• 대한화학회지
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• 제38권5호
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• pp.391-396
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• 1994

강산성 용액에서 $\alpha$-벤족시스티렌(1)의 가수분해를 속도론적으로 다루었다. 과염소산이 5.5M보다 낮은 농도($H_o$ < -3.0)에서 수화파라메타 $\omega$ = + 7.6, $\Phi$ = + 0.54를 얻었다. 용매동위원소효과 $k_{H_2O}/k_{D_2O}$는 0.72였고, Hammett $\sigma^+$ 상수에 대한 치환기 효과 $\rho$ = -0.60이었다. 이 결과와 다른 증거로부터 이 산도 범위에서 엔올에스테르의 가수분해는 $A_{AL}$2 형태의 메카니즘에 의해 진행되었다. 과염소산 농도가 5.5 M 이상에서는 동위원소효과, $k_{H_2O}/_{D_2O}$는 3.32이었고, 치환기 효과, $\rho$=-1.6이었으며, 속도상수는 산도함수, $H_o$에 비례하였다. 따라서 반응메카니즘은 변하여 올레핀이 양성자화되는 첫단계가 속도결정단계가 된다.

• Biotechnology and Bioprocess Engineering:BBE
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• 제6권2호
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• pp.89-94
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• 2001

The binding of cellobiohydrolases to cullulose is a crucial initial step in cellulose hydrolysis. In the search for a detailed understanding of the function of cellobiohydrolases, much information concerning how the enzymes and their constituent catalytic and cellulose-binding changes during hydrolysis is still needed. The adsorption of purified two cellobiohydrolases (Ce17A and Ce16A) from Trichoderma reesei cellulase to microcrystalline cellulose has been studied. Cellobiohydrolase II (Ce16A) does not affect the adsorption of cellobiohydrolase I (Ce17A) significantly, and there are specific binding sites for both Ce17A and Ce16A. The adsorption affinity and tightness of the cullulase binding domain (CBD) for Ce17A are larger than those of the CBD for Ce16A. The CBD for Ce17A binds more rapidly and tightly to Avicel than the CBD for Ce16A. The decrease in adsorption observed when the two cellobihydrolases are studied together would appear to be the result of competition for binding sites on the cellulose. Ce17A competes more efficiently for binding sites than Ce16A. Competition for binding sites is the dominating factor when the two enzymes are acting together, furthermore adsorption to sites specific for Ce17A and Ce16A, also contributes to the total adsorption.

• Environmental Engineering Research
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• 제24권3호
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• pp.449-455
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• 2019

To investigate the effect of seaweed (SW) addition on anaerobic co-digestion of food waste (FW) and sewage sludge (SS), batch experiments were conducted at various substrate concentrations (2.5, 5.0, 7.5, and 10.0 g volatile solids (VS)/L) and mixing ratios ((FW or SS):SW = 100:0, 75:25, 50:50, 25:75, and 0:100 on a VS basis). The effect of SW addition on FW digestion was negligible at low substrate concentration, while it was substantial at high substrate concentrations by balancing the rate of acidogenesis and methanogenesis. At 10 g VS/L, $CH_4$ production yield was increased from 103 to $350mL\;CH_4/g$ VS by SW addition (FW:SW = 75:25). On the other hand, SW addition to SS enhanced the digestion performance at all substrate concentrations, by providing easily biodegradable organics, which promoted the hydrolysis of SS. $k_{hyd}$ (hydrolysis constant) value was increased from 0.19 to $0.28d^{-1}$ by SW addition. The calculation showed that the synergistic $CH_4$ production increment by co-digesting with SW accounted for up to 24% and 20% of total amount of $CH_4$ production in digesting FW and SS, respectively.

• 대한화학회지
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• 제30권3호
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• pp.307-311
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• 1986

착물 $trans^-[Cr(en)_2F(H_2O)]^{2+}$의 hydrolysis에 대한 속도상수를 분광광도법으로 여러가지 온도와 압력에서 측정하였다. 온도 범위는 30${\circ}C$ ~ 50${\circ}C$까지이고 압력은 1bar에서 1500bar까지 변화시켰다. 1bar, 30${\circ}C$에서 측정된 속도상수는 $2.632{\times}10^{-5}sec^{-1}$였다. 속도상수는 일정온도에서 압력이 증가함에 따라 감소하였다. 활성화 부피와 다른 활성화 파라미터들은 이러한 속도상수로 부터 계산되었다. 활성화 부피는 모두 양의 값을 가졌으며 0.447에서 3.152$cm^3$/mol내에 있고, 활성화 엔트로피는 작은 값을 가진다. 이 반응은 흡열반응이고, 실험적인 온도에서 엔탈피 지배 반응이다.

• 한국군사과학기술학회지
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• 제3권1호
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• pp.164-175
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• 2000

Three compounds of Cu(II)-loaded N,N,N'-trimethylethylenediaminated Merrifield-type polymers were synthesized with yields higher than 80%, and the hydrolysis reaction rates of O-isopropylmethyl-phosphonofluoridate(GB) and O-pinacolylmethylphosphonofluoridate (GD) catalyzed by them have been surveyed. GB and GD hydrolysis by Cu(II)-loaded polymers occurs via intermediate complex mechanism where rapid equilibrium to form intermediate complex between substrate and Cu(II)-loaded polymers($K_f$) is followed by rate determining hydrolysis step($k_1$). The measured activation parameters for $k_1$ are ${\Delta}H^{\ddag}$ : $17.75{\pm}0.98kJ/mol$ ${\Delta}S^{\ddag}$ / : $-218.42{\pm}3.35J/mol$ K, $E^{\circ}_a$ : $20.22{\pm}0.98kJ/mo1$ for GB and ${\Delta}H^{\ddag}$ / : $11.16{\pm}1.15kJ/mol,$${\Delta}S^{\ddag}$ /: $-258.57{\pm}3.93J/mol$ K, $E^{\circ}_a$ : $13.64{\pm}1.15 kJ/mol$ for GD. Standard enthalpy/entropy changes corresponding to the intermediate complex formation constant $K_f$ are ${\Delta}H^{\circ}$ : $37.05{\pm}2.19 kJ/mo1,$$ {\Delta}S^{\circ}$ : $163.12{\pm}7.49 J/mol$ K and ${\Delta}H^{\circ}$ : 418.59{\pm}2.04 kJ/mol,$ ${\Delta}S^{\circ}$ : 4111.92{\pm}6.98 J/mol$ K for GB and GD, respectively, The electron push-pull mechanism by Cu(II)-loaded polymers lowers the P-F bond breaking energy(~400 kJ/mol) to less than 1/20 compared to the case in which no Cu(II)-loaded resin presents. Analysis of $K_f$ and 4k_1$ over pH=6.5~8.0 range suggest that the GB and GD hydrolysis occurs intramolecularily with $pK_a$ =7.29 for ligated $H_2O$ and $t_{1/2}$=36.9 sec, $pK_a$ = 7.06 and $t_{1/2}$=177.7 sec for GB and GD, respectively.

• Environmental Analysis Health and Toxicology
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• 제19권1호
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• pp.33-40
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• 2004

Benzoyl peroxide is a High Production Volume Chemical, which is produced about 1,371 tons/year in Korea as of 2001 survey. The substance is mainly used as initiators in polymerization, catalysts in the plastics industry, bleaching agents for flour and medication for acne vulgaris. In this study, Quantitative Structure-Activity Relationships (QSAR) are used for getting adequate information on the physical -chemical properties of this chemical. And hydrolysis in water, acute toxicity to aquatic and terrestrial organisms for benzoyl peroxide were studied. The physical -chemical properties of benzoyl peroxide were estimated as followed; vapor pressure=0.00929 Pa, Log $K_{ow}$ = 3.43, Henry's Law constant=3.54${\times}$10$^{-6}$ atm-㎥/mole at $25^{\circ}C$, the half-life of photodegradation=3 days and bioconcentration factor (BCF)=92. Hydrolysis half-life of benzoyl peroxide in water was 5.2 hr at pH 7 at $25^{\circ}C$ and according to the structure of this substance hydrolysis product was expected to benzoic acid. Benzoyl peroxide has toxic effects on the aquatic organisms. 72 hr-Er $C_{50}$ (growth rate) for algae was 0.44 mg/1.,48 hr-E $C_{50}$ for daphnia was 0.07mg/L and the 96hr-L $C_{50}$ of acute toxicity to fish was 0.24mg/L. Acute toxicity to terrestrial organisms (earth worm) of benzoyl peroxide was low (14 day-L $C_{50}$ = > 1,000 mg/kg). Although benzoyl peroxide is high toxic to aquatic organisms, the substance if not bioaccumulated because of the rapid removal by hydrolysis (half-life=5.2 hr at pH 7 at $25^{\circ}C$) and biodegradation (83% by BOD after 21 days). The toxicity observed is assumed to be due to benzoyl peroxide rather than benzoic acid, which shows much lower toxicity to aquatic organisms. One can assume that effects occur before hydrolysis takes place. From the acute toxicity value of algae, daphnia and fish, an assessment factor of 100 was used to determine the predicted no effect concentration (PNEC). The PNEC was calculated to be 0.7$\mu\textrm{g}$/L based on the 48 hr-E $C_{50}$ daphnia (0.07 mg/L). The substance shows high acute toxicity to aquatic organisms and some information indicates wide-dispersive ore of this substance. So this substance is, a candidate for further work, even if it hydrolysis rapidly and has a low bioaccumulation potential. This could lead to local concern for the aquatic environment and therefore environmental exposure assessment is recommended.

• 에너지공학
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• 제14권2호
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• pp.105-111
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• 2005

본 연구는 마이크로 채널 반응기를 이용하여 다양한 실험조건에서 D-glucose용액을 이용하여 광촉매 분해특성을 연구하였다. Titanium oxysulfate의 수산화반응을 통하여 합성한 $TiO_2$수용액을 이용하여 마이크로 채널 반응기에 $TiO_2$를 코팅하였다. D-glucose광촉매 분해특성은 반응기의 주입유속이 증가함에 따라 증가하는 것으로 나타났으며 반응속도 상수와 Langmuir 흡수 제수를 다양한 실험조건에서 계산하였다. 또한 반응 시스템에서의 광효율을 계산하였다 따라서 이 연구는 배치 시스템에 적용된 $TiO_2$코팅이 되어 있는 마이크로 채널 반응기의 광분해 특성을 이해하기 위한 것이다.

• 한국미생물·생명공학회지
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• 제15권2호
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• pp.122-128
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• 1987

Candida rugosa와 Rhizopus arrhizus 리파제를 photocrosslinkable resin prepolymer에 고정화시켜서 이소옥탄을 유기용매로 사용한 이상계를 이용해서 유지분해 및 에스테르교환 반응을 보고자했다. Dioctylsulfosuccinate가 가장 좋은 surfactant였다. 소수성 젤인 ENTP-3000에 고정된 리파제가 좋은 활성을 나타냈고 친수성 젤인 ENT-4000에 고정된 리파제가 유기용매에 대해 안정했다. 고정화 matrix의 소수성이 증가될수록Vm(app)는 증가되었으나 Km(app)는 거의 일정했다. 리파제의 최적 pH는 소수성 젤인 ENTP-3000에 고정된 경우 C. rugosa와 R. arrhizus 리파제에 대해서 각각 6.0과 6.5였으나, 친수성 젤에 고정된 리파제는 짧은 시간 반응에는 pH에 크게 영향을 받지 않았으나 긴 시간 동안 반응시킬 때는 역시 pH6.0과 6.5에서 각각 C. rugosa와 R. arrhizus 리파제가 높은 양의 지방산을 분해시켰다. 리파제를 entrapment 시키면 열안정성이 증가됨을 알 수 있었다.

• 대한화학회지
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• 제54권2호
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• pp.208-214
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• 2010

포스포리파제 D(PLD)는 알코올 존재 하에서 포스파티딜 전달반응이 일어나며 동시에 PLD의 전체 반응속도도 증가하는 것으로 알려져 있다. 이 포스파티딜 전달반응을 자세히 구명하기위해 본 실험에서는 양배추에서 정제한 ${\alpha}$-type PLD를 가지고 여러 종류의 알코올 존재 하에서 포스파티딜 전달반응의 반응속도를 검토하였다. 실험 결과 검토한 1차 알코올들에 의해 PLD의 포스파티딜 전달반응 속도는 기대했던 대로 크게 증가하였다. 부탄올의 경우 2차 반응속도는 $33.33{\pm}1.33M^{-1}sec^{-1}$로 얻어졌으며, 이 전달반응 속도를 물의 농도를 고려한 가수분해 속도($0.078M^{-1}sec^{-1}$)와 비교하면 무려 400배 이상의 격차를 보여주었다. 알코올의 $pK_a$과 포스파티딜 전달반응 속도와의 자유에너지 선형 관계로부터 브뢴스테드 ${\beta}_{nu}$ 값 $0.12{\pm}0.03$을 얻었다. 비교적 적은 ${\beta}_{nu}$ 값으로 미루어보아 끊어지는 포스파티딜-효소 중간체(E-P)의 전이상태는 상당히 해리된 상태일 것으로 추정된다. 이들 결과와 양배추 PLD의 활성부위의 히스티딘 잔기를 참작하여 양배추 PLD의 반응메커니즘을 제안하였다.

• 약학회지
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• 제23권3_4호
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• pp.147-152
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• 1979

Experiments were carried out to investigate for the interaction between FAD solution and synthetic resin containers made of polyvinylchloride(PVC), polyethylene(PE), and polycarbonate(PC), and for the effect of glycyrrhizine or malic acid on stabilization of FAD in aqueous solution by accelerated stability analysis. Analysis of FAD was determined by means of spectrometer and by separating by paper chromatography and metal ions were detected by atomic absorption spectrophotometer, which were extracted from containers by means of Food and Additive Regulation Standard. The thermal decomposition of FAD in aqueous solution was pseudo first order reaction and it was inhibited by adding glycyrrhizine or malic into the solution. PVC, PE and PC containers accelerated the decomposition of FAD in solution. It is assumed that bivalent heavy metals in resin containers may catalize the hydrolysis of FAD. The metals detected from the containers were Ca, Zn, Cu, Fe, Pb and Cd. And the total amounts of detected metals from PVC were 6.2mcg/cm$^{2}$, PE, 5.5mcg/cm$^{2}$, and PC, 2.7mcg/cm$^{2}$ which were proportional to the rate constant of FAD decomposition in aqueous solution.