Journal of the Korean Applied Science and Technology
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제7권1호
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pp.93-105
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1990
Semicarbazone formation of nine monosubstituted benzaldehydes was studied kinetically in 20% methanol buffer solution at 15, 25, 35, and $45^{circ}C$. The rate of p-nitrobenzaldehyde semicarbazone formation is 2.7 times as fast as that of benzaldehyde, while p-hvdroxybenzaldehyde is 3.6 times as slow as that of benzaldehyde. Activation energies for p-chlorobenzaldehyde, benzaldehyde, p-methylbenzaldehyde, p-methoxybenzaldshyde, p-hydroxybenzaldehyde, and p-dimethylaminobenzaldehyde semicarbazone formation are calculated as 5.80, 6.19, 6.57, 7.06, 8.03, and 6.46 kcal/mol respectively. It is concluded from the effect of ionic strength that the reaction is affected by not ions but neutral molecules involving hydrogen bonding between oxygen atom of carbonyl group and hydrogen atom of acid-catalyst, and concerted attack of the necleophilic reagent, free base on carbonyl compound. Also, the effect of solvent composition is small in 20% and 50% methanol (and ethanol) aqueous solutions. The ${\rho}-{\sigma}$ plots for the rates of semicarbazone formation at pH 7.1 show a linear ${\rho}-{\sigma}$ relationship (${\rho}=0.14l$, in contrast to that at pH 2.75 and pH 5.4 corresponding to ${\rho}-{\sigma}$ correlations reparted by Jencks. The rate of semicarbazone formation at pH 5.4 show a relationship which is convex upward, resulting in a break in the curve but at pH 2.75, slight difference from a linear relationship. As a result of studying citric acid catalysis, second-order rate constants increase linearly with citric acid concentration and show a 2 times increase as the catalyst concentration is varied from 0.025 to 0.1 mol/1 at pH 2,9, but slight increase at pH 5.3. The rate-determining step is addition below pH 5 but is dehydration between pH 5 and 7. Conclusively, the rate-determining step of the reaction changes from dehydration to addition in respect to hydrogen ion activity near pH 5. The ortho: para rate ratio of the hydroxybenzaldehydes for semicarbazone formation is about 17 at $15^{\circ}C$. It is concluded that the results constitute strong evidence in favor of greater stabilization of p- than o-hydroxybenzaldehyde by substituent which donate electrons by resonance and is due to hydrogen bonding between the carbon-bound hydrogen of the-CHO group and the oxygen atom of the substituent.
Proceedings of the Korean Vacuum Society Conference
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한국진공학회 2010년도 제39회 하계학술대회 초록집
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pp.173-173
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2010
$Bi_4Ti_3O_{12}$ ($B_4T_3$) is a unique ferroelectric material that has a relatively high dielectric constant, high Curie temperature, high breakdown strength, and large spontaneous polarization. As a result this material has been widely studied for many applications, including nonvolatile ferroelectric random memories, microelectronic mechanical systems, and nonlinear-optical devices. Several reports have appeared on the use of Mn dopants to improve the electrical properties of $B_4T_3$ thin films. Mn ions have frequently been used for this purpose in thin films and multilayer capacitors in situations where intrinsic oxygen vacancies are the major defects. However, no systematic study of the optical properties of $B_4T_3$ films has appeared to date. Here, we report optical data for these films, determined by spectroscopic ellipsometry (SE). We also report the effects of thermal annealing and Mn doping on the optical properties. The SE data were analyzed using a multilayer model that is consistent with the original sample structure, specifically surface roughness/$B_4T_3$ film/Pt/Ti/$SiO_2$/c-Si). The data are well described by the Tauc-Lorentz dispersion function, which can therefore be used to model the optical properties of these materials. Parameters for reconstructing the dielectric functions of these films are also reported. The SE data show that thermal annealing crystallizes $B_4T_3$ films, as confirmed by the appearance of $B_4T_3$ peaks in X-ray diffraction patterns. The bandgap of $B_4T_3$ red-shifts with increasing Mn concentration. We interpret this as evidence of the existence deep levels generated by the Mn transition-metal d states. These results will be useful in a number of contexts, including more detailed studies of the optical properties of these materials for engineering high-speed devices.
Neutrophil elastases were purified by a three step procedure consiting of one Sephadex G-75 and two HPLC elutions. The elastases cross-reacted with antibodies to human neutrophil elastase. Three bands with molecular weights between 26,000 and 29,700 were observed by gel electrophoresis. At each stage of purification the quantity of Zn increased, reaching molar ratio of 2:1 with elastase in the most purified samples. Calcium content. was seletively elevated during the earlier stages of purification but decreased to a ratio of 0.25 to 1 with elastase at the final step of purfication. Neutrophil elastase could be inhibited by EDTA, EGTA and 1,10-phenanthroline. EGTA inhbition was noncompetitive inhibition and reversible only if the time of preincubation was relatively short, indicating the instability of the apoenzyme. The concentration of chelator required to show significant inhibition of elastase was also dependent upon the stage of purity and the ionic strength of the reaction mixture. Inhibition by EGTA, followed by the removal of EGTA, could be reversed by Zn. In the presence of EGTA the enzyme could be returened to full activity by the addition of Zn, Mn and Ca, but not Mg or Na. All of the above evidence strongly supports human neturophil elastase could be a metalloenzyme as well as a serine protease.
Zhu, Hai-Li;Bao, Ji-Ming;Lin, Pei-Xin;Li, Wen-Xia;Zou, Zhen-Ning;Huang, Ye-En;Chen, Qing;Shen, Hong
Asian Pacific Journal of Cancer Prevention
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제15권16호
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pp.6619-6625
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2014
Background: Numerous studies have explored the influence of XPD Lys751Gln and/or Asp312Asn polymorphisms on skin cancer susceptibility. However, the results remain inconclusive. To derive a more precise estimation, we conducted a comprehensive search to identify all available published studies and performed a meta-analysis. Materials and Methods: Electronic literature searches of the PubMed, CBM and CNKI databases were performed up to March 2014. Odds ratios (ORs) with 95% confidence intervals (CIs) were applied to assess the strength of associations. Results: Seventeen case-control studies were included with a total sample size of 6, 113 cases and 11, 074 controls for the XPD Lys751Gln polymorphism, and 10 studies (3, 840cases and 7, 637 controls) for the XPD Asp312Asn polymorphism were pooled for analysis. Overall, no significant associations were found between the XPD Lys751Gln polymorphism and skin cancer risk in any genetic model. On stratified analysis by tumor type, XPD Lys751Gln polymorphism was not associated with increased risk of non-melanoma skin cancer, but was significantly related with increased risk of cutaneous melanoma (Gln/Gln vs Lys/Lys: OR=1.15, 95%CI=1.02-1.29, p=0.023; dominant model: OR=1.09, 95%CI=1.01-1.18, p=0.036). For the XPD Asp312Asn polymorphism, no significant association with skin cancer risk was observed in overall or subgroup analyses. Conclusions: The present meta-analysis suggests that the XPD Lys751Gln polymorphism may contribute to the risk of cutaneous melanoma from currently available evidence. Further investigations are needed to obtain more insight into possible roles of these two polymorphisms in skin carcinogenesis.
Lacquer is one of the most widely used natural resin in East Asia since Neolithic Age. As a major ingredient of lacquerware, lacquer is waterproof, insect-proof and rot-proof to be durable and anti-abrasion, generally utilized for mainly painting purpose. According to lacquerware excavated from several sites of Japan and China, lacquerware seems to appear in Neolithic Age. On the other hand in case of excavation research in Korea, lacquerwares are found after the Bronze Age. The initial purpose of lacquer is estimated to be adhesive, regarding the literatures mentioning bitumen(Yeoksceong ), animal glue(Kyeo) and egg alumen(Nanbaek). Especially piece of jar coffin unearthed in Pyeongtaek Daechu-ri site had trace of restoration by lacquer and hemp as an evidence of lacquer for adhesion in Pre-Three Kingdoms period. Since then a trend to restore the broken ceramics with lacquer and decorate with golden foil lasted especially in Joseon Dynasty. In the field of gold plated lacquer method, mother-of-pearl inlaying technique for lacquerware and restoration of buildings, lacquer is still used as adhesive. Due to matter of reversibility lacquer is being avoided for conservation and restoration of cultural heritage. Lacquer as a traditional material for adhesive since ancient times, however, has advantage in adhesion strength and durability. Because synthetic resin adhesive has problem of emission of volatile organic compounds and aging over time, lacquer receives attention recently. On the contrary, by combination adhesive from mixing lacquer and animal glue, already proved the possibility of applicability and chemical modification. A research to utilize lacquer as modern paint or functional material is also conducted continuously also in China and Japan. To put traditional material into practical use and modernize, chemical research from the molecular level of the lacquer is necessary in the near future.
Background: Previous studies evaluating the association between the xeroderma pigmentosum group G (XPG) Asp1104His polymorphism and head and neck cancer susceptibility have proven controversial. This meta-analysis of the literature was performed to obtain a more precise estimation of the relationship. Materials and Methods: We systematically searched PubMed, Embase and Web of Science with a time limit of Dec 18, 2014. Odds ratios (ORs) with 95% confidence intervals (CIs) were used to assess the strength of any association. Results: We performed a meta-analysis of eight published case-control studies, including 3,621 cases and 5,475 controls. Overall, no significant association was found between the XPG Asp1104His polymorphism and head and neck cancer susceptibility under all genetic models. In the subgroup analysis by ethnicity, the XPG Asp1104His polymorphism had statistically significant association with elevated head and neck cancer risk under CC vs GG (OR=1.24, 95% CI=1.00~1.54) and the recessive model (OR=1.22, 95%CI=1.01~1.46) in Asian populations. A similar result was found under CC vs GG (OR =1.22, 95%CI=1.01~1.47) in the population based subgroup by source of control. When performed by tumor site, the XPG Asp1104His polymorphism had statistically significant association with elevated laryngeal cancer under all genetic models (CC vs GG: OR=1.59, 95% CI=1.16~2.19; GC vs GG: OR=1.38, 95%CI=1.10~1.72; dominant model: OR=1.42, 95% CI=1.15~1.74; recessive model: OR=1.36, 95% CI=1.02~1.81). Conclusions: This meta-analysis suggested that the XPG Asp1104His polymorphism is a risk factor for head and neck cancer susceptibility, especially for laryngeal cancer and in Asian populations.
Zhou, Jue-Yu;He, Li-Wen;Liu, Jie;Yu, Hai-Lang;Wei, Min;Ma, Wen-Li;Shi, Rong
Asian Pacific Journal of Cancer Prevention
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제15권21호
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pp.9347-9353
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2014
Background: Excision repair crossing-complementing group 2 (ERCC2), also called xeroderma pigmentosum complementary group D (XPD), plays a crucial role in the nucleotide excision repair (NER) pathway. Previous epidemiological studies have reported associations between ERCC2 polymorphisms and non-Hodgkin lymphoma (NHL) risk, but the results have remained controversial. Materials and Methods: We conducted this meta-analysis based on eligible case-control studies to investigate the role of two ERCC2 polymorphisms (Lys751Gln and Asp312Asn) in determining susceptibility to NHL. Ten case-control studies from several electronic databases were included in our study up to August 14, 2014. Pooled odds ratios (ORs) and 95% confidence intervals (CIs) were calculated using fixed- or random-effects models to estimate the association strength. Results: The combined results based on all studies did not show any association between Lys751Gln/Asp312Asn polymorphisms and NHL risk for all genetic models. Stratified analyses by histological subtype and ethnicity did not indicate any significant association between Lys751Gln polymorphism and NHL risk. However, a significant reduced risk of NHL was found among population-based studies (Lys/Gln versus Lys/Lys: OR=0.87, 95% CI=0.77-0.99, P=0.037) but not hospital-based studies. As for Asp312Asn polymorphism, there was no evidence for the association between this polymorphism and the risk of NHL in all subgroup analyses. Conclusions: This meta-analysis suggests that there may be no association between Lys751Gln/Asp312Asn polymorphism and the risk of NHL and its two subtypes, whereas ERCC2 Lys751Gln heterozygote genotype may provide protective effects against the risk of NHL in population-based studies. Therefore, large-scale and well-designed studies are needed to clarify the effects of haplotypes, gene-gene, and gene-environment interactions on these polymorphisms and the risk of NHL and its different histological subtypes in an ethnicity specific population.
Energy policy is known to have higher path dependency among policy fields (Kuper and van Soest, 2003; OECD, 2012; Kikkawa, 2013) and is a critical component of the infrastructure development undertaken in the early stages of nation building. Actor roles, such as those played by interest groups, are firmly formed, making it unlikely that institutional change can be implemented. In resource-challenged Japan, energy policy is an especially critical policy area for the Japanese government. In comparing energy policy making in Japan and Germany, Japan’s policy community is relatively firm (Hartwig et al., 2015), and it is improbable that institutional change can occur. The Japanese government’s approach to energy policy has shifted incrementally in the past half century, with the most recent being the 2012 implementation of the “Feed-In Tariff Law” (Act on Special Measures Concerning Procurement of Renewable Electric Energy by Operators of Electric Utilities), which encourages new investment in renewable electricity generation and promotes the use of renewable energy. Yet, who were the actors involved and the factors that influenced the establishment of this new law? This study attempts to assess the factors associated with implementing the law as well as the roles of the relevant major actors. In answering this question, we focus on identifying the policy networks among government, political parties, and interest groups, which suggests that success in persuading key economic groups could be a factor in promoting the law. Our data is based on the “Global Environmental Policy Network Survey 2012-2013 (GEPON2)” which was conducted immediately after the March 11, 2011 Great East Japan Earthquake with respondents including political parties, the government, interest groups, and civil society organizations. Our results suggest that the Feed in Tariff (FIT) Law’s network structure is similar to the information network and support network, and that the actors at the center of the network support the FIT Law. The strength of our research lays in our focus on political networks and their contributing mechanism to the law’s implementation through analysis of the political process. From an academic perspective, identifying the key actors and factors may be significant in explaining institutional change in policy areas with high path dependency. Close examination of this issue also has implications for a society that can promote renewable and sustainable energy resources.
Thermal degradation of thermoplasitc polyurethane modified polycarbonate has been investigated by means of DSC, GPC and FT-IR techniques. The polyurethanes used in this study are TPU-35 and TPU-53 containing 35.5 and 53.4 wt% of hard segments, respectively. The more content of hard segment, the higher the glass transition temperature (T$_{g}$) of TPU was observed. On the other hand, the T$_{g}$ of the TPU modified PC decreased with the content of TPU and the annealing temperature regardless of the hard segment contents. The latter behavior nay arise from the thermal degradation of TPU upon annealing process: the observed thermal degradation temperatures were at 240 and 25$0^{\circ}C$ for the PC/TPU-35 and PC/TPU-53, respectively. The molecular weight, molecular weight distribution and viscosity agree well with the DSC measurement, which implicates a thermal degradation of TPU. In addition, thermal stability of the TPU modified PC linearly decreased with an incorporation of TPU. Transesterification or any interaction was not observed using FT-IR: the evidence was no frequency shift or any variance betwere the carbonyl stretching and NH group. For the specimens prepared below the degradation temperature, the enhancement of the thickness dependent impact strength of the PC/TPU blend was observed, and the morphology of the two blends was compared.d.
Park, Chang-Su;Cho, Hyun-Kyung;Cho, Nam-Chul;Kang, Dai-Ill
Journal of Conservation Science
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제28권1호
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pp.53-62
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2012
The archival objects are tangible evidence related to the public service. They are unique and offer information representing the specific events, time or person. The archival objects as modern cultural heritage do not have the guideline to classify, manage and conserve them. Especially, it is difficult to apply general conservation process for burial artifacts, because there are few study example of conservation for metal archival objects and they have complex administrative value. We tried to find suitable material and application method for consolidation of copper alloy archival object. We choose three kinds of wax and acrylic resin for burial artifacts and had done comparative analysis of their characterizations following kinds and coating methods. As a result of evaluation by several surface analysis such as optical microscope, measuring film thickness, adhesive strength, contact angle and yellowing test, acrylic resin can use to archival objects of copper alloy, effectively but the method of heating after dip-coating with Wax B used before can get best effect of consolidation.
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