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Kinetics and Mechanism of the Anilinolysis of Dicyclohexyl Phosphinic Chloride in Acetonitrile

  • Hoque, Md. Ehtesham Ul;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.32 no.6
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    • pp.1997-2002
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    • 2011
  • The nucleophilic substitution reactions of dicyclohexyl phosphinic chloride [3; $cHex_2$P(=O)Cl] with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at 60.0 $^{\circ}C$. The anilinolysis rate is too slow to be rationalized by the stereoelectronic effects. The rate is contrary to expectations for the electronic influence of the two ligands and exhibits exceptionally great negative deviation from the Taft's eq. The deuterium kinetic isotope effects (DKIEs) involving deuterated anilines invariably change from primary normal ($k_H/k_D$ > 1; max $k_H/k_D$ = 1.10 with X = 4-MeO) with the strongly basic anilines (X = 4-MeO, 4-Me, 3-Me) to secondary inverse ($k_H/k_D$ < 1; min $k_H/k_D$ = 0.673 with X = 3-Cl) with the weakly basic anilines (X = H, 4-F, 4-Cl, 3-Cl). A concerted $S_N2$ mechanism is proposed on the basis of both secondary inverse and primary normal DKIEs. The obtained DKIEs imply that the fraction of a frontside attack increases as the aniline becomes more basic. A hydrogen-bonded, four-center-type transition state is suggested for a frontside attack, while the trigonal bipyramidal pentacoordinate transition state is suggested for a backside attack.

Poly(Dimethylaminoethyl Methacrylate)-Based pH-Responsive Hydrogels Regulate Doxorubicin Release at Acidic Condition

  • Lee, Seung-Hun;You, Jin-Oh
    • Journal of the Korean Applied Science and Technology
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    • v.32 no.2
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    • pp.202-214
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    • 2015
  • Stimuli-responsive biomaterials that alter their function through sensing local molecular cues may enable technological advances in the fields of drug delivery, gene delivery, actuators, biosensors, and tissue engineering. In this research, pH-responsive hydrogel which is comprised of dimethylaminoethyl methacylate (DMAEMA) and 2-hydroxyethyl methacrylate (HEMA) was synthesized for the effective delivery of doxorubicin (Dox) to breast cancer cells. Cancer and tumor tissues show a lower extracellular pH than normal tissues. DMAEMA/HEMA hydrogels showed significant sensitivity by small pH changes and each formulation of hydrogels was examined by scanning electron microscopy, mechanical test, equilibrium mass swelling, controlled Dox release, and cytotoxicity. High swelling ratios and Dox release were obtained at low pH buffer condition, low cross-linker concentration, and high content of DMAEMA. Dox release was accelerated to 67.3% at pH 5.5 for 6-h incubation at $37^{\circ}C$, while it was limited to 13.8% at pH7.4 at the same time and temperature. Cell toxicity results to breast cancer cells indicate that pH-responsive DMAEMA/HEMA hydrogels may be used as an efficient matrix for anti-cancer drug delivery with various transporting manners. Also, pH-responsive DMAEMA/HEMA hydrogels may be useful in therapeutic treatment which is required a triggered release at low pH range such as gene delivery, ischemia, and diabetic ketoacidosis.

Kinetics and Mechanism of the Anilinolysis of Diisopropyl Chlorophosphate in Acetonitrile

  • Hoque, Md. Ehtesham Ul;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.32 no.9
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    • pp.3245-3250
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    • 2011
  • The nucleophilic substitution reactions of diisopropyl chlorophosphate (3) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $55.0^{\circ}C$. The anilinolysis rate of 3 is rather slow to be rationalized by the conventional stereoelectronic effects. The obtained deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are secondary inverse ($k_H/k_D$ = 0.71-0.95) with maximum magnitude at X = H.A concerted mechanism involving predominant backside nucleophilic attack is proposed on the basis of the secondary inverse DKIEs.

Effect of Cationic and Anionic Porphyrins on the Structure and Activity of Adenosine Deaminase

  • Ajloo, Davood;Hajipour, Samaneh;Saboury, Ali Akbar;Zakavi, Saeed
    • Bulletin of the Korean Chemical Society
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    • v.32 no.9
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    • pp.3411-3420
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    • 2011
  • Kinetic and structural studies have been carried out on the effects of meso-tetrakis(4-sulfonatophenyl)-porphyrin ($H_2TPPS_4$) as an anionic and meso-tetrakis(3-N-methyl-pyridyl)porphyrin ($H_2TMPYP$) as a cationic porphyrin with adenosine deaminase (ADA) in 25 mM citrate/phosphate buffer, pH = 4-8, at $37^{\circ}C$ using UVvis spectrophotometry, circular dichroism (CD), fluorescence spectrophotometry as well as molecular dynamics (MD) and molecular docking. Kinetic results showed that the two porphyrins are non-competitive inhibitors. Increasing pH, increases $K_I$ and cationic porphyrin has a higher $K_I$ and lower binding constant ($K_b$) at all pH ranges. Analyzing the secondary structure revealed that both ligands decrease the secondary structure and that the anionic porphyrin is more effective.

Kinetics and Mechanism of the Anilinolysis of Diethyl Thiophosphinic Chloride in Acetonitrile

  • Hoque, Md. Ehtesham Ul;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.32 no.7
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    • pp.2306-2310
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    • 2011
  • The nucleophilic substitution reactions of diethyl thiophosphinic chloride with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at 55.0 $^{\circ}C$. The values of deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) invariably increase from secondary inverse ($k_H/k_D$ < 1) to primary normal (kH/kD > 1) as the nucleophiles change from the strongly basic to weakly basic anilines. The secondary inverse with the strongly basic anilines and primary normal DKIEs with the weakly basic anilines are rationalized by the gradual transition state (TS) variation from a predominant backside attack, via invariably increasing the fraction of a frontside attack, to a predominant frontside attack, in which the reaction mechanism is a concerted $S_N2$ pathway. A frontside attack involving a hydrogen bonded, four-center-type TS is substantiated by the primary normal DKIEs.

Effcts of pH, sodium chloride and potassium sorbate on the germination of Bacillus cereus spores in cooked rice homogenate (Bacills cereus 포자에 대한 pH, 식염 및 솔빈산 칼륨의 영향)

  • Lee Myeong Sook;Choi Jong Duck;Chang Dong Suck
    • Korean Journal of Fisheries and Aquatic Sciences
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    • v.16 no.1
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    • pp.37-43
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    • 1983
  • The effects of pH, sodium chloride and potassium sorbate on the germination of Bacillus cereus spores in the medium of cooked rice homogenate were studied. At the range of pH $4.5{\sim}10.0$, the germination of spores were observed. Germinated spores were reached to the number of $10^7/ml$ within 5 hours at $32^{\circ}C$ under the condition of pH 7.0, which was found as optimum pH of germination. In the range of sodium chloride $2{\sim}10\%$, the maximum growth were exhibited under $2\%$ concentration, while it proportionally decreased under the salinity condition higher than $5\%$. The growth of Bacillus cereus were inversely related to the concentration of potassium sorbate within the range of $0{\sim}0.2\%$. Maximum sporulation ratio was observed under the culturing condition: $10\%$ NaCl and $0.2\%$ potassium sorbate in the medium of cooked rice homogenate.

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Environmentally Friendly Phytal Animal Removal for Re-use of Holdfasts of Sargassum fusiforme (Harvey) Setchell: pH and Salinity (갈조류 톳의 포복지 재활용을 위한 친환경적 해적생물 구제: pH와 염분)

  • Hwang, Eun Kyoung;Yoo, Ho Chang;Kim, Se Mi;Yoo, Hyun Il;Baek, Jae Min;Park, Chan Sun
    • Korean Journal of Environmental Biology
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    • v.32 no.4
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    • pp.306-310
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    • 2014
  • The brown seaweed Sargassum fusiforme is an edible and highly valued in Korea. During the summer season, phytal organisms graze heavily on young algal blades and holdfastsof the species and substantially reduce harvestable biomass. Here, in this study, we investigated the effects of pH (range: 2~13) and salinity (range: 0~44 psu) on the removal of two major phytal animals, Caprella scaura and Gammaropsis utinomi, associated with S. fusiforme. We also examined the optimum quantum yield (Fv/Fm) of algae in the same experimental conditions to quantify the tolerance of algae to acid and salinity treatments. It was observed that the phytal animals showed more than 80% mortality at pH lower that pH 4 and the extreams of salinity (0~10 psu and 44 psu) after a 5 min of immersion. However, the quantum yield of S. fusiforme was not significantly different from controls within the pH 3~11 range, and the 0~44 psu salinity range. Precisely, if the pH and salinity conditions outside these ranges were used in comercial Sargassum culture, the removal of the animal species would be higher, but with reduced quantum yield of algae. Taken together, our study results indicated that the pH and salinity treatments could allow multiple harvests from the same holdfast of S. fusiforme.

Pharmacokinetics of oxytetracycline in olive flounder (Paralichthys olivaceus) by dipping and oral administration (Oxytetracycline의 약욕 및 경구투여에 따른 넙치(Paralichthys olivaceus) 체내 약물동태학적 특성)

  • Jung, Sung-Hee;Choi, Dong-Lim;Kim, Jin-Woo;Jo, Mi-Ra;Seo, Jung-Soo;Jee, Bo-Young
    • Journal of fish pathology
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    • v.21 no.2
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    • pp.107-117
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    • 2008
  • The pharmacokinetic properties of oxytetracycline (OTC) were studied after dipping and oral administration to cultured olive flounder, Paralichthys olivaceus (600 g). Plasma concentrations of OTC were determined after oral dosage (50, 100 and 200 mg/kg body weight) and dipping (50, 100 and 200 ppm, 1 h) in olive flounder (average 600 g, 23±1℃). Plasma samples were taken at 3, 5, 10, 15, 24, 32, 48, 72, 120, 168 and 240 h post-dose. In oral dosage of 50, 100 and 200 mg/kg, the peak plasma concentrations of OTC, which attained at 3 h post-dose, were 0.34, 0.44 and 1.18 ㎍/㎖, respectively. In dipping of 50, 100 and 200 ppm, those of OTC which also observed at 5 h post-dose, were 0.43, 0.38 and 0.64 ㎍/㎖, respectively. Plasma concentrations of OTC were not measurable at 240 h post-dose in all experiments. The kinetic profile of absorption, distribution and elimination of OTC in plasma were analyzed fitting to a one-compartment model by WinNonlin program. The following parameters were calculated for a single dosage of 50, 100 and 200 mg/kg body weight, respectively: AUC (the area under the concentration-time curve)=31.40, 28.07 and 32.97 ㎍∙h/㎖; T1/2 (half-life)􀆫0.89, 1.12 and 0.43 h; Tmax (time for maximum concentration)= 5.25, 3.70 and 7.30 h, Cmax (maximum concentration)=0.25, 0.38 and 0.61 ㎕/㎖. Following dipping at 50, 100 and 200 ppm, these parameters were AUC􀆫15.51, 14.63 and 19.72 ㎍∙h/㎖; T1/2= 0.75, 0.41 and 0.74 h; Tmax=4.90, 7.08 and 4.68 h, Cmax=0.40, 0.32 and 0.46 ㎕/㎖.

The Influence of Optical Porosity of Tree Windbreaks on Windward Wind Speed, Erosive Force and Sand Deposition

  • Dafa-Alla, M.D.;Al-Amin, Nawal K.N.
    • Journal of Forest and Environmental Science
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    • v.32 no.2
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    • pp.212-218
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    • 2016
  • The research was conducted windward of an irrigated Acacia amplicips Maslin windbreak established to protect As Salam Cement Plant from winds and moving sands. Two belts with approximate optical porosities of 50% and 20% were studied in River Nile State, Sudan. The research aimed at assessing the efficiency of the two belts in wind speed reduction and sand deposition. Research methods included: (i) estimation of optical porosity, (ii) measurements of windward wind speeds at a control and at distances of 0.5 h (h stands for windbreak height), 1 h and 2 h at two vertical levels of 0.25 h and 0.5 h, (iii) estimation of relative wind speeds at the three positions (distance and height) at windward and (iv) estimation of wind erosive forces and prediction of zones of sand deposition. Results show that while the two belts reduced windward wind speeds at the two levels for the three distances, belt II was more effective. Nearest sand deposition occurred at 2 h and 1h windward of belt II and belt I, respectively, at level 0.25 h. At level 0.5 h, sand was deposited only at 2 h windward of belt II and no sand deposition occurred windward of belt I. The study concludes that less porous windbreaks are more effective in reducing wind speed and in depositing sand in windward direction at a distance of not less than twice the belt height.

Quality Characteristics of Salted Tomato Powder (가염 토마토 분말의 품질특성에 관한 연구)

  • Cho, Sung-Hyun;Yoo, Seung-Seok
    • Korean journal of food and cookery science
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    • v.32 no.2
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    • pp.211-221
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    • 2016
  • Purpose: This study was conducted to investigate the physical and sensory properties of seasoned powders utilizing tomato. Methods: Tests of salted tomato powder were performed for the physiochemical properties (moisture content, pH value, titratable acidity, color value, salinity content, and solubility content), sensory characteristics and sensory preference. Results: Moisture content of salted tomato powder containing fully ripened tomato (RT) was higher than that of salted tomato powder containing cherry tomato (CT), with the exception of CT 10%. The pH values of RT was relatively high and increased salt addition increased the pH as well. The titratable acidity was opposite the result of pH measurement. The color values of RT was higher than that of CT for the L, a, and b values. The salt content of RT was higher than that of CT. RT 10% showed the highest dissolution followed by CT 10%. In addition, the sensory preference for CT 10% was the highest, with the best scores for appearance and taste. Conclusion: It was concluded that 10% salt addition is the most suitable sensually for the manufacture of salted tomato powder.