Critical Mole Fraction Research Articles

Suppression of fuel and air stream diluted methane–air partially premixed flames in normal and microgravity

The effects of fuel and air stream dilution (ASD) with carbon dioxide on the suppression of normal and microgravity laminar methane–air partially premixed coflow jet flames were experimentally and numerically investigated. Experiments were conducted both in our normal-gravity laboratory and at the NASA Glenn Research Center 2.2 s drop tower. Measurements included flame topology and liftoff heights of diluted flames, critical diluent mole fractions for flame blowout, and the radiant heat loss from flames. The flames were also simulated using an axisymmetric unsteady numerical code that utilizes detailed chemistry and transport models. In addition, counterflow flame simulation results were used to examine similitude between the counterflow and coflow flame suppression, and further characterize the effectiveness of fuel stream versus ASD on flame extinction. A smaller relative fuel stream dilution (FSD) extinguishes partially premixed flames (PPFs) with increasing premixing as compared to dilution of the air stream. Conversely, smaller ASD is required to extinguish PPFs as they become less premixed and approach nonpremixed (NP) behavior. Fuel stream diluted PPFs and air stream diluted NP flames extinguish primarily through a reactant dilution effect while fuel stream diluted NP flames and air stream diluted PPF are extinguished primarily by a thermal cooling effect. Normal gravity flames lift off and blow out with a smaller diluent mole fraction than microgravity flames. The difference between the fuel and ASD effectiveness increases as the gravitational acceleration is reduced. Radiation heat losses are observed to increase with increasing diluent mole fraction and decreasing gravity.

Activity coefficients at infinite dilution for surfactants

A new alternative is presented for activity coefficients at infinite dilution determination via surface tension data of low vapour pressure substances. It was found that experimental data for surfactants follows Volmer's surface equation of state behaviour over the diluted region until the critical micelle concentration. The key operations are: the choice of the same standard conditions for the bulk and the surface phases, the combination of Gibbs and Volmer equations and the use of the symmetric activity coefficients convention. An exact relation between the activity coefficient at infinite dilution and the reciprocal of the critical micelle mole fraction was found which allowed us the verification of the model.

Modulation of Reconstituted Pig Kidney Na+/K+-ATPase Activity by Cholesterol in Endogenous Lipid Vesicles: Role of Lipid Domains

Diverse experimental and theoretical evidence suggests that plasma membranes contain cholesterol-induced segregated domains that could play a key role in the modulation of membrane functions, including intrinsic enzyme activity. To gain insight into the role of cholesterol, we reconstituted pig kidney Na+/K+-ATPase into unilamellar vesicles of endogenous lipids mimicking the natural membrane and addressed the question of how modification of the cholesterol content could affect the ATPase activity via changes in the membrane lipid phase and in the protein structure and dynamics. We used steady-state and time-resolved fluorescence spectroscopy with the lipid phase probes DPH and Laurdan and the protein probe fluorescein and also used infrared spectroscopy using attenuated total reflectance. Upon modification of membrane cholesterol content, the ATPase activity did not change monotonically but instead exhibited abrupt changes resulting in two peaks at or close to critical cholesterol mole fractions (25 and 33.3 mol %) predicted by the superlattice or regular distribution model. Fluorescence parameters associated with the membrane probes also showed abrupt changes with peaks, coincident with the cholesterol concentrations associated with the peaks in the enzyme activity, while parameters associated with the protein probes also showed slight but abrupt changes resulting in dips at the same cholesterol concentrations. Notably, the IR amide I band maximum also showed spectral shifts, characterized by a frequency variation pattern with peaks at the same cholesterol concentrations. Overall, these results indicate that the lipid phase had slightly lower hydration, at or near the two critical cholesterol concentrations predicted by the superlattice theory. However, in the protein domains monitored there was a slight but significant hydration increase along with increased peptide backbone flexibility at these cholesterol concentrations. We propose that in the vicinity of the critical mole fractions, where superlattice formation can occur, minute changes in cholesterol concentration produce abrupt changes in the membrane organization, increasing interdomain surfaces. These changes, in turn, induce small changes in the protein's structure and dynamics, therefore acting to fine-tune the enzyme.

이산화탄소로 희석된 메탄-공기 확산화염의 에지화염 불안정성

Experiments in low strain rate methane-air counterflow diffusion flames diluted with CO₂ have been conducted to investigate the flame extinction behavior and edge flame oscillation in which flame length is less than the burner diameter and thus lateral conductive heat loss in addition to radiative loss could be remarkable at low global strain rates. The critical mole fraction at flame extinction is examined in terms of velocity ratio and global strain rate. It is seen that flame length is closely relevant to lateral heat loss, and this affects flame extinction and edge flame oscillation considerably. Lateral heat loss causes flame oscillation even at fuel Lewis number less than unity. Edge flame oscillations are categorized into three: a growing-, a harmonic- and a decaying-oscillation mode. Onset conditions of the edge flame oscillation and the relevant modes are examined with global strain rate and CO₂ mole fraction in fuel stream. A flame stability map based on the flame oscillation modes is also provided at low strain rate flames.

Edge flame instability in low-strain-rate counterflow diffusion flames

Experiments in low-strain-rate methane–air counterflow diffusion flames diluted with nitrogen have been conducted to study flame extinction behavior and edge flame oscillation in which flame length is less than the burner diameter and thus lateral conductive heat loss, in addition to radiative loss, could be high at low global strain rates. The critical mole fraction at flame extinction is examined in terms of velocity ratio and global strain rate. Onset conditions of the edge flame oscillation and the relevant modes are also provided with global strain rate and nitrogen mole fraction in the fuel stream or in terms of fuel Lewis number. It is observed that flame length is intimately relevant to lateral heat loss, and this affects flame extinction and edge flame oscillation considerably. Lateral heat loss causes flame oscillation even at fuel Lewis number less than unity. Edge flame oscillations, which result from the advancing and retreating edge flame motion of the outer flame edge of low-strain-rate flames, are categorized into three modes: a growing, a decaying, and a harmonic-oscillation mode. A flame stability map based on the flame oscillation modes is also provided for low-strain-rate flames. The important contribution of lateral heat loss even to edge flame oscillation is clarified finally.

Experimentally determined growth exponents during the late stage of spinodal demixing in binary liquid mixtures

Spinodal demixing was initiated in two systems, with critical and off-critical compositions, using nanosecond pulsed laser-induced temperature jumps (T-jumps) of various magnitude. In this way, deep quenches could be imposed on the systems. One system was the simple triethylamine (TEA)/water mixture and the other was the ionic mixture of 2-butoxyethanol (2BE)/water/KCl. The demixing process was followed using the technique of nanosecond time-resolved microscopic shadowgraphy. The growth of the evolving phase-separated domains followed a simple power law with respect to time in every case. For a given composition, the magnitude of the T-jump had little effect on the growth exponent, however the composition was found to influence the rate of domain growth. At off-critical mole fractions of 0.2 with respect to TEA, the domains grew according to the following expression: L(t)=t(0.70) (where L(t)= the domain size) whereas at the critical TEA mole fraction of 0.08 the domains grew as L(t)=t(0.52). 2BE/water/KCl mixtures quenched at the just off-critical composition of fraction with respect to 2BE evolved as L(t)=t(0.63). These results will be compared to theoretical models and simulations and discussed in terms of estimated Reynolds numbers as well as the consumption and conversion of the available surface energy that fuels the demixing process.

Dielectric relaxation processes in water mixtures of tripropylene glycol

Broadband dielectric measurements for anhydrous tripropylene glycol (3PG) and 96, 92, 84, 80, 74, 71, and 68 wt % 3PG-water mixtures are performed in the frequency range of 10(-2)-10(7) Hz and in the temperature range of 123-243 K. We examined the effect of adding water into anhydrous 3PG on relaxation dynamics. Apart from the two well-known relaxation processes, i.e., alpha and beta for anhydrous 3PG we observed new relaxation peak (beta') for all aqueous mixtures of 3PG. In addition we found the critical mole fraction of water x(w)=0.67 in which relaxation dynamics changes its behavior. According to the Sudo approach [S. Sudo et al., J. Non-Cryst. Solids 307-310, 356 (2002)], the behavior of relaxation processes was interpreted assuming the existence of three kinds of cooperative domains (CDs): containing only 3PG molecules, including only water molecules, and including both 3PG and water molecules, which molecules of each kind CD are bound by hydrogen bonds.

Studies of dynamic interactions between a pyrene-labeled polyelectrolyte and an oppositely charged rodlike micelle by a fluorescence quenching technique with use of a hydrophobic quencher

Electrostatic interactions of poly(sodium 2-(acrylamido)-2-methylpropanesulfonate) (PyPAMPS) labeled with pyrene and a rodlike micelle of dimethyloleylamine oxide (DMOAO), an amine oxide type surfactant, mixed with varying mole fractions (Y) of hexadecyltrimethylammonium chloride (CTAC), a cationic surfactant, were investigated by a fluorescence quenching technique using 3,4′-dimethylbenzophenone (DBP), a hydrophobic quencher, that can only reside in the micellar phase. Fluorescence measurements were performed under homogeneous conditions in the region 0<Y<Yp, where Yp is the critical mole fraction of CTAC at which macroscopic phase separation of resulting polymer–micelle complexes occurs. There was no fluorescence quenching and hence no interaction occurred between PyPAMPS and the DMOAO/CTAC mixed micelle when Y was below a certain value (Yc) depending on the ionic strength (μ), e.g., Yc≈0.005 at μ=0.05. When Y>Yc, the fluorescence was efficiently quenched by DBP-carrying DMOAO/CTAC mixed micelles, both steady-state and time-dependent fluorescence data indicating that the degree of the quenching and hence the extent of the complex formation increased significantly with increasing Y. Applying a kinetic model to the steady-state and time-dependent fluorescence data, the residence time for PyPAMPS in the polymer–micelle complex was calculated. The residence time was found to depend on both Y and μ, e.g., when Y was increased from 0.01 to 0.03, the residence time increased from 4 to 80 μs at μ=0.05 whereas little or no increase in the residence time was observed in this range of Y at μ=0.20. At this higher ionic strength, the residence time increased only moderately from 3 to 10 μs when Y was increased from 0.01 to 0.09.

Thermal analysis of γ-butyrolactone + 1 butyl-3-methyl-imidazolium ionic liquids mixtures

Thermal properties of mixtures of γ-butyrolactone (BL) with 1-butyl-3-methyl-imidazolium tetrafluoroborate (BMIBF4) or hexafluorophosphate (BMIPF6) have been investigated from −120 °C to 400 °C by differential scanning calorimetry (DSC) and X-ray Diffraction (XRD). From the result of these experiments, the liquid–solid phase diagrams of these mixtures have been inferred. The phase diagrams obtained with the two anions are similar but differ strongly from those obtained for organic solvent mixtures. The apparition of a vitreous phase is observed when the mole fraction in ionic liquid is higher than a critical mole fraction (xcritic). From this value, the number of solvent molecules in the solvation shell of BMI+ ion has been evaluated. Thermal analysis of the mixtures at high temperature have been run and show that the thermal decomposition is strongly dependent on the nature of the anion and that BL-BMIBF4 mixtures are more stable than BL-BMIPF6 mixtures at high temperature.

Role of Sterol Superlattice in Free Radical-Induced Sterol Oxidation in Lipid Membranes

We developed a new fluorescence assay for sterol oxidation and used it to study the relationship between free radical-induced sterol oxidation and membrane sterol lateral organization. This assay used dehydroergosterol (DHE) as both a membrane probe and a membrane component. Sterol oxidation was induced by a free radical generator, AAPH (2,2'-azobis(2-amidinopropane)dihydrochloride). Using this new assay, we found that, in unilamellar vesicles composed of DHE and 1-palmitoyl-2-oleoyl-l-alpha-phosphatidylcholine (POPC), the initial rate of DHE oxidation induced by AAPH changed with membrane sterol content in an alternating manner, exhibiting a local maximum at 20.3, 22.2, 25.0, 32.3, and 40.0 mol % DHE. These mole fractions correspond to the critical sterol mole fractions C(r) predicted for maximal sterol superlattice formation. In three-component bilayers composed of POPC, cholesterol, and DHE (fixed at 1 and 5 mol %), the initial rate of AAPH-induced DHE oxidation exhibited a biphasic change whenever the total sterol mole fraction, irrespective of the DHE content, was near C(r), indicating that the correlation between sterol oxidation and sterol superlattice formation revealed in this study is not an artifact due to the use of the fluorescent cholesterol analogue DHE. The alternating variation of AAPH-induced sterol oxidation with sterol content also appeared in multicomponent unilamellar vesicles containing bovine brain sphingomyelins (bbSPM), POPC, and DHE. The present work and our previous study on cholesterol oxidase-induced sterol oxidation [Wang et al. (2004) Biochemistry 43, 2159-2166] suggest that sterol oxidation in general, either by reactive oxygen species or by enzymes, may be regulated by the extent of sterol superlattice in the membrane and thus regulated by the membrane sterol content in a fine-tuning manner.

Adsorption of biopolymers at hydrophilic cellulose–water interface

The extent of adsorption (Gamma2(1)) of bovine serum albumin (BSA), beta-lactoglobulin, lysozyme, gelatin, and DNA from aqueous solution onto the hydrophilic surface of cellulose has been measured as function of biopolymer concentration at different temperatures, pHs, and ionic strengths, and in the presence of a high concentration of inorganic salts and denaturants. In all cases, the value of Gamma2(1) increases with the increase of biopolymer concentration (X2) in bulk and it attains a maximum value at a critical mole fraction concentration X2m. The value of Gamma2m depends upon the nature of protein, temperature, pH, and ionic strength, as well as the nature of neutral salts present in excess. Gamma2m for proteins at a fixed physicochemical condition stands in the following order: Gelatin>betalactoglobulin>lysozyme>BSA. The isotherms for adsorption of DNA nucleotides on cellulose surface at pH 4.0 have been compared at different temperatures and ionic strengths, and in the presence of high concentration of inorganic salts LiCl, NaCl, KCl, and Na2SO4. Values of Gamma2m for different systems have been evaluated and critically compared. At pH 6.0 and 8.0, Gamma2(1) values of DNA nucleotides on cellulose are all negative due to the excess positive hydration of cellulose. At pH 4.0, adsorption of nucleotides of acid, alkali, and heat-denatured DNA widely differ from each other and in the presence of excess concentration of urea becomes negative. The probable mechanisms of biopolymer-cellulose adsorption in terms of polymer hydration, steric interaction, London-van der Waals, hydrophobic, and other types of interactions have been discussed qualitatively. The standard free energy change for the adsorption of protein and DNA nucleotides on the cellulose surface at the state of adsorption saturation has been calculated in kJ per kg of cellulose using an integrated form of the Gibbs adsorption equation. The relation between DeltaG degrees and maximum affinities between biopolymers and the polysaccharide interface have been discussed for various systems.

Apparent Dipole Moments of 1-Alkanols in Cyclohexane and n-Heptane, and Excess Molar Volumes of (1-Alkanol + Cyclohexane or n-Heptane) at 298.15 K

Excess molar volumes and relative permittivities at a frequency of 30 kHz were determined precisely for the binary mixtures of 1-alkanols, C n H2n+1OH for n = 1 to 10, with cyclohexane or n-heptane to the mole fraction of 1-alkanol, x, to 0.1 at a temperature of 298.15 K. Apparent dipole moments, μ, of the 1-alkanols were calculated by using the Frohlich equation, and the limiting values, μ0, were determined by extrapolating to infinite dilution. The solvent effect on μ0 was very small. The value of μ0 was largest in methanol and decreased with increasing n. It was found that the alkanols were isolated up to x ≈ 0.003. The threshold of molecular interaction beyond this critical mole fraction was ascertained by means of FT-IR spectra. The dipole moments of the 1-alkanols for n = 1–4 were evaluated by ab initio calculations. The average values of μ0 for the rotational configurations calculated by assuming the Boltzmann distribution agreed excellently with the observed ones. The excess partial molar volumes of 1-alkanols determined at the infinite dilution depended on n as well as the solvent. These results are discussed from the viewpoint of the interactions between the solute and solvent molecules.

Soot formation in inverse diffusion flames of diluted ethene

Experimental measurements of flame structure and soot characteristics were performed for ethene inverse diffusion flames (IDFs). IDFs are considered as an ideal flow field for studying incipient soot because the soot particles do not experience the oxidation process. In this study, an laser-induced fluorescence image clarified the reaction zone of IDFs with OH signal and polycyclic aromatic hydrocarbon distribution. A laser scattering technique also identified the soot particles. To address the degree of soot maturing, the carbon to hydrogen ratio and morphology of the soot sample were investigated. From the measurements, the effect of flow residence time and temperature on soot inception could be estimated, and more details on soot characteristics in the IDFs were determined according to the fuel dilution ratio and air/fuel ratio. Fuel dilution results in a decrease of temperature and an enhancement of residence time, but the critical dilution mole fraction is found for which temperature does not effect soot growth. Soot inception is also found to be weakly dependent on temperature as influenced by fuel dilution.

Liquid−Liquid Equilibria in Binary Mixtures of Water with Malonitrile, Succinonitrile, and Glutaronitrile

Liquid−liquid equilibria of binary mixtures of water and dinitrile solvents malononitrile, succinonitrile, and glutraronitrile have been studied in temperature range of 15 to 70 °C. The phase diagrams show that the critical mole fraction and consolate temperature (°C) (xc, Tc) are (0.25, 58) for malononitrile and (0.19, 56) and (0.12, 68) for succinonitrile and glutraronitrile, respectively. The nonrandom two-liquid (NRTL) equation has been used to correlate of the activity coefficients of the components in binary mixtures. The parameters needed for the calculation are the energy parameters (g12 − g22) and (g21 − g11) and the nonrandom parameter α, which are determined by solving the NRTL equation with the aid of a nonlinear least-squares curve-fitting program. From the parameters of this equation, the excess Gibbs energies, GE, were calculated. Good agreement between the experimental data of phase diagrams and model results was achieved.

Salt effect on the complex formation between cationic gemini surfactant and anionic polyelectrolyte in aqueous solution.

Salt effect on the interaction of anionic polyelectrolyte sodium carboxymethylcellulose (NaCMC) with cationic gemini surfactant hexamethylene-1,6-bis(dodecyldimethylammonium bromide) [C12H25(CH3)2N(CH2)6N(CH3)2C12H25]Br2 (C12C6C12Br2) has been investigated using turbidimetric titration, steady-state fluorescence, and mobility measurement. It is found that the critical aggregation concentration(cac) for C12C6C12Br2/NaCMC complexes depends little on addition of sodium bromide (NaBr). However, in the presence of nonionic surfactant Triton X-100 (TX100), the critical ionic surfactant mole fraction for the onset of complex formation (Yc) increases markedly with increasing NaBr concentration. These salt effects are supposed as the overall result from competition between the increase of interaction and the screening of interaction. The increase of interaction is referred to as the effect that the larger micelle with higher surface charge density induced by salt has a stronger interaction with oppositely charged polyelectrolyte. The screening of interaction is referred to as the salt screening of electrostatic attraction between the polymer chain and the surfactant. For complex formation between C12C6C12Br2 and NaCMC, the increase of interaction probably compensates the screening of interaction, leading to constant cac values at different salt concentrations. For complex formation between the C12C6C12Br2/TX100 mixed micelle and NaCMC, the screening of interaction probably plays a dominant role, leading to higher suppression of electrostatic binding of micelles to polyelectrolyte.

에틸렌/공기 역 확산화염에서의 나노 매연 입자 생성

Experimental measurements of flame structure and soot characteristics were performed fur ethene inverse diffusion flames (IDF). IDF has been considered as the excellent flow field to study the incipient soot because soot particle do not experience the oxidation process. In this study, LIF image clarified the reaction zone of IDF with OH signal and PAH distribution. laser light scattering technique also identified the being of soot particle. To address the degree of soot maturing, C/H ratio and morphology of soot sample were investigated. From these measurements, the effect of flow residence time and temperature on soot inception could be suggested, and more details on soot characteristic in the IDF was determined according to fuel dilution and flame condition. The fuel dilution results in a decrease of temperature and enhancement of residence time, but the critical dilution mole fraction is existed for temperature not to effect on soot growth. Also, the soot inception evolved on the specific temperature and its morphology are independent of the fuel dilution ratio of fuel.

Variegated micelle surfaces: correlating the microstructure of mixed surfactant micelles with bulk solution properties.

Electron paramagnetic resonance, viscosity, and small-angle neutron scattering (SANS) measurements have been used to study the interaction of mixed anionic/nonionic surfactant micelles with the polyampholytic protein gelatin. Sodium dodecyl sulfate (SDS) and the nonionic surfactant dodecylmalono-bis-N-methylglucamide (C12BNMG) were chosen as "interacting" and "noninteracting" surfactants, respectively; SDS micelles bind strongly to gelatin but C12BNMG micelles do not. Further, the two surfactants interact synergistically in the absence of the gelatin. The effects of total surfactant concentration and surfactant mole fraction have been investigated. Previous work (Griffiths et al. Langmuir 2000, 16 (26), 9983-9990) has shown that above a critical solution mole fraction, mixed micelles bind to gelatin. This critical mole fraction corresponds to a micelle surface that has no displaceable water (Griffiths et al. J. Phys. Chem. B 2001, 105 (31), 7465). On binding of the mixed micelle, the bulk solution viscosity increases, with the viscosity-surfactant concentration behavior being strongly dependent on the solution surfactant mole fraction. The viscosity at a stoichiometry of approximately one micelle per gelatin molecule observed in SDS-rich mixtures scales with the surface area of the micelle occupied by the interacting surfactant, SDS. Below the critical solution mole fraction, there is no significant increase in viscosity with increasing surfactant concentration. Further, the SANS behavior of the gelatin/mixed surfactant systems below the critical micelle mole fraction can be described as a simple summation of those arising from the separate gelatin and binary mixed surfactant micelles. By contrast, for systems above the critical micelle mole fraction, the SANS data cannot be described by such a simple approach. No signature from any unperturbed gelatin could be detected in the gelatin/mixed surfactant system. The gelatin scattering is very similar in form to the surfactant scattering, confirming the widely accepted picture that the polymer "wraps" around the micelle surface. The gelatin scattering in the presence of deuterated surfactants is insensitive to the micelle composition provided the composition is above the critical value, suggesting that the viscosity enhancement observed arises from the number and strength of the micelle-polymer contact points rather than the gelatin conformation per se.

Modeling of the target surface modification by reactive ion implantation during magnetron sputtering

The erosion rate of an aluminum target bombarded with Ar+ and O2+ ions was simulated using TRIDYN. An abrupt change of the erosion rate is noticed at a critical mole fraction of O2+ ions. This target behavior can also be described by a simple analytical model showing that the abrupt change finds its origin in an avalanche induced by reaction ion implantation. Indeed, by the reduction of the average sputter yield by compound formation, more reactive ions become implanted into the target as the number of implanted ions depends inversely on the average sputter yield. As such, an avalanche situation can develop which finally results in a completely oxidized target. It is also shown that the critical mole fraction depends linearly on the sputter yield of the target material and that target poisoning induced by ion implantation can result in a hysteresis behavior for the target condition.

Bulk and interfacial properties of binary polymer mixtures.

A microscopic density functional theory is used to investigate a binary mixture of polymers, built of freely jointed tangent hard spheres. The difference in the chain length and in the segment diameter of polymers gives rise to a demixing transition. We evaluate the bulk fluid phase equilibria (binodal) and the limit of stability of a mixed state (spinodal) for selected systems, and analyze the decay of the critical packing fraction, critical mole fraction, and critical pressure with an increase of the chain length. The bulk results are subsequently used in the calculations of the density profiles across the fluid-fluid interface. The obtained profiles are smooth and do not exhibit any oscillations on the length scale of the segment diameter. Upon approaching the critical point the interfacial tension vanishes as (Deltarho)3, where Deltarho is the difference between bulk densities of one component in bulk phases rich and poor in that species. This indicates that the microscopic density functional theory applied here is of a mean-field type.

Cholesterol superlattice modulates the activity of cholesterol oxidase in lipid membranes.

Here, the interplay between membrane cholesterol lateral organization and the activity of membrane surface-acting enzymes was addressed using soil bacteria cholesterol oxidase (COD) as a model. Specifically, the effect of the membrane cholesterol mole fraction on the initial rate of cholesterol oxidation catalyzed by COD was investigated at 37 degrees C using cholesterol/1-palmitoyl-2-oleoyl-l-alpha-phosphatidylcholine (POPC) large unilamellar vesicles (LUVs, approximately 800 nm in diameter). In the three concentration ranges examined (18.8-21.2, 23.6-26.3, and 32.2-34.5 mol % cholesterol), the initial activity of COD changed with cholesterol mole fraction in a biphasic manner, exhibiting a local maximum at 19.7, 25.0, and 33.4 mol %. Within the experimental errors, these mole fractions agree with the critical cholesterol mole fractions (C(r)) (20.0, 25.0, and 33.3) theoretically predicted for maximal superlattice formation. The activity variation with cholesterol content was correlated well with the area of regular distribution (A(reg)) in the plane of the membrane as determined by nystatin fluorescence. A similar biphasic change in COD activity was detected at the critical sterol mole fraction 20 mol % in dehydroergosterol (DHE)/POPC LUVs (approximately 168 nm in diameter). These results indicate that the activity of COD is regulated by the extent of sterol superlattice for both sterols (DHE and cholesterol) and for a wide range of vesicle sizes (approximately 168-800 nm). The present work on COD and the previous study on phospholipase A(2) (sPLA(2)) [Liu and Chong (1999) Biochemistry 38, 3867-3873] suggest that the activities of some surface-acting enzymes may be regulated by the extent of sterol superlattice in the membrane in a substrate-dependent manner. When the substrate is a sterol, as it is with COD, the enzyme activity reaches a local maximum at C(r). When phospholipid is the substrate, the minimum activity is at C(r), as is the case with sPLA(2). Both phenomena are in accordance with the sterol superlattice model and manifest the functional importance of membrane cholesterol content.