Elongation flow studies of DNA as a function of temperature

The response of T4‐phage DNA molecules to an elongational flow field was monitored by flow‐induced birefringence as a function of temperature. The flow‐induced birefringence observed in this study was localized in the pure elongational flow area with a critical strain rate, indicating that the birefringence was attributed to a coil–stretch transition of DNA molecules. The slight decrease in the birefringence intensity with increases in temperature to 40°C was explained by a thermal‐activation process. At temperatures above 50°C, flow‐induced birefringence decreased remarkably, and no birefringence was observed at temperatures above 60°C. After the flow experiments, ambient temperature was reduced back to room temperature, and flow experiments at room temperature were performed again. Flow‐induced birefringence was recovered almost completely in samples for which the first flow measurements were made at temperatures below 53°C. Irreversible changes were observed for samples for which the first flow experiments were performed at temperatures above 55°C. The temperature dependence of UV‐absorption spectra revealed that the double‐strand DNA helix began to partially untwine at a temperature over 50°C, and duplexes became almost completely untwined at a temperature over 55°C. A comparison of electrophoresis patterns for untwined molecules showed that flow‐induced scission of DNA molecules occurred in a sample solution in flow experiments performed at 65°C, while no molecular weight reduction was observed in the sample solution at 55°C. In this article, this difference between the untwined DNA molecules is discussed on the basis of the thermally activated bond scission (TABS) model. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1357–1365, 2002     

Study on conformational transition phenomena of poly(methyl methacrylate) in acetonitrile near theta conditions

The coil–globule transition for poly(methyl methacrylate) (PMMA) has been studied in a theta solvent, acetonitrile (Θ = 45 °C). The viscosity of PMMA was measured as a function of temperature in the range 26–55 °C. The contraction and expansion of the molecular chains are determined using the measured viscosity values. The temperature dependence of the intrinsic viscosity can be represented by a master curve in a versus |τ|M _w^1/2 (g^1/2 mol^−1/2) plot, where τ = |T − Θ|/T is the reduced temperature and M_w‐is the weight‐average molecular weight. A universal plot of reduced viscosity versus reduced blob parameter (N/N_c) shows the attainment of the collapsed state below the theta temperature. The dimensions of PMMA in acetonitrile (M_w = 3.15 × 10⁶ g mol⁻¹) decrease to 63 % at 26 °C of those in the unperturbed state. The results in this work are compared with those previously published. © 2000 Society of Chemical Industry     

Application of time–temperature superposition principle to polymer transition kinetics

The time–temperature equivalence equation is deduced simply in view of the transition kinetics of a polymer. The independent variables time and temperature are separated in the two sides of the resulting equation. Thus, a physical property of the polymer, which is temperature dependent, can be matched with the theoretical calculated curve from a supposed model of transition kinetics in which only time is involved as the independent variable. By comparing different models, one may judge which model is probably more correct. The procedure of data fitting is described. As an application example, the measured viscosity data at different temperatures for the coil–globule transition of poly(N‐isopropylacrylamide) in aqueous solution is tested to judge its transition mechanism. A transition mechanism involving a two‐stage reversible reaction fits the experimental data in a satisfactory way. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1767–1772, 2006     

Inception and termination of the core‐annular flow pattern for oil‐water downflow through a vertical pipe

Different flow patterns for lube oil–water and for kerosene‐water downflow through a vertical glass tube have been analyzed with the help of flow visualization. Core‐annular flow is the dominant flow regime, with oil forming the core, and water is forming the wall film. When the velocities are increased, transition to slug flow and transition to dispersed flow are found. The waves found during the transition to slug flow depend on oil viscosity: axisymmetric bamboo waves are seen in kerosene‐water downflow and the waves are asymmetric in case of lube oil–water flow where they have a cork‐screw shape. Based on the experimental observations, simple mathematical models have been proposed for predicting the flow pattern transition curves. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

Sorption studies of propylene in polypropylene. Diffusivity in polymer particles formed by different polymerization processes

Propylene was polymerized in gas phase and liquid phase by using a novel nonporous Ziegler–Natta‐catalyst system. The polymer particles formed at different polymerization times were used for sorption measurements. In both cases it was found that the effective diffusion coefficient is increasing with increasing size of polymer particles and the effective diffusion coefficients of polymer particles formed by liquid‐phase polymerization are larger than those of polymer particles produced by gas‐phase polymerization. The effective diffusion coefficients of polymer particles are in the range of 2 × 10^?11 to 1.6 × 10^?10 m²/s with activation energies from 34 to 22 kJ/mol. The analyzed polymer particles have average diameters between 250 and 875 μm. The solubility of propylene in polypropylene particles can be described by the law of Henry at conditions studied. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2642–2648, 2006     

Moisture diffusion in epoxy systems

The moisture diffusion process of an epoxy system is studied as a function of epoxy‐amine stoichiometry and the resulting microstructure. Differences in diffusion behavior are related to the relative importance of diffusion through the low‐density and high‐density microstructural phases for different stoichiometries. Also, changes in saturation level with stoichiometry are explained by competing effects of free volume versus the content of the low‐density phase. Increasing the humidity level causes a corresponding increase in saturation level, while increasing the temperature causes more pronounced non‐Fickian behavior. The effects of absorbed moisture on the thermomechanical properties of the epoxies are also investigated. Reductions in the glass transition temperature, T_g, and moisture‐induced swelling strains are measured after exposure of samples to the three conditioning environments. Moisture‐induced swelling strains increase with increasing moisture content. The reductions in T_g range from 5 to 20°C and are generally larger for amine‐rich samples than for epoxy‐rich and stoichiometric samples. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 787–798, 1999     

Counter‐ion‐specific helix formation of poly(γ‐methyl L‐glutamate) derivatives containing sulfonate group in aqueous alcohols

Charged polypeptides containing sulfonate groups were prepared by transesterification of poly(γ‐methyl L ‐glutamate) with isethionic acid. The coil–helix transition of the sulfonated polypeptides was investigated in aqueous alcohols. Marked counter‐ion specificity was observed for helix formation: Li⁺ < Na⁺ < Cs⁺ ≦ Rb⁺ ≦ K⁺; this was different to that for poly(L ‐glutamate) (PLG): Cs⁺ ? K⁺ < Li⁺ < Na⁺. Specific helix stabilization by counter‐ion mixing, which has been found for the PLG system, was not observed for the sulfonated polypeptides. The counter‐ion‐ and solvent‐specific helix formation is discussed and compared with that in PLG. © 2001 Society of Chemical Industry     

Effect of tube diameter on two‐phase flow patterns in mini tubes

The effect of tube diameter on two‐phase flow patterns was investigated in circular tubes with inner diameters of 0.6, 1.2, 1.7, 2.6, and 3.4 mm using air and water. The gas and liquid superficial velocity ranges were 0.01–50 and 0.01–3 m/s, respectively. The gas and liquid flow rates were measured and the two‐phase flow pattern images were recorded using high‐speed CMOS camera. The flow patterns observed were dispersed bubbly, bubbly, slug, slug‐annular, wavy‐annular, stratified, and annular flows. These flow patterns were not observed in all the test diameters, but were found to be unique to particular tube diameters, confirming the effect of tube diameter on the flow pattern. The data obtained were compared to existing experimental data and flow regime transition maps which show generally reasonable overall agreement at the larger diameters, but significant differences were observed with the smaller diameter tubes.     

Urea‐induced conformational changes of chitosan molecules and the shift of break point of Mark–Houwink equation by increasing urea concentration

Chitosan solutions of the same 83% degree of deacetylation (DD) but different weight average molecular weights (M_ws) (78–914 kDa) in 0.01M HCl containing different concentrations of urea (0–6M) were prepared. Intrinsic viscosity ([η]) and weight average molecular weight (M_w) of chitosan were measured with a capillary viscometer and light scattering, respectively. Mark–Houwink exponent a was used as the parameter of conformational index. The Mark–Houwink exponent a increased with increasing concentrations of urea. When solutions contained 0, 2, 3, 4, and 6M urea, the value of a increased from 0.715 to 0.839, 0.894, 1.000, and 1.060, respectively. This indicates the occurrence of urea‐induced conformational transitions of chitosans. The break point shifted from 223 kDa in solutions containing no urea to 280 kDa in 2M urea solutions, to 362 kDa in 4M urea solutions and further to 481 kDa in 6M urea solutions. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 452–457, 2000     

Shear flow effect on the crystalline forms in polyamide 6/montmorillonite nanocomposites

The influence of shear flow on the crystallization of polyamide 6/MMT nanocomposites prepared by melt intercalation process was investigated in detail by differential scanning calorimetry. The melted nanocomposites were controlled sheared in the steady and oscillatory shear flow, using a rotational rheometer, and cooled in an inert atmosphere. The effects of shear rate or frequency, clay concentration, and crystallization conditions on PA 6 crystalline phase development were studied. As expected, an opposite impact of shearing on γ‐phase formation in the nanocomposites and neat matrix was found. Surprisingly, a critical shear frequency for the onset of γ‐form crystallinity formation in the nanocomposites, increasing with the filler content as a consequence of polymer chains confinement within oriented clay platelets was found. At higher shear frequencies, the proportion of γ‐form in the nanocomposites increased dramatically with the clay concentration and reached 30–40%. The shear flow effects were influenced by cooling conditions, and more significant effect for rapidly cooled samples was observed. The isothermal crystallization at the solidification temperature 205°C reduced the γ‐form content. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Characteristics of air–water two‐phase flow in a 3‐mm smooth tube

Two‐phase flow pattern and friction characteristics for an air–water system in a 3.17 mm smooth tube are reported in this study. The range of mass flux is between 50 and 700 kg/m²s. The experimental data show that the two‐phase friction multipliers are strongly related to the flow pattern. For a stratified‐wavy flow pattern, a mass‐flux dependence of the two‐phase multipliers is seen. For a non‐stratified flow pattern, the two‐phase frictional multipliers are comparatively independent of mass flux. Correlations of the frictional multipliers are developed for stratified and non‐stratified flow. To use the appropriate correlation in different regime, a simple criterion is proposed.     

Treatment of the refinery wastewater in a gas–liquid–solid three‐phase flow airlift loop bioreactor

Aerobic treatment of refinery wastewater was carried out in a 200 dm³ gas–liquid–solid three‐phase flow airlift loop bioreactor, in which a biological membrane replaced the activated sludge. The influences of temperature, pH, gas–liquid ratio and hydraulic residence time on the reductions in chemical oxygen demand (COD) and NH₄‐N were investigated and discussed. The optimum operation conditions were obtained as temperature of 25–35 °C, pH value of 7.0–8.0, gas–liquid ratio of 50 and hydraulic residence time of 4 h. The radial and axial positions had little influence on the local profiles of COD and NH₄‐N. Under the optimum operating conditions, the effluent COD and NH₄‐N were less than 100 mg dm^?3 and 15 mg dm^?3 respectively for more than 40 days, satisfying the national primary discharge standard of China (GB 8978‐1996). Copyright © 2005 Society of Chemical Industry     

Preparation of sorbitol from D‐glucose hydrogenation in gas–liquid–solid three‐phase flow airlift loop reactor

A new process for D ‐glucose hydrogenation in 50 wt% aqueous solution, into sorbitol in a 1.5 m³ gas–liquid–solid three‐phase flow airlift loop reactor (ALR) over Raney Nickel catalysts has been developed. Five main factors affecting the reaction time and molar yield to sorbitol, including reaction temperature (T_R), reaction pressure (P_R), pH, hydrogen gas flowrate (Q_g) and content of active hydrogen, were investigated and optimized. The average reaction time and molar yield were 70 min and 98.6% under the optimum operating conditions, respectively. The efficiencies of preparation of sorbitol between the gas–liquid–solid three‐phase flow ALR and stirred tank reactor (STR) under the same operating conditions were compared. Copyright © 2004 Society of Chemical Industry     

Direct meso‐scale simulations of fibres in turbulent liquid flow

A procedure for direct, meso‐scale simulations of flexible fibres immersed in liquid flow is introduced. The fibres are composed of chains of spherical particles connected through ball joints with the bending stiffness of the joints as a variable. The motion of the fibres and the liquid is two‐way coupled with full resolution of the solid–liquid interface. First the simulation procedure is validated by means of an analytical solution for sphere doublets in zero‐Reynolds simple shear flow. Subsequently we use the numerical method to study inertial flows with fibres, more specifically the interaction of a fibre with isotropic turbulence.     

Higher‐Order Human Telomeric G‐Quadruplex DNA Metalloenzymes Enhance Enantioselectivity in the Diels–Alder Reaction

Short human telomeric (HT) DNA sequences form single G‐quadruplex (G₄) units and exhibit structure‐based stereocontrol for a series of reactions. However, for more biologically relevant higher‐order HT G₄‐DNAs (beyond a single G₄ unit), the catalytic performances are unknown. Here, we found that higher‐order HT G₄‐DNA copper metalloenzymes (two or three G₄ units) afford remarkably higher enantioselectivity (>90 % ee) and a five‐ to sixfold rate increase, compared to a single G₄ unit, for the Diels–Alder reaction. Electron paramagnetic resonance (EPR) and enzymatic kinetic studies revealed that the distinct catalytic function between single and higher‐order G₄‐DNA copper metalloenzymes can be attributed to different Cu^II coordination environments and substrate specificity. Our finding suggests that, like protein enzymes and ribozymes, higher‐order structural organization is crucial for G₄‐DNA‐based catalysis.     

Hydrodynamic modeling on the external liquid–solid wetting efficiency in a trickling flow reactor

A three‐region model was proposed, which considers the bed cross section being composed of a stagnant liquid region, a liquid film region, and a rivulet flow region. To estimate the fractions of the three regions, the fraction of film flow was evaluated first, by transforming the complex trickling flow texture into pure liquid film flow. Through the measurements of liquid holdup and pressure drop for the film flow, a relationship between relative permeability and gas saturation was established, and from which the fraction of film flow region was obtained. It shows packing size is most important to the faction of rivulet flow. The external wetting efficiency of the packing was correlated as the sum of two‐third power of the liquid film fraction and the rivulet flow fraction, besides, a correlation based on Reynolds and Galileo numbers of the two phases in the form of was proposed. © 2012 American Institute of Chemical Engineers AIChE J, 59: 283–294, 2013     

Hydrodynamics and mass transfer of gas–liquid flow in a falling film microreactor

In this article, flow pattern of liquid film and flooding phenomena of a falling film microreactor (FFMR) were investigated using high‐speed CCD camera. Three flow regimes were identified as “corner rivulet flow,” “falling film flow with dry patches,” and “complete falling film flow” when liquid flow rate increased gradually. Besides liquid film flow in microchannels, a flooding presented as the flow of liquid along the side wall of gas chamber in FFMR was found at high liquid flow rate. Moreover, the flooding could be initiated at lower flow rate with the reduction of the depth of the gas chamber. CO₂ absorption was then investigated under the complete falling flow regime in FFMR, where the effects of liquid viscosity and surface tension on mass transfer were demonstrated. The experimental results indicate that k_L is in the range of 5.83 to 13.4 × 10^?5 m s^?1 and an empirical correlation was proposed to predict k_L in FFMR. © 2009 American Institute of Chemical Engineers AIChE J, 2009