• Title/Summary/Keyword: $S_N2$ mechanism

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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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    • v.25 no.2
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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.

Solvolysis of 3-Chloro-1,2-benzisothiazole-1,1-dioxide (pseudosaccharin chloride (3-Chloro-1,2-benzisothiazole-1,1-dioxide (pseudosaccharin chloride)의 가용매 분해반응)

  • In-Sun Koo;Jeong-Ja Kim;Yong-Jin Yoon;Ikchoon Lee
    • Journal of the Korean Chemical Society
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    • v.30 no.3
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    • pp.296-300
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    • 1986
  • The pseudo-first order rate constants have been obtained for the solvolysis of pseudo-saccharinechloride in MeOH-$H_2O$, EtOH-$H_2O$, MeOH-MeCN and MeOH-$(Me)_2$CO solvents mixtures at various temperatures. Values of n and m in the Kivinen and Grunwald-Winstein plots, respectively, have been determined and the Taft's solvatochromic parameters were obtained; based on these solvent effect parameters as well as on the activation parameters it was concluded that reaction proceeds via an $S_N2$ mechanism.

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Kinetic Studies on the Nucleophilic Substitution Reaction of 4-X-Substituted-2,6-dinitrochlorobenzene with Pyridines in MeOH-MeCN Mixtures

  • Sung, Ryun-Youn;Choi, Ho-june;Lee, Jong-Pal;Park, Jong-Keun;Yang, Ki-Yull;Koo, In-Sun
    • Bulletin of the Korean Chemical Society
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    • v.30 no.7
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    • pp.1579-1582
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    • 2009
  • The reaction rates of 4-X-2,6-dinitrochlorobenzenes (X = $NO_2,\;CN,\;CF_3$) with Y-substituted pyridines (Y = 3-$OCH_3,\;H,\;3-CH_3,\;4-CH_3$) in methanol-acetonitrile mixtures were measured by conductometry at 25 ${^{\circ}C}$. It was observed that the rate constant increased in the order of X = 4-$NO_2\;>\;4-CN\;>\;4-CF_3$ and the rate constant also increased in the order of Y = 4-$CH_3\;>\;3-CH_3\;>\;H\;>\;3-OCH_3$. When the solvent composition was varied, the rate constant increased in order of MeCN > 50% MeOH > MeOH. The electrophilic catalysis by methanol may be ascribed to the formation of hydrogen bonds between alcoholic hydrogen and nitrogen of pyridines in ground state. Based on the transition parameters, ${\rho}_S,\;{\rho}_N,\;{\beta}_Y,\;{\rho}_{XY}$ and solvent effects, the reaction seems to proceed via $S_N$Ar-Ad.E mechanism. We also estimated the isokinetic solvent mixtures (${\rho}_{XY}$ = 0) based on cross-interaction constants, where the substituent effects of the substrate and nucleophile are compensated.

Impedance Spectroscopy Studies on Corrosion Inhibition Behavior of Synthesized N,N’-bis(2,4-dihydroxyhydroxybenzaldehyde)-1,3-Propandiimine for API-5L-X65 Steel in HCl Solution

  • Danaee, I.;Bahramipanah, N.;Moradi, S.;Nikmanesh, S.
    • Journal of Electrochemical Science and Technology
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    • v.7 no.2
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    • pp.153-160
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    • 2016
  • The inhibition ability of N,N-bis(2,4-dihydroxyhydroxybenzaldehyde)-1,3-Propandiimine (DHBP) as a schiff base against the corrosion of API-5L-X65 steel in 1 M HCl solution was evaluated by electrochemical impedance spectroscopy, potentiodynamic polarization and scanning electron microscopy. Electrochemical impedance studies indicated that DHBP inhibited corrosion by blocking the active corrosion sites. The inhibition efficiency increased with increasing inhibitor concentrations. EIS data was analysed to equivalent circuit model and showed that the charge transfer resistance of steel increased with increasing inhibitor concentration whilst the double layer capacitance decreased. The adsorption of this compound obeyed the Langmuir adsorption isotherm. Gibbs free energy of adsorption was calculated and indicated that adsorption occurred through physical and spontaneous process. The corrosion inhibition mechanism was studied by potential of zero charge. Polarization studies indicated that DHBP retards both the cathodic and anodic reactions through adsorption on steel surface. Scanning electron microscopy was used to study the steel surface with and without inhibitor.

Reviews on Very High Cycle Fatigue Behaviors of Structural Metals (구조용 금속의 초고주기피로 거동에 대한 연구 동향)

  • Han, Seung-Wook;Park, Jung-Hoon;Myeong, No-Jun;Choi, Nak-Sam
    • Transactions of the Korean Society of Automotive Engineers
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    • v.22 no.2
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    • pp.134-140
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    • 2014
  • The paper presents an overview of the present state of study on the fatigue behaviors at very high number of cycles ($N_f$ > $10^7$). A classification of materials with typical S-N curves and influencing factors such as notches, residual stresses, temperatures, corrosion environments and stress ratios are given. The microstructural inhomogeneities of materials and micro-cracks played an important roles in very high cycle fatigue behaviors. The failure mechanisms for the fatigue design of materials and components are mentioned.

Nucleophilic Substitution at a Carbonyl Carbon Atom (VII). Kinetic Studies on the Sovolysis of 2-Thenoyl Chloride in Binary Mixtures of Acetone-Water and Ethanol-Water (카르보닐 탄소원자의 친핵성 치환반응 (제7보). 물-에탄올 및 물-아세톤 혼합용매속에서 2-염화테노일의 가용매 분해반응)

  • Sohn, Jin Eon;Yoon, Sang Kee;Lee, Ik Choon
    • Journal of the Korean Chemical Society
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    • v.20 no.5
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    • pp.333-339
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    • 1976
  • The rates of solvolysis for 2-thenoyl chloride have been measured in aqueous acetone and aqueous ethanol at various temperatures ranging from 20 to $40^{circ}C$. The activation parameters and the Grundwald-Winstein's slope are determined by the analysis of solvolysis rates. The results indicated that the reaction rates of solvolysis are considerably slower than those of the reaction for benzoyl chloride due to the electron donating effect of thiophene nucleus. The results also showed that the reaction proceeds with the $S_N1$ mechanism in water-rich solvents whereas the $S_N2$ character increases with the decrease of water content, and overall reaction is subject to entropy control.

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Stoichiometric Solvation Effects. Solvolysis of Trifluoromethanesulfonyl Chloride

  • Koo, In-Sun;Yang, Ki-Yull;Park, Jong-Kuen;Woo, Mi-Young;Cho, Jun-Mi;Lee, Jong-Pal;Lee, Ik-Choon
    • Bulletin of the Korean Chemical Society
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    • v.26 no.8
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    • pp.1241-1245
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    • 2005
  • Solvolyses of trifluoromethanesulfonyl chloride (TFMSC) in water and in aqueous binary mixtures of acetone, ethanol and methanol are investigated at 25, 35 and 45 ${^{\circ}C}$. The Grunwald-Winstein plot of first-order rate constants for the solvolytic reaction of TFMSC with YCl (based on 2-adamantyl chloride) shows marked dispersions into three separate curves for three aqueous mixtures. The extended Grunwald-Winstein plots for the solvolysis of TFMSC show better correlation. The large negative ${\Delta}S^{\neq}$ and relatively small positive ${\Delta}H^{\neq}$ reveals that the solvolytic reaction proceeds via a typical bimolecular reaction mechanism. The l and m values determined in various solvents are consistent with the proposed mechanism of the general base catalysis $S_AN/S_N2$reaction mechanism for TFMSC solvolyses based on mass law and stoichiometric solvation effect studies.

Influence of the Optical Characteristics and Conductive Mechanism depending on the Deposition Condition of BCP (BCP의 증착 조건에 따른 광학적 특성 및 전도 기구에 미치는 영향)

  • Kim, Weon-Jong;Hong, Jin-Woong
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.22 no.11
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    • pp.980-986
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    • 2009
  • In a triple-layered structure of ITO/N,N'-diph enyl-N,N'bis(3-methylphenyl)-1,1' - biphenyl-4,4'-diamine(TPD)/tris(8-hydroxyquinoline)aluminum($Alq_3$)/(2,9-Dimethyl-4,7-diphenyl-1,10-phenanthroline(BCP)/Al device, we have studied the electrical and optical characteristics of organic light-emitting diodes(OLEDs) depending on the deposition condition of BCP layer. Several different sizes of holes on boat and several different deposition rates were employed in evaporating the organic materials. And then, electrical properties of the organic light-emitting diodes were measured and the performance of the devices was analyzed. It was found that the hole-size of crucible boat and the evaporation rate affect on the surface roughness of BCP layer as well as the performance of the device. When the hole-size of crucible boat and the deposition rate of BCP are 1.2 mm and $1.0\;{\AA}/s$, respectively, average surface roughness of BCP layer is lower and the efficiency of the device is higher than the ones made with other conditions. From the analysis of current density-luminance-voltage characteristics of a triple layered device, we divided the conductive mechanism by four region according to applied voltage. So we have obtained a coefficient of ${\beta}_{ST}$ in schottky region is $3.85{\times}10^{-24}$, a coefficient of ${\beta}_{PF}$ in Poole-Frenkel region is $7.35{\times}10^{-24}$, and a potential barrier of ${\phi}_{FN}$ in Fower-Nordheim region is 0.39 eV.

Pyridinolysis of O-Aryl Phenylphosphonochloridothioates in Acetonitrile

  • Lumbiny, Bilkis Jahan;Adhikary, Keshab Kumar;Lee, Bon-Su;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.29 no.9
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    • pp.1769-1773
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    • 2008
  • fThe kinetics and mechanism of the reactions of Y-O-aryl phenylphosphonochloridothioates with X-pyridines are investigated in acetonitrile at 35.0 ${^{\circ}C}$. The negative value of the cross-interaction constant, $\rho$XY = −0.46, indicates that the reaction proceeds by concerted $S_N2$ mechanism. The observed $k_H/k_D$ values involving d-5 pyridine ($C_5D_5N$) nucleophiles are greater than unity (1.05-1.11). The net primary deuterium kinetic isotope effects, $(k_H/k_D)_{net}$ = 1.28-1.35, excluding the increased $pK_a$ effect of d-5 pyridine are obtained. The transition state with a hydrogen bond between the leaving group Cl and the hydrogen (deuterium) atom in the C-H(D) is suggested for the studied reaction system.

Sulphur Supply Level Effects on the Assimilation of Nitrate and Sulphate into Amino Acids and Protein in Forage Rape (Brassica napus L.)

  • Lee, Bok-Rye;Kim, Tae-Hwan
    • Journal of The Korean Society of Grassland and Forage Science
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    • v.32 no.4
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    • pp.343-352
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    • 2012
  • Sulphur deficiency has become widespread over the past several decades in most of the agricultural area. Oilseed rape (Brassica napus L.) is a very sensitive to S limitation which is becoming reduction of quality and productivity of forage. Few studies have assessed the sulphur mobilization in the source-sink relationship, very little is known about the regulatory mechanism in interaction between sulphur and nitrogen during the short-term sulphur deficiency. In this study, therefore, amount of sulphur and nitrogen incorporated into amino acids and proteins as affected by different S-supplied level (Control: 1 mM ${SO_4}^{2-}$, S-deficiency: 0.1 mM ${SO_4}^{2-}$, and S-deprivation: 0 mM ${SO_4}^{2-}$) were examined. The amount of sulphur in sulphate (S-sulphate) was significantly decreased by 25.8% in S-deprivation condition, compare to control, but not nitrogen in nitrate (N-nitrate). The markedly increase of sulphur and nitrogen incorporated amino acids (S-amino acids and N-amino acids) was observed in both S-deficiency and S-deprivation treatments. The amount of nitrogen incorporated proteins (N-protein) was strongly decreased as sulphur availability while the amount of sulphur incorporated into proteins (S-protein) was not affected. A highly significant ($p{\leq}0.001$) relationship between S-sulphate and S-amino acid was observed whereas the increase of N-amino acids is closely associated with decrease of N-proteins. These data indicate that increase of sulphur and nitrogen incorporated into amino acids was from different nitrogen and sulphur metabolites, respectively