Search results for: laser ultrasound

Authors: Bastian Waduge Naveen Harindu Hemasiri, Jae-Kwan Kim, Ji-Myon Lee

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Indium tin oxide (ITO) remains the industrial standard transparent conducting oxides with better performances. Recently, graphene becomes as a strong material with unique properties to replace the ITO. However, graphene/ITO hybrid composite material is a newly born field in the electronic world. In this study, the graphene/ITO composite bi-film was synthesized by a two steps process. 10 wt.% tin-doped, ITO thin films were produced by an environmentally friendly aqueous sol-gel spin coating technique with economical salts of In(NO3)3.H2O and SnCl4 without using organic additives. The wettability and surface free energy (97.6986 mJ/m2) enhanced oxygen plasma treated glass substrates were used to form voids free continuous ITO film. The spin-coated samples were annealed at 600 0C for 1 hour under low vacuum conditions to obtained crystallized, ITO film. The crystal structure and crystalline phases of ITO thin films were analyzed by X-ray diffraction (XRD) technique. The Scherrer equation was used to determine the crystallite size. Detailed information about chemical composition and elemental composition of the ITO film were determined by X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray spectroscopy (EDX) coupled with FE-SEM respectively. Graphene synthesis was done under chemical vapor deposition (CVD) method by using Cu foil at 1000 0C for 1 min. The quality of the synthesized graphene was characterized by Raman spectroscopy (532nm excitation laser beam) and data was collected at room temperature and normal atmosphere. The surface and cross-sectional observation were done by using FE-SEM. The optical transmission and sheet resistance were measured by UV-Vis spectroscopy and four point probe head at room temperature respectively. Electrical properties were also measured by using V-I characteristics. XRD patterns reveal that the films contain the In2O3 phase only and exhibit the polycrystalline nature of the cubic structure with the main peak of (222) plane. The peak positions of In3d5/2 (444.28 eV) and Sn3d5/2 (486.7 eV) in XPS results indicated that indium and tin are in the oxide form only. The UV-visible transmittance shows 91.35 % at 550 nm with 5.88 x 10-3 Ωcm specific resistance. The G and 2D band in Raman spectroscopy of graphene appear at 1582.52 cm-1 and 2690.54 cm-1 respectively when the synthesized CVD graphene on SiO2/Si. The determined intensity ratios of 2D to G (I2D/IG) and D to G (ID/IG) were 1.531 and 0.108 respectively. However, the above-mentioned G and 2D peaks appear at 1573.57 cm-1 and 2668.14 cm-1 respectively when the CVD graphene on the ITO coated glass, the positions of G and 2D peaks were red shifted by 8.948 cm-1 and 22.396 cm-1 respectively. This graphene/ITO bi-film shows modified electrical properties when compares with sol-gel derived ITO film. The reduction of sheet resistance in the bi-film was 12.03 % from the ITO film. Further, the fabricated graphene/ITO bi-film shows 88.66 % transmittance at 550 nm wavelength.

Keywords: chemical vapor deposition, graphene, ITO, Raman Spectroscopy, sol-gel

Procedia PDF Downloads 235

Authors: Rubaiat S. Ahmed, Jemer Garrido, Sergey M. Motov

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Clinical informatics (CI) enables the transformation of data into a systematic organization that improves the quality of care and the generation of positive health outcomes.Innovative technology through informatics that compiles accurate data on analgesic utilization in the emergency department can enhance pain management in this important clinical setting. We aim to establish a simplified reporting system through CI to examine and assess the analgesic prescribing practices in the EDthrough executing a U.S. federal grant project on opioid reduction initiatives. Queried data points of interest from a level-one trauma ED’s electronic medical records were used to create data sets and develop informational/visual reporting dashboards (on Microsoft Excel and Google Sheets) concerning analgesic usage across several pre-defined parameters and performance metrics using CI. The data was then qualitatively analyzed to evaluate ED analgesic prescribing trends by departmental clinicians and leadership. During a 12-month reporting period (Dec. 1, 2020 – Nov. 30, 2021) for the ongoing project, about 41% of all ED patient visits (N = 91,747) were for pain conditions, of which 81.6% received analgesics in the ED and at discharge (D/C). Of those treated with analgesics, 24.3% received opioids compared to 75.7% receiving opioid alternatives in the ED and at D/C, including non-pharmacological modalities. Demographics showed among patients receiving analgesics, 56.7% were aged between 18-64, 51.8% were male, 51.7% were white, and 66.2% had government funded health insurance. Ninety-one percent of all opioids prescribed were in the ED, with intravenous (IV) morphine, IV fentanyl, and morphine sulfate immediate release (MSIR) tablets accounting for 88.0% of ED dispensed opioids. With 9.3% of all opioids prescribed at D/C, MSIR was dispensed 72.1% of the time. Hydrocodone, oxycodone, and tramadol usage to only 10-15% of the time, and hydromorphone at 0%. Of opioid alternatives, non-steroidal anti-inflammatory drugs were utilized 60.3% of the time, 23.5% with local anesthetics and ultrasound-guided nerve blocks, and 7.9% with acetaminophen as the primary non-opioid drug categories prescribed by ED providers. Non-pharmacological analgesia included virtual reality and other modalities. An average of 18.5 ED opioid orders and 1.9 opioid D/C prescriptions per 102.4 daily ED patient visits was observed for the period. Compared to other specialties within our institution, 2.0% of opioid D/C prescriptions are given by ED providers, compared to the national average of 4.8%. Opioid alternatives accounted for 69.7% and 30.3% usage, versus 90.7% and 9.3% for opioids in the ED and D/C, respectively.There is a pressing need for concise, relevant, and reliable clinical data on analgesic utilization for ED providers and leadership to evaluate prescribing practices and make data-driven decisions. Basic computer software can be used to create effective visual reporting dashboards with indicators that convey relevant and timely information in an easy-to-digest manner. We accurately examined our ED's analgesic prescribing practices using CI through dashboard reporting. Such reporting tools can quickly identify key performance indicators and prioritize data to enhance pain management and promote safe prescribing practices in the emergency setting.

Keywords: clinical informatics, dashboards, emergency department, health informatics, healthcare informatics, medical informatics, opioids, pain management, technology

Procedia PDF Downloads 119

Authors: Nipa Debnath, Harinarayan Das, Takahiko Kawaguchi, Naonori Sakamoto, Kazuo Shinozaki, Hisao Suzuki, Naoki Wakiya

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Nowadays spinel ferrite magnetic thin films have drawn considerable attention due to their interesting magnetic and electrical properties with enhanced chemical and thermal stability. Spinel ferrite magnetic films can be implemented in magnetic data storage, sensors, and spin filters or microwave devices. It is well established that the structural, magnetic and transport properties of the magnetic thin films are dependent on microstructure. Spinodal decomposition (SD) is a phase separation process, whereby a material system is spontaneously separated into two phases with distinct compositions. The periodic microstructure is the characteristic feature of SD. Thus, SD can be exploited to control the microstructure at the nanoscale level. In bulk spinel ferrites having general formula, MₓFe₃₋ₓ O₄ (M= Co, Mn, Ni, Zn), phase separation via SD has been reported only for cobalt ferrite (CFO); however, long time post-annealing is required to occur the spinodal decomposition. We have found that SD occurs in CoF thin film without using any post-deposition annealing process if we apply magnetic field during thin film growth. Dynamic Aurora pulsed laser deposition (PLD) is a specially designed PLD system through which in-situ magnetic field (up to 2000 G) can be applied during thin film growth. The in-situ magnetic field suppresses the recombination of ions in the plume. In addition, the peak’s intensity of the ions in the spectra of the plume also increases when magnetic field is applied to the plume. As a result, ions with high kinetic energy strike into the substrate. Thus, ion-impingement occurred under magnetic field during thin film growth. The driving force of SD is the ion-impingement towards the substrates that is induced by in-situ magnetic field. In this study, we report about the occurrence of phase separation through SD and evolution of microstructure after phase separation in spinel ferrite thin films. The surface morphology of the phase separated films show checkerboard like domain structure. The cross-sectional microstructure of the phase separated films reveal columnar type phase separation. Herein, the decomposition wave propagates in lateral direction which has been confirmed from the lateral composition modulations in spinodally decomposed films. Large magnetic anisotropy has been found in spinodally decomposed nickel ferrite (NFO) thin films. This approach approves that magnetic field is also an important thermodynamic parameter to induce phase separation by the enhancement of up-hill diffusion in thin films. This thin film deposition technique could be a more efficient alternative for the fabrication of self-organized phase separated thin films and employed in controlling of the microstructure at nanoscale level.

Keywords: Dynamic Aurora PLD, magnetic anisotropy, spinodal decomposition, spinel ferrite thin film

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Authors: A. C. Facin, M. C. Maronezi , M. P. Menezes, G. L. Montanhim, L. Pavan, M. A. R. Feliciano, R. P. Nociti, R. A. R. Uscategui, P. C. Moraes

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The incidence of brachycephalic syndrome (BS) in the clinical routine of small animals has increased significantly giving the higher proportion of brachycephalic pets in the last years and has been considered as an animal welfare problem. The treatment of BS is surgical and the clinical signs related can be considerably attenuated. Nevertheless, the systemic effects of the BS are still poorly reported and little is known about these when the surgical correction is not performed early. Affected dogs are more likely to develop cardiopulmonary, gastrointestinal and sleep disorders in which the chronic hypoxemia plays a major role. This syndrome is compared with the obstructive sleep apnea (OSA) in humans, both considered as causes of systemic and metabolic dysfunction. Among the several consequences of the BS little is known if the syndrome also affects the hepatic tissue of brachycephalic patients. Elastography is a promising ultrasound technique that evaluates tissue elasticity and has been recently used with the purpose of diagnosis of liver fibrosis. In medicine, it is a growing concern regarding the hepatic injury of patients affected by OSA. This prospective study hypothesizes if there is any consequence of BS in the hepatic parenchyma of brachycephalic dogs that don’t receive any surgical treatment. This study was conducted following the approval of the Animal Ethics and Welfare Committee of the Faculdade de Ciências Agrárias e Veterinárias, UNESP, Campus Jaboticabal, Brazil (protocol no 17944/2017) and funded by Sao Paulo Research Foundation (FAPESP, process no 2017/24809-4). The methodology was based in ARFI elastography using the ACUSON S2000/SIEMENS device, with convex multifrequential transducer and specific software as well as clinical evaluation of the syndrome, in order to determine if they can be used as a prognostic non-invasive tool. On quantitative elastography, it was collected three measures of shear wave velocity (meters per second) and depth in centimeters in the left lateral, left medial, right lateral, right medial and caudate lobe of the liver. The brachycephalic patients, 16 pugs and 30 french bulldogs, were classified using a previously established 4-point functional grading system based on clinical evaluation before and after a 3-minute exercise tolerance test already established and validated. The control group was based on the same features collected in 22 beagles. The software R version 3.3.0 was used for the analysis and the significance level was set at 0.05. The data were analysed for normality of residuals and homogeneity of variances by Shapiro-Wilks test. Comparisons of parametric continuous variables between breeds were performed by using ANOVA with a post hoc test for pair wise comparison. The preliminary results show significant statistic differences between the brachycephalic groups and the control group in all lobes analysed (p ≤ 0,05), with higher values of shear wave velocities in the hepatic tissue of brachycephalic dogs. In this context, the results obtained in this study contributes to the understanding of BS as well as its consequences in our patients, reflecting in evidence that one more systemic consequence of the syndrome may occur in brachycephalic patients, which was not related in the veterinary literature yet.

Keywords: airway obstruction, brachycephalic airway obstructive syndrome, hepatic injury, obstructive sleep apnea

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Authors: Luxi He, Tianfang Zhang, Zhengbin He, Songlin Yi

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Heat treatment has been widely recognized for its effectiveness in enhancing the physicochemical properties of wood, including hygroscopicity and dimensional stability. Nonetheless, the non-negligible volumetric shrinkage and loss of mechanical strength resulting from heat treatment may diminish the wood recovery and its product value. In this study, tung oil was used to alleviate heat-induced shrinkage and reduction in mechanical properties of wood during heat treatment. Tung oil was chosen as a modifier because it is a traditional Chinese plant oil that has been widely used for over a thousand years to protect wooden furniture and buildings due to its biodegradable and non-toxic properties. The effects of different heating media (air, tung oil) and their effective treatment parameters (temperature, duration) on the changes in the physical properties (morphological characteristics, pore structures, micromechanical properties), and chemical properties (chemical structures, chemical composition) of wood were investigated by using scanning electron microscopy, confocal laser scanning microscopy, atomic force microscopy, X-ray photoelectron spectroscopy, and dynamic vapor sorption. Meanwhile, the correlation between the mass changes and the color change, volumetric shrinkage, and hygroscopicity was also investigated. The results showed that the thermal degradation of wood cell wall components was the most important factor contributing to the changes in heat-induced shrinkage, color, and moisture adsorption of wood. In air-heat-treated wood samples, there was a significant correlation between mass change and heat-induced shrinkage, brightness, and moisture adsorption. However, the presence of impregnated tung oil in oil-heat-treated wood appears to disrupt these correlations among physical properties. The results of micromechanical properties demonstrated a significant decrease in elastic modulus following high-temperature heat treatment, which was mitigated by tung oil treatment. Chemical structure and compositional analyses indicated that the changes in chemical structure primarily stem from the degradation of hemicellulose and cellulose, and the presence of tung oil created an oxygen-insulating environment that slowed down this degradation process. Morphological observation results showed that tung oil permeated the wood structure and penetrated the cell walls through transportation channels, altering the micro-morphology of the cell wall surface, obstructing primary water passages (e.g., vessels and pits), and impeding the release of volatile degradation products as well as the infiltration and diffusion of water. In summary, tung oil treatment represents an environmentally friendly and efficient method for maximizing wood recovery and increasing product value. This approach holds significant potential for industrial applications in wood heat treatment.

Keywords: tung oil, heat treatment, physicochemical properties, wood cell walls

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Authors: Vijay Samuel, Tina Thekkekkara, Shoma Ganguly

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There is no reported Hanta Seoul virus infection in children in the UK so far, making it quite challenging for clinicians in diagnosing, predicting and prognosticating the outcome of the infection to patients and parents. We report a case of a ten-year-old girl who presented with pyrexia associated with headache, photophobia and abdominal pain. The family had recently acquired two pet rats six weeks ago. She appeared flushed with peri-oral pallor, coated the strawberry tongue, inflamed tonsils and bilateral cervical lymphadenopathy. Her liver and splenic edges were palpable. Investigations showed that she was thrombocytopenic with deranged renal and liver functions. An ultrasound abdomen demonstrated a mildly enlarged spleen, peripancreatic lymph node and an acalculous cholecystitis. In view of her clinical presentation, a diagnosis of leptospirosis was considered and she was commenced on intravenous benzylpenicillin. The following day she became oliguric, developed significant proteinuria and her renal function deteriorated. Following conservative management, her urine output gradually improved along with her renal function, proteinuria and thrombocytopaenia. Serology for leptospirosis and various other viruses were negative. Following discussion with the Rare and Imported Pathogens Laboratory at Porton hanta virus serology was requested and found to be strongly positive for Seoul hanta virus. Following discharge she developed palpitations, fatigue, severe headache and cognitive difficulties including memory loss and difficulties in spelling, reading and mathematics. Extensive investigations including ECG, MRI brain and CSF studies were performed and revealed no significant abnormalities. Since 2012, there have been six cases of acute kidney injury due to Hantavirus infection in the UK. Two cases were from the Humber region and were exposure to wild rats and the other four were exposed to specially bred pet fancy rats. Hanta virus infections can cause mild flu like symptoms but two clinical syndromes are associated with severe disease including haemorrhagic fever with renal syndrome, which may be associated with thrombocytopenia and Hantavirus cardiopulmonary syndrome. Neuropsychological impairments reported following hantavirus pulmonary syndrome and following Puumala virus infection have been reported. Minor white matter lesions were found in about half of the patients investigated with MRI brain. Seoul virus has a global distribution owing to the dispersal of its carrier host rats, through global trade. Several ports in the region could explain the possible establishment of Seoul virus in local populations of rats in the Yorkshire and Humber region. The risk of infection for occupationally exposed groups is 1-3% compared to 32.9% for specialist pet rat owners. The report highlight’s the importance of routinely asking about pets in the family. We hope to raise awareness of the emergence of hantavirus infection in the UK, particularly in the Yorkshire and Humber region. Clinicians should consider hantavirus infection as a potential cause of febrile illness causing renal impairment in children. Awareness of the possible neuro-cognitive sequele would help the clinicians offer appropriate information and support to children and their families. Contacting Rare and Imported Pathogens Laboratory at Porton is a useful resource for clinicians in UK when they consider unusual infections.

Keywords: Seoul hantavirus in child Porton, UK Acute kidney injury

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Authors: Laura Helena Caicedo Lopez, Luis Miguel Contreras Medina, Ramon Gerardo Guevara Gonzales, Juan E. Andrade

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In this study, we evaluated the effect of three different hydric stress conditions: Low (LHS), medium (MHS), and high (HHS) on capsaicinoid content and enzyme regulation of C. annuum plants. Five main peaks were detected using a 2 Hz resolution vibrometer laser (Polytec-B&K). These peaks or “characteristic frequencies” were used as acoustic emissions (AEs) treatment, transforming these signals into audible sound with the frequency (Hz) content of each hydric stress. Capsaicinoids (CAPs) are the main, secondary metabolites of chili pepper plants and are known to increase during hydric stress conditions or short drought-periods. The AEs treatments were applied in two plant stages: the first one was in the pre-anthesis stage to evaluate the genes that encode the transcription of enzymes responsible for diverse metabolic activities of C. annuum plants. For example, the antioxidant responses such as peroxidase (POD), superoxide dismutase (Mn-SOD). Also, phenyl-alanine ammonia-lyase (PAL) involved in the biosynthesis of the phenylpropanoid compounds. The chalcone synthase (CHS) related to the natural defense mechanisms and species-specific aquaporin (CAPIP-1) that regulate the flow of water into and out of cells. The second stage was at 40 days after flowering (DAF) to evaluate the biochemical effect of AEs related to hydric stress on capsaicinoids production. These two experiments were conducted to identify the molecular responses of C. annuum plants to AE. Moreover, to define AEs could elicit any increase in the capsaicinoids content after a one-week exposition to AEs treatments. The results show that all AEs treatment signals (LHS, MHS, and HHS) were significantly different compared to the non-acoustic emission control (NAE). Also, the AEs induced the up-regulation of POD (~2.8, 2.9, and 3.6, respectively). The gene expression of another antioxidant response was particularly treatment-dependent. The HHS induced and overexpression of Mn-SOD (~0.23) and PAL (~0.33). As well, the MHS only induced an up-regulation of the CHs gene (~0.63). On the other hand, CAPIP-1 gene gas down-regulated by all AEs treatments LHS, MHS, and HHS ~ (-2.4, -0.43 and -6.4, respectively). Likewise, the down-regulation showed particularities depending on the treatment. LHS and MHS induced downregulation of the SOD gene ~ (-1.26 and -1.20 respectively) and PAL (-4.36 and 2.05, respectively). Correspondingly, the LHS and HHS showed the same tendency in the CHs gene, respectively ~ (-1.12 and -1.02, respectively). Regarding the elicitation effect of AE on the capsaicinoids content, additional treatment controls were included. A white noise treatment (WN) to prove the frequency-selectiveness of signals and a hydric stressed group (HS) to compare the CAPs content. Our findings suggest that WN and NAE did not present differences statically. Conversely, HS and all AEs treatments induced a significant increase of capsaicin (Cap) and dihydrocapsaicin (Dcap) after one-week of a treatment. Specifically, the HS plants showed an increase of 8.33 times compared to the NAE and WN treatments and 1.4 times higher than the MHS, which was the AEs treatment with a larger induction of Capsaicinoids among treatments (5.88) and compared to the controls.

Keywords: acoustic emission, capsaicinoids, elicitors, hydric stress, plant signaling

Procedia PDF Downloads 139

Authors: Tianfang Zhang, Luxi He, Zhengbin He, Songlin Yi

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Moso bamboo is a common non-wood forest resource in Asia that is widely used in construction, furniture, and other fields. Influenced by the heterogeneous structure and various hygroscopic groups of bamboo, the deformation occurs as moisture absorption and desorption when the environment temperature and humidity conditions change. Thermal modification is a well-established commercial technology for improving the dimensional stability of bamboo. However, the higher energy consumption and carbon emissions limit its further development. Previous studies have indicated that inorganic salt-assisted thermal modification could lead to significant reductions in moisture absorption and energy consumption. Represented by metal chlorides, it could show Lewis acid properties when dissolved in water, generating metal ion ligand complexes. In addition, ultrasonic treatment, as an efficient and environmentally friendly physical treatment method, improved the accessibility of pretreatment chemical impregnation agents and intensified mass and heat transfer during reactions. To save energy and reduce deformation, this study elucidates the influence of zinc chloride-ultrasonic treatment on the physicochemical properties of heat-treated bamboo, and the details of the bamboo deformation mechanism with Lewis acid are explained. Three sets of parameters (inorganic salt concentration, ultrasonic frequency and heat treatment temperature) were designed, and an optimized process was proposed to clarify this scientific question, that is: 5% (w/w) zinc chloride solution, 40 kHz ultrasonic waves and heat treatment at 160 °C. The samples were characterized by different means to analyze changes in their macroscopic features, pore structure, chemical structure and chemical composition. The results suggested that the maximum weight loss rate was reduced by at least 19.75%. The maximum thermal degradation peak of hemicellulose was significantly shifted forward. The hygroscopicity was reduced by 10.15%, the relative crystallinity was increased by 4.4%, the surface contact angle was increased by 25.2%, and the color change was increased by 23.60 in the optimal condition. From the electron microscope observation, the treated surface became rougher, and cracks appeared in some weaker areas, accelerating starch loss and removing granular attachments around the pits. By ion diffusion, zinc ions diffused into hemicellulose and a partial amorphous region of cellulose. Parts of the cell wall structure were subjected to swelling and degradation, leading to the broken state of parenchyma cells. From the Raman spectrum, compared to conventional thermal modifications, hemicellulose thermal degradation and lignin migration is promoted by Lewis acid under dilute acid-thermal condition. As shown in this work, the combined Lewis acid and ultrasonic pretreatment as an environmentally friendly, safe, and efficient physic-chemical combined pretreatment method improved the dimensional stability of Moso bamboo and lowered the thermal degradation conditions. This method has great potential for development in the field of bamboo heat treatment, and it might provide some guidance for making dark bamboo flooring.

Keywords: Moso bamboo, Lewis acid, ultrasound, heat treatment

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Authors: Marian Mihalik, Kornel Csach, Martin Kovalik, Matúš Mihalik, Martina Kubovčíková, Maria Zentková, Martin Vavra, Vladimír Girman, Jaroslav Briančin, Marija Perovic, Marija Boškovic, Magdalena Fitta, Robert Pelka

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Current nanomaterials for use in biomedicine are based mainly on iron oxides and on present knowledge on magnetic nanostructures. Manganites can represent another material which can be used optionally. Manganites and their unique electronic properties have been extensively studied in the last decades not only due to fundamental interest but to possible applications of colossal magnetoresistance, magnetocaloric effect, and ferroelectric properties. It was found that the oxygen-reduction reaction on perovskite oxide is intimately connected with metal ion e.g., orbital occupation. The effect of oxygen deviation from the stoichiometric composition on crystal structure was studied very carefully by many authors on LaMnO₃. Depending on oxygen content, the crystal structure changes from orthorhombic one to rhombohedric for oxygen content 3.1. In the case of hole-doped manganites, the change from the orthorhombic crystal structure, which is typical for La1-xCaxMnO3 based manganites, to the rhombohedric crystal structure (La1-xMxMnO₃ where M = K, Ag, and Sr based materials) results in an enormous increase of the Curie temperature. In our paper, we study the effect of oxygen content on crystal structure, thermal, and magnetic properties (including magnetocaloric effect) of La1-xAgxMnO₃nano particle system. The content of oxygen in samples was tuned by heat treatment in different thermal regimes and in various environment (air, oxygen, argon). Water nanosuspensions based on La0.80Ag0.15MnO₃ magnetic particles with the Curie temperature of about 43oC were prepared by two different approaches. First, by using a laboratory circulation mill for milling of powder in the presence of sodium dodecyl sulphate (SDS) and subsequent centrifugation. Second nanosuspension was prepared using an agate bowl, etching in citric acid and HNO3, ultrasound homogeniser, centrifugation, and dextran 40 kDA or 15 kDA as surfactant. Electrostatic stabilisation obtained by the first approach did not offer long term kinetic and aggregation colloidal stability and was unable to compensate for attractive forces between particles under a magnetic field. By the second approach, we prepared suspension oversaturated by dextran 40 kDA for steric stabilisation, with evidence of the presence of superparamagnetic behaviour. Low concentration of nanoparticles and not ideal coverage of nanoparticles impacting the stability of ferrofluids was the disadvantage of this approach. Strong steric stabilisation was observable at alcaic conditions under pH = ~10. Application of dextran 15 kDA leads to relatively stable ferrofluid with pH around physiological conditions, but desegregation of powder by HNO₃ was not effective enough, and the average size of fragments was to large of about 150 nm, and we did not see any signature of superparamagnetic behaviour. The prepared ferrofluids were characterised by scanning and transition microscope method, thermogravimetry, magnetization, and AC susceptibility measurements. Specific Absorption Rate measurements were undertaken on powder as well on ferrofluids in order to estimate the potential application of La₀.₈₀Ag₀.₁₅MnO₃ magnetic particles based ferrofluid for hyperthermia. Our complex study contains an investigation of biocompatibility and potential biohazard of this material.

Keywords: manganites, magnetic nanoparticles, oxygen content, magnetic phase transition, magnetocaloric effect, ferrofluid, hyperthermia

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Authors: Ali Baker, Russel Krawitz

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This paper describes a rare occurrence where a potentially fatal complication of COVID-19 infection (MIS-A) was misdiagnosed as an acute abdomen. As most patients with this syndrome present with fever and gastrointestinal symptoms, they may inadvertently fall under the care of the surgical unit. However, unusual imaging findings and a poor response to anti-microbial therapy should prompt clinicians to suspect a non-surgical etiology. More than half of MIS-A patients require ICU admission and vasopressor support. Prompt referral to a physician is key, as the cornerstone of treatment is IVIG and corticosteroid therapy. A 32 year old woman presented with right sided abdominal pain and fevers. She had also contracted COVID-19 two months earlier. Abdominal examination revealed generalised right sided tenderness. The patient had raised inflammatory markers, but other blood tests were unremarkable. CT scan revealed extensive lymphadenopathy along the ileocolic chain. The patient proved to be a diagnostic dilemma. She was reviewed by several surgical consultants and discussed with several inpatient teams. Although IV antibiotics were commenced, the right sided abdominal pain, and fevers persisted. Pan-culture returned negative. A mild cholestatic derangement developed. On day 5, the patient underwent preparation for colonoscopy to assess for a potential intraluminal etiology. The following day, the patient developed sinus tachycardia and hypotension that was refractory to fluid resuscitation. That patient was transferred to ICU and required vasopressor support. Repeat CT showed peri-portal edema and a thickened gallbladder wall. On re-examination, the patient was Murphy’s sign positive. Biliary ultrasound was equivocal for cholecystitis. The patient was planned for diagnostic laparoscopy. The following morning, a marked rise in cardiac troponin was discovered, and a follow-up echocardiogram revealed moderate to severe global systolic dysfunction. The impression was post-COVID MIS with myocardial involvement. IVIG and Methylprednisolone infusions were commenced. The patient had a great response. Vasopressor support was weaned, and the patient was discharged from ICU. The patient continued to improve clinically with oral prednisolone, and was discharged on day 17. Although MIS following COVID-19 infection is well-described syndrome in children, only recently has it come to light that it can occur in adults. The exact incidence is unknown, but it is thought to be rare. A recent systematic review found only 221 cases of MIS-A, which could be included for analysis. Symptoms vary, but the most frequent include fever, gastrointestinal, and mucocutaneous. Many patients progress to multi-organ failure and require vasopressor support. 7% succumb to the illness. The pathophysiology of MIS is only partly understood. It shares similarities with Kawasaki disease, macrophage activation syndrome, and cytokine release syndrome. Importantly, by definition, the patient must have an absence of severe respiratory symptoms. It is thought to be due to a dysregulated immune response to the virus. Potential mechanisms include reduced levels of neutralising antibodies and autoreactive antibodies that promote inflammation. Further research into MIS-A is needed. Although rare, this potentially fatal syndrome should be considered in the unwell surgical patient who has recently contracted COVID-19 and poses a diagnostic dilemma.

Keywords: acute-abdomen, MIS, COVID-19, ICU

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Authors: Julia Gontar, Natalia Buderatskaya, Igor Ilyin, Olga Parnitskaya, Sergey Lavrynenko, Eduard Kapustin, Ekaterina Ilyina, Yana Lakhno

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Introduction: It is well known that oocytes obtained from older reproductive women have accumulated mitochondrial DNA mutations, which negatively affects the morphology of a developing embryo and may lead to the birth of a child with mitochondrial disease. Special techniques have been developed to allow a donor oocyte cytoplasmic transfer with the parents’ biological nuclear DNA retention. At the same time, it is important to understand whether the procedure affects the future embryonic chromosome sets as the nuclear DNA is the transfer subject in this new complex procedure. Material and Methods: From July 2015 to July 2016, the investigation was carried out in the Medical Centre IGR. 34 donor oocytes (group A) were used for the manipulation with the aim of donating cytoplasm: 21 oocytes were used for zygotes pronuclear transfer and oocytes 13 – for the spindle transfer. The mean age of the oocyte donors was 28.4±2.9 years. The procedure was performed using Nikon Ti Eclipse inverted microscope equipped with the micromanipulators Narishige system (Japan), Saturn 3 laser console (UK), Oosight imaging systems (USA). For the preimplantation genetic screening (PGS) blastocyst biopsy was performed, trophectoderm samples were diagnosed using fluorescent in situ hybridization on chromosomes 9, 13, 15, 16, 17, 18, 21, 22, X, Y. For comparison of morphological characteristics and euploidy, was chosen a group of embryos (group B) with the amount of 121 blastocysts obtained from 213 oocytes, which were gotten from the donor programs of assisted reproductive technologies (ART). Group B was not subjected to donor oocyte cytoplasmic transfer procedure and studied on the above mentioned chromosomes. Statistical analysis was carried out using the criteria t, x^2 at a significance levels p<0.05, p<0.01, p<0.001. Results: After the donor cytoplasm transfer process the amount of the third day developing embryos was 27 (79.4%). In this stage, the group B consisted of 189 (88.7%) developing embryos, and there was no statistically significant difference (SSD) between the two groups (p>0.05). After a comparative analysis of the morphological characteristics of the embryos on the fifth day, we also found no SSD among the studied groups (p>0.05): from 34 oocytes exposed to manipulation, 14 (41.2%) blastocysts was obtained, while the group B blastocyst yield was 56.8% (n=121) from 213 oocytes. The following results were obtained after PGS performing: in group A euploidy in studied chromosomes were 28.6%(n=4) blastocysts, whereas in group B this rate was 40.5%(n=49), 28.6%(n=4) and 21.5%(n=26) of mosaic embryos and 42.8%(n=6) and 38.0%(n=46) aneuploid blastocysts respectively were identified. None of these specified parameters had an SSD (p>0.05). But attention was drawn by the blastocysts in group A with identified mosaicism, which was chaotic without any cell having euploid chromosomal set, in contrast to the mosaic embryos in group B where identified chaotic mosaicism was only 2.5%(n=3). Conclusions: According to the obtained results, there is no direct procedural effect on the chromosome in embryos obtained following donor oocyte cytoplasmic transfer. Thus, the technology introduction will enhance the infertility treating effectiveness as well as avoiding having a child with mitochondrial disease.

Keywords: donor oocyte cytoplasmic transfer, embryos’ chromosome set, oocyte spindle transfer, pronuclear transfer

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Authors: S.V. Kleyn, S.Yu. Zagorodnov, А.А. Kokoulina

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Technogenic emissions of the mining and processing complex are characterized by a high content of chemical components and solid dust particles. However, each industrial enterprise and the surrounding area have features that require refinement and parameterization. Numerous studies have shown the negative impact of fine dust PM10 and PM2.5 on the health, as well as the possibility of toxic components absorption, including heavy metals by dust particles. The target of the study was the quantitative assessment of the fractional and particle size composition of ambient air dust in the area of impact by primary magnesium production complex. Also, we tried to describe the morphology features of dust particles. Study methods. To identify the dust emission sources, the analysis of the production process has been carried out. The particulate composition of the emissions was measured using laser particle analyzer Microtrac S3500 (covered range of particle size is 20 nm to 2000 km). Particle morphology and the component composition were established by electron microscopy by scanning microscope of high resolution (magnification rate - 5 to 300 000 times) with X-ray fluorescence device S3400N ‘HITACHI’. The chemical composition was identified by X-ray analysis of the samples using an X-ray diffractometer XRD-700 ‘Shimadzu’. Determination of the dust pollution level was carried out using model calculations of emissions in the atmosphere dispersion. The calculations were verified by instrumental studies. Results of the study. The results demonstrated that the dust emissions of different technical processes are heterogeneous and fractional structure is complicated. The percentage of particle sizes up to 2.5 micrometres inclusive was ranged from 0.00 to 56.70%; particle sizes less than 10 microns inclusive – 0.00 - 85.60%; particle sizes greater than 10 microns - 14.40% -100.00%. During microscopy, the presence of nanoscale size particles has been detected. Studied dust particles are round, irregular, cubic and integral shapes. The composition of the dust includes magnesium, sodium, potassium, calcium, iron, chlorine. On the base of obtained results, it was performed the model calculations of dust emissions dispersion and establishment of the areas of fine dust РМ 10 and РМ 2.5 distribution. It was found that the dust emissions of fine powder fractions PM10 and PM2.5 are dispersed over large distances and beyond the border of the industrial site of the enterprise. The population living near the enterprise is exposed to the risk of diseases associated with dust exposure. Data are transferred to the economic entity to make decisions on the measures to minimize the risks. Exposure and risks indicators on the health are used to provide named patient health and preventive care to the citizens living in the area of negative impact of the facility.

Keywords: dust emissions, еxposure assessment, PM 10, PM 2.5

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Authors: Aleksandra Chałupnik, Zuzanna Chilimoniuk, Joanna Borowik, Aleksandra Borkowska, Anna Torres

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Background: Precocious puberty is the occurrence of secondary sexual characteristics in girls before the age of 8. The diverse etiology of premature puberty is crucial to determine whether it is true precocious puberty, depending on the activation of the hypothalamic-pituitary-gonadal axis, or pseudo-precocious, which is independent of the activation of this axis. Whatever the cause, premature action of the sex hormones leads to the common symptoms of various forms of puberty. These include the development of sexual characteristics, acne, acceleration of growth rate and acceleration of skeletal maturation. Due to the possible genetic basis of the disorders, an interdisciplinary search for the cause is needed. Case report: The case report concerns a patient of a pediatric gynecology clinic who, at the age of two years, developed advanced thelarhe (M3) and started recurrent vaginal bleeding. In August 2019, gonadotropin suppression initially and after LHRH stimulation and high estradiol levels were reported at the Endocrinology Department. Imaging examinations showed a cyst in the right ovary projection. The bone age was six years. The entire clinical picture indicated pseudo- (peripheral) precocious in the course of ovarian autonomic cyst. In the follow-up ultrasound performed in September, the image of the cyst was stationary and normalization of estradiol levels and clinical symptoms was noted. In December 2019, cyst regression and normal gonadotropin and estradiol concentrations were found. In June 2020, white mucus tinged with blood on the underwear, without any other disturbing symptoms, was observed for several days. Two consecutive USG examinations carried out in the same month confirmed the change in the right ovary, the diameter of which was 25 mm with a very high level of estradiol. Germinal tumor markers were normal. On the Tanner scale, the patient scored M2P1. The labia and hymen had puberty features. The correct vaginal entrance was visible. Another active vaginal bleeding occurred in the first week of July 2020. The considered laparoscopic treatment was abandoned due to the lack of oncological indications. Treatment with Tamoxifen was recommended in July 2020. In the initiating period of treatment, no maturation progression, and even reduction of symptoms, no acceleration of growth and a marked reduction in the size of the cysts were noted. There was no bleeding. After the size of the cyst and hormonal activity increased again, the treatment was changed to Anastrozole, the effect of which led to a reduction in the size of the cyst. Conclusions: The entire clinical picture indicates alleged (peripheral) puberty. Premature puberty in girls, which is manifested as enlarged mammary glands with high levels of estrogens secreted by autonomic ovarian cysts and prepubertal levels of gonadotropins, may indicate McCune-Albright syndrome. Vaginal bleeding may also occur in this syndrome. Cancellation of surgical treatment of the cyst made it impossible to perform a molecular test that would allow to confirm the diagnosis. Taking into account the fact that cysts are often one of the first symptoms of McCune-Albrigt syndrome, it is important to remember about multidisciplinary care for the patient and careful search for skin and bone changes or other hormonal disorders.

Keywords: McCune Albrigth's syndrome, ovarian cyst, pediatric gynaecology, precocious puberty

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Authors: Elena Parmentier, Henrik Endeman

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Introduction: Large mediastinal masses often present with diagnostic and clinical challenges due to compression of the respiratory and hemodynamic system. We present a case of a mediastinal mass with symptomatic mechanical compression of the trachea, resulting in challenging airway management. Methods: We present a case of 66-year-old male, complaining of progressive dysphagia. Initial esophagogastroscopy revealed a stenosis secondary to external compression, biopsies were inconclusive. Additional CT scan showed a large mediastinal mass of unknown origin, situated between the vertebrae and esophagus. Symptoms progressed and patient developed dyspnea and stridor. A new CT showed quick growth of the mass with compression of the trachea, subglottic to just above the carina. A tracheal covered stent was successfully placed. Endobronchial ultrasound revealed a large irregular mass without tracheal invasion, biopsies were taken. 4 days after stent placement, the patients’ condition deteriorated with worsening of stridor, dyspnea and desaturation. Migration of the tracheal stent into the right main bronchus was seen on chest X ray, with obstruction of the left main bronchus and secondary atelectasis. Different methods have been described in the literature for tracheobronchial stent removal (surgical, endoscopic, fluoroscopyguided), our first choice in this case was flexible bronchoscopy. However, this revealed tracheal compression above the migrated stent and passage of the scope occurred impossible. Patient was admitted to the ICU, high-flow nasal oxygen therapy was started and the situation stabilized, giving time for extensive assessment and preparation of the airway management approach. Close cooperation between the intensivist, pulmonologist, anesthesiologist and otorhinolaryngologist was essential. Results: In case of sudden deterioration, a protocol for emergency situations was made. Given the increased risk of additional tracheal compression after administration of neuromuscular blocking agents, an approach with awake fiberoptic intubation maintaining spontaneous ventilation was proposed. However, intubation without retrieval of the tracheal stent was found undesirable due to expected massive shunting over the left atelectatic lung. As rescue option, assistance of extracorporeal circulation was considered and perfusionist was kept on standby. The patient stayed stable and was transferred to the operating theatre. High frequency jet ventilation under general anesthesia resulted in desaturations up to 50%, making rigid bronchoscopy impossible. Subsequently an endotracheal tube size 8 could be placed successfully and the stent could be retrieved via bronchoscopy over (and with) the tube, after which the patient was reintubated. Finally, a tracheostomy (Shiley™ Tracheostomy Tube With Cuff, size 8) was placed, fiberoptic control showed a patent airway. Patient was readmitted to the ICU and could be quickly weaned of the ventilator. Pathology was positive for rhabdomyosarcoma, without indication for systemic therapy. Extensive surgery (laryngectomy, esophagectomy) was suggested, but patient refused and palliative care was started. Conclusion: Due to meticulous planning in an interdisciplinary team, we showed a successful airway management approach in this complicated case of critical airway compression secondary to a rare rhabdomyosarcoma, complicated by tracheal stent migration. Besides presenting our thoughts and considerations, we support exploring other possible approaches of this specific clinical problem.

Keywords: airway management, rhabdomyosarcoma, stent displacement, tracheal stenosis

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Authors: Antonina Semakova, Karim Mynbaev, Nikolai Bazhenov, Anton Chernyaev, Sergei Kizhaev, Nikolai Stoyanov

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At present, heterostructures are used for fabrication of almost all types of optoelectronic devices. Our research focuses on the optoelectronic properties of InAs(Sb) solid solutions that are widely used in fabrication of light emitting diodes (LEDs) operating in middle wavelength infrared range (MWIR). This spectral range (2-6 μm) is relevant for laser diode spectroscopy of gases and molecules, for systems for the detection of explosive substances, medical applications, and for environmental monitoring. The fabrication of MWIR LEDs that operate efficiently at room temperature is mainly hindered by the predominance of non-radiative Auger recombination of charge carriers over the process of radiative recombination, which makes practical application of LEDs difficult. However, non-radiative recombination can be partly suppressed in quantum-well structures. In this regard, studies of such structures are quite topical. In this work, electroluminescence (EL) of LED heterostructures based on InAs(Sb) epitaxial films with the molar fraction of InSb ranging from 0 to 0.09 and multi quantum-well (MQW) structures was studied in the temperature range 4.2-300 K. The growth of the heterostructures was performed by metal-organic chemical vapour deposition on InAs substrates. On top of the active layer, a wide-bandgap InAsSb(Ga,P) barrier was formed. At low temperatures (4.2-100 K) stimulated emission was observed. As the temperature increased, the emission became spontaneous. The transition from stimulated emission to spontaneous one occurred at different temperatures for structures with different InSb contents in the active region. The temperature-dependent carrier lifetime, limited by radiative recombination and the most probable Auger processes (for the materials under consideration, CHHS and CHCC), were calculated within the framework of the Kane model. The effect of various recombination processes on the carrier lifetime was studied, and the dominant role of Auger processes was established. For MQW structures quantization energies for electrons, light and heavy holes were calculated. A characteristic feature of the experimental EL spectra of these structures was the presence of peaks with energy different from that of calculated optical transitions between the first quantization levels for electrons and heavy holes. The obtained results showed strong effect of the specific electronic structure of InAsSb on the energy and intensity of optical transitions in nanostructures based on this material. For the structure with MQWs in the active layer, a very weak temperature dependence of EL peak was observed at high temperatures (>150 K), which makes it attractive for fabricating temperature-resistant gas sensors operating in the middle-infrared range.

Keywords: Electroluminescence, InAsSb, light emitting diode, quantum wells

Procedia PDF Downloads 174

Authors: Tom S. Owens, Tom A. Calverley, Benjamin S. Stacey, Christopher J. Marley, George Rose, Lewis Fall, Gareth L. Jones, Priscilla Williams, John P. R. Williams, Martin Steggall, Damian M. Bailey

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Introduction and aims: Sports-related concussion (SRC) represents a significant and growing public health concern in rugby union, yet remains one of the least understood injuries facing the health community today. Alongside increasing SRC incidence rates, there is concern that prior recurrent concussion may contribute to long-term neurologic sequelae in later-life. This may be due to an accelerated decline in cerebral perfusion, a major risk factor for neurocognitive decline and neurodegeneration, though the underlying mechanisms remain to be established. The present study hypothesised that recurrent concussion in current professional rugby union players would result in elevated systemic oxidative-nitrosative stress, reflected by a free radical-mediated reduction in nitric oxide (NO) bioavailability and impaired cerebrovascular and cognitive function. Methodology: A longitudinal study design was adopted across the 2017-2018 rugby union season. Ethical approval was obtained from the University of South Wales Ethics Committee. Data collection is ongoing, and therefore the current report documents result from the pre-season and first half of the in-season data collection. Participants were initially divided into two subgroups; 23 professional rugby union players (aged 26 ± 5 years) and 22 non-concussed controls (27 ± 8 years). Pre-season measurements were performed for cerebrovascular function (Doppler ultrasound of middle cerebral artery velocity (MCAv) in response to hypocapnia/normocapnia/hypercapnia), cephalic venous concentrations of the ascorbate radical (A•-, electron paramagnetic resonance spectroscopy), NO (ozone-based chemiluminescence) and cognition (neuropsychometric tests). Notational analysis was performed to assess contact in the rugby group throughout each competitive game. Results: 1001 tackles and 62 injuries, including three concussions were observed across the first half of the season. However, no associations were apparent between number of tackles and any injury type (P > 0.05). The rugby group expressed greater oxidative stress as indicated by increased A•- (P < 0.05 vs. control) and a subsequent decrease in NO bioavailability (P < 0.05 vs. control). The rugby group performed worse in the Ray Auditory Verbal Learning Test B (RAVLT-B, learning, and memory) and the Grooved Pegboard test using both the dominant and non-dominant hands (visuomotor coordination, P < 0.05 vs. control). There were no between-group differences in cerebral perfusion at baseline (MCAv: 54 ± 13 vs. 59 ± 12, P > 0.05). Likewise, no between-group differences in CVRCO2Hypo (2.58 ± 1.01 vs. 2.58 ± 0.75, P > 0.05) or CVRCO2Hyper (2.69 ± 1.07 vs. 3.35 ± 1.28, P > 0.05) were observed. Conclusion: The present study identified that the rugby union players are characterized by impaired cognitive function subsequent to elevated systemic-oxidative-nitrosative stress. However, this appears to be independent of any functional impairment in cerebrovascular function. Given the potential long-term trajectory towards accelerated cognitive decline in populations exposed to SRC, prophylaxis to increase NO bioavailability warrants consideration.

Keywords: cognition, concussion, mild traumatic brain injury, rugby

Procedia PDF Downloads 142

Authors: Sri Sharath Kulkarni, Pauline Janssen, Alberto Berardi, Bastiaan Dickhoff, Sander van Gessel

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Blending is a common process in the production of pharmaceutical dosage forms where the high shear is used to obtain a homogenous dosage. The shear required can lead to uncontrolled attrition of excipients and affect API’s. This has an impact on the performance of the formulation as this can alter the structure of the mixture. Therefore, it is important to understand the driving mechanisms for attrition. The aim of this study was to increase the fundamental understanding of the attrition behavior of excipients. Attrition behavior of the excipients was evaluated using a high shear blender (Procept Form-8, Zele, Belgium). Twelve pure excipients are tested, with morphologies varying from crystalline (sieved), granulated to spray dried (round to fibrous). Furthermore, materials include lactose, microcrystalline cellulose (MCC), di-calcium phosphate (DCP), and mannitol. The rotational speed of the blender was set at 1370 rpm to have the highest shear with a Froude (Fr) number 9. Varying blending times of 2-10 min were used. Subsequently, after blending, the excipients were analyzed for changes in particle size distribution (PSD). This was determined (n = 3) by dry laser diffraction (Helos/KR, Sympatec, Germany). Attrition was found to be a surface phenomenon which occurs in the first minutes of the high shear blending process. An increase of blending time above 2 mins showed no change in particle size distribution. Material chemistry was identified as a key driver for differences in the attrition behavior between different excipients. This is mainly related to the proneness to fragmentation, which is known to be higher for materials such as DCP and mannitol compared to lactose and MCC. Secondly, morphology also was identified as a driver of the degree of attrition. Granular products consisting of irregular surfaces showed the highest reduction in particle size. This is due to the weak solid bonds created between the primary particles during the granulation process. Granular DCP and mannitol show a reduction of 80-90% in x10(µm) compared to a 20-30% drop for granular lactose (monohydrate and anhydrous). Apart from the granular lactose, all the remaining morphologies of lactose (spray dried-round, sieved-tomahawk, milled) show little change in particle size. Similar observations have been made for spray-dried fibrous MCC. All these morphologies have little irregular or sharp surfaces and thereby are less prone to fragmentation. Therefore, products containing brittle materials such as mannitol and DCP are more prone to fragmentation when exposed to shear. Granular products with irregular surfaces lead to an increase in attrition. While spherical, crystalline, or fibrous morphologies show reduced impact during high shear blending. These changes in size will affect the functionality attributes of the formulation, such as flow, API homogeneity, tableting, formation of dust, etc. Hence it is important for formulators to fully understand the excipients to make the right choices.

Keywords: attrition, blending, continuous manufacturing, excipients, lactose, microcrystalline cellulose, shear

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Authors: Simran Baweja, Bhavika Kalal, Surajit Maity

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Photoinduced tautomerization reactions have been the centre of attention among scientific community over past several decades because of their significance in various biological systems. 7-azaindole (7AI) is considered as a model system for DNA base pairing and to understand the role of such tautomerization reactions in mutations. To the best of our knowledge, extensive studies have been carried on 7-azaindole and its solvent clusters exhibiting proton/ hydrogen transfer in both solution as well as gas phase. Derivatives of above molecule, like 2,7- and 2,6-diazaindoles are proposed to have even better photophysical properties due to the presence of -aza group on the 2nd position. However, there are a few studies in the solution phase which suggest the relevance of these molecules, but there are no experimental studies reported in the gas phase yet. In our current investigation, we present the first gas phase spectroscopic data of 2,7-diazaindole (2,7-DAI) and its solvent cluster (2,7-DAI-H2O). In this, we have employed state-of-the-art laser spectroscopic methods such as fluorescence excitation (LIF), dispersed fluorescence (DF), resonant two-photon ionization time of flight mass spectrometry (2C-R2PI), photoionization efficiency spectroscopy (PIE), IR-UV double resonance spectroscopy i.e. fluorescence-dip infrared spectroscopy (FDIR) and resonant ion-dip infrared spectroscopy (IDIR) to understand the electronic structure of the molecule. The origin band corresponding to S1 ← S0 transition of the bare 2,7-DAI is found to be positioned at 33910 cm-1 whereas the origin band corresponding to S1 ← S0 transition of the 2,7-DAI-H2O is positioned at 33074 cm-1. The red shifted transition in case of solvent cluster suggests the enhanced feasibility of excited state hydrogen/ proton transfer. The ionization potential for the 2,7-DAI molecule is found to be 8.92 eV, which is significantly higher that the previously reported 7AI (8.11 eV) molecule, making it a comparatively complex molecule to study. The ionization potential is reduced by 0.14 eV in case of 2,7-DAI-H2O (8.78 eV) cluster compared to that of 2,7-DAI. Moreover, on comparison with the available literature values of 7AI, we found the origin band of 2,7-DAI and 2,7-DAI-H2O to be red shifted by -729 and -280 cm-1 respectively. The ground and excited state N-H stretching frequencies of the 27DAI molecule were determined using fluorescence-dip infrared spectra (FDIR) and resonant ion dip infrared spectroscopy (IDIR), obtained at 3523 and 3467 cm-1, respectively. The lower value of vNH in the electronic excited state of 27DAI implies the higher acidity of the group compared to the ground state. Moreover, we have done extensive computational analysis, which suggests that the energy barrier in excited state reduces significantly as we increase the number of catalytic solvent molecules (S= H2O, NH3) as well as the polarity of solvent molecules. We found that the ammonia molecule is a better candidate for hydrogen transfer compared to water because of its higher gas-phase basicity. Further studies are underway to understand the excited state dynamics and photochemistry of such N-rich chromophores.

Keywords: photoinduced tautomerization reactions, gas phse spectroscopy, ), IR-UV double resonance spectroscopy, resonant two-photon ionization time of flight mass spectrometry (2C-R2PI)

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Authors: Baha Eddine Aissou, Aichouche Belhadj Aissa

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Light detection and ranging (LiDAR) is an active remote sensing technology used for several applications. Airborne LiDAR is becoming an important technology for the acquisition of a highly accurate dense point cloud. A classification of airborne laser scanning (ALS) point cloud is a very important task that still remains a real challenge for many scientists. Support vector machine (SVM) is one of the most used statistical learning algorithms based on kernels. SVM is a non-parametric method, and it is recommended to be used in cases where the data distribution cannot be well modeled by a standard parametric probability density function. Using a kernel, it performs a robust non-linear classification of samples. Often, the data are rarely linearly separable. SVMs are able to map the data into a higher-dimensional space to become linearly separable, which allows performing all the computations in the original space. This is one of the main reasons that SVMs are well suited for high-dimensional classification problems. Only a few training samples, called support vectors, are required. SVM has also shown its potential to cope with uncertainty in data caused by noise and fluctuation, and it is computationally efficient as compared to several other methods. Such properties are particularly suited for remote sensing classification problems and explain their recent adoption. In this poster, the SVM classification of ALS LiDAR data is proposed. Firstly, connected component analysis is applied for clustering the point cloud. Secondly, the resulting clusters are incorporated in the SVM classifier. Radial basic function (RFB) kernel is used due to the few numbers of parameters (C and γ) that needs to be chosen, which decreases the computation time. In order to optimize the classification rates, the parameters selection is explored. It consists to find the parameters (C and γ) leading to the best overall accuracy using grid search and 5-fold cross-validation. The exploited LiDAR point cloud is provided by the German Society for Photogrammetry, Remote Sensing, and Geoinformation. The ALS data used is characterized by a low density (4-6 points/m²) and is covering an urban area located in residential parts of the city Vaihingen in southern Germany. The class ground and three other classes belonging to roof superstructures are considered, i.e., a total of 4 classes. The training and test sets are selected randomly several times. The obtained results demonstrated that a parameters selection can orient the selection in a restricted interval of (C and γ) that can be further explored but does not systematically lead to the optimal rates. The SVM classifier with hyper-parameters is compared with the most used classifiers in literature for LiDAR data, random forest, AdaBoost, and decision tree. The comparison showed the superiority of the SVM classifier using parameters selection for LiDAR data compared to other classifiers.

Keywords: classification, airborne LiDAR, parameters selection, support vector machine

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Authors: R. P. Hewawasam, A. F. Dulhunty

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The ryanodine receptor (RyR) is an intracellular ion channel that releases Ca2+ from the sarcoplasmic reticulum and is essential for the excitation-contraction coupling and contraction in striated muscle. Human muscle specific glutathione transferase M2-2 (GSTM2-2) is a highly specific inhibitor of cardiac ryanodine receptor (RyR2) activity. Single channel-lipid bilayer studies and Ca2+ release assays performed using the C-terminal half of the GSTM2-2 and its mutants F157A and Y160A confirmed the ability of the C terminal domain of GSTM2-2 to specifically inhibit the cardiac ryanodine receptor activity. Objective of the present study is to determine the effect of C terminal domain of GSTM2-2 (GSTM2-2C) and the mutants, F157A and Y160A on the Ca2+ transients of neonatal ventricular cardiomyocytes. Primary cardiomyocytes were cultured from neonatal rats. They were treated with GSTM2-2C and the two mutants F157A and Y160A at 15µM and incubated for 2 hours. Then the cells were led with Fluo-4AM, fluorescent Ca2+ indicator, and the field stimulated (1 Hz, 3V and 2ms) cells were excited using the 488 nm argon laser. Contractility of the cells were measured and the Ca2+ transients in the stained cells were imaged using Leica SP5 confocal microscope. Peak amplitude of the Ca2+ transient, rise time and decay time from the peak were measured for each transient. In contrast to GSTM2C which significantly reduced the % shortening (42.8%) in the field stimulated cells, F157A and Y160A failed to reduce the % shortening.Analysis revealed that the average amplitude of the Ca2+ transient was significantly reduced (P<0.001) in cells treated with the wild type GSTM2-2C compared to that of untreated cells. Cells treated with the mutants F157A and Y160A didn’t change the Ca2+ transient significantly compared to the control. A significant increase in the rise time (P< 0.001) and a significant reduction in the decay time (P< 0.001) were observed in cardiomyocytes treated with GSTM2-2C compared to the control but not with F157A and Y160A. These results are consistent with the observation that GSTM2-2C reduced the Ca2+ release from the cardiac SR significantly whereas the mutants, F157A and Y160A didn’t show any effect compared to the control. GSTM2-2C has an isoform-specific effect on the cardiac ryanodine receptor activity and also it inhibits RyR2 channel activity only during diastole. Selective inhibition of RyR2 by GSTM2-2C has significant clinical potential in the treatment of cardiac arrhythmias and heart failure. Since GSTM2-2C-terminal construct has no GST enzyme activity, its introduction to the cardiomyocyte would not exert any unwanted side effects that may alter its enzymatic action. The present study further confirms that GSTM2-2C is capable of decreasing the Ca2+ release from the cardiac SR during diastole. These results raise the future possibility of using GSTM2-2C as a template for therapeutics that can depress RyR2 function when the channel is hyperactive in cardiac arrhythmias and heart failure.

Keywords: arrhythmia, cardiac muscle, cardiac ryanodine receptor, GSTM2-2

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Authors: Abdulaziz Bashir Kutawa1, 2, *, Khairulmazmi Ahmad 1, 3, Mohd Zobir Hussein 4, Asgar Ali 5, * Mohd Aswad Abdul Wahab1, Amara Rafi3, Mahesh Tiran Gunasena1, 6, Muhammad Ziaur Rahman1, 7, Md Imam Hossain1, And Syazwan Afif Mohd Zobir1

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Various abiotic and biotic stresses have an impact on rice production all around the world. The most serious and prevalent disease in rice plants, known as rice blast, is one of the major obstacles to the production of rice. It is one of the diseases that has the greatest negative effects on rice farming globally, the disease is caused by a fungus called Magnaporthe grisae. Since nanoparticles were shown to have an inhibitory impact on certain types of fungus, nanotechnology is a novel notion to enhance agriculture by battling plant diseases. Utilizing nanocarrier systems enables the active chemicals to be absorbed, attached, and encapsulated to produce efficient nanodelivery formulations. The objectives of this research work were to determine the efficacy and mode of action of the nanofungicides (in-vitro) and in field conditions (in-vivo). Ionic gelation method was used in the development of the nanofungicides. Using the poisoned media method, the synthesized agronanofungicides' in-vitro antifungal activity was assessed against M. grisae. The potato dextrose agar (PDA) was amended in several concentrations; 0.001, 0.005, 0.01, 0.025, 0.05, 0.1, 0.15, 0.20, 0.25, 0.30, and 0.35 ppm for the nanofungicides. Medium with the only solvent served as a control. Every day, mycelial growth was measured, and PIRG (percentage inhibition of radial growth) was also computed. Every day, mycelial growth was measured, and PIRG (percentage inhibition of radial growth) was also computed. Based on the results of the zone of inhibition, the chitosan-hexaconazole agronanofungicide (2g/mL) was the most effective fungicide to inhibit the growth of the fungus with 100% inhibition at 0.2, 0.25, 0.30, and 0.35 ppm, respectively. Then followed by carbendazim analytical fungicide that inhibited the growth of the fungus (100%) at 5, 10, 25, 50, and 100 ppm, respectively. The least were found to be propiconazole and basamid fungicides with 100% inhibition only at 100 ppm. The scanning electron microscope (SEM), confocal laser scanning microscope (CLSM), and transmission electron microscope (TEM) were used to study the mechanisms of action of the M. grisae fungal cells. The results showed that both carbendazim, chitosan-hexaconazole, and HXE were found to be the most effective fungicides in disrupting the mycelia of the fungus, and internal structures of the fungal cells. The results of the field assessment showed that the CHDEN treatment (5g/L, double dosage) was found to be the most effective fungicide to reduce the intensity of the rice blast disease with DSI of 17.56%, lesion length (0.43 cm), DR of 82.44%, AUDPC of 260.54 Unit2, and PI of 65.33%, respectively. The least treatment was found to be chitosan-hexaconazole-dazomet (2.5g/L, MIC). The usage of CHDEN and CHEN nanofungicides will significantly assist in lessening the severity of rice blast in the fields, increasing output and profit for rice farmers.

Keywords: chitosan, hexaconazole, disease incidence, and magnaporthe grisae

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Authors: L. Le Priol, A. Nesterenko, K. El Kirat, K. Saleh

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Introduction and objectives: Polyunsaturated fatty acids (PUFAs) omega-3 and omega-6 are widely recognized as being beneficial to the health and normal growth. Unfortunately, due to their highly unsaturated nature, these molecules are sensitive to oxidation and thermic degradation leading to the production of toxic compounds and unpleasant flavors and smells. Hence, it is necessary to find out a suitable way to protect them. Microencapsulation by spray-drying is a low-cost encapsulation technology and most commonly used in the food industry. Many compounds can be used as wall materials, but there is a growing interest in the use of biopolymers, such as proteins and polysaccharides, over the last years. The objective of this study is to increase the oxidative stability of sunflower oil by microencapsulation in plant protein matrices using spray-drying technique. Material and methods: Sunflower oil was used as a model substance for oxidable food oils. Proteins from brown rice, hemp, pea, soy and sunflower seeds were used as emulsifiers and microencapsulation wall materials. First, the proteins were solubilized in distilled water. Then, the emulsions were pre-homogenized using a high-speed homogenizer (Ultra-Turrax) and stabilized by using a high-pressure homogenizer (HHP). Drying of the emulsion was performed in a Mini Spray Dryer. The oxidative stability of the encapsulated oil was determined by performing accelerated oxidation tests with a Rancimat. The size of the microparticles was measured using a laser diffraction analyzer. The morphology of the spray-dried microparticles was acquired using environmental scanning microscopy. Results: Pure sunflower oil was used as a reference material. Its induction time was 9.5 ± 0.1 h. The microencapsulation of sunflower oil in pea and soy protein matrices significantly improved its oxidative stability with induction times of 21.3 ± 0.4 h and 12.5 ± 0.4 h respectively. The encapsulation with hemp proteins did not significantly change the oxidative stability of the encapsulated oil. Sunflower and brown rice proteins were ineffective materials for this application, with induction times of 7.2 ± 0.2 h and 7.0 ± 0.1 h respectively. The volume mean diameter of the microparticles formulated with soy and pea proteins were 8.9 ± 0.1 µm and 16.3 ± 1.2 µm respectively. The values for hemp, sunflower and brown rice proteins could not be obtained due to the agglomeration of the microparticles. ESEM images showed smooth and round microparticles with soy and pea proteins. The surfaces of the microparticles obtained with sunflower and hemp proteins were porous. The surface was rough when brown rice proteins were used as the encapsulating agent. Conclusion: Soy and pea proteins appeared to be efficient wall materials for the microencapsulation of sunflower oil by spray drying. These results were partly explained by the higher solubility of soy and pea proteins in water compared to hemp, sunflower, and brown rice proteins. Acknowledgment: This work has been performed, in partnership with the SAS PIVERT, within the frame of the French Institute for the Energy Transition (Institut pour la Transition Energétique (ITE)) P.I.V.E.R.T. (www.institut-pivert.com) selected as an Investments for the Future (Investissements d’Avenir). This work was supported, as part of the Investments for the Future, by the French Government under the reference ANR-001-01.

Keywords: biopolymer, edible oil, microencapsulation, oxidative stability, release, spray-drying

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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: Aidan Ryan, Nahima Miah, Sahaj Kaur, Imogen Sutherland, Mohamed Saleh

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Pulmonary symptoms are a common presentation to the emergency department. Due to a lack of understanding of the underlying pathophysiology, chronic liver disease is not often considered a cause of dyspnea. We present three patients who were admitted with significant respiratory distress secondary to hepatopulmonary syndrome, portopulmonary hypertension, and hepatic hydrothorax. The first is a 27-year-old male with a 6-month history of progressive dyspnea. The patient developed a severe type 1 respiratory failure with a PaO₂ of 6.3kPa and was escalated to critical care, where he was managed with non-invasive ventilation to maintain oxygen saturation. He had an agitated saline contrast echocardiogram, which showed the presence of a possible shunt. A CT angiogram revealed significant liver cirrhosis, portal hypertension, and large para esophageal varices. Ultrasound of the abdomen showed coarse liver echo patter and enlarged spleen. Along with these imaging findings, his biochemistry demonstrated impaired synthetic liver function with an elevated international normalized ratio (INR) of 1.4 and hypoalbuminaemia of 28g/L. The patient was then transferred to a tertiary center for further management. Further investigations confirmed a shunt of 56%, and liver biopsy confirmed cirrhosis suggestive of alpha-1-antitripsyin deficiency. The findings were consistent with a diagnosis of hepatopulmonary syndrome, and the patient is awaiting a liver transplant. The second patient is a 56-year-old male with a 12-month history of worsening dyspnoea, jaundice, confusion. His medical history included liver cirrhosis, portal hypertension, and grade 1 oesophageal varices secondary to significant alcohol excess. On admission, he developed a type 1 respiratory failure with PaO₂ of 6.8kPa requiring 10L of oxygen. CT pulmonary angiogram was negative for pulmonary embolism but showed evidence of chronic pulmonary hypertension, liver cirrhosis, and portal hypertension. An echocardiogram revealed a grossly dilated right heart with reduced function, pulmonary and tricuspid regurgitation, and pulmonary artery pressures estimated at 78mmHg. His biochemical markers showed impaired synthetic liver function with an INR of 3.2, albumin of 29g/L, along with raised bilirubin of 148mg/dL. During his long admission, he was managed with diuretics with little improvement. After three weeks, he was diagnosed with portopulmonary hypertension and was commenced on terlipressin. This resulted in successfully weaning off oxygen, and he was discharged home. The third patient is a 61-year-old male who presented to the local ambulatory care unit for therapeutic paracentesis on a background of decompensated liver cirrhosis. On presenting, he complained of a 2-day history of worsening dyspnoea and a productive cough. Chest x-ray showed a large pleural effusion, increasing in size over the previous eight months, and his abdomen was visibly distended with ascitic fluid. Unfortunately, the patient deteriorated, developing a larger effusion along with an increase in oxygen demand, and passed away. Without underlying cardiorespiratory disease, in the presence of a persistent pleural effusion with underlying decompensated cirrhosis, he was diagnosed with hepatic hydrothorax. While each presented with dyspnoea, the cause and underlying pathophysiology differ significantly from case to case. By describing these complications, we hope to improve awareness and aid prompt and accurate diagnosis, vital for improving outcomes.

Keywords: dyspnea, hepatic hydrothorax, hepatopulmonary syndrome, portopulmonary syndrome

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Authors: Katherine Dropiewski, Michael Yakimov, Vadim Tokranov, Allan Minns, Pavel Murat, Serge Oktyabrsky

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InAs Quantum Dots (QDs) in a GaAs matrix is a well-documented luminescent material with high light yield, as well as thermal and ionizing radiation tolerance due to quantum confinement. These benefits can be leveraged for high-efficiency, room temperature scintillation detectors. The proposed scintillator is composed of InAs QDs acting as luminescence centers in a GaAs stopping medium, which also acts as a waveguide. This system has appealing potential properties, including high light yield (~240,000 photons/MeV) and fast capture of photoelectrons (2-5ps), orders of magnitude better than currently used inorganic scintillators, such as LYSO or BaF2. The high refractive index of the GaAs matrix (n=3.4) ensures light emitted by the QDs is waveguided, which can be collected by an integrated photodiode (PD). Scintillation structures were grown using Molecular Beam Epitaxy (MBE) and consist of thick GaAs waveguiding layers with embedded sheets of modulation p-type doped InAs QDs. An AlAs sacrificial layer is grown between the waveguide and the GaAs substrate for epitaxial lift-off to separate the scintillator film and transfer it to a low-index substrate for waveguiding measurements. One consideration when using a low-density material like GaAs (~5.32 g/cm³) as a stopping medium is the matrix thickness in the dimension of radiation collection. Therefore, luminescence properties of very thick (4-20 microns) waveguides with up to 100 QD layers were studied. The optimization of the medium included QD shape, density, doping, and AlGaAs barriers at the waveguide surfaces to prevent non-radiative recombination. To characterize the efficiency of QD luminescence, low temperature photoluminescence (PL) (77-450 K) was measured and fitted using a kinetic model. The PL intensity degrades by only 40% at RT, with an activation energy for electron escape from QDs to the barrier of ~60 meV. Attenuation within the waveguide (WG) is a limiting factor for the lateral size of a scintillation detector, so PL spectroscopy in the waveguiding configuration was studied. Spectra were measured while the laser (630 nm) excitation point was scanned away from the collecting fiber coupled to the edge of the WG. The QD ground state PL peak at 1.04 eV (1190 nm) was inhomogeneously broadened with FWHM of 28 meV (33 nm) and showed a distinct red-shift due to self-absorption in the QDs. Attenuation stabilized after traveling over 1 mm through the WG, at about 3 cm⁻¹. Finally, a scintillator sample was used to test detection and evaluate timing characteristics using 5.5 MeV alpha particles. With a 2D waveguide and a small area of integrated PD, the collected charge averaged 8.4 x10⁴ electrons, corresponding to a collection efficiency of about 7%. The scintillation response had 80 ps noise-limited time resolution and a QD decay time of 0.6 ns. The data confirms unique properties of this scintillation detector which can be potentially much faster than any currently used inorganic scintillator.

Keywords: GaAs, InAs, molecular beam epitaxy, quantum dots, III-V semiconductor

Procedia PDF Downloads 235

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

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Authors: Poojan Gharat, Haridas Pal, Sharmistha Dutta Choudhury

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Tuning photophysical properties of guest dyes through host-guest interactions involving macrocyclic hosts are the attractive research areas since past few decades, as these changes can directly be implemented in chemical sensing, molecular recognition, fluorescence imaging and dye laser applications. Excited state intramolecular proton transfer (ESIPT) is an intramolecular prototautomerization process display by some specific dyes. The process is quite amenable to tunability by the presence of different macrocyclic hosts. The present study explores the interesting effect of p-sulfonatocalix[n]arene (SCXn) and cyclodextrin (CD) hosts on the excited-state prototautomeric equilibrium of Chrysazine (CZ), a model antitumour drug. CZ exists exclusively in its normal form (N) in the ground state. However, in the excited state, the excited N* form undergoes ESIPT along with its pre-existing intramolecular hydrogen bonds, giving the excited state prototautomer (T*). Accordingly, CZ shows a single absorption band due to N form, but two emission bands due to N* and T* forms. Facile prototautomerization of CZ is considerably inhibited when the dye gets bound to SCXn hosts. However, in spite of lower binding affinity, the inhibition is more profound with SCX6 host as compared to SCX4 host. For CD-CZ system, while prototautomerization process is hindered by the presence of β-CD, it remains unaffected in the presence of γCD. Reduction in the prototautomerization process of CZ by SCXn and βCD hosts is unusual, because T* form is less dipolar in nature than the N*, hence binding of CZ within relatively hydrophobic hosts cavities should have enhanced the prototautomerization process. At the same time, considering the similar chemical nature of two CD hosts, their effect on prototautomerization process of CZ would have also been similar. The atypical effects on the prototautomerization process of CZ by the studied hosts are suggested to arise due to the partial inclusion or external binding of CZ with the hosts. As a result, there is a strong possibility of intermolecular H-bonding interaction between CZ dye and the functional groups present at the portals of SCXn and βCD hosts. Formation of these intermolecular H-bonds effectively causes the pre-existing intramolecular H-bonding network within CZ molecule to become weak, and this consequently reduces the prototautomerization process for the dye. Our results suggest that rather than the binding affinity between the dye and host, it is the orientation of CZ in the case of SCXn-CZ complexes and the binding stoichiometry in the case of CD-CZ complexes that play the predominant role in influencing the prototautomeric equilibrium of the dye CZ. In the case of SCXn-CZ complexes, the results obtained through experimental findings are well supported by quantum chemical calculations. Similarly for CD-CZ systems, binding stoichiometries obtained through geometry optimization studies on the complexes between CZ and CD hosts correlate nicely with the experimental results. Formation of βCD-CZ complexes with 1:1 stoichiometry while formation of γCD-CZ complexes with 1:1, 1:2 and 2:2 stoichiometries are revealed from geometry optimization studies and these results are in good accordance with the observed effects by the βCD and γCD hosts on the ESIPT process of CZ dye.

Keywords: intermolecular proton transfer, macrocyclic hosts, quantum chemical studies, photophysical studies

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

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

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

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Authors: Laura Kocsor, Laszlo Peter, Laszlo Kovacs, Zsolt Kis

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The aim of our research is to prepare rare-earth-doped lithium niobate (LiNbO3) nanocrystals, having only a few dopant ions in the focal point of an exciting laser beam. These samples will be used to achieve individual addressing of the dopant ions by light beams in a confocal microscope setup. One method for the preparation of nanocrystalline materials is to reduce the particle size by mechanical grinding. High-energy ball-milling was used in several works to produce nano lithium niobate. Previously, it was reported that dry high-energy ball-milling of lithium niobate in a shaker mill results in the partial reduction of the material, which leads to a balanced formation of bipolarons and polarons yielding gray color together with oxygen release and Li2O segregation on the open surfaces. In the present work we focus on preparing LiNbO3 nanocrystals by high-energy ball-milling using a Fritsch Pulverisette 7 planetary mill. Every ball-milling process was carried out in zirconia vial with zirconia balls of different sizes (from 3 mm to 0.1 mm), wet grinding with water, and the grinding time being less than an hour. Gradually decreasing the ball size to 0.1 mm, an average particle size of about 10 nm could be obtained determined by dynamic light scattering and verified by scanning electron microscopy. High-energy ball-milling resulted in sample darkening evidenced by optical absorption spectroscopy measurements indicating that the material underwent partial reduction. The unwanted lithium oxide loss decreases the Li/Nb ratio in the crystal, strongly influencing the spectroscopic properties of lithium niobate. Zirconia contamination was found in ground samples proved by energy-dispersive X-ray spectroscopy measurements; however, it cannot be explained based on the hardness properties of the materials involved in the ball-milling process. It can be understood taking into account the presence of lithium hydroxide formed the segregated lithium oxide and water during the ball-milling process, through chemically induced abrasion. The quantity of the segregated Li2O was measured by coulometric titration. During the wet milling process in the planetary mill, it was found that the lithium oxide loss increases linearly in the early phase of the milling process, then a saturation of the Li2O loss can be seen. This change goes along with the disappearance of the relatively large particles until a relatively narrow size distribution is achieved in accord with the dynamic light scattering measurements. With the 3 mm ball size and 1100 rpm rotation rate, the mean particle size achieved is 100 nm, and the total Li2O loss is about 1.2 wt.% of the original LiNbO3. Further investigations have been done to minimize the Li2O segregation during the ball-milling process. Since the Li2O loss was observed to increase with the growing total surface of the particles, the influence of ball-milling parameters on its quantity has also been studied.

Keywords: high-energy ball-milling, lithium niobate, mechanochemical reaction, nanocrystals

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

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

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

Procedia PDF Downloads 188