Interfacial and intrafacial linkage isomerizations of rhenium complexes with aromatic molecules

The mechanisms for the interconversion of facial diastereomers of a variety of TpRe(CO)(L)(eta(2)-L(Ar)) complexes [L = (t)BuNC, pyridine (py), PMe(3), or 1-methylimidazole (MeIm); L(Ar) = benzene, anisole, naphthalene, 1-methylpyrrole, furan, or thiophene; Tp = hydridotris(pyrazolyl)borate] have been investigated by (1)H NMR spin saturation experiments. In addition, the rates and free energies of activation for these processes were calculated from spin saturation experiments and T(1) measurements. The operative mechanisms for interconversion of the pi diastereomers were found to be nondissociative, undergoing either an interfacial or intrafacial linkage isomerization. A comparison of the kinetic parameters for isomerization of related eta(2)-olefin complexes of the [TpRe(CO)(PMe(3))] and [CpRe(NO)(PPh(3))](+) fragments is also presented.     

Evaporation of a sub-micrometer droplet

Evaporation of a spherically symmetric sub-micrometer size liquid droplet is studied using a diffuse interface hydrodynamic model supplemented by the van der Waals equation of state with parameters characteristic for argon. The droplet, surrounded by saturated vapor, is held in a container with the temperature of the walls kept fixed. The evaporation is triggered by a sudden rise of the temperature of the walls. Time and space evolution of the basic thermodynamic quantities is presented. The time and space scales studied range from picoseconds to microseconds and from nanometers to micrometers, respectively. We find that the temperature and chemical potential are both continuous at the interface on the scale larger than the interfacial width. We find that at long times the radius R of the droplet changes with time t as R(2)(t) = R(2)(0) - 2tkappa(v)(T(w) - T(l))/ln(l), where kappa(v) is the heat conductivity of the vapor, n(l) and T(l) are the density and the temperature of liquid inside the droplet, respectively, l is the latent heat of transition per molecule, and T(w) is the temperature of the ambient vapor.     

Surface adsorption behaviour of milk whey protein and pectin mixtures under conditions of air-water interface saturation

Milk whey proteins (MWP) and pectins (Ps) are biopolymer ingredients commonly used in the manufacture of colloidal food products. Therefore, knowledge of the interfacial characteristics of these biopolymers and their mixtures is very important for the design of food dispersion formulations (foams and/or emulsions). In this paper, we examine the adsorption and surface dilatational behaviour of MWP/Ps systems under conditions in which biopolymers can saturate the air-water interface on their own. Experiments were performed at constant temperature (20 °C), pH 7 and ionic strength 0.05 M. Two MWP samples, β-lactoglobulin (β-LG) and whey protein concentrate (WPC), and two Ps samples, low-methoxyl pectin (LMP) and high-methoxyl pectin (HMP) were evaluated. The contribution of biopolymers (MWP and Ps) to the interfacial properties of mixed systems was evaluated on the basis of their individual surface molecular characteristics. Biopolymer bulk concentration capable of saturating the air-water interface was estimated from surface pressure isotherms. Under conditions of interfacial saturation, dynamic adsorption behaviour (surface pressure and dilatational rheological characteristics) of MWP/Ps systems was discussed from a kinetic point of view, in terms of molecular diffusion, penetration and configurational rearrangement at the air-water interface. The main adsorption mechanism in MWP/LMP mixtures might be the MWP interfacial segregation due to the thermodynamic incompatibility between MWP and LMP (synergistic mechanism); while the interfacial adsorption in MWP/HMP mixtures could be characterized by a competitive mechanism between MWP and HMP at the air-water interface (antagonistic mechanism). The magnitude of these phenomena could be closely related to differences in molecular composition and/or aggregation state of MWP (β-LG and WPC).     

Effect of acidic surface treatment of red mud on mechanical interfacial properties of epoxy/red mud nanocomposites

In this work, red mud (RM) was chemically modified by 0.1, 1, and 5 M H(3)PO(4) solution to prepare epoxy/RM nanocomposites. The effect of chemical treatment on a RM surface was studied in terms of pH, acid-base values, N(2)/77 K gas adsorption, equilibrium spreading pressure (pi(e)), and surface free energy. The mechanical interfacial properties of epoxy/RM nanocomposites was measured in the context of critical stress intensity factor (K(IC)) and critical strain energy release rate (G(IC)) measurements. From the experimental results, the acidic surface treatment led to a modification of the RM surface properties, such as the surface acid values, porosity, specific surface area, pi(e), and London dispersive component (gamma(S)(L)) of surface free energy of the treated RM as an increase of the treatment concentration. In the fracture toughness (K(IC) and G(IC)) measurements, the mechanical interfacial properties of epoxy/treated RM nanocomposites were intimately correlated with the improvement of interfacial adhesion between the RM surface and a matrix and the increase of gamma(S)(L) of surface free energy of the RM due to the development of S(BET) or porosity of RM surfaces.     

Poly(D,L-lactide-co-glycolide) dispersions containing pluronics: from particle preparation to temperature-triggered aggregation

In this work the preparation mechanism, properties and temperature-triggered aggregation of poly(D, L-lactide- co-glycolide) (PLGA) dispersions are investigated. The dispersions were prepared by interfacial deposition in aqueous solution containing Pluronic L62 (EO(6)PO(30)EO(6)) or F127NF (EO(101)PO(56)EO(101)), where EO and PO are ethylene oxide and propylene oxide, respectively. PLGA dispersions were also prepared in the absence of added Pluronic for comparison. The PLGA particles were characterized using SEM, photon correlation spectroscopy and electrophoretic mobility measurements. It was found that the hydrodynamic diameter (d) increased with PLGA concentration used in the organic solvent phase ( C PLGA(o) ). The value for d was proportional to C(PLGA)(o) (1/3). The value for d increased upon addition of 0.04 M NaNO(3) which demonstrated the importance of electrostatic interactions during particle formation. Electrophoretic mobility measurements were conducted as a function of pH and the data used to estimate the Pluronic layer thicknesses on the PLGA particles. The layer thickness was greatest for the PLGA particles prepared in the presence of Pluronic F127NF. PLGA dispersions containing Pluronic L62 exhibited temperature-triggered aggregation in the presence of 0.15 M NaNO(3). It was found that the critical temperature for dispersion aggregation (T(crit)) was comparable to the cloud point temperature ( T(cp)) for the parent Pluronic L62 solution. Conditions were established for achieving temperature-triggered aggregation at body temperature for PLGA particle/Pluronic L62 dispersions under physiological ionic strength and pH conditions. The PLGA/Pluronic L62 mixtures studied may have potential for use as injectable biodegradable implants for controlled release applications.     

Bridging QTAIM with vibrational spectroscopy: the energy of intramolecular hydrogen bonds in DNA-related biomolecules

Physical properties of over 8000 intramolecular hydrogen bonds (iHBs), including 2901 ones of the types OH···O, OH···N, NH···O and OH···C, in 4244 conformers of the DNA-related molecules (four canonical 2'-deoxyribonucleotides, 1,2-dideoxyribose-5-phosphate, and 2-deoxy-D-ribose in its furanose, pyranose and linear forms) have been investigated using quantum theory of atoms in molecules (QTAIM) and vibrational analysis. It has been found that for all iHBs with positive red-shift of the proton donating group stretching frequency the shift value correlates with ρ(cp)-the electron charge density at the (3,-1)-type bond critical point. Combining QTAIM and spectroscopic data new relationships for estimation of OH···O, OH···N, NH···O and OH···C iHB enthalpy of formation (kcal mol(-1)) with RMS error below 0.8 kcal mol(-1) have been established: E(OH···O) = -3.09 + 239·ρ(cp), E(OH···N) = 1.72 + 142·ρ(cp), E(NH···O) = -2.03 + 225·ρ(cp), E(OH···C) = -0.29 + 288·ρ(cp), where ρ(cp) is in e a(0)(-3) (a(0)- the Bohr radius). It has been shown that XHY iHBs with red-shift values over 40 cm(-1) are characterized by the following minimal values of the XHY angle, ρ(cp) and nubla(2)ρ(cp): 112°, 0.005 e a(0)(-3) and 0.016 e a(0)(-5), respectively. New relationships have been used to reveal the strongest iHBs in canonical 2'-deoxy- and ribonucleosides and the O(5')H···N(3) H-bond in ribonucleoside guanosine was found to have the maximum energy (8.1 kcal mol(-1)).     

Water evaporation rates across hydrophobic acid monolayers at equilibrium spreading pressure

The effect of alkanoic acid [CH(3)(CH(2))(n-2)COOH; HCn] and perfluoroalkanoic acid [CF(3)(CF(2))(n-2)COOH; FCn] monolayers on the water evaporation rate was investigated by thermogravimetry tracing the decrease in amount of water with time. The evaporation rate from the surface covered by a monolayer was measured as a function of temperature and hydrophobic chain length of the acids, where the monolayer was under an equilibrium spreading pressure. From thermal behavior of the crystallized acids, their solid states are C-type in crystalline state over the temperature range from 298.2 to 323.2 K. The dry air was flowed through a furnace tube of a thermogravimetry apparatus at the flow rate of 80 mL min(-1), where the evaporation rate becomes almost constant irrespective of the flow rate. The temperature dependence of the evaporation rate was analyzed kinetically to evaluate the activation energy and thermodynamics values for the activated complex, which demonstrated that these values were almost the same for both alkanoic acids and perfluoroalkanoic acids, although the effect of perfluoroalkanoic acids on the evaporation rate was smaller than that of corresponding hydrogenated fatty acids. The difference in the evaporation rate between FCn and HCn was examined by atomic force microscopy (AFM), Brewster angle microscopy (BAM), surface potential (DeltaV) at equilibrium spreading pressure, and Langmuir curve (pi-A isotherm), and their results were consistent and supported the difference.     

Kinetics of the NCN + NO reaction over a broad temperature and pressure range

Rate coefficients for the reaction (3)NCN + NO → products (R3) were measured in the temperature range 251-487 K at pressures from 10 mbar up to 50 bar with helium as the bath gas. The experiments were carried out in slow-flow reactors by using pulsed excimer laser photolysis of NCN(3) at 193 or 248 nm for the production of NCN. Pseudo-first-order conditions ([NCN](0) ? NO) were applied, and NCN was detected time-resolved by resonant laser-induced fluorescence excited near 329 nm. The measurements at the highest pressures yielded values of k(3) ～ 8 × 10(-12) cm(3) s(-1) virtually independent of temperature and pressure, which indicates a substantially smaller high-pressure limiting value of k(3) than predicted in earlier works. Our experiments at pressures below 1 bar confirm the negative temperature and positive pressure dependence of the rate coefficient k(3) found in previous investigations. The falloff behavior of k(3) was rationalized by a master equation analysis based on a barrierless association step (3)NCN + NO ? NCNNO((2)A″) followed by a fast internal conversion NCNNO((2)A″) ? NCNNO((2)A'). From 251-487 K and above 30 mbar, the rate coefficient k(3) is well represented by a Troe parametrization for a recombination/dissociation reaction, k(3)(T,P) = k(4)(∞)k(4)(0)[M]F(k(4)(0)[M] + k(4)(∞))(-1), where k(4) represents the rate coefficient for the recombination reaction (3)NCN + NO. The following parameters were determined (30% estimated error of the absolute value of k(3)): k(4)(0)[M=He] = 1.91 × 10(-30)(T/300 K)(-3.3) cm(6) s(-1)[He], k(4)(∞) = 1.12 × 10(-11) exp(-23 K/T) cm(3) s(-1), and F(C) = 0.28 exp(173 K/T).     

Hyperbranched polymers with thermoresponsive property highly sensitive to ions

The salt effects on the water solubility of thermoresponsive hyperbranched polyethylenimine and polyamidoamine possessing large amounts of isobutyramide terminal groups (HPEI-IBAm and HPAMAM-IBAm) were studied systematically. Eight anions with sodium as the counterion and ten cations with chloride as the counterion were used to measure the anion and cation effects on the cloud point temperature (T(cp)) of these dendritic polymers in water. It was found that the T(cp) of these dendritic polymers was much more sensitive to the addition of salts than that of the traditional thermoresponsive linear polymers. At low anion concentration, the electrostatic interaction between anions and the positively charged groups of these polymers was dominant, resulting in the unusual anion effect on the T(cp) of these polymers in water, including (1) T(cp) of these dendritic polymers decreasing nonlinearly with the increase of kosmotropic anion concentration; (2) the chaotropic anions showing abnormal salting-out property at low salt concentration and the stronger chaotropes having much pronounced salting-out ability; (3) anti-Hofmeister ordering at low salt concentration. At moderate to high salt concentration, the specific ranking of these anions in reducing the T(cp) of HPEI-IBAm and HPAMAM-IBAm polymers was PO(4)(3-) > CO(3)(2-) > SO(4)(2-) > S(2)O(3)(2-) > F(-) > Cl(-) > Br(-) > I(-), in accordance with the well-known Hofmeister series. At moderate to high salt concentration, the specific ranking order of inorganic cations in reducing the T(cp) of HPEI-IBAm polymer was Sr(2+) ≈ Ba(2+) > Na(+) ≈ K(+) ≈ Rb(+) > Cs(+) > NH(4)(+) ≈ Ca(2+) > Li(+) ≈ Mg(2+). This sequence was only partially similar to the typical Hofmeister cation series, whereas at low salt concentration the cation effect on T(cp) of the dendritic polymer was insignificant and no obvious specific ranking order could be found.     

The pressure- and temperature-induced wetting transitions in the binary water + ethylene glycol monoisobutyl ether mixture

A homemade pendent drop/bubble tensiometer is applied to perform the surface/interfacial tension measurements for the binary water + ethylene glycol monoisobutyl ether (iso-C4E1) mixture over the temperature range from 25 to 150 degrees C and over the pressure range up to 100 bar. The symbol C(i)E(j) is the abbreviation of a nonionic polyoxyethylene alcohol C(i)H(2i+1)(OCH2CH2)(j)OH. The wetting behavior of the iso-C4E1-rich phase at the surface of the aqueous phase is systematically examined according to the wetting coefficient determined from the experimental results of surface/interfacial tensions. It is found that the iso-C4E1-rich phase exhibits a sequence of wetting transitions, nonwetting --> partial wetting --> complete wetting, at the water surface in the water + iso-C4E1 system along with increasing temperature. On the other hand, the iso-C4E1-rich phase undergoes a wetting transition from partial wetting to nonwetting at the surface of the aqueous phase by increasing the system pressure at a fixed temperature near the lower critical solution temperature (LCST) of the closed-loop miscibility gap in the water + iso-C4E1 system.     

Pressure and temperature jump relaxation kinetics of the conformational change in Salmonella typhimurium tryptophan synthase L-serine complex: large activation compressibility and heat capacity changes demonstrate the contribution of solvation

Tryptophan synthase is an alpha2beta2 multienzyme complex that exhibits coupling of the alpha- and beta-subunit reactions by tightly controlled allosteric interactions. A wide range of parameters can affect the allosteric interactions, including monovalent cations, pH, alpha-site and beta-site ligands, temperature, and pressure. Rapid changes in hydrostatic pressure (P-jump) and temperature (T-jump) were used to examine the effects of pressure and temperature on the rates of the interconversion of external aldimine and aminoacrylate intermediates in the Tryptophan synthase-L-Ser complex. The intense fluorescence emission of the Tryptophan synthase L-Ser external aldimine complex at 495 nm, with 420 nm excitation, provides a probe of the conformational state of Trp synthase. P-jump measurements allowed the determination of rate constants for the reactions in the presence of Na(+), Na(+) with benzimidazole (BZI), and NH4(+). The data require a compressibility term, beta(o)(double dagger), to obtain good fits, especially for the NH4(+) and BZI/Na(+) data. The compressibility changes are consistent with changes in solvation in the transition state. The transition state for the relaxation is more similar in volume to the closed aminoacrylate complex in the presence of Na(+), while it is more similar to the open external aldimine in the presence of NH4(+). Differences between the relaxations for positive and negative P-jumps may arise from changing relative populations of microstates with pressure. T-jump experiments of the Na(+) form of the tryptophan synthase-L-Ser complex show large changes in rate and amplitude over the temperature range from 7 to 45 degrees C. The Arrhenius plots show strong curvature, and hence require a heat capacity term, DeltaC(p)(double dagger), to obtain good fits. The values of DeltaC(p)(double dagger) are very large and negative (-3.6 to -4.4 kJ mol(-1) K(-1)). These changes are also consistent with large changes in solvation in the transition state for interconversion of external aldimine and aminoacrylate intermediates in the Tryptophan synthase-L-Ser complex.     

On scale dependence in friction: transition from intimate to monolayer-lubricated contact

Scale dependence in friction is studied in the present paper using the newly developed mesoscale friction tester (MFT). A transition in frictional shear strength from several hundreds of MPa to several tens of MPa was observed over a very limited range of contact radii (20-30 nm) in both ambient and dry environments. Thus, a single apparatus has been able to establish these two limits which are consistent with the values previously obtained from friction experiments using atomic force microscopy (AFM) and the surface force apparatus (SFA), respectively. Consequently, it is hypothesized here that a shear strength in the hundreds of MPa results from intimate contact (solid-solid) and a shear strength in the tens of MPa results from a monolayer-lubricated contact. Furthermore, both the probe size and the normal pressure govern the interfacial conditions in the contact zone and it is these conditions, rather than the nominal environment, which in turn determine the resulting shear strengths. A continuum analysis based on the Lifshitz theory for van der Waals interactions is used to explain the quantized shear strengths which were obtained from our experiments and previous AFM and SFA friction experiments. This quantized friction behavior [J.N. Israelachvili, P.M. McGuiggan, A.M. Homola, Science 240 (1988) 189] results from the discrete separation due to the different interfacial conditions that can arise between two sliding surfaces. The consistency between the analysis and the experimental results shows that this analysis is applicable for nonwear friction with single asperity contact.     

Temperature and composition dependence of the Soret coefficient in Lennard-Jones mixtures presenting evaporation/condensation phase transition

The thermodiffusive behavior of a Lennard-Jones binary mixture has been studied by using nonequilibrium molecular dynamics. In particular, the dependence of the Soret coefficient, S(T), on the temperature and composition has been investigated, exploring a wide range of temperatures from 1000 K to the condensation temperature of the mixture. In a previous paper the dependence of S(T) on the temperature and the composition was studied for Lennard-Jones binary mixtures presenting mixing/demixing (consolute) phase transition, and the results allowed the formulation of a very simple expression with the computed values of S(T) in the one phase region outside the critical region closely fitted by the function [T - T(c)(x(1))](-1), with T(c)(x(1)) the demixing temperature of the mixture under study. The results of the present work show that the same expression of S(T) can be found for the one phase region outside the evaporation/condensation region but now with T(c) representing the condensation temperature of the mixture under study.     

Interfacial rheology and conformations of triblock copolymers adsorbed onto the water-oil interface

The conformation and the dilatational properties of three non-ionic triblock PEO-PPO-PEO (where PEO is polyethyleneoxide and PPO is polypropyleneoxide) copolymers of different hydrophobicity and molecular weight were investigated at the water-hexane interface. The interfacial behavior of the copolymers was studied by combining dilatational rheology using the oscillating drop method and ellipsometry. From the dilatational rheology measurements the limiting elasticity values, E(0), of the Pluronics as function of surface pressure, Π, and adsorption time were obtained, i.e. E(0)(t) and E(0)(Π). Here, it is shown that E(0)(t) depends on the number of PEO units and on the bulk concentration, showing maximum and minimum surface elasticity values which indicate conformational changes in the interfacial layer. Furthermore, in the framework of the polymer scaling law theory, conformational transitions were discussed in E(0) vs. Π plots. In a dilute regime (Π<14 mN m(-1)) at the water-hexane interface, E(0)=2Π fits well all the data, which indicates a two-dimensional "stretched chain" conformation. Increasing Π, two other interfacial transitions could take place. The different behavior of Pluronic copolymers could be also described by the local minima of E(0), which depends on the hydrophobicity of the copolymers. Conformational transitions observed by interfacial rheology were compared to ellipsometric data. Experimental results were discussed and explained on the basis of two- and three-dimensional copolymer structure taking into account that PPO chains could be partially immersed in hexane and water.     

Dynamic processes in a silicate liquid from above melting to below the glass transition

We collect and critically analyze extensive literature data, including our own, on three important kinetic processes--viscous flow, crystal nucleation, and growth--in lithium disilicate (Li(2)O·2SiO(2)) over a wide temperature range, from above T(m) to 0.98T(g) where T(g) ≈ 727 K is the calorimetric glass transition temperature and T(m) = 1307 K, which is the melting point. We found that crystal growth mediated by screw dislocations is the most likely growth mechanism in this system. We then calculated the diffusion coefficients controlling crystal growth, D(eff)(U), and completed the analyses by looking at the ionic diffusion coefficients of Li(+1), O(2-), and Si(4+) estimated from experiments and molecular dynamic simulations. These values were then employed to estimate the effective volume diffusion coefficients, D(eff)(V), resulting from their combination within a hypothetical Li(2)Si(2)O(5) "molecule". The similarity of the temperature dependencies of 1/η, where η is shear viscosity, and D(eff)(V) corroborates the validity of the Stokes-Einstein/Eyring equation (SEE) at high temperatures around T(m). Using the equality of D(eff)(V) and D(eff)(η), we estimated the jump distance λ ~ 2.70 ? from the SEE equation and showed that the values of D(eff)(U) have the same temperature dependence but exceed D(eff)(η) by about eightfold. The difference between D(eff)(η) and D(eff)(U) indicates that the former determines the process of mass transport in the bulk whereas the latter relates to the mobility of the structural units on the crystal/liquid interface. We then employed the values of η(T) reduced by eightfold to calculate the growth rates U(T). The resultant U(T) curve is consistent with experimental data until the temperature decreases to a decoupling temperature T(d)(U) ≈ 1.1-1.2T(g), when D(eff)(η) begins decrease with decreasing temperature faster than D(eff)(U). A similar decoupling occurs between D(eff)(η) and D(eff)(τ) (estimated from nucleation time-lags) but at a lower temperatureT(d)(τ) ≈ T(g). For T > T(g) the values of D(eff)(τ) exceed D(eff)(η) only by twofold. The different behaviors of D(eff)(τ)(T) and D(eff)(U)(T) are likely caused by differences in the mechanisms of critical nuclei formation. Therefore, we have shown that at low undercoolings, viscosity data can be employed for quantitative analyses of crystal growth rates, but in the deeply supercooled liquid state, mass transport for crystal nucleation and growth are not controlled by viscosity. The origin of decoupling is assigned to spatially dynamic heterogeneity in glass-forming melts.     

Thermo-elastic and thermodynamic properties of light and heavy crude oil

Three different experiments, viz., ultrasound interferometry, differential scanning calorimetry, and density measurements were carried out over a wide range of temperature varying from 20°C to 70°C in light, heavy, and a mixture of light and heavy crude oil samples which differ considerably in its American Petroleum Institute gravity. The properties of the mixture have been discussed in terms of its deviation from the ideal values of mixing. The directly measured quantities such as the compression wave velocity, the specific heat at constant pressure, and the density were used to evaluate the temperature dependence of adiabatic compressibility, coefficient of volume expansion and the acoustic impedance. A correlation between thermo-elastic and thermodynamic functions of crude oils has been investigated. In particular, the ratio of the specific heats has been determined by making use of the thermo-elastic functions, which was further used to estimate the specific heat at constant volume. The values of the isothermal compressibility and the coefficient of volume expansion are used to evaluate the pressure–temperature dependence of crude oil conforming to in-situ reservoir conditions.     

Solution, solid state, and film properties of a structurally characterized highly luminescent molecular europium plastic material excitable with visible light

The synthesis and X-ray crystal structure of the ligand L (4,7-dicarbazol-9-yl-[1,10]-phenanthroline) are reported, as well as those of the molecular complex, [Eu(tta)(3)(L)] (1), (tta = 2-thenoyl trifluoroacetylacetonate). Their photophysical properties have been investigated both in solution and in the solid state. It was shown that the ligands used for designing 1 are well-suited for sensitizing the Eu(III) ion emission, thanks to a favorable position of the triplet state as investigated in the Gd(III) complex [Gd(tta)(3)(L)], (2). The low local symmetry of the Eu(III) ion shown by the X-ray crystal structure of 1 is also revealed by luminescence spectroscopy. Because of interesting volatility and solubility properties, 1 is shown to behave as a real molecular material that can be processed both by thermal evaporation and from solution. When doped in poly(methylmethacrylate) (PMMA), 1 forms air-stable and highly red-emitting plastic materials that can be excited in a wide range of wavelengths from the UV to the visible part of the electromagnetic spectrum (250-560 nm). Absolute quantum yields of 80% have been obtained for films comprising 1-3% of 1. Ellipsometry measurements have been introduced to gain information on physical data of 1. They have been performed on thin films of 1 deposited by thermal evaporation and gave access to the refractive index, n, and the absorption coefficient, k, as a function of the wavelength. A value of 1.70 has been found for n at 633 nm. These thin films also show interesting air-stability.     

Use of IR thermography to investigate heated droplet evaporation and contact line dynamics

In this paper we present the results of an experimental study investigating interfacial properties during the evaporation of sessile water droplets on a heated substrate. This study uses infrared thermography to map the droplet interfacial temperature. The measurements evidence nonuniform temperature and gradients that evolve in time during the evaporation process. A general scaling law for the interfacial temperature is deduced from the experimental observations. A theoretical analysis is performed to predict the local evaporation rates and their evolution in time. The use of energy conservation laws enabled us to deduce a general expression for the interfacial temperature. The comparison between the theory and experiments shows good agreement and allows us to rationalize the experimental observations. The thermography analysis also enabled the detection of the three-phase contact line location and its dynamics. To our knowledge, such measurements are performed for the first time using thermography.     

Solution behavior of normal and reverse triblock copolymers (pluronic L44 and 10R5) individually and in binary mixture

Solution properties of pluronics L44 or L [(PEO)(10)(PPO)(23)(PEO)(10)] and 10R5 or R [(PPO)(8)(PEO)(22)(PPO)(8)] were studied individually as well in their binary mixtures in aqueous medium. The critical micelle concentration (CMC), critical micelle temperature, and cloud point (CP) were determined. Ideal and nonideal behaviors of their mixtures in the formation of CMC and CP were observed; the energetics of the studied processes were determined. Spectrophotometry, isothermal titration calorimetry and dynamic light scattering (DLS) methods were used for evaluations. Morphologies of the dispersed L, R, and their mixtures along with their polydispersities were determined from DLS measurements. Atomic force microscopy was also employed. The interfacial properties of L and R were investigated forming Langmuir monolayers in a surface balance. The surface pressures (π) generated by the compounds were moderate, the area per molecule was higher for R than L. R has shown antibacterial activity against both gram positive and gram negative bacteria whereas L was inactive in this respect.