Characterization of methanol-water and acetonitrile-water association using multivariate curve resolution methods

The solvatochromic comparison method has been used to probe the interactions of solutes with binary solvent mixtures of methanol-water and acetonitrile-water. The solute spectra recorded in these mixtures are composed of the additive spectral contributions of the different solvated species of the solute, i.e., the water-solvated species, the cosolvent-solvated species, and the species solvated by water-solvent complexes. Multivariate curve resolution-alternating least squares has been used to model the solvation of the solutes as a function of the composition of the binary solvent mixture. Spectra and concentration profiles of the dye surrounded by the different solvation environments have been isolated. For the first time, solute spectra solvated exclusively by methanol-water and acetonitrile-water complexes have been obtained, and the solvatochromic parameters of dipolarity/polarizability and hydrogen-bonding acidity have been estimated for these complex species.     

Effect of polymer concentration on partitioning and molecular recognition in plasticized poly(vinyl chloride)

Mixtures of poly(vinyl chloride) (PVC) with plasticizers have been used in ion-selective electrodes for many years. The same material has proven useful in solid-phase microextraction (SPME), both with and without artificial receptors. We hypothesized that by changing the polymer concentration in plasticized PVC membranes containing artificial receptor from the standard 33 wt %, the selectivity of the extraction of barbiturates over similar molecules could be improved. Partition coefficients and receptor-substrate formation constants of a target species, phenobarbital, in membranes with various polymer concentrations were determined. Diffusion coefficients of the solute phenobarbital in receptor-free membranes were also determined. Kamlet-Taft solvatochromic properties beta and pi* were measured for the PVC/dioctyl sebacate materials. Cohesive energy densities were calculated for the same materials. Partition coefficients for phenobarbital (from aqueous solution to membrane) decrease as [PVC] increases, while the formation constants for the complex of the solute with its receptor increase. Diffusion coefficients decrease as the polymer concentration increases as well. The increase in polymer concentration brings about a decrease in hydrogen-bonding basicity and an increase in dipolarity and cohesive energy density. The values of the solvatochromic parameters determined at various compositions are highly correlated; thus, it is impossible to calculate how much each factor contributes to the changes associated with partition and complex formation. The solvatochromic "polarizability correction factor" has been determined to be 0 for PVC. In SPME experiments at 30%, 40%, and 50% (w/w) PVC, as polymer concentration increases, selectivity for barbiturate extraction over other cyclic imides becomes better in the presence of barbiturate receptor and worse without receptor.     

Characterization of chemical selectivity in micellar electrokinetic chromatography. 4. Effect of surfactant headgroup

The influence of surfactant headgroups on migration behavior in micellar electrokinetic chromatography is examined. Using linear solvation energy relationships (LSER) and functional group selectivity studies, the effect of six anionic headgroups on chemical selectivity is characterized. The sodium dodecyl surfactants of the sulfate [SO4-], sulfonate [SO3-], carboxylate [CO2-], carbonyl valine [OC(O)NHCH(CH(CH3)2)CO2-], and sulfoacetate [OC(O)CH2SO3-] anions are investigated. Solute size and the hydrogen-bond-donating ability of the micellar phase play the most significant roles in solute retention in all of the surfactants studied. While solute-micelle hydrogen bonding plays a dominant role in the observed selectivity, the dipolarity and polarizability of the micellar phase also have a small influence. The results also suggest that the hydrogen-bond-accepting ability for surfactants is inversely proportional to the proton acidity (pKa) of its headgroup. The observed hydrogen-bond-donating ability and dipolarity of surfactant systems are believed to be a result of the water that resides near the micelle surface.     

Prediction of retention in micellar electrokinetic chromatography from solute structure. 1. Sodium dodecyl sulfate micelles.

Like other chromatographic techniques, retention factor, k, in micellar electrokinetic chromatography (MEKC) is directly related to solute partition coefficient and the chromatographic phase ratio as k = Kphi. Unlike conventional chromatography, however, the phase ratio and partition coefficient can be accurately determined in MEKC for a given micellar pseudostationary phase. This means that retention factor in MEKC can be predicted for solutes with known micelle-water partition coefficients without any prior experimentation. In this paper, the use of this simple relationship for prediction of retention behavior in MEKC is examined. The principle of additivity of functional group contribution to partitioning is used to calculate the micelle-water partition coefficient, Kmw, for SDS micellar pseudophase. The micellar substituent constants for 20 functional groups (training set) were determined. Using these substituent constants, the Kmw and retention factors for a group of 80 neutral solutes (test set) were predicted. The linear plot of predicted versus observed log k had an R2 = 0.97 and a slope equal to 1.01. It is shown that the retention times (thus chromatograms) in MEKC can be predicted from the calculated retention factors after only one initial experiment to measure teo and t(mc) under the experimental conditions.     

Predictions of micelle-water partition coefficients and retention in micellar electrokinetic chromatography from solute structure. 2. Fragmental constant approach

The fragmental constant approach (FCA) was used to calculate water-sodium dodecyl sulfate (SDS) micelle partition coefficients, K(mw), for uncharged solutes from their structure. Subsequently, the availability of K(mw) values allows prediction of retention factor, k, in micellar electrokinetic chromatography (MEKC) using the simple relationship k = K(mw)phi, where phi is the phase ratio. The FCA model describes a micelle-water partition coefficient as the sum of the partition coefficients of the constituent atomic/molecular fragments, measured by fragmental constant values, f (i), as well as correction factors to account for various "intramolecular effects" that cause deviations from the predicted partition coefficients as, log K(mw) = sum(n)(i=1)aif i+sum(m)(i=1)kiCm. The fragmental constants for a set of 41 fragments were determined using a training set of 229 aromatic solutes and 198 aliphatic compounds. The K(mw) of the aromatic compounds in the training set were determined by MEKC, while the K(mw) of the aliphatic solutes were estimated using the linear solvation energy relationship (LSER) for the SDS micelles. The fragments consisted of both aromatic fragments (i.e., directly attached to an aromatic ring) and aliphatic fragments. The FCA predictions agree nicely with the observed and LSER partition coefficient values, even for complex molecular structures such as beta-blocker drugs. The results show the great potential of the FCA for a priori prediction of retention behavior in MEKC from solute structure.     

Study of interactions in supercritical fluids and supercritical fluid chromatography by solvatochromic linear solvation energy relationships

Linear solvation energy relationships were used to study the retention process in supercritical fluid chromatography (SFC) and to gain a better understanding of intermolecular interactions in supercritical fluids. Correlation of SFC retention data with a set of solute solvatochromic parameters, which are also applicable to gas and liquid chromatography, yields information regarding the relative contributions of dispersion, cavity formation, dipolar, and hydrogen-bonding processes to retention. Dispersion interactions and cavity formation processes dominate retention on an open tubular poly(dimethylsiloxane) stationary phase with pure carbon dioxide as the mobile phase. Dipolar interactions and hydrogen-bonding interactions are of decidedly less importance but do contribute significantly to retention. Based on prior solvatochromic studies of poly(dimethylsiloxane) and carbon dioxide, the changes in the regression coefficients with temperature and pressure are interpreted chemically. The relative importance of these contributions changes with temperature and pressure. As pressure increases, the carbon dioxide becomes more dense, and dispersion interactions between the solute and the mobile phase increase. A temperature increase at constant pressure decreases dispersion interactions with the stationary phase, as in gas chromatography, but also decreases dispersion interactions with the mobile phase, due to a decrease in carbon dioxide density. On the basis of the solvatochromic coefficients, carbon dioxide acts as both a Lewis base and a Lewis acid. The quality of fit for these correlations is very high and compares favorably with similar studies in gas chromatography and liquid chromatography, permitting the prediction of retention behavior from a solute's solvatochromic parameters.     

Systematic Approach to Links between Separations in MEKC and Reversed-Phase HPLC

Retention factors and partition coefficients in micellar electrokinetic chromatography (MEKC) and reversed-phase high-performance liquid chromatography (RP-HPLC) are compared for a series of alkylbenzenes and substituted phenols. In both techniques, separations are based on partitioning between an aqueous phase and an alkyl phase. In MEKC, this was an SDS (C12) micellar pseudostationary phase, and in RP-HPLC an ODS 2 (C18) stationary phase. A nonporous silica (Micra 1.5-μm NPS), which has a low carbon loading, was used rather than a standard porous silica to avoid excessive retention in HPLC and to allow identical mobile phase conditions to be used in both separation modes. The average ratio of analyte retention factors, k(MEKC):k(HPLC), was found to be equal to the ratio β(MEKC):β(HPLC), where β is the phase ratio. This implies that partition coefficients, P, are similar in both MEKC and HPLC, since P = k/β, and that the dominant contribution to stability within each alkyl phase arises from hydrophobic interactions which are common to both separation media. Since partition coefficients are similar in MEKC and HPLC under aqueous buffer conditions, information on retention in one technique may be transferred to the other, provided that the phase ratios are known. In MEKC and HPLC, linear correlations of log octanol-water partition coefficients, K(ow), vs log k for the test compounds were transformed, knowing the phase ratio, to give log P values as a function of log K(ow). This allows quantitative links between MEKC and HPLC to be extended to include octanol-water partitioning. The addition of acetonitrile as an organic modifier over the concentration range 0-20% (v/v) was found to have a greater effect on k in HPLC than in MEKC. This could be a result of a decrease in the MEKC phase ratio due to an increase in the critical micelle concentration.     

反相悬浮酚醛树脂对苯和苯胺的吸附动力学及热力学

液蜡为分散相,span80为分散剂,乙二醇为致孔剂,反相悬浮法制备了羟基修饰氢键型酚醛树脂LM-4。根据热力学分析,苯胺和苯在LM-4上的吸附焓和吸附熵均大于零,表明吸附包含解吸水分子和吸附吸附质两个过程。对苯胺的吸附焓达到34.06kJ/mol,说明树脂与苯胺分子间存在氢键。Lagergren模型拟合吸附动力学数据表明颗粒内扩散、膜扩散均是速率控制步骤之一,Dumwald-Wagner二级速率方程更适合于描述LM-4对苯的吸附,Kannan-Sundaram模型的拟合则说明树脂对苯胺的吸附为"优惠吸附"。     

Orientation effects on the electrophoretic mobility of rod-shaped molecules in free solution

The effect of molecular orientation on the electrophoretic mobility of rod-shaped polylons as measured by free solution capillary electrophoresis is studied by using the tobacco mosaic virus (TMV) as a model solute. This orientational dependence of molecular mobility is measured by observing the influence of electrical field strength (up to 400 V/cm) on the electrophoretic mobility of TMV. The electrophoretic mobility of TMV increases with increasing field strength. This increase can be quantitatively correlated with the decrease in the translational frictional coefficient (f) due to the increasing alignment of TMV with the electric field. A model is developed relating the decrease in f to the alignment of TMV with the electric field through its polarizability and aspect ratio. To confirm the observed orientational affects on mobility, control experiments were performed with 0.364 micron diameter Latex spheres. Due to their spherical symmetry, no orientational effects would be expected. Indeed, no increase in mobility was observed for these spherical particles. Calculations are presented to demonstrate that the increase in mobility is unlikely to be caused by either the Wien effect or any temperature variation resulting from Joule heating of the electrophoresis buffer.     

Structure-function relationships in high-density octadecylsilane stationary phases by Raman spectroscopy. 4. Effects of neutral and basic aromatic compounds

The effects of aromatic compounds (toluene, benzene, p-xylene, anisole, aniline, and pyridine), temperature, and surface grafting method (surface- or solution-polymerized) on alkyl chain rotational and conformational order in a series of high-density octadecylsilane stationary phases ranging in surface coverage from 3.09 to 6.45 micromol/m2 are examined by Raman spectroscopy. Rotational and conformational order are assessed using the intensity ratio of the antisymmetric to symmetric v(CH2) modes as well as the frequency at which the symmetric v(CH2) band is observed. Alkyl rotational and conformational order decrease with decreasing surface coverage in these aromatic compounds, which is consistent with the behavior of these materials in air and in other solvents. In addition, order of the alkyl chains is dependent on solvent hydrophobicity, hydrogen-bonding ability, and basicity. The most hydrophobic compounds impart disorder to the stationary phase; the hydrogen-bonding aromatics increase the rotational order of homogeneously distributed, high-surface-coverage materials; and basic aromatic compounds increase the conformational order of high- and low-coverage materials as the basic compounds undergo silanophilic interactions with exposed surface silanols. From these observations, molecular pictures of the chromatographic interface that display interactions between the alkyl chains and these aromatic compounds are proposed.     

Morphology-tuning by changing the composition of a binary hydrogel comprising thymidine and melamine

We report on the self-assembly of a new two-component hydrogel of thymidine (T) and melamine (M) which formed supramolecular complex (≥ 0.1%, w/v) based on intermolecular hydrogen-bonding. The 3D morphologies were tuned by changing the molar ratio of T and M in aqueous medium from 3/1 to 1/3. The xerogels respectively showed rod, sheet and flower structures as observed under SEM. Fourier transform infrared (FT-IR) spectroscopy and wide angle X-ray scattering (WAXD) patterns confirmed that thymidine and melamine form supramolecular complexes through intermolecular hydrogen-bonding. The different structures of the complexes are proposed for the different compositions of the components.     

Power-law decay in rate of solute removal from ground water with various exponents associated with matrix diffusion in granular packed bed

Power-law decay of pollutant concentration in flushing gas is often observed during the remediation of contaminated groundwater. However, the underlying mechanisms that cause the power law are not clear in many cases and the variations of the exponent of the power law can not be explained by the existing models with a solid physical basis. In order to obtain a variety of the values of exponent, we propose a simple two-fluid cubic lattice model. We first created a complex interfacial geometry between gas and liquid in a granular packed bed using a percolation model, and then calculated the removal rate of solute with matrix diffusion by performing the random walk of solute particles in the invaded liquid phase until the random walkers of solute reach to the gas/liquid interface. A significant power law was observed in the dissipation rate of solute particles with the proposed model. As the saturation of the invading gas in the matrix increases, the absolute value of exponent increased from 0.5, up to approximately 1.0, which cannot be reproduced by the previous analytical models. We successfully showed that the matrix diffusion with a complicated gas/liquid interface causes the power-law behavior with various exponents.     

A fluorescence detection scheme for capillary electrophoresis of N-methylcarbamates with on-column thermal decomposition and derivatization

This paper describes a fluorescence detection method for N-methylcarbamate (NMC) pesticides in micellar electrokinetic chromatography (MEKC) separation. Fulfillment of the fluorescence detection hinged on the discovery that quaternary ammonium surfactants (particularly cetyltrimethylammonium bromide, CTAB), besides serving as hydrophobic pseudophases in MEKC, are also capable of catalyzing the thermal decomposition of NMCs to liberate methylamine. Thus, a multifunctional MEKC medium consisting of borate buffer, CTAB, and derivatizing components (o-phthaldialdehyde/2-mercaptoethanol) was formulated, which allowed first normal MEKC separation, subsequent thermal decomposition, and finally in situ derivatization of NMCs. With careful optimization of the operation conditions, fluorescence detection of 10 NMC compounds was achieved, with column efficiencies typically higher than 50,000 and detection limits better than 0.5 ppm. The present work represents an unprecedented effort in capillary electrophoresis (CE), in which an intact capillary was consecutively utilized as chambers for separation, decomposition, derivatization, and detection, without involving any interfacing features. The success in the implementation of such a detection system resulted in strikingly simple instrumentation as compared with the traditional postcolumn fluorescence determination of NMCs by reversed-phase HPLC. Similar protocols should be workable in the determination of a wide range of pesticides and pharmaceuticals in CE formats.     

Micellar electrokinetic capillary chromatography of acidic solutes: migration behavior and optimization strategies.

Micellar electrokinetic capillary chromatography (MECC) is suitable for the separation of mixtures of uncharged and charged solutes. In this paper, the migration behavior of acidic compounds in MECC is quantitatively described in terms of different models. These equations describe the relationships between the two migration parameters in MECC (retention factor and mobility) and the two important experimental parameters (pH and micelle concentration) that have a great influence on the migration behavior and selectivity. Interestingly, the mobility and retention factor of a given solute could behave differently with the variations in pH. This would raise a question of which parameter actually represents the migration behavior of a solute in MECC: retention factor (a chromatographic parameter) or mobility (an electrophoretic parameter). The consequences of micellar-mediated shifts of ionization constants on selectivity and optimization strategies in MECC are discussed. The mathematical models would allow the prediction of migration behavior of solutes based on a limited number of initial experiments. This would greatly facilitate the method development and optimization of separations of ionizable compounds by MECC and, in addition, important physical and chemical characteristics of solutes such as their apparent ionization constants in micellar media and their partition coefficients into micelles (over a wide range pH values) can be determined. The models were verified, as good agreements were observed between the predicted and the experimentally observed migration behavior. Based on the preliminary results, the pH and micelle concentration are likely to be interactive parameters in many situations. As a result, simultaneous optimization of these two parameters would be the most effective strategy to enhance the MECC separation of acidic solutes.     

Two-dimensional electrophoretic separation of proteins using poly(methyl methacrylate) microchips

The work presented herein describes highly efficient, two-dimensional (2D) electrophoretic separations of proteins in a PMMA-based microchip. Sodium dodecyl sulfate microcapillary gel electrophoresis (SDS micro-CGE) and micellar electrokinetic chromatography (MEKC) were used as the separation modes for the first and second dimension of the electrophoresis, respectively. The microchip was prepared by hot embossing into PMMA from a brass mold master fabricated via high-precision micromilling. The microchip incorporated a 30-mm SDS micro-CGE and a 10-mm MEKC dimension length. Electrokinetic injection and separation were used with field strengths of up to 400 V/cm. Alexa Fluor 633 conjugated proteins, ranging in size from 38 to 110 kDa, were detected using laser-induced fluorescence with excitation/emission at 633/652 nm. Average plate numbers (N) of 4.8 x 10(4) and 1.2 x 10(4) were obtained in the SDS micro-CGE and MEKC separation dimensions, respectively, for the investigated proteins corresponding to plate heights (H) of 0.62 and 0.87 microm. Effluents from the first dimension (SDS micro-CGE) were repetitively transferred into the second dimension every 0.5 s of run time in the first dimension with the electrophoresis run time in the MEKC dimension being 10 s. The 2D separation was performed on the investigated proteins in approximately 12 min and provided a peak capacity of approximately 1000.     

Solvatochromic Study of Poly(vinyl chloride) Plasticizers and Their Solutions in Chloroform: Application to Phenobarbital Partitioning and Molecular Recognition of Phenobarbital

The possibility now exists, with the availability of several families of artificial molecular receptors, to create selective extraction media. More selective extractions will lead to cleaner chromatograms, with lower detection limits and perhaps higher accuracy for trace organic analysis by chromatography. Furthermore, laboratories will be expected to minimize the use of volatile organic solvents. Consequently, nonvolatile, reusable solvents will be the basis for extractions. In addition, as artificial molecular receptors become more widely available, these solvents will be used to support molecular recognition. We have focused on plasticizers of poly(vinyl chloride) as examples of these solvents. We have determined solvatochromic parameters of several plasticizers and their solutions in chloroform. These parameters, along with cohesive energy density and solvent molar volume, were used to derive linear free energy relationships for the free energies of phenobarbital partitioning between solvent and aqueous solution, receptor solubility, formation of a complex with a barbiturate receptor [1,3-bis[[[6-(1-butyrylamino)pyrid-2-yl]amino]carbonyl]benzene (2)], and the transfer of the complex (artificial receptor and phenobarbital) from chloroform to other solvents. Solvent dipolarity/polarizability and hydrogen bond basicity, but not acidity, support complex dissociation. Solvents with large molar volumes dissolve the polar solutes, phenobarbital, receptor, and complex more poorly than solvents with lower molar volume, but there is no influence of molar volume on complex formation.     

Temperature-jump investigation of alkyl chain length effects on sorption/desorption kinetics at reversed-phase chromatographic interfaces

The influence of the alkyl chain length on the kinetics of solute retention at reversed-phase chromatographic surfaces is examined. A Joule-discharge temperature-jump relaxation experiment was used to monitor reversible sorption/desorption kinetics at C4- and C8-modified silica/solution interfaces. Biexponential sorption/desorption relaxation kinetics were observed for a charged fluorescent probe, 1-anilino-8-naphthalenesulfonate (ANS), on both C4- and C8-silica surfaces. Both relaxation rates on C4 surfaces were sufficiently slow to be measured and increased linearly with solute concentration. One of the relaxations on a C8 surface is too fast to be resolved from the heating rate, similar to behavior of the solute on a longer chain C18-silica. These observations suggest that sorption kinetics on the intermediate chain length surfaace, C4-silica, are different from kinetics on longer chain length surfaces, C8- and C18-silica. From a fit of the data to a two-step kinetic model, the rates of both adsorption and partition of the ionic probe on the C4 chain are estimated; both rates exhibit significant influence over the equilibrium constant. The relaxation rate of a neutral probe, N-phenyl-1-naphthylamine, is also measured; the results indicate a fast (diffusion-controlled) adsorption step, followed by a detectable barrier to partition that is similar to the partition barrier for ANS on the C4-silica surface. These results show that the alkyl chain length of modified silica strongly influences retention kinetics.     

Polymeric sulfated amino acid surfactants: a class of versatile chiral selectors for micellar electrokinetic chromatography (MEKC) and MEKC-MS

In this work, three amino acid-derived (l-leucinol, l-isoleucinol, l-valinol) sulfated chiral surfactants are synthesized and polymerized. These chiral sulfated surfactants are thoroughly characterized to determine critical micelle concentration, aggregation number, polarity, optical rotation, and partial specific volume. For the first time the morphological behavior of polymeric sulfated surfactants is revealed using cryogenic high-resolution electron microscopy. The polysodium N-undecenoyl-l-leucine sulfate shows distinct tubular structure, while polysodium N-undecenoyl-l-valine sulfate also shows tubular morphology but without any distinct order of the tubes. On the other hand, polysodium N-undecenoyl-l-isoleucine sulfate (poly-l-SUCILS) displays random distribution of coiled/curved filaments with heavy association of tightly and loosely bound water. All three polymeric sulfated surfactants are compared for enantioseparation of a broad range of structurally diverse racemic compounds at very acidic, neutral, and basic pH conditions in micellar electrokinetic chromatography (MEKC). A small combinatorial library of 10 structurally related phenylethylamines (PEAs) is investigated for chiral separation under acidic and moderately acidic to neutral pH conditions using an experimental design. In contrast to neutral pH conditions, at acidic pH, significantly enhanced chiral resolution is obtained for class I and class II PEAs due to the compact structure of polymeric sulfated surfactants. It is observed that the presence of a hydroxy group on the benzene ring of PEAs resulted in deterioration of enantioseparation. A sensitive MEKC-mass spectrometry (MS) method is developed for one of the PEAs (e.g., (+/-)-pseudoephedrine) in human urine. Very low limit of detection (LOD) is obtained at pH 2.0 (LOD 325 ng/mL), which is approximately 16 times better compared to pH 8.0 (LOD 5.2 microg/mL). Another broad range of chiral analytes (beta-blockers, phenoxypropionic acid, benzoin derivatives, PTH-amino acids, benzodiazepinones) studied also provided improved chiral separation at low pH compared to high-pH conditions. Among the three polymeric sulfated surfactants, poly-l-SUCILS with two chiral centers on the polymer head group provided overall higher enantioresolution for the investigated acidic, basic, and neutral compounds. This work clearly demonstrates for the first time the superiority of chiral separation and sensitive MS detection at low pH over conventional high-pH chiral separation and detection employing anionic chiral polymeric surfactants in MEKC and MEKC-MS.     

An FTIR spectroscopic study of hydrogen-bonding competition in entrainer-cosolvent mixtures

In chemical separation processes such as supercritical extraction the use of an entrainer cosolvent can dramatically improve selectivity and yield. Ideally, in an extraction process, an entrainer cosolvent should complex with only the desired solute, pulling it from the feed. But not all cosolvents are entrainers, and a cosolvent that is effective in one application may not be effective in others. Often, competing hydrogen bonding interactions limit the effectiveness of an entrainer cosolvent. In this paper FTIR spectroscopy is used to study hydrogen bonding competition in solute/solvent/entrainer cosolvent mixtures. The extent of hydrogen bonding is determined from analysis of hydrogen-bonded and non-hydrogen-bonded infrared absorption peaks. Since these peaks overlap, curvefitting and Fourier self-deconvolution techniques are used to resolve them. Concentrations of monomeric and hydrogen-bonded species are modeled using the associated perturbed anisotropic chain theory (APACT). Using APACT it is shown that the equilibrium constant, derived from activities, can be written as the product of a temperature-dependent term and the ratio of concentrations: K=(RT) ^vIIC _i ^vi . This gives a statistical mechanical basis for the empirical observation that for hydrogen-bonding equilibria, the ratio of concentrations is approximately equal to the ratio of activities.Paper presented at the Tenth Symposium on Thermophysical Properties, June 20–23, 1988, Gaithersburg, Maryland, U.S.A.