• Title/Summary/Keyword: $S_N2$ reaction

Search Result 1,099, Processing Time 0.033 seconds

Kinetic Study on Nucleophilic Displacement Reactions of Y-Substituted-Phenyl 2-Methylbenzoates with Cyclic Secondary Amines in Acetonitrile: Effects of Modification of 2-MeO in Benzoyl Moiety by 2-Me on Reactivity and Reaction Mechanism

  • Lee, Ji-Youn;Kim, Mi-Yeon;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
    • /
    • v.34 no.12
    • /
    • pp.3795-3799
    • /
    • 2013
  • The second-order rate constants ($k_N$) have been measured spectrophotometrically for nucleophilic substitution reactions of Y-substituted-phenyl 2-methylbenzoates (6a-e) with a series of cyclic secondary amines in MeCN at $25.0{\pm}0.1^{\circ}C$. Comparison of the $k_N$ values for the reactions of 4-nitrophenyl 2-methylbenzoate (6d) with those reported previously for the corresponding reactions of 4-nitrophenyl 2-methoxybenzoate (5) reveals that 6d is significantly less reactive than 5, indicating that modification of 2-MeO in the benzoyl moiety of 5 by 2-Me (i.e., $5{\rightarrow}6d$) causes a significant decrease in reactivity. This supports our previous report that aminolysis of 5 proceeds through a six-membered cyclic intermediate, which is highly stabilized through intramolecular H-bonding interactions. The Br${\o}$nsted-type plot for the reactions of 6d with a series of cyclic secondary amines is linear with ${\beta}_{nuc}=0.71$, which appears to be a lower limit of ${\beta}_{nuc}$ for a stepwise mechanism with breakdown of an intermediate ($T^{\pm}$) being rate-determining step (RDS). The Br${\o}$nsted-type plot for the reactions of 6a-e with piperidine is curved, i.e., the slope of Br${\o}$nsted-type plot (${\beta}_{lg}$) decreases from -1.05 to -0.41 as the leaving-group basicity decreases. The nonlinear Br${\o}$nsted-type plot has been taken as evidence for a stepwise mechanism with a change in RDS (e.g., from the $k_2$ step to the $k_1$ process as the leaving-group basicity decreases). Dissection of $k_N$ into the microscopic rate constants associated with the reactions of 6a-e with piperidine (e.g., $k_1$ and $k_2/k_{-1}$ ratio) also supports the proposed mechanism.

Control of Graphene's Electrical Properties by Chemical Doping Methods

  • Lee, Seung-Hwan;Choi, Min-Sup;La, Chang-Ho;Yoo, Won-Jong
    • Proceedings of the Korean Vacuum Society Conference
    • /
    • 2011.08a
    • /
    • pp.119-119
    • /
    • 2011
  • This study examined the synthesis of large area graphene and the change of its characteristics depending on the ratio of CH4/H2 by using the thermal CVD methods and performed the experiments to control the electron-hole conduction and Dirac-point of graphene by using chemical doping methods. Firstly, with regard to the characteristics of the large area graphene depending on the ratio of CH4/H2, hydrophobic characteristics of the graphene changed to hydrophilic characteristics as the ratio of CH4/H2 reduces. The angle of contact also increased to 78$^{\circ}$ from 58$^{\circ}$. According to the results of Raman spectroscopy showing the degree of defect, the ratio of I(D)/I(G) increases to 0.42% from 0.25% and the surface resistance also increased to 950 ${\Omega}$ from 750 ${\Omega}$/sq. As for the graphene synthesis at the high temperature of 1,000$^{\circ}$ by using CH4/H2 in a Cu-Foil, the possibility of graphene formation was determined as a function of the ratio of H2 included in the fixed quantity of CH4 as per specifications of every equipment. It was observed that the excessive amount of H2 prevented graphene from forming, as extra H-atoms and molecules activated the reaction to C-bond of graphene. Secondly, in the experiment for the electron-hole conduction and the Dirac-point of graphene using the chemical doping method, the shift of Dirac-point and the change in the electron-hole conduction were observed for both the N-type (PEI) and the P-type (Diazonium) dopings. The ID-VG results show that, for the N-type (PEI) doped graphene, Dirac-point shifted to the left (-voltage direction) by 90V at an hour and by 130 V at 2 hours respectively, compared to the pristine graphene. Carrier mobility was also reduced by 1,600 cm2/Vs (1 hour) and 1,100 cm2/Vs (2 hours), compared to the maximum hole mobility of the pristine graphene.

  • PDF

Degradation of Taste-and-Odor Compounds and Toxins in Water Supply Source Using Plasma (플라즈마를 이용한 상수원 이취미 및 독성물질 분해 연구)

  • Jo, Jin Oh;Kim, Sang Don;Lim, Byung-Jin;Hyun, Young Jin;Mok, Young Sun
    • Applied Chemistry for Engineering
    • /
    • v.24 no.5
    • /
    • pp.518-524
    • /
    • 2013
  • This study investigated the degradation of taste-and-odor compounds and toxins using dielectric barrier discharge plasma. The degradation of taste-and-odor compounds was conducted on geosmin and 2-methyl isoborneol (2-MIB), and the toxins investigated were microcystin-LR (MC-LR), microcystin-RR (MC-RR), microcystin-YR (MC-YR) and anatoxin-a. Largely depending on the type of gas fed to the plasma reactor, the degradation efficiencies of the taste-and-odor compounds decreased in order of oxygen (100%) > dry air (96%) > nitrogen (5%) for geosmin and in order of oxygen (100%) > dry air (94%) > nitrogen (2%) for 2-MIB on the basis of 150 s reaction time. This result suggests that the oxidative reactive species generated during plasma treatment, especially long-lived ozone, are mainly responsible for the degradation of these compounds. When using oxygen as the feed gas, geosmin and 2-MIB were totally degraded within 150 s, microcystins within 10 s, and anatoxin-a within 30 s. It was found that the taste-and-odor compounds and toxins were degraded more rapidly in real lake water than in distilled water.

Preparation and Flame Retardancy of Poly(benzoxazole imide) Having Trifluoromethyl Group in the Main Chain (주사슬에 Trifluoromethyl 그룹을 갖는 Poly(benzoxazole imide)의 제조 및 난연 특성)

  • Yeom, Jin-Seok;Choi, Jae-Kon;Lee, Chang-Hoon
    • Elastomers and Composites
    • /
    • v.47 no.4
    • /
    • pp.355-363
    • /
    • 2012
  • A series of poly(hydroxyamide)s (PHAs) having trifluoromethyl group were prepared by direct polycondensation of aromatic diimide-dicarboxylic acids with 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane by thionyl chloride and triethyl amine in N-methyl-2-pyrrolidinone (NMP). The PHAs exhibited inherent viscosity in the range of 0.54-0.96 dL/g at $35^{\circ}C$ in DMAc solution. All PHAs were readily soluble in a variety of organic solvents, whereas the polybenzoxazoles (PBOs) were quite insoluble except partially soluble in sulfuric acid. PHAs were converted to PBOs by thermal cycling reaction with heat of endotherm. The maximum weight loss temperature of the PHAs occurred in the range of $559-567^{\circ}C$. The PBOs showed relatively high char yields in the range of 47-59%. Pyrolysis Combustion Flow Calorimeter (PCFC) results of the PBOs showed 12-19 W/g heat release rate (HRR), and 2.7-3.6 kJ/g total heat release (total HR). The HRR of PBO 1 showed the lowest value of 12 W/g, which was 37% lower than that of PBO 3 (19 W/g).

Pre-seasonal Physical Examination of Professional Soccer Team (프로 축구팀의 시즌 전 체력검사)

  • Lee, Kyung-Tai;Choi, Byung-Ok
    • Journal of Korean Orthopaedic Sports Medicine
    • /
    • v.5 no.2
    • /
    • pp.129-134
    • /
    • 2006
  • Purpose: In the professional soccer team, we performed pre-seasonal physical examination and analyzed the results to establish a standardization data in relation to their position. Materials and Methods: We performed physical examination to the professional soccer team, consisted 34 player's average age 24.9 years. The examination performed were questionnaire on history, musculoskeletal examination, muscle power test, physiologic test, functional test. Results: According to the relationship between player position and injury pattern,. Knee injuries are most frequent on history. Physical examination outcome was that forward were prone to flexor hallucis longus tendinitis, midfielder for chronic ankle instability, defender for achilles tendinitis. Isokinetic test was done at dominant side, Peak torque to body weight ratio was 55.1%. Physiologic test checked body fat percentage was midfielder was superior as 19.8 (SD 2.9). Functional test out-come was that back strength 125 N. sergeant jump 59.6 cm, reaction time 208.5 sec, flexibility 19.2 m/s, side step 39.9 cm. Conclusion: Pre-seasonal physical examination gave us the standardization data and preventive measurement could be advocated from this results.

  • PDF

Polymorphisms of the NR3C1 gene in Korean children with nephrotic syndrome (한국 신증후군 환아에서 NR3C1 유전자 다형성 분석)

  • Cho, Hee Yeon;Choi, Hyun Jin;Lee, So Hee;Lee, Hyun Kyung;Kang, Hee Kyung;Ha, Il Soo;Choi, Yong;Cheong, Hae Il
    • Clinical and Experimental Pediatrics
    • /
    • v.52 no.11
    • /
    • pp.1260-1266
    • /
    • 2009
  • Purpose : Idiopathic nephrotic syndrome (NS) can be clinically classified as steroid-sensitive and steroid-resistant. The detailed mechanism of glucocorticoid action in NS is currently unknown. Methods : In this study, we investigated 3 known single nucleotide polymorphisms (SNPs) (ER22/23EK, N363S, and BclI) of the glucocorticoid receptor gene (the NR3C1 gene) in 190 children with NS using polymerase chain reaction-restriction fragment length polymorphism and analyzed the correlation between the genotypes and clinicopathologic features of the patients. Results : Eighty patients (42.1%) were initial steroid nonresponders, of which 31 (16.3% of the total) developed end-stage renal disease during follow-up. Renal biopsy findings of 133 patients were available, of which 36 (31.9%) showed minimal changes in NS and 77 (68.1%) had focal segmental glomerulosclerosis. The distribution of the BclI genotypes was comparable between the patient and control groups, and the G allele frequencies in both the groups were almost the same. The ER22/23EK and N363S genotypes were homogenous as ER/ER and NN, respectively, in all the patients and in 100 control subjects. The BclI genotype showed no correlation with the NS onset age, initial steroid responsiveness, renal pathologic findings, or progression to end-stage renal disease. Conclusion : These data suggested that the ER22/23EK, N363S, and BclI SNPs in the NR3C1 gene do not affect the development of NS, initial steroid responsiveness, renal pathologic lesion, and progression to end-stage renal disease in Korean children with NS.

Cloning and Characterization of Pseudomonas mucidolens Exoinulinase

  • Kwon, Young-Man;Kim, Hwa-Young;Choi, Yong-Jin
    • Journal of Microbiology and Biotechnology
    • /
    • v.10 no.2
    • /
    • pp.238-243
    • /
    • 2000
  • An exoinulinase (${\beta}-D-fructofuranosidase$) gene was cloned by chromosome walking along the upstream region of the endoinulinase gene of Pseudomonas mucidolens isolated from soil. the exoinulinase gene consisted of an ORF of 0,506 bp encoding a polypeptide of 501 amino acids with a deduced molecular weight of 55,000. The exoinulinase produced by the recombinant Escherichia coli $DH5{\alpha}$ strain was also purified to homogeneity as determined by SDS-PAGE and a zymogram. The molecular weight of the purified exoinulinase according to both SDS-PAGE and gel filtration matched the deduced molecular weight of the protein described above, thereby indicating that the native form of the exoinulinase was a monomer. The purified enzyme hydrolyzed activity value of 2.0. Furthermore, no inulo-oligomers were liberated from the inulin substrate in the enzymatic reaction mixtures incubated for 90 min at $55^{\circ}C$. Taken together, these results indicate that the purified ${\beta}-D-fructofuranosidase$ was an exoinulinase. The pH and temperature optima of the exoinulinase were pH 6.0 and $55^{\circ}C$, respectively. the enzymehad no apparent requirement for a cofactor, and its activity was completely inactivated by $Ag^{+},{\;}Hg^{2+},{\;}and{\;}Zn^{2+}$. Kinetic experiments gave $K_m,{\;}V_{max},{\;}and{\;}K_{cat}$ values for inulin of 11.5 mM, 18 nM/s, and $72{\;}s^{-1}$, respectively. the exoinulinase was fairly stable in broad pH conditions (pH 5-9), and at pH 6.0 it showed a residual activity of about 70% after 4 h incubation at $55^{\circ}C$.

  • PDF

Effects of Structural Difference of Ionic Liquids on the Catalysis of Horseradish Peroxidase

  • Hong, Eun-Sik;Park, Jung-Hee;Yoo, Ik-Keun;Ryu, Keun-Garp
    • Journal of Microbiology and Biotechnology
    • /
    • v.19 no.7
    • /
    • pp.713-717
    • /
    • 2009
  • The dependence of the catalytic properties of horseradish peroxidase on the structural changes of ionic liquids was investigated with two water-miscible ionic liquids, N-butyl-3methypyridinium tetraftuoroborate ([$BMP_y$][$BF_4$]) and 1-butyl-3-methylimidazolium methylsulfate ([BMIM][$MeSO_4$]), each of which shares an anion ($BF_4^-$) or a cation ($BMIM^+$) with 1-butyl-3-methylimidazolium tetraftuoroborate ([BMIM][$BF_4$]), respectively. The oxidation of guaiacol (2-methoxyphenol) with $H_2O_2$was used as a model reaction. In order to minimize the effect of solution viscosity on the kinetic constants of the enzymatic catalysis, the enzymatic reactions for the kinetic study were performed in water-ionic liquid mixtures containing 25% (v/v) ionic liquid at maximum. Similarly to the previously reported results for [BMIM][$BF_4$], as the concentration of [$BMP_y$][$BF_4$] increased, the $K_m$value increased with a decrease in the $k_{cat}$value: the $K_m$value increased markedly from 2.8 mM in 100% water to 12.6 mM in 25% (v/v) ionic liquid, indicating that ionic liquid significantly weakens the binding affinity of guaiacol to the enzyme. On the contrary, [BMIM][$MeSO_4$] decreased the Km value to 1.4 mM in 25% (v/v) ionic liquid. [BMIM][$MeSO_4$] also decreased $k_{cat}$more than 3-folds [from 13.8 $s^{-1}$in 100% water to 4.1 $s^{-1}$in 25% (v/v) ionic liquid]. These results indicate that the ionic liquids interact with the enzyme at the molecular level as well as at a macroscopic thermodynamic scale. Specifically, the anionic component of the ionic liquids influenced the catalysis of horseradish peroxidase in different ways.

Pattern of Pharmacist Consultation among the Health Counseling Services via Internet Portal Sites: A Pilot Study (국내 포털사이트에서의 지식검색서비스를 이용한 약사와의 상담 패턴에 대한 시험적 연구)

  • Kim, Heejin;Park, Jun Ha;Ji, Eunhee
    • Korean Journal of Clinical Pharmacy
    • /
    • v.26 no.4
    • /
    • pp.324-329
    • /
    • 2016
  • Background: With the development of information and communication technology, there is a growing number of people looking for health information on the internet. This pilot study was performed to analyze the pattern of pharmacist consultation on the internet portal site. Methods: Questions and answers posted on the portal site "Naver Jisik-iN" from March 1st to 31th in 2016 were collected. Medications asked were categorized into prescription drugs, nonprescription drugs, sanitary aids, emergency drugs, functional health foods, and others. Medications were subcategorized into 14 according to the anatomical therapeutic chemical classification system. Questions were divided into 10 categories based on Hepler's drug-related problems. Results: Of the 955 cases, females accounted for 59.5% and inquirers from 11 to 40 years old, 89.4%. The number of prescription drugs, nonprescription drugs, sanitary aids, emergency drugs, functional health foods, and others were 428 (44.8%), 328 (34.3%), 31 (3.3%), 2 (0.2%), 122 (12.8%), and 44 (4.6%), respectively. Questions for drugs acting on alimentary tract and metabolism took up 27.4% followed by those on nervous system, 13.6% and anti-infectives for systemic use, 12.2%. Pharmacist consultation regarding drug information, drug interaction, and adverse reaction occupied 47.9%, 15.2%, and 12.3%, respectively. Conclusion: Health counseling through online is predicted to increase steadily, so pharmacists should broaden their boundaries beyond off-line pharmacies to meet social needs.

Temperature dependence of optical energy gaps and thermodynamic function of $Zn_{4}SnSe_{6}$ and $Zn_{4}SnSe_{6}:Co^{2+}$ single crystals ($Zn_{4}SnSe_{6}$$Zn_{4}SnSe_{6}:Co^{2+}$ 단결정에서 광학적 에너지 띠 및 열역학적 함수의 온도의존성 연구)

  • Kim, D.T.;Kim, N.O.;Choi, Y.I.;Kim, B.C.;Kim, H.G.;Hyun, S.C.;Kim, B.I.;Song, C.I.
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
    • /
    • 2002.08a
    • /
    • pp.25-30
    • /
    • 2002
  • The ternary semiconducting compounds of the $A_{4}BX_{6}$(A=Cd, Zn, Hg; B=Si, Sn, Ge; X=S, Se, Te) type exhibit strong fluorescence and high photosensitivity in the visible and near infrared ranges, so these are supposed to be materials applicable to photoelectrical devices. These materials were synthesized and single crystals were first grown by Nitsche, who identified the crystal structure of the single crystals. In this paper. author describe the undoped and $Co^{2+}$-doped $Zn_{4}SnSe_{6}$ single crystals were grown by the chemical transport reaction(CTR) method using iodine of $6mg/cm^{3}$ as a transport agent. For the crystal. growth, the temperature gradient of the CTR furnace was kep at $700^{\circ}C$ for the source aone and at $820^{\circ}C$ for the growth zone for 7-days. It was found from the analysis of x-ray diffraction that undoped and $Co^{2+}$-doped $Zn_{4}SnSe_{6}$ compounds have a monoclinic structure. The optical absorption spectra obtained near the fundamental absorption edge showed that these compounds have a direct energy gaps. These temperature dependence of the optical energy gap were closely investigated over the temperature range 10[K]~300[K]

  • PDF