Studies of redox polymerization. I. Aqueous polymerization of acrylamide by an ascorbic acid–peroxydisulfate system

The polymerization of acrylamide initiated by an ascorbic acid–peroxydisulfate redox system was studied in aqueous solution at 35 ± 0.2°C in the presence of air. The concentrations studied were [monomer] = (2.0–15.0) × 10^?2 mole/liter; [peroxydisulfate] = (1.5–10.0) × 10^?3 mole/liter; and [ascorbic acid] = (2.84–28.4) × 10^?4 mole/liter; temperatures were between 25–50°C. Within these ranges the initial rate showed a half-order dependence on peroxydisulfate, a first-order dependence on an initial monomer concentration, and a first-order dependence on a low concentration of ascorbic acid [(2.84–8.54) × 10^?4 mole/liter]. At higher concentrations of ascorbic acid the rate remained constant in the concentration range (8.54–22.72) × 10^?4 mole/liter, then varied as an inverse halfpower at still higher concentrations of ascorbic acid [(22.72–28.4) × 10^?4 mole/liter]. The initial rate increased with an increase in polymerization temperature. The overall energy of activation was 12.203 kcal/mole in a temperature range of 25–50°C. Water-miscible organic solvents depressed the initial rate and the limiting conversion. The viscometric average molecular weight increased with an increase in temperature and initial monomer concentration but decreased with increasing concentration of peroxydisulfate and an additive, dimethyl formamide (DMF).     

Thermal oxidation of polyacetylene

The thermal oxidation of undoped trans-polyacetylene powder in dry air has been studied and the principal features of the mechanism have been developed. Thermogravimetric and differential thermal analysis reveal an exothermic process that first leads to a weight increase, followed by precipitous weight loss above 240°C due to formation of volatile oxidation products. Isothermal weight gain studies between 25 and 142°C show first-order kinetics below 90°C with a rate constant of 3.10^?7 s^?1 at 25°C and an apparent activation energy of 16 kcal/mol. A weight gain of more than 40% has been observed at 25°C after 2000 h of exposure to air. A change in first-order kinetics occurs at temperatures above 90°C. Identification of solid oxidation products with photoacoustic infrared spectroscopy reveals that oxygen intercalates into the polymer structure in large concentrations, similar to other electron acceptors. However, oxidative attack on the polymer backbone occurs simultaneously. At elevated temperatures or for long-term oxygen exposure, the concentration of dopant oxygen decreases, probably by intramolecular regrouping of hydrogen atoms, resulting in the formation of hydroxyl groups and enhanced polymer degradation. This mechanism is consistent with the finding of others that the conductivity of polyacetylene upon oxygen exposure increases initially before decreasing significantly with continued exposure, especially at elevated temperatures.     

Charge transfer complex between methylviologen and ferrocyanide

Charge transfer complex between methylviologen and ferrocyanide has been studied spectrophotometrically at different temperatures. From the thermodynamic association constants (320 ± 30 M⁻¹, 380 ± 30 M⁻¹ and 460 ± 40 M⁻¹ at 15, 25 and 30°C respectively), the enthalpy of formation, ΔH° (− 3.4 ± 1.5 kcal/mole), and the related entropy change, ΔS°(0.4 ± 5 e.u), have been calculated. The average extinction values of coefficients are 69±6 M⁻¹ cm⁻¹, 70±4 M⁻¹ cm⁻¹ and 72±5 M⁻¹ cm⁻¹ at 15, 25 and 35°C respectively.     

Investigating the influence of pH,temperature and agitation speed on yellow pigment production by Penicillium aculeatum ATCC 10409

In this study, the combined effect of pH, temperature and agitation speed on yellow pigment production and mycelial growth of Penicillium aculeatum ATCC 10409 was investigated in whey media. Different pH levels (5, 6.5 and 8), temperatures (25, 30 and 35°C) and agitation speed levels (100 and 150 rpm) were tested to determine the best conditions to produce a fungal yellow pigment under submerged fermentation. The best production of yellow pigment (1.38 g/L) was obtained with a pH value of 6.5, a temperature of 30°C and an agitation speed of 150 rpm. In contrast, the maximal biomass concentration (11.12 g/L) was obtained at pH value of 8, a temperature of 30°C and an agitation speed of 100 rpm. These results demonstrated that biomass and yellow pigment production were not directly associated. The identification of the structure of unknown P. aculeatum yellow pigment was detected using UV absorption spectrum and FT-IR spectroscopy.     

Experimental study of the ignition temperatures of low-rank coals using TGA under oxygen-deficient conditions

The factors affecting the ignition temperatures of two low-rank coals were experimentally studied using thermogravimetric analysis. The experiments were conducted with coal powders of four different particle size distributions. The thermogravimetric analyzer was operated at three heating rates, 10, 20, and 30 °C min^?1 and four oxygen concentrations of 3, 6, 9, and 12%. The results showed that the ignition temperature decreased by about 25 °C as the oxygen concentration increased from 3% to 12%. The standard deviation of the activation energy was 16.75% at a conversion degree of less than 0.4, and it decreased to 1.35% at the end of the combustion process. At a heating rate of 10 °C min^?1, the ignition temperature increased by about 8 °C as the coal particle size increased by 100 μm. At a heating rate of 30 °C min^?1, the effect of the particle size on the ignition temperature was enhanced and the ignition temperature increased to 15 °C.

     

Long term stability of organic selenium species in aqueous solutions

Long term stability of organic selenium compounds (selenocystine, selenomethionine, trimethylselenonium ion) has been studied over a one year period for 2 analyte concentrations: 25 and 150 μg/L Se, at pH 4.5 in the dark, under different storage conditions: temperature of –20°C, 4°C, 20°C, 40°C; in Pyrex, Teflon, or polyethylene containers; in an aqueous matrix or in the presence of a chromatographic counter ion (pentyl sulfonate at 10^–4 mol/L concentration). Light effects have also been tested. The stability of the selenium species was monitored by HPLC-ICP/MS. Storage conditions can drastically alter the stability of organic selenium species. Organoselenium compounds were shown to be stable in the dark over a one year period in an aqueous matrix at pH 4.5 in Pyrex containers at both 4°C and 20°C. Pyrex vials exposed to natural sunlight at room temperature resulted in a steady decrease of the selenoamino acid concentration. Teflon containers caused losses of less than 25% at both 4° C and 20° C in the dark. However, polyethylene vials presented, at all temperatures tested, a rapid decrease of the TMSe⁺ concentration. The stability of the Se species studied did not show significant differences between 4° C and 20° C in any container material used. Storage of solutions at 40° C led to slight differences between the Pyrex and Teflon containers. However, polyethylene presented a drastic decrease of the three species over time at this higher temperature. Solutions frozen at –20° C in polyethylene vials did not stabilize the TMSe⁺ signal. Finally, concentrations and matrices of the samples did not significantly affect the stability of the species. Received: 15 July 1996 / Revised: 14 July 1997 / Accepted: 18 July 1997     

Evidence for Conformational Transitions in Amylose1

Abstract

The flow behavior, dynamic viscoelasticity, and optical rotation of an aqueous solution of amylose were measured using a rheogoniometer and a polarimeter, respectively. The amylose solutions showed shear-thinning behavior at a concentration of 1.2%, but plastic behavior above 1.4% at 25 °C. With increasing amylose concentrations the viscosity decreased rapidly with increasing temperature from 20 to 25, 30, and 35 °C. These latter temperatures are estimated to be first transition temperatures at the respective concentrations. Viscosities were scarcely changed until temperatures reached 70, 90, and 90 °C, which were estimated to be second transition temperatures, for 1.2, 1.4, and 1.6% solutions, respectively. Gelation occurred at a concentration of 1.2% at room temperature (2.5 °C). The dynamic modulus of amylose increased gradually with increasing temperature from 20 to 30 °C and kept a constant value until the temperature reached 65, 75, and 80 °C for 1.0, 1.2 and 1.4% solutions, respectively, which were estimated to be transition temperatures, then dynamic modulus decreased rapidly. The dynamic modulus of amylose stayed at a very low value with addition of urea (4.0 M). The optical rotation of amylose solution (1.0%) increased a little with deceasing temperature up to 25 °C, then it increased rapidly with further decrease of the temperature. Possible mode of intra- and intermolecular hydrogen bonding within and between amylose molecules were proposed.     

Radiation-induced ionic polymerization of isobutyl vinyl ether in bulk

The radiation-induced ionic polymerization of isobutyl vinyl ether was investigated under conditions where the monomer was dried with molecular sieves. The investigation covered the temperature range from ?16°C to 90°C, and the dose-rate range from 10¹⁵ to 10²⁰ eV/g-sec, using both γ-rays and electrons. A very high overall activation energy of 15.9 kcal/mole was found for the process below 30°C. Above 30°C, however, the value of the overall activation energy dropped to 4.9 kcal/mole, a phenomenon which is ascribed to the solvation of the propagating carbonium ion below 30°C. The dose-rate dependence of the rate of polymerization was found to be 0.58 over the entire dose-rate range investigated. The molecular weight of the polymer was found to be far less sensitive to trace amounts of water than the rate of polymerization. The molecular weight of the polymer depended strongly on the irradiation temperature, reaching a maximum value of about 120,000 at 35°C. It is shown that at temperatures above 20°C regenerative chain transfer processes play an important role in determining the molecular weight of the polymer.     

Pretreatment of swine wastewater using anaerobic filter

Efforts were made to assess the efficiency of an anaerobic filter packed with porous floating ceramic media and to identify the optimum operational condition of anaerobic filter as a pretreatment of swine wastewater for the subsequent biological removal of nitrogen and phosphorus. A stepwise decrease in hydraulic retention time (HRT) and an increase in organic loading rate (OLR) were utilized in an anaerobic filter reactor at mesophilic temperature (35°C). The optimum operating condition of the anaerobic filter was found to be at an HRT of 1 d. A soluble chemical oxygen demand (COD) removal efficiency of 62% and a total suspended solids removal efficiency of 39% at an HRT of 1 d were achieved with an OLR of 16.0 kg total COD/(m³·d), respectively. The maximum methane production rate approached 1.70 vol of biogas produced per volume of reactor per day at an HRT of 1 d. It was likely that the effluent COD/total Kjeldahl nitrogen ratio, of 22, the COD/total phosphorous ratio of 47, and the high effluent alkalinity >2500 mg/L as CaCO₃ of the anaerobic filter operated at an HRT of 1 d was adequate for the subsequent biological removal of nitrogen and phosphorus.     

Dynamic mechanical behaviour of styrene/butadiene copolymers and their blends

The dynamic mechanical behaviour of high impact polystyrene (PS-HI), styrene/butadiene/styrene block copolymer (SBS) and PS-HI + SBS blends were investigated. Dynamic mechanical analysis (DMA) was performed in the temperature range −100°C to 100°C. The primary viscoelastic functions were determined. The copolymers PS-HI and SBS as well as PS-HI+SBS blends were investigated in creep-fatigue regime and relaxation at temperatures 25, 30, 35, 40 and 45°C. Dynamic mechanical behavior of PS-HI, SBS and PS-HI + SBS blends depends on the copolymer and blends composition, the hard phase content, time and temperature. With the decrement of the hard phase PS concentration, the loss tangent of the soft phase increases while the loss tangent of the hard phase and the storage modulus decrease. All samples have a single T_g of the hard phase and a single T_g of the soft phase. The glass transition temperatures decrease as the content of the PS phase decreases. At the constant load the creep values increase and those of creep modulus decrease over a period of time, for all examined samples. These effects are more pronounced in samples with lower content of hard phase and at higher temperatures. The time-temperature correspondence principle was applied to create master curves for the reference temperature 25°C for the creep modulus of PS-HI, SBS and PS-HI + SBS blends on a time scale far outside of the range measured by DMA experiments. These results enable us to predict the useful life of our copolymers and their blends in a wide range of time and temperature.     

Evaluation of carob pod as a substrate for pullulan production byAureobasidium pullulans

The production of extracellular polysaccharides from carob pod extract by Aureobasidium pullulans in batch fermentation was investigated. Optimum conditions for polysaccharide productivity, polysaccharide yield, and fermentation efficiency were: initial sugar concentration of 25 g/L, initial pH 6.5, and temperature 25–30°C. A maximum polysaccharide concentration (6.5 g/L), polysaccharide productivity (2.16 g/L/d), total biomass concentration (6.3 g/L), and polysaccharide yield (30%) were obtained with inoculum at 10% (v/v), initial sugars in carob pod extract of 25 g/L, pH 6.5, and 25°C. The highest values of pullulan proportion (70% of total polysaccharides) and fermentation efficiency (89%) were assumed at initial sugar concentration of 25 g/L, pH 6.5 and 30°C. Structural characterization of purified pullulan samples by monosaccharide and methylation analyses, 13C-NMR, and pullulanase digestion combined with size-exclusion chromatography revealed the presence of mainly α-(l → 4) (68%) and α-(l → 6) (31%) glucosidic linkages; however, small amounts (<1%) of triply linked (1, 3, 4-and 1, 4, 6-Glc) glucose residues were detected. The molecularsize distribution and intrinsic viscosity of pullulan derived from culture grown at pH 4.5 (30°C) showed a higher molecular weight than its counterpart obtained at pH 6.5 (30°C).     

Characterization of the cis/trans Isomerization of Resveratrol by High-Performance Liquid Chromatography

trans-Resveratrol was evaluated in a stability study. Reverse-phase high-performance liquid chromatography with a diode array detector was used for the comparison of stressed and reference samples. Aqueous ethanolic solutions were examined under variable conditions. The following parameters were investigated: the time of storage, exposure to sunlight for up to 30 days, temperature from 5 to 80°C, pH from 2.9 to 10.2, trans-resveratrol concentrations from 0.5 to 100?mg?L^?1, and 3, 10, 20, and 50% ethanol. The cis/trans equilibrium position was significantly influenced by the resveratrol concentration. The trans-resveratrol isomer was stable only at solutions more concentrated than 25?mg?L^?1 that were stable for 30 days in a refrigerator or at room temperature protected from light. Degradation of no more than 10% was observed at temperatures lower than 50°C and pH values lower 7.43.     

A new lidocaine-selective membrane electrode based on its sulfathiazole ion-pair

A novel lidocaine ion-selective electrode is prepared, characterized and used in pharmaceutical analysis. The electrode incorporates PVC-membrane with lidocaine-sulfathiazole ion pair complex. The influences of membrane composition, temperature, pH of the test solution, and foreign ions on the electrode performance were investigated. The electrode showed a Nernstian response over a lidocaine concentration range from 1.0 ×10⁻⁵ to 1.0 × 10⁻¹ mol L⁻¹ with a slope of 60.1 ± 0.2 mV per decade at 25°C and was found to be very selective, precise, and usable within the pH range 5–9.5. The standard electrode potentials, E ^o, were determined at 10, 15, 20, 25, 30, 35 and 40°C, and used to calculate the isothermal temperature coefficient (dE ^o/dT=−0.0003 V °C⁻¹) of the electrode. However, the electrode performance is significantly decreased at temperatures higher than 45°C. The electrode was successfully used for potentiometric determination of lidocaine hydrochloride in pharmaceutical products. The article is published in the original.     

Effect of Linear and Ring-like Co-units on the Temperature Dependence of Nucleation and Growth in II-I Phase Transition of Butene-1 Copolymers

The phase transition from tetragonal form II to hexagonal form I was studied for the butene-1/ethylene and butene-1/1,5-hexadiene random copolymers, which have comparable molecular weight but distinct linear ethylene and ringlike methylene-1,3-cyclopentane (MCP) structural co-units, respectively. It is known that this solid phase transition follows the nucleation-growth mechanism, so the stepwise annealing protocol was utilized to investigate the influences of co-units on the optimal nucleation and growth temperatures. Compared with optimal nucleation and growth temperatures of ?10 and 35 °C, respectively, in polybutene-1 homopolymer, two butene-1/ethylene copolymers with 1.5 mol% and 4.3 mol% co-units have the slightly lower optimal nucleation temperature of ?15 °C but much higher optimal growth temperature of 50 °C. Clearly, the effect of ethylene co-unit is more significant on varying optimal temperature for growth than for nucleation. Furthermore, when the incorporated co-unit is ringlike MCP, the optimal nucleation temperature is ?15 °C for 2.15 mol% co-units, the same with above BE copolymers, but ?13 °C for a very low concentration of 0.65 mol%. Interestingly, the optimal growth temperature of butene-1/1,5-hexadiene copolymers with 0.65 mol%?2.15 mol% MCP counits increases to 55 °C, which is also independent on co-unit concentration. These obtained values of optimal temperatures provide crucial parameters for rapid II-I phase transition.     

Effect of Temperature on the Catalytic Ability of Electrochemically Active Biofilm as Anode Catalyst in Microbial Fuel Cells

In this study we report the effect of temperature on the catalytic ability of an electrochemically active biofilm based on mixed‐culture to oxidize acetate and found the optimum temperature showing maximal catalytic activity and power output. Electrochemical characterization of biofilm and power output and internal resistance of microbial fuel cell (MFC) have been investigated at different temperatures. When temperature increased from 30 to 45 °C the catalytic ability of biofilms to oxidize acetate increased following the Arrhenius law with apparent activation energy of 44.85 kJ/mol. At temperatures higher than 48 °C, however, the bioelectrocatalytic current decreased. At 53 °C the bacterial metabolism was in inactivation. The optimum working temperature of the biofilm was 45 °C, producing current of 1339 µA cm^?2. This current was almost three times higher than 527 µA cm^?2 at 30 °C. The MFC performance at different temperatures showed consistent temperature dependence to that of a semi‐batch cell, which implies that anode catalytic ability in MFC is the main limit factor for increasing power output. A maximum power output of 1065 mW m^?2 was also observed at 45 °C and it was 1.5 times higher than 764 mW m^?2 at 30 °C. The increased MFC performance from 30 °C to 45 °C is lower in comparison with about three times higher increase in semi‐batch cells. This could be due to other factors such as proton migration rate in membrane of MFC, which can be seen from that the internal resistance value of 121.5 Ω in the MFC at 45 °C was only slightly lower than 177.6 Ω at 30 °C. Also, some other factors such as cell configuration which would limit the power output and can be further optimized. This work contributes to the study of influence from temperature on anodic electrochemically active biofilm activity and their subsequent influence on MFC performance and reports the optimal temperature for biofilm activity based on mixed‐culture.     

Kinetics of ethanol production from carob pods extract by immobilizedSaccharomyces cerevisiae cells

Kinetics of ethanol production from carob pods extract by immobilizedS. cerevisiae cells in static and shake flask fermentation have been investigated. Shake flask fermentation proved to be a better fermentation system for the production of ethanol than static fermentation. The optimum values of ethanol concentration, ethanol productivity, ethanol yield, and fermentation efficiency were obtained at pH range 3.5–6.5 and temperature between 30–35°C. A maximum ethanol concentration (65 g/L), ethanol productivity (8.3 g/Lh), ethanol yield (0.44 g/g), and fermentation efficiency (95%) was achieved at an initial sugar concentration of 200, 150, 100, and 200 g/L, respectively. The highest values of specific ethanol production rate and specific sugar uptake rate were obtained at pH 6.5, temperature 40°C, and initial sugar concentration of 100 g/L. Other kinetic parameters, biomass concentration, biomass yield, and specific biomass production rate were maximum at pH 5.5, temperature 30°C, and initial sugar concentration 150 g/L. Under the same fermentation conditions non-sterilized carob pod extract gave higher ethanol concentration than sterilized medium. In repeated batch fermentations, the immobilizedS. cerevisiae cells in Ca-alginate beads retained their ability to produce ethanol for 5 d.     

Aqueous Polymerization on Clay Surface. 2. The Polymerization of Methyl Methacrylate on Hydrogen Bentonite: Effect of Monomer Concentration and Temperature

Aqueous free radical polymerizations of methyl methacrylate with the hydrogen bentonite/ethanol system have been accomplished with less transfer to monomer in spite of high monomer concentrations and temperature. The overall initial rate has a first-order dependence on monomer. It is proposed that initiation does not occur in the aqueous phase. The apparent activation energy of 15 kcal/mol corroborates a twofold increase in rate for a 10°C rise in temperature. The frequency of bimolecular termination is quite small as is evident from k_p ² /k_t, values at various temperatures.     

Application of Artificial Neural Network and Particle Swarm Optimization for modelling and optimization of biosorption of Lead(II) and Nickel(II) from wastewater using dead cyanobacterial biomass

Removal of heavy metals through biosorption using biomass offers several advantages over other conventional techniques such as low cost, high efficiency, environmentally friendly, etc. In the present article, biosorption of Nickel(II) and Lead(II)was investigated using dried biomass of cyanobacterial consortium. OFAT (one-factor-at-a-time) analysis was used to assess the effect of input parameters on the removal of potentially toxic elements by varying initial metal ion concentration (2–10 mgL⁻¹), adsorbent dose (0.1–1.0 gL^-1), pH (for Pb(II): 2–6, for Ni(II): 2–8) and temperature (25°C–45°C) individually, at constant shaking speed of 150 ​rpm. Results showed that removal using biomass attained highest values in as short time as 15 ​min. The investigations also showed the removal is highly effective at lower initial concentrations of heavy metals. Maximum removal of Lead(II) (87.27 ​± ​1.75%) and Nickel(II) (92.57 ​± ​0.77%) was obtained at pH 6 and 45°C and at pH 7 and 25°C, respectively, within 15 ​min with 0.1 gL^-1 biomass. Both the Langmuir model and Freundlich model were seen to fit the equilibrium data. Further, Artificial Neural Network was used to model the biosorption process. Subsequently, Particle Swarm Optimization was applied to optimize the operating conditions for the removal of both the metals.     

Polymer-Bromine Interactions. I. Interactions with Polyacrylonitrile

The present paper deals with the interactions of bromine with poly-acrylonitrile (PAN). Kinetics and equilibria of the sorption of Br₂ on PAN were studied at a concentration range of 0.01–0.1 mol/L and a temperature range of 25–40°C. Two kinds of sorption were found: a “reversible” sorption removable by water and an “irreversible” sorption removable by aqueous ammonia solutions. The irreversibly sorbed bromine is presumably linked by charge transfer to the nitrile groups of the PAN, as evidenced by UV spectra. The irreversible sorption follows the reversible sorption and is slower. Partition coefficients obtained from the linear Freundlich isotherms increased with temperature and, at 40°C, the values obtained were 97, 65, and 32 L/kg for the total, irreversible, and reversible sorptions, respectively. At 25°C the chemical potential, enthalpy, and change in entropy for the irreversible sorption were ?2.0 kcal/mol, 9.4 kcal/mol, and 38 cal·mol^?1·K^?1. Effects of a 6-day Br₂ treatment and ammonia rinse were: decrease in dry T _g from 74.5 to 61°C and in water from 38 to 35°C; no significant decrease in M _W ; decrease in tensile strength measured after the bromine stage, and improvement after ammonia stage; increased swollen dimensions from 57% in water to 75%; and stabilization of swollen dimensions upon drying. The results support the existence of two phases in the less ordered regions of PAN.     

Sorption and addition of bromine from aqueous solutions on cis-1,4-polyisoprene

The sorption of bromine from bromine water on cis-1,4-polyisoprene film and the initial stages of bromination are studied at concentrations of 0.002–0.1 mol/l and temperatures of 15–35°C. The diffusion coefficient of bromine into natural rubber (NR) is 1.3–2.0 × 10^?6 cm²/sec for the total sorption and 5–13 × 10^?7 cm²/sec for the irreversible sorption. The partition coefficient of bromine between water and rubber increased from 17.3 at 15°C to 37.1 l/kg at 35°C. The chemical potential, enthalpy and change in entropy of partition are, at 25°C, respectively: ?1.9 kcal/mol, 6.6 kcal/mol and 28.4 cal/mol. K. The irreversible sorption is due to a charge-transfer complex between bromine molecules and double bonds of the rubber. The complex is the first stage of the addition reaction, which becomes noticeable at concentrations above 0.012 mol/l. With increasing bromine concentration the concentration of the complex decreases and the added bromine increases. The charge transfer complex appears to change the conformation of the cis-NR chains so that the bromine addition occurs in the trans-conformation, as shown by FT–IR spectra. The bromination is accompanied by a marked crystallization effect as illustrated by thermal analysis and WAXS measurements.