Search results for: radical reactions

Authors: Carlos A. C. G. Neto, Natan C. G. Silva, Thais O. Costa, Luciana R. B. Goncalves, Maria v. P. Rocha

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Galactosidases are enzymes responsible for catalyzing lactose hydrolysis reactions and also favoring transgalactosylation reactions for the production of prebiotics, among which lactulose stands out. These enzymes, when immobilized, can have some enzymatic characteristics substantially improved, and the coating of supports with multifunctional polymers in immobilization processes is a promising alternative in order to extend the useful life of the biocatalysts, for example, the coating with polyethyleneimine (PEI). PEI is a flexible polymer that suits the structure of the enzyme, giving greater stability, especially for multimeric enzymes such as β-galactosidases and also protects it from environmental variations, for example, pH and temperature. In addition, it can substantially improve the immobilization parameters and also the efficiency of enzymatic reactions. In this context, the aim of the present work was first to develop biocatalysts of β-galactosidase from Kluyveromyces lactis immobilized on PEI coated agarose, determining the immobilization parameters, its operational and thermal stability, and then to apply it in the hydrolysis of lactose and synthesis of lactulose, using whey as a substrate. This immobilization strategy was chosen in order to improve the catalytic efficiency of the enzyme in the transgalactosylation reaction for the production of prebiotics, and there are few studies with β-galactosidase from this strain. The immobilization of β-galactosidase in agarose previously functionalized with 48% (w/v) glycidol and then coated with 10% (w/v) PEI solution was evaluated using an enzymatic load of 10 mg/g of protein. Subsequently, the hydrolysis and transgalactosylation reactions were conducted at 50 °C, 120 RPM for 20 minutes, using whey (66.7 g/L of lactose) supplemented with 133.3 g/L fructose at a ratio of 1:2 (lactose/fructose). Operational stability studies were performed in the same conditions for 10 cycles. Thermal stabilities of biocatalysts were conducted at 50 ºC in 50 mM phosphate buffer, pH 6.6, with 0.1 mM MnCl2. The biocatalysts whose supports were coated were named AGA_GLY_PEI_GAL, and those that were not coated were named AGA_GLY_GAL. The coating of the support with PEI considerably improved immobilization yield (2.6-fold), the biocatalyst activity (1.4-fold), and efficiency (2.2-fold). The biocatalyst AGA_GLY_PEI_GAL was better than AGA_GLY_GAL in hydrolysis and transgalactosylation reactions, converting 88.92% of lactose at 5 min of reaction and obtaining a residual concentration of 5.24 g/L. Besides that, it was produced 13.90 g/L lactulose in the same time interval. AGA_GLY_PEI_GAL biocatalyst was stable during the 10 cycles evaluated, converting approximately 80% of lactose and producing 10.95 g/L of lactulose even after the tenth cycle. However, the thermal stability of AGA_GLY_GAL biocatalyst was superior, with a half-life time 5 times higher, probably because the enzyme was immobilized by covalent bonding, which is stronger than adsorption (AGA_GLY_PEI_GAL). Therefore, the strategy of coating the supports with PEI has proven to be effective for the immobilization of β-galactosidase from K. lactis, considerably improving the immobilization parameters, as well as the enzyme, catalyzed reactions. In addition, the use of whey as a raw material for lactulose production has proved to be an industrially advantageous alternative.

Keywords: β-galactosidase, immobilization, lactulose, polyethylenimine, whey

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Authors: Edwin Oviedo, Carlos Linares, Philippe Ayrault, Sylvette Brunet

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Nowadays, light conventional crude oils are going down. Therefore, the exploitation of heavy crude oils has been increasing. Hence, a major quantity of refractory sulfur compounds such as dibenzothiophene (DBT) should be removed. Many efforts have been carried out to modify hydrotreatment typical supports in order to increase hydrodesulfurization (HDS) reactions. The present work shows the synthesis of tertiaries MgFeAl(0.16), MgFeAl(0.32), CoFeAl, ZnFeAl hydrotalcites, as supports of CoMo based catalysts, where 0.16 and 0.32 are the Fe3+/Al3+ molar ratio. Solids were characterized by different techniques (XRD, CO2-TPD, H2-TPR, FT-IR, BET, Chemical Analysis and HRTEM) and tested in the DBT HDS reaction. The reactions conditions were: Temp=325°C, P=40 Bar, H2/feed=475. Results show that the catalysts CoMo/MgFeAl(0.16) and CoMo/MgFeAl(0.32), which were the most basics, reduced the sulfur content from 500ppm to less than 1 ppm, increasing the cyclohexylbenzene content, i.e. presented a higher selective toward the HYD pathway than reference catalyst CoMo/γ- Al2O3. This is suitable for improving the fuel quality due to the increase of the cetane number. These catalysts were also more active to the HDS reaction increasing the direct desulfurization (DDS) way and presented a good stability. It is advantageous when the gas oil centane number should be improved. Cobalt, iron or zinc species inside support could avoid the Co and Mo dispersion or form spinel species which could be less active to hydrodesulfuration reactions, while hydrotalcites containing Mg increases the HDS activity probably due to improved Co/Mo ratio.

Keywords: catalyst, cetane number, dibenzothiophene, diesel, hydrodesulfurization, hydrotreatment, MoS2

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Authors: Hannes Koester

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Driven by difficult market conditions and increasing regulations, many banks are making the strategic decision to restructure their portfolio by divesting several business segments. Using a unique dataset of 727 portfolio restructuring announcements by 161 international listed banks over the period 1999 to 2015, we investigate the impact of restructuring measurements on the stock performance as well as on the banks’ profitability and risk. Employing the event study methodology, we detect positive stock market reactions on the announcement of restructuring measurements. These positive stock market reactions indicate that shareholders reward banks’ specialization activities. However, the results of the system GMM regressions show a negative relation between restructuring measurements and banks’ return on assets and a positive relation towards the individual and systemic risk of banks. These empirical results indicate that there is no guarantee that portfolio restructurings will result in a more profitable and less risky institution.

Keywords: bank performance, bank risk, divestiture, restructuring, systemic risk

Procedia PDF Downloads 287

Authors: Lubomir Vecera, Tomas Gabrhelik, Benjamin Tolmaci, Josef Srovnal, Emil Berta, Petr Prasil, Petr Stourac

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Cancer is the second leading cause of death worldwide and colon cancer is the second most common type of cancer. Currently, there are only a few studies evaluating the effect of postoperative analgesia on the prognosis of patients undergoing radical colon cancer surgery. Postoperative analgesia in patients undergoing colon cancer surgery is usually managed in two ways, either with strong opioids (morphine, piritramide) or epidural analgesia. In our prospective study, we evaluated the effect of postoperative analgesia on the presence of circulating tumor cells or minimal residual disease after colon cancer surgery. A total of 60 patients who underwent radical colon cancer surgery were enrolled in this prospective, randomized, two-center study. Patients were randomized into three groups, namely piritramide, morphine and postoperative epidural analgesia. We evaluated the presence of carcinoembryonic antigen (CEA) and cytokeratin 20 (CK-20) mRNA positive circulating tumor cells in peripheral blood before surgery, immediately after surgery, on postoperative day two and one month after surgery. The presence of circulating tumor cells was assessed by quantitative real-time reverse transcriptase-polymerase chain reaction (qRT-PCR). In the priritramide postoperative analgesia group, the presence of CEA mRNA positive cells was significantly lower on a postoperative day two compared to the other groups (p=0.04). The value of CK-20 mRNA positive cells was the same in all groups on all days. In all groups, both types of circulating tumor cells returned to normal levels one month after surgery. Demographic and baseline clinical characteristics were similar in all groups. Compared with morphine and epidural analgesia, piritramide significantly reduces the amount of CEA mRNA positive circulating tumor cells after radical colon cancer surgery.

Keywords: cancer progression, colon cancer, minimal residual disease, perioperative analgesia.

Procedia PDF Downloads 156

Authors: Aigin Bashti

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Preparation of multicomponent reactions (MCRs) via a simple one-pot strategy is considered a novel procedure which has attracted a lot of interest from organic and medicinal chemists. Due to the great importance of phthalazide triones, it was decided to introduce a novel and cost-effective green procedure for the preparation of these derivatives. In this methodology, an efficient 4,4ʹ-Bipyridinium Dichloride Ordered Mesoporous Silica functionalized catalyst (BP-SBA-15) was utilized. The catalyst was characterized by X-ray diffraction analysis (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), thermo-gravimetric analysis (TGA), and Fourier-transform infrared spectroscopy (FT-IR) analysis. In conclusion, it should be mentioned that this methodology has some advantages, including short reaction time, high yield of the products, recyclable catalyst, green procedure, and facile work-up procedure. The catalyst was successfully utilized for the one-pot preparation of various phthalazinetrione derivatives.

Keywords: dimedone, green procedure, multicomponent reactions, phthalhydrazide

Procedia PDF Downloads 65

Authors: Rohit Kothari

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Background: Leprosyis a chronic granulomatous diseasecaused by Mycobacterium leprae (M. Lepra). Reactions may interrupt its usual chronic course.Type-1 (T1R)and type-2 lepra reaction(T2R) are acute events and signifytype-IV and type-III hypersensitivity responses, respectively. Various chemokines like CCL3, 5, 11, and CCL24 may be increased during the course of leprosy or during reactions and may serve as markers of early diagnosis, response to therapy, and prognosis. Objective: To find correlation of CCL3, 5, 11, and CCL24 in leprosy patients on multidrug therapy and their family contacts after ruling out active disease during leprosy treatment and during periods of lepra reactions. Methodology: This randomized control trial was conducted in 50 clinico-histopathologically diagnosed cases of leprosy in a tertiary care hospital in Bengaluru, India. 50 of their family contacts were adequately examined and investigated should the need be to rule out active disease. The two study-groups comprised of leprosy cases, and the age, sex, and area of residence matched healthy contactswho were given single-dose rifampicin prophylaxis, respectively. Blood samples were taken at baseline, six months, and after one yearin both the groups (on completion of MDT in leprosy cases)and also during periods of reaction if occurred in leprosy cases. Results: Our study found that at baseline, CCL5, 11, and 24 were higher in leprosy cases as compared to the healthy contacts, and the difference was statistically significant.CCL3 was also found to be higherat baseline in leprosy cases, however, the difference was not statistically significant. At six months and one year, the levels of CCL 5, 11, and 24 reduced, and the difference was statistically significant in leprosy cases, whereas it remained almost static in all the healthy contacts. Twenty patients of leprosy developed lepra reaction during the course of one year, and during reaction, the increase in CCL11 and 24 was statistically significant from baseline, whereas CCL3 and 5 did not rise significantly. One of the healthy contacts developed signs of leprosy in the form of hypopigmented numb patch and was clinico-histopathologically, and CCL11 and 24 were found to be higher with a statistically significant difference from the baseline values. Conclusion: CCL5, 11, and 24 are sensitive markers of diagnosing leprosy, response to MDT, and prognosis and are not increased in healthy contacts. CCL11 and 24 are sensitive markers of lepra reactions and may serve as one of the early diagnostic modalities for identifying lepra reaction and also leprosy in healthy contacts. To the best of our knowledge, this is the first study to evaluate these biomarkers in leprosy cases and their healthy contacts with a follow-up of upto one year with one of them developing the disease, and the same was confirmed based on these biomarkers as well.

Keywords: chemokine profile, healthy contacts, leprosy, lepra reactions

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Authors: M. Shahana

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Introduction: Leprosy (Hansens) is one of the major health problems in the developing countries. Sixty percent of the world leprosy cases are in India. According to the 2006 census India has about 54% of the total new cases detected globally. The National Leprosy Elimination Programme in 2012 has reported 9.7% of childhood leprosy. There are only few studies related to paediatric leprosy. Aim: To study the epidemiology and various clinical presentations of leprosy in the paediatric age group. Material and Methods: A 4-year prospective study was done in the out-patient department of dermatology in a tertiary care hospital. All the patients were screened for leprosy and children with a confirmed diagnosis of leprosy were taken up for the study. Results: Total of 321 cases of Hansens were recorded during this period out of which 41 were children. The male to female ratio was 2.72:1. A positive family history was found in 18%. Most of them presented with single hypopigmented hypoanesthetic patch. Conclusions: Children presented with more of Borderline tuberculoid type and reactions or deformities were less common.

Keywords: Hansens, hypoaneasthetic patch, leprosy, reactions

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Authors: Bai-Jing Peng, Shyh-Chyun Yang

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Organic reactions in water have recently attracted much attention, not only because unique reactivity is often observed in water but also because water is a safe and economical substitute for conventional organic solvents. Thus, development of environmental safe, atom-economical reactions in water is one of the most important goals of synthetic chemistry. The recent paper has documented renewed interest in the use of allylic substrates in the synthesis of new C−C, C−N, and C−O bonds. We have reported our attempts and some successful applications of a process involving the C-O bond cleavage catalyzed by palladium or platinum complexes in water. Because of the importance of heterocycle indole derivatives, much effort has been directed toward the development of methods for functionalization of the indole nucleus at N1 site. In our research, the palladium-catalyzed 2,3-disubstitued indoles with allylic alcohols was investigated under different conditions. Herein, we will establish a simple, convenient, and efficient method, which affords high yields of allylated indoles.

Keywords: palladium-catalyzed, allylic alcohols, indoles, water, allylation

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Authors: Yu-Hong Lin

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Background: An adverse drug reaction (ADR) reported is an injury which caused by taking medicines. Sometimes the severity of ADR reported may be minor, but sometimes it could be a life-threatening situation. In order to provide healthcare professionals as a better reference in clinical practice, we do data collection and analysis from our hospital. Methods: This was a retrospective study of ADRs reported performed from 2014 to 2015 in our hospital in Taiwan. We collected assessment items of ADRs reported, which contain gender and age, occurring sources, Anatomical Therapeutic Chemical (ATC) classification of suspected drugs, types of adverse reactions, Naranjo score calculating by Naranjo Adverse Drug Reaction Probability Scale and so on. Results: The investigation included two hundred and seven ADRs reported. Most of ADRs reported were occurring in outpatient department (92%). The average age of ADRs reported was 65.3 years. Less than 65 years of age were in the majority in this study (54%). Majority of all ADRs reported were males (51%). According to ATC classification system, the major classification of suspected drugs was cardiovascular system (19%) and antiinfectives for systemic use (18%) respectively. Among the adverse reactions, Dermatologic Effects (35%) were the major type of ADRs. Also, the major Naranjo scores of all ADRs reported ranged from 1 to 4 points (91%), which represents a possible correlation between ADRs reported and suspected drugs. Conclusions: Definitely, ADRs reported is still an extremely important information for healthcare professionals. For that reason, we put all information of ADRs reported into our hospital's computer system, and it will improve the safety of medication use. By hospital's computer system, it can remind prescribers to think of information about patient's ADRs reported. No drugs are administered without risk. Therefore, all healthcare professionals should have a responsibility to their patients, who themselves are becoming more aware of problems associated with drug therapy.

Keywords: adverse drug reaction, Taiwan, healthcare professionals, safe use of medicines

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Authors: Fatiha Bedjou, Meriem Meddas, Tadjajikt Chekkal

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The present work aims to evaluate the antioxidant activity of ethanolic extracts and essential oils of aromatic plants of the Lamiaceae family: Thymus algeriensis and Salvia rosmarinus, and Anacardiaceae: Pistacia lentiscus, Myrtaceae: Eucalyptus polybracetea. The polyphenols were measured using the Folin-Ciocalteu method; the results showed that the essential oils studied as well as the ethanolic extracts are relatively rich in polyphenols. Their antioxidant properties were tested by the synthetic DPPH radical trapping method. The IC50 values were determined according to the graph representing the percentage of inhibition of the DPPH radical by essential oils and by ethanolic extracts, according to our results there is a correlation between the level of polyphenols present in the different essential oils and different ethanolic extracts and their ability to neutralize free radicals. Several combinations were carried out between the essential oils and also between the ethanolic extracts in order to determine the type of interactions existing between the combined substances, the results were represented in the form of isobolograms. Additive and super-additive effects were observed in combinations of essential oils, and super-additive and sub-additive effects were observed for combinations of ethanolic extracts.

Keywords: essential oils, ethanolic extracts, DPPH, combination

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Authors: Emmanuel Temitope Adaranijo

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Medical error is on the increase in many nations and like many developing nations, Nigeria is not excluded and more importantly, Lafia, Nasarawa state, where the study was carried. The study was undertaken to explore Patients' knowledge and their reactions to medical errors in hospitals in Lafia Local Government Area; therefore, five objectives were formulated to guide the study. The survey research design was employed and triangulation of quantitative and qualitative instruments was used to collect data. The total population for the study was 330,712 and the sample size was 400; however, only 343 patients and three doctors responded to the quantitative and qualitative study, respectively. Frequency distribution, simple percentage, and r test were used to analyze the data obtained from respondents. The findings revealed that medical errors are prevalent in hospitals in Lafia and the patients are neither aware nor willing to report such occurrence. The study recommends that social workers, hospital management, and governments should take up their roles in reducing the occurrence of medical errors.

Keywords: health, hospital, medical errors, social work

Procedia PDF Downloads 103

Authors: Chih-Hsiang Chang, Pei-Shan Kao

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This paper discusses the reaction of investors in the Taiwan stock market to the most probable unknown earnings-related information and the most probable known earnings-related information. As compared with the previous literature regarding the effect of an official announcement of earnings forecast revision, this paper further analyzes investors’ cognitive bias toward the unknown and known earnings-related information, and the role of media during the investors' reactions to the foresaid information shocks. The empirical results show that both the unknown and known earnings-related information provides useful information content for a stock market. In addition, cognitive bias and disposition effect are the behavioral pitfalls that commonly occur in the process of the investors' reactions to the earnings-related information. Finally, media coverage has a remarkable influence upon the investors' trading decisions.

Keywords: cognitive bias, role of media, disposition effect, earnings-related information, behavioral pitfall

Procedia PDF Downloads 197

Authors: Salima Tabti, Chaima Maouche, Tinhinene Louaileche, Amel Djedouani, Ismail Warad

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Novel Schiff base ligand HL has been synthesized by condensation of aromatic amine and DHA. It was characterized by UV-Vis, FT-IR, SM, NMR (1H, 13C) and also by single-crystal X-ray diffraction. The crystal structure shows that compound crystallized in a triclinic system in P-1 space group and with a two unit per cell (Z = 2).The asymmetric unit, contains one independent molecules, the conformation is determined by an intermolecular N-H…O hydrogen bond with an S(6) ring motif. The molecule have an (E) conformation about the C=N bond. The dihedral angles between the phenyl and pyran ring planes is 89.37 (1), the two plans are approximately perpendicular. The catecholase activity of is situ copper complexes of this ligand has been investigated against catechol. The progress of the oxidation reactions was closely monitored over time following the strong peak of catechol using UV-Vis. Oxidation rates were determined from the initial slope of absorbance. time plots, then analyzed by Michaelis-Menten equations. Catechol oxidation reactions were realized using different concentrations of copper acetate and ligand (L/Cu: 1/1, 1/2, 2/1). The results show that all complexes were able to catalyze the oxidation of catechol. Acetate complexes have the highest activity. Catalysis is a branch of chemical kinetics that, more generally, studies the influence of all physical or chemical factors determining reaction rates. It solves a lot of problems in the chemistry reaction process, especially for a green, economic and less polluting chemistry. For this reason, the search for new catalysts for known organic reactions, occupies a very advanced place in the themes proposed by the chemists.

Keywords: dehydroacetic acid, catechol, copper, catecholase activity, x-ray

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Authors: Stefanie Rukavina, Sascha Gruss, Steffen Walter, Holger Hoffmann, Harald C. Traue

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OPEN-EmoRecII is an open multimodal corpus with experimentally induced emotions. In the first half of the experiment, emotions were induced with standardized picture material and in the second half during a human-computer interaction (HCI), realized with a wizard-of-oz design. The induced emotions are based on the dimensional theory of emotions (valence, arousal and dominance). These emotional sequences - recorded with multimodal data (mimic reactions, speech, audio and physiological reactions) during a naturalistic-like HCI-environment one can improve classification methods on a multimodal level. This database is the result of an HCI-experiment, for which 30 subjects in total agreed to a publication of their data including the video material for research purposes. The now available open corpus contains sensory signal of: video, audio, physiology (SCL, respiration, BVP, EMG Corrugator supercilii, EMG Zygomaticus Major) and mimic annotations.

Keywords: open multimodal emotion corpus, annotated labels, intelligent interaction

Procedia PDF Downloads 383

Authors: Zohreh Derikvand

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Nanoreactors Zr-MCM-41were prepared via the reaction of ZrOCl2, Fumed silica, sodium hydroxide and cethyltrimethyl ammonium bromide under hydrothermal condition. The prepared nanoreactors were characterized by FT-IR spectroscopy, X-ray diffraction (XRD), Scanning electron micrographs (SEM) and nitrogen adsorption-desorption. The XRD pattern of Zr-MCM-41 exhibits a high-intensity (100) and two low-intensity reflections (110 and 200) which are characteristic of hexagonal structure, exhibiting the long-range order and good textural uniformity of mesoporous structure. Based on the green chemistry approach, we report an efficient and environmentally benign protocol to study the catalytic activity of Zr-MCM-41 in the Biginelli type reactions initially. Nanoreactors Zr-MCM-41 were used as highly recoverable and reusable catalyst for synthesis of 3,4-dihydropyrimidin-2(1H)-one, octahydroquinazolinone, benzimidazolo-quinazolineone and 4,6-diarylpyrimidin-2(1H)-one. The methodology offers several advantages such as short reaction time, high yields and simple operation. The catalyst was active up to three cycles.

Keywords: Zr-MCM-41 nanoreactors, Biginelli like reactions, 3, 4-dihydropyrimidin-2(1H)-ones, ctahydroquinazolinones

Procedia PDF Downloads 175

Authors: Hye Rim Kang, So Yae Koh, Ji-Yeon Ryu, Chang Kyu Lee, Ji Hee Lim, Hyeon A. Kim, Geun Hyung Im, Somi Kim Cho

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In this study, antioxidant properties and compositional analysis of fermented chocolate were examined. Chocolate was fermented with Lactobacillus plantarum CK10. As fermentation time went by, pH was decreased (5.26±0.02 to 3.98±0.06) while titratable acidity was increased (5.36±0.19 to 13.31±0.34). The total polyphenol contents were maintained through the fermentation. The contents of total polyphenol were slightly increased at 8 hr (6.34±0.12 mg GAE (Gallic acid equivalent)/g), and it reached to comparable levels of the control at 24 hr (control, 5.47±0.36 mg GAE/g); 24 hr, 5.19±0.23 mg GAE/g). Similarly, the total flavonoid contents were not significantly changed during fermentation. The pronounced radical scavenging activities of chocolate, against DPPH-, ABTS-, and Alkyl radical, were observed. The levels of antioxidant activities were not dramatically altered in the course of fermentation. By gas chromatography-mass spectrometry analysis, the increase in lactic acid was measured and four major compounds, HMF, xanthosine, caffeine, and theobromine, were identified. The relative peak area of caffeine and theobromine was considerably changed during fermentation. However, no significant difference in the levels of caffeine and theobromine were observed by high-performance liquid chromatography analysis.

Keywords: antioxidant, chocolate, compositional analysis, fermentation, Lactobaillus plantarum

Procedia PDF Downloads 263

Authors: Ralene Sim, Stefan Mueller, N. Gopalakrishna Iyer, Ngian Chye Tan, Khee Chee Soo, R. Shetty Mahalakshmi, Hiang Khoon Tan

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Background: Regional failure in nasopharyngeal carcinoma (NPC) is managed by salvage treatment in the form of neck dissection. Radical neck dissection (RND) is preferred over modified radical neck dissection (MRND) since it is traditionally believed to offer better long-term disease control. However, with the advent of more advanced imaging modalities like high-resolution Magnetic Resonance Imaging, Computed Tomography, and Positron Emission Tomography-CT scans, earlier detection is achieved. Additionally, concurrent chemotherapy also contributes to reduced tumour burden. Hence, there may be a lesser need for an RND and a greater role for MRND. With this retrospective study, the primary aim is to ascertain whether MRND, as opposed to RND, has similar outcomes and hence, whether there would be more grounds to offer a less aggressive procedure to achieve lower patient morbidity. Methods: This is a retrospective study of 66 NPC patients treated at Singapore General Hospital between 1994 to 2016 for histologically proven regional recurrence, of which 41 patients underwent RND and 25 who underwent MRND, based on surgeon preference. The type of ND performed, primary treatment mode, adjuvant treatment, and pattern of recurrence were reviewed. Overall survival (OS) was calculated using Kaplan-Meier estimate and compared. Results: Overall, the disease parameters such as nodal involvement and extranodal extension were comparable between the two groups. Comparing MRND and RND, the median (IQR) OS is 1.76 (0.58 to 3.49) and 2.41 (0.78 to 4.11) respectively. However, the p-value found is 0.5301 and hence not statistically significant. Conclusion: RND is more aggressive and has been associated with greater morbidity. Hence, with similar outcomes, MRND could be an alternative salvage procedure for regional failure in selected NPC patients, allowing similar salvage rates with lesser mortality and morbidity.

Keywords: nasopharyngeal carcinoma, neck dissection, modified neck dissection, radical neck dissection

Procedia PDF Downloads 140

Authors: David Ryan, Martin Breugst, Turlough Downes, Peter A. Byrne, Gerard P. McGlacken

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An ambident nucleophile is a nucleophile that possesses two or more distinct nucleophilic sites that are linked through resonance and are effectively “in competition” for reaction with an electrophile. Examples include enolates, pyridone anions, and nitrite anions, among many others. Reactions of ambident nucleophiles and electrophiles are extremely prevalent at all levels of organic synthesis. The principle of hard and soft acids and bases (the “HSAB principle”) is most commonly cited in the explanation of selectivities in such reactions. Although this rationale is pervasive in any discussion on ambident reactivity, the HSAB principle has received considerable criticism. As a result, the principle’s supplantation has become an area of active interest in recent years. This project focuses on developing a model for rationalizing ambident reactivity. Presented here is an approach that incorporates computational calculations and experimental kinetic data to construct Gibbs energy profile diagrams. The preferred site of alkylation of nitrite anion with a range of ‘hard’ and ‘soft’ alkylating agents was established by ¹H NMR spectroscopy. Pseudo-first-order rate constants were measured directly by ¹H NMR reaction monitoring, and the corresponding second-order constants and Gibbs energies of activation were derived. These, in combination with computationally derived standard Gibbs energies of reaction, were sufficient to construct Gibbs energy wells. By representing the ambident system as a series of overlapping Gibbs energy wells, a more intuitive picture of ambident reactivity emerges. Here, previously unexplained switches in reactivity in reactions involving closely related electrophiles are elucidated.

Keywords: ambident, Gibbs, nucleophile, rates

Procedia PDF Downloads 56

Authors: Friday A. Ogori, Ojotu M. Eke, Oneh J. Abu, Abraham T. Girgih

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B.aeqygtiaca del (Balanites aegyptiaca del) seed protein concentrate (APC) was hydrolyzed using different enzymes such as pepsin+pancreatin (PP), Alcalase (Alca), and Flavourzyme (Flav). The Alca has higher yield (100%) when compared to PP (83.23%) and Flav (62.90%). The hydrophobic amino acid and Sulphur containing amino acid (40.19%, 7.04%) in PP hydrolysate were higher compared to Alcalase (38.92%, 6.69%), Flavourenzyme (37.43%,6.35%), and APC (39.97%, 6.95%) samples. The PP has stronger DPPH, Hydroxyl radical quenching, Ferric reducing activity, and linoleic acid peroxidation activity, followed by the protein concentrate (APC) and Alcalase (Alca), while Flavourenzyme (Flav) derived hydrolysate was least in scavenging and inhibiting radical peroxidation properties. Flavourenzyme derived hydrolysate had stronger Ferric reducing antioxidant potential and metal chelating property. The result showed that the Alcalase hydrolysate has promising peptide yield, and PP hydrolysate had excellent amino acid residues and good in-vitro antioxidant potentials and could be a preferred ingredients in the nutraceutical and functional food emerging industries.

Keywords: balanites aegyptiaca del, protein concentrate, protein hydrolysates, enzymatic hydrolysis, antioxidants

Procedia PDF Downloads 44

Authors: A. M. Plante, F. O’Halloran, A. L. McCarthy

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By 2050 it is projected that 2 billion of the global population will be more than 60 years old. Older adults have unique dietary requirements and aging is associated with physiological changes that affect appetite, sensory perception, metabolism, and digestion. Therefore, it is essential that foods recommended and designed for older adults promote healthy aging. To assess cheese as a functional food for the elderly, a range of commercial cheese products were selected and compared for their antioxidant properties. Cheese from various milk sources (bovine, goats, sheep) with different textures and fat content, including cheddar, feta, goats, brie, roquefort, halloumi, wensleydale and gouda, were initially digested with two different simulated in vitro gastrointestinal digestion (SGID) models. One SGID model represented a validated in vitro adult digestion system and the second model, an elderly SGID, was designed to consider the physiological changes associated with aging. The antioxidant potential of all cheese digestates was investigated using in vitro chemical-based antioxidant assays, (2,2-Diphenyl-1-picrylhydrazyl (DPPH) radical scavenging, ferric reducing antioxidant power (FRAP) and total phenolic content (TPC)). All adult model digestates had high antioxidant activity across both DPPH ( > 70%) and FRAP ( > 700 µM Fe²⁺/kg.fw) assays. Following in vitro digestion using the elderly SGID model, full-fat red cheddar, low-fat white cheddar, roquefort, halloumi, wensleydale, and gouda digestates had significantly lower (p ≤ 0.05) DPPH radical scavenging properties compared to the adult model digestates. Full-fat white cheddar had higher DPPH radical scavenging activity following elderly SGID digestion compared to the adult model digestate, but the difference was not significant. All other cheese digestates from the elderly model were comparable to the digestates from the adult model in terms of radical scavenging activity. The FRAP of all elderly digestates were significantly lower (p ≤ 0.05) compared to the adult digestates. Goats cheese was significantly higher (p ≤ 0.05) in FRAP (718 µM Fe²/kg.fw) compared to all other digestates in the elderly model. TPC levels in the soft cheeses (feta, goats) and low-fat cheeses (red cheddar, white cheddar) were significantly lower (p ≤ 0.05) in the elderly digestates compared to the adult digestates. There was no significant difference in TPC levels, between the elderly and adult model for full-fat cheddar (red, white), roquefort, wensleydale, gouda, and brie digestates. Halloumi cheese was the only cheese that was significantly higher in TPC levels following elderly digestion compared to adult digestates. Low fat red cheddar had significantly higher (p ≤ 0.05) TPC levels compared to all other digestates for both adult and elderly digestive systems. Findings from this study demonstrate that aging has an impact on the bioactivity of cheese, as antioxidant activity and TPC levels were lower, following in vitro elderly digestion compared to the adult model. For older adults, soft cheese, particularly goats cheese, was associated with high radical scavenging and reducing power, while roquefort cheese had low antioxidant activity. Also, elderly digestates of halloumi and low-fat red cheddar were associated with high TPC levels. Cheese has potential as a functional food for the elderly, however, bioactivity can vary depending on the cheese matrix. Funding for this research was provided by the RISAM Scholarship Scheme, Cork Institute of Technology, Ireland.

Keywords: antioxidants, cheese, in-vitro digestion, older adults

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Authors: W. Jahouach-Rabai, J. Aribi, Z. Azzouz-Berriche, R. Lahsni, F. Hosni

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Gamma irradiation applied in removing pharmaceutical contaminants from wastewater is an effective advanced oxidation process (AOP), considered as an alternative to conventional water treatment technologies. In this purpose, the degradation efficiency of several detected contaminants under gamma irradiation was evaluated. In fact, radiolysis of organic pollutants in aqueous solutions produces powerful reactive species, essentially hydroxyl radical ( ·OH), able to destroy recalcitrant pollutants in water. Pharmaceuticals considered in this study are aqueous solutions of paracetamol, ibuprofen, and diclofenac at different concentrations 0.1-1 mmol/L, which were treated with irradiation doses from 3 to 15 kGy. The catalytic oxidation of these compounds by gamma irradiation was investigated using hydrogen peroxide (H₂O₂) as a convenient oxidant. Optimization of the main parameters influencing irradiation process, namely irradiation doses, initial concentration and oxidant volume (H₂O₂) were investigated, in the aim to release high degradation efficiency of considered pharmaceuticals. Significant modifications attributed to these parameters appeared in the variation of degradation efficiency, chemical oxygen demand removal (COD) and concentration of radio-induced radicals, confirming them synergistic effect to attempt total mineralization. Pseudo-first-order reaction kinetics could be used to depict the degradation process of these compounds. A sophisticated analytical study was released to quantify the detected radio-induced radicals (electron paramagnetic resonance spectroscopy (EPR) and high performance liquid chromatography (HPLC)). All results showed that this process is effective for the degradation of many pharmaceutical products in aqueous solutions due to strong oxidative properties of generated radicals mainly hydroxyl radical. Furthermore, the addition of an optimal amount of H₂O₂ was efficient to improve the oxidative degradation and contribute to the high performance of this process at very low doses (0.5 and 1 kGy).

Keywords: AOP, COD, hydroxyl radical, EPR, gamma irradiation, HPLC, pharmaceuticals

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Authors: Michalina Aniola, Andrzej Katrusiak

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4,4-Bipyridine is an important compound often used in chemical practice and more recently frequently applied for designing new metal organic framework (MoFs). Here we present a systematic high-pressure study of its hydrobromide salt. 4,4-Bipyridine hydrobromide monohydrate, 44biPyHBrH₂O, at ambient-pressure is orthorhombic, space group P212121 (phase a). Its hydrostatic compression shows that it is stable to 1.32 GPa at least. However, the recrystallization above 0.55 GPa reveals a new hidden b-phase (monoclinic, P21/c). Moreover, when the 44biPyHBrH2O is heated to high temperature the chemical reactions of this compound in methanol solution can be observed. High-pressure experiments were performed using a Merrill-Bassett diamond-anvil cell (DAC), modified by mounting the anvils directly on the steel supports, and X-ray diffraction measurements were carried out on a KUMA and Excalibur diffractometer equipped with an EOS CCD detector. At elevated pressure, the crystal of 44biPyHBrH₂O exhibits several striking and unexpected features. No signs of instability of phase a were detected to 1.32 GPa, while phase b becomes stable at above 0.55 GPa, as evidenced by its recrystallizations. Phases a and b of 44biPyHBrH2O are partly isostructural: their unit-cell dimensions and the arrangement of ions and water molecules are similar. In phase b the HOH-Br- chains double the frequency of their zigzag motifs, compared to phase a, and the 44biPyH+ cations change their conformation. Like in all monosalts of 44biPy determined so far, in phase a the pyridine rings are twisted by about 30 degrees about bond C4-C4 and in phase b they assume energy-unfavorable planar conformation. Another unusual feature of 44biPyHBrH2O is that all unit-cell parameters become longer on the transition from phase a to phase b. Thus the volume drop on the transition to high-pressure phase b totally depends on the shear strain of the lattice. Higher temperature triggers chemical reactions of 44biPyHBrH2O with methanol. When the saturated methanol solution compound precipitated at 0.1 GPa and temperature of 423 K was required to dissolve all the sample, the subsequent slow recrystallization at isochoric conditions resulted in disalt 4,4-bipyridinium dibromide. For the 44biPyHBrH2O sample sealed in the DAC at 0.35 GPa, then dissolved at isochoric conditions at 473 K and recrystallized by slow controlled cooling, a reaction of N,N-dimethylation took place. It is characteristic that in both high-pressure reactions of 44biPyHBrH₂O the unsolvated disalt products were formed and that free base 44biPy and H₂O remained in the solution. The observed reactions indicate that high pressure destabilized ambient-pressure salts and favors new products. Further studies on pressure-induced reactions are carried out in order to better understand the structural preferences induced by pressure.

Keywords: conformation, high-pressure, negative area compressibility, polymorphism

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Authors: Durata Haciu, Ozgur Birer

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Zinc acetate solution is sonicated at high power in water and in ethanol in the absence and presence of various peroxides. In the absence of peroxides, the products are zinc oxide and layered hydroxy zinc acetate in water and in ethanol, respectively. Layered basic zinc acetate are prepared for the first time using sonochemical methods. The addition of peroxides alters the reaction mechanisms. In water, insoluble peroxides produce zinc oxides while the water soluble peroxide, i.e.hydrogen peroxide, completely destroyed the structure and casted a doubt on the accepted peroxide initiated mechanism of reactions. In ethanol,peroxide addition caused the reaction mechanism to change and some oxide formation is observed. The reaction mechanism is sensitive to water/ethanol amounts as well as the peroxide to zinc ion mole ratio.Thin zinc oxide wafers (ca. 30 nm) with band gaps of 3.24 eV were obtained.

Keywords: ultrasound, zinc oxide, hydroxy zinc acetate, fenton, peroxide initiation

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Authors: Jyotika Chopra, Dinesh Goyal

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A study was initiated to examine the effects of corn gluten hydrolysate on seedlings growth and its development. Corn gluten is the byproduct of starch industry rich in proteins was hydrolysed by acid and alkali, and the impact of hydrolysate was studied on seed germination of Vigna radiata, Phaseolus vulagris (Fabaceae) and Triticum aestivum and Oryza sativa (Gramineae). For this, the optimum hydrolysis was obtained by 4NHCl and 4M NaOH where insoluble protein in gluten was broken down to glutamic acid, alanine, aspartic acid which was initially confirmed by biuret test, xanthoproteic, solubility and chromatographic tests. The seeds of above families were separately treated with different dilutions of corn gluten hydrolysate ranging from 1-100% to see effects produced by these dilutions on seed germination, plumule, and radical growth. The seedlings were put in the Petri plates and placed in the optimized conditions of temperature (37˚C) and photoperiod of 16:8 hours. The results indicate the plumule of all seeds shows the increase in growth pattern up to 25.75%. Whereas radical shows the increase in growth up to 25.88% till 10% of dilution of corn and wheat gluten hydrolysate with respect to water as blank. Further, there is decrease in growth from 30- 100% of dilutions of both, the hydrolysate indicates the inhibitory effects which unveil about the careful usage of gluten hydrolysate.

Keywords: corn gluten, characterization, hydrolysis, seedling growth

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Authors: Marasri Junsi, Sunisa Siripongvutikorn, Chutha Takahashi Yupanqui, Worrapong Usawakesmanee

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Thunbergia laurifolia has been used for folklore medicine purposes and consumed in the form of herbal tea in Thailand since ancient times. To evaluate the bioactive compounds of aqueous leave extract possessed antioxidant and anti-inflammatory activities. The antioxidant activities were examined by total extractable phenolic content (TPC), total extractable flavonoid content (TFC), ABTS radical scavenging, DPPH radical scavenging, FRAP reducing antioxidant power expressed as mg of gallic acid trolox and caffeic acid for the equivalents. Results indicated that the extract had high TPC and antioxidant activities. In addition, the HPLC-DAD analysis of phenolics and flavonoids indicated the presence of caffeic acid and rutin as bioactive compounds. Exposure of cells with the extract using nitric oxide (NO) production in RAW 264.7 murine macrophage cell line induced by lipopolysaccharide (LPS) was significantly reduced NO production and increased cell proliferation. The obtained results demonstrated that the extract contains a high potential to be used as anti-inflammatory and antioxidant substances.

Keywords: Thunbergia laurifolia, anti-inflammatory, antioxidant activities, RAW264.7

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Authors: Gokhan Zengin, Cengiz Sarikurkcu, Abdurrahman Aktumsek, Ramazan Ceylan

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The present study was designated to characterize the essential oil from S. galatica (SGEOs) and evaluate its antioxidant and enzyme inhibitory activities. Antioxidant capacity were tested different methods including free radical scavenging (DPPH, ABTS and NO), reducing power (FRAP and CUPRAC), metal chelating and phosphomolybdenum. Inhibitory activities were analyzed on acetylcholiesterase, butrylcholinesterase, α-amylase and α-glucosidase. SGEOs were chemically analyzed and identified by gas chromatography (GC) and gas chromatography/mass spectrophotometry (GC/MS). 23 components, representing 98.1% of SGEOs were identified. Monoterpene hydrocarbons (74.1%), especially α- (23.0%) and β-pinene (32.2%), were the main constituents in SGEOs. The main sesquiterpene hydrocarbons were β-caryophyllene (16.9%), Germacrene-D (1.2%) and Caryophyllene oxide (1.2%), respectively. Generally, SGEOs has shown moderate free radical, reducing power, metal chelating and enzyme inhibitory activities. These activities related to chemical profile in SGEOs. Our findings supported that the possible utility of SGEOs is a source of natural agents for food, cosmetics or pharmaceutical industries.

Keywords: sideritis galatica, antioxidant, monoterpenes, cholinesterase, anti-diabetic

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Authors: Nadjet Mekaouche, Hanane Zitouni, Fatma Boudia, Habiba Fetati, A. Saleh, A. Lardjam, H. Geniaux, A. Coubret, H. Toumi

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Medicines have undeniably played a major role in prolonging shelf life and improving quality. The absolute efficacy of the drug remains a lever for innovation, its benefit/risk balance is not always assured and it does not always have the expected effects. Prior to marketing, knowledge about adverse drug reactions is incomplete. Once on the market, phase IV drug studies begin. For years, the drug was prescribed with less care to a large number of very heterogeneous patients and often in combination with other drugs. It is at this point that previously unknown adverse effects may appear, hence the need for the implementation of a pharmacovigilance system. Pharmacovigilance represents all methods for detecting, evaluating, informing and preventing the risks of adverse drug reactions. The most severe adverse events occur frequently in hospital and that a significant proportion of adverse events result in hospitalizations. In addition, the consequences of hospital adverse events in terms of length of stay, mortality and costs are considerable. It, therefore, appears necessary to develop ‘hospital pharmacovigilance’ aimed at reducing the incidence of adverse reactions in hospitals. The most widely used monitoring method in pharmacovigilance is spontaneous notification. However, underreporting of adverse drug reactions is common in many countries and is a major obstacle to pharmacovigilance assessment. It is in this context that this study aims to describe the experience of the pharmacovigilance service at the University Hospital of Oran (EHUO). This is a retrospective study extending from 2011 to 2017, carried out on archived records of declarations collected at the level of the EHUO Pharmacovigilance Department. Reporting was collected by two methods: ‘spontaneous notification’ and ‘active pharmacovigilance’ targeting certain clinical services. We counted 217 statements. It involved 56% female patients and 46% male patients. Age ranged from 5 to 78 years with an average of 46 years. The most common adverse reaction was drug toxidermy. For the drugs in question, they were essentially according to the ATC classification of anti-infectives followed by anticancer drugs. As regards the evolution of declarations by year, a low rate of notification was noted in 2011. That is why we decided to set up an active approach at the level of some services where a resident of reference attended the staffs every week. This has resulted in an increase in the number of reports. The declarations came essentially from the services where the active approach was installed. This highlights the need for ongoing communication between all relevant health actors to stimulate reporting and secure drug treatments.

Keywords: adverse drug reactions, hospital, pharmacovigilance, spontaneous notification

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Authors: Melaku Takele Abate, Abbi Lemma Wodajo, Adula Bekele Hunde

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This study aimed at exploring mathematics teachers' reactions, learning, school leaders’ support, and use of the Lesson Study for Transformative Assessment (LSforTA) program ideas in practice. The LSforTA program was new, and therefore, a local and grounded approach was needed to examine teachers’ knowledge and skills acquired using LSforTA. So, a design-based research approach was selected to evaluate and refine the LSforTA approach. The results showed that LSforTA increased teachers' knowledge and use of different levels of mathematics assessment tasks. The program positively affected teachers' practices of transformative assessment and enhanced their knowledge and skills in assessing students in a transformative way. The paper concludes how the LSforTA procedures were adapted in response to this evaluation and provides suggestions for future development and research.

Keywords: classroom assessment, feedback practices, lesson study, mathematics, design-based research

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Authors: Mirko Ante, Şeniz Sörgel, Andreas Bund

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Li-S- (Lithium-Sulfur-) battery systems provide very high specific gravimetric energy (2600 Wh/kg) and volumetric energy density (2800Wh/l). Hence, Li-S batteries are one of the key technologies for both the upcoming electromobility and stationary applications. Furthermore, the Li-S battery system is potentially cheap and environmentally benign. However, the technical implementation suffers from cycling stability, low charge and discharge rates and incomplete understanding of the complex polysulfide reaction mechanism. The aim of this work is to develop an effective electrocatalyst for the polysulfide reactions so that the electrode kinetics of the sulfur half-cell will be improved. Accordingly, the overvoltage will be decreased, and the efficiency of the cell will be increased. An enhanced electroactive surface additionally improves the charge and discharge rates. To reach this goal, functionalized electrocatalytic coatings are investigated to accelerate the kinetics of the polysulfide reactions. In order to determine a suitable electrocatalyst, apparent exchange current densities of a variety of materials (Ni, Co, Pt, Cr, Al, Cu, ITO, stainless steel) have been evaluated in a polysulfide containing electrolyte by potentiodynamic measurements and a Butler-Volmer fit including diffusion limitation. The samples have been examined by Scanning Electron Microscopy (SEM) after the potentiodynamic measurements. Up to now, our work shows that cobalt is a promising material with good electrocatalytic properties for the polysulfide reactions and good chemical stability in the system. Furthermore, an electrodeposition from a modified Watt’s nickel electrolyte with a sulfur source seems to provide an autocatalytic effect, but the electrocatalytic behavior decreases after several cycles of the current-potential-curve.

Keywords: electrocatalyst, energy storage, lithium sulfur battery, sulfur electrode materials

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Authors: S. Assylbekova, D. Zolotareva, A. Dauletbakov, Ye. Belyankova, S. Bayazit, A. Basharimova, A. Zazybin, A. Isimberlenova, A. Kakim, M. Aydemir

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Transfer hydrogenation (TH) is a key process in organic chemistry, particularly in pharmaceutical and agrochemical synthesis, offering a safer and more sustainable approach compared to traditional methods. This work focuses on the synthesis and utilization of ruthenium catalysts containing phosphinite ligands in TH reactions. The aim is to develop an efficient catalyst that can selectively reduce various substrates to yield important alcohols for pharmaceutical and agrochemical applications. The work addresses key challenges in sustainable chemistry, reducing environmental impact, enhancing access to pharmaceutical intermediates, improving chemical manufacturing, and advancing catalysis science. The methodology involves the synthesis of a phosphinite ligand and a ruthenium complex, followed by TH reactions of acetophenone and its derivatives using the resulting catalyst. This research contributes to the development of greener and more efficient synthetic routes, with potential implications for diverse industries reliant on chemical synthesis.

Keywords: transfer hydrogenation, ruthenium, catalysts, phosphinite ligands

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