal or maternal) and on the genotype of the animal. miRNAs offer a particularly new approach to study IUGR. Corresponding tissue samples were collected according to the standard veterinary protocols according to the European Union Normative for Care and Use of Experimental Animals. All animal experiments were approved by the Animal Ethics Committee of the State Provincial Office of Southern Finland (ESAVI-2010-08583/YM-23).

Keywords: placenta, intrauterine growth restriction, miRNA, cattle

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Authors: Khalid Omari, Rene Chenier, Enrique Blondel, Ryan Ahola

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Northern Canadian coasts have vulnerable and very dynamic intertidal zones with very high tides occurring in several areas. The impact of climate change presents challenges not only for maintaining this biodiversity but also for navigation safety adaptation due to the high sediment mobility in these coastal areas. Thus, frequent mapping of shorelines and intertidal changes is of high importance. To help in quantifying the changes in these fragile ecosystems, remote sensing provides practical monitoring tools at local and regional scales. Traditional methods based on high-resolution optical sensors are often used to map intertidal areas by benefiting of the spectral response contrast of intertidal classes in visible, near and mid-infrared bands. Tidal areas are highly reflective in visible bands mainly because of the presence of fine sand deposits. However, getting a cloud-free optical data that coincide with low tides in intertidal zones in northern regions is very difficult. Alternatively, the all-weather capability and daylight-independence of the microwave remote sensing using synthetic aperture radar (SAR) can offer valuable geophysical parameters with a high frequency revisit over intertidal zones. Multi-polarization SAR parameters have been used successfully in mapping intertidal zones using incoherence target decomposition. Moreover, the crustal displacements caused by ocean tide loading may reach several centimeters that can be detected and quantified across differential interferometric synthetic aperture radar (DInSAR). Soil moisture change has a significant impact on both the coherence and the backscatter. For instance, increases in the backscatter intensity associated with low coherence is an indicator for abrupt surface changes. In this research, we present primary results obtained following our investigation of the potential of the fully polarimetric Radarsat-2 data for mapping an inter-tidal zone located on Tasiujaq on the south-west shore of Ungava Bay, Quebec. Using the repeat pass cycle of Radarsat-2, multiple seasonal fine quad (FQ14W) images are acquired over the site between 2016 and 2018. Only 8 images corresponding to low tide conditions are selected and used to build an interferometric stack of data. The observed displacements along the line of sight generated using HH and VV polarization are compared with the changes noticed using the Freeman Durden polarimetric decomposition and Touzi degree of polarization extrema. Results show the consistency of both approaches in their ability to monitor the changes in intertidal zones.

Keywords: SAR, degree of polarization, DInSAR, Freeman-Durden, polarimetry, Radarsat-2

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Authors: Patrícia Severino, Luciana Nalone, Daniele Martins, Marco Chaud, Classius Ferreira, Cristiane Bani, Ricardo Albuquerque

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Hydrogels produced with polymers have been used in the development of dressings for wound treatment and tissue revitalization. Our study on polymer nanocomposites containing silver nanoparticles shows antimicrobial activity and applications in wound healing. The effects are linked with the slow oxidation and Ag⁺ liberation to the biological environment. Furthermore, bacterial cell membrane penetration and metabolic disruption through cell cycle disarrangement also contribute to microbial cell death. The silver antimicrobial activity has been known for many years, and previous reports show that low silver concentrations are safe for human use. This work aims to develop a hydrogel using natural polymers (sodium alginate and gelatin) combined with silver nanoparticles for wound healing and with antimicrobial properties in cutaneous lesions. The hydrogel development utilized different sodium alginate and gelatin proportions (20:80, 50:50 and 80:20). The silver nanoparticles incorporation was evaluated at the concentrations of 1.0, 2.0 and 4.0 mM. The physico-chemical properties of the formulation were evaluated using ultraviolet-visible (UV-Vis) absorption spectroscopy, Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), and thermogravimetric (TG) analysis. The morphological characterization was made using transmission electron microscopy (TEM). Human fibroblast (L2929) viability assay was performed with a minimum inhibitory concentration (MIC) assessment as well as an in vivo cicatrizant test. The results suggested that sodium alginate and gelatin in the (80:20) proportion with 4 mM of AgNO₃ in the (UV-Vis) exhibited a better hydrogel formulation. The nanoparticle absorption spectra of this analysis showed a maximum band around 430 - 450 nm, which suggests a spheroidal form. The TG curve exhibited two weight loss events. DSC indicated one endothermic peak at 230-250 °C, due to sample fusion. The polymers acted as stabilizers of a nanoparticle, defining their size and shape. Human fibroblast viability assay L929 gave 105 % cell viability with a negative control, while gelatin presented 96% viability, alginate: gelatin (80:20) 96.66 %, and alginate 100.33 % viability. The sodium alginate:gelatin (80:20) exhibited significant antimicrobial activity, with minimal bacterial growth at a ratio of 1.06 mg.mL⁻¹ in Pseudomonas aeruginosa and 0.53 mg.mL⁻¹ in Staphylococcus aureus. The in vivo results showed a significant reduction in wound surface area. On the seventh day, the hydrogel-nanoparticle formulation reduced the total area of injury by 81.14 %, while control reached a 45.66 % reduction. The results suggest that silver-hydrogel nanoformulation exhibits potential for wound dressing therapeutics.

Keywords: nanocomposite, wound healing, hydrogel, silver nanoparticle

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Authors: Andrea Hernandez Hurtado

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Research on social networks (SNs) -- the interactions individuals share with others has shed important light in helping to explain differential use of variable linguistic forms, both in L1s and L2s. Nevertheless, the acquisition of nonstandard L2 Spanish in the Region of Murcia, Spain, and how learners interact with other speakers while sojourning there have received little attention. Murcian Spanish (MuSp) was widely influenced by Panocho, a divergent evolution of Hispanic Latin, and differs from the more standard Peninsular Spanish (StSp) in phonology, morphology, and lexicon. For instance, speakers from this area will most likely palatalize diminutive endings, producing animalico [̩a.ni.ma.ˈli.ko] instead of animalito [̩a.ni.ma.ˈli.to] ‘little animal’. Because L1 speakers of the area produce and prefer salient regional lexicon and morphology (particularly the palatalized diminutive -ico) in their speech, the current research focuses on how international residents in the Region of Murcia use Spanish: (1) whether or not they acquire (perceptively and/or productively) any of the salient regional features of MuSp, and (2) how their SNs explain such acquisition. This study triangulates across three tasks -recognition, production, and preference- addressing both lexicon and morphology, with each task specifically created for the investigation of MuSp features. Among other variables, the effects of L1, residence, and identity are considered. As an ongoing dissertation research, data are currently being gathered through an online questionnaire. So far, 7 participants from multiple nationalities have completed the survey, although a minimum of 25 are expected to be included in the coming months. Preliminary results revealed that MuSp lexicon and morphology were successfully recognized by participants (p<.001). In terms of regional lexicon production (10.0%) and preference (47.5%), although participants showed higher percentages of StSp, results showed that international residents become aware of stigmatized lexicon and may incorporate it into their language use. Similarly, palatalized diminutives (production 14.2%, preference 19.0%) were present in their responses. The Social Network Analysis provided information about participants’ relationships with their interactants, as well as among them. Results indicated that, generally, when residents were more immersed in the culture (i.e., had more Murcian alters) they produced and preferred more regional features. This project contributes to the knowledge of language variation acquisition in L2 speakers, focusing on a stigmatized Spanish dialect and exploring how stigmatized varieties may affect L2 development. Results will show how L2 Spanish speakers’ language is affected by their stay in Murcia. This, in turn, will shed light on the role of SNs in language acquisition, the acquisition of understudied and marginalized varieties, and the role of immersion on language acquisition. As the first systematic account on the acquisition of L2 Spanish lexicon and morphology in the Region of Murcia, it lays important groundwork for further research on the connection between SNs and the acquisition of regional variants, applicable to Murcia and beyond.

Keywords: international residents, L2 Spanish, lexicon, morphology, nonstandard language acquisition, social networks

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Authors: Bishnupriya Sahoo, Prasad K. Bhaskaran

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Tropical cyclone is one among the worst natural hazards that results in a trail of destruction causing enormous damage to life, property, and coastal infrastructures. In a global perspective, the Indian Ocean is considered as one of the cyclone prone basins in the world. Specifically, the frequency of cyclogenesis in the Bay of Bengal is higher compared to the Arabian Sea. Out of the four maritime states in the East coast of India, Odisha is highly susceptible to tropical cyclone landfall. Historical records clearly decipher the fact that the frequency of cyclones have reduced in this basin. However, in the recent decades, the intensity and size of tropical cyclones have increased. This is a matter of concern as the risk and vulnerability level of Odisha coast exposed to high wind speed and gusts during cyclone landfall have increased. In this context, there is a need to assess and evaluate the severity of coastal risk, area of exposure under risk, and associated vulnerability with a higher dimension in a multi-risk perspective. Changing climate can result in the emergence of a new hazard and vulnerability over a region with differential spatial and socio-economic impact. Hence there is a need to have coastal vulnerability projections in a changing climate scenario. With this motivation, the present study attempts to estimate the destructiveness of tropical cyclones based on Power Dissipation Index (PDI) for those cyclones that made landfall along Odisha coast that exhibits an increasing trend based on historical data. The study also covers the futuristic scenarios of integral coastal vulnerability based on the trends in PDI for the Odisha coast. This study considers 11 essential and important parameters; the cyclone intensity, storm surge, onshore inundation, mean tidal range, continental shelf slope, topo-graphic elevation onshore, rate of shoreline change, maximum wave height, relative sea level rise, rainfall distribution, and coastal geomorphology. The study signifies that over a decadal scale, the coastal vulnerability index (CVI) depends largely on the incremental change in variables such as cyclone intensity, storm surge, and associated inundation. In addition, the study also performs a critical analysis on the modulation of PDI on storm surge and inundation characteristics for the entire coastal belt of Odisha State. Interestingly, the study brings to light that a linear correlation exists between the storm-tide with PDI. The trend analysis of PDI and its projection for coastal Odisha have direct practical applications in effective coastal zone management and vulnerability assessment.

Keywords: Bay of Bengal, coastal vulnerability index, power dissipation index, tropical cyclone

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Authors: Simona Perga, Chiara Beltramo, Floriana Fruscione, Isabella Martini, Federica Cavallo, Federica Riccardo, Paolo Buracco, Selina Iussich, Elisabetta Razzuoli, Katia Varello, Lorella Maniscalco, Elena Bozzetta, Angelo Ferrari, Paola Modesto

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Introduction: Human and canine melanoma have common clinical, histologic characteristics making dogs a good model for comparative oncology. The identification of specific genes and a better understanding of the genetic landscape, signaling pathways, and tumor–microenvironmental interactions involved in the cancer onset and progression is essential for the development of therapeutic strategies against this tumor in both species. In the present study, the differential expression of genes in spontaneously occurring canine melanoma and in paired normal tissue was investigated by targeted RNAseq. Material and Methods: Total RNA was extracted from 17 canine malignant melanoma (CMM) samples and from five paired normal tissues stored in RNA-later. In order to capture the greater genetic variability, gene expression analysis was carried out using two panels (Qiagen): Human Immuno-Oncology (HIO) and Mouse-Immuno-Oncology (MIO) and the miSeq platform (Illumina). These kits allow the detection of the expression profile of 990 genes involved in the immune response against tumors in humans and mice. The data were analyzed through the CLCbio Genomics Workbench (Qiagen) software using the Canis lupus familiaris genome as a reference. Data analysis were carried out both comparing the biologic group (tumoral vs. healthy tissues) and comparing neoplastic tissue vs. paired healthy tissue; a Fold Change greater than two and a p-value less than 0.05 were set as the threshold to select interesting genes. Results and Discussion: Using HIO 63, down-regulated genes were detected; 13 of those were also down-regulated comparing neoplastic sample vs. paired healthy tissue. Eighteen genes were up-regulated, 14 of those were also down-regulated comparing neoplastic sample vs. paired healthy tissue. Using the MIO, 35 down regulated-genes were detected; only four of these were down-regulated, also comparing neoplastic sample vs. paired healthy tissue. Twelve genes were up-regulated in both types of analysis. Considering the two kits, the greatest variation in Fold Change was in up-regulated genes. Dogs displayed a greater genetic homology with humans than mice; moreover, the results have shown that the two kits are able to detect different genes. Most of these genes have specific cellular functions or belong to some enzymatic categories; some have already been described to be correlated to human melanoma and confirm the validity of the dog as a model for the study of molecular aspects of human melanoma.

Keywords: animal model, canine melanoma, gene expression, spontaneous tumors, targeted RNAseq

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Authors: Kaleem Ahmed, Jamal A. Khan

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Grouping patterns, habitat use, and overlap studies were conducted on five sympatric ungulate species sambar (Cervus unicolor), chital (Axis axis), muntjac (Muntiacus muntjac), goral (Nemorhaedus goral), and serow (Capricornis sumatraensis) in the Dabka watershed area within Indian West Himalayan range. Data on age, sex composition, group size, and various ecological and topographical factors governing the presence/absence of species within the study area were collected using a 250 km of a trail walk, 95 permanent circular plots of 10 m radius, and 3 vantage points with 58 scannings. The highest mean group size was recorded for chital (6.35 ± 0.50), followed by sambar (1.35 ± 0.10), goral (1.25 ±0.63), muntjac (1.12 ± 0.05), and serow (1.00 ± 0.00). Grouping pattern significantly varied among sympatric species (F = 85.10, df. = 6, P = 0.000). The highest mean pellet group density (/ha ± SE) was recorded for sambar (41.56 ± 3.51), followed by goral (23.31 ± 3.45), chital (19.21 ± 3.51), muntjac (7.43 ± 1.21), and serow (1.02 ± 0.10). Two-way variance analysis showed a significant difference in the density of the pellet group of all ungulate species across different study area habitats (F = 6.38, df = 4, P = 0.027). The availability-utilization (AU) analysis reveals that goral was mostly sighted in steep slopes, preferred > 2100 m altitudinal range with low shrub understory, avoided dense forest, and relatively more southern aspects were used. Chital had used a wide range of tree and shrub coverings with a preference towards moderate cover range (26-50%), preferred areas with low slope category ( < 25), avoided areas of high altitude > 900 m. Sambar avoided less tree cover (0-25), preferred slope category (26-500), altitudes between 1600-2100 m, and preferred dense forest with northern aspects. Muntjac used all elevation ranges in the study area with a preference towards the dense forest and northern aspects. Serow preferred high tree cover > 75%, avoided low shrub cover (0-25%), preferred high shrub cover 51-75%, utilized higher elevation > 2100 m, avoided low elevation range and northern aspects. All species occupied similar habitat types, forest or scrub, except for the goral, which preferred open spaces. Between muntjac and sambar, the highest overlap was found (65%), and there was no overlap between chital and serow, chital and goral. Aspect, slope, altitude, and vegetation characteristics were found to be important factors for the overlap of ungulate sympatric species. One major reason for their ecological separation at the fine-scale level is the differential use of altitude by ungulates in the present study. This is confirmed by the avoidance by chital of altitudes > 900 m and serow of < 2100 m.

Keywords: altitude, grouping pattern, Himalayas, overlap, ungulates

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Authors: Ladislav Écsi, Roland Jančo

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Contemporary multiplicative plasticity models assume that the body's intermediate configuration consists of an assembly of locally unloaded neighbourhoods of material particles that cannot be reassembled together to give the overall stress-free intermediate configuration since the neighbourhoods are not necessarily compatible with each other. As a result, the plastic deformation gradient, an inelastic component in the multiplicative split of the deformation gradient, cannot be integrated, and the material particle moves from the initial configuration to the intermediate configuration without a position vector and a plastic displacement field when plastic flow occurs. Such behaviour is incompatible with the continuum theory and the continuum physics of elastoplastic deformations, and the related material models can hardly be denoted as truly continuum-based. The paper presents a proper continuum-based reformulation of current problems in finite strain plasticity. It will be shown that the incompatible neighbourhoods in real material are modelled by the product of the plastic multiplier and the yield surface normal when the plastic flow is defined in the current configuration. The incompatible plastic factor can also model the neighbourhoods as the solution of the system of differential equations whose coefficient matrix is the above product when the plastic flow is defined in the intermediate configuration. The incompatible tensors replace the compatible spatial plastic velocity gradient in the former case or the compatible plastic deformation gradient in the latter case in the definition of the plastic flow rule. They act as local imperfections but have the same position vector as the compatible plastic velocity gradient or the compatible plastic deformation gradient in the definitions of the related plastic flow rules. The unstressed intermediate configuration, the unloaded configuration after the plastic flow, where the residual stresses have been removed, can always be calculated by integrating either the compatible plastic velocity gradient or the compatible plastic deformation gradient. However, the corresponding plastic displacement field becomes permanent with both elastic and plastic components. The residual strains and stresses originate from the difference between the compatible plastic/permanent displacement field gradient and the prescribed incompatible second-order tensor characterizing the plastic flow in the definition of the plastic flow rule, which becomes an assignment statement rather than an equilibrium equation. The above also means that the elastic and plastic factors in the multiplicative split of the deformation gradient are, in reality, gradients and that there is no problem with the continuum physics of elastoplastic deformations. The formulation is demonstrated in a numerical example using the regularized Mooney-Rivlin material model and modified equilibrium statements where the intermediate configuration is calculated, whose analysis results are compared with the identical material model using the current equilibrium statements. The advantages and disadvantages of each formulation, including their relationship with multiplicative plasticity, are also discussed.

Keywords: finite strain plasticity, continuum formulation, regularized Mooney-Rivlin material model, compatibility

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Authors: E. Obreque-Slier, J. Laqui-Estaña, A. Peña-Neira, M. Medel-Marabolí

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Wine is an important source of polyphenols. Red wines show important concentrations of nonflavonoid (gallic acid, ellagic acid, caffeic acid and coumaric acid) and flavonoid compounds [(+)-catechin, (-)-epicatechin, (+)-gallocatechin and (-)-epigallocatechin]. However, a significant variability in the quantitative and qualitative distribution of chemical constituents in wine has to be expected depending on an array of important factors, such as the varietal differences of Vitis vinifera and cultural practices. It has observed that Carménère grapes present a differential composition and evolution of phenolic compounds when compared to other varieties and specifically with Cabernet Sauvignon grapes. Likewise, among the cultural practices, the aging in contact with oak wood is a high relevance factor. Then, the extraction of different polyphenolic compounds from oak wood into wine during its ageing process produces both qualitative and quantitative changes. Recently, many new techniques have been introduced in winemaking. One of these involves putting new pieces of wood (oak chips or inner staves) into inert containers. It offers some distinct and previously unavailable flavour advantages, as well as new options in wine handling. To our best knowledge, there is not information about the behaviour of Carménère wines (Chilean emblematic cultivar) in contact with oak wood. In addition, the effect of aging time and wood product (barrels, chips or staves) on the phenolic composition in Carménère wines has not been studied. This study aims at characterizing the condensed and hydrolyzable tannins from Carménère wines during the aging with staves, chips and barrels from French oak wood. The experimental design was completely randomized with two independent assays: aging time (0-12 month) and different formats of wood (barrel, chips and staves). The wines were characterized by spectrophotometric (total tannins and fractionation of proanthocyanidins into monomers, oligomers and polymers) and HPLC-DAD (ellagitannins) analysis. The wines in contact with different products of oak wood showed a similar content of total tannins during the study, while the control wine (without oak wood) presented a lower content of these compounds. In addition, it was observed that the polymeric proanthocyanidin fraction was the most abundant, while the monomeric fraction was the less abundant fraction in all treatments in two sample. However, significative differences in each fractions were observed between wines in contact from barrel, chips, and staves in two sample dates. Finally, the wine from barrels presented the highest content of the ellagitannins from the fourth to the last sample date. In conclusion, the use of alternative formats of oak wood affects the chemical composition of wines during aging, and these enological products are an interesting alternative to contribute with tannins to wine.

Keywords: enological inputs, oak wood aging, polyphenols, red wine

Procedia PDF Downloads 141

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 151