Thermal Diffusion Forced Rayleigh Scattering Research Articles

Complementary Experimental Methods to Obtain Thermodynamic Parameters of Protein Ligand Systems.

In recent years, thermophoresis has emerged as a promising tool for quantifying biomolecular interactions. The underlying microscopic physical effect is still not understood, but often attributed to changes in the hydration layer once the binding occurs. To gain deeper insight, we investigate whether non-equilibrium coefficients can be related to equilibrium properties. Therefore, we compare thermophoretic data measured by thermal diffusion forced Rayleigh scattering (TDFRS) (which is a non-equilibrium process) with thermodynamic data obtained by isothermal titration calorimetry (ITC) (which is an equilibrium process). As a reference system, we studied the chelation reaction between ethylenediaminetetraacetic acid (EDTA) and calcium chloride (CaCl2) to relate the thermophoretic behavior quantified by the Soret coefficient ST to the Gibb's free energy ΔG determined in the ITC experiment using an expression proposed by Eastman. Finally, we have studied the binding of the protein Bovine Carbonic Anhydrase I (BCA I) to two different benzenesulfonamide derivatives: 4-fluorobenzenesulfonamide (4FBS) and pentafluorobenzenesulfonamide (PFBS). For all three systems, we find that the Gibb's free energies calculated from ST agree with ΔG from the ITC experiment. In addition, we also investigate the influence of fluorescent labeling, which allows measurements in a thermophoretic microfluidic cell. Re-examination of the fluorescently labeled system using ITC showed a strong influence of the dye on the binding behavior.

Thermophoretic microfluidic cells for evaluating Soret coefficient of colloidal particles

Thermodiffusion or thermophoresis gained much interest in bio, chemical, and energy engineering. Although there are several methods to measure thermophoresis, they consume large sample volumes, are limited to binary mixtures, and give only indirect access to the applied temperature profile. Herein, we propose a thermophoretic microfluidic cell for quantitative measurements of the Soret coefficient of colloids. The actual microscale measuring channel lies between cooling and heating channels to achieve a one-dimensional temperature gradient. Fluorescence lifetime imaging microscopy with Rhodamine B is utilized to measure the spatial temperature profile in the channel. The fluorescence intensity of fluorescently labeled polystyrene particles with a diameter of 25 nm is used to monitor the concentration profile. The observed temperature and concentration profiles are one-dimensional, as gradients in the longitudinal and height directions can be neglected. In the investigated temperature range, the averaged difference between the measured Soret coefficients with the cell and determined with the Thermal Diffusion Forced Rayleigh Scattering set-up is less than 8%.

Towards understanding specific ion effects in aqueous media using thermodiffusion

Specific ion effects play an important role in scientific and technological processes. According to Hofmeister, the influence on the hydrogen bond network depends on the ion and leads to a specific order of the ions. Also thermodiffusion the mass transport caused by a temperature gradient is very sensitive to changes of the hydrogen bond network leading to a ranking according to hydrophilicity of the salt. Hence, we investigate various salt solutions in order to compare with the Hofmeister concept. We have studied three different sodium salts in water as a function of temperature (25–45^circ C) and concentration (0.5–5 mol kg^{-1}) using Thermal Diffusion Forced Rayleigh Scattering (TDFRS). The three anions studied, carbonate, acetate and thiocyanate, span the entire range of the Hofmeister series from hydrophilic to hydrophobic. We compare the results with the recent measurements of the corresponding potassium salts to see to what extent the cation changes the thermodiffusion of the salt.Graphic abstract

Temperature profile characterization with fluorescence lifetime imaging microscopy in a thermophoretic chip

This study introduces a thermophoretic lab-on-a-chip device to measure the Soret coefficient. We use resistive heating of a microwire on the chip to induce a temperature gradient, which is measured by fluorescence lifetime imaging microscopy (FLIM). To verify the functionality of the device, we used dyed polystyrene particles with a diameter of 25 nm. A confocal microscope is utilized to monitor the concentration profile of colloidal particles in the temperature field. Based on the measured temperature and concentration differences, we calculate the corresponding Soret coefficient. The same particles have been recently investigated with thermal diffusion forced Rayleigh scattering (TDFRS) and we find that the obtained Soret coefficients agree with literature results. This chip offers a simple way to study the thermophoretic behavior of biological systems in multicomponent buffer solutions quantitatively, which are difficult to study with optical methods solely relying on the refractive index contrast.Graphic abstract

Thermophoresis: The Case of Streptavidin and Biotin.

Thermophoretic behavior of a free protein changes upon ligand binding and gives access to information on the binding constants. The Soret effect has also been proven to be a promising tool to gain information on the hydration layer, as the temperature dependence of the thermodiffusion behavior is sensitive to solute–solvent interactions. In this work, we perform systematic thermophoretic measurements of the protein streptavidin (STV) and of the complex STV with biotin (B) using thermal diffusion forced Rayleigh scattering (TDFRS). Our experiments show that the temperature sensitivity of the Soret coefficient is reduced for the complex compared to the free protein. We discuss our data in comparison with recent quasi-elastic neutron scattering (QENS) measurements. As the QENS measurement has been performed in heavy water, we perform additional measurements in water/heavy water mixtures. Finally, we also elucidate the challenges arising from the quantiative thermophoretic study of complex multicomponent systems such as protein solutions.

Correlation between thermophoretic behavior and hydrophilicity for various alcohols⋆.

Recent experiments for various amides and sugars showed a clear correlation of the temperature dependence of the Soret coefficient with the hydrophilicity, quantitatively described by the logarithm of the 1-octanol/water partition coefficient logP . This coefficient is a measure for the hydrophilicity/hydrophobicity balance of a solute and is often used to model the transport of a compound in the environment or to screen for potential pharmaceutical compounds. In order to validate whether this concept works also for other water soluble molecules we investigated systematically the thermophoresis of mono- and polyhydric alcohols. As experimental method we use a holographic grating technique called infrared Thermal Diffusion Forced Rayleigh Scattering (IR-TDFRS). Experiments showed that the temperature dependence of the Soret coefficient of polyhydric alcohols also correlates with logP and lies on the same master plot as amides and sugars.

Soret forced Rayleigh scattering instrument for simultaneous detection of two-wavelength signals to measure Soret coefficient and thermodiffusion coefficient in ternary mixtures.

We describe an instrument for the measurement of the Soret and thermodiffusion coefficients in ternary systems based on the transient holographic grating technique, which is called Soret forced Rayleigh scattering (SFRS) or thermal diffusion forced Rayleigh scattering (TDFRS). We integrated the SFRS technique and the two-wavelength detection technique, which enabled us to obtain two different signals to determine the two independent Soret coefficients and thermodiffusion coefficients in ternary systems. The instrument has been designed to read the mass transport simultaneously by two-wavelength lasers with wavelengths of λ = 403 nm and λ = 639 nm. The irradiation time of the probing lasers is controlled to reduce the effect of laser absorption to the sample with dye (quinizarin), which is added to convert the interference pattern of the heating laser of λ = 532 nm to the temperature grating. The result of the measurement of binary benchmark mixtures composed of 1,2,3,4-tetrahydronaphthalene (THN), isobutylbenzene (IBB), and n-dodecane (nC12) shows that the simultaneous two-wavelength observation of the Soret effect and the mass diffusion are adequately performed. To evaluate performance in the measurement of ternary systems, we carried out experiments on the ternary benchmark mixtures of THN/IBB/nC12 with the mass fractions of 0.800/0.100/0.100 at a temperature of 298.2 K. The Soret coefficient and thermodiffusion coefficient agreed with the ternary benchmark values within the range of the standard uncertainties (23% for the Soret coefficient of THN and 30% for the thermodiffusion coefficient of THN).

Influence of temperature and charge effects on thermophoresis of polystyrene beads⋆.

We study the thermodiffusion behavior of spherical polystyrene beads with a diameter of 25 nm by infrared thermal diffusion Forced Rayleigh Scattering (IR-TDFRS). Similar beads were used to investigate the radial dependence of the Soret coefficient by different authors. While Duhr and Braun (Proc. Natl. Acad. Sci. U.S.A. 104, 9346 (2007)) observed a quadratic radial dependence Braibanti et al. (Phys. Rev. Lett. 100, 108303 (2008)) found a linear radial dependence of the Soret coefficient. We demonstrated that special care needs to be taken to obtain reliable thermophoretic data, because the measurements are very sensitive to surface properties. The colloidal particles were characterized by transmission electron microscopy and dynamic light scattering (DLS) experiments were performed. We carried out systematic thermophoretic measurements as a function of temperature, buffer and surfactant concentration. The temperature dependence was analyzed using an empirical formula. To describe the Debye length dependence we used a theoretical model by Dhont. The resulting surface charge density is in agreement with previous literature results. Finally, we analyze the dependence of the Soret coefficient on the concentration of the anionic surfactant sodium dodecyl sulfate (SDS), applying an empirical thermodynamic approach accounting for chemical contributions.

Accumulation of formamide in hydrothermal pores to form prebiotic nucleobases

Formamide is one of the important compounds from which prebiotic molecules can be synthesized, provided that its concentration is sufficiently high. For nucleotides and short DNA strands, it has been shown that a high degree of accumulation in hydrothermal pores occurs, so that temperature gradients might play a role in the origin of life [Baaske P, et al. (2007)Proc Natl Acad Sci USA104(22):9346-9351]. We show that the same combination of thermophoresis and convection in hydrothermal pores leads to accumulation of formamide up to concentrations where nucleobases are formed. The thermophoretic properties of aqueous formamide solutions are studied by means of Infrared Thermal Diffusion Forced Rayleigh Scattering. These data are used in numerical finite element calculations in hydrothermal pores for various initial concentrations, ambient temperatures, and pore sizes. The high degree of formamide accumulation is due to an unusual temperature and concentration dependence of the thermophoretic behavior of formamide. The accumulation fold in part of the pores increases strongly with increasing aspect ratio of the pores, and saturates to highly concentrated aqueous formamide solutions of ∼85 wt% at large aspect ratios. Time-dependent studies show that these high concentrations are reached after 45-90 d, starting with an initial formamide weight fraction of[Formula: see text]wt % that is typical for concentrations in shallow lakes on early Earth.

What can be learned from optical two-color diffusion and thermodiffusion experiments on ternary fluid mixtures?

A number of optical techniques have been developed during the recent years for the investigation of diffusion and thermodiffusion in ternary fluid mixtures, both on ground and on-board the International Space Station. All these methods are based on the simultaneous measurement of refractive index changes at two different wavelengths. Here, we discuss and compare different techniques with the emphasis on optical beam deflection (OBD), optical digital interferometry, and thermal diffusion forced Rayleigh scattering (TDFRS). We suggest to formally split the data evaluation into a phenomenological parameterization of the measured transients and a subsequent transformation from the refractive index into the concentration space. In all experiments, the transients measured at two different detection wavelengths can be described by four amplitudes and two eigenvalues of the diffusion coefficient matrix. It turns out that these six parameters are subjected to large errors and cannot be determined reliably. Five good quantities, which can be determined with a high accuracy, are the stationary amplitudes, the initial slopes as defined in TDFRS experiments and by application of a heuristic criterion for similar curves, a certain mean diffusion coefficient. These amplitudes and slopes are directly linked to the Soret and thermodiffusion coefficients after transformation with the inverse contrast factor matrix, which is frequently ill-conditioned. Since only five out of six free parameters are reliably determined, including the single mean diffusion coefficient, the determination of the four entries of the diffusion matrix is not possible. We apply our results to new OBD measurements of the symmetric (mass fractions 0.33/0.33/0.33) ternary benchmark mixture n-dodecane/isobutylbenzene/1,2,3,4-tetrahydronaphthalene and existing literature data for the same system.

Thermodiffusion, molecular diffusion and Soret coefficient of binary and ternary mixtures of n-hexane, n-dodecane and toluene.

In this study, the thermodiffusion, molecular diffusion, and Soret coefficients of 12 binary mixtures composed of toluene, n-hexane and n-dodecane in the whole range of concentrations at atmospheric pressure and temperatures of 298.15 K and 308.15 K have been determined. The experimental measurements have been carried out using the Thermogravitational Column, the Sliding Symmetric Tubes and the Thermal Diffusion Forced Rayleigh Scattering techniques. The results obtained using the different techniques show a maximum deviation of 9% for the thermodiffusion coefficient, 8% for the molecular diffusion coefficient and 2% for the Soret coefficient. For the first time we report a decrease of the thermodiffusion coefficient with increasing ratio of the thermal expansion coefficient and viscosity for a binary mixture of an organic ring compound with a short n-alkane. This observation is discussed in terms of interactions between the different components. Additionally, the thermogravitational technique has been used to measure the thermodiffusion coefficients of four ternary mixtures consisting of toluene, n-hexane and n-dodecane at 298.15 K. In order to complete the study, the values obtained for the molecular diffusion coefficient in binary mixtures, and the thermodiffusion coefficient of binary and ternary mixtures have been compared with recently derived correlations.

How does thermodiffusion of aqueous solutions depend on concentration and hydrophobicity?

The thermal diffusion of aqueous solutions of mono-, di-ethylene glycols, poly(ethylene glycol), methanol, and glycerol is investigated systematically as a function of concentration using the Thermal Diffusion Forced Rayleigh Scattering (TDFRS). For all investigated binary mixtures, the Soret coefficient, S(T), decays with increasing concentration of the non-aqueous component showing two regions. For aqueous solution of ethylene glycol, at a very low solute content the decay is steep, while it becomes less steep for higher solute concentration. All mixtures show a sign change of S(T) with concentration. The sign change concentration is discussed with respect to chemical structures of solute molecules and the partition coefficient, log p. It turns out that the number of hydroxyl groups plays an important role. For the investigated aqueous mixtures, we find empirical linear relations between the sign change concentration and the ratio of the number of hydroxyl groups to the number of carbon atoms as well as the partition coefficient, log p.

Temperature dependence of thermal diffusion for aqueous solutions of monosaccharides, oligosaccharides, and polysaccharides

We studied the thermal diffusion behavior for binary aqueous solutions of glucose, maltotriose, maltohexaose, pullulan, and dextran by means of thermal diffusion forced Rayleigh scattering (TDFRS). The investigated saccharides with molar masses between 0.180 and 440 kg mol(-1) were studied in the temperature range between 15 and 55 °C. The thermal diffusion coefficient D(T) and the Soret coefficient S(T) of all solutions increase with increasing temperature. For maltohexaose and the polymers the thermal diffusion coefficient changes sign from negative to positive with increasing temperature, whereas glucose and maltotriose show only positive values in the entire investigated temperature range. While we were able to find a master curve to describe the temperature dependence of D(T), we were not able to find a similar expression for S(T). This comprehensive study allows for the first time the determination of the interaction parameters for the polymer and the solvent within the theoretical framework suggested by Würger [Phys. Rev. Lett., 2009, 102, 078302].

The Soret effect of mono-, di- and tri-glycols in ethanol

We employed thermal diffusion forced Rayleigh scattering (TDFRS) to investigate the chain length dependence of the thermal diffusion behavior of short glycols in ethanol. We studied three glycols, monoethylenglycol (MEG), diethylenglycol (DEG) and triethylenglycol (TEG), in an ethanol solution. In contrast to the polymer polyethylenglycol, the shorter glycols used within the framework of this study are completely soluble in ethanol, at least for low molar fractions. In order to guarantee a good solubility of the glycols, the measurements were limited to molar fractions of 10% and 20%. As the different glycols only differ by their chain length it will be possible to deduce its influence on the thermal diffusion properties. Due to the fairly short persistence length of the glycols, D(T) reaches already for the dimer a plateau value. This finding agrees with simulation results. Furthermore, the thermal expansion and the kinematic viscosity are measured to investigate if empirical correlations seen for other systems could be confirmed.

Temperature Dependence of Soret Coefficient in Aqueous and Nonaqueous Solutions of Pullulan

We present experimental results of the temperature dependence of the Ludwig-Soret effect for pullulan solutions. The Soret coefficients of 5.0 g L(-1) pullulan in water and in dimethyl sulfoxide (DMSO) were determined in the experimental temperature range between 20.0 and 50.0 degrees C by means of thermal diffusion Forced Rayleigh scattering (TDFRS). The sign of the Soret coefficient of pullulan in water is negative at room temperature, which indicates that the pullulan molecules migrate to the warm side of the fluid. The Soret coefficient of pullulan increases steeply with increase of the solution temperature and shows a sign change from negative to positive at 41.7 degrees C. The positive sign of the Soret coefficient means the pullulan molecules move to the cold side. In contrast to the aqueous solution, the solution of pullulan in DMSO shows a very weak temperature dependence of the Soret coefficient and has always a positive sign. In addition to the TDFRS experiments, we also performed light scattering (LS) experiments for the pullulan solutions under homogeneous temperature condition in a temperature range between 20.0 and 55.0 degrees C. The thermodynamic properties of pullulan solutions obtained by LS show no pronounced correlation with the thermal diffusion behavior of pullulan. These results indicate the existence of a special role of interactions due to solvation on the temperature dependence of the thermal diffusion behavior of polysaccharide solutions.

Soret Effect of n-Octyl β-d-Glucopyranoside (C8G1) in Water around the Critical Micelle Concentration

We studied the thermal diffusion behavior of the nonionic surfactant C(8)G(1) (n-octyl beta-D-glucopyranoside) in water for different concentrations between w = 0.25 wt% and w = 2.0 wt% in a temperature range from T = 15 to 60 degrees C using the classical and infrared thermal diffusion forced Rayleigh scattering (TDFRS) setup. The purpose of the present paper is the investigation of the thermal diffusion behavior of surfactant systems around the critical micelle concentration (cmc), which is independently determined by surface tension measurements. In the classical TDFRS, the surfactant solutions show in the presence of a light-absorbing dye a pronounced change of the thermal diffusion coefficient (D(T)) and the Soret coefficient (S(T)) at the cmc. This result agrees with a recent thermal lens study [Santos et al., Phys. Rev. E 2008, 77, 011403], which also showed in the presence of dye a pronounced change of the thermal lens matter signal around the cmc. We found that this change becomes less pronounced, if the dye is absent or a light source is used, which is not absorbed by the dye. At higher concentrations, we observed a temperature-dependent sign change of S(T) as has also been found for solutions of hard spheres at higher concentrations.

Investigation of the Soret effect in aqueous and non-aqueous mixtures by the thermal lens technique

In the present work we investigate the thermal diffusion behavior of three different binary mixtures with a thermal lens (TL) setup. In the setup used in this study we avoid the addition of a dye for systems, such as aqueous mixtures, with a weak absorption band at a wavelength of 980 nm. In some aqueous systems with a complex phase behavior the addition of dye significantly affects the apparent measured thermal diffusion properties. The studied systems are dimethylsulfoxide (DMSO) in water, the ionic liquid 1-ethyl-3-methylimidazolium ethylsulfate (EMIES) in butanol and a non-ionic surfactant hexaethylene glycol monododecyl ether (C(12)E(6)) in water. The Soret coefficients of the selected systems cover a range of two orders of magnitude. For DMSO in water with a very low Soret coefficient of the order of S(T) approximately 10(-3) K(-1) we find for a low DMSO content (c = 0.33) a reasonable agreement with previous measurements, while the weak thermal lens signal for the DMSO-rich mixture (c = 0.87) leads to 20% too large Soret coefficients with an uncertainty of more than 30%. Secondly we studied a liquid salt 1-ethyl-3-methylimidazolium ethylsulfate (EMIES) in butanol with a roughly ten times higher Soret coefficient of S(T) approximately 10(-2) K(-1). For this system we performed additional measurements with another experimental technique, the classical thermal diffusion forced Rayleigh scattering (TDFRS), which requires the addition of a small amount of dye to increase the absorption. In the entire investigated concentration range the results obtained with the TL and classical TDFRS technique agree within the error bars. As a third system we studied a non-ionic surfactant hexaethylene glycol monododecyl ether (C(12)E(6)) in water with a Soret coefficient of the order of S(T) approximately 10(-1) K(-1). For this system we find good agreement with previous measurements. We conclude that the TL technique is a reliable method for systems with a strong optical contrast and fairly large Soret coefficient of the order of S(T) approximately 10(-2) K(-1).

Soret Effect of Nonionic Surfactants in Water Studied by Different Transient Grating Setups

We studied the thermal diffusion behavior of the nonionic surfactant solutions C 12E 6/water and C 12E 5/water at different concentrations and temperatures using thermal diffusion forced Rayleigh scattering (TDFRS). Two different types of TDFRS setups have been applied. In the classical TDFRS, we use an argon laser to write the optical grating into the sample by using a small amount of ionic dye to convert the optical grating into a temperature grating. In the other setup, called IR-TDFRS, we use an infrared laser as the writing beam, which utilizes the water absorption band to convert the optical grating into a temperature grating. The measurements by IR-TDFRS show a one-mode signal for all concentrations and temperatures, while the signal in the classical TDFRS consists of two modes for higher temperatures and lower surfactant concentrations (Ning, H.; et al. J. Phys. Chem. B 2006, 110, 10746). We find good agreement between the Soret coefficient determined in the IR-TDFRS and the one derived from the first fast mode in the previous studies. The Soret coefficient of the nonionic solutions is positive and enhanced at the critical point. In general, the Soret coefficient of the micelles tends to increase with temperature. We found that the presence of the second mode observed in the classical TDFRS is related to the addition of the ionic dye, but even with the ionic dye it is not possible to observe a second mode in the IR-TDFRS. The origin of the second mode is discussed in terms of charged micelles and an inhomogenous dye distribution in the temperature gradient.

Thermal Diffusion and Molecular Diffusion Values for Some Alkane Mixtures: A Comparison between Thermogravitational Column and Thermal Diffusion Forced Rayleigh Scattering

In the present work we studied the thermal diffusion behavior of n-decane in various alkanes by thermogravitational column (TC) technique and the thermal diffusion forced Rayleigh scattering (TDFRS) method. The investigated lighter alkanes compared to n-decane are n-pentane, n-hexane, n-heptane, n-octane, and the heavier ones are n-tetradecane, n-pentadecane, n-hexadecane, n-heptadecane, n-octadecane, and n-eicosane. The binary mixture n-decane/ n-pentane we investigated at several different concentrations; all other mixtures were only investigated at a mass fraction of 50%. Even for the volatile n-pentane/ n-decane mixture the deviations between the thermal diffusion coefficients determined by the different methods agreed within the error bars. Typically the agreement between the two methods was in the order of 5%. In comparison to recently published TC and TDFRS data we found deviations in the order of 30% up to 40%. We analyze and discuss the possible reasons for the discrepancies for the present and the past publications.

Thermal Diffusion Forced Rayleigh Scattering Setup Optimized for Aqueous Mixtures

We developed a thermal diffusion forced Rayleigh scattering (TDFRS) setup operating at a writing wavelength of 980 nm, which corresponds to an absorption band of water with an absorption coefficient of approximately 0.5 cm(-1). Therefore, aqueous mixtures require no dye to convert the light into heat energy. Especially for aqueous system with a complex phase behavior such as surfactant systems, the addition of a water soluble dye can cause artifacts. The infrared-TDFRS (IR-TDFRS) setup has been validated for water/ethanol mixtures with water weight fractions c = 0.5-0.95 and in a temperature range between T = 15 degrees C to T = 35 degrees C. Comparison with literature data shows an excellent agreement. The addition of a small amount (c(dye) approximately 10(-6) wt) of adsorbing dye at the writing wavelength allows also the investigation of organic mixtures. We investigated the three binary mixtures of dodecane, isobutylbenzene, and 1,2,3,4-tetrahydronaphthalene at a weight fraction of c = 0.5 at a temperature of 25 degrees C and found good agreement with the Soret coefficients, which had been obtained in a benchmark test under the same conditions. Therefore, the presented setup is suitable for the investigation of the thermal diffusion behavior in aqueous and organic mixtures, and in the case of aqueous systems, the addition of a dye can be avoided.