Enantioselective Reduction of Citral Isomers in NCR Ene Reductase: Analysis of an Active‐Site Mutant Library

A deeper understanding of the >99 % S‐selective reduction of both isomers of citral catalyzed by NCR ene reductase was achieved by active‐site mutational studies and docking simulation. Though structurally similar, the E/Z isomers of citral showed a significantly varying selectivity response to introduced mutations. Although it was possible to invert (E)‐citral reduction enantioselectivity to ee 46 % (R) by introducing mutation W66A, for (Z)‐citral it remained ≥88 % (S) for all single‐residue variants. Residue 66 seems to act as a lever for opposite binding modes. This was underlined by a W66A‐based double‐mutant library that enhanced the (E)‐citral derived enantioselectivity to 63 % (R) and significantly lowered the S selectivity for (Z)‐citral to 44 % (S). Formation of (R)‐citronellal from an (E/Z)‐citral mixture is a desire in industrial (?)‐menthol synthesis. Our findings pave the way for a rational enzyme engineering solution.     

Weekly Weather Generation for a Nitrogen Turnover Model

Three methods of deriving weather for use in a nitrogen decision support system with a weekly time-step are described and evaluated. The simplest of these is simply the mean (M) of the three weather variables: Rainfall (R), evapotranspiration (ET) and temperature (T). To represent the variability of weather, many sets of generated data are needed but this is not possible with mean values. Two methods of generating rainfall are described: a fully stochastic simulator (FS) and a method based on partitioning the distribution into sections (SM). Temperature, T, and evapotranspiration ET are represented in both generators by sinusoidal functions. The amount of R is modelled as an empirical distribution, rain persistence as a Markov chain. All three means of deriving weather were compared directly with actual weather from the historical record and in use with the SUNDIAL DSS. The mean values of R, ET and T were reproduced satisfactorily (r > 0.99) by both FS and SM, but variability less accurately (r > 0.80 for the standard deviations of T, r > 0.97 for R and ET). The mean values of several components of the nitrogen cycle sim ulated with SUNDIAL were generally reproduced well for both methods of weather generation, but less accurately for mean weather. For leaching, the root mean square errors were 2.6, 2.3 and 11.4 kg/ha for FS, SM and M, respectively. The sectioning method generally gave a poor estimate of variation, which was significantly underestimated for the majority of variables, in the case of leaching by a factor of three. Where variance is important, FS is preferred; weather data generated by this method may be used with confidence for risk assessments of denitrification and crop N uptake.     

Synthesis of C‐Glucosylated Octaketide Anthraquinones in Nicotiana benthamiana by Using a Multispecies‐Based Biosynthetic Pathway

Carminic acid is a C‐glucosylated octaketide anthraquinone and the main constituent of the natural dye carmine (E120), possessing unique coloring, stability, and solubility properties. Despite being used since ancient times, longstanding efforts to elucidate its route of biosynthesis have been unsuccessful. Herein, a novel combination of enzymes derived from a plant (Aloe arborescens, Aa), a bacterium (Streptomyces sp. R1128, St), and an insect (Dactylopius coccus, Dc) that allows for the biosynthesis of the C‐glucosylated anthraquinone, dcII, a precursor for carminic acid, is reported. The pathway, which consists of AaOKS, StZhuI, StZhuJ, and DcUGT2, presents an alternative biosynthetic approach for the production of polyketides by using a type III polyketide synthase (PKS) and tailoring enzymes originating from a type II PKS system. The current study showcases the power of using transient expression in Nicotiana benthamiana for efficient and rapid identification of functional biosynthetic pathways, including both soluble and membrane‐bound enzymes.     

Prediction of Henry's law constants by matrix completion

Methods for predicting Henry's law constants H_ij are important as experimental data are scarce. We introduce a new machine learning approach for such predictions: matrix completion methods (MCMs) and demonstrate its applicability using a data base that contains experimental H_ij values for 101 solutes i and 247 solvents j at 298 K. Data on H_ij are only available for 2661 systems i + j. These H_ij are stored in a 101 × 247 matrix; the task of the MCM is to predict the missing entries. First, an entirely data-driven MCM is presented. Its predictive performance, evaluated using leave-one-out analysis, is similar to that of the Predictive Soave-Redlich-Kwong equation-of-state (PSRK-EoS), which, however, cannot be applied to all studied systems. Furthermore, a hybrid of MCM and PSRK-EoS is developed in a Bayesian framework, which yields an unprecedented performance for the prediction of H_ij of the studied data set.     

Power Consumption in Dual Impeller Gas‐Liquid Contactors: Impeller Spacing,Gas Flow Rate,and Viscosity Effects

The dependence of power consumption on impeller spacing, and also in relation to gas flow rate and viscosity, in unaerated and aerated gas‐liquid contactors agitated by dual Rushton‐ and by dual pitched blade turbines was comparatively studied. In tap water the two Rushton impellers acted independently for spacings greater than ΔH = 1.65d, while in glycerol solutions the impellers acted independently on reaching an impeller spacing equal to 1.20d; the corresponding values for the two pitched blade impellers were 1.50d for tap water, 1.07d for relatively high viscosities, and 0.53d for very high viscosity values. The Newton number Ne decreases with increasing viscosity for the dual Rushton turbine systems, while an increase of Ne can be observed with increasing viscosity for the corresponding pitched blade systems. For the dual Rushton turbines, gas flow number Q has no effect on Ne, at very high values of viscosity, while at low and relatively high viscosity values a small effect of Q on Ne can be detected. As observed for the dual Rushton turbine systems, Ne is also not affected by Q for the corresponding pitched blade systems at very high viscosity values. Flow number Q does not significantly affect the Newton number for the water‐glycerol solutions with a relatively high viscosity agitated by dual pitched blade turbines, while for the aerated water systems a decrease of Ne can be observed at relatively small gas flow numbers; high values of Q do not affect the Newton number.     

Liquid solidification in low peclet number pipe flows

The combined effects of axial conduction and solidification on heat transfer and pressure drop in pipe flows are investigated by the use of a modified Galerkin finite element method. To allow for the upstream heat conduction, the domain of study is extended from X = -∞ to X = -∞ as has been done in previous analyses. As a preliminary study on the effect of axial conduction, the present investigation assumes a superheat ratio that is sufficiently large (T_o > T_f or T_w ≈ T_f) such that solidification begins at a location near X = 0. For numerical convenience, the infinite domain -∞ ≤ X ≤ ∞ is transformed onto a finite domain -1 ≤ z ≤ 1. The energy equation for the liquid-phase is then solved by a modified Galerkin finite element method. For better numerical stability, a procedure is proposed for controlling the numerical error that might propagate from the singular point (X, R) = (O, R_o). The profile of the solid-liquid interface, the heat transfer rate and the pressure drop are presented for various values of Peclet number, Pe = 1, 3, 5, 10 and 30, and for the modified superheat ratio, c = 0.1, 0.5, 5.0, and ∞.     

Species segregation of binary mixtures and a continuous size distribution of Group B particles in riser flow

Experiments involving a gas–solid, pilot-scale circulating fluidized bed (CFB) have been carried out, with a focus on species segregation measurements in a riser. Three mixtures were considered: (i) a binary mixture with particles of different sizes (d_ave) but same material density (ρ_s), (ii) a binary mixture with particles of different material densities (ρ_s) but same size (d_ave), and (iii) a continuous particle size distribution (PSD). Local measurements of the composition (i.e., species segregation) of each mixture were obtained over a range of operating conditions. Similar to previous works, the results show that the more massive species (i.e., greater d_ave or ρ_s) preferentially segregates toward the wall in all cases. Several new trends were also observed. First, for the binary mixtures, composition of the more massive species increases with riser height at the wall under some operating conditions. The operating conditions that cause this phenomenon are mutually exclusive for the size-difference and density-difference systems. Second, for the continuous PSD, radial segregation is observed even when there is a net positive flux in the annular region, contrary to previous findings which indicated segregation only for conditions leading to a net downward flux in the annular region. Finally, two qualitative differences between the binary and continuous mixtures were noted: (i) a monotonic decrease in species segregation is observed for the binary mixtures with an increase in the solid loading (m), while a non-monotonic trend is observed for the continuous PSD, and (ii) while the shape of the radial segregation profile is flattest at the riser bottom for the binary mixtures, the flattest radial profile is at the riser top for the continuous PSD.     

Production of (S)-β-Nitro Alcohols by Enantioselective C−C Bond Cleavage with an R-Selective Hydroxynitrile Lyase

Hydroxynitrile lyase (HNL)-catalysed stereoselective synthesis of β-nitro alcohols from aldehydes and nitroalkanes is considered an efficient biocatalytic approach. However, only one S-selective HNL—Hevea brasiliensis (HbHNL)—exists that is appropriate for the synthesis of (S)-β-nitro alcohols from the corresponding aldehydes. Further, synthesis catalysed by HbHNL is limited by low specific activity and moderate yields. We have prepared a number of (S)-β-nitro alcohols, by kinetic resolution with the aid of an R-selective HNL from Arabidopsis thaliana (AtHNL). Optimization of the reaction conditions for AtHNL-catalysed stereoselective C−C bond cleavage of racemic 2-nitro-1-phenylethanol (NPE) produced (S)-NPE (together with benzaldehyde and nitromethane, largely from the R enantiomer) in up to 99 % ee and with 47 % conversion. This is the fastest HNL-catalysed route known so far for the synthesis of a series of (S)-β-nitro alcohols. This approach widens the application of AtHNL for the synthesis not only of (R)- but also of (S)-β-nitro alcohols from the appropriate substrates. Without the need for the discovery of a new enzyme, but rather by use of a retro-Henry approach, it was used to generate a number of (S)-β-nitro alcohols by taking advantage of the substrate selectivity of AtHNL.     

A novel method for color determination of edible oils in L*a*b* format

A simple method that uses visible spectrophotometer data and an artificial neural network (ANN) was developed to determine edible oil color based on the L*a*b* format. The 100 oil samples consisted of nine pure oils, a sesame oil blend and three heated oils. Binary, ternary and quaternary mixtures of these 13 oils in different ratios were prepared, and absorbance values of the samples were measured in the visible region (380–700 nm). The absorbance values at wavelengths of 416, 456, 483, 537, 611 and 672 nm were used to train, validate and test the network. Strong correlations between the instrumental L*a*b*ΔE and the estimated L*a*b*ΔE were found for the test samples, with correlation coefficients (R²) of 0.989, 0.984, 0.996 and 0.992 for L*, a*, b*, and ΔE, respectively. The effects of number and combination of the wavelengths used for training of the ANN on the estimation capability of the network for the test samples were also investigated. Although a good agreement, average R² of 0.991– 0 993 for L*a*b*, was obtained for combinations composed of three to six wavelengths with 483 and 537 nm in common, the best R² value was obtained when all six wavelengths were used to train the ANN. The developed method is objective, cost effective and simple, and allows the color measurement with a basic visible spectrophotometer and disposable cuvettes.     

Recoverable shear strain of liquid crystal‐forming concentrated hydroxypropyl cellulose solutions

The recoverable shear strain (S_R) for the liquid crystal‐forming hydroxypropyl cellulose solutions was determined by means of a concentric cylinder rotational apparatus as functions of shear stress prior to recovery and concentration of the solutions at 30°C. S_R greatly depended on shear stress and concentration; the phase of the solution (the single phase or biphase) governed the dependences of S_R on stress and concentration. S_R increased with increasing stress for the single phase and decreased for the biphase. S_R seemed to be related to the die swell (B): S_R ∝ Bⁿ. S_R exhibited a maximum and a minimum with respect to concentration. S_R for the cellulosic cholesteric liquid crystalline solutions was greater than that for the isotropic solutions. A model was proposed for explaining the greater S_R. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 865–872, 2002     

AN ADHESIVE PROBLEM FOR A POWER-LAW FLUID

The flow caused by the pulling of a circular disk away from a plane rigid surface is investigated when the disk and the surface are separated by a thin layer of power-law fluid of thickness h(t). It is observed that the force exerted by the fluid on the disk is a suction force F, which tends to make the disk adhere to the rigid surface. The variation of F/k (where k is the power-law consistency index) with time t is computed for h(t) = t + 5.0 for both pseudoplastic (with power-law exponent n satisfying 0 < n < 1) and dilatant fluids (with n > 1). It is found that at a given instant, |F|/k for any pseudoplastic fluid is larger than that for a dilatant fluid. Further, the values of F for several realistic pseudoplastic fluids are computed at a given instant for both linear and quadratic variation of h(t) with t. The analysis further reveals that for a realistic pseudoplastic fluid, |F| at a given instant corresponding to a linear variation of h(t) is larger for a layer of given thickness than |F| at that instant for a layer of larger thickness.     

Dimensional Analysis of Crossflow Microfiltration Data

Abstract

A new approach to correlating crossflow microfiltration (CFMF) data based on dimensional analysis is presented. The steady state flux was assumed to be a function of the trans‐membrane pressure (ΔP), the crossflow velocity (u), the particle concentration (c), filtrate viscosity (μ), and membrane resistance (R _m). Correlations of the form J/u=K(ΔP/cu ²) ^a (ΔP/μuR _m) ^b were tested on three sets of published data: one for CFMF of dried yeast suspensions in a laminar flow hollow fiber module, one for dried yeast suspensions in a turbulent flow tubular module and one for suspensions of latex particles in a laminar flow flat sheet module. The R ² values for the fits of the correlations to the data were 0.98, 0.94, and 0.91 respectively.     

Some Aspects of Thermal Stability and the Characteristics of Poly(ethylene terephthalate) (PET) under Stress

In this work we use thermal shrinkage for estimating the internal stresses accumulated in a sample during a technological process. This can be a precious instrument available for every manufacturer interested in the thermal treatment efficiency. Based on the Kelvin‐Voight rheological model, we have established a correlation between the internal stresses appearing during the technological formation processes of yarns and their shrinkage at different temperatures. In this work (PET) fibers were used for study, with different birefringences ranging between 4.2×10^–3–2.2×10^–3. Thermal treatment was performed with warm air at temperatures between 333–453 K. The applied unitary stress changed within the range 5.09×10¹⁰–18.84×10¹³ N·m^–2. From the examination of the curves obtained for free contraction Δε = f (T) for different birefringences Δn for the preoriented PET fibers, contraction increases with increasing temperature up to a maximum situated at ≈ 353 K and then decreases to a constant value. From the examination of the curves, the dimensional change vs. contraction σ = f (Δε), to a thermal treatment under stress for different birefringences Δn, when an external stress σ is applied the thermal stability of the fibers already having on orientation, made evident by the birefringence magnitude, that in the case of a slight orientation, the retraction decreases with increasing temperature. Singular points registered for fibers with Δn = 22×10^–3 for a temperature exceeding 393 K indicate that for the partially orientated fibers the sample is subjected to a stretching process during the thermal stability under stress. We established experimentally a correlation between the strain σ and Δn, Δn = ct. σ/T, i. e., a decrease of the birefringence with increasing temperature.     

Significance of the solubility of hydrocarbon gases in liquids in relation to the intermolecular structure of liquids and the essential pattern of data for all gases

Solubility data expressed as mole ratio, x_RH (moles of RH per mole of liquid S) have been measured for propane and n-butane in a number of type-representative organic liquids, S, at different temperatures, t °C, and pressures, p_RH ≤ 760 mm. These data, and those for methane, ethane and radon, afford support in the development of the essential pattern of data for all gases, A, and all liquids, S. This pattern indicates that the first factor determining the solubility of any gas, A, in any liquid, S, is its tendency to condense to a liquid at the operational temperature, t °C (e.g. 0 °C to 25 °C), shown by its vapour pressure p°_A over liquid A (or its equivalent for a gas above the critical temperature) at t °C. Since p°_A emerges from the b.p. of A at 1 atm, and b.p. data are readily seen in text-books, the b.p. may be taken as an initial index of the first factor. In the N_A–p_A diagram for a given gas A and different liquids, S, at a fixed t °C, N_A being the mole fraction of A, the straight line joining p°_A with p_A = 0 is herein called the reference line, the R-line, of A; it is a real property of A, and it represents the plot of N_A–p_A for a hypothetical liquid, S, having in effect an overall inter-molecular structure equivalent to liquid A, in imagination, A itself. The N_A–p_A plot for another liquid, S, involves a second and a third factor, the second being the intermolecular structure of S, in a dynamic sense, and the third, the inevitable interaction of A with S. These factors are deemed to emerge from changes in electron density, designated for the present as acid-base functions. The spread of x_RH values is indicated by x_PrH = 0.322, x_BuH = 5.25, for di-n-octyl ether; x_PrH = about 0.000042, x_BuH = about 0.000040, for water, for 5 °C and P_RH = 760 mmHg.     

Design of a Tubular Ceramic Membrane for Gas Separation in a PEMFC System

The objective of this study is to introduce a shortcut in the method of design for a tubular ceramic membrane (TCM) for gas separation. Generally, it explains the permeation of the multi component gas using cross flow models in a porous membrane and the surface area of the membrane required. The novel aspect of this method is that the expression for the length of the membrane is simplified to a number unit (NTU) and a height of transfer unit (HTU). The HTU term for porous membranes is characterised by the physical properties of the membrane; the feed flow rate, n_F, membrane thickness, l_M, feed pressure, P_F, K the permeability of gas and the diameter of the membrane, D_M. The integral for NTU of a porous membrane is the solution for the local permeate along the length of the membrane. It is found that, NTU mainly depends on the rejection stream, x_R,, along the membrane and it describes the relative degree of separation. The Proton Electrolyte Membrane Fuel Cell (PEMFC) system is taken as the case study. CO is the main culprit in reducing the performance of the PEMFC and will act as a catalyst poison for the fuel cell anode at a concentration as low as 100 ppm. Thus, the reformate, from primary reforming, contains a significant amount of CO and must be purified. The effect of some important parameters such as temperature, pressure and the thickness of membrane to the degree of separation are presented in this paper. From the results, it can be seen that the system could reduce the CO concentration from 2000 – 500 ppm. Basically the TCM will operate, in series, with a pressure swing adsorber in order to further reduce the concentration of CO to less than 10 ppm before entering the fuel cell stack. However, this paper only focuses on the design of the TCM. Besides this, it is observed that the purity of the hydrogen increased from 72.8 – 96% (at θ = 0.5) after the membrane.     

Gas permeation of polymer blends. III. Poly(vinyl chloride) (PVC)/chlorinated polyethylene (CPE)

The permeability P, diffusivity D, and activation energy for diffusion, E_D, of He, O₂, N₂, and CO₂ were determined for blends of PVC/chlorinated polyethylene (CPE), where the chlorine content of the CPE components varied: 36 wt-% for CPE-1, 42 wt-% for CPE-2, and 48 wt-% for CPE-3. The difference in thermal expansion coefficients Δα above and below the glass transition temperature T_g of the polymers and the fractional free volume V_g of the polymers at their T_g were determined. Density and crystallinity measurements for the blends were also carried out as in the earlier work (Shur and Rånby, J. Appl. Polym. Sci., 19 , 1337 (1975)). Dynamic mechanical measurements of the blends were made using a torsion pendulum at about 1 Hz. P and D decreased, but E_D increased with increasing CI content of CPE in the blends. P and D for the blends showed no additivity. The permeability indicated phase inversion for blend compositions at about 10% of CPE-1 and CPD-2 by weight. The experimental and the calculated densities were largely the same for PVC/CPE-1 blends; but for PVC/CPE-2 and PVC/CPE-3 blends, the experimental values were higher than the calculated ones. The Δα and V_g values for PVC and the three CPE samples decreased with increasing CI content in the polymers. Dynamic mechanical measurements indicate that PVC/CPE-1 and PVC/CPE-2 blends form largely incompatible blends, while PVC/CPE-3 blends are compatible to some extent. There is some weak interaction between PVC and CPE-3 giving a low level of compatibility. The solubility of gases obtained from time-lag measurements of diffusion for 50/50 blends decreased for He, O₂, and N₂, but increased for CO₂ with increasing Cl content in CPE. The solubility of He, O₂ and N₂ shows a positive correlation with the Lennard-Jones force constant ?/k. However, a deviation from the linear relation between ?/k and In S was observed for CO₂ and the deviation became larger with increasing Cl content in CPE. The abnormally high solubility of CO₂ is probably due to the high polarizability of this gas. The heat of solution ΔH_s indicates that for He the sorption process may be a molecular slip process (endothermic), but for other gases the sorption may proceed by a dissolution process (exothermic). There is a large difference between the calculated solubility for the blends assuming incompatibility and the experimental values from time-lag measurements. This may partly be due to the uncertainty of sorption values obtained from the time-lag method and/or partly to changes of sorption modes by interaction between PVC and CPE in the blends. The resulting transport behavior of the blends is discussed on the basis of the free volume concept and of phase–phase interaction in the blends.     

Synergies between plant antioxidant blends in preventing peroxidation reactions in model and food oil systems

A study was conducted to investigate the oxidative behavior of various mixtures of rosemary, sage, and citric acid in a linoleic acid model system by oxygen consumption measurement and in a palm olein system by differential scanning calorimetry (DSC) analysis. Response surface methodology was used to optimize the use of the mixtures. Results showed that rosemary and sage were two important factors for the protective index (PI). The two antioxidants were highly significantly (P<0.001) in influencing PI values. There was a significant (P<0.01) synergistic effect between rosemary and sage on PI values. Citric acid was also found to be significant (P<0.05) for PI. With respect to onset time (T _o ), all three antioxidants were significant (P<0.05). However, no significant interaction among antioxidants was found for T _o . Mathematical models for both PI and T _o could be developed with confidence. The R ² values for PI and T _o were 0.992 and 0.926, respectively. A combination of 0.078% rosemary, 0.067% sage and 0.037% citric acid was the optimal combination for PI, whereas a combination of 0.068% rosemary, 0.075% sage, and 0.039% citric acid was required to reach the optimal T _o value.     

Unified study of flow regimes and gas holdup in the presence of positive and negative surfactants in a non-uniformly aerated bubble column

In this paper, a study on the global gas holdup and hydrodynamic flow regimes developed in a partially aerated bubble column at variable air superficial velocities (U_G) in the presence of positive and negative surfactants is presented. According to the results obtained, despite the different liquid phase properties variation caused by the presence of positive (alcohols) and negative (electrolytes) surfactants, both reduce coalescence and the effect in the gas holdup (ε_G) is equivalent: it increases with the surfactant concentration (C) but only when the (C/C_t) ratio is clearly above 1, being C_t the transition concentration. Contrary to the results obtained for totally aerated bubble columns, for lower values of the (C/C_t) ratio, the holdup remains practically invariable. Considering the crucial role that C and C_t play in the resulting ε_G, a new prediction equation for ε_G accounting for the ratio (C/C_t) and U_G is presented and its performance for both types of surfactants validated. Additionally, visual and wall pressure fluctuations studies reveal that the vortical flow (VF), characterized by an oscillating bubble plume, prevails in ultrapure water (UPW) but results destabilized in the presence of surfactants. This destabilization results in an evolution to a pseudo-steady flow regime, the double cell turbulent flow regime (DCTF), characterized by a quasi-static bubble jet, located at the column centerline that determines the appearance of two static symmetrical vortices     

The influence of power‐law rheology on flow distribution in coathanger manifolds

Coathanger dies are effective in delivering uniform flow if a polymer melt; however, when the fluid flow index varies from the design values, the flow is not uniform. Although mechanisms such as die lip adjustments have been effective tools for adjusting flow profiles, the issue of a variable flow index has not been fully addressed at the design stage. An analytical solution, based on the assumptions present in the 1‐D design equation, has been developed for the flow distribution in a coathanger manifold. This solution determines the flow distribution for a power‐law fluid with a flow index n* in a manifold designed for a separate flow index n*. From this solution, a uniformity index and a critical design angle are defined. The critical design angle is the angle at which the local derivative of the uniformity index with respect to n* approaches a maximum (for n* < n) or a minimum (for n* > n) as a function of the design angle. The critical design angle is independent of n and is presented as a function of the manifold aspect ratio.     

Some properties of low molecular weight polybutadiene and polytetrahydrofuran

The proposition, that low molecular weight polymer fractions in good solvents behave as if they were under ? conditions, has been examined experimentally. Series of monodisperse hydroxy-terminated polytetrahydrofuran (PTHF), 82% 1,4-polybutadiene (PBD), and 30% 1,4-PBD were prepared, and values of M?_n obtained by vapor-pressure osmometry and endgroup analysis. The Mark–Houwink viscosity parameters K and ν were determined in a number of solvents. The general conclusion is that the proposition is invalid for these systems notwithstanding the fact that ν = 0.50 for one of them [82% 1,4-PBD in methyl ethyl ketone (MEK) at 25°C]. For this particular case, the following evidence suggests that these are actually ? conditions so that the apparent fulfilment of the proposition is fortuitous. (1) Cloud-point precipitation yields ? = 26 ± 3°C in MEK. (2) The value of K is close to that of K_? found elsewhere for PBD in a different solvent at a similar temperature. (3) Application of the Kurata-Stockmayer iterative procedure for estimating K_? from data in good and bad solvents yields a reasonably small discrepancy (10%) between the K_? values from data in toluene and MEK at 25°C for this polymer and only a 3% difference in the unperturbed dimensions (〈r₀²〉/M)^1/2 derived from them. Measured melting points T_m of PTHF (M?_n = 1000–13000), plotted as a function of chain length Z, viz., 1/T_m = 1/T_m0 + 2R/ZΔH_f, yield 43 ± 3°C and 1.6 kcal/submole, respectively, for the limiting melting point T_m0 and the heat of fusion ΔH_f. The former is in good agreement with the value obtained dilatometrically for high molecular weight polymer, while the latter indicates a degree of crystallinity of ca. 54%.