Rate Constants For Formation Research Articles

Coordination Chemistry of Cu2+ Complexes of Small N-Alkylated Tetra-azacyclophanes with SOD Activity.

A new tetraaza-pyridinophane macrocycle (L1) N-alkylated with two isopropyl and one methyl groups symmetrically disposed has been prepared and its behavior compared with those of the unsubstituted pyridinophane (L3) and the related compound with three methyl groups (L2). The protonation studies show that, first, a proton binds to the central methylated amine group of L1, while, second protonation leads to a reorganization of the protons that are at this stage attached to the lateral isopropylated amines. The X-ray structure of [HL1]+ agrees with the UV-vis and NMR studies as well as with the results of DFT calculations. The stability of the Cu2+ complexes decreases on increasing the bulkiness of the alkyl substituents of the amine groups. The crystal structures of [CuL1Cl](ClO4) and [CuL1(H2O)](ClO4)2·H2O show square pyramidal coordination geometries with the ligands disposed in a bent L-shaped conformation. Kinetic studies indicate that the rates of both complexation and ligand dissociation decrease with the bulkiness of the substituents, so that the stability changes are surely the results of compensating effects, complex formation dominating over complex dissociation. The pH dependence of the rate constants for complex formation cannot be explained by consideration of rapid pre-equilibria involving the different protonated forms of the ligand, and it has been interpreted in terms of a mechanism involving an acid-base equilibrium for a reaction intermediate. NBT SOD studies show that the Cu2+ complex of the bulkiest L1 ligand is the one having the highest activity (IC50 = 0.26(5) μM, kcat = 13.7 × 106 M-1 s-1) which can be associated with the poorer σ-donor ability of the tertiary amino groups, and the rigidity of the system, caused by the bulky isopropyl groups.

Stability, reactivity and dynamic study of switchable intermolecular hydrogen bonding in dinitrobenzene isomers: A theoretical – Experimental approach

Among several non-covalent weak interaction(s), hydrogen bonding is predominantly considered as a key factor in some biological events i.e. information transfer at intra cellular and/or intra/inter organelle level. Dinitroaromatics contain –NO2 group(s) which strongly facilities electron and/or proton transfer, could be envisaged to be used as an active group in a drug molecule. We have decided to investigate dinitroaromatics as model substances for the following reasons (a) low reduction potential, (b) multi-electron accepting ability of NO2 groups, (c) formation of stable anion radicals and dianions. Linear scan and cyclic voltammetry were used for study. It was found that DNBs in the presence of HB-agents exhibit switchable H-bonding via electro-reduction steps and formation of DNB−./2-⋯(HB)n or m. HB strength significantly perturbs chemical equilibrium and/or kinetic process, hence, an array of strong, intermediate and weak type interactions was considered for investigation. Experimental values of stability constant, Keq, rate constant of formation of H-bond, k, and number of bonds formed were evaluated for corresponding process(es) (i) DNB−.+n[HB]⇄DNB−.(HB)n and (ii) DNB2−+(m−n)[HB]⇄DNB2−(HB)m−n. Values of Keq for processes (i) and (ii) were found to be within the range of 1.9–9.0 M-n and 7.0–9.4 × 104 M-m, whereas, k values were moderate to high as 0.23–26.1 M-n.s−1 and 3.3–6.5 × 106 M-m.s−1, respectively. A more plausible assumption is the existence of 1:1 or 1:2 associates between (X)DNB2− (where, X = 1,2-,1,3-,1,4-) and HB-agents. Quantum chemical calculations were carried out for (X)DNB−./2-⋯(HB)n or m, vis-a-vis geometry optimization leading to better understanding of structural array in three dimensional space.

Oxygen Reduction Reaction Promoted by Manganese Porphyrins

The oxygen reduction reaction (ORR) is catalyzed by manganese(II) porphyrins in the presence of Bronsted acids (HAs). Analyses of the catalytic cyclic voltammetric profiles have permitted the ORR mechanism to be constructed and rate constants to be extracted for both the formation of the initial oxygen adduct and the O–O bond cleavage event for a series of HAs. The dependence of the formation rate constant of the oxygen adduct on reactant concentrations reveals a rate law that is first order in Mn porphyrin and oxygen substrate. A second order dependence in HA is observed for unadorned Mn porphyrin platforms whereas with Mn hangman porphyrin, a proton is provided intramolecular to the oxygen adduct and consequently the HA order is reduced to unity. The stabilization of the oxygen adduct with an additional hydrogen bond from HA engenders a rate-determining step involving O–O bond cleavage, resulting in the rare instance where the activation of the O–O bond is directly observed.

Clathrate hydrate formation in NaCl and MgCl2 brines at low pressure conditions

Hydrate-based desalination (HBD) has been developed to obtain fresh water from seawater in an economic and environmental sustainable manner. As a low-pressure hydrate former for the HBD process, chlorodifluoromethane (R22) hydrates were formed in the pressure range of 1–6 bar under brine environments, aqueous NaCl and MgCl2 solutions. Synchrotron X-ray diffraction and Raman spectroscopy measurements revealed that the R22 hydrates formed with NaCl and MgCl2 show structure I and enclathration of R22 molecules into the large cages. These results also confirmed that the salt ions cannot be encaged in the gas hydrate framework, reflecting the ion exclusion behavior for HBD above the eutectic of water and hydrated salts. The formation kinetics of R22 clathrate hydrate in the presence of salts show that both the initial growth rate and pressure drop of the R22 hydrates heavily depend on the salinity of aqueous solutions. A new theoretical approach adopting the transient time-dependent apparent rate constant of hydrate formation with salts was proposed to predict the formation kinetics of R22 hydrates under brine environments, which was in good agreements with the experimental results. These results provide good information for separating ionic compounds from aqueous solutions by hydrate-based separation processes.

Exploring potential crossing seams in periodic systems: Intersystem crossing pathways in the benzene crystal.

The intersystem crossing (ISC) pathways of triplet benzene molecules in a benzene crystal were investigated theoretically. A combination of the gradient projection (GP) method, which is a standard method for optimizing the crossing seam of two potential energy surfaces, and the single-component artificial-force-induced reaction (SC-AFIR) method (GP/SC-AFIR) was used. This is the first reported use of a GP/SC-AFIR calculation using a density functional theory calculation with periodic boundary conditions. A systematic search for the minimum-energy structures in the seams of crossing of the singlet (S0) and triplet (T1) potential energy surfaces (S0/T1-MESX structures) found 39 independent S0/T1-MESX structures. Energy barriers between the S0/T1-MESX and the stationary structure of the triplet state (T1-MIN) were computed, and then two competing ISC pathways were extracted; the calculated overall energy barrier to the intermolecular C-C-bonded type (SX3) and the out-of-plane bent C-H type (SX15) S0/T1-MESX structures from T1-MIN were 0.26 and 0.27 eV, respectively. The rate constants for SX3 and SX15 formation were estimated to be 5.07 × 108 and 2.17 × 108 s-1 (at 273 K), respectively, or 9.73 × 10-5 and 4.78 × 10-6 s-1 (at 77 K), respectively. At 273 K, which is close to the melting point of the benzene crystal (278.5 K), SX3 and SX15 are easily accessible from T1-MIN, and ISC could occur through the S0/T1-MESX points. By contrast, at 77 K, T1-MIN survives long enough for phosphorescence to compete with ISC.

A model of the chemical composition and pyrolysis kinetics of lignin

This study presents a novel approach for the chemical representation of lignin for modelling the reaction kinetics of lignin in lignocellulosic biomass. This methodology relies on the definition of dimeric pseudo-components containing phenolic functionalities, i.e., p-hydroxyphenyl, guaiacyl and syringyl groups, as measured in real biomass and native lignin through wet chemistry and spectroscopic techniques. The reactivities of the lignin pseudo-components are modelled through a series of lumped unidirectional reactions, whose product formation and reaction rate constants are optimised to replicate a comprehensive experimental dataset gathered from several works available in the literature. The new kinetic model contributes to the state-of-the-art by providing a more accurate depiction of the conversion rates, selectivity of char vs. volatiles, and aromatic composition in condensable products in line with the inherent reactivity of lignin functionalities and the empirical observations of lignin depolymerisation and thermal degradation at low (<1 K/s) and high heating rates (>50 K/s).

Methane hydrate formation in mixed-size porous media with gas circulation: Effects of sediment properties on gas consumption, hydrate saturation and rate constant

Being a promising potential source for natural gas, methane hydrate (MH) is attracting increasing interest due to its great amount and diverse geographic distribution. The formation of MH is significantly influenced by the properties of sediment media such as porosity and permeability. In this study, in order to have a better understanding on the relationship between MH formation behavior and sediment properties, as well as to synthesize representative hydrate samples, MH was formed in six different sets of mixed-size porous media composed of clay, silt and fine sand, with saline water and circulating methane gas to reflect MH formation with free methane flux in marine sediment. The sediment composition, experimental pressure (15 MPa) and temperature (286.2 K) were chosen based on the SH2 drilling site in the Shenhu area in South China Sea. A two-stage growing behavior was observed for all systems. The gas consumption and hydrate formation rate exhibited positive relations with the permeability and porosity of the sediments. Furthermore, hydrates were found to be preferably formed in the bottom layer of the sediment, which could be attributed to the drastic drop of permeability at the early stage of hydrate formation. Lastly, the hydrate formation rate constant was calculated based on the intrinsic kinetic model and found to be a good reflection of the mass transfer properties of different porous media.

Reliable Strategy for Analysis of Complex Biosensor Data

When using biosensors, analyte biomolecules of several different concentrations are percolated over a chip with immobilized ligand molecules that form complexes with analytes. However, in many cases of biological interest, e.g., in antibody interactions, complex formation steady-state is not reached. The data measured are so-called sensorgram, one for each analyte concentration, with total complex concentration vs time. Here we present a new four-step strategy for more reliable processing of this complex kinetic binding data and compare it with the standard global fitting procedure. In our strategy, we first calculate a dissociation graph to reveal if there are any heterogeneous interactions. Thereafter, a new numerical algorithm, AIDA, is used to get the number of different complex formation reactions for each analyte concentration level. This information is then used to estimate the corresponding complex formation rate constants by fitting to the measured sensorgram one by one. Finally, all estimated rate constants are plotted and clustered, where each cluster represents a complex formation. Synthetic and experimental data obtained from three different QCM biosensor experimental systems having fast (close to steady-state), moderate, and slow kinetics (far from steady-state) were evaluated using the four-step strategy and standard global fitting. The new strategy allowed us to more reliably estimate the number of different complex formations, especially for cases of complex and slow dissociation kinetics. Moreover, the new strategy proved to be more robust as it enables one to handle system drift, i.e., data from biosensor chips that deteriorate over time.

Plasmochemical preparation of silver nanoparticles: thermodynamics and kinetics analysis of the process

The thermodynamics and kinetics analysis of the plasmochemical formation of silver nanoparticles is performed. The thermodynamics analysis is made on the basis of calculation of the Gibbs free energy of formation of silver nanoparticles in an aqueous medium by various methods. It was found that the Gibbs free energy in aqueous solutions increases with decreasing size of silver particles. Based on experimental data, it was determined that the average size of plasmochemically prepared particles depends on the initial concentration of silver ions in the solution and equals 36.5–60.1 nm for 0.25–3.0 mmol/l. The kinetics of chemical conversion in aqueous solutions of silver nitrate under plasma treatment conditions in a gas-liquid plasmochemical batch reactor is investigated. The curves of Ag + dependence on duration of plasmochemical treatment of solutions and initial concentration of silver ions are given. It is found that the process of plasmochemical formation of silver nanoparticles is the second-order reaction. The rate constant of formation of silver nanoparticles is k=0.07–1.53 mol -1 ∙dm 3 ∙min -1 depending on the initial concentration of silver ions. It is shown that the formation of silver nanodispersions under plasma discharge impact is characterized by the presence of the peak λ max =400–440 nm.

Extending a Systems Model of the APP Pathway: Separation of β- and γ-Secretase Sequential Cleavage Steps of APP.

The abnormal accumulation of amyloid-β (Aβ) in the brain parenchyma has been posited as a central event in the pathophysiology of Alzheimer's disease. Recently, we have proposed a systems pharmacology model of the amyloid precursor protein (APP) pathway, describing the Aβ APP metabolite responses (Aβ40, Aβ42, sAPPα, and sAPPβ) to β-secretase 1 (BACE1) inhibition. In this investigation this model was challenged to describe Aβ dynamics following γ-secretase (GS) inhibition. This led an extended systems pharmacology model, with separate descriptions to characterize the sequential cleavage steps of APP by BACE1 and GS, to describe the differences in Aβ response to their respective inhibition. Following GS inhibition, a lower Aβ40 formation rate constant was observed, compared with BACE1 inhibition. Both BACE1 and GS inhibition were predicted to lower Aβ oligomer levels. Further model refinement and new data may be helpful to fully understand the difference in Aβ dynamics following BACE1 versus GS inhibition.

Hydration dynamics of a lipid membrane: Hydrogen bond networks and lipid-lipid associations

Dynamics of hydration layers of a dimyristoylphosphatidylcholine (DMPC) bilayer are investigated using an all atom molecular dynamics simulation. Based upon the geometric criteria, continuously residing interface water molecules which form hydrogen bonds solely among themselves and then concertedly hydrogen bonded to carbonyl, phosphate, and glycerol head groups of DMPC are identified. The interface water hydrogen bonded to lipids shows slower relaxation rates for translational and rotational dynamics compared to that of the bulk water and is found to follow sub-diffusive and non-diffusive behaviors, respectively. The mean square displacements and the reorientational auto-correlation functions are slowest for the interfacial waters hydrogen bonded to the carbonyl oxygen since these are buried deep in the hydrophobic core among all interfacial water studied. The intermittent hydrogen bond auto-correlation functions are calculated, which allows breaking and reformations of the hydrogen bonds. The auto-correlation functions for interfacial hydrogen bonded networks develop humps during a transition from cage-like motion to eventual power law behavior of t−3/2. The asymptotic t−3/2 behavior indicates translational diffusion dictated dynamics during hydrogen bond breaking and formation irrespective of the nature of the chemical confinement. Employing reactive flux correlation analysis, the forward rate constant of hydrogen bond breaking and formation is calculated which is used to obtain Gibbs energy of activation of the hydrogen bond breaking. The relaxation rates of the networks buried in the hydrophobic core are slower than the networks near the lipid-water interface which is again slower than bulk due to the higher Gibbs energy of activation. Since hydrogen bond breakage follows a translational diffusion dictated mechanism, chemically confined hydrogen bond networks need an activation energy to diffuse through water depleted hydrophobic environments. Our calculations reveal that the slow relaxation rates of interfacial waters in the vicinity of lipids are originated from the chemical confinement of concerted hydrogen bond networks. The analysis suggests that the networks in the hydration layer of membranes dynamically facilitate the water mediated lipid-lipid associations which can provide insights on the thermodynamic stability of soft interfaces relevant to biological systems in the future.

Theoretical Study on the Kinetics of the Reaction of C2H with C2H2

In this theoretical research, the mechanism of the C2H + C2H2 reaction is studied by high-level quantum-chemical methods and kinetics of the reaction is investigated by statistical rate theories. High-level electronic structure calculation methods including M06-2X, CCSD(T), CBS-Q and G4 methods are employed to explore the doublet potential energy surface of the reaction and compute the molecular properties necessary for carrying out the statistical rate theory calculations. After locating stationary points of the reaction, steady-state approximation to the chemically-activated intermediates along with some statistical manipulations are applied to derive some practical integral equations for the rate constants of formation of all possible products of the reaction. Unimolecular rate constants are computed by RRKM theory. VRC-TST is used to compute the sum of quantum states for internal degrees of freedom of loose transition states. The present calculations reveal that the product HCCCCH + H (P8) is the dominant product over whole pressure and temperature range considered in the present study. Nonetheless, at low temperatures and high pressures, other intermediate products especially HCC(H)CCH and H2CCCCH, become significant. The overall computed rate constants are nearly constant over the temperature range 100-500 K and slightly increase at higher temperatures.

Mechanism of Initial Stage of Pore Formation Induced by Antimicrobial Peptide Magainin 2.

Antimicrobial peptide magainin 2 forms pores in lipid bilayers, a property that is considered the main cause of its bactericidal activity. Recent data suggest that tension or stretching of the inner monolayer plays an important role in magainin 2-induced pore formation in lipid bilayers. Here, to elucidate the mechanism of magainin 2-induced pore formation, we investigated the effect on pore formation of asymmetric lipid distribution in two monolayers. First, we developed a method to prepare giant unilamellar vesicles (GUVs) composed of dioleoylphosphatidylglycerol (DOPG), dioleoylphosphatidylcholine (DOPC), and lyso-PC (LPC) in the inner monolayer and of DOPG/DOPC in the outer monolayer. We consider that in these GUVs, the lipid packing in the inner monolayer was larger than that in the outer monolayer. Next, we investigated the interaction of magainin 2 with these GUVs with an asymmetric distribution of LPC using the single GUV method, and found that the rate constant of magainin 2-induced pore formation, kp, decreased with increasing LPC concentration in the inner monolayer. We constructed a quantitative model of magainin 2-induced pore formation, whereby the binding of magainin 2 to the outer monolayer of a GUV induces stretching of the inner monolayer, causing pore formation. A theoretical equation defining kp as a function of magainin 2 surface concentration, X, reasonably explains the experimental relationship between kp and X. This model quantitatively explains the effect on kp of the LPC concentration in the inner monolayer. On the basis of these results, we discuss the mechanism of the initial stage of magainin 2-induced pore formation.

Effect of Carboxylate Ligands on Alkane Dehydrogenation with (dmPhebox)Ir Complexes

A series of carboxylate-ligated iridium complexes (dmPhebox)Ir(O2CR)2(H2O) (R = −CH3, −CH2CH3, −CMe3, −CH2C6H5, and −CH═CMe2) were designed and synthesized to understand the carboxylate ligand effects on the reactivity of the complex for alkane dehydrogenation. Kinetic studies showed that the different R groups of the carboxylate iridium complexes can affect the reactivity with octane in the β-H elimination step. The rate constants for octene formation with different carboxylate ligands follow the order R = −CH═CMe2 > −CMe3 > −CH2CH3 > −CH3 > −CH2C6H5. In contrast, there is no significant effect of carboxylate ligand on the rate of the C–H activation step at 160 °C. These experimental results support the findings in the previously reported density functional theory study of the (dmPhebox)Ir complex in alkane C–H activation.

Effect of Cholesterol on Membrane Pore Formation by Amyloid β25-35

One of the cytotoxicity mechanisms of amyloid β (Aβ) peptide in Alzheimer's disease is membrane permeabilization, yet the mechanism of pore formation remains unclear. Here, Ca2+-permeable membrane pore formation by a cytotoxic fragment of Aβ (Aβ25-35) has been analyzed by biophysical methods. Quin-2-loaded lipid vesicles composed of 0.3 mole fraction of anionic lipid 1-palmitoyl-2-oleoyl-phosphatidylglycerol, xchol mole fraction of cholesterol, and (0.7 - xchol) mole fraction of zwitterionic lipid 1-palmitoyl-2-oleoyl-phosphatidylcholine were prepared at xchol = 0, 0.05, 0.1, 0.2 and 0.4. CaCl2 was added externally so that Quin-2 was sequestered from Ca2+ ions. Quin-2 fluorescence increased exponentially upon addition of Aβ25-35, which was interpreted as membrane pore formation by the peptide, calcium influx and binding to intravesicular Quin-2. The kinetics and the magnitude of fluorescence enhancement were used to evaluate the second order rate constant of pore formation (ka), the affinity constant between the peptide molecules (Kp), and the number of peptide units in the pore (n). Circular dichroism suggested mostly β-sheet structure for the peptide in the presence of lipid vesicles. Attenuated total reflection Fourier transform infrared experiments were performed on Aβ25-35 embedded in lipid multilayers deposited on a germanium plate. These data suggested α-helical and β-sheet structures for the peptide in a lipid environment. The structure of the peptide, i.e., the α-helix/β-sheet ratio, varied as a function of cholesterol content in the membranes. These conformational transitions correlated with changes in pore formation parameters (Kp, ka, n). The data suggest that cholesterol affects Aβ membrane pore formation by multiple mechanisms. At moderate concentration (xchol< 0.1), cholesterol supports pore formation possibly through cholesterol-peptide interactions. Further increase in xchol causes pore inhibition by a membrane solidification mechanism. At xchol = 0.4, cholesterol causes lipid disorder and membrane destabilization.

Oxidative dehalogenation and denitration by a flavin-dependent monooxygenase is controlled by substrate deprotonation.

Enzymes that are capable of detoxifying halogenated phenols (HPs) and nitrophenols (NPs) are valuable for bioremediation and waste biorefining. HadA monooxygenase was found to perform dual functions of oxidative dehalogenation (hydroxylation plus halide elimination) and denitration (hydroxylation plus nitro elimination). Rate constants associated with individual steps of HadA reactions with phenol, halogenated phenols and nitrophenols were measured using combined transient kinetic approaches of stopped-flow absorbance/fluorescence and rapid-quench flow techniques. Density functional theory was used to calculate the thermodynamic and electronic parameters associated with hydroxylation and group elimination steps. These parameters were correlated with the rate constants of hydroxylation, group elimination, and overall product formation to identify factors controlling individual steps. The results indicated that the hydroxylation rate constant is higher when the pK a of the phenolic group is lower, i.e. it is more easily deprotonated, but not higher when the energy gap between the E LUMO of the C4a-hydroperoxy-FAD intermediate and the E HOMO of the phenolate substrate is lower. These data suggest that the substrate deprotonation has a higher energy barrier than the -OH transfer, and thus controls the hydroxylation step. For the group elimination, the process is controlled by the ability of the C-X bond to break. For the overall product formation (hydroxylation and group elimination combined), this analysis showed that the rate constant of product formation is dependent on the pK a value of the substrate, indicating that the overall reaction is controlled by substrate deprotonation. This step also likely has the highest energy barrier and thus controls the overall process of oxidative dehalogenation and denitration by HadA. This report is the first to identify a key mechanistic factor controlling the enzymatic processes of oxidative dehalogenation and denitration.

Anaerobic biotransformation of N‐methyl perfluorobutanesulfonamido ethanol and N‐ethyl perfluorooctanesulfonamido ethanol

Some fluorochemical products are manufactured using N-methyl perfluorobutanesulfonamido ethanol (MeFBSE), a short-chain replacement for perfluorooctyl-based chemistries N-methyl and N-ethyl perfluorooctanesulfonamido ethanols (EtFOSE). The present study shows for the first time the anaerobic biodegradation of MeFBSE and EtFOSE in municipal digester sludge under methanogenic conditions. Both MeFBSE and EtFOSE were incubated for 108 d with anaerobic digester sludge. Although sterile controls did not remove MeFBSE, it was degraded in live sludge. The loss of MeFBSE coincided with production of N-methyl perfluorobutanesulfonamido acetate (MeFBSAA) and perfluorobutane sulfinate (PFBSI). The biodegradation appeared biphasic, with pseudo first-order loss between days 0 and 70, resulting in approximately 75% removal but no further depletion of MeFBSE between days 70 and 108. By day 108 MeFBSAA and PFBSI accounted for 57 and 40 mol% of initial dose, respectively. Mass balance values in live cultures on days 0, 10, 21, 29, 70, and 108 were 103, 92, 94, 100, 93, and 122%, respectively. The apparent first-order biodegradation rate constant for MeFBSE over the first 70 d was 0.0194 d-1 , and the apparent half-life was 35.8 d. Incubation of EtFOSE with live digester sludge resulted in low-level formation of N-ethyl perfluorooctane-sulfonamido acetate and perfluorooctane sulfinate, which did not form in sterile controls. Although it was not measurably lost, 2 to 3% loss of EtFOSE was calculated based on product concentrations. The total product formation rate constant was determined by first-order kinetic evaluation over the first 72 d to estimate a first-order biodegradation rate constant for EtFOSE at 0.000374 d-1 , and the apparent half-life time was 1860 d. Environ Toxicol Chem 2018;37:768-779. © 2017 SETAC.

Numerical simulation of pore-scale formation of methane hydrate in the sand sediment using the phase-field model

Methane hydrate is considered as a promising energy resource for the near future. To predict the gas productivity from the methane hydrate in the subsea sand-sediment, it is important to know effective permeability accurately of the sediment bearing methane hydrate. Hence, the hydrate morphological distribution: namely, what is the shape and morphology of hydrate, in the sediment should be elucidated, because the permeability is strongly affected by the hydrate distribution. In this study, to know where hydrate is formed in the pore of porous media, we proposed a numerical model for estimating the microscopic distribution of methane hydrate in sand sediment, using the classical nucleation theory and the phase-field model. The former theory gave the probabilities of hydrate nucleation positions in the gas-water-sand three-phases and the latter method provided the mobility of the front of the hydrate formation. A necessary hydrate formation rate constant was determined by history-matching with an experiment in the literature. Using the obtained rate constant, we numerically simulated hydrate formations within the microscopic computational domains.

Characterization of the Distribution of Pyrene Molecules in Confined Geometries with the Model Free Analysis.

Evidence is provided showing that global Model Free Analysis (MFA) of monomer and excimer fluorescence decays of pyrene dissolved in aqueous solutions of sodium dodecyl sulfate (SDS) provides the same structural and dynamic information on SDS micelles as the well-established Micelle Model (MM) does. Both MFA and MM were employed to characterize the quenching kinetics between dyes and quenchers located in surfactant micelles and the aggregation number of surfactant micelles. However, contrary to the MM, which assumes that dyes and quenchers distribute themselves among SDS micelles according to a Poisson distribution and react with a rate constant that is proportional to the number of reactants in a micelle, the MFA accomplishes this task without making any assumption about the process of pyrene excimer formation in SDS micelles. The ability of the MFA to retrieve accurately the molar fraction of pyrene molecules that are isolated in SDS micelles and do not form excimers was taken advantage of to establish that it equaled the Poisson probability of exciting micelles that contained a single pyrene. The molar fraction of isolated pyrenes could then be utilized to determine the aggregation number of the SDS micelles, and the rate constant of excimer formation between one excited- and one ground-state pyrene located inside a same micelle. Within experimental error, both the MFA and MM yielded the same micelle aggregation number and rate constant of excimer formation, with the MFA making no prior assumptions about the physical principles underlying the process of excimer formation contrary to the MM. The ability of the MFA to retrieve quantitative parameters providing structural and dynamic information about macromolecular systems with no prior knowledge about their architecture or labeling scheme implies that it can be applied to characterize a wide range of macromolecular architectures in solution.

Excimer Formation Dynamics of Dipyrenyldecane in Structurally Different Ionic Liquids.

Ionic liquids, being composed of ions alone, may offer alternative pathways for molecular aggregation. These pathways could be controlled by the chemical structure of the cation and the anion of the ionic liquids. Intramolecular excimer formation dynamics of a bifluorophoric probe, 1,3-bis(1-pyrenyl)decane [1Py(10)1Py], where the fluorophoric pyrene moieties are separated by a long decyl chain, is investigated in seven different ionic liquids in 10-90 °C temperature range. The long alkyl separator allows for ample interaction with the solubilizing milieu prior to the formation of the excimer. The ionic liquids are composed of two sets, one having four ionic liquids of 1-butyl-3-methylimidazolium cation ([bmim+]) with different anions and the other having four ionic liquids of bis(trifluoromethylsulfonyl)imide anion ([Tf2N-]) with different cations. The excimer-to-monomer emission intensity ratio (IE/IM) is found to increase with increasing temperature in sigmoidal fashion. Chemical structure of the ionic liquid controls the excimer formation efficiency, as IE/IM values within ionic liquids with the same viscosities are found to be significantly different. The excited-state intensity decay kinetics of 1Py(10)1Py in ionic liquids do not adhere to a simplistic Birk's scheme, where only one excimer conformer forms after excitation. The apparent rate constants of excimer formation (ka) in highly viscous ionic liquids are an order of magnitude lower than those reported in organic solvents. In general, the higher the viscosity of the ionic liquid, the more sensitive is the ka to the temperature with higher activation energy, Ea. The trend in Ea is found to be similar to that for activation energy of the viscous flow (Ea,η). Stokes-Einstein relationship is not followed in [bmim+] ionic liquids; however, with the exception of [choline][Tf2N], it is found to be followed in [Tf2N-] ionic liquids suggesting the cyclization dynamics of 1Py(10)1Py to be diffusion-controlled and to depend on the viscosity of the ionic liquid irrespective of the identity of the cation. The dependence of ionic liquid structure on cyclization dynamics to form intramolecular excimer is amply highlighted.