• 제목/요약/키워드: $S_N1$ mechanism

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Envelope Proteins Pertain with Evolution and Adaptive Mechanism of the Novel Influenza A/H1N1 in Humans

  • Mondal, Shakhinur Islam;Zubaer, Abdullah;Thapa, Simrika;Saha, Chinmoy;Alum, Md. Asraful;Reza, Md. Salman;Akter, Arzuba;Azad, Abul Kalam
    • Journal of Microbiology and Biotechnology
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    • 제20권11호
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    • pp.1500-1505
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    • 2010
  • The novel swine-origin influenza A/H1N1 virus (S-OIV) first detected in April 2009 has been identified to transmit from humans to humans directly and is the cause of the currently emerged pandemic. In this study, nucleotide and deduced amino acid sequences of the hemagglutinin (HA) and neuraminidase (NA) of the S-OIV and other influenza A viruses were analyzed through bioinformatic tools for phylogenetic analysis, genetic recombination, and point mutation to investigate the emergence and adaptation of the S-OIV in humans. The phylogenetic analysis showed that the HA comes from triple reassortant influenza A/H1N2 and the NA from Eurasian swine influenza A/H1N1, indicating that HA and NA descend from different lineages during the genesis of the S-OIV. Recombination analysis ified the possibility of occurrence of recombination in HA and NA, denoting the role of reassortment in the outbreak. Several conservative mutations were observed in the amino acid sequences of the HA and NA, and these mutated residues were identical in the S-OIV. The results reported herein suggest the notion that the recent pandemic is the result of reassortment of different genes from different lineages of two envelope proteins, HA and NA, which are responsible for the antigenic activity of the virus. This study further suggests that the adaptive capability of the S-OIV in humans is acquired by the unique mutations generated during emergence.

Kinetics and Mechanism of the Anilinolysis of Bis(aryl) Chlorophosphates in Acetonitrile

  • Barai, Hasi Rani;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • 제32권6호
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    • pp.1939-1944
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    • 2011
  • The nucleophilic substitution reactions of bis(Y-aryl) chlorophosphates (1) with substituted anilines and deuterated anilines are investigated kinetically in acetonitrile at 35.0 $^{\circ}C$. The kinetic results of 1 are compared with those of Y-aryl phenyl chlorophosphates (2). The substrate 1 has one more identical substituent Y compared to substrate 2. The cross-interaction between Y and Y, due to additional substituent Y, is significant enough to result in the change of the sign of cross-interaction constant (CIC) from negative ${\rho}_{XY}$ = -1.31 (2) to positive ${\rho}_{XY}$ = +1.91 (1), indicating the change of reaction mechanism from a concerted $S_N2$ (2) to a stepwise mechanism with a rate-limiting leaving group departure from the intermediate (1). The deuterium kinetic isotope effects (DKIEs) involving deuterated anilines ($XC_6H_4ND_2$) show secondary inverse, $k_H/k_D$ = 0.61-0.87. The DKIEs invariably increase as substituent X changes from electron-donating to electron-withdrawing, while invariably decrease as substituent Y changes from electron-donating to electron-withdrawing. A stepwise mechanism with a rate-limiting bond breaking involving a predominant backside attack is proposed on the basis of positive sign of ${\rho}_{XY}$ and secondary inverse DKIEs.

Kinetics and Mechanism of the Anilinolysis of (2R,4R,5S)-(+)-2-Chloro-3,4-dimethyl -5-phenyl-1,3,2-oxazaphospholidine 2-Sulfide in Acetonitrile

  • Barai, Hasi Rani;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • 제33권3호
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    • pp.1037-1041
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    • 2012
  • The nucleophilic substitution reactions of (2R,4R,5S)-(+)-2-chloro-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidine 2-sulfide (3) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $5.0^{\circ}C$. The anilinolysis rate of 3 involving a cyclic five-membered ring is considerably fast because of small negative value of the entropy of activation (${\Delta}S^\neq=-2cal\;mol^{-1}\;K^{-1}$) over considerably unfavorable enthalpy of activation (${\Delta}H^\neq=18.0\;kcal\;mol^{-1}$). Great enthalpy and small negative entropy of activation are ascribed to sterically congested transition state (TS) and bulk solvent structure breaking in the TS. A concerted $S_N2$ mechanism with a backside nucleophilic attack is proposed on the basis of the secondary inverse deuterium kinetic isotope effects, $k_H/k_D$ < 1.

S35C강의 피로균열 발생 및 진전에 관한 연구 (The Research of Fatigue-Crack Initiation and Propagation for S35C Steel)

  • 진영준
    • 한국안전학회지
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    • 제16권1호
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    • pp.31-36
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    • 2001
  • Surface crack growth characteristics and influence of the stress amplitude in rotary bending fatigue test were evaluated for annealed S35C steel, and than fractal dimensions of fatigue crack paths estimated using the box counting method. The following results that will be helpful to understand the fatigue crack growth mechanism were obtained. (1) Crack growth rate ds/dN and db/dN (s : half crack length at the surface crack, b : crack depth) depended on stress amplitude (${\Delta}{\sigma}/2$), stress intensity factor range (${\Delta}K_A, {\Delta}K_C$) and crack length. (2) At the effect area of 0.3 mm hole notch (s<0.5 mm) crack growth rate did not depend on these factors. (3) The fractal dimensions (D) increased with stress amplitude (${\Delta}{\sigma}/2$) but decreased with cyclic number.

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친핵성치환반응에서 압력과 온도변화에 따른 친핵체 효과 (Nucleophile Effects for the Reactions of Nucleophilic Substitution by Pressure and Temperature)

  • 김세경;최성용;고영신
    • 대한화학회지
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    • 제48권5호
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    • pp.461-466
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    • 2004
  • 고진공 및 고압에서 친핵체변화에 따른 반응을 온도변화에 따라 속도론적으로 연구하였다. 유사1차반응속도상수, 2차반응속도상수, 열역학함수 및 Hammett ${\rho}$ 값을 구하였다. ${\Delta}V^{\neq},\;{\Delta}{\beta}^{\neq}\;및\;{\Delta}S^{\neq}$는 모두 음의 값을 나타내었으며, 모든 압력 조건에서 친핵체의 치환기효과 ${\rho}$x는 음의 값을 나타내었다. 전체적인 반응은 전형적인 $S_N2$ 반응메카니즘을 따르며, 압력과 친핵체 변화에 따라 반응메카니즘에 변화가 생김을 알 수 있다.

Kinetics Studies on the Mechanism of Hydrolysis of S-Phenyl-S-vinyl-N-p-tosylsulfilimine Derivatives

  • Pyun, Sang-Yong;Kim, Tae-Rin;Lee, Chong-Ryoul;Kim, Whan-Gi
    • Bulletin of the Korean Chemical Society
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    • 제24권3호
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    • pp.306-310
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    • 2003
  • Hydrolysis reactions of S-phenyl-S-vinyl-N-p-tosylsulfilimine (VSI) and its derivatives at various pH have been investigated kinetically. The hydrolysis reactions produced phenylvinylsulfoxide and p-toluene sulfonamide as the products. The reactions are first order and Hammett ρ values for pH 1.0, 6.0, and 11.0 are 0.82, 0.45, and 0.57, respectively. This reaction is not catalyzed by general base. The plot of k vs pH shows that there are three different regions of the rate constants $(k_t)$ in the profile.; At pH < 2 and pH > 10, the rate constants are directly proportional to the concentrations of hydronium and hydroxide ion catalyzed reactions, respectively. The rate constant remains nearly the same at 2 < pH < 10. On the bases of these results, the plausible hydrolysis mechanism and a rate equation have been proposed: At pH < 2.0, the reaction proceeds via the addition of water molecule to sulfur after protonation at the nitrogen atom of the sulfilimine, whereas at pH > 10.0, the reaction proceeds by the addition of hydroxide ion to sulfur directly. In the range of pH 2.0-10.0, the addition of water to sulfur of sulfilimine appears to be the rate controlling step.

SERKOWSKI'S EMPIRICAL RELATION FOR INTERSTELLAR LINEAR POLARIZATION VIEWED FROM DAVIS-GREENSTEIN ALIGNMENT MECHANISM

  • Hong, Seung-Soo;Lee, Hyung-Mok
    • 천문학회지
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    • 제11권1호
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    • pp.31-36
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    • 1978
  • Although Serkowski used a single value K=1.15 in representing all the observed interstellar linear polarization curves by his empirical relation $p({\lambda})/P_{max}$=exp (-K $1n^2({\lambda}_{max}/{\lambda})$), where $p_{max}$ is the maximum polarization at wavelength ${\lambda}_{max}$, we have noticed a meaningful variation in K from observations of 72 stars. By comparing K's with $P_{max}/E_{B-V}\;and\;with\;{\lambda}_{max}$, we have examined how the shape of the polarization curve is related with the degree of grain alignment on one hand, and with grain sizes on the other. We have shown that correlations between K, $P_{max}/E_{B-V}\;and\;with\;{\lambda}_{max}$, are consistent with the idea of Davis-Greenstein mechanism for grain alignment.

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거풍지보단(祛風至寶丹)의 혈관이완 효능과 기전에 관한 연구 (Studies on the Effect and Mechanism of Geupoongjibo-dan's Relaxation on a Blood Vessel)

  • 김동은;박동완;정승현;신길조;이원철;한성호
    • 대한한방내과학회지
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    • 제22권2호
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    • pp.119-125
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    • 2001
  • Objectives : This study was conducted to evaluate the effect and mechanism of Geupoongjibo-dan's relaxation of the tension of the blood vessel caused by Phenylephrine and KCI. Methods : In order to study the effect of Geupoongjibo-dan's relaxation of the blood vessel tension, Geupoongjibo-dan extract was infused into Phenylephrine and KCI-induced contracted rabbit aorta strips. To analyze the mechanism of Geupoongjibo-dan's effect on the blood vessel, Geupoongjibo-dan extract infused into Phenylephrine and KCI-induced contracted strips induced by agonists after treatment of N${\omega}$-nitro-L-arginine, Methylene Blue. Results : 1. Geupoongjibo-dan was very effective in relaxing the blood vessels contracted by Phenylephrine. 2. Geupoongjibo-dan was effective against Phenylephrine, than against KCI. 3. Geupoongjibo-dan's more relaxation effect on a blood vessel was terminated by N${\omega}$-nitro-L-arginine and methylene treatment. Conclusion : THis study showed that Geupoongjibo-dan's relaxation effect on a blood vessel is irrelevant to ${\alpha}$-adrenalin receptor, and it relaxes contracted vessels through cGMP channel.

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Antibiofilm activity of polyethylene glycol-quercetin nanoparticles-loaded gelatin-N,O-carboxymethyl chitosan composite nanogels against Staphylococcus epidermidis

  • Wanhe Luo;Yongtao Jiang;Jinhuan Liu;Beibei Sun;Xiuge Gao;Samah Attia Algharib;Dawei Guo;Jie Wei;Yurong Wei
    • Journal of Veterinary Science
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    • 제25권2호
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    • pp.30.1-30.16
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    • 2024
  • Background: Biofilms, such as those from Staphylococcus epidermidis, are generally insensitive to traditional antimicrobial agents, making it difficult to inhibit their formation. Although quercetin has excellent antibiofilm effects, its clinical applications are limited by the lack of sustained and targeted release at the site of S. epidermidis infection. Objectives: Polyethylene glycol-quercetin nanoparticles (PQ-NPs)-loaded gelatin-N,O-carboxymethyl chitosan (N,O-CMCS) composite nanogels were prepared and assessed for the on-demand release potential for reducing S. epidermidis biofilm formation. Methods: The formation mechanism, physicochemical characterization, and antibiofilm activity of PQ-nanogels against S. epidermidis were studied. Results: Physicochemical characterization confirmed that PQ-nanogels had been prepared by the electrostatic interactions between gelatin and N,O-CMCS with sodium tripolyphosphate. The PQ-nanogels exhibited obvious pH and gelatinase-responsive to achieve on-demand release in the micro-environment (pH 5.5 and gelatinase) of S. epidermidis. In addition, PQ-nanogels had excellent antibiofilm activity, and the potential antibiofilm mechanism may enhance its antibiofilm activity by reducing its relative biofilm formation, surface hydrophobicity, exopolysaccharides production, and eDNA production. Conclusions: This study will guide the development of the dual responsiveness (pH and gelatinase) of nanogels to achieve on-demand release for reducing S. epidermidis biofilm formation.

확장된 Grunwald-Winstein 식에 의한 Di-n-butyl Phosphorochloridate의 가용매 분해반응 연구 (Studies of Solvolyses of Di-n-butyl Phosphorochloridate by Extended Grunwald-Winstein Equation)

  • 강민성;김철주;강석진;고한중
    • 대한화학회지
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    • 제59권5호
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    • pp.373-378
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    • 2015
  • Di-n-butyl phosphorochloridate((CH3CH2CH2CH2O)2POCl, 1)의 가용매 분해반응의 속도상수를 여러 가지 용매 중에서 구하였다. 반응용매 28개의 속도상수를 이용하여 확장된 Grunwald-Winstein 식에 의하여 구한 용매의 친핵성도와 이온화력에 대한 기질의 민감도(l = 1.40, m = 0.42)는 SN2 반응임을 예상할 수 있다. 이를 뒷받침할 수 있는 추가 요소들은 상대적으로 작은 양의 값의 ΔH (8.0 ~ 15.9 kcal·mol−1)와 큰 음의 값의 ΔS(−25.8~−53.1 cal·mol−1·K−1), Kivinen의 n 값(0.9~1.7) 그리고 용매동위원소효과 값(1.69)이다.