Showing papers in "Journal of Physical Chemistry B in 2007"
TL;DR: An improved and extended version of the coarse grained lipid model is presented, coined the MARTINI force field, based on the reproduction of partitioning free energies between polar and apolar phases of a large number of chemical compounds to reproduce the free energies of these chemical building blocks.
Abstract: We present an improved and extended version of our coarse grained lipid model. The new version, coined the MARTINI force field, is parametrized in a systematic way, based on the reproduction of partitioning free energies between polar and apolar phases of a large number of chemical compounds. To reproduce the free energies of these chemical building blocks, the number of possible interaction levels of the coarse-grained sites has increased compared to those of the previous model. Application of the new model to lipid bilayers shows an improved behavior in terms of the stress profile across the bilayer and the tendency to form pores. An extension of the force field now also allows the simulation of planar (ring) compounds, including sterols. Application to a bilayer/cholesterol system at various concentrations shows the typical cholesterol condensation effect similar to that observed in all atom representations.
4,580 citations
TL;DR: This study provides the first experimental evidence of the existence of nanoscale heterogeneities in neat liquid and supercooled RTILs, such as 1-alkyl-3-methyl imidazolium-based salts, using X-ray diffraction, showing a behavior that resembles the density one only below the glass transition, thus suggesting a complex behavior above this temperature.
Abstract: Room-temperature ionic liquids (RTILs) are organic salts that are characterized by low melting points. They are considered to possess a homogeneous microscopic structure. We provide the first experimental evidence of the existence of nanoscale heterogeneities in neat liquid and supercooled RTILs, such as 1-alkyl-3-methyl imidazolium-based salts, using X-ray diffraction. These heterogeneities are of the order of a few nanometers and their size is proportional to the alkyl chain length. These results provide strong support to the findings from recent molecular dynamics simulations, which proposed the occurrence of nanostructures in RTILs, as a consequence of alkyl chains segregation. Moreover, our study addresses the issue of the temperature dependence of the heterogeneities size, showing a behavior that resembles the density one only below the glass transition, thus suggesting a complex behavior above this temperature. These results will provide a novel interpretation approach for the unique chemical physi...
1,144 citations
TL;DR: A detailed critique of the present work on the potential dependence of double-layer capacitance at a planar metal-ionic liquid interface is provided, promoting the point of view that future considerations of ionic liquids should be based on the modern statistical mechanics of dense Coulomb systems, or density-functional theory, rather than classical electrochemical theories which hinge on a dilute-solution approximation.
Abstract: Applications of ionic liquids at electrified interfaces to energy-storage systems, electrowetting devices, or nanojunction gating media cannot proceed without a deep understanding of the structure and properties of the interfacial double layer. This article provides a detailed critique of the present work on this problem. It promotes the point of view that future considerations of ionic liquids should be based on the modern statistical mechanics of dense Coulomb systems, or density-functional theory, rather than classical electrochemical theories which hinge on a dilute-solution approximation. The article will, however, contain more questions than answers. To trigger the discussion, it starts with a simplified original result. A new analytical formula is derived to rationalize the potential dependence of double-layer capacitance at a planar metal−ionic liquid interface. The theory behind it has a mean-field character, based on the Poisson−Boltzmann lattice-gas model, with a modification to account for the...
1,092 citations
TL;DR: Results show that ionic liquids containing increased fluoroalkyl chains on either the cation or anion do improve CO2 solubility when compared to less fluorinated ionic liquid previously studied, and it was found that it was possible to obtain similar, high levels of CO2solubility in nonfluorous ionic fluids.
Abstract: Previously we showed that CO2 could be used to extract organic molecules from ionic liquids without contamination of the ionic liquid. Consequently a number of other groups demonstrated that ionic liquid/CO2 biphasic systems could be used for homogeneously catalyzed reactions. Large differences in the solubility of various gases in ionic liquids present the possibility of using them for gas separations. More recently we and others have shown that the presence of CO2 increases the solubility of other gases that are poorly soluble in the ionic liquid phase. Therefore, a knowledge and understanding of the phase behavior of these ionic liquid/CO2 systems is important. With the aim of finding ionic liquids that improve CO2 solubility and gaining more information to help us understand how to design CO2-philic ionic liquids, we present the low- and high-pressure measurements of CO2 solubility in a range of ionic liquids possessing structures likely to increase the solubility of CO2. We examined the CO2 solubilit...
704 citations
TL;DR: It is theoretically demonstrated for the first time that the selected hydrogen bonds are transiently strengthened in the excited states for facilitating the ultrafast solute-solvent intermolecular ET reaction.
Abstract: Solute−solvent intermolecular photoinduced electron transfer (ET) reaction was proposed to account for the drastic fluorescence quenching behaviors of oxazine 750 (OX750) chromophore in protic alcoholic solvents. According to our theoretical calculations for the hydrogen-bonded OX750−(alcohol)n complexes using the time-dependent density functional theory (TDDFT) method, we demonstrated that the ET reaction takes place from the alcoholic solvents to the chromophore and the intermolecular ET passing through the site-specific intermolecular hydrogen bonds exhibits an unambiguous site selectivity. In our motivated experiments of femtosecond time-resolved stimulated emission pumping fluorescence depletion spectroscopy (FS TR SEP FD), it could be noted that the ultrafast ET reaction takes place as fast as 200 fs. This ultrafast intermolecular photoinduced ET is much faster than the diffusive solvation process, and even significantly faster than the intramolecular vibrational redistribution (IVR) process of the ...
698 citations
TL;DR: Assays of cell viability such as mitochondrial function (MTT) and luminescent ATP production showed that nanodiamonds were not toxic to a variety of cell types, and results suggest that nandiamonds could be ideal for many biological applications in a diverse range ofcell types.
Abstract: Finely divided carbon particles, including charcoal, lampblack, and diamond particles, have been used for ornamental and official tattoos since ancient times. With the recent development in nanoscience and nanotechnology, carbon-based nanomaterials (e.g., fullerenes, nanotubes, nanodiamonds) attract a great deal of interest. Owing to their low chemical reactivity and unique physical properties, nanodiamonds could be useful in a variety of biological applications such as carriers for drugs, genes, or proteins; novel imaging techniques; coatings for implantable materials; and biosensors and biomedical nanorobots. Therefore, it is essential to ascertain the possible hazards of nanodiamonds to humans and other biological systems. We have, for the first time, assessed the cytotoxicity of nanodiamonds ranging in size from 2 to 10 nm. Assays of cell viability such as mitochondrial function (MTT) and luminescent ATP production showed that nanodiamonds were not toxic to a variety of cell types. Furthermore, nanodiamonds did not produce significant reactive oxygen species. Cells can grow on nanodiamond-coated substrates without morphological changes compared to controls. These results suggest that nanodiamonds could be ideal for many biological applications in a diverse range of cell types.
664 citations
TL;DR: It is found that water molecules in the hydration shell of K+ are orientationally more disordered than those hydrating a Na+ ion and are inclined to orient their dipole moments tangentially to the Hydration sphere.
Abstract: Neutron diffraction data with hydrogen isotope substitution on aqueous solutions of NaCl and KCl at concentrations ranging from high dilution to near-saturation are analyzed using the Empirical Potential Structure Refinement technique. Information on both the ion hydration shells and the microscopic structure of the solvent is extracted. Apart from obvious effects due to the different radii of the three ions investigated, it is found that water molecules in the hydration shell of K+ are orientationally more disordered than those hydrating a Na+ ion and are inclined to orient their dipole moments tangentially to the hydration sphere. Cl- ions form instead hydrogen-bonded bridges with water molecules and are readily accommodated into the H-bond network of water. The results are used to show that concepts such as structure maker/breaker, largely based on thermodynamic data, are not helpful in understanding how these ions interact with water at the molecular level.
587 citations
TL;DR: It is shown that the folding free energy landscape can be fully characterized starting from an extended conformation with use of only 40 ns of simulation on 8 replicas, and allows exploring complex free energy landscapes with high efficiency.
Abstract: By suitably extending a recent approach [Bussi, G.; et al. J. Am. Chem. Soc. 2006, 128, 13435] we introduce a powerful methodology that allows the parallel reconstruction of the free energy of a system in a virtually unlimited number of variables. Multiple metadynamics simulations of the same system at the same temperature are performed, biasing each replica with a time-dependent potential constructed in a different set of collective variables. Exchanges between the bias potentials in the different variables are periodically allowed according to a replica exchange scheme. Due to the efficaciously multidimensional nature of the bias the method allows exploring complex free energy landscapes with high efficiency. The usefulness of the method is demonstrated by performing an atomistic simulation in explicit solvent of the folding of a Triptophane cage miniprotein. It is shown that the folding free energy landscape can be fully characterized starting from an extended conformation with use of only 40 ns of sim...
524 citations
TL;DR: A perspective on the relations between inorganic and organic cation ionic liquids (ILs), including members with melting points that overlap around the borderline 100 degrees C, and a basis for assessing their relation to aprotic ILs by means of a Gurney-type proton-transfer free energy level diagram.
Abstract: We give a perspective on the relations between inorganic and organic cation ionic liquids (ILs), including members with melting points that overlap around the borderline 100 °C. We then present data on the synthesis and properties (melting, boiling, glass temperatures, etc.) of a large number of an intermediate group of liquids that cover the ground between equimolar molecular mixtures and ILs, depending on the energetics of transfer of a proton from one member of the pair to the other. These proton-transfer ILs have interesting properties, including the ability to serve as electrolytes in solvent-free fuel cell systems. We provide a basis for assessing their relation to aprotic ILs by means of a Gurney-type proton-transfer free energy level diagram, with approximate values of the energy levels based on free energy of formation and pKa data. The energy level scheme allows us to verify the relation between solvent-free acidic and basic electrolytes, and the familiar aqueous variety, and to identify neutral...
483 citations
TL;DR: In this paper, the relative solvation free energies of ions and ion−solvent clusters in methanol, acetonitrile, and dimethyl sulfoxide (DMSO) have been determined using a combination of experimental and theoretical gas-phase free energies, solution-phase reduction potentials and acid dissociation constants.
Abstract: The division of thermodynamic solvation free energies of electrolytes into contributions from individual ionic constituents is conventionally accomplished by using the single-ion solvation free energy of one reference ion, conventionally the proton, to set the single-ion scales. Thus, the determination of the free energy of solvation of the proton in various solvents is a fundamental issue of central importance in solution chemistry. In the present article, relative solvation free energies of ions and ion−solvent clusters in methanol, acetonitrile, and dimethyl sulfoxide (DMSO) have been determined using a combination of experimental and theoretical gas-phase free energies of formation, solution-phase reduction potentials and acid dissociation constants, and gas-phase clustering free energies. Applying the cluster pair approximation to differences between these relative solvation free energies leads to values of −263.5, −260.2, and −273.3 kcal/mol for the absolute solvation free energy of the proton in me...
441 citations
TL;DR: The structure of confined water, the surface polarity, and the contact angle are in a direct correspondence to each other, and therefore, each quantifies the hydrophobicity/hydrophilicity of the surface.
Abstract: We perform molecular dynamics simulations of water in the presence of hydrophobic/hydrophilic walls at T = 300 K and P = 0 GPa. For the hydrophilic walls, we use a hydroxylated silica model introduced in previous simulations [Lee, S. H.; Rossky, P. J. J. Chem. Phys. 1994, 100, 3334. Giovambattista, N.; Rossky, P. J.; Debenedetti, P. G.; Phys. Rev. E 2006, 73, 041604.]. By rescaling the physical partial atomic charges by a parameter 0 ≤ k ≤ 1, we can continuously transform the hydrophilic walls (hydroxylated silica, k = 1) into hydrophobic apolar surfaces (k = 0). From a physical point of view, k is the normalized magnitude of a surface dipole moment, and thus it quantifies the polarity of the surface. We calculate the contact angle of water for 0 ≤ k ≤ 1. We find that, at least for the present homogeneous, atomically flat, and defect-free surface model, the magnitude of the surface dipole correlates with the contact angle in a one-to-one correspondence. In particular, we find that polar surfaces with 0 < ...
TL;DR: The simulations of nanostructural organization in mixtures of 1-octyl-3-methylimidazolium nitrate ionic liquid and water at multiple water concentrations show that within the range of water contents examined, polar networks, water networks, and micelles possess an approximately invariant characteristic length.
Abstract: Molecular dynamics simulations have been carried out to investigate nanostructural organization in mixtures of 1-octyl-3-methylimidazolium nitrate ionic liquid and water at multiple water concentrations. Evolution of the polar network, water network, and micelle structures is visualized and analyzed via partial radial distribution functions. The calculated static partial structure factors show that within the range of water contents examined, polar networks, water networks, and micelles possess an approximately invariant characteristic length at around 20 A. Furthermore, the above calculations point out that, as the amount of water increases, the polar network is continuously broken up (screened) by the intruding water, while the structural organization of the water network and the micelle exhibits a turnover. At the turnover point, the most ordered micelle (cation−cation) structure and water (water−anion−water) network are formed. Thereafter, the structural organization abates drastically, and only loose...
TL;DR: Standard free energies of aggregation DeltaGom of various ILs derived using the refractive index/concentration profiles were found comparable to those of classical ionic surfactants.
Abstract: Self aggregation of the ionic liquids, 1-butyl-3-methylimidazolium chloride [C4mim][Cl], 3-methyl-1-octylimidazolium chloride [C8mim][Cl], 1-butyl-3-methylimidazolium tetrafluoroborate [C4mim][BF4], N-butyl-3-methylpyridinium chloride [C4mpy][Cl], in aqueous solution has been investigated through 1H nuclear magnetic resonance (NMR) and steady-state fluorescence spectroscopy. Aggregation properties were determined by application of mass action theory to the concentration dependence of 1H NMR chemical shifts. Aggregation properties showed fairly good agreement with the previously reported results obtained from small angle neutron scattering, conductivity, and surface tension measurements. A detailed analysis of chemical shifts of water and various protons in ILs has been employed to probe the aggregate structure. Fluorescence spectroscopy provided important information about the critical aggregation concentration (cac) and the microenvironment of the aggregates. We could also observe a break point quite con...
TL;DR: The increase of the surface charges (zeta potentials) of the microbubbles, which were measured during their collapse, supported the hypothesis that the significant increase in ion concentration around the shrinking gas-water interface provided the mechanism for radical generation.
Abstract: Free radicals are generated by the collapse of ultrasound-induced cavitation bubbles when they are forcefully compressed by dynamic stimuli. Radical generation occurs as a result of the extremely high temperatures induced by adiabatic compression during the violent collapse process. It is generally believed that extreme conditions are required for this type of radical generation. However, we have demonstrated free-radical generation from the collapse of microbubbles (diameter = <50 μm) in the absence of a harsh dynamic stimulus. In contrast to ultrasound-induced cavitation bubbles, which collapse violently after microseconds, the microbubbles collapsed softly under water after several minutes. Electron spin-resonance spectroscopy confirmed free-radical generation by the collapsing microbubbles. The increase of the surface charges (ζ potentials) of the microbubbles, which were measured during their collapse, supported the hypothesis that the significant increase in ion concentration around the shrinking ga...
TL;DR: A recently developed surface-bulk partitioning model is applied to interpret the effects of individual Hofmeister cations and anions on the surface tension of water, findingSemiquantitative agreement with surface-sensitive spectroscopy data and molecular dynamics simulations is attained.
Abstract: We apply a recently developed surface-bulk partitioning model to interpret the effects of individual Hofmeister cations and anions on the surface tension of water. The most surface-excluded salt (Na2SO4) provides a minimum estimate for the number of water molecules per unit area of the surface region of 0.2 H2O A-2. This corresponds to a lower bound thickness of the surface region of ∼6 A, which we assume is a property of this region and not of the salt investigated. At salt concentrations ≲1 m, single-ion partition coefficients Kp,i, defined relative to Kp,Na+ = Kp,SO42− = 0, are found to be independent of bulk salt concentration and additive for different salt ions. Semiquantitative agreement with surface-sensitive spectroscopy data and molecular dynamics simulations is attained. In most cases, the rank orders of Kp,i for both anions and cations follow the conventional Hofmeister series, qualitative rankings of ions based on their effects on protein processes (folding, precipitation, assembly). Most ani...
TL;DR: The conductivity, viscosity, density, and surface tension of a number of glycolic mixtures with choline chloride are measured and it is proposed that the composition at which the measured conductivity matches the theoretical value is the point at which hole mobility becomes the dominant mechanism for charge mobility.
Abstract: Eutectic mixtures of quaternary ammonium salts with Lewis or Bronsted acids have been described as ionic liquid, but doubt exists over the compositional range for which this description is valid. In the current work, the conductivity, viscosity, density, and surface tension of a number of glycolic mixtures with choline chloride are measured over the mole fraction range 0 to 0.33. The data are fitted to hole theory, and it is proposed that the composition at which the measured conductivity matches the theoretical value is the point at which hole mobility becomes the dominant mechanism for charge mobility. For the mixtures of ethylene glycol and butanediol, this occurs at a ChCl mole fraction of approximately 0.2.
TL;DR: From experimental measurements of the temperature dependence of ionic liquid solubilities in water, the thermodynamic molar functions of solution, such as Gibbs energy, enthalpy, and entropy at infinite dilution were determined, showing that the solubility of these ILs in water is entropically driven and that the anion solvation at the IL-rich phase controls their solubabilities in water.
Abstract: The ionic nature of ionic liquids (ILs) results in a unique combination of intrinsic properties that produces increasing interest in the research of these fluids as environmentally friendly “neoteric” solvents. One of the main research fields is their exploitation as solvents for liquid−liquid extractions, but although ILs cannot vaporize leading to air pollution, they present non-negligible miscibility with water that may be the cause of some environmental aquatic risks. It is thus important to know the mutual solubilities between ILs and water before their industrial applications. In this work, the mutual solubilities of hydrophobic yet hygroscopic imidazolium-, pyridinium-, pyrrolidinium-, and piperidinium-based ILs in combination with the anions bis(trifluoromethylsulfonyl)imide, hexafluorophosphate, and tricyanomethane with water were measured between 288.15 and 318.15 K. The effect of the ILs structural combinations, as well as the influence of several factors, namely cation side alkyl chain length,...
TL;DR: The average aggregation number of [C(n)mim]Br (n = 8, 10, 12) has been determined by the steady-state fluorescence quenching technique, and predicted from a simple geometrical mode and it is found that the experimental values are in good agreement with the predicted ones.
Abstract: Densities, conductivities, and polarity indexes of pyrene for aqueous solutions of a series of ionic liquids [Cnmim]Br (n = 4, 6, 8, 10, 12 ) and [C4mim][BF4] have been determined at 298.15 K as a function of ionic liquid concentrations. It was shown that possible aggregation appeared for the ionic liquids in aqueous solutions except for [C4mim]Br. The critical aggregation concentration (CAC) of the ionic liquids, the ionization degree of aggregates (β), the standard Gibbs energy of aggregation ( ), the limiting molar conductivity ( ), and the standard partial molar volume ( ) for the ionic liquids were derived from the experimental data. The dependence of the CAC, , , and on the length of the alkyl chain of the cations was examined. It was further suggested from volumetric data that a micelle was formed for [C8mim]Br, [C10mim]Br, and [C12mim]Br in aqueous solutions. Their apparent molar volumes at the critical micelle concentration (VΦ,CMC), apparent molar volumes in the micelle phase ( ), and the change...
TL;DR: The study provides further evidence that a key aspect of D MSO's mechanism of action is pore formation, which explains the significant enhancement in permeability of membranes to hydrophilic molecules by DMSO as well as DMSo's cryoprotectant activity.
Abstract: Dimethyl sulfoxide (DMSO) is a small amphiphilic molecule which is widely employed in cell biology as an effective penetration enhancer, cell fusogen, and cryoprotectant. Despite the vast number of experimental studies, the molecular basis of its action on lipid membranes is still obscure. A recent simulation study employing coarse-grained models has suggested that DMSO induces pores in the membrane (Notman, R.; Noro, M.; O'Malley, B.; Anwar, J. J. Am. Chem. Soc. 2006, 128, 13982-13983). We report here the molecular mechanism for DMSO's interaction with phospholipid membranes ascertained from atomic-scale molecular dynamics simulations. DMSO is observed to exhibit three distinct modes of action, each over a different concentration range. At low concentrations, DMSO induces membrane thinning and increases fluidity of the membrane's hydrophobic core. At higher concentrations, DMSO induces transient water pores into the membrane. At still higher concentrations, individual lipid molecules are desorbed from the membrane followed by disintegration of the bilayer structure. The study provides further evidence that a key aspect of DMSO's mechanism of action is pore formation, which explains the significant enhancement in permeability of membranes to hydrophilic molecules by DMSO as well as DMSO's cryoprotectant activity. The reduction in the rigidity and the general disruption of the membrane induced by DMSO are considered to be prerequisites for membrane fusion processes. The findings also indicate that the choice of DMSO concentration for a given application is critical, as the concentration defines the specific mode of the solvent's action. Knowledge of the distinct modes of action of DMSO and associated concentration dependency should enable optimization of current application protocols on a rational basis and also promote new applications for DMSO.
TL;DR: The results reveal three distinct and successive steps in the binding of calcium to alginate with increased concentration of Ca ions, which closely correlate with the Ca/guluronate stoichiometry expected for egg-box dimers and multimers with 2/1 helical chains.
Abstract: Previous research on the binding and gelation of calcium/alginate in aqueous solution were mostly conducted in the (semi-)concentrated regime, and it did not provide details of the binding process and the formation of egg-box junctions. In the present investigation, the binding of calcium to alginate, of low and high molecular weight and different guluronate/mannuronate ratios, was investigated in dilute solutions using isothermal titration calorimetry (ITC), Ca2+-selective potentiometry, and viscometry techniques. The results reveal three distinct and successive steps in the binding of calcium to alginate with increased concentration of Ca ions. They were assigned to (i) interaction of Ca2+ with a single guluronate unit forming monocomplexes; (ii) propagation and formation of egg-box dimers via pairing of these monocomplexes; and (iii) lateral association of the egg-box dimers, generating multimers. The third step has different association modes depending on the molecular weight of alginate. The boundaries between these steps are reasonably critical, and they closely correlate with the Ca/guluronate stoichiometry expected for egg-box dimers and multimers with 2/1 helical chains. The formation of egg-box dimers and their subsequent association are thermodynamically equivalent processes and can be fitted by a model of independent binding sites. The binding of Ca to alginates of different guluronate contents is controlled by a balance between enthalpy and entropy.
TL;DR: It is hypothesized that the effects due to a loss in hydrogen bonding are outweighed by those due to the reduction in entropy, which leads to greater ordering within the liquid raising the melting point and increasing viscosity.
Abstract: 1-Butyl-3-methyl-imidazolium chloride ([C4C1im]Cl) is a prototypical ionic liquid. Substitution for a methyl group at the 2-position of the cation to form 1-butyl-2,3-dimethyl-imidazolium ([C4C1mim]+) eliminates the main hydrogen-bonding interaction between the Cl anion and the imidazolium cation. Loss of this hydrogen-bonding interaction could be expected to lead to a reduction in melting point and a decrease in viscosity; however the opposite is observed experimentally; melting points and viscosity increase. The gas-phase structure and electronic properties of ion pairs formed from [C4C1mim]+ and Cl- are investigated to offer insight into this counter-intuitive behavior. We hypothesize that the effects due to a loss in hydrogen bonding are outweighed by those due to a loss in entropy. The amount of disorder in the system is reduced in two ways: elimination of ion-pair conformers, which are stable for [C4C1im]Cl but not [C4C1mim]Cl, and an increase in the rotational barrier of the butyl chain, which lim...
TL;DR: The possibility of utilizing the AIE effect for protein detection and quantification is explored using bovine serum albumin (BSA) as a model protein, with salt 3 being found to perform as a stable, sensitive, and selective bioprobe.
Abstract: Three functionalized derivatives of tetraphenylethylene (TPE), namely, 1,2-bis(4-methoxyphenyl)-1,2-diphenylethene (1), 1,2-bis(4-hydroxyphenyl)-1,2-diphenylethene (2), and 1,2-bis[4-(3-sulfonatopropoxyl)phenyl]-1,2-diphenylethene sodium salt (3), were synthesized and their fluorescence properties were investigated. All the TPE molecules are nonluminescent in the solution state but are induced to emit efficiently by aggregate formation. This novel process of aggregation-induced emission (AIE) is rationalized to be caused by the restriction of intramolecular rotations of the dye molecules in the aggregate state. The possibility of utilizing the AIE effect for protein detection and quantification is explored using bovine serum albumin (BSA) as a model protein, with salt 3 being found to perform as a stable, sensitive, and selective bioprobe.
TL;DR: The solvation structure of the lithium ion in room-temperature ionic liquids 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl) imide and BMP(+0TFSI(-)) has been studied by Raman spectroscopy and DFT calculations and it is concluded that the C(1) conformer is more preferred to the C-2 conformer in the vicinity of the Lithium ion.
Abstract: The solvation structure of the lithium ion in room-temperature ionic liquids 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl) imide (EMI(+)TFSI(-)) and N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl) imide (BMP(+0TFSI(-)) has been studied by Raman spectroscopy and DFT calculations. Raman spectra of EMI(+)TFSI(-) and BMP(+)TFSI(-) containing Li(+)TFSI(-) over the range 0.144-0.589 and 0.076-0.633 mol dm(-3), respectively, were measured at 298 K. A strong 744 cm-1 band of the free TFSI(-) ion in the bulk weakens with increasing concentration of the lithium ion, and it revealed by analyzing the intensity decrease that the two TFSI(-) ions bind to the metal ion. The lithium ion may be four-coordinated through the O atoms of two bidentate TFSI(-) ions. It has been established in our previous work that the TFSI(-) ion involves two conformers of C(1) (cis) and C(2) (trans) symmetries in equilibrium, and the dipole moment of the C(1) conformer is significantly larger than that of the C(2) conformer. On the basis of these facts, the geometries and SCF energies of possible solvate ion clusters [Li(C(1)-TFSI(-))(2)](-), [Li(C(1)-TFSI(-))(C(2)-TFSI(-))](-), and [Li(C(2)-TFSI(-))(2)](-) were examined using the theoretical DFT calculations. It is concluded that the C(1) conformer is more preferred to the C(2) conformer in the vicinity of the lithium ion.
TL;DR: Steady-state and time-resolved emission spectroscopy with 25 ps resolution are used to measure equilibrium and dynamic aspects of the solvation of coumarin 153 (C153) in a diverse collection of 21 room-temperature ionic liquids.
Abstract: Steady-state and time-resolved emission spectroscopy with 25 ps resolution are used to measure equilibrium and dynamic aspects of the solvation of coumarin 153 (C153) in a diverse collection of 21 room-temperature ionic liquids. The ionic liquids studied here include several phosphonium and imidazolium liquids previously reported as well as 12 new ionic liquids that incorporate two homologous series of ammonium and pyrrolidinium cations. Steady-state absorption and emission spectra are used to extract solvation free energies and reorganization energies associated with the S0 ↔ S1 transition of C153. These quantities, especially the solvation free energy, vary relatively little in ionic liquids compared to conventional solvents. Some correlation is found between these quantities and the mean separation between ions (or molar volume). Time-resolved anisotropies are used to observe solute rotation. Rotation times measured in ionic liquids correlate with solvent viscosity in much the same way that they do in ...
TL;DR: A Pd overlayer on a Pd3Fe(111) alloy, was predicted to lie on top of the volcano plot, and thus, it appears to be the most active catalyst among investigated ones because of its moderate interaction with oxygen.
Abstract: We explored the origin of the enhanced activity of Pd-alloy electrocatalysts for the O2 reduction reaction by correlating the electrocatalytic activity of intrinsic Pd and Pt surfaces and Pd and Pt overlayers on several substrates with their electronic properties, and established the volcano-type dependence of O2 reduction activity on the binding energy of oxygen and the d-band center of the top metal layer. Intrinsic Pd and Pt surfaces bind oxygen too firmly to allow efficient removal of the adsorbed reaction intermediates. Therefore, they do not have the highest activity and are not on the top of the volcano plot. A Pd overlayer on a Pd3Fe(111) alloy, was predicted to lie on top of the volcano plot, and thus, it appears to be the most active catalyst among investigated ones because of its moderate interaction with oxygen. The results can help in designing better electrocatalysts for fuel cells and other applications.
TL;DR: The results presented here suggest that triblock copolymer gelation is a promising way to develop highly conductive ion gels and provides many advantages in terms of variety and processing.
Abstract: We report a new way of developing ion gels through the self-assembly of a triblock copolymer in a room-temperature ionic liquid. Transparent ion gels were achieved by gelation of a poly(styrene-block-ethylene oxide-block-styrene) (SOS) triblock copolymer in 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]) with as low as 5 wt % SOS triblock copolymer. The gelation behavior, ionic conductivity, rheological properties, and microstructure of the ion gels were investigated. The ionic conductivity of the ion gels is only modestly affected by the triblock copolymer network. Its temperature dependence nearly tracks that of the bulk ionic liquid viscosity. The ion gels are thermally stable up to at least 100 °C and possess significant mechanical strength. The results presented here suggest that triblock copolymer gelation is a promising way to develop highly conductive ion gels and provides many advantages in terms of variety and processing.
TL;DR: The first theoretical development of empirical equations based on applying the new fundamental approach to kinetics of interfacial transport called the Statistical Rate Theory are proposed and it is shown that these empirical equations are simplified forms of a more general equation developed here, for the case when the adsorption kinetics is governed by the rate of surface reactions.
Abstract: For practical applications of solid/solution adsorption processes, the kinetics of these processes is at least as much essential as their features at equilibrium. Meanwhile, the general understanding of this kinetics and its corresponding theoretical description are far behind the understanding and the level of theoretical interpretation of adsorption equilibria in these systems. The Lagergren empirical equation proposed at the end of 19th century to describe the kinetics of solute sorption at the solid/solution interfaces has been the most widely used kinetic equation until now. This equation has also been called the pseudo-first order kinetic equation because it was intuitively associated with the model of one-site occupancy adsorption kinetics governed by the rate of surface reaction. More recently, its generalization for the two-sites-occupancy adsorption was proposed and called the pseudo-second-order kinetic equation. However, the general use and the wide applicability of these empirical equations during more than one century have not resulted in a corresponding fundamental search for their theoretical origin. Here the first theoretical development of these equations is proposed, based on applying the new fundamental approach to kinetics of interfacial transport called the Statistical Rate Theory. It is shown that these empirical equations are simplified forms of a more general equation developed here, for the case when the adsorption kinetics is governed by the rate of surface reactions. The features of that general equation are shown by presenting exhaustive model investigations, and the applicability of that equation is tested by presenting a quantitative analysis of some experimental data reported in the literature.
TL;DR: The remarkable variations in the photophysical properties of Cy3-DNA constructs demonstrate that caution should be used when Cy3 is used in studies employing DNA conjugates, and it is observed that the activation energy for photoisomerization depends strongly on the microenvironment in which the dye is located.
Abstract: The sulfoindocyanine Cy3 is one of the most commonly used fluorescent dyes in the investigation of the structure and dynamics of nucleic acids by means of fluorescence methods. In this work, we report the fluorescence and photophysical properties of Cy3 attached covalently to single-stranded and duplex DNA. Steady-state and time-resolved fluorescence techniques were used to determine fluorescence quantum yields, emission lifetimes, and fluorescence anisotropy decays. The existence of a transient photoisomer was investigated by means of transient absorption techniques. The fluorescence quantum yield of Cy3 is highest when attached to the 5‘ terminus of single-stranded DNA (Cy3−5‘ ssDNA), and decreases by a factor of 2.4 when the complementary strand is annealed to form duplex DNA (Cy3−5‘ dsDNA). Substantial differences were also observed between the 5‘-modified strands and strands modified through an internal amino-modified deoxy uridine. The fluorescence decay of Cy3 became multiexponential upon conjugati...
TL;DR: Applications of computer simulations to a number of important and interesting systems will be presented, highlighting the roles of charge delocalization and Grotthuss shuttling, a phenomenon unique in many ways to the excess proton in water.
Abstract: The excess proton in aqueous media plays a pivotal role in many fundamental chemical (e.g., acid-base chemistry) and biological (e.g., bioenergetics and enzyme catalysis) processes. Understanding the hydrated proton is, therefore, crucial for chemistry, biology, and materials sciences. Although well studied for over 200 years, excess proton solvation and transport remains to this day mysterious, surprising, and perhaps even misunderstood. In this feature article, various efforts to address this problem through computer modeling and simulation will be described. Applications of computer simulations to a number of important and interesting systems will be presented, highlighting the roles of charge delocalization and Grotthuss shuttling, a phenomenon unique in many ways to the excess proton in water.
TL;DR: The current state of understanding of metal binding plays in determining the physical, structural, biological, and photochemical properties of melanin is examined.
Abstract: Metal chelation is often invoked as one of the main biological functions of melanin. In order to understand the interaction between metals and melanin, extensive studies have been carried out to determine the nature of the metal binding sites, binding capacity, and affinity. These data are central to efforts aimed at elucidating the role metal binding plays in determining the physical, structural, biological, and photochemical properties of melanin. This article examines the current state of understanding of this field.