Search results for: liquid oxygen

Authors: Subhojyoti Chatterjee, Peter J. Mahon, Feng Wang

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Resveratrol (RvL), a phenolic compound, is a key ingredient in wine and tomatoes that has been studied over the years because of its important bioactivities such as anti-oxidant, anti-aging and antimicrobial properties. Out of the two isomeric forms of resveratrol i.e. trans and cis, the health benefit is primarily associated with the trans form. Thus, studying the structural properties of the isomers will not only provide an insight into understanding the RvL isomers, but will also help in designing parameters for differentiation in order to achieve 99.9% purity of trans-RvL. In the present study, density function theory (DFT) study is conducted, using the B3LYP/6-311++G** model to explore the through bond and through space intramolecular interactions. Properties such as vibrational spectroscopy (IR and Raman), nuclear magnetic resonance (NMR) spectra, excess orbital energy spectrum (EOES), energy based decomposition analyses (EDA) and Fukui function are calculated. It is discovered that the structure of trans-RvL, although it is C1 non-planar, the backbone non-H atoms are nearly in the same plane; whereas the cis-RvL consists of two major planes of R1 and R2 that are not in the same plane. The absence of planarity gives rise to a H-bond of 2.67Å in cis-RvL. Rotation of the C(5)-C(8) single bond in trans-RvL produces higher energy barriers since it may break the (planar) entire conjugated structure; while such rotation in cis-RvL produces multiple minima and maxima depending on the positions of the rings. The calculated FT-IR spectrum shows very different spectral features for trans and cis-RvL in the region 900 – 1500 cm-1, where the spectral peaks at 1138-1158 cm-1 are split in cis-RvL compared to a single peak at 1165 cm-1 in trans-RvL. In the Raman spectra, there is significant enhancement of cis-RvL in the region above 3000cm-1. Further, the carbon chemical environment (13C NMR) of the RvL molecule exhibit a larger chemical shift for cis-RvL compared to trans-RvL (Δδ = 8.18 ppm) for the carbon atom C(11), indicating that the chemical environment of the C group in cis-RvL is more diverse than its other isomer. The energy gap between highest occupied molecular orbital (HOMO) and the lowest occupied molecular orbital (LUMO) is 3.95 eV for trans and 4.35 eV for cis-RvL. A more detailed inspection using the recently developed EOES revealed that most of the large energy differences i.e. Δεcis-trans > ±0.30 eV, in their orbitals are contributed from the outer valence shell. They are MO60 (HOMO), MO52-55 and MO46. The active sites that has been captured by Fukui function (f + > 0.08) are associated with the stilbene C=C bond of RvL and cis-RvL is more active at these sites than in trans-RvL, as cis orientation breaks the large conjugation of trans-RvL so that the hydroxyl oxygen’s are more active in cis-RvL. Finally, EDA highlights the interaction energy (ΔEInt) of the phenolic compound, where trans is preferred over the cis-RvL (ΔΔEi = -4.35 kcal.mol-1) isomer. Thus, these quantum mechanics results could help in unwinding the diversified beneficial activities associated with resveratrol.

Keywords: resveratrol, FT-IR, Raman, NMR, excess orbital energy spectrum, energy decomposition analysis, Fukui function

Procedia PDF Downloads 180

Authors: Y. Mateyshina, A.Ulihin, N.Uvarov

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Electrolytes with different type of charge carrier can find widely application in different using, e.g. sensors, electrochemical equipments, batteries and others. One of important components ensuring stable functioning of the equipment is electrolyte. Electrolyte has to be characterized by high conductivity, thermal stability, and wide electrochemical window. In addition to many advantageous characteristic for liquid electrolytes, the solid state electrolytes have good mechanical stability, wide working range of temperature range. Thus search of new system of solid electrolytes with high conductivity is an actual task of solid state chemistry. Families of alkali perchlorates and nitrates have been investigated by us earlier. In literature data about transport properties of alkali nitrites are absent. Nevertheless, alkali nitrites MeNO2 (Me= Li+, Na+, K+, Rb+ and Cs+), except for the lithium salt, have high-temperature phases with crystal structure of the NaCl-type. High-temperature phases of nitrites are orientationally disordered, i.e. non-spherical anions are reoriented over several equivalents directions in the crystal lattice. Pure lithium nitrite LiNO2 is characterized by ionic conductivity near 10-4 S/cm at 180°C and more stable as compared with lithium nitrate and can be used as a component for synthesis of composite electrolytes. In this work composite solid electrolytes in the binary system LiNO2 - A (A= MgO, -Al2O3, Fe2O3, CeO2, SnO2, SiO2) were synthesized and their structural, thermodynamic and electrical properties investigated. Alkali nitrite was obtained by exchange reaction from water solutions of barium nitrite and alkali sulfate. The synthesized salt was characterized by X-ray powder diffraction technique using D8 Advance X-Ray Diffractometer with Cu K radiation. Using thermal analysis, the temperatures of dehydration and thermal decomposition of salt were determined.. The conductivity was measured using a two electrode scheme in a forevacuum (6.7 Pa) with an HP 4284A (Precision LCR meter) in a frequency range 20 Hz < ν < 1 MHz. Solid composite electrolytes LiNO2 - A A (A= MgO, -Al2O3, Fe2O3, CeO2, SnO2, SiO2) have been synthesized by mixing of preliminary dehydrated components followed by sintering at 250°C. In the series of nitrite of alkaline metals Li+-Cs+, the conductivity varies not monotonically with increasing radius of cation. The minimum conductivity is observed for KNO2; however, with further increase in the radius of cation in the series, the conductivity tends to increase. The work was supported by the Russian Foundation for Basic research, grant #14-03-31442.

Keywords: conductivity, alkali nitrites, composite electrolytes, transport properties

Procedia PDF Downloads 299

Authors: Lisa Shambare, Jean Mulopo, Sehliselo Ndlovu

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One of the major challenges of sustainable development is promoting an industry which is both ecologically durable and economically viable. This requires processes that are material and energy efficient whilst also being able to limit the production of waste and toxic effluents through effective methods of process synthesis and intensification. In South Africa and globally, both miniaturisation and technological advances have substantially increased the amount of electronic wastes (e-waste) generated annually. Vast amounts of e-waste are being generated yearly with only a minute quantity being recycled officially. The passion for electronic devices cannot ignore the scarcity and cost of mining the noble metal resources which contribute significantly to the efficiency of most electronic devices. It has hence become imperative especially in an African context that sustainable strategies which are environmentally friendly be developed for recycling of the noble metals from e-waste. This paper investigates the recovery of gold, silver and palladium from electronic wastes, which consists of a vast array of metals, using ionic liquids which have the potential of reducing the gaseous and aqueous emissions associated with existing hydrometallurgical and pyrometallurgical technologies while also maintaining the economy of the overall recycling scheme through solvent recovery. The ionic liquids 1-butyl-3-methyl imidazolium hydrogen sulphate (BmimHSO4) which behaves like a protic acid and was used in the present research for the selective leaching of gold and silver from e-waste. Different concentrations of the aqueous ionic liquid were used in the experiments ranging from 10% to 50%. Thiourea was used as the complexing agent in the investigation with Fe3+ as the oxidant. The pH of the reaction was maintained in the range of 0.8 to 1.5. The preliminary investigations conducted were successful in the leaching of silver and palladium at room temperature with optimum results being at 48hrs. The leaching results could not be explained because of the leaching of palladium with the absence of gold. Hence a conclusion could not be drawn and there was the need for further experiments to be run. The leaching of palladium was carried out with hydrogen peroxide as oxidant and 1-butyl-3-methyl imidazolium chloride (BmimCl) as the solvent. The experiments at carried out at a temperature of 60 degrees celsius and a very low pH. The chloride ion was used to complex with palladium metal. From the preliminary results, it could be concluded that pretreatment of the treatment e-waste was necessary to improve the efficiency of the metal recovery process. A conclusion could not be drawn for the leaching experiments.

Keywords: BmimCl, BmimHSO4, gold, palladium, silver

Procedia PDF Downloads 266

Authors: A. B. Moldes, X. Vecino, L. Rodriguez-López, J. M. Dominguez, J. M. Cruz

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The concept of the circular economy is focus on the importance of providing goods and services sustainably. Thus, in a future it will be necessary to respond to the environmental contamination and to the use of renewables substrates by moving to a more restorative economic system that drives towards the utilization and revalorization of residues to obtain valuable products. During its evolution our industrial economy has hardly moved through one major characteristic, established in the early days of industrialization, based on a linear model of resource consumption. However, this industrial consumption system will not be maintained during long time. On the other hand, there are many industries, like the corn milling industry, that although does not consume high amount of non renewable substrates, they produce valuable streams that treated accurately, they could provide additional, economical and environmental, benefits by the extraction of interesting commercial renewable products, that can replace some of the substances obtained by chemical synthesis, using non renewable substrates. From this point of view, the use of streams from corn milling industry to obtain surface-active compounds will decrease the utilization of non-renewables sources for obtaining this kind of compounds, contributing to a circular and global economy. However, the success of the circular economy depends on the interest of the industrial sectors in the revalorization of their streams by developing relevant and new business models. Thus, it is necessary to invest in the research of new alternatives that reduce the consumption of non-renewable substrates. In this study is proposed the utilization of a corn milling industry stream to obtain an extract with surfactant capacity. Once the biosurfactant is extracted, the corn milling stream can be commercialized as nutritional media in biotechnological process or as animal feed supplement. Usually this stream is combined with other ingredients obtaining a product namely corn gluten feed or may be sold separately as a liquid protein source for beef and dairy feeding, or as a nutritional pellet binder. Following the productive scheme proposed in this work, the corn milling industry will obtain a biosurfactant extract that could be incorporated in its productive process replacing those chemical detergents, used in some point of its productive chain, or it could be commercialized as a new product of the corn manufacture. The biosurfactants obtained from corn milling industry could replace the chemical surfactants in many formulations, and uses, and it supposes an example of the potential that many industrial streams could offer for obtaining valuable products when they are manage properly.

Keywords: biosurfactantes, circular economy, corn, sustainability

Procedia PDF Downloads 243

Authors: K. Mondal, S. Talapatra, M. Terrones, S. Pokhrel, C. Frizzel, B. Sumpter, V. Meunier, A. L. Elias

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Worldwide energy independence is reliant on the ability to leverage locally available resources for fuel production. Recently, syngas produced through gasification of carbonaceous materials provided a gateway to a host of processes for the production of various chemicals including transportation fuels. The basis of the production of gasoline and diesel-like fuels is the Fischer Tropsch Synthesis (FTS) process: A catalyzed chemical reaction that converts a mixture of carbon monoxide (CO) and hydrogen (H₂) into long chain hydrocarbons. Until now, it has been argued that only transition metal catalysts (usually Co or Fe) are active toward the CO hydrogenation and subsequent chain growth in the presence of hydrogen. In this paper, we demonstrate that carbon nanotube (CNT) surfaces are also capable of hydro-deoxygenating CO and producing long chain hydrocarbons similar to that obtained through the FTS but with orders of magnitude higher conversion efficiencies than the present state-of-the-art FTS catalysts. We have used advanced experimental tools such as XPS and microscopy techniques to characterize CNTs and identify C-O functional groups as the active sites for the enhanced catalytic activity. Furthermore, we have conducted quantum Density Functional Theory (DFT) calculations to confirm that C-O groups (inherent on CNT surfaces) could indeed be catalytically active towards reduction of CO with H₂, and capable of sustaining chain growth. The DFT calculations have shown that the kinetically and thermodynamically feasible route for CO insertion and hydro-deoxygenation are different from that on transition metal catalysts. Experiments on a continuous flow tubular reactor with various nearly metal-free CNTs have been carried out and the products have been analyzed. CNTs functionalized by various methods were evaluated under different conditions. Reactor tests revealed that the hydrogen pre-treatment reduced the activity of the catalysts to negligible levels. Without the pretreatment, the activity for CO conversion as found to be 7 µmol CO/g CNT/s. The O-functionalized samples showed very activities greater than 85 µmol CO/g CNT/s with nearly 100% conversion. Analyses show that CO hydro-deoxygenation occurred at the C-O/O-H functional groups. It was found that while the products were similar to FT products, differences in selectivities were observed which, in turn, was a result of a different catalytic mechanism. These findings now open a new paradigm for CNT-based hydrogenation catalysts and constitute a defining point for obtaining clean, earth abundant, alternative fuels through the use of efficient and renewable catalyst.

Keywords: CNT, CO Hydrodeoxygenation, DFT, liquid fuels, XPS, XTL

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Authors: Leonardo Parra, Daniel Martínez, Jorge Pizarro, Fernando Ortega, Manuel Chacón-Fuentes, Andrés Quiroz

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Control of Dalaca pallens or blackworms, one of the most important hypogeous pest in grassland in southern Chile, is based on the use of broad-spectrum insecticides such as organophosphates and pyrethroids. However, the rapid development of insecticide resistance in field populations of this insect and public concern over the environmental impact of these insecticides has resulted in the search for other control methods. Specifically, the use of endophyte fungi for controlling pest has emerged as an interesting and promising strategy. Endophytes from ryegrass (Lolium perenne), establish a biotrophic relationship with the host, defined as mutualistic symbiosis. The plant-fungi association produces alkaloids where peramine is the main toxic substance against Listronotus bonariensis, the most important epigean pest of ryegrass. Nevertheless, the effect of peramina on others pest insects, such as D. pallens, to our knowledge has not been studied, and also its possible metabolization in the body of the larvae. Therefore, we addressed the following research question: Do larvae of D. pallens store peramine after consumption of ryegrass endophyte infected (E+)? For this, specimens of blackworms were fed with ryegrass plant of seven experimental lines and one commercial cultivar endophyte free (E-) sown at the Instituto de Investigaciones Agropecuarias Carillanca (Vilcún, Chile). Once the feeding period was over, ten larvae of each treatment were examined. Individuals were dissected, and their gut was removed to exclude any influence of remaining material. The rest of the larva's body was dried at 60°C by 24-48 h and ground into a fine powder using a mortar. 25 mg of dry powder was transferred to a microcentrifuge tube and extracted in 1 mL of a mixture of methanol:water:formic acid. Then, the samples were centrifuged at 16,000 rpm for 3 min, and the supernatant was colected and injected in the liquid chromatography of high resolution (HPLC). The results confirmed the presence of peramine in the larva's body of D. pallens. The insects that fed the experimental lines LQE-2 and LQE-6 were those where peramine was present in high proportion (0.205 and 0.199 ppm, respectively); while LQE-7 and LQE-3 obtained the lowest concentrations of the alkaloid (0.047 and 0.053 ppm, respectively). Peramine was not detected in the insects when the control cultivar Jumbo (E-) was tested. These results evidenced the storage and metabolism of peramine during consumption of the larvae. However, the effect of this alkaloid present in 'future ryegrass cultivars' (LQE-2 and LQE-6) on the performance and survival of blackworms must be studied and confirmed experimentally.

Keywords: blackworms, HPLC, alkaloid, pest

Procedia PDF Downloads 282

Authors: Chalermporn Jindapeng

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The main objective of the study of the suitable operating conditions of hot water generators combined with central air package units: a case study of Tipco Building Group was to analyze the suitable operating conditions and energy-related costs in each operating condition of hot water generators combined with central air package units which resulted in water-cooled packages. Thermal energy from vapor form refrigerants at high pressures and temperatures was exchanged with thermal energy of the water in the swimming pool that required suitable temperature control for users with the use of plate heat exchangers before refrigerants could enter the condenser in its function to change the status of vapor form refrigerants at high pressures and temperatures to liquid form at high pressures and temperatures. Thus, if this was used to replace heat pumps it could reduce the electrical energy that was used to make hot water and reduce the cost of the electrical energy of air package units including the increased efficacy of air package units. Of the analyses of the suitable operating conditions by means of the study of the elements involved with actual measurements from the system that had been installed at the Tipco Building Group hot water generators were combined with air package units which resulted in water-cooled packages with a cooling capacity of 75 tonnes. Plate heat exchangers were used in the transfer of thermal energy from refrigerants to one set of water with a heat exchanger area of 1.5 m² which was used to increase the temperature of swimming pool water that has a capacity of 240 m³. From experimental results, it was discovered after continuous temperature measurements in the swimming pool every 15 minutes that swimming pool water temperature increased by 0.78 ⁰C 0.75 ⁰C 0.74 ⁰C and 0.71 ⁰C. The rates of flow of hot water through the heat exchangers were equal to 14, 16, 18 and 20 litres per minute respectively where the swimming pool water temperature was at a constant value and when the rate of flow of hot water increased this caused hot water temperatures to decrease and the coefficient of performance of the air package units to increase from 5.9 to 6.3, 6.7, 6.9 and 7.6 while the rates of flow of hot water were equal to 14, 16, 18 and 20 litres per minute, respectively. As for the cooling systems, there were no changes and the system cooling functions were normal as the cooling systems were able to continuously transfer incoming heat for the swimming pool water which resulted in a constant pressure in the cooling system that allowed its cooling functions to work normally.

Keywords: central air package units, heat exchange, hot water generators, swimming pool

Procedia PDF Downloads 237

Authors: M. S. Alatas, H. D. Umucalilar

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SARA is a common and serious metabolic disorder in early lactation in dairy cattle and in finishing beef cattle, caused by diets with high inclusion of cereal grain. This experiment was performed to determine the efficacy of Megasphaera elsdenii, a major lactate-utilizing bacterium in prevention/treatment of SARA in vivo. In vivo experimentation, it was used eight ruminally cannulated rams and it was applied the rapid adaptation with the mixture of grain based on wheat (%80 wheat, %20 barley) and barley (%80 barley, %20 wheat). During the systematic adaptation, it was followed the probability of SARA formation by being measured the rumen pH with two hours intervals after and before feeding. After being evaluated the data, it was determined the ruminal pH ranged from 5,2-5,6 on the condition of feeding with 60 percentage of grain mixture based on barley and wheat, that assured the definite form of subacute acidosis. In four days SARA period, M. elsdenii (1010 cfu ml-1) was inoculated during the first two days. During the SARA period, it was observed the decrease of feed intake with M. elsdenii inoculation. Inoculation of M. elsdenii was caused to differentiation of rumen pH (P < 0,0001), while it was found the pH level approximately 5,55 in animals applied the inoculation, it was 5,63 pH in other animals. It was observed that total VFA with the bacterium inoculation tended to change in terms of grain feed (P < 0,07). It increased with the effect of total VFA inoculation in barley based diet, but it was more stabilized in wheat based diet. Bacterium inoculation increased the ratio of propionic acid (18,33%-21,38%) but it caused to decrease the butyric acid, and acetic/propionic acid. During the rapid adaptation, the concentration of lactic acid in the rumen liquid increased depending upon grain level (P<0,0001). On the other hand bacterium inoculation did not have an effect on concentration of lactic acid. M. elsdenii inoculation did not affect ruminal ammonia concentration. In the group that did not apply inoculation, the level of ruminal ammonia concentration was higher than the others applied inoculation. M. elsdenii inoculation did not changed protozoa count in barley-based diet whereas it decreased in wheat-based diet. In the period of SARA, it was observed that the level of blood glucose, lactate and hematocrit increased greatly after inoculation (P < 0,0001). When it is generally evaluated, it is seen that M. elsdenii inoculation has not a positive impact on rumen parameters. Therefore, to reveal the full impact of the inoculation with different strains, feedstuffs and animal groups, further research is required.

Keywords: In vivo, Subactute ruminal acidosis, Megasphaera elsdenii, Rumen fermentation

Procedia PDF Downloads 617

Authors: Vladimir Messerle, Alexandr Ustimenko, Oleg Lavrichshev

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This work presents plasma technology for solid fuel ignition and combustion. Plasma activation promotes more effective and environmentally friendly low-rank coal ignition and combustion. To realise this technology at coal fired power plants plasma-fuel systems (PFS) were developed. PFS improve efficiency of power coals combustion and decrease harmful emission. PFS is pulverized coal burner equipped with arc plasma torch. Plasma torch is the main element of the PFS. Plasma forming gas is air. It is blown through the electrodes forming plasma flame. Temperature of this flame is varied from 5000 to 6000 K. Plasma torch power is varied from 100 to 350 kW and geometrical sizes are the following: the height is 0.4-0.5 m and diameter is 0.2-0.25 m. The base of the PFS technology is plasma thermochemical preparation of coal for burning. It consists of heating of the pulverized coal and air mixture by arc plasma up to temperature of coal volatiles release and char carbon partial gasification. In the PFS coal-air mixture is deficient in oxygen and carbon is oxidised mainly to carbon monoxide. As a result, at the PFS exit a highly reactive mixture is formed of combustible gases and partially burned char particles, together with products of combustion, while the temperature of the gaseous mixture is around 1300 K. Further mixing with the air promotes intensive ignition and complete combustion of the prepared fuel. PFS have been tested for boilers start up and pulverized coal flame stabilization in different countries at power boilers of 75 to 950 t/h steam productivity. They were equipped with different types of pulverized coal burners (direct flow, muffle and swirl burners). At PFS testing power coals of all ranks (lignite, bituminous, anthracite and their mixtures) were incinerated. Volatile content of them was from 4 to 50%, ash varied from 15 to 48% and heat of combustion was from 1600 to 6000 kcal/kg. To show the advantages of the plasma technology before conventional technologies of coal combustion numerical investigation of plasma ignition, gasification and thermochemical preparation of a pulverized coal for incineration in an experimental furnace with heat capacity of 3 MW was fulfilled. Two computer-codes were used for the research. The computer simulation experiments were conducted for low-rank bituminous coal of 44% ash content. The boiler operation has been studied at the conventional mode of combustion and with arc plasma activation of coal combustion. The experiments and computer simulation showed ecological efficiency of the plasma technology. When a plasma torch operates in the regime of plasma stabilization of pulverized coal flame, NOX emission is reduced twice and amount of unburned carbon is reduced four times. Acknowledgement: This work was supported by Ministry of Education and Science of the Republic of Kazakhstan and Ministry of Education and Science of the Russian Federation (Agreement on grant No. 14.613.21.0005, project RFMEFI61314X0005).

Keywords: coal, ignition, plasma-fuel system, plasma torch, thermal power plant

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Authors: W. Baumgartner, M. Welti, N. Hild, S. C. Hess, W. J. Stark, G. Meier Bürgisser, P. Giovanoli, J. Buschmann

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Perfusion bioreactors are used to solve problems in tissue engineering in terms of sufficient nutrient and oxygen supply. Such problems especially occur in critical size grafts because vascularization is often too slow after implantation ending up in necrotic cores. Biominerizable and biocompatible nanocomposite materials are attractive and suitable scaffold materials for bone tissue engineering because they offer mineral components in organic carriers – mimicking natural bone tissue. In addition, human adipose derived stem cells (ASCs) can potentially be used to increase bone healing as they are capable of differentiating towards osteoblasts or endothelial cells among others. In the present study, electrospun nanocomposite disks of poly-lactic-co-glycolic acid and amorphous calcium phosphate nanoparticles (PLGA/a-CaP) were seeded with human ASCs and eight disks were stacked in a bioreactor running with normal culture medium (no differentiation supplements). Under continuous perfusion and uniaxial cyclic compression, load-displacement curves as a function of time were assessed. Stiffness and energy dissipation were recorded. Moreover, stem cell densities in the layers of the piled scaffold were determined as well as their morphologies and differentiation status (endothelial cell differentiation, chondrogenesis and osteogenesis). While the stiffness of the cell free constructs increased over time caused by the transformation of the a-CaP nanoparticles into flake-like apatite, ASC-seeded constructs showed a constant stiffness. Stem cell density gradients were histologically determined with a linear increase in the flow direction from the bottom to the top of the 3.5 mm high pile (r2 > 0.95). Cell morphology was influenced by the flow rate, with stem cells getting more roundish at higher flow rates. Less than 1 % osteogenesis was found upon osteopontin immunostaining at the end of the experiment (9 days), while no endothelial cell differentiation and no chondrogenesis was triggered under these conditions. All ASCs had mainly remained in their original pluripotent status within this time frame. In summary, we have fabricated a critical size bone graft based on a biominerizable bone-biomimetic nanocomposite with preserved stiffness when seeded with human ASCs. The special feature of this bone graft was that ASC densities inside the piled construct varied with a linear gradient, which is a good starting point for tissue engineering interfaces such as bone-cartilage where the bone tissue is cell rich while the cartilage exhibits low cell densities. As such, this tissue-engineered graft may act as a bone-cartilage interface after the corresponding differentiation of the ASCs.

Keywords: bioreactor, bone, cartilage, nanocomposite, stem cell gradient

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Authors: K. X. Cheng, A. L. Goh, K. T. Ooi

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The effectiveness of microchannels in enhancing heat transfer has been demonstrated in the semiconductor industry. In order to tap the microscale heat transfer effects into macro geometries, overcoming the cost and technological constraints, microscale passages were created in macro geometries machined using conventional fabrication methods. A cylindrical insert was placed within a pipe, and geometrical profiles were created on the outer surface of the insert to enhance heat transfer under steady-state single-phase liquid flow conditions. However, while heat transfer coefficient values of above 10 kW/m2·K were achieved, the heat transfer enhancement was accompanied by undesirable pressure drop increment. Therefore, this study aims to address the high pressure drop issue using Constructal theory, a universal design law for both animate and inanimate systems. Two designs based on Constructal theory were developed to study the effectiveness of Constructal features in reducing the pressure drop increment as compared to parallel channels, which are commonly found in microchannel fabrication. The hydrodynamic and heat transfer performance for the Tree insert and Constructal fin (Cfin) insert were studied using experimental methods, and the underlying mechanisms were substantiated by numerical results. In technical terms, the objective is to achieve at least comparable increment in both heat transfer coefficient and pressure drop, if not higher increment in the former parameter. Results show that the Tree insert improved the heat transfer performance by more than 16 percent at low flow rates, as compared to the Tree-parallel insert. However, the heat transfer enhancement reduced to less than 5 percent at high Reynolds numbers. On the other hand, the pressure drop increment stayed almost constant at 20 percent. This suggests that the Tree insert has better heat transfer performance in the low Reynolds number region. More importantly, the Cfin insert displayed improved heat transfer performance along with favourable hydrodynamic performance, as compared to Cfinparallel insert, at all flow rates in this study. At 2 L/min, the enhancement of heat transfer was more than 30 percent, with 20 percent pressure drop increment, as compared to Cfin-parallel insert. Furthermore, comparable increment in both heat transfer coefficient and pressure drop was observed at 8 L/min. In other words, the Cfin insert successfully achieved the objective of this study. Analysis of the results suggests that bifurcation of flows is effective in reducing the increment in pressure drop relative to heat transfer enhancement. Optimising the geometries of the Constructal fins is therefore the potential future study in achieving a bigger stride in energy efficiency at much lower costs.

Keywords: constructal theory, enhanced heat transfer, microchannel, pressure drop

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Authors: Yana Posmitnaya, Galina Rudnitskaya, Tatyana Lukashenko, Anton Bukatin, Anatoly Evstrapov

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An important area of biological and medical research is the study of genetic mutations and polymorphisms that can alter gene function and cause inherited diseases and other diseases. The following methods to analyse DNA fragments are used: capillary electrophoresis and electrophoresis on microfluidic chip (MFC), mass spectrometry with electrophoresis on MFC, hybridization assay on microarray. Electrophoresis on MFC allows to analyse small volumes of samples with high speed and throughput. A soft lithography in polydimethylsiloxane (PDMS) was chosen for operative fabrication of MFCs. A master-form from silicon and photoresist SU-8 2025 (MicroChem Corp.) was created for the formation of micro-sized structures in PDMS. A universal topology which combines T-injector and simple cross was selected for the electrophoretic separation of the sample. Glass K8 and PDMS Sylgard® 184 (Dow Corning Corp.) were used for fabrication of MFCs. Electroosmotic flow (EOF) plays an important role in the electrophoretic separation of the sample. Therefore, the estimate of the quantity of EOF and the ways of its regulation are of interest for the development of the new methods of the electrophoretic separation of biomolecules. The following methods of surface modification were chosen to change EOF: high-frequency (13.56 MHz) plasma treatment in oxygen and argon at low pressure (1 mbar); 1% aqueous solution of polyvinyl alcohol; 3% aqueous solution of Kolliphor® P 188 (Sigma-Aldrich Corp.). The electroosmotic mobility was evaluated by the method of Huang X. et al., wherein the borate buffer was used. The influence of physical and chemical methods of treatment on the wetting properties of the PDMS surface was controlled by the sessile drop method. The most effective way of surface modification of MFCs, from the standpoint of obtaining the smallest value of the contact angle and the smallest value of the EOF, was the processing with aqueous solution of Kolliphor® P 188. This method of modification has been selected for the treatment of channels of MFCs, which are used for the separation of mixture of oligonucleotides fluorescently labeled with the length of chain with 10, 20, 30, 40 and 50 nucleotides. Electrophoresis was performed on the device MFAS-01 (IAI RAS, Russia) at the separation voltage of 1500 V. 6% solution of polydimethylacrylamide with the addition of 7M carbamide was used as the separation medium. The separation time of components of the mixture was determined from electropherograms. The time for untreated MFC was ~275 s, and for the ones treated with solution of Kolliphor® P 188 – ~ 220 s. Research of physical-chemical methods of surface modification of MFCs allowed to choose the most effective way for reducing EOF – the modification with aqueous solution of Kolliphor® P 188. In this case, the separation time of the mixture of oligonucleotides decreased about 20%. The further optimization of method of modification of channels of MFCs will allow decreasing the separation time of sample and increasing the throughput of analysis.

Keywords: electrophoresis, microfluidic chip, modification, nucleic acid, polydimethylsiloxane, soft lithography

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Authors: Ramzi Farra, Detre Teschner, Marc Willinger, Robert Schlögl

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Introduction: The conventional approach of characterizing solid catalysts under static conditions, i.e., before and after reaction, does not provide sufficient knowledge on the physicochemical processes occurring under dynamic conditions at the molecular level. Hence, the necessity of improving new in situ characterizing techniques with the potential of being used under real catalytic reaction conditions is highly desirable. In situ Prompt Gamma Activation Analysis (PGAA) is a rapidly developing chemical analytical technique that enables us experimentally to assess the coverage of surface species under catalytic turnover and correlate these with the reactivity. The catalytic HCl oxidation (Deacon reaction) over bulk ceria will serve as our example. Furthermore, the in situ Transmission Electron Microscopy is a powerful technique that can contribute to the study of atmosphere and temperature induced morphological or compositional changes of a catalyst at atomic resolution. The application of such techniques (PGAA and TEM) will pave the way to a greater and deeper understanding of the dynamic nature of active catalysts. Experimental/Methodology: In situ Prompt Gamma Activation Analysis (PGAA) experiments were carried out to determine the Cl uptake and the degree of surface chlorination under reaction conditions by varying p(O2), p(HCl), p(Cl2), and the reaction temperature. The abundance and dynamic evolution of OH groups on working catalyst under various steady-state conditions were studied by means of in situ FTIR with a specially designed homemade transmission cell. For real in situ TEM we use a commercial in situ holder with a home built gas feeding system and gas analytics. Conclusions: Two complimentary in situ techniques, namely in situ PGAA and in situ FTIR were utilities to investigate the surface coverage of the two most abundant species (Cl and OH). The OH density and Cl uptake were followed under multiple steady-state conditions as a function of p(O2), p(HCl), p(Cl2), and temperature. These experiments have shown that, the OH density positively correlates with the reactivity whereas Cl negatively. The p(HCl) experiments give rise to increased activity accompanied by Cl-coverage increase (opposite trend to p(O2) and T). Cl2 strongly inhibits the reaction, but no measurable increase of the Cl uptake was found. After considering all previous observations we conclude that only a minority of the available adsorption sites contribute to the reactivity. In addition, the mechanism of the catalysed reaction was proposed. The chlorine-oxygen competition for the available active sites renders re-oxidation as the rate-determining step of the catalysed reaction. Further investigations using in situ TEM are planned and will be conducted in the near future. Such experiments allow us to monitor active catalysts at the atomic scale under the most realistic conditions of temperature and pressure. The talk will shed a light on the potential and limitations of in situ PGAA and in situ TEM in the study of catalyst dynamics.

Keywords: CeO2, deacon process, in situ PGAA, in situ TEM, in situ FTIR

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Authors: A. Julio, R. Caparica, S. Costa Lima, S. Reis, J. G. Costa, P. Fonte, T. Santos De Almeida

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The Mycobacterium leprae causes a chronic and infectious disease called leprosy, which the most common symptoms are peripheral neuropathy and deformation of several parts of the body. The pharmacological treatment of leprosy is a combined therapy with three different drugs, rifampicin, clofazimine, and dapsone. However, clofazimine and dapsone have poor solubility in water and also low bioavailability. Thus, it is crucial to develop strategies to overcome such drawbacks. The use of ionic liquids (ILs) may be a strategy to overcome the low solubility since they have been used as solubility promoters. ILs are salts, liquid below 100 ºC or even at room temperature, that may be placed in water, oils or hydroalcoholic solutions. Another approach may be the encapsulation of drugs into polymeric nanoparticles, which improves their bioavailability. In this study, two different classes of ILs were used, the imidazole- and the choline-based ionic liquids, as solubility enhancers of the poorly soluble antileprotic drugs. Thus, after the solubility studies, it was developed IL-PLGA nanoparticles hybrid systems to deliver such drugs. First of all, the solubility studies of clofazimine and dapsone were performed in water and in water: IL mixtures, at ILs concentrations where cell viability is maintained, at room temperature for 72 hours. For both drugs, it was observed an improvement on the drug solubility and [Cho][Phe] showed to be the best solubility enhancer, especially for clofazimine, where it was observed a 10-fold improvement. Later, it was produced nanoparticles, with a polymeric matrix of poly(lactic-co-glycolic acid) (PLGA) 75:25, by a modified solvent-evaporation W/O/W double emulsion technique in the presence of [Cho][Phe]. Thus, the inner phase was an aqueous solution of 0.2 % (v/v) of the above IL with each drug to its maximum solubility determined on the previous study. After the production, the nanosystem hybrid was physicochemically characterized. The produced nanoparticles had a diameter of around 580 nm and 640 nm, for clofazimine and dapsone, respectively. Regarding the polydispersity index, it was in agreement of the recommended value of this parameter for drug delivery systems (around 0.3). The association efficiency (AE) of the developed hybrid nanosystems demonstrated promising AE values for both drugs, given their low solubility (64.0 ± 4.0 % for clofazimine and 58.6 ± 10.0 % for dapsone), that prospects the capacity of these delivery systems to enhance the bioavailability and loading of clofazimine and dapsone. Overall, the study achievement may signify an upgrading of the patient’s quality of life, since it may mean a change in the therapeutic scheme, not requiring doses of drug so high to obtain a therapeutic effect. The authors would like to thank Fundação para a Ciência e a Tecnologia, Portugal (FCT/MCTES (PIDDAC), UID/DTP/04567/2016-CBIOS/PRUID/BI2/2018).

Keywords: ionic liquids, ionic liquids-PLGA nanoparticles hybrid systems, leprosy treatment, solubility

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Authors: Tais Basaco, Stefanie Pektor, Josue A. Moreno, Matthias Miederer, Andreas Türler

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Radiopharmaceuticals based in monoclonal anti-body (mAb) via chemical linkers have become a potential tool in nuclear medicine because of their specificity and the large variability and availability of therapeutic radiometals. It is important to identify the conjugation sites and number of attached chelator to mAb to obtain radioimmunoconjugates with required immunoreactivity and radiostability. Girentuximab antibody (G250) is a potential candidate for radioimmunotherapy of clear cell carcinomas (RCCs) because it is reactive with CAIX antigen, a transmembrane glycoprotein overexpressed on the cell surface of most ( > 90%) (RCCs). G250 was conjugated with the bifunctional chelating agent DOTA (1,4,7,10-Tetraazacyclododecane-N,N’,N’’,N’’’-tetraacetic acid) via a benzyl-thiocyano group as a linker (p-SCN-Bn-DOTA). DOTA-G250 conjugates were analyzed by size exclusion chromatography (SE-HPLC) and by electrophoresis (SDS-PAGE). The potential site-specific conjugation was identified by liquid chromatography–mass spectrometry (LC/MS-MS) and the number of linkers per molecule of mAb was calculated using the molecular weight (MW) measured by matrix assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS). The average number obtained in the conjugates in non-reduced conditions was between 8-10 molecules of DOTA per molecule of mAb. The average number obtained in the conjugates in reduced conditions was between 1-2 and 3-4 molecules of DOTA per molecule of mAb in the light chain (LC) and heavy chain (HC) respectively. Potential DOTA modification sites of the chelator were identified in lysine residues. The biological activity of the conjugates was evaluated by flow cytometry (FACS) using CAIX negative (SKRC-18) and CAIX positive (SKRC-52). The DOTA-G250 conjugates were labelled with 177Lu with a radiochemical yield > 95% reaching specific activities of 12 MBq/µg. The stability in vitro of different types of radioconstructs was analyzed in human serum albumin (HSA). The radiostability of 177Lu-DOTA-G250 at high specific activity was increased by addition of sodium ascorbate after the labelling. The immunoreactivity was evaluated in vitro and in vivo. Binding to CAIX positive cells (SK-RC-52) at different specific activities was higher for conjugates with less DOTA content. Protein dose was optimized in mice with subcutaneously growing SK-RC-52 tumors using different amounts of 177Lu- DOTA-G250.

Keywords: mass spectrometry, monoclonal antibody, radiopharmaceuticals, radioimmunotheray, renal cancer

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Authors: Bjorn Kierulf, Arun Chundru

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Over the past decade, collegiate rocketry teams have emerged across the country with various goals: space, liquid-fueled flight, etc. A critical piece of the development of knowledge within a club is the use of so-called "sounding rockets," whose goal is to take in-flight measurements that inform future rocket design. Common measurements include acceleration from inertial measurement units (IMU's), and altitude from barometers. With a properly tuned filter, these measurements can be used to find velocity, but are susceptible to noise, offset, and filter settings. Instead, velocity can be measured more directly and more instantaneously using a pitot tube, which operates by measuring the stagnation pressure. At supersonic speeds, an additional thermodynamic property is necessary to constrain the upstream state. One possibility is the stagnation temperature, measured by a thermocouple in the pitot tube. The routing of the pitot tube from the nosecone tip down to a pressure transducer is complicated by the nosecone's structure. Commercial-off-the-shelf (COTS) nosecones come with a removable metal tip (without a pitot tube). This provides the opportunity to make custom tips with integrated measurement systems without making the nosecone from scratch. The main design constraint is how the nosecone tip is held down onto the nosecone, using the tension in a threaded rod anchored to a bulkhead below. Because the threaded rod connects into a threaded hole in the center of the nosecone tip, the pitot tube follows a winding path, and the pressure fitting is off-center. Two designs will be presented in the paper, one with a curved pitot tube and a coaxial design that eliminates the need for the winding path by routing pressure through a structural tube. Additionally, three manufacturing methods will be presented for these designs: bound powder filament metal 3D printing, stereo-lithography (SLA) 3D printing, and traditional machining. These will employ three different materials, copper, steel, and proprietary resin. These manufacturing methods and materials are relatively low cost, thus accessible to student researchers. These designs and materials cover multiple use cases, based on how fast the sounding rocket is expected to travel and how important heating effects are - to measure and to avoid melting. This paper will include drawings showing key features and an overview of the design changes necessitated by the manufacture. It will also include a look at the successful use of these nosecone tips and the data they have gathered to date.

Keywords: additive manufacturing, machining, pitot tube, sounding rocketry

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Authors: Navid Kaboudi, Ali Shayanfar

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Introduction: Feeding infants with safe milk from the beginning of their life is an important issue. Drugs which are used by mothers can affect the composition of milk in a way that is not only unsuitable, but also toxic for infants. Consuming permeable drugs during that sensitive period by mother could lead to serious side effects to the infant. Due to the ethical restrictions of drug testing on humans, especially women, during their lactation period, computational approaches based on structural parameters could be useful. The aim of this study is to develop mechanistic models to predict the M/P ratio of drugs during breastfeeding period based on their structural descriptors. Methods: Two hundred and nine different chemicals with their M/P ratio were used in this study. All drugs were categorized into two groups based on their M/P value as Malone classification: 1: Drugs with M/P>1, which are considered as high risk 2: Drugs with M/P>1, which are considered as low risk Thirty eight chemical descriptors were calculated by ACD/labs 6.00 and Data warrior software in order to assess the penetration during breastfeeding period. Later on, four specific models based on the number of hydrogen bond acceptors, polar surface area, total surface area, and number of acidic oxygen were established for the prediction. The mentioned descriptors can predict the penetration with an acceptable accuracy. For the remaining compounds (N= 147, 158, 160, and 174 for models 1 to 4, respectively) of each model binary regression with SPSS 21 was done in order to give us a model to predict the penetration ratio of compounds. Only structural descriptors with p-value<0.1 remained in the final model. Results and discussion: Four different models based on the number of hydrogen bond acceptors, polar surface area, and total surface area were obtained in order to predict the penetration of drugs into human milk during breastfeeding period About 3-4% of milk consists of lipids, and the amount of lipid after parturition increases. Lipid soluble drugs diffuse alongside with fats from plasma to mammary glands. lipophilicity plays a vital role in predicting the penetration class of drugs during lactation period. It was shown in the logistic regression models that compounds with number of hydrogen bond acceptors, PSA and TSA above 5, 90 and 25 respectively, are less permeable to milk because they are less soluble in the amount of fats in milk. The pH of milk is acidic and due to that, basic compounds tend to be concentrated in milk than plasma while acidic compounds may consist lower concentrations in milk than plasma. Conclusion: In this study, we developed four regression-based models to predict the penetration class of drugs during the lactation period. The obtained models can lead to a higher speed in drug development process, saving energy, and costs. Milk/plasma ratio assessment of drugs requires multiple steps of animal testing, which has its own ethical issues. QSAR modeling could help scientist to reduce the amount of animal testing, and our models are also eligible to do that.

Keywords: logistic regression, breastfeeding, descriptors, penetration

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Authors: Ghaneshree Moonsamy, Nodumo N. Zulu, Rajesh Lalloo, Suren Singh, Santosh O. Ramchuran

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The abalone industry of South Africa is under severe pressure due to illegal harvesting and poaching of this seafood delicacy. These abalones are harvested excessively; as a result, these animals do not have a chance to replace themselves in their habitats, ensuing in a drastic decrease in natural stocks of abalone. Abalone has an extremely slow growth rate and takes approximately four years to reach a size that is market acceptable; therefore, it was imperative to investigate methods to boost the overall growth rate and immunity of the animal. The University of Cape Town (UCT) began to research, which resulted in the isolation of two microorganisms, a yeast isolate Debaryomyces hansenii and a bacterial isolate Vibrio midae, from the gut of the abalone and characterised them for their probiotic abilities. This work resulted in an internationally competitive concept technology that was patented. The next stage of research was to develop a suitable bioprocess to enable commercial production. Numerous steps were taken to develop an efficient production process for V. midae, one of the isolates found by UCT. The initial stages of research involved the development of a stable and robust inoculum and the optimization of physiological growth parameters such as temperature and pH. A range of temperature and pH conditions were evaluated, and data obtained revealed an optimum growth temperature of 30ᵒC and a pH of 6.5. Once these critical growth parameters were established further media optimization studies were performed. Corn steep liquor (CSL) and high test molasses (HTM) were selected as suitable alternatives to more expensive, conventionally used growth medium additives. The optimization of CSL (6.4 g.l⁻¹) and HTM (24 g.l⁻¹) concentrations in the growth medium resulted in a 180% increase in cell concentration, a 5716-fold increase in cell productivity and a 97.2% decrease in the material cost of production in comparison to conventional growth conditions and parameters used at the onset of the study. In addition, a stable market-ready liquid probiotic product, encompassing the viable but not culturable (VBNC) state of Vibrio midae cells, was developed during the downstream processing aspect of the study. The demonstration of this technology at a full manufacturing scale has further enhanced the attractiveness and commercial feasibility of this production process.

Keywords: probiotics, abalone aquaculture, bioprocess technology, manufacturing scale technology development

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Authors: Alice Robba, Renaud Bouchet, Celine Barchasz, Jean-Francois Colin, Erik Elkaim, Kristina Kvashnina, Gavin Vaughan, Matjaz Kavcic, Fannie Alloin

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With their high theoretical energy density (~2600 Wh.kg-1), lithium/sulfur (Li/S) batteries are highly promising, but these systems are still poorly understood due to the complex mechanisms/equilibria involved. Replacing S8 by Li2S as the active material allows the use of safer negative electrodes, like silicon, instead of lithium metal. S8 and Li2S have different conductivity and solubility properties, resulting in a profoundly changed activation process during the first cycle. Particularly, during the first charge a high polarization and a lack of reproducibility between tests are observed. Differences observed between raw Li2S material (micron-sized) and that electrochemically produced in a battery (nano-sized) may indicate that the electrochemical process depends on the particle size. Then the major focus of the presented work is to deepen the understanding of the Li2S material charge mechanism, and more precisely to characterize the effect of the initial Li2S particle size both on the mechanism and the electrode preparation process. To do so, Li2S nanoparticles were synthetized according to two ways: a liquid path synthesis and a dissolution in ethanol, allowing Li2S nanoparticles/carbon composites to be made. Preliminary chemical and electrochemical tests show that starting with Li2S nanoparticles could effectively suppress the high initial polarization but also influence the electrode slurry preparation. Indeed, it has been shown that classical formulation process - a slurry composed of Polyvinylidone Fluoride polymer dissolved in N-methyle-2-pyrrolidone - cannot be used with Li2S nanoparticles. This reveals a complete different Li2S material behavior regarding polymers and organic solvents when going at the nanometric scale. Then the coupling between two operando characterizations such as X-Ray Diffraction (XRD) and X-Ray Absorption and Emission Spectroscopy (XAS/XES) have been carried out in order to interpret the poorly understood first charge. This study discloses that initial particle size of the active material has a great impact on the working mechanism and particularly on the different equilibria involved during the first charge of the Li2S based Li-ion batteries. These results explain the electrochemical differences and particularly the polarization differences observed during the first charge between micrometric and nanometric Li2S-based electrodes. Finally, this work could lead to a better active material design and so to more efficient Li2S-based batteries.

Keywords: Li-ion/Sulfur batteries, Li2S nanoparticles effect, Operando characterizations, working mechanism

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Authors: C. A. Sharma, Birendra P. Singh

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We recovered 40 well preserved ribbon-shaped, meandering specimens of S. ningqiangensis from the Earthy Dolomite Member (Krol Group) and calcareous siltstone beds of the Earthy Siltstone Member (Tal Group) showing closely spaced annulations that lacked branching. The beginning and terminal points are indistinguishable. In certain cases, individual specimens are characterized by irregular, low-angle to high-angle sinuosity. It has been variously described as body fossil, ichnofossil and algae. Detailed study of this enigmatic fossil is needed to resolve the long standing controversy regarding its phylogenetic and stratigraphic placements, which will be an important contribution to the evolutionary history of metazoans. S. ningqiangensis has been known from the late Neoproterozoic (Ediacaran) of southern and central China (Sichuan, Shaanxi, Quinghai and Guizhou provinces and Ningxia Hui Autonomous region), Siberian platform and across Pc/C Boundary from latest Neoprterozoic to earliest Cambrian of northern India. Shaanxilithes is considered an Ediacaran organism that spans the Precambrian–Cambrian boundary, an interval marked by significant taphonomic and ecological transformations that include not only innovation but also probable extinction. All the past well constrained finds of S. ningqiangensis are restricted to Ediacaran age. However, due to the new recoveries of the fossil from Nigalidhar Syncline, the stratigraphic status of S. ningqiangensis-bearing Earthy Siltstone Member of the Shaliyan Formation of the Tal Group (Cambrian) is rendered uncertain, though the overlying Chert Member in the adjoining Korgai Syncline has yielded definite early Cambrian acritarchs. The moot question is whether the Earthy Siltstone Member represents an Ediacaran or an early Cambrian age?. It would be interesting to find if Shaanxilithes, so far known from Ediacaran sequences, could it transgress to the early Cambrian or in simple words could it withstand the Pc/C Boundary event? GC-MS data shows the S. ningqiangensis structure is formed by hydrocarbon organic compounds which are filled with inorganic elements filler like silica, Calcium, phosphorus etc. The S. ningqiangensis structure is a mixture of organic compounds of high molecular weight, containing several saturated rings with hydrocarbon chains having an occasional isolated carbon-carbon double bond and also containing, in addition, to small amounts of nitrogen, sulfur and oxygen. Data also revealed that the presence of nitrogen which would be either in the form of peptide chains means amide/amine or chemical form i.e. nitrates/nitrites etc. The formula weight and the weight ratio of C/H shows that it would be expected for algae derived organics, since algae produce fatty acids as well as other hydrocarbons such as cartenoids.

Keywords: GC-MS Analysis, lesser himalaya, Pc/C Boundary, shaanxilithes

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Authors: Marie Davin, Marie-Laure Fauconnier, Gilles Colinet

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In Wallonia, there are 6,000 estimated brownfields (rising to over 3.5 million in Europe) that require remediation. Polycyclic Aromatic Hydrocarbons (PAHs) are a class of recalcitrant carcinogenic/mutagenic organic compounds of major concern as they accumulate in the environment and represent 17% of all encountered pollutants. As an alternative to environmentally aggressive, expensive and often disruptive soil remediation strategies, a lot of research has been directed to developing techniques targeting organic pollutants. The following experiment, based on the observation that PAHs soil content decreases in the presence of plants, aimed at improving our understanding of the underlying mechanisms involved in phytoremediation. It focusses on plant root exudates and whether they improve PAHs solubilization, which would make them more available for bioremediation by soil microorganisms. The effect of saponin, a natural surfactant found in some plant roots such as members of the Fabaceae family, on PAHs solubilization was also investigated as part of the implementation of the experimental protocol. The experiments were conducted on soil collected from a brownfield in Saint-Ghislain (Belgium) and presenting weathered PAHs contamination. Samples of soil were extracted with different solutions containing either plant root exudates or commercial saponin. Extracted PAHs were determined in the different aqueous solutions using High-Performance Liquid Chromatography and Fluorimetric Detection (HPLC-FLD). Both root exudates of alfalfa (Medicago sativa L.) or red clover (Trifolium pratense L.) and commercial saponin were tested in different concentrations. Distilled water was used as a control. First of all, results show that PAHs are more extracted using saponin solutions than distilled water and that the amounts generally rise with the saponin concentration. However, the amount of each extracted compound diminishes as its molecular weight rises. Also, it appears that passed a certain surfactant concentration, PAHs are less extracted. This suggests that saponin might be investigated as a washing agent in polluted soil remediation techniques, either for ex-situ or in-situ treatments, as an alternative to synthetic surfactants. On the other hand, preliminary results on experiments using plant root exudates also show differences in PAHs solubilization compared to the control solution. Further results will allow discussion as to whether or not there are differences according to the exudates provenance and concentrations.

Keywords: brownfield, Medicago sativa, phytoremediation, polycyclic aromatic hydrocarbons, root exudates, saponin, solubilization, Trifolium pratense

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Authors: Yi-Ting Chen, Yu-Fang Huang, Pei-Wei Wang, Hai-Wei Liang, Chun-Hao Lai, Mei-Lien Chen

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Background: Bisphenol A (BPA) is commonly used in consumer products, such as inner coatings of cans and polycarbonated bottles. BPA is considered to be an endocrine disrupting substance (EDs) that affects normal human hormones and may cause adverse effects on human health. Pregnant women and fetuses are susceptible groups of endocrine disrupting substances. Prenatal exposure to BPA has been shown to affect the fetus through the placenta. Therefore, it is important to evaluate the potential health risk of fetal exposure to BPA during pregnancy. The aims of this study were (1) to determine the urinary concentration of BPA in pregnant women, and (2) to investigate the association between BPA exposure during pregnancy and birth outcomes. Methods: This study recruited 117 pregnant women and their fetuses from 2012 to 2014 from the Taiwan Maternal- Infant Cohort Study (TMICS). Maternal urine samples were collected in the third trimester and questionnaires were used to collect socio-demographic characteristics, eating habits and medical conditions of the participants. Information about birth outcomes of the fetus was obtained from medical records. As for chemicals analysis, BPA concentrations in urine were determined by off-line solid-phase extraction-ultra-performance liquid chromatography coupled with a Q-Tof mass spectrometer. The urinary concentrations were adjusted with creatinine. The association between maternal concentrations of BPA and birth outcomes was estimated using the logistic regression model. Results: The detection rate of BPA is 99%; the concentration ranges (μg/g) from 0.16 to 46.90. The mean (SD) BPA levels are 5.37(6.42) μg/g creatinine. The mean ±SD of the body weight, body length, head circumference, chest circumference and gestational age at birth are 3105.18 ± 339.53 g, 49.33 ± 1.90 cm, 34.16 ± 1.06 cm, 32.34 ± 1.37 cm and 38.58 ± 1.37 weeks, respectively. After stratifying the exposure levels into two groups by median, pregnant women in higher exposure group would have an increased risk of lower body weight (OR=0.57, 95%CI=0.271-1.193), smaller chest circumference (OR=0.70, 95%CI=0.335-1.47) and shorter gestational age at birth newborn (OR=0.46, 95%CI=0.191-1.114). However, there are no associations between BPA concentration and birth outcomes reach a significant level (p < 0.05) in statistics. Conclusions: This study presents prenatal BPA profiles and infants in northern Taiwan. Women who have higher BPA concentrations tend to give birth to lower body weight, smaller chest circumference or shorter gestational age at birth newborn. More data will be included to verify the results. This report will also present the predictors of BPA concentrations for pregnant women.

Keywords: bisphenol A, birth outcomes, biomonitoring, prenatal exposure

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Authors: K. Graniczkowska, N. Beloglazova, S. De Saeger

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The threat of synthetic drugs is one of the most significant current drug problems worldwide. The use of drugs of abuse has increased dramatically during the past three decades. Among others, Amphetamine-Type Stimulants (ATS) are globally the second most widely used drugs after cannabis, exceeding the use of cocaine and heroin. ATS are potent central nervous system (CNS) stimulants, capable of inducing euphoric static similar to cocaine. Recreational use of ATS is widespread, even though warnings of irreversible damage of the CNS were reported. ATS pose a big problem and their production contributes to the pollution of the environment by discharging big volumes of liquid waste to sewage system. Therefore, there is a demand to develop robust and sensitive sensors that can detect ATS and their intermediates in environmental water samples. A rapid and simple test is required. Analysis of environmental water samples (which sometimes can be a harsh environment) using antibody-based tests cannot be applied. Therefore, molecular imprinted polymers (MIPs), which are known as synthetic antibodies, have been chosen for that approach. MIPs are characterized with a high mechanical and thermal stability, show chemical resistance in a broad pH range and various organic or aqueous solvents. These properties make them the preferred type of receptors for application in the harsh conditions imposed by environmental samples. To the best of our knowledge, there are no existing MIPs-based sensors toward amphetamine and its intermediates. Also not many commercial MIPs for this application are available. Therefore, the aim of this study was to compare different techniques to obtain MIPs with high specificity towards ATS and characterize them for following use in a sensing unit. MIPs against amphetamine and its intermediates were synthesized using a few different techniques, such as electro-, thermo- and UV-initiated polymerization. Different monomers, cross linkers and initiators, in various ratios, were tested to obtain the best sensitivity and polymers properties. Subsequently, specificity and selectivity were compared with commercially available MIPs against amphetamine. Different linkers, such as lipoic acid, 3-mercaptopioponic acid and tyramine were examined, in combination with several immobilization techniques, to select the best procedure for attaching particles on sensor surface. Performed experiments allowed choosing an optimal method for the intended sensor application. Stability of MIPs in extreme conditions, such as highly acidic or basic was determined. Obtained results led to the conclusion about MIPs based sensor applicability in sewage system testing.

Keywords: amphetamine type stimulants, environment, molecular imprinted polymers, MIPs, sensor

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Authors: Hellen L. De Castro e Silva, Ana A. Robles Aguilar, Erik Meers

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Digestates are residual by-products, rich in nutrients and trace elements, which can be used as organic fertilisers on soils. However, due to the non-digestibility of these elements and reduced dry matter during the anaerobic digestion process, metal concentrations are higher in digestates than in feedstocks, which might hamper their use as fertilisers according to the threshold values of some country policies. Furthermore, there is uncertainty regarding the required assimilated amount of these elements by some crops, which might result in their bioaccumulation. Therefore, further processing of the digestate to obtain safe fertilizing products has been recommended. This research aims to analyze the effect of applying the hydrothermal carbonization process to manure-derived digestates as a thermal treatment to reduce the bioavailability of heavy metals in mono and co-digestates derived from pig manure and maize from contaminated land in France. This study examined pig manure collected from a novel stable system (VeDoWs, province of East Flanders, Belgium) that separates the collection of pig urine and feces, resulting in a solid fraction of manure with high up-concentration of heavy metals and nutrients. Mono-digestion and co-digestion processes were conducted in semi-continuous reactors for 45 days at mesophilic conditions, in which the digestates were dried at 105 °C for 24 hours. Then, hydrothermal carbonization was applied to a 1:10 solid/water ratio to guarantee controlled experimental conditions in different temperatures (180, 200, and 220 °C) and residence times (2 h and 4 h). During the process, the pressure was generated autogenously, and the reactor was cooled down after completing the treatments. The solid and liquid phases were separated through vacuum filtration, in which the solid phase of each treatment -hydrochar- was dried and ground for chemical characterization. Different fractions (exchangeable / adsorbed fraction - F1, carbonates-bound fraction - F2, organic matter-bound fraction - F3, and residual fraction – F4) of some heavy metals (Cd, Cr, Ni, and Cr) have been determined in digestates and derived hydrochars using the modified Community Bureau of Reference (BCR) sequential extraction procedure. The main results indicated a difference in the heavy metals fractionation between digestates and their derived hydrochars; however, the hydrothermal carbonization operating conditions didn’t have remarkable effects on heavy metals partitioning between the hydrochars of the proposed treatments. Based on the estimated potential ecological risk assessment, there was one level decrease (considerate to moderate) when comparing the HMs partitioning in digestates and derived hydrochars.

Keywords: heavy metals, bioavailability, hydrothermal treatment, bio-based fertilisers, agriculture

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Authors: Satam Alotibi, Muhammad J. Al-Zahrani, Fahd K. Al-Naqidan, Turki S. Hussein, Moteb Alotaibi, Mohammed Alyami, Mahdy M. Elmahdy, Abdellah Kaiba, Fatehia S. Alhakami, Talal F. Qahtan

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Water pollution is a critical global challenge that demands scalable and effective solutions for water decontamination. In this captivating research, we unveil a groundbreaking strategy for harnessing solar energy to synthesize silver (Ag) clusters on stable titanium dioxide (TiO₂) nanoparticles dispersed in water, without the need for traditional stabilization agents. These Ag-loaded TiO₂ nanoparticles exhibit exceptional photocatalytic activity, surpassing that of pristine TiO₂ nanoparticles, offering a promising solution for highly efficient water decontamination under sunlight irradiation. To the best knowledge, we have developed a unique method to stabilize TiO₂ P25 nanoparticles in water without the use of stabilization agents. This breakthrough allows us to create an ideal platform for the solar-driven synthesis of Ag clusters. Under sunlight irradiation, the stable dispersion of TiO₂ P25 nanoparticles acts as a highly efficient photocatalyst, generating electron-hole pairs. The photogenerated electrons effectively reduce silver ions derived from a silver precursor, resulting in the formation of Ag clusters. The Ag clusters loaded on TiO₂ P25 nanoparticles exhibit remarkable photocatalytic activity for water decontamination under sunlight irradiation. Acting as active sites, these Ag clusters facilitate the generation of reactive oxygen species (ROS) upon exposure to sunlight. These ROS play a pivotal role in rapidly degrading organic pollutants, enabling efficient water decontamination. To confirm the success of our approach, we characterized the synthesized Ag-loaded TiO₂ P25 nanoparticles using cutting-edge analytical techniques, such as transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), and spectroscopic methods. These characterizations unequivocally confirm the successful synthesis of Ag clusters on stable TiO₂ P25 nanoparticles without traditional stabilization agents. Comparative studies were conducted to evaluate the superior photocatalytic performance of Ag-loaded TiO₂ P25 nanoparticles compared to pristine TiO₂ P25 nanoparticles. The Ag clusters loaded on TiO₂ P25 nanoparticles exhibit significantly enhanced photocatalytic activity, benefiting from the synergistic effect between the Ag clusters and TiO₂ nanoparticles, which promotes ROS generation for efficient water decontamination. Our scalable strategy for synthesizing Ag clusters on stable TiO₂ P25 nanoparticles without stabilization agents presents a game-changing solution for highly efficient water decontamination under sunlight irradiation. The use of commercially available TiO₂ P25 nanoparticles streamlines the synthesis process and enables practical scalability. The outstanding photocatalytic performance of Ag-loaded TiO₂ P25 nanoparticles opens up new avenues for their application in large-scale water treatment and remediation processes, addressing the urgent need for sustainable water decontamination solutions.

Keywords: water pollution, solar energy, silver clusters, TiO₂ nanoparticles, photocatalytic activity

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Authors: J. A. N. Sandamali, R. P. Hewawasam, K. A. P. W. Jayatilaka, L. K. B. Mudduwa

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Introduction: Doxorubicin is widely used in the treatment of solid organ tumors and hematological malignancies, but the dose-dependent cardiotoxicity due to free radical formation compromises its clinical utility. Therapeutic strategies which enhance cellular endogenous defense systems have been identified as promising approaches to combat oxidative stress-associated conditions. Cinnamomum zeylanicum (Ceylon cinnamon) has a number antioxidant compounds, which can effectively scavenge reactive oxygen including superoxide anions, hydroxyl radicals and as well as other free radicals. Therefore, the objective of the study was to elucidate the most effective dose of Cinnamomum bark extract which ameliorates doxorubicin-induced cardiotoxicity. Materials and methods: Wistar rats were divided into seven groups of 10 animals in each. Group 1: normal control (distilled water, orally, for 14 days, 10 mL/kg saline, ip, after 16 hours fast on the 11th day); Group 2: doxorubicin control (distilled water, orally, for 14 days, 18 mg/kg doxorubicin, ip, after 16 hour fast on the 11th day); Groups 3-7: five doses of freeze dried aqueous bark extracts (0.125, 0.25, 0.5, 1.0, 2.0g/kg, orally, daily for 14 days, 18 mg/kg doxorubicin, ip, after 16 hours fast on the 11th day). Animals were sacrificed on the 15th day and blood was collected for the estimation of cardiac troponin I (cTnI), AST and LDH concentrations and myocardial tissues were collected for histopathological assessment of myocardial damage and irreversible changes were graded by developing a score. Results: cTnI concentration of groups 1-7 were 0, 161.9, 128.6, 95.9, 38, 19.41 & 12.36 pg/mL showing significant differences (p<0.05) between group 2 and groups 4-7. In groups 1-7, serum AST concentration were 26.82, 68.1, 37.18, 36.23, 26.8, 26.62 & 22.43U/L and LDH concentrations were 1166.13, 2428.84, 1658.35, 1474.34, 1277.58, 1110.21 & 974.40U/L and a significant difference (p<0.05) was observed between group 2 and groups 3-7. The maximum score for myocardial necrosis was observed in group 2. Parallel to the increase of the dosage of plant extract, a gradual reduction of the score for myocardial necrosis was observed in groups 3-7. Reversible histological changes such as vacuolation, congestion were observed in group 2 and all plant treated groups. Haemorrhages, inflammatory cell infiltrations, and interstitial oedema were observed in group 2, but absent in groups treated with higher doses of the plant extract. Discussion & Conclusion: According to the in vitro antioxidant assays performed, Cinnamomum zeylanicum (Ceylon cinnamon) bark possesses high amounts of polyphenolic substances and high antioxidant activity. The present study showed that Cinnamomum zeylanicum extract at 2.0 g/kg possesses the most significant cardioprotective effect against doxorubicin-induced cardiotoxicity. It can be postulated that pretreatment with Cinnamomum bark extract may replenish the cardiomyocytes with antioxidants that are needed for the defense against oxidative stress induced by doxorubicin.

Keywords: cardioprotection, Cinnamomum zeylanicum, doxorubicin, free radicals

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Authors: Sanjay K. Behera, Debasish Saha, Paramesh Gadige, Ranjini Bandyopadhyay

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The zero shear viscosity (η₀) of a suspension of hard sphere colloids characterized by a significant polydispersity (≈10%) increases with increase in volume fraction (ϕ) and shows a dramatic increase at ϕ=ϕg with the system entering a colloidal glassy state. Fragility which is the measure of the rapidity of approach of these suspensions towards the glassy state is sensitive to its size polydispersity and stiffness of the particles. Soft poly(N-isopropylacrylamide) (PNIPAM) particles deform in the presence of neighboring particles at volume fraction above the random close packing volume fraction of undeformed monodisperse spheres. Softness, therefore, enhances the packing efficiency of these particles. In this study PNIPAM particles of a nearly constant swelling ratio and with polydispersities varying over a wide range (7.4%-48.9%) are synthesized to study the effects of polydispersity on the dynamics of suspensions of soft PNIPAM colloidal particles. The size and polydispersity of these particles are characterized using dynamic light scattering (DLS) and scanning electron microscopy (SEM). As these particles are deformable, their packing in aqueous suspensions is quantified in terms of effective volume fraction (ϕeff). The zero shear viscosity (η₀) data of these colloidal suspensions, estimated from rheometric experiments as a function of the effective volume fraction ϕeff of the suspensions, increases with increase in ϕeff and shows a dramatic increase at ϕeff = ϕ₀. The data for η₀ as a function of ϕeff fits well to the Vogel-Fulcher-Tammann equation. It is observed that increasing polydispersity results in increasingly fragile supercooled liquid-like behavior, with the parameter ϕ₀, extracted from the fits to the VFT equation shifting towards higher ϕeff. The observed increase in fragility is attributed to the prevalence of dynamical heterogeneities (DHs) in these polydisperse suspensions, while the simultaneous shift in ϕ₀ is ascribed to the decoupling of the dynamics of the smallest and largest particles. Finally, it is observed that the intrinsic nonlinearity of these suspensions, estimated at the third harmonic near ϕ₀ in Fourier transform oscillatory rheological experiments, increases with increase in polydispersity. These results are in agreement with theoretical predictions and simulation results for polydisperse hard sphere colloidal glasses and clearly demonstrate that jammed suspensions of polydisperse colloidal particles can be effectively fluidized with increasing polydispersity. Suspensions of these particles are therefore excellent candidates for detailed experimental studies of the effects of polydispersity on the dynamics of glass formation.

Keywords: dynamical heterogeneity, effective volume fraction, fragility, intrinsic nonlinearity

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Authors: Asma Bashir, Neha Farid, Kashif Ali, Kiran Fatima

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Background: Bacteriocins are a subclass of antimicrobial peptides that are becoming extremely important in treatments. It is possible to utilise bacteriocins in place of or in addition to traditional antibiotics. It is possible to treat a variety of infections, including Vancomycin-Resistant Staphylococcus aureus (VRSA) and Methicillin-Resistant Staphylococcus aureus (MRSA), using the targeted spectrum of activity of these microorganisms. Method: This study aimed to examine the efficiency of antibiotics and bacteriocin against VRSA and MRSA. The effects of bacteriocins, such as enterocin KAE01, enterocin KAE03, enterocin KAE05, and enterocin KAE06 isolated from Enterococcus faecium strains, alone and in combination with vancomycin and methicillin antibiotics were examined. The selection technique utilized the minimum inhibitory concentrations (MICs) against Gram-positive indicator strain ATCC 6538 Methicillin-Resistant Staphylococcus aureus (MRSA) and indicator strain KSA 02 Vancomycin-Resistant Staphylococcus aureus (VRSA). Results: We report the isolation and identification of enterocins KAE01, KAE03, KAE05, and KAE06 from food isolates of Enterococcus faecium (KAE01, KAE03, KAE05, and KAE06). After isolating the protein, it was partially purified with ammonium sulphate precipitation and purified with fast protein liquid chromatography (FPLC) procedures. Combinations of enterocin KAE01, 1 citric acid, 1 lactic acid, and microcin J25, 1 reuterin, 1 citric acid, and microcin J25, 1 reuterin, 1 lactic acid shown synergistic benefits (FIC index = 0.5) against Vancomycin-Resistant Staphylococcus aureus (VRSA). In addition, a moderately synergistic (FIC index = 0.75) interaction was seen between pediocin PA-1, 1 citric acid, 1 lactic acid, and reuterin 1 citric acid, 1 lactic acid against L. ivanovii HPB28. In the presence of acids, nisin Z exhibited a modestly synergistic effect (FIC index = 0.625-0.75); however, it exhibited additive effects (FIC index = 1) when combined with reuterin or pediocin PA-1 against L. ivanovii HPB28. The efficacy of synergistic consortiums against Gram-positive bacteria was examined. Conclusion: Combining antimicrobials with various modes of action boosted efficacy and expanded the spectrum of inhibition, particularly against multidrug-resistant pathogens, according to our research.

Keywords: Enterococcus faecium, bacteriocin, antimicrobial resistance, antagonistic activity, vancomycin-resistant Staphylococcus aureus, methicillin-resistant Staphylococcus aureus

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Authors: Jeet Chakraborty, Sanjay Dutta

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Antibiotic resistance by bacteria has proved to be a severe threat to mankind in recent times, and this fortifies an urgency to design and develop potent antibacterial small molecules/compounds with nonconventional mechanisms than the conventional ones. DNA carries the genetic signature of any organism, and bacteria maintain their genomic DNA inside the cell in a well-regulated compact form with the help of various nucleoid associated proteins like HU, HNS, etc. These proteins control various fundamental processes like gene expression, replication, etc., inside the cell. Alteration of the native DNA structure of bacteria can lead to severe consequences in cellular processes inside the bacterial cell that ultimately result in the death of the organism. The change in the global DNA structure by small molecules initiates a plethora of cellular responses that have not been very well investigated. Echinomycin and Triostin-A are biologically active Quinoxaline small molecules that typically consist of a quinoxaline chromophore attached with an octadepsipeptide ring. They bind to double-stranded DNA in a sequence-specific way and have high activity against a wide variety of bacteria, mainly against Gram-positive ones. To date, few synthetic quinoxaline scaffolds were synthesized, displaying antibacterial potential against a broad scale of pathogenic bacteria. QNOs (Quinoxaline N-oxides) are known to target DNA and instigate reactive oxygen species (ROS) production in bacteria, thereby exhibiting antibacterial properties. The divergent role of Quinoxaline small molecules in medicinal research qualifies them for the evaluation of their antimicrobial properties as a potential candidate. The previous study from our lab has given new insights on a 6-nitroquinoxaline derivative 1d as an intercalator of DNA, which induces conformational changes in DNA upon binding.7 The binding event observed was dependent on the presence of a crucial benzyl substituent on the quinoxaline moiety. This was associated with a large induced CD (ICD) appearing in a sigmoidal pattern upon the interaction of 1d with dsDNA. The induction of DNA superstructures by 1d at high Drug:DNA ratios was observed that ultimately led to DNA condensation. Eviction of invitro-assembled nucleosome upon treatment with a high dose of 1d was also observed. In this work, monoquinoxaline derivatives of 1d were synthesized by various modifications of the 1d scaffold. The set of synthesized 6-nitroquinoxaline derivatives along with 1d were all subjected to antibacterial evaluation across five different bacteria species. Among the compound set, 3a displayed potent antibacterial activity against Staphylococcus aureus bacteria. 3a was further subjected to various biophysical studies to check whether the DNA structural alteration potential was still intact. The biological response of S. aureus cells upon treatment with 3a was studied using various cell biology processes, which led to the conclusion that 3d can initiate DNA damage in the S. aureus cells. Finally, the potential of 3a in disrupting preformed S.aureus and S.epidermidis biofilms was also studied.

Keywords: DNA structural change, antibacterial, intercalator, DNA superstructures, biofilms

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Authors: Rebecca Dewfall, Mark Coleman, Vladimir Basabe

Abstract:

Oxide scale growth is an inevitable byproduct of the high temperature processing of steel. Blister is a phenomenon that occurs due to oxide growth, where high temperatures result in the swelling of surface scale, producing a bubble-like feature. Blisters can subsequently become embedded in the steel substrate during hot rolling in the finishing mill. This rolled in scale defect causes havoc within industry, not only with wear on machinery but loss of customer satisfaction, poor surface finish, loss of material, and profit. Even though blister is a highly prevalent issue, there is still much that is not known or understood. The classic iron oxidation system is a complex multiphase system formed of wustite, magnetite, and hematite, producing multi-layered scales. Each phase will have independent properties such as thermal coefficients, growth rate, and mechanical properties, etc. Furthermore, each additional alloying element will have different affinities for oxygen and different mobilities in the oxide phases so that oxide morphologies are specific to alloy chemistry. Therefore, blister regimes can be unique to each steel grade resulting in a diverse range of formation mechanisms. Laboratory conditions were selected to simulate industrial hot rolling with temperature ranges approximate to the formation of secondary and tertiary scales in the finishing mills. Samples with composition: 0.15Wt% C, 0.1Wt% Si, 0.86Wt% Mn, 0.036Wt% Al, and 0.028Wt% Cr, were oxidised in a thermo-gravimetric analyser (TGA), with an air velocity of 10litresmin-1, at temperaturesof 800°C, 850°C, 900°C, 1000°C, 1100°C, and 1200°C respectively. Samples were held at temperature in an argon atmosphere for 10minutes, then oxidised in air for 600s, 60s, 30s, 15s, and 4s, respectively. Oxide morphology and Blisters were characterised using EBSD, WDX, nanoindentation, FIB, and FEG-SEM imaging. Blister was found to have both a nucleation and growth process. During nucleation, the scale detaches from the substrate and blisters after a very short period, roughly 10s. The steel substrate is then exposed inside of the blister and further oxidised in the reducing atmosphere of the blister, however, the atmosphere within the blister is highly dependent upon the porosity of the blister crown. The blister crown was found to be consistently between 35-40um for all heating regimes, which supports the theory that the blister inflates, and the oxide then subsequently grows underneath. Upon heating, two modes of blistering were identified. In Mode 1 it was ascertained that the stresses produced by oxide growth will increase with increasing oxide thickness. Therefore, in Mode 1 the incubation time for blister formation is shortened by increasing temperature. In Mode 2 increase in temperature will result in oxide with a high ductility and high oxide porosity. The high oxide ductility and/or porosity accommodates for the intrinsic stresses from oxide growth. Thus Mode 2 is the inverse of Mode 1, and incubation time is increased with temperature. A new phenomenon was reported whereby blister formed exclusively through cooling at elevated temperatures above mode 2.

Keywords: FEG-SEM, nucleation, oxide morphology, surface defect

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