• Title/Summary/Keyword: Pd(0)

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Mechanistic insights of metal acetylacetonate-aided dehydrocoupling of liquid-state ammonia borane NH3BH3

  • Pereza, Manon;Mieleb, Philippe;Demirci, Umit B.
    • Advances in Energy Research
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    • v.4 no.2
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    • pp.177-187
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    • 2016
  • Ammonia borane $NH_3BH_3$ solubilized in organic solvent is a potential liquid-state chemical hydrogen storage material. In this study, metal acetylacetonates like $Fe(O_2C_5H_7)_3$, $Co(O_2C_5H_7)_2$, $Ni(O_2C_5H_7)_2$, $Pd(O_2C_5H_7)_2$, $Pt(O_2C_5H_7)_2$ and $Ru(O_2C_5H_7)_3$ are considered for assisting dehydrocoupling of ammonia borane in diglyme (0.135 M) at $50^{\circ}C$. The molar ratio between ammonia borane and metal acetylacetonate is fixed at 100. A protocol for the separation of the soluble and insoluble fractions present in the slurry is proposed; it consists in using acetonitrile to make the precipitation of metal-based compounds easier and to solubilize boron-based intermediates/products. The nature of the metal does not affect the dehydrocoupling mechanisms, the $^{11}B\{^1H\}$ NMR spectra showing the formation of the same reaction intermediates. The aforementioned metal acetylacetonates do mainly have effect on the kinetics of dehydrocoupling. Dehydrocoupling takes place heterogeneously and dehydrogenation of ammonia borane in these conditions leads to the formation of polyborazylene via intermediates like e.g., B-(cyclodiborazanyl) amine-borane and borazine. Our main results are reported and discussed herein.

Impact of Various Tumor Markers in Prognosis of Gastric Cancer -A Hospital Based Study from Tertiary Care Hospital of Kathmandu Valley

  • Mittal, Ankush;Gupta, Satrudhan Pd.;Jha, Dipendra Kumar;Sathian, Brijesh;Poudel, Bibek
    • Asian Pacific Journal of Cancer Prevention
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    • v.14 no.3
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    • pp.1965-1967
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    • 2013
  • Background: To obtain the maximum additional information about the prognosis of gastric cancer, we compared CA-50 with other previously defined markers. Materials and Methods: This hospital based study was carried out in the Department of Biochemistry of Nepalese Army Institute of Health Sciences between $1^{st}$ July 2012 and $31^{st}$ December 2012. The variables collected were age, gender, AFP, CEA, CA19-9, and CA50, assayed with ELISA reader for all cases. The cut off values for serum AFP, CEA, CA19-9, and CA-50 were 10 ${\mu}g/l$, 10 ${\mu}g/l$, 37 U/ml, and 20 U/ml, respectively according to the manufacturer's instructions. Approval for the study was obtained from the institutional research ethical committee. Results: Of the 40 examined patients, 13 patients had tumors located in the upper third of the stomach, 6 patients had tumors in the middle third, 16 patients had tumors in the lower third, and 5 patients had tumors occupying two-thirds of the stomach or more. The distribution of lymph node staging of the patients was as follows: 7 patients belonged to N0, 9 patients to N1 stage, 10 patients to N2 stage, and 14 patients to N3 stage. The statistical method of Cox proportional hazards using multivariate analysis also illustrated that tumor markers including CEA (2.802), CA19-9 (2.690), CA50 (2.101), were independent prognostic factors, as tumor size (1.603), and lymph node stage (1.614). Conclusions: The tumour markers now available, like CEA, CA 19-9 and CA 50, chiefly perceive advanced gastric cancer. The preoperative rise in those tumour marker level have a prognostic significance and may be clinically helpful in choosing patients for adjuvant management.

Synthesis and Biological Activity Test of the Sex Pheromone of the Diamond Back Moth (배추좀나방의 성 페로몬의 합성과 생물활성시험)

  • Suk-Ku Kang;Chul-Hee Lee;Jung Han Kim;Jeong-Oon Lee
    • Journal of the Korean Chemical Society
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    • v.32 no.1
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    • pp.60-64
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    • 1988
  • Synthesis and biological activity test are described for the (Z)-11-hexadecen-1-ol, (Z)-11-hexadecen-1-yl acetate, and (Z)-11-hexadecen-l-al, the sex pheromone of the diamond back moth, Plutella xylostella L.. Lithium acetylide was alkylated with 10-bromodecan-1-ol THP ether to give 11-hexadecyn-l-ol THP ether. 11-Hexadecyn-l-ol THP ether was stereoselectively reduced over Pd/BaSO4to yield (Z)-11-hexadecen-l-ol THP ether, which was in turn deprotected to provide (Z)-11-hexadecen-l-ol. (Z)-11-Hexadecen-l-ol was acetylated and oxidized to afford (Z)-11-hexadecen-1-yl acetate and (Z)-11-hexadecen-l-al, respectively. Biological activity test of the synthetic compounds, (Z)-11-hexadecen-l-ol, (Z)-11-hexadecen-1-yl acetate, and (Z)-11-hexadecen-l-al in the ratio of 0.1 : 5 : 5 was tested in the field using polyethylene capsules as containers. The numbers of moth trapped with pheromone vials were counted.

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Ring-Opening Metathesis Polymerization and Hydrogenation of Ethyl-substituted Tetracyclododecene

  • Kwon, Oh-Joon;Vo, Huyen Thanh;Lee, Sul-Bee;Kim, Tae-Kyung;Kim, Hoon-Sik;Lee, Hyun-Joo
    • Bulletin of the Korean Chemical Society
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    • v.32 no.8
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    • pp.2737-2742
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    • 2011
  • Ring-opening metathesis polymerization (ROMP) of an ethyl-substituted tetracyclododecene (8-ethyltetracyclo[$4.4.0.1^{2,5}.1^{7,10}$] dodec-3-ene, Et-TCD) was carried out in the presence of a ternary catalyst system consisting of $WCl_6$, triisobutyl aluminium (iso$Bu_3Al$), and ethanol. The optimal molar ratio of Et-TCD/$WCl_3$/iso-$Bu_3Al$/ethanol was found as 500/1/3/2 at which the yield of ring-opened polymer was 100%. 1-Hexene was shown to be an effective molecular weight controlling agent for ROMP reaction of Et-TCD. The hydrogenation of the ring opened polymer (p-Et-TCD) was conducted successfully using Pd(5 wt %)/${\gamma}$-$Al_2O_3$ at $80^{\circ}C$ for 1 h. Chemical structures of p-Et-TCD and its hydrogenated product($H_2$-p-Et-TCD) were characterized using 2D NMR techniques ($^1H-^1H$ COSY and $^1H-^{13}C$ HSQC). The changes of physical properties such as thermal stability, glass transition temperature and light transmittance after the hydrogenation were also investigated using TGA, DSC, and UV.

Clinical Study on Lobaplatin Combined with 5-Fu and Concurrent Radiotherapy in Treating Patients with Inoperable Esophageal Cancer

  • Jia, Xiao-Jing;Huang, Jing-Zi
    • Asian Pacific Journal of Cancer Prevention
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    • v.16 no.15
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    • pp.6595-6597
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    • 2015
  • Objective: To investigate short- and long-term treatment effects and side reactions of lobaplatin plus 5-Fu combined and concurrent radiotherapy in treating patients with inoperable middle-advanced stage esophageal cancer. Methods: Sixty patients with middle-advanced stage esophageal squamous cell cancer were retrospectively analyzed. All patients were administered lobaplatin (50 mg intravenously) for 2 h on day 1, and 5-Fu ($500mg/m^2$) injected intravenously from day 1 to 5 for 1 cycle, in an interval of 21 days for totally 4 cycles. At the same time, late-course accelerated hyperfractionated three-dimensional conformal radiotherapy was performed. Patients were firstly treated with conventional fractionated irradiation (1.8 Gy/d, 5 times/week, a total of 23 treatments, and DT41.4 Gy), and then treated with accelerated hyperfractionated irradiation (1.5 Gy, 2 times/d, a total of 27 Gy in 9 days, an entire course of 6-7 weeks, and DT 68.4Gy). Results: All patients completed treatment, including 10 complete response (CR), 41 partial response (PR), 7 stable disease (SD), and 2 progressive disease (PD). The total effective rate was 85.0% (51/60). Thirty-nine patients had an increased KPS score. One-, 2-, and 3-year survival rates were 85.3%, 57.5%, and 41.7%, respectively. The median survival time was 27 months. The adverse reactions included myelosuppression, which was mainly degree I and II. The occurrence rate of radiation esophagitis was 17.5%. No significant hepatic or renal toxicity was observed. Conclusion: Lobaplatin plus 5-Fu combined with concurrent radiotherapy is safe and effective in treating patients with middle-advanced stage esophageal cancer. However, this result warrants further evaluation by randomized clinical studies.

Micro Power Properties of Harvesting Devices as a Function of PZT cantilever length and gross area (PZT 캔틸레버의 길이와 면적에 따른 에너지 하베스팅 장치의 출력 특성)

  • Kim, I.S.;Joo, H.K.;Song, J.S.;Kim, M.S.;Jeong, S.J.;Lee, D.S.
    • Proceedings of the KIEE Conference
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    • 2008.07a
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    • pp.1246-1247
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    • 2008
  • With recent advanced in portable electric devices, wireless sensor, MEMS and bio-Mechanics device, the new typed power supply, not conventional battery but self-powered energy source is needed. Particularly, the system that harvests from their environments are interests for use in self powered devices. For very low powered devices, environmental energy may be enough to use power source. Therefore, in other to made piezoelectric energy harvesting device, PMN-PZT thick film was formed by the screen printing method on the Ag/Pd coated alumina substrate. The layer was 8 layers and slurry where a-terpineol, ethycellulose, ferro B-75001 as Vehicle, PMN-PZT powder used are fabricated by ball mill. The output power quality was be also investigated by changing the load resistance, weight and frequency. The made piezoelectric energy harvesting device was resulted from the conditions of 33$k{\Omega}$, 0.25g, 197Hz respectively. The thick film was prepared at the condition of 2.75Vrms, and its power was 230${\mu} W$ and its thickness was 56${mu}m$. The piezoelectric energy harvesting device output voltage was increased, when the load weight, load resistance was increasing and resonance frequency was diminishing. The other side, resonance frequency was diminished, when the weight was increasing. And output power was continuously it changed by load resistance, output voltage, weight and resonance frequency.

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Diabetes Mellitus and Renal Cell Carcinoma - A Hospital Based Study from Kathmandu Valley

  • Gupta, Satrudhan Pd.;Mittal, Ankush;Jha, Dipendra Kumar;Pandeya, Dipendra Raj;Sathian, Brijesh
    • Asian Pacific Journal of Cancer Prevention
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    • v.13 no.10
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    • pp.4963-4965
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    • 2012
  • Objective: To diagnose renal cell carcinoma at early stages and for better prognosis, the main objective of our current study was to understand any association with diabetes with relation to age, gender, history of disease, diabetic laboratory parameters, tumor size and grade. Materials and Methods: This hospital based study was carried out using data retrieved from the register maintained in the Department of Biochemistry of Nepalese Army Institute of Health Sciences between $1^{st}$ December, 2011 and $31^{st}$ May, 2012. The variables collected were age, gender, HbA1c, serum creatinine, fasting blood glucose. One way ANOVA was applied to examine statistical significance of differences between groups. The LSD post hoc test was used for the comparison of means of case groups. Results: Of the total 140 cases of renal cell carcinoma, 79 patients were also suffering from diabetes mellitus. The number of females (47) was more in diabetic RCC patients when compared to males (32). Significance was observed in levels of serum creatinine for tumor size >10cm ($0.0001^*$). The highest value of glycated hemoglobin (8.9%) and fasting blood sugar(148.3mg/dl)in cases of renal cell carcinoma along with diabetes mellitus was found in tumour size of 1-5cm. Conclusion: Diabetes mellitus has independent prognostic significance in RCC in relation to tumour size and grade.

Association of Type II Diabetes Mellitus with Hepatocellular Carcinoma Occurrence - a Case Control Study from Kathmandu Valley

  • Jha, Dipendra Kumar;Mittal, Ankush;Gupta, Satrudhan Pd.;Pandeya, Dipendra Raj;Sathian, Brijesh
    • Asian Pacific Journal of Cancer Prevention
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    • v.13 no.10
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    • pp.5097-5099
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    • 2012
  • Objective: To assess associations of Type II DM with hepatocellular carcinoma occurrence in Nepal. Materials and Methods: This case control study was carried out using data retrieved from the register maintained in the Department of Biochemistry of Nepalese Army Institute of Health Sciences between 1st January, 2012, and 31st August, 2012. The variables collected were age, gender, HbA1c. All biochemical parameters were analyzed in the Central Laboratory of our hospital by standard validated methods. One way ANOVA was used to examine the statistical significant difference between groups with the LSD post-hoc test for comparison of means of case groups. Odds ratios (OR) were calculated using simple logistic-regression analysis. Results: Etiological factors for HCC were HBV, HCV, alcohol and cryptogenic cirrhosis. The highest age group belonged to the etiological category of HCV with a mean of $71.9{\pm}3.6$ (CI 69.3, 74.5) years and the lowest age group to the etiological category of HBV with $61.7{\pm}5.3$(CI 57.9, 65.5) years. The main imperative basis of HCC in present study was HCV (39.5%) and second most significant cause of HCC was alcohol (26%). Glycated hemoglobin was found to be more in males with HCC (7.9%) as compared to females (7.3%). The percentage of Type II diabetes mellitus was greater in HCC patients when compared to controls. This difference was statistically significant with an odd ratio of 4.63 (p<0.001). Conclusion: Type II DM influences incidence, risk of recurrence, overall survival, and treatment-related complications in HCC patients.

Effect of Hesperidin Supplementation on Lipid and Antioxidant Metabolism in Ethanol-fed Rats

  • Kim, Soon-Ja;Seo, Hyun-Ju;Kim, Hye-Jin;Cho, Yun-Young;Kwon, Eun-Young;Lee, Hyo-Sun;Choi, Myung-Sook
    • Preventive Nutrition and Food Science
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    • v.11 no.4
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    • pp.289-297
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    • 2006
  • This study examined the effect of hesperidin supplementation with an ethanol diet on lipid and antioxidant metabolism in rats. Male Sprague-Dawley rats were divided into two groups (n=10), and were assigned to one of two dietary categories: $E_8$, ethanol diet (50 g/L) for 8 wks; $E_8H_4$, ethanol diet for the first 4 wks and hesperidin (0.02%, w/w) supplemented ethanol diet for the last 4 wks. The plasma and hepatic lipids, hepatic cholesterol regulating enzyme activity, hepatic antioxidant enzyme activity and lipid peroxidation were determined. Supplementation with hesperidin for the last 4 wks during the 8 wks period of the ethanol diet, significantly increased the ADH activity. In conjunction with the chronic administration of ethanol, hesperidin supplementation resulted in a significant decrease in the hepatic cholesterol and triglyceride concentrations compared to the $E_8$ group. The hepatic HMG-CoA reductase and ACAT activities were significantly lower in the hesperidin-supplemented group. When comparing hepatic antioxidant enzyme activities, SOD, GSH-Px, and G6PD activities and GSH level were significantly higher in the $E_8H_4$ group than in the E8 group. Plasma TBARS levels were significantly lower in rats fed ethanol with hesperidin compared to the rats fed only ethanol; however, the hepatic TBARS levels were not significantly different between the groups. Accordingly, the additional hesperidin supplement with an ethanol diet might be effective for improving the hepatic lipid metabolism and antioxidant defense system.

p38 Kinase Regulates Nitric Oxide-induced Dedifferentiation and Cyclooxygenase-2 Expression of Articular Chondrocytes

  • Yu, Seon-Mi;Cheong, Seon-Woo;Cho, Sam-Rae;Kim, Song-Ja
    • IMMUNE NETWORK
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    • v.6 no.3
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    • pp.117-122
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    • 2006
  • Background: Caveolin, a family of integral membrane proteins are a principal component of caveolae membranes. In this study, we investigated the effect of p38 kinase on differentiation and on inflammatory responses in sodium nitroprusside (SNP)-treated chondrocytes. Methods: Rabbit articular chondrocytes were prepared from cartilage slices of 2-week-old New Zealand white rabbits by enzymatic digestion. SNP was used as a nitric oxide (NO) donor. In this experiments measuring SNP dose response, primary chondrocytes were treated with various concentrations of SNP for 24h. The time course of the SNP response was determined by incubating cells with 1mM SNP for the indicated time period $(0{\sim}24h)$. The cyclooxygenase-2 (COX-2) and type II collagen expression levels were determined by immunoblot analysis, and prostaglandin $E_2\;(PGE_2)$ assay was used to measure the COX-2 activity. The tyrosine phosphorylation of caveolin-1 was determined by immunoblot analysis and immunostaining. Results: SNP treatment stimulated tyrosine phosphorylation of caveolin-1 and activation of p38 kinase. SNP additionally caused dedifferentiation and inflammatory response. We showed previously that SNP treatment stimulated activation of p38 kinase and ERK-1/-2. Inhibition of p38 kinase with SB203580 reduced caveolin-1 tyrosine phosphorylation and COX-2 expression but enhanced dedifferentiation, whereas inhibition of ERK with PD98059 did not affect caveolin-1 tyrosine phosphorylation levels, suggesting that ERK at least is not related to dedifferentiation and COX-2 expression through caveolin-1 tyrosine phosphorylation. Conclusion: Our results indicate that SNP in articular chondrocytes stimulates dedifferentiation and inflammatory response via p38 kinase signaling in association with caveolin-1 phosphorylation.