Search results for: abnormal dispersion

Authors: Rahaf Mandura, Fatmah Abusharkh, Layan Kurdi, Rahaf Shigdar, Khadijah Alattas

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Introduction: Age-related macular degeneration (AMD) in older individuals are serious health issues that severely impact the quality of life of millions globally. In 2020, the fourth leading cause of blindness worldwide was AMD. The global prevalence of AMD is estimated to be around 8.7%. AMD is a progressive disease involving the macular region of the retina, and it has a complex pathophysiology. RPE cell dysfunction plays a crucial step in the pathway leading to irreversible degeneration of photoreceptors with yellowish lipid-rich, protein-containing drusen deposits accumulating between Bruch's membrane and the RPE. Furthermore, lipofuscinogenesis, drusogenesis, inflammation, and neovascularization are four main processes responsible for the formation of the two types of AMD: the wet (exudative, neovascular) and dry (non-exudative, geographic atrophy) types. We retrospectively evaluated the prevalence of AMD among patients visiting the retina clinic at King Abdulaziz University Hospital (Jeddah, Makkah Province, Saudi Arabia) to identify the commonly associated risk factors of AMD. Methods: The records of 3,067 individuals from 2017 to 2021 were reviewed. Of these, 1,935 satisfied the inclusion criteria and were included in this study. We excluded all patient below 18 years, and those who did not undergo fundus imaging or attend their booked appointments, follow-ups, treatments, and referrals were excluded. Results: The prevalence of AMD among the patients was 4%. The age of patients with AMD was significantly greater than those without AMD (72.4 ± 9.8 years vs. 57.2 ± 15.5 years; p < 0.001). Participants with a family history of AMD tended to have the disease more than those without such a history (85.7% vs. 45%; p = 0.043). Ex- and current smokers were more likely to have AMD than non-smokers (34% and 18.6% vs. 7.2%; p < 0.001). Patients with hypertension and those without type 1 diabetes were at a higher risk of developing AMD than those without hypertension (5.5% vs. 2.8%; p = 0.002) and those with type 1 diabetes (4.2% vs. 0.8%; p = 0.040). In contrast, sex, nationality, type 2 diabetes, and abnormal lipid profile were not significantly associated with AMD. Regarding the clinical characteristics of AMD cases, most cases (70.4%) were of the dry type and affected both eyes (77.2%). The disease duration was ≥5 years in 43.1% of the patients. The most frequent chronic diseases associated with AMD were type 2 diabetes (69.1%), hypertension (61.7%), and dyslipidemia (18.5%). Conclusion: In summary, our single tertiary center study showed that AMD is widely prevalent in Jeddah, Saudi Arabia (4%) and linked to a wide range of risk factors. Some of these are modifiable risk factors that can be adjusted to help reduce AMD occurrence. Furthermore, this study has shown the importance of screening and follow-up of family members of patients with AMD to promote early detection and intervention of AMD. We recommend conducting further research on AMD in Saudi Arabia. Concerning the study design, a community-based cross-sectional study would be more helpful for assessing the disease's prevalence. Finally, recruiting a larger sample size is required for more accurate estimation.

Keywords: age related macular degeneration, prevelence, risk factor, dry AMD

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Authors: Elvis Medina, Alejandro Karelovic, Romel Jiménez

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Catalytic ammonia decomposition represents an attractive alternative due to its high H₂ content (17.8% w/w), a product stream free of COₓ, among others; however, challenges need to be addressed for its consolidation as an H₂ chemical storage technology, especially, those focused on the synthesis of efficient bimetallic catalytic systems, as an alternative to the price and scarcity of ruthenium, the most active catalyst reported. In this sense, from the perspective of rational catalyst design, adjusting the main catalytic activity descriptor, a screening of supported catalysts with different compositional settings of cobalt-molybdenum metals is presented to evaluate their effect on the catalytic decomposition rate of ammonia. Subsequently, a kinetic study on the supported monometallic Co and Mo catalysts, as well as on the bimetallic CoMo catalyst with the highest activity is shown. The synthesis of catalysts supported on γ-alumina was carried out using the Charge Enhanced Dry Impregnation (CEDI) method, all with a 5% w/w loading metal. Seeking to maintain uniform dispersion, the catalysts were oxidized and activated (In-situ activation) using a flow of anhydrous air and hydrogen, respectively, under the same conditions: 40 ml min⁻¹ and 5 °C min⁻¹ from room temperature to 600 °C. Catalytic tests were carried out in a fixed-bed reactor, confirming the absence of transport limitations, as well as an Approach to equilibrium (< 1 x 10⁻⁴). The reaction rate on all catalysts was measured between 400 and 500 ºC at 53.09 kPa NH3. The synergy theoretically (DFT) reported for bimetallic catalysts was confirmed experimentally. Specifically, it was observed that the catalyst composed mainly of 75 mol% cobalt proved to be the most active in the experiments, followed by the monometallic cobalt and molybdenum catalysts, in this order of activity as referred to in the literature. A kinetic study was performed at 10.13 – 101.32 kPa NH3 and at four equidistant temperatures between 437 and 475 °C the data were adjusted to an LHHW-type model, which considered the desorption of nitrogen atoms from the active phase surface as the rate determining step (RDS). The regression analysis were carried out under an integral regime, using a minimization algorithm based on SLSQP. The physical meaning of the parameters adjusted in the kinetic model, such as the RDS rate constant (k₅) and the lumped adsorption constant of the quasi-equilibrated steps (α) was confirmed through their Arrhenius and Van't Hoff-type behavior (R² > 0.98), respectively. From an energetic perspective, the activation energy for cobalt, cobalt-molybdenum, and molybdenum was 115.2, 106.8, and 177.5 kJ mol⁻¹, respectively. With this evidence and considering the volcano shape described by the ammonia decomposition rate in relation to the metal composition ratio, the synergistic behavior of the system is clearly observed. However, since characterizations by XRD and TEM were inconclusive, the formation of intermetallic compounds should be still verified using HRTEM-EDS. From this point onwards, our objective is to incorporate parameters into the kinetic expressions that consider both compositional and structural elements and explore how these can maximize or influence H₂ production.

Keywords: CEDI, hydrogen carrier, LHHW, RDS

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Authors: Bamikole J. Adeyemi, Prashant Jadhawar, Lateef Akanji

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Liquid-liquid interfacial flow is an important process that has applications across many spheres. One such applications are residual oil mobilization, where crude oil and low salinity water are emulsified due to lowered interfacial tension under the condition of low shear rates. The amphiphilic components (asphaltenes and resins) in crude oil are considered to assemble at the interface between the two immiscible liquids. To justify emulsification, drag and snap-off suppression as the main effects of low salinity water, mobilization of residual oil is visualized as thickening and slip of the wetting phase at the brine/crude oil interface which results in the squeezing and drag of the non-wetting phase to the pressure sinks. Meanwhile, defining the boundary conditions for such a system can be very challenging since the interfacial dynamics do not only depend on interfacial tension but also the flow rate. Hence, understanding the flow boundary condition at the brine/crude oil interface is an important step towards defining the influence of low salinity water composition on residual oil mobilization. This work presents a numerical evaluation of three slip boundary conditions that may apply at liquid-liquid interfaces. A mathematical model was developed to describe the evolution of a viscoelastic interfacial thin liquid film. The base model is developed by the asymptotic expansion of the full Navier-Stokes equations for fluid motion due to gradients of surface tension. This model was upscaled to describe the dynamics of the film surface deformation. Subsequently, Jeffrey’s model was integrated into the formulations to account for viscoelastic stress within a long wave approximation of the Navier-Stokes equations. To study the fluid response to a prescribed disturbance, a linear stability analysis (LSA) was performed. The dispersion relation and the corresponding characteristic equation for the growth rate were obtained. Three slip (slip, 1; locking, -1; and no-slip, 0) boundary conditions were examined using the resulted characteristic equation. Also, the dynamics of the evolved interfacial thin liquid film were numerically evaluated by considering the influence of the boundary conditions. The linear stability analysis shows that the boundary conditions of such systems are greatly impacted by the presence of amphiphilic molecules when three different values of interfacial tension were tested. The results for slip and locking conditions are consistent with the fundamental solution representation of the diffusion equation where there is film decay. The interfacial films at both boundary conditions respond to exposure time in a similar manner with increasing growth rate which resulted in the formation of more droplets with time. Contrarily, no-slip boundary condition yielded an unbounded growth and it is not affected by interfacial tension.

Keywords: boundary conditions, liquid-liquid interfaces, low salinity water, residual oil mobilization

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Authors: Dorottya Guban, Irina Borbath, Istvan Bakos, Peter Nemeth, Andras Tompos

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One of the greatest challenges of the implementation of polymer electrolyte membrane fuel cells (PEMFCs) is to find active and durable electrocatalysts. The cell performance is always limited by the oxygen reduction reaction (ORR) on the cathode since it is at least 6 orders of magnitude slower than the hydrogen oxidation on the anode. Therefore high loading of Pt is required. Catalyst corrosion is also more significant on the cathode, especially in case of mobile applications, where rapid changes of loading have to be tolerated. Pt-Sn bulk alloys and SnO2-decorated Pt3Sn nanostructures are among the most studied bimetallic systems for fuel cell applications. Exclusive formation of supported Sn-Pt alloy phases with different Pt/Sn ratios can be achieved by using controlled surface reactions (CSRs) between hydrogen adsorbed on Pt sites and tetraethyl tin. In this contribution our results for commercial and a home-made 20 wt.% Pt/C catalysts modified by tin anchoring via CSRs are presented. The parent Pt/C catalysts were synthesized by modified NaBH4-assisted ethylene-glycol reduction method using ethanol as a solvent, which resulted either in dispersed and highly stable Pt nanoparticles or evenly distributed raspberry-like agglomerates according to the chosen synthesis parameters. The 20 wt.% Pt/C catalysts prepared that way showed improved electrocatalytic performance in the ORR and stability in comparison to the commercial 20 wt.% Pt/C catalysts. Then, in order to obtain Sn-Pt/C catalysts with Pt/Sn= 3 ratio, the Pt/C catalysts were modified with tetraethyl tin (SnEt4) using three and five consecutive tin anchoring periods. According to in situ XPS studies in case of catalysts with highly dispersed Pt nanoparticles, pre-treatment in hydrogen even at 170°C resulted in complete reduction of the ionic tin to Sn0. No evidence of the presence of SnO2 phase was found by means of the XRD and EDS analysis. These results demonstrate that the method of CSRs is a powerful tool to create Pt-Sn bimetallic nanoparticles exclusively, without tin deposition onto the carbon support. On the contrary, the XPS results revealed that the tin-modified catalysts with raspberry-like Pt agglomerates always contained a fraction of non-reducible tin oxide. At the same time, they showed increased activity and long-term stability in the ORR than Pt/C, which was assigned to the presence of SnO2 in close proximity/contact with Pt-Sn alloy phase. It has been demonstrated that the content and dispersion of the fcc Pt3Sn phase within the electrocatalysts can be controlled by tuning the reaction conditions of CSRs. The bimetallic catalysts displayed an outstanding performance in the ORR. The preparation of a highly dispersed 20Pt/C catalyst permits to decrease the Pt content without relevant decline in the electrocatalytic performance of the catalysts.

Keywords: anode catalyst, cathode catalyst, controlled surface reactions, oxygen reduction reaction, PtSn/C electrocatalyst

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Authors: Loganathan Kumaresan, Velusamy Chidambaram, Arumugam Velayutham Karthikeyani, Alex Cheru Pulikottil, Madhusudan Sau, Gurpreet Singh Kapur, Sankara Sri Venkata Ramakumar

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Environmentally driven regulations throughout the world stipulate dramatic improvements in the quality of transportation fuels and refining operations. The exhaust gases like CO, NOx, and SOx from stationary sources (e.g., refinery) and motor vehicles contribute to a large extent for air pollution. The refining industry is under constant environmental pressure to achieve more rigorous standards on sulphur content in the fuel used in the transportation sector and other off-gas emissions. Fluid catalytic cracking unit (FCCU) is a major secondary process in refinery for gasoline and diesel production. CO-combustion promoter additive and gasoline sulphur reduction (GSR) additive are catalytic systems used in FCCU to assist the combustion of CO to CO₂ in the regenerator and regulate sulphur in gasoline faction respectively along with main FCC catalyst. Effectiveness of these catalysts is governed by the active metal used, its dispersion, the type of base material employed, and retention characteristics of additive in FCCU such as attrition resistance and density. The challenge is to have a high-density microsphere catalyst support for its retention and high activity of the active metals as these catalyst additives are used in low concentration compare to the main FCC catalyst. The present paper discusses in the first part development of high dense microsphere of nanocrystalline alumina by hydro-thermal method for CO combustion promoter application. Performance evaluation of additive was conducted under simulated regenerator conditions and shows CO combustion efficiency above 90%. The second part discusses the efficacy of a co-precipitation method for the generation of the active crystalline spinels of Zn, Mg, and Cu with aluminium oxides as an additive. The characterization and micro activity test using heavy combined hydrocarbon feedstock at FCC unit conditions for evaluating gasoline sulphur reduction activity are studied. These additives were characterized by X-Ray Diffraction, NH₃-TPD & N₂ sorption analysis, TPR analysis to establish structure-activity relationship. The reaction of sulphur removal mechanisms involving hydrogen transfer reaction, aromatization and alkylation functionalities are established to rank GSR additives for their activity, selectivity, and gasoline sulphur removal efficiency. The sulphur shifting in other liquid products such as heavy naphtha, light cycle oil, and clarified oil were also studied. PIONA analysis of liquid product reveals 20-40% reduction of sulphur in gasoline without compromising research octane number (RON) of gasoline and olefins content.

Keywords: hydrothermal, nanocrystalline, spinel, sulphur reduction

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Authors: A. C. Blaga, A. Cârlescu, M. Turnea, A. I. Galaction, D. Caşcaval

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The performance of an aerobic stirred bioreactor for fungal fermentation was analyzed on the basis of mixing time and oxygen mass transfer coefficient, by quantifying the influence of some specific geometrical and operational parameters of the bioreactor, as well as the rheological behavior of Penicillium chrysogenum broth (free mycelia and mycelia aggregates). The rheological properties of the fungus broth, controlled by the biomass concentration, its growth rate, and morphology strongly affect the performance of the bioreactor. Experimental data showed that for both morphological structures the accumulation of fungus biomass induces a significant increase of broths viscosity and modifies the rheological behavior. For lower P. chrysogenum concentrations (both morphological conformations), the mixing time initially increases with aeration rate, reaches a maximum value and decreases. This variation can be explained by the formation of small bubbles, due to the presence of solid phase which hinders the bubbles coalescence, the rising velocity of bubbles being reduced by the high apparent viscosity of fungus broths. By biomass accumulation, the variation of mixing time with aeration rate is gradually changed, the continuous reduction of mixing time with air input flow increase being obtained for 33.5 g/l d.w. P. chrysogenum. Owing to the superior apparent viscosity, which reduces considerably the relative contribution of mechanical agitation to the broths mixing, these phenomena are more pronounced for P. chrysogenum free mycelia. Due to the increase of broth apparent viscosity, the biomass accumulation induces two significant effects on oxygen transfer rate: the diminution of turbulence and perturbation of bubbles dispersion - coalescence equilibrium. The increase of P. chrysogenum free mycelia concentration leads to the decrease of kla values. Thus, for the considered variation domain of the main parameters taken into account, namely air superficial velocity from 8.36 10-4 to 5.02 10-3 m/s and specific power input from 100 to 500 W/m3, kla was reduced for 3.7 times for biomass concentration increase from 4 to 36.5 g/l d.w. The broth containing P. crysogenum mycelia aggregates exhibits a particular behavior from the point of view of oxygen transfer. Regardless of bioreactor operating conditions, the increase of biomass concentration leads initially to the increase of oxygen mass transfer rate, the phenomenon that can be explained by the interaction of pellets with bubbles. The results are in relation with the increase of apparent viscosity of broths corresponding to the variation of biomass concentration between the mentioned limits. Thus, the apparent viscosity of the suspension of fungus mycelia aggregates increased for 44.2 times and fungus free mycelia for 63.9 times for CX increase from 4 to 36.5 g/l d.w. By means of the experimental data, some mathematical correlations describing the influences of the considered factors on mixing time and kla have been proposed. The proposed correlations can be used in bioreactor performance evaluation, optimization, and scaling-up.

Keywords: biomass concentration, mixing time, oxygen mass transfer, P. chrysogenum broth, stirred bioreactor

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Authors: Victoria Esteves

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Online memes have not only impacted different aspects of culture, but they have also left their mark on particular subcultures, where memes have reflected issues and debates surrounding specific spheres of interest. This is the first study that outlines how memes can address cultural intersections within the Lolita fashion community, which are much more specific and which fall outside of the broad focus of politics and/or social commentary. This is done by looking at the way online memes are used in this particular subculture as a form of meaning-making and group identity reinforcement, demonstrating not only the adaptability of online memes to specific cultural groups but also how subcultures tailor these digital objects to discuss both community-centered topics and more broad societal aspects. As part of an online ethnography, this study focuses on qualitative content analysis by taking a look at some of the meme communication that has permeated Lolita fashion communities. Examples of memes used in this context are picked apart in order to understand this specific layered phenomenon of communication, as well as to gain insights into how memes can operate as visual shorthand for the remix of meaning-making. There are existing parallels between internet culture and cultural behaviors surrounding Lolita fashion: not only is the latter strongly influenced by the former (due to its highly globalized dispersion and lack of physical shops, Lolita fashion is almost entirely reliant on the internet for its existence), both also emphasize curatorial roles through a careful collaborative process of documenting significant aspects of their culture (e.g., Know Your Meme and Lolibrary). Further similarities appear when looking at ideas of inclusion and exclusion that permeate both cultures, where memes and language are used in order to both solidify group identity and to police those who do not ascribe to these cultural tropes correctly, creating a feedback loop that reinforces subcultural ideals. Memes function as excellent forms of communication within the Lolita community because they reinforce its coded ideas and allows a kind of participation that echoes other cultural groups that are online-heavy such as fandoms. Furthermore, whilst the international Lolita community was mostly self-contained within its LiveJournal birthplace, it has become increasingly dispersed through an array of different social media groups that have fragmented this subculture significantly. The use of memes is key in maintaining a sense of connection throughout this now fragmentary experience of fashion. Memes are also used in the Lolita fashion community to bridge the gap between Lolita fashion related community issues and wider global topics; these reflect not only an ability to make use of a broader online language to address specific issues of the community (which in turn provide a very community-specific engagement with remix practices) but also memes’ ability to be tailored to accommodate overlapping cultural and political concerns and discussions between subcultures and broader societal groups. Ultimately, online memes provide the necessary elasticity to allow their adaption and adoption by subcultural groups, who in turn use memes to extend their meaning-making processes.

Keywords: internet culture, Lolita fashion, memes, online community, remix

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Authors: S. Jimenez, R.Duarte, J.Sanchez-Choliz, I. Villanua

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There is a certain consensus in economic literature about the factors that have influenced in historical differences in growth rates observed between developed and developing countries. However, it is less clear what elements have marked different paths of growth in developed economies in recent decades. R&D has always been seen as one of the major sources of technological progress, and productivity growth, which is directly influenced by technological developments. Following recent literature, we can say that ‘innovation pushes the technological frontier forward’ as well as encourage future innovation through the creation of externalities. In other words, productivity benefits from innovation are not fully appropriated by innovators, but it also spread through the rest of the economies encouraging absorptive capacities, what have become especially important in a context of increasing fragmentation of production This paper aims to contribute to this literature in two ways, first, exploring alternative indexes of R&D flows embodied in inter-country, inter-sectorial flows of good and services (as approximation to technology spillovers) capturing structural and technological characteristic of countries and, second, analyzing the impact of direct and embodied R&D on the evolution of labor productivity at the country/sector level in recent decades. The traditional way of calculation through a multiregional input-output framework assumes that all countries have the same capabilities to absorb technology, but it is not, each one has different structural features and, this implies, different capabilities as part of literature, claim. In order to capture these differences, we propose to use a weight based on specialization structure indexes; one related with the specialization of countries in high-tech sectors and the other one based on a dispersion index. We propose these two measures because, as far as we understood, country capabilities can be captured through different ways; countries specialization in knowledge-intensive sectors, such as Chemicals or Electrical Equipment, or an intermediate technology effort across different sectors. Results suggest the increasing importance of country capabilities while increasing the trade openness. Besides, if we focus in the country rankings, we can observe that with high-tech weighted R&D embodied countries as China, Taiwan and Germany arose the top five despite not having the highest intensities of R&D expenditure, showing the importance of country capabilities. Additionally, through a fixed effects panel data model we show that, in fact, R&D embodied is important to explain labor productivity increases, in fact, even more that direct R&D investments. This is reflecting that globalization is more important than has been said until now. However, it is true that almost all analysis done in relation with that consider the effect of t-1 direct R&D intensity over economic growth. Nevertheless, from our point of view R&D evolve as a delayed flow and it is necessary some time to be able to see its effects on the economy, as some authors have already claimed. Our estimations tend to corroborate this hypothesis obtaining a gap between 4-5 years.

Keywords: economic growth, embodied, input-output, technology

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Authors: Anna Krukowska, Tomasz Klimczuk, Adriana Zaleska-Medynska

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Photoactive materials have attracted attention due to their potential application in the degradation of environmental pollutants to non-hazardous compounds in an eco-friendly route. Among semiconductor photocatalysts, tantalates such as potassium tantalate (KTaO3) is one of the excellent functional photomaterial. However, tantalates-based materials are less active under visible-light irradiation, the enhancement in photoactivity could be improved with the modification of opto-eletronic properties of KTaO3 by doping rare earth metal (Er) and further photodeposition of noble metal nanoparticles (Pt). Inclusion of rare earth element in orthorhombic structure of tantalate can generate one high-energy photon by absorbing two or more incident low-energy photons, which convert visible-light and infrared-light into the ultraviolet-light to satisfy the requirement of KTaO3 photocatalysts. On the other hand, depositions of noble metal nanoparticles on the surface of semiconductor strongly absorb visible-light due to their surface plasmon resonance, in which their conducting electrons undergo a collective oscillation induced by electric field of visible-light. Furthermore, the high dispersion of Pt nanoparticles, which will be obtained by photodeposition process is additional important factor to improve the photocatalytic activity. The present work is aimed to study the effect of photocatalytic process of the prepared Er-doped KTaO3 and further incorporation of Pt nanoparticles by photodeposition. Moreover, the research is also studied correlations between photocatalytic activity and physico-chemical properties of obtained Pt/Er-KTaO3 samples. The Er-doped KTaO3 microcomposites were synthesized by a hydrothermal method. Then photodeposition method was used for Pt loading over Er-KTaO3. The structural and optical properties of Pt/Er-KTaO3 photocatalytic were characterized using scanning electron microscope (SEM), X-ray diffraction (XRD), volumetric adsorption method (BET), UV-Vis absorption measurement, Raman spectroscopy and luminescence spectroscopy. The photocatalytic properties of Pt/Er-KTaO3 microcomposites were investigated by degradation of phenol in aqueous phase as model pollutant under visible and ultraviolet-light irradiation. Results of this work show that all the prepared photocatalysis exhibit low BET surface area, although doping of the bare KTaO3 with rare earth element (Er) presents a slight increase in this value. The crystalline structure of Pt/Er-KTaO3 powders exhibited nearly identical positions for the main peak at about 22,8o and the XRD pattern could be assigned to an orthorhombic distorted perovskite structure. The Raman spectra of obtained semiconductors confirmed demonstrating perovskite-like structure. The optical absorption spectra of Pt nanoparticles exhibited plasmon absorption band for main peaks at about 216 and 264 nm. The addition of Pt nanoparticles increased photoactivity compared to Er-KTaO3 and pure KTaO3. Summary optical properties of KTaO3 change with its doping Er-element and further photodeposition of Pt nanoparticles.

Keywords: heterogeneous photocatalytic, KTaO3 photocatalysts, Er3+ ion doping, Pt photodeposition

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Authors: Mrunal Phatak

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Introduction: Thyroid hormone is important for the normal function of the auditory system. Hearing impairment can occur insidiously in subclinical hypothyroidism. The present study was undertaken with the aim of evaluating audiological tests like tuning fork tests, pure tone audiometry, brainstem evoked auditory potentials (BAEPs), and auditory reaction time (ART) in hypothyroid women and in age and sex-matched controls to evaluate the effect of thyroid hormone on hearing. The objective of the study was to investigate hearing status by the audiological profile in hypothyroidism (group 1) and healthy controls (group 2) to compare the audiological profile between these groups and find the correlation of levels of TSH, T3 and T4 with the above parameters. Material and methods: A total sample size of 124 women in the age group of 30 to 50 years was recruited and divided into the Cases group comprising 62 newly diagnosed hypothyroid women and a Control group having 62 women with normal thyroid profiles. Otoscopic examination, tuning fork tests, Pure tone audiometry tests (PTA). Brain Stem Auditory Evoked Potential (BAEP) and Auditory Reaction Time (ART) were done in both ears, i.e., a total of 248 ears of all subjects. Results: By BAEPs, hearing impairment was detected in a total of 64 years (51.61%). A significant increase was seen in Wave V latency, IPL I-V and IPL III-V, and the decrease was seen in the amplitude of Wave I and V in both the ears cases. A positive correlation of Wave V latency of the Right and Left ears is seen with TSH levels (p < 0.001) and a negative correlation with T3 (>0.05) and with T4 (p < 0.01). The negative correlation of wave V amplitude of the Right and Left ears is seen with TSH levels (p < 0.001), and a significant positive correlation is seen with T3 and T4. Pure tone audiometry parameters showed hearing impairment of conductive (31.29%), sensorineural (36.29%), as well as mixed type (15.32%). Hearing loss was mild in 65.32% of ears and moderate in 17.74% of ears. Pure tone averages (PTA) were significantly increased in cases than in controls in both ears. A significant positive correlation of PTA of Right and Left ears is seen with TSH levels (p<0.05). A negative correlation between T3 and T4 is seen. A significant increase in HF ART and LF ART is seen in cases as compared to controls. A positive correlation between ART of high frequency and low frequency is seen with TSH levels and a negative correlation with T3 and T4 (p > 0.05). Conclusion: The abnormal BAEPs in hypothyroid women suggest an impaired central auditory pathway. BAEP abnormalities are indicative of a nonspecific injury in the bulbo-ponto-mesencephalic centers. The results of auditory investigations suggest a causal relationship between hypothyroidism and hearing loss. The site of lesion in the auditory pathway is probably at several levels, namely, in the middle ear and at cochlear and retrocochlear sites. Prolonged ART also suggests an impairment in central processing mechanisms. The results of the present study conclude that the probable reason for hearing impairment in hypothyroidism may be delayed impulse conduction in the acoustic nerve up to the level of the midbrain (IPL I-V, III-V), particularly the inferior colliculus (wave V). There is also impairment in central processing mechanisms, as shown by prolonged ART.

Keywords: hypothyroidism, deafness, pure tone audiometry, brain stem auditory evoked potential

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Authors: Guilherme M. Pereira, Kimmo Teinïla, Danilo Custódio, Risto Hillamo, Célia Alves, Pérola de C. Vasconcellos

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South American large cities often present serious air pollution problems and their atmosphere composition is influenced by a variety of emissions sources. The South American Emissions Megacities, and Climate project (SAEMC) has focused on the study of emissions and its influence on climate in the South American largest cities and it also included Lima (Peru) and Medellin (Colombia), sites where few studies of the genre were done. Lima is a coastal city with more than 8 million inhabitants and the second largest city in South America. Medellin is a 2.5 million inhabitants city and second largest city in Colombia; it is situated in a valley. The samples were collected in quartz fiber filters in high volume samplers (Hi-Vol), in 24 hours of sampling. The samples were collected in intensive campaigns in both sites, in July, 2010. Several species were determined in the aerosol samples of Lima and Medellin. Organic and elemental carbon (OC and EC) in thermal-optical analysis; biomass burning tracers (levoglucosan - Lev, mannosan - Man and galactosan - Gal) in high-performance anion exchange ion chromatography with mass spectrometer detection; water soluble ions in ion chromatography. The average particulate matter was similar for both campaigns, the PM10 concentrations were above the recommended by World Health Organization (50 µg m⁻³ – daily limit) in 40% of the samples in Medellin, while in Lima it was above that value in 15% of the samples. The average total ions concentration was higher in Lima (17450 ng m⁻³ in Lima and 3816 ng m⁻³ in Medellin) and the average concentrations of sodium and chloride were higher in this site, these species also had better correlations (Pearson’s coefficient = 0,63); suggesting a higher influence of marine aerosol in the site due its location in the coast. Sulphate concentrations were also much higher at Lima site; which may be explained by a higher influence of marine originated sulphate. However, the OC, EC and monosaccharides average concentrations were higher at Medellin site; this may be due to the lower dispersion of pollutants due to the site’s location and a larger influence of biomass burning sources. The levoglucosan average concentration was 95 ng m⁻³ for Medellin and 16 ng m⁻³ and OC was well correlated with levoglucosan (Pearson’s coefficient = 0,86) in Medellin; suggesting a higher influence of biomass burning over the organic aerosol in this site. The Lev/Man ratio is often related to the type of biomass burned and was close to 18, similar to the observed in previous studies done at biomass burning impacted sites in the Amazon region; backward trajectories also suggested the transport of aerosol from that region. Biomass burning appears to have a larger influence on the air quality in Medellin, in addition the vehicular emissions; while Lima showed a larger influence of marine aerosol during the study period.

Keywords: aerosol transport, atmospheric particulate matter, biomass burning, SAEMC project

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Authors: Mrunal Phatak, Suvarna Raut

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Introduction: Thyroid hormone is important for the normal function of the auditory system. Hearing impairment can occur insidiously in subclinical hypothyroidism. The present study was undertaken with the aims of evaluating audiological tests like tuning fork tests, pure tone audiometry, brainstem evoked auditory potentials (BAEPs), and auditory reaction time (ART) in hypothyroid women and in age and sex matched controls so as to evaluate the effect of thyroid hormone on hearing. The objective of the study was to investigate hearing status by the audiological profile in hypothyroidism (group 1) and healthy controls ( group 2) to compare the audiological profile between these groups and find the correlation of levels of TSH, T3, and T4 with the above parameters. Material and methods: A total sample size of 124 women in the age group of 30 to 50 years was recruited and divided into the Cases group comprising of 62 newly diagnosed hypothyroid women and the Control group having 62 women with normal thyroid profile. Otoscopic examination, tuning fork tests, Pure tone audiometry tests (PTA). Brain Stem Auditory Evoked Potential (BAEP) and Auditory Reaction Time (ART) were done in both ears, i.e. total 248 ears of all subjects. Results: By BAEPs, hearing impairment was detected in total 64 ears (51.61%). A significant increase was seen in Wave V latency, IPL I-V, and IPL III-V, and the decrease was seen in the amplitude of Wave I and V in both the ears in cases. Positive correlation of Wave V latency of Right and Left ears is seen with TSH levels (p < 0.001) and a negative correlation with T3 (>0.05) and with T4 (p < 0.01). Negative correlation of wave V amplitude of Right and Left ears is seen with TSH levels (p < 0.001), and a significant positive correlation is seen with T3 and T4. Pure tone audiometry parameters showed hearing impairment of conductive (31.29%), sensorineural (36.29%), as well as the mixed type (15.32%). Hearing loss was mild in 65.32% of ears and moderate in 17.74% of ears. Pure tone averages (PTA) were significantly increased in cases than in controls in both the ears. Significant positive correlation of PTA of Right and Left ears is seen with TSH levels (p<0.05). Negative correlation with T3 and T4 is seen. A significant increase in HF ART and LF ART is seen in cases as compared to controls. Positive correlation of ART of high frequency and low frequency is seen with TSH levels and a negative correlation with T3 and T4 (p > 0.05). Conclusion: The abnormal BAEPs in hypothyroid women suggest an impaired central auditory pathway. BAEP abnormalities are indicative of a nonspecific injury in the bulbo-ponto-mesencephalic centres. The results of auditory investigations suggest a causal relationship between hypothyroidism and hearing loss. The site of lesion in the auditory pathway is probably at several levels, namely, in the middle ear and at cochlear and retrocochlear sites. Prolonged ART also suggests the impairment in central processing mechanisms. The results of the present study conclude that the probable reason for hearing impairment in hypothyroidism may be delayed impulse conduction in acoustic nerve up to the level of the midbrain (IPL I-V, III-V), particularly inferior colliculus (wave V). There is also impairment in central processing mechanisms, as shown by prolonged ART.

Keywords: deafness, pure tone audiometry, brain stem auditory evoked potential, hyopothyroidism

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Authors: Bryan Low

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In the coming decades, the global maritime industry will face a most formidable environmental challenge -achieving net zero carbon emissions by 2050. To meet this target, the Maritime Port Authority of Singapore (MPA) has worked to establish green shipping and digital corridors with ports of several other countries around the world where ships will use low-carbon alternative fuels such as ammonia for power generation. While this paradigm shift to the bunkering of greener fuels is encouraging, fuels like ammonia will also introduce a new and unique type of environmental risk in the unlikely scenario of a spill. While numerous modelling studies have been conducted for oil spills and their associated environmental impact on coastal and marine ecosystems, ammonia spills are comparatively less well understood. For example, there is a knowledge gap regarding how the complex hydrodynamic conditions of the Singapore Straits may influence the dispersion of a hypothetical ammonia plume, which has different physical and chemical properties compared to an oil slick. Chemically, ammonia can be absorbed by phytoplankton, thus altering the balance of the marine nitrogen cycle. Biologically, ammonia generally serves the role of a nutrient in coastal ecosystems at lower concentrations. However, at higher concentrations, it has been found to be toxic to many local species. It may also have the potential to trigger eutrophication and harmful algal blooms (HABs) in coastal waters, depending on local hydrodynamic conditions. Thus, the key objective of this research paper is to support the development of a model-based forecasting system that can predict ammonia plume behaviour in coastal waters, given prevailing hydrodynamic conditions and their environmental impact. This will be essential as ammonia bunkering becomes more commonplace in Singapore’s ports and around the world. Specifically, this system must be able to assess the HAB-triggering potential of an ammonia plume, as well as its lethal and sub-lethal toxic effects on local species. This will allow the relevant authorities to better plan risk mitigation measures or choose a time window with the ideal hydrodynamic conditions to conduct ammonia bunkering operations with minimal risk. In this paper, we present the first part of such a forecasting system: a jointly coupled hydrodynamic-water quality model that can capture how advection-diffusion processes driven by ocean currents influence plume behaviour and how the plume interacts with the marine nitrogen cycle. The model is then applied to various ammonia spill scenarios where the results are discussed in the context of current ammonia toxicity guidelines, impact on local ecosystems, and mitigation measures for future bunkering operations conducted in the Singapore Straits.

Keywords: ammonia bunkering, forecasting, harmful algal blooms, hydrodynamics, marine nitrogen cycle, oceanography, water quality modeling

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Authors: Xiaoyong He

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

Keywords: graphene, metamaterials, terahertz, tunable

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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: Jessie Rapoza, Petr Moroshkin, Jimmy Xu

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Chirality is omnipresent, in nature, in life, and in the field of physics. One intriguing example is the homochirality that has remained a great secret of life. Another is the pairs of mirror-image molecules – enantiomers. They are identical in atomic composition and therefore indistinguishable in the scalar physical properties. Yet, they can be either therapeutic or toxic, depending on their chirality. Recent studies suggest a potential link between abnormal levels of certain D-amino acids and some serious health impairments, including schizophrenia, amyotrophic lateral sclerosis, and potentially cancer. Although indistinguishable in their scalar properties, the chirality of a molecule reveals itself in interaction with the surrounding of a certain chirality, or more generally, a broken mirror-symmetry. In this work, we report on a system for chiral molecule detection, in which the mirror-symmetry is doubly broken, first by asymmetric structuring a nanopatterned plasmonic surface than by the incidence of circularly polarized light (CPL). In this system, the incident circularly-polarized light induces a surface plasmon polariton (SPP) wave, propagating along the asymmetric plasmonic surface. This SPP field itself is chiral, evanescently bound to a near-field zone on the surface (~10nm thick), but with an amplitude greatly intensified (by up to 104) over that of the incident light. It hence probes just the molecules on the surface instead of those in the volume. In coupling to molecules along its path on the surface, the chiral SPP wave favors one chirality over the other, allowing for chirality detection via the change in an optical rectification current measured at the edges of the sample. The asymmetrically structured surface converts the high-frequency electron plasmonic-oscillations in the SPP wave into a net DC drift current that can be measured at the edge of the sample via the mechanism of optical rectification. The measured results validate these design concepts and principles. The observed optical rectification current exhibits a clear differentiation between a pair of enantiomers. Experiments were performed by focusing a 1064nm CW laser light at the sample - a gold grating microchip submerged in an approximately 1.82M solution of either L-arabinose or D-arabinose and water. A measurement of the current output was then recorded under both rights and left circularly polarized lights. Measurements were recorded at various angles of incidence to optimize the coupling between the spin-momentums of the incident light and that of the SPP, that is, spin-momentum locking. In order to suppress the background, the values of the photocurrent for the right CPL are subtracted from those for the left CPL. Comparison between the two arabinose enantiomers reveals a preferential signal response of one enantiomer to left CPL and the other enantiomer to right CPL. In sum, this work reports on the first experimental evidence of the feasibility of chiral molecule detection via optical rectification in a metal meta-grating. This nanoscale interfaced electrical detection technology is advantageous over other detection methods due to its size, cost, ease of use, and integration ability with read-out electronic circuits for data processing and interpretation.

Keywords: Chirality, detection, molecule, spin

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Authors: Xuechun Kan, Dongdong Li, Fan Li, Peidang Liu

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Triple-negative breast cancer (TNBC) is the most malignant subtype of breast cancer with a poor prognosis, and radiotherapy is one of the main treatment methods. However, due to the obvious resistance of tumor cells to radiotherapy, high dose of ionizing radiation is required during radiotherapy, which causes serious damage to normal tissues near the tumor. Therefore, how to improve radiotherapy resistance and enhance the specific killing of tumor cells by radiation is a hot issue that needs to be solved in clinic. Recent studies have shown that silver-based nanoparticles have strong radiosensitization, and silver nanoclusters (AgNCs) also provide a broad prospect for tumor targeted radiosensitization therapy due to their ultra-small size, low toxicity or non-toxicity, self-fluorescence and strong photostability. Aptamer 5TR1 is a 25-base oligonucleotide aptamer that can specifically bind to mucin-1 highly expressed on the membrane surface of TNBC 4T1 cells, and can be used as a highly efficient tumor targeting molecule. In this study, AgNCs were synthesized by DNA template based on 5TR1 aptamer (NC-T5-5TR1), and its role as a targeted radiosensitizer in TNBC radiotherapy was investigated. The optimal DNA template was first screened by fluorescence emission spectroscopy, and NC-T5-5TR1 was prepared. NC-T5-5TR1 was characterized by transmission electron microscopy, ultraviolet-visible spectroscopy and dynamic light scattering. The inhibitory effect of NC-T5-5TR1 on cell activity was evaluated using the MTT method. Laser confocal microscopy was employed to observe NC-T5-5TR1 targeting 4T1 cells and verify its self-fluorescence characteristics. The uptake of NC-T5-5TR1 by 4T1 cells was observed by dark-field imaging, and the uptake peak was evaluated by inductively coupled plasma mass spectrometry. The radiation sensitization effect of NC-T5-5TR1 was evaluated through cell cloning and in vivo anti-tumor experiments. Annexin V-FITC/PI double staining flow cytometry was utilized to detect the impact of nanomaterials combined with radiotherapy on apoptosis. The results demonstrated that the particle size of NC-T5-5TR1 is about 2 nm, and the UV-visible absorption spectrum detection verifies the successful construction of NC-T5-5TR1, and it shows good dispersion. NC-T5-5TR1 significantly inhibited the activity of 4T1 cells and effectively targeted and fluoresced within 4T1 cells. The uptake of NC-T5-5TR1 reached its peak at 3 h in the tumor area. Compared with AgNCs without aptamer modification, NC-T5-5TR1 exhibited superior radiation sensitization, and combined radiotherapy significantly inhibited the activity of 4T1 cells and tumor growth in 4T1-bearing mice. The apoptosis level of NC-T5-5TR1 combined with radiation was significantly increased. These findings provide important theoretical and experimental support for NC-T5-5TR1 as a radiation sensitizer for TNBC.

Keywords: 5TR1 aptamer, silver nanoclusters, radio sensitization, triple-negative breast cancer

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Authors: George Zhou, Yunchan Chen, Candace Chien

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Kidney replacement therapy is the current standard of care for end-stage renal diseases. In-center or home hemodialysis remains an integral component of the therapeutic regimen. Arteriovenous fistulas (AVF) make up the vascular circuit through which blood is filtered and returned. Naturally, AVF patency determines whether adequate clearance and filtration can be achieved and directly influences clinical outcomes. Our aim was to build a deep learning model for automated AVF stenosis screening based on the sound of blood flow through the AVF. A total of 311 patients with AVF were enrolled in this study. Blood flow sounds were collected using a digital stethoscope. For each patient, blood flow sounds were collected at 6 different locations along the patient’s AVF. The 6 locations are artery, anastomosis, distal vein, middle vein, proximal vein, and venous arch. A total of 1866 sounds were collected. The blood flow sounds are labeled as “patent” (normal) or “stenotic” (abnormal). The labels are validated from concurrent ultrasound. Our dataset included 1527 “patent” and 339 “stenotic” sounds. We show that blood flow sounds vary significantly along the AVF. For example, the blood flow sound is loudest at the anastomosis site and softest at the cephalic arch. Contextualizing the sound with location metadata significantly improves classification performance. How to encode and incorporate categorical metadata is an active area of research1. Herein, we study ordinal (i.e., integer) encoding schemes. The numerical representation is concatenated to the flattened feature vector. We train a vision transformer (ViT) on spectrogram image representations of the sound and demonstrate that using scalar multiples of our integer encodings improves classification performance. Models are evaluated using a 10-fold cross-validation procedure. The baseline performance of our ViT without any location metadata achieves an AuROC and AuPRC of 0.68 ± 0.05 and 0.28 ± 0.09, respectively. Using the following encodings of Artery:0; Arch: 1; Proximal: 2; Middle: 3; Distal 4: Anastomosis: 5, the ViT achieves an AuROC and AuPRC of 0.69 ± 0.06 and 0.30 ± 0.10, respectively. Using the following encodings of Artery:0; Arch: 10; Proximal: 20; Middle: 30; Distal 40: Anastomosis: 50, the ViT achieves an AuROC and AuPRC of 0.74 ± 0.06 and 0.38 ± 0.10, respectively. Using the following encodings of Artery:0; Arch: 100; Proximal: 200; Middle: 300; Distal 400: Anastomosis: 500, the ViT achieves an AuROC and AuPRC of 0.78 ± 0.06 and 0.43 ± 0.11. respectively. Interestingly, we see that using increasing scalar multiples of our integer encoding scheme (i.e., encoding “venous arch” as 1,10,100) results in progressively improved performance. In theory, the integer values do not matter since we are optimizing the same loss function; the model can learn to increase or decrease the weights associated with location encodings and converge on the same solution. However, in the setting of limited data and computation resources, increasing the importance at initialization either leads to faster convergence or helps the model escape a local minimum.

Keywords: arteriovenous fistula, blood flow sounds, metadata encoding, deep learning

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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: Tanya Kaur Bedi, Shankha Pratim Bhattacharya

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The US Environmental Protection Agency defines indoor air quality as “The air quality within and around buildings, especially as it relates to the health and comfort of building occupants”. According to the 2021 report by the Energy Policy Institute at Chicago, Indian residents, a country which is home to the highest levels of air pollution in the world, lose about 5.9 years from life expectancy due to poor air quality and yet has numerous dwellings dependent on natural ventilation. Currently the urban population spends 90% of the time indoors, this scenario raises a concern for occupant health and well-being. The built environment can affect health directly and indirectly through immediate or long-term exposure to indoor air pollutants. Health effects associated with indoor air pollutants include eye/nose/throat irritation, respiratory diseases, heart disease, and even cancer. This study attempts to demonstrate the causal relationship between the indoor air quality and its determining aspects. Detailed indoor air quality audits were conducted in residential buildings located in Kolkata, India in the months of December and January 2021. According to the air pollution knowledge assessment city program in India, Kolkata is also the second most polluted mega-city after Delhi. Although the air pollution levels are alarming year-long, the winter months are most crucial due to the unfavorable environmental conditions. While emissions remain typically constant throughout the year, cold air is denser and moves slower than warm air, trapping the pollution in place for much longer and consequently is breathed in at a higher rate than the summers. The air pollution monitoring period was selected considering environmental factors and major pollution contributors like traffic and road dust. This study focuses on the relationship between the built environment and the spatial-temporal distribution of air pollutants in and around it. The measured parameters include, temperature, relative humidity, air velocity, particulate matter, volatile organic compounds, formaldehyde, and benzene. A total of 56 rooms were audited, selectively targeting the most dominant middle-income group. The data-collection was conducted using a set of instruments positioned in the human breathing-zone. The study assesses indoor air quality based on factors determining natural ventilation and air pollution dispersion such as surrounding environment, dominant wind, openable window to floor area ratio, windward or leeward side openings, and natural ventilation type in the room: single side or cross-ventilation, floor height, residents cleaning habits, etc.

Keywords: indoor air quality, occupant health, urban housing, air pollution, natural ventilation, architecture, urban issues

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Authors: Ewelina Grabowska, Martyna Marchelek

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Among the various semiconductors, nanosized TiO2 has been widely studied due to its high photosensitivity, low cost, low toxicity, and good chemical and thermal stability. However, there are two main drawbacks to the practical application of pure TiO2 films. One is that TiO2 can be induced only by ultraviolet (UV) light due to its intrinsic wide bandgap (3.2 eV for anatase and 3.0 eV for rutile), which limits its practical efficiency for solar energy utilization since UV light makes up only 4-5% of the solar spectrum. The other is that a high electron-hole recombination rate will reduce the photoelectric conversion efficiency of TiO2. In order to overcome the above drawbacks and modify the electronic structure of TiO2, some semiconductors (eg. CdS, ZnO, PbS, Cu2O, Bi2S3, and CdSe) have been used to prepare coupled TiO2 composites, for improving their charge separation efficiency and extending the photoresponse into the visible region. It has been proved that the fabrication of p-n heterostructures by combining n-type TiO2 with p-type semiconductors is an effective way to improve the photoelectric conversion efficiency of TiO2. SrTiO3 is a good candidate for coupling TiO2 and improving the photocatalytic performance of the photocatalyst because its conduction band edge is more negative than TiO2. Due to the potential differences between the band edges of these two semiconductors, the photogenerated electrons transfer from the conduction band of SrTiO3 to that of TiO2. Conversely, the photogenerated electrons transfer from the conduction band of SrTiO3 to that of TiO2. Then the photogenerated charge carriers can be efficiently separated by these processes, resulting in the enhancement of the photocatalytic property in the photocatalyst. Additionally, one of the methods for improving photocatalyst performance is addition of nanoparticles containing one or two noble metals (Pt, Au, Ag and Pd) deposited on semiconductor surface. The mechanisms were proposed as (1) the surface plasmon resonance of noble metal particles is excited by visible light, facilitating the excitation of the surface electron and interfacial electron transfer (2) some energy levels can be produced in the band gap of TiO2 by the dispersion of noble metal nanoparticles in the TiO2 matrix; (3) noble metal nanoparticles deposited on TiO2 act as electron traps, enhancing the electron–hole separation. In view of this, we recently obtained series of TiO2@SrTiO3 and SrTiO3 photocatalysts loaded with noble metal NPs. using photodeposition method. The M- TiO2@SrTiO3 and M-SrTiO3 photocatalysts (M= Rh, Rt, Pt) were studied for photodegradation of phenol in aqueous phase under UV-Vis and visible irradiation. Moreover, in the second part of our research hydroxyl radical formations were investigated. Fluorescence of irradiated coumarin solution was used as a method of ˙OH radical detection. Coumarin readily reacts with generated hydroxyl radicals forming hydroxycoumarins. Although the major hydroxylation product is 5-hydroxycoumarin, only 7-hydroxyproduct of coumarin hydroxylation emits fluorescent light. Thus, this method was used only for hydroxyl radical detection, but not for determining concentration of hydroxyl radicals.

Keywords: composites TiO2, SrTiO3, photocatalysis, phenol degradation

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Authors: William Ho, Agus Wicaksana

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Anecdotal evidence in the last decade shows that the occurrence of disruptive events and uncertainties in the supply chain is increasing. The coupling of these events with the nature of an increasingly complex and interdependent business environment leads to devastating impacts that quickly propagate within and across organizations. For example, the recent COVID-19 pandemic increased the global supply chain disruption frequency by at least 20% in 2020 and is projected to have an accumulative cost of $13.8 trillion by 2024. This crisis raises attention to organizational resilience to weather business uncertainty. However, the concept has been criticized for being vague and lacking a consistent definition, thus reducing the significance of the concept for practice and research. This study is intended to solve that issue by providing a comprehensive review of the conceptualization, measurement, and antecedents of operational resilience that have been discussed in the supply chain risk management literature (SCRM). We performed a Scholarly Network Analysis, combining citation-based and text-based approaches, on 252 articles published from 2000 to 2021 in top-tier journals based on three parameters: AJG ranking and ABS ranking, UT Dallas and FT50 list, and editorial board review. We utilized a hybrid scholarly network analysis by combining citation-based and text-based approaches to understand the conceptualization, measurement, and antecedents of operational resilience in the SCRM literature. Specifically, we employed a Bibliographic Coupling Analysis in the research cluster formation stage and a Co-words Analysis in the research cluster interpretation and analysis stage. Our analysis reveals three major research clusters of resilience research in the SCRM literature, namely (1) supply chain network design and optimization, (2) organizational capabilities, and (3) digital technologies. We portray the research process in the last two decades in terms of the exemplar studies, problems studied, commonly used approaches and theories, and solutions provided in each cluster. We then provide a conceptual framework on the conceptualization and antecedents of resilience based on studies in these clusters and highlight potential areas that need to be studied further. Finally, we leverage the concept of abnormal operating performance to propose a new measurement strategy for resilience. This measurement overcomes the limitation of most current measurements that are event-dependent and focus on the resistance or recovery stage - without capturing the growth stage. In conclusion, this study provides a robust literature review through a scholarly network analysis that increases the completeness and accuracy of research cluster identification and analysis to understand conceptualization, antecedents, and measurement of resilience. It also enables us to perform a comprehensive review of resilience research in SCRM literature by including research articles published during the pandemic and connects this development with a plethora of articles published in the last two decades. From the managerial perspective, this study provides practitioners with clarity on the conceptualization and critical success factors of firm resilience from the SCRM perspective.

Keywords: supply chain risk management, organizational resilience, scholarly network analysis, systematic literature review

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Authors: Maja Benkovic, Dubravka Novotni, Bojana Voucko, Duska Curic, Damir Jezek, Nikolina Cukelj

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Cryo-grinding is an ultra-fine grinding method used in the pharmaceutical industry, production of herbs and spices and in the production and handling of cereals, due to its ability to produce powders with small particle sizes which maintain their favorable bioactive profile. The aim of this study was to determine the particle size distributions of the proso millet (Panicum miliaceum) bran fraction grinded at cryogenic temperature (using liquid nitrogen (LN₂) cooling, T = - 196 °C), in comparison to non-cooled grinding. Proso millet bran is primarily used as an animal feed, but has a potential in food applications, either as a substrate for extraction of bioactive compounds or raw material in the bakery industry. For both applications finer particle sizes of the bran could be beneficial. Thus, millet bran was ground for 2, 4, 8 and 12 minutes using the ball mill (CryoMill, Retsch GmbH, Haan, Germany) at three grinding modes: (I) without cooling, (II) at cryo-temperature, and (III) at cryo-temperature with included 1 minute of intermediate cryo-cooling step after every 2 minutes of grinding, which is usually applied when samples require longer grinding times. The sample was placed in a 50 mL stainless steel jar containing one grinding ball (Ø 25 mm). The oscillation frequency in all three modes was 30 Hz. Particle size distributions of the bran were determined by a laser diffraction particle sizing method (Mastersizer 2000) using the Scirocco 2000 dry dispersion unit (Malvern Instruments, Malvern, UK). Three main effects of the grinding set-up were visible from the results. Firstly, grinding time at all three modes had a significant effect on all particle size parameters: d(0.1), d(0.5), d(0.9), D[3,2], D[4,3], span and specific surface area. Longer grinding times resulted in lower values of the above-listed parameters, e.g. the averaged d(0.5) of the sample (229.57±1.46 µm) dropped to 51.29±1.28 µm after 2 minutes grinding without LN₂, and additionally to 43.00±1.33 µm after 4 minutes of grinding without LN₂. The only exception was the sample ground for 12 minutes without cooling, where an increase in particle diameters occurred (d(0.5)=62.85±2.20 µm), probably due to particles adhering to one another and forming larger particle clusters. Secondly, samples with LN₂ cooling exhibited lower diameters in comparison to non-cooled. For example, after 8 minutes of non-cooled grinding d(0.5)=46.97±1.05 µm was achieved, while the LN₂ cooling enabled collection of particles with average sizes of d(0.5)=18.57±0.18 µm. Thirdly, the application of intermediate cryo-cooling step resulted in similar particle diameters (d(0.5)=15.83±0.36 µm, 12 min of grinding) as cryo-milling without this step (d(0.5)=16.33±2.09 µm, 12 min of grinding). This indicates that intermediate cooling is not necessary for the current application, which consequently reduces the consumption of LN₂. These results point out the potential beneficial effects of millet bran grinding at cryo-temperatures. Further research will show if the lower particle size achieved in comparison to non-cooled grinding could result in increased bioavailability of bioactive compounds, as well as protein digestibility and solubility of dietary fibers of the proso millet bran fraction.

Keywords: ball mill, cryo-milling, particle size distribution, proso millet (Panicum miliaceum) bran

Procedia PDF Downloads 142

Authors: Bashar Mahmoud, Lee Mortimer, Michael Fairweather

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New methods have recently been introduced to improve the thermal property values of molten nitrate salts (a binary mixture of NaNO3:KNO3in 60:40 wt. %), by doping them with minute concentration of nanoparticles in the range of 0.5 to 1.5 wt. % to form the so-called: Nano-heat-transfer-fluid, apt for thermal energy transfer and storage applications. The present study aims to assess the stability of these nanofluids using the advanced computational modelling technique, Lagrangian particle tracking. A multi-phase solid-liquid model is used, where the motion of embedded nanoparticles in the suspended fluid is treated by an Euler-Lagrange hybrid scheme with fixed time stepping. This technique enables measurements of various multi-scale forces whose characteristic (length and timescales) are quite different. Two systems are considered, both consisting of 50 nm Al2O3 ceramic nanoparticles suspended in fluids of different density ratios. This includes both water (5 to 95 °C) and molten nitrate salt (220 to 500 °C) at various volume fractions ranging between 1% to 5%. Dynamic properties of both phases are coupled to the ambient temperature of the fluid suspension. The three-dimensional computational region consists of a 1μm cube and particles are homogeneously distributed across the domain. Periodic boundary conditions are enforced. The particle equations of motion are integrated using the fourth order Runge-Kutta algorithm with a very small time-step, Δts, set at 10-11 s. The implemented technique demonstrates the key dynamics of aggregated nanoparticles and this involves: Brownian motion, soft-sphere particle-particle collisions, and Derjaguin, Landau, Vervey, and Overbeek (DLVO) forces. These mechanisms are responsible for the predictive model of aggregation of nano-suspensions. An energy transport-based method of predicting the thermal conductivity of the nanofluids is also used to determine thermal properties of the suspension. The simulation results confirms the effectiveness of the technique. The values are in excellent agreement with the theoretical and experimental data obtained from similar studies. The predictions indicates the role of Brownian motion and DLVO force (represented by both the repulsive electric double layer and an attractive Van der Waals) and its influence in the level of nanoparticles agglomeration. As to the nano-aggregates formed that was found to play a key role in governing the thermal behavior of nanofluids at various particle concentration. The presentation will include a quantitative assessment of these forces and mechanisms, which would lead to conclusions about nanofluids, heat transfer performance and thermal characteristics and its potential application in solar thermal energy plants.

Keywords: thermal energy storage, molten salt, nano-fluids, multi-scale computational modelling

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Authors: C. Silveira, A. Ascenso, J. Ferreira, A. I. Miranda, P. Tuccella, G. Curci

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Poor air quality is one of the main environmental causes of premature deaths worldwide, and mainly in cities, where the majority of the population lives. It is a consequence of successive land cover (LC) and use changes, as a result of the intensification of human activities. Knowing these landscape modifications in a comprehensive spatiotemporal dimension is, therefore, essential for understanding variations in air pollutant concentrations. In this sense, the use of air quality models is very useful to simulate the physical and chemical processes that affect the dispersion and reaction of chemical species into the atmosphere. However, the modelling performance should always be evaluated since the resolution of the input datasets largely dictates the reliability of the air quality outcomes. Among these data, the updated LC is an important parameter to be considered in atmospheric models, since it takes into account the Earth’s surface changes due to natural and anthropic actions, and regulates the exchanges of fluxes (emissions, heat, moisture, etc.) between the soil and the air. This work aims to evaluate the performance of the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem), when different LC classifications are used as an input. The influence of two LC classifications was tested: i) the 24-classes USGS (United States Geological Survey) LC database included by default in the model, and the ii) CLC (Corine Land Cover) and specific high-resolution LC data for Portugal, reclassified according to the new USGS nomenclature (33-classes). Two distinct WRF-Chem simulations were carried out to assess the influence of the LC on air quality over Europe and Portugal, as a case study, for the year 2015, using the nesting technique over three simulation domains (25 km², 5 km² and 1 km² horizontal resolution). Based on the 33-classes LC approach, particular emphasis was attributed to Portugal, given the detail and higher LC spatial resolution (100 m x 100 m) than the CLC data (5000 m x 5000 m). As regards to the air quality, only the LC impacts on tropospheric ozone concentrations were evaluated, because ozone pollution episodes typically occur in Portugal, in particular during the spring/summer, and there are few research works relating to this pollutant with LC changes. The WRF-Chem results were validated by season and station typology using background measurements from the Portuguese air quality monitoring network. As expected, a better model performance was achieved in rural stations: moderate correlation (0.4 – 0.7), BIAS (10 – 21µg.m^-3) and RMSE (20 – 30 µg.m^-3), and where higher average ozone concentrations were estimated. Comparing both simulations, small differences grounded on the Leaf Area Index and air temperature values were found, although the high-resolution LC approach shows a slight enhancement in the model evaluation. This highlights the role of the LC on the exchange of atmospheric fluxes, and stresses the need to consider a high-resolution LC characterization combined with other detailed model inputs, such as the emission inventory, to improve air quality assessment.

Keywords: land use, spatial resolution, WRF-Chem, air quality assessment

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Authors: Elissandro Voigt Beier, Cristiano Poleto

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The main objective of the research is to assess the loss through the quantification of material culture (archaeological fragments) in rural areas, sites explored economically by machining on seasonal crops, and also permanent, in a hydrographic subsystem Camaquã River in the state of Rio Grande do Sul, Brazil. The study area consists of different micro basins and differs in area, ranging between 1,000 m² and 10,000 m², respectively the largest and the smallest, all with a large number of occurrences and outcrop locations of archaeological material and high density in intense farm environment. In the first stage of the research aimed to identify the dispersion of points of archaeological material through field survey through plot points by the Global Positioning System (GPS), within each river basin, was made use of concise bibliography on the topic in the region, helping theoretically in understanding the old landscaping with preferences of occupation for reasons of ancient historical people through the settlements relating to the practice observed in the field. The mapping was followed by the cartographic development in the region through the development of cartographic products of the land elevation, consequently were created cartographic products were to contribute to the understanding of the distribution of the absolute materials; the definition and scope of the material dispersed; and as a result of human activities the development of revolving letter by mechanization of in situ material, it was also necessary for the preparation of materials found density maps, linking natural environments conducive to ancient historical occupation with the current human occupation. The third stage of the project it is for the systematic collection of archaeological material without alteration or interference in the subsurface of the indigenous settlements, thus, the material was prepared and treated in the laboratory to remove soil excesses, cleaning through previous communication methodology, measurement and quantification. Approximately 15,000 were identified archaeological fragments belonging to different periods of ancient history of the region, all collected outside of its environmental and historical context and it also has quite changed and modified. The material was identified and cataloged considering features such as object weight, size, type of material (lithic, ceramic, bone, Historical porcelain and their true association with the ancient history) and it was disregarded its principles as individual lithology of the object and functionality same. As observed preliminary results, we can point out the change of materials by heavy mechanization and consequent soil disturbance processes, and these processes generate loading of archaeological materials. Therefore, as a next step will be sought, an estimate of potential losses through a mathematical model. It is expected by this process, to reach a reliable model of high accuracy which can be applied to an archeological site of lower density without encountering a significant error.

Keywords: degradation of heritage, quantification in archaeology, watershed, use and occupation of land

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Authors: M. Grandcolas, N. Rival, H. Bu, S. Jahren, R. Schmid, H. Johnsen

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The concept of an autonomic self-healing material, where initiation of repair is integrated to the material, is now being considered for engineering applications and is a hot topic in the literature. Among several concepts/techniques, two are most interesting: i) Capsules: Integration of microcapsules in or at the surface of coatings or fibre-like structures has recently gained much attention. Upon damage-induced cracking, the microcapsules are broken by the propagating crack fronts resulting in a release of an active chemical (healing agent) by capillary action, subsequently repairing and avoiding further crack growth. ii) Self-healing polymers: Interestingly, the introduction of dynamic covalent bonds into polymer networks has also recently been used as a powerful approach towards the design of various intrinsically self-healing polymer systems. The idea behind this is to reconnect the chemical crosslinks which are broken when a material fractures, restoring the integrity of the material and thereby prolonging its lifetime. We propose here to integrate both self-healing concepts (capsules, self-healing polymers) in electrospun fibres and coatings. Different capsule preparation approaches have been investigated in SINTEF. The most advanced method to produce capsules is based on emulsification to create a water-in-oil emulsion before polymerisation. The healing agent is a polyurethane-based dispersion that was encapsulated in shell materials consisting of urea-benzaldehyde resins. Results showed the successful preparation of microcapsules and release of the agent when capsules break. Since capsules are produced in water-in-oil systems we mainly investigated organic solvent based coatings while a major challenge resides in the incorporation of capsules into water-based coatings. We also focused on developing more robust microcapsules to prevent premature rupture of the capsules. The capsules have been characterized in terms of size, and encapsulation and release might be visualized by incorporating fluorescent dyes and examine the capsules by microscopy techniques. Alternatively, electrospinning is an innovative technique that has attracted enormous attention due to unique properties of the produced nano-to-micro fibers, ease of fabrication and functionalization, and versatility in controlling parameters. Especially roll-to-roll electrospinning is a unique method which has been used in industry to produce nanofibers continuously. Electrospun nanofibers can usually reach a diameter down to 100 nm, depending on the polymer used, which is of interest for the concept with self-healing polymer systems. In this work, we proved the feasibility of fabrication of POSS-based (POSS: polyhedral oligomeric silsesquioxanes, tradename FunzioNano™) nanofibers via electrospinning. Two different formulations based on aqueous or organic solvents have shown nanofibres with a diameter between 200 – 450nm with low defects. The addition of FunzioNano™ in the polymer blend also showed enhanced properties in term of wettability, promising for e.g. membrane technology. The self-healing polymer systems developed are here POSS-based materials synthesized to develop dynamic soft brushes.

Keywords: capsules, coatings, electrospinning, fibers

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Authors: Anna Kolanowska, Anna Kuziel, Sławomir Boncel

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Carbon nanotubes (CNTs) represent a combination of lightness and nanoscopic size with high tensile strength, excellent thermal and electrical conductivity. By now, CNTs have been used as a support in heterogeneous catalysis (CuCl anchored to pre-functionalized CNTs) in the Ullmann-type coupling with aryl halides toward formation of C-N and C-O bonds. The results indicated that the stability of the catalyst was much improved and the elaborated catalytic system was efficient and recyclable. However, CNTs have not been considered as the substrate itself in the Ullmann-type reactions. But if successful, this functionalization would open new areas of CNT chemistry leading to enhanced in-solvent/matrix nanotube individualization. The copper-catalyzed Ullmann-type reaction is an attractive method for the formation of carbon-heteroatom and carbon-carbon bonds in organic synthesis. This condensation reaction is usually conducted at temperature as high as 200 oC, often in the presence of stoichiometric amounts of copper reagent and with activated aryl halides. However, a small amount of organic additive (e.g. diamines, amino acids, diols, 1,10-phenanthroline) can be applied in order to increase the solubility and stability of copper catalyst, and at the same time to allow performing the reaction under mild conditions. The copper (pre-)catalyst is prepared by in situ mixing of copper salt and the appropriate chelator. Our research is focused on the application of Ullmann-type reaction for the covalent functionalization of CNTs. Firstly, CNTs were chlorinated by using iodine trichloride (ICl3) in carbon tetrachloride (CCl4). This method involves formation of several chemical species (ICl, Cl2 and I2Cl6), but the most reactive is the dimer. The fact (that the dimer is the main individual in CCl4) is the reason for high reactivity and possibly high functionalization levels of CNTs. This method, indeed, yielded a notable amount of chlorine onto the MWCNT surface. The next step was the reaction of CNT-Cl with three substrates: aniline, iodobenzene and phenol for the formation C-N, C-C and C-O bonds, respectively, in the presence of 1,10-phenanthroline and cesium carbonate (Cs2CO3) as a base. As the CNT substrates, two multi-wall CNT (MWCNT) types were used: commercially available Nanocyl NC7000™ (9.6 nm diameter, 1.5 µm length, 90% purity) and thicker MWCNTs (in-house) synthesized in our laboratory using catalytic chemical vapour deposition (c-CVD). In-house CNTs had diameter ranging between 60-70 nm and length up to 300 µm. Since classical Ullmann reaction was found as suffering from poor yields, we have investigated the effect of various solvents (toluene, acetonitrile, dimethyl sulfoxide and N,N-dimethylformamide) on the coupling of substrates. Owing to the fact that the aryl halides show the reactivity order of I>Br>Cl>F, we have also investigated the effect of iodine presence on CNT surface on reaction yield. In this case, in first step we have used iodine monochloride instead of iodine trichloride. Finally, we have used the optimized reaction conditions with p-bromophenol and 1,2,4-trihydroxybenzene for the control of CNT dispersion.

Keywords: carbon nanotubes, coupling reaction, functionalization, Ullmann reaction

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Authors: Banafsheh Nikmehr, Mohsen Bahrami, Yueqiang Song, Anuradha Koduru, Ayse K. Vuruskan, Hongkun Lu, Mallory Pitts, Tolga B. Mesen, Tamer M. Yalcinkaya

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The number of people who receive in vitro fertilization (IVF) treatment has increased on a startling trajectory over the past two decades. Despite advances in this field, particularly the introduction of intracytoplasmic sperm injection (ICSI) and the preimplantation genetic screening (PGS), the IVF success remains low. A major factor contributing to IVF failure is embryonic aneuploidy (abnormal chromosome content), which often results in miscarriage and birth defects. Although PGS is often used as the standard diagnostic tool to identify aneuploid embryos, it is an invasive approach that could affect the embryo development, and yet inaccessible to many patients due its high costs. As such, there is a clear need for a non-invasive cost-effective approach to identify euploid embryos for single embryo transfer (SET). The reported differences between morphokinetic behaviors of aneuploid and euploid embryos has shown promise to address this need. However, current literature is inconclusive and further research is urgently needed to translate current findings into clinical diagnostics. In this ongoing study, we found significant differences between morphokinetic behaviors of euploid and aneuploid embryos that provides important insights and reaffirms the promise of such behaviors for developing non-invasive methodologies. Methodology—A total of 242 embryos (euploid: 149, aneuploid: 93) from 74 patients who underwent IVF treatment in Carolinas Fertility Clinics in Winston-Salem, NC, were analyzed. All embryos were incubated in an EmbryoScope incubator. The patients were randomly selected from January 2019 to June 2021 with most patients having both euploid and aneuploid embryos. All embryos reached the blastocyst stage and had known PGS outcomes. The ploidy assessment was done by a third-party testing laboratory on day 5-7 embryo biopsies. The morphokinetic variables of each embryo were measured by the EmbryoViewer software (Uniesense FertiliTech) on time-lapse images using 7 focal depths. We compared the time to: pronuclei fading (tPNf), division to 2,3,…,9 cells (t2, t3,…,t9), start of embryo compaction (tSC), Morula formation (tM), start of blastocyst formation (tSC), blastocyst formation (tB), and blastocyst expansion (tEB), as well as intervals between them (e.g., c23 = t3 – t2). We used a mixed regression method for our statistical analyses to account for the correlation between multiple embryos per patient. Major Findings— The average age of the patients was 35.04 yrs. The average patient age associated with euploid and aneuploid embryos was not different (P = 0.6454). We found a significant difference in c45 = t5-t4 (P = 0.0298). Our results indicated this interval on average lasts significantly longer for aneuploid embryos - c45(aneuploid) = 11.93hr vs c45(euploid) = 7.97hr. In a separate analysis limited to embryos from the same patients (patients = 47, total embryos=200, euploid=112, aneuploid=88), we obtained the same results (P = 0.0316). The statistical power for this analysis exceeded 87%. No other variable was different between the two groups. Conclusion— Our results demonstrate the importance of morphokinetic variables as potential biomarkers that could aid in non-invasively characterizing euploid and aneuploid embryos. We seek to study a larger population of embryos and incorporate the embryo quality in future studies.

Keywords: IVF, embryo, euploidy, aneuploidy, morphokinteic

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Authors: Nazila Dehbari, Javad Tavakoli, Yakani Kambu, Youhong Tang

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Superabsorbent hydrogels (SAP), as an enviro-sensitive material have been widely used for industrial and biomedical applications due to their unique structure and capabilities. Poor mechanical properties of SAPs - which is extremely related to their large volume change – count as a great weakness in adopting for high-tech applications. Therefore, improving SAPs’ mechanical properties via toughening methods by mixing different types of cross-linked polymer or introducing energy-dissipating mechanisms is highly focused. In this work, in order to change the intrinsic brittle character of commercialized Poly Acrylic Acid (here as SAP) to be semi-ductile, a commercial available highly branched tree-like dendritic polymers with numerous –OH end groups known as hyper-branched polymer (HB) has been added to PAA-SAP system in a single step, cost effective and environment friendly solvent casting method. Samples were characterized by FTIR, SEM and TEM and their physico-chemical characterization including swelling capabilities, hydraulic permeability, surface tension and thermal properties had been performed. Toughness energy, stiffness, elongation at breaking point, viscoelastic properties and samples extensibility were mechanical properties that had been performed and characterized as a function of samples lateral cracks’ length in different HB concentration. Addition of HB to PAA-SAP significantly improved mechanical and surface properties. Increasing equilibrium swelling ratio by about 25% had been experienced by the SAP-HB samples in comparison with SAPs; however, samples swelling kinetics remained without changes as initial rate of water uptake and equilibrium time haven’t been subjected to any changes. Thermal stability analysis showed that HB is participating in hybrid network formation while improving mechanical properties. Samples characterization by TEM showed that, the aggregated HB polymer binders into nano-spheres with diameter in range of 10–200 nm. So well dispersion in the SAP matrix occurred as it was predictable due to the hydrophilic character of the numerous hydroxyl groups at the end of HB which enhance the compatibility of HB with PAA-SAP. As the profused -OH groups in HB could react with -COOH groups in the PAA-SAP during the curing process, the formation of a 2D structure in the SAP-HB could be attributed to the strong interfacial adhesion between HB and the PAA-SAP matrix which hinders the activity of PAA chains (SEM analysis). FTIR spectra introduced new peaks at 1041 and 1121 cm-1 that attributed to the C–O(–OH) stretching hydroxyl and O–C stretching ester groups of HB polymer binder indicating the incorporation of HB polymer into the SAP structure. SAP-HB polymer has significant effects on the final mechanical properties. The brittleness of PAA hydrogels are decreased by introducing HB as the fracture energies of hydrogels increased from 8.67 to 26.67. PAA-HBs’ stretch ability enhanced about 10 folds while reduced as a function of different notches depth.

Keywords: superabsorbent polymer, toughening, viscoelastic properties, hydrogel network

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