Effect of temperature on sulfate transport in two Penicillia

We studied the effects of temperature on the sulfate permease of Penicillium chrysogenum (PC) (a mesophile with a growth temperature range of 4-35°C) and Penicillium duponti (PD) (a thermophile with a growth temperature range of 27-58°C). Arrhenius plots of sulfate permease activity from mycelia grown at 50°C (PD), 30°C (PD and PC) or 8°C (PC) indicate that at temperatures below the transition point there is little difference in the activation energy of sulfate permease in mycelia from PD grown at 50°C or 30°C or PC grown at 30°C or 8°C; however, the temperature of the transition point for the permease from each set of mycelia assayed reflects the optimum growth temperature of the fungal source. Transitions occur at 15 °C for mycelia from PC and 35 ° C for PD mycelia. Kinetic measurements indicate that the K_m of sulfate permease in PC cells grown at a variety of temperatures is essentially the same at various temperatures. As an example, the K_m of 8°C or 30°C grown PC is about 55 μM at 25°C and 45 μM at 8°C. V_max measurements reflect growth conditions such as temperature and growth stage. p]Lipid composition of the mycelia dramatically reflect growth temperatures. Double bond index values vary from 1.94 for PC grown at 8°C to 0.81 for PD grown at 50°C. The percentage of total fatty acid represented by linolenic acid varies from 45% in 8°C grown PC to 4.2% or less in 30°C grown PC. No linolenic is found in mycelia from PD.     

Synthesis and Properties of Poly(Organophosphazenes) Electrolyte

Abstract

To prepare electrolytes using poly(organophosphazenes), poly(bisanilinophosphazene) selected was carried out with the various concentration of sulfonic chloride in tetra-chloroethane solvent using vigorously sterring at room temperature for 4 hr. The products prepared were determined with IR and chemical analysis. It was found that the -SO₃H groups in the product appeared at 1,1050 cm^?1, 1,030 cm^?1 and 550 cm^?1, and the reaction rate of sulfonic chloride was about 34%-55% under this experimental conditions. Also, the products had two kind of glass transition temperatures such as 63°C and -18°C, respectively, and the values were lower in comparison with that of starting polymer. Furthermore, the conductivity of the product at room temperature was determined and the conductivity was increased the concentration of -SO₃H groups. It was found that the product having -SO₃H groups was able to ion exchange with Li⁺ or Cu²⁺ ions under aqueous solution. Also, the ion exchange rate was determined with the titration of alkaline aqueous solution with a standard solution of HCl. The products formed after the ion exchange reaction had higher conductivity in comparison with that of the polymer.     

Acceleration of the cationic polymerization of an epoxy with hexanediol

Thin films of 3,4-epoxycyclohexylmethyl 3',4'-epoxycyclohexane carboxylate were UV irradiated (1.1 J cm^-2) under isothermal conditions ranging from 0 to 50°C. Under these conditions the polymerization advanced quickly but only to a conversion level of less than 10% before the reaction rate slowed by more than an order of magnitude. This drop off in rate was not caused by the glass transition temperature, T _g, reaching or exceeding the reaction temperature, T _rxn, since the epoxide's T _g remained at least 40°C below T _rxn. Raising the sample temperature above 60°C caused a sharp increase in the conversion level. At 100°C conversion exceeds 80% and the ultimate T _g approaches 190°C. The addition of 10 mass% 1,6-hexanediol, HD, to the epoxy caused the conversion at room temperature to quintuple over the level obtained without the alcohol present. The heat liberated from this alcohol epoxy blend during cure on a UV conveyor belt system caused the sample's temperature to increase by about 100°C above ambient whereas the epoxy alone under these conditions only experienced a modest temperature rise of about 26°C. If the amount of HD in the blend is increased above 10% the heat of reaction at 23°C decreases due to HD being trapped in a nonreactive crystalline phase. Boosting reaction temperatures above 50°C melts the HD crystals and yields significantly improved conversion ratios. As the level of alcohol blended with the epoxy is raised its ultimate T _g is lowered and when the concentration of alcohol in the blend nears 30 mass%T _g drops below room temperature. This revised version was published online in July 2006 with corrections to the Cover Date.     

A Study of the Activation of Carbon Using Sample Controlled Thermal Analysis

A constant rate method involving the control of the concentration of evolved CO₂ at a constant level was used to study the air activation of pure and copper-doped carbon prepared from sodium carboxymethylcellulose. Whereas under a linear heating regime, both types of carbon reacted suddenly and quickly with O₂, under constant rate conditions this violent reaction was avoided and oxidation proceeded steadily at a lower temperature until complete burn off of the carbon was achieved. The catalytic effect of the copper on carbon gasification was noted with lower reaction temperatures for both linear heating (380°C compared to 500°C) and for the constant rate experiments (320°C compared to 400°C). This revised version was published online in July 2006 with corrections to the Cover Date.     

Avoiding Self‐Poisoning: A Key Feature for the High Activity of Au/Mg(OH)2 Catalysts in Continuous Low‐Temperature CO Oxidation

Au/Mg(OH)₂ catalysts have been reported to be far more active in the catalytic low‐temperature CO oxidation (below 0 °C) than the thoroughly investigated Au/TiO₂ catalysts. Based on kinetic and in situ infrared spectroscopy (DRIFTS) measurements, we demonstrate that the comparatively weak interaction of Au/Mg(OH)₂ with CO₂ formed during the low‐temperature reaction is the main reason for the superior catalyst performance. This feature enables rapid product desorption and hence continuous CO oxidation at temperatures well below 0 °C. At these temperatures, Au/TiO₂ also catalyzes CO₂ formation, but does not allow for CO₂ desorption, which results in self‐poisoning. At higher temperatures (above 0 °C), however, CO₂ formation is rate‐limiting, which results in a much higher activity for Au/TiO₂ under these reaction conditions.     

Asymmetric Solvents Regulated Crystallization-Limited Electrolytes for All-Climate Lithium Metal Batteries

Electrolytes that can keep liquid state are one of the most important physical metrics to ensure the ions transfer with stable operation of rechargeable lithium-based batteries at a wide temperature window. It is generally accepted that strong polar solvents with high melting points favor the safe operation of batteries above room temperatures but are susceptible to crystallization at low temperatures (≤−40 °C). Here, a crystallization limitation strategy was proposed to handle this issue. We demonstrate that, although the high melting points of ethylene sulfite (ES, −17 °C) and fluoroethylene carbonate (FEC, ≈23 °C), their mixtures can avoid crystallization at low temperatures, which can be attributed to low intermolecular interactions and altered molecular motion dynamics. A suitable ES/FEC ratio (10 % FEC) can balance the bulk and interface transport of ions, enabling LiNi_0.8Mn_0.1Co_0.1O₂||lithium (NCM811||Li) full cells to deliver excellent temperature resilience and cycling stability over a wide temperature range from −50 °C to +70 °C. More than 66 % of the capacity retention was achieved at −50 °C compared to room temperature. The NCM811||Li pouch cells exhibit high cycling stability under realistic conditions (electrolyte weight to cathode capacity ratio (E/C)≤3.5 g Ah⁻¹, negative to positive electrode capacity ratio (N/P)≤1.09) at different temperatures.     

Effects of Low Moisture Anhydrous Ammonia (LMAA) Pretreatment at Controlled Ammoniation Temperatures on Enzymatic Hydrolysis of Corn Stover

Corn stover was treated using low-moisture anhydrous ammonia (LMAA) at controlled ammoniation temperature. Moisturized corn stover (50 % moisture) was contacted with anhydrous ammonia (0.1 g NH₃/g-biomass) in a batch reactor at various temperatures (ambient to 150 °C). After ammoniation at elevated and controlled temperature, ammoniated corn stover was pretreated at various temperatures (60–150 °C) for 72–144 h. Change in composition was marginal at low pretreatment temperature but was relatively severe with pretreatment at high temperature (130–150 °C). The latter resulted in low enzymatic digestibility. It was also observed that extreme levels (either high or low) of residual ammonia affected enzymatic digestibility, while residual ammonia improved by 1.0–1.5 %. The LMAA method enhanced enzymatic digestibility compared to untreated corn stover (29.8 %). The highest glucan and xylan digestibility (84.1 and 73.6 %, respectively) was obtained under the optimal LMAA conditions (i.e., ammoniation at 70 °C for 20 min, followed by pretreatment at 90 °C for 48 h).     

Product distribution in pyrolysis of cellulose in a microfluidized bed

A study of flash pyrolysis of cellulose was carried out in the temperature range from 313 to 770°C in a microfluidized bed. Chemical analysis was done for gaseous and liquid products using gas chromatography. Levoglucosan was measured after silylation of the tar fraction. In the fluidized bed, residence times were of the order of 1 s, while heating rates were estimated at higher than 100,000°C/s for cellulose particles of 60 μm diameter and about 1000°C/s for cellulose particles having about 0.6 mm mean particle diameter. No pronounced effects of particle size were observed. Logarithms of product yields as wt.% of sample correlate linearly with bed temperature. Transitions in these curves are observed between 500 and 600°C corresponding roughly to decomposition of levoglucosan. Effects of atmosphere were also studied by comparing the effect of various atmospheres (CO, CO₂, H₂ + N₂) with pure N₂. Only a slight effect was noted on the product distribution. It appears that levoglucosan, a major product obtained from the slow pyrolysis of cellulose, is not a primary product under flash pyrolysis conditions.     

In vacuo reduction of silver orthophosphate with graphite for high‐precision oxygen isotope analysis

The reduction of silver phosphate with graphite under vacuum conditions was studied at final reaction temperatures varying from 430 to 915°C to determine: (i) the CO₂ extraction yield, and (ii) the oxygen isotopic composition of CO₂. The CO₂ yield and oxygen isotopic composition were determined on a calibrated dual inlet and triple collector isotope ratio mass spectrometer. We observed the following three stages of the reduction process. (1) At temperatures below 590°C only CO₂ is formed, while silver orthophosphate decays to pyrophosphate. (2) At higher temperatures, 590–830°C, predominantly CO is formed from silver pyrophosphate which decays to metaphosphate; this CO was always converted into CO₂ by the glow discharge method. (3) At temperatures above 830°C the noticeable sublimation of silver orthophosphate occurs. This observation was accompanied by the oxygen isotope analysis of the obtained CO₂. The measured δ¹⁸O value varied from ?11.93‰ (at the lowest temperature) to ?20.32‰ (at the highest temperature). The optimum reduction temperature range was found to be 780–830°C. In this temperature range the oxygen isotopic composition of CO₂ is nearly constant and the reaction efficiency is relatively high. The determined difference between the δ¹⁸O value of oxygen in silver phosphate and that in CO₂ extracted from this phosphate is +0.70‰. Copyright © 2010 John Wiley & Sons, Ltd.     

Effects of pretreatment temperature on the analysis of size-fractionated aerosol particles using ToF-SIMS

Size-fractionated aerosol particles were collected with a MOUDI 10-stage cascade impactor from an urban roadside place in a downtown area of Hong Kong. Fine aerosol particulate samples from stage 6 (aerodynamic particle diameter between 0.56 and 1 μm) and stage 9 (aerodynamic particle diameter between 0.10 and 0.18 μm) were pretreated at a chosen temperature, including −100°C, −50°C, 25°C, and 60°C, in a load lock chamber and then analyzed using time-of-flight secondary ion mass spectrometry (ToF-SIMS) at the same temperature (−100°C). Principal component analysis (PCA) was applied to further analyze ToF-SIMS spectra of aerosol particles with different pretreatment temperatures from two selected stages. ToF-SIMS results showed that the intensities of aliphatic hydrocarbon ions such as C₄H₇⁺ and C₄H₉⁺ and amine ions such as C₂H₈N⁺ and C₄H₁₂N⁺ decreased with an increase of the pretreatment temperature under ultrahigh vacuum conditions. We have shown that analyses of this type of aerosol particles using ToF-SIMS should not be conducted at ambient temperature but at low temperature (eg, −50°C). In addition, we also developed a procedure that can be used to analyze aerosol particle samples under ultrahigh vacuum environment.     

Evolution of water vapor from indium-tin-oxide transparent conducting films fabricated by dip coating process

Tin-doped indium oxide In₂O₃ (indium-tin-oxide) transparent conducting films were fabricated on silicon substrates by a dip coating process. The thermal analysis of the ITO films was executed by temperature-programmed desorption (TPD) or thermal desorption spectroscopy (TDS) in high vacuum. Gas evolution from the ITO film mainly consisted of water vapor. The total amount of evolved water vapor increased on increasing the film thickness from approx. 25 to 250 nm and decreased by increasing the preparation temperature from 365 to 600°C and by annealing at the same temperature for extra 10 h. The evolution occurred via two steps; the peak temperatures for 250 nm thick films were approx. 100-120 and 205-215°C. The 25 nm thick films evolved water vapor at much higher temperatures; a shoulder at approx. 150-165°C and a peak at approx. 242°C were observed. The evolution temperatures increased by increasing the preparation and the annealing temperatures except in case of the second peak of the 25 nm thick films. The evolution of water vapor at high temperature was tentatively attributed to thermal decomposition of indium hydroxide, In(OH)₃, formed on the surface of the nm-sized ITO particles. This revised version was published online in August 2006 with corrections to the Cover Date.     

Synthesis of nanocrystalline silicon carbide using the sol-gel technique

Highly disperse silicon carbide is synthesized using a hybrid method comprising the sol-gel step to provide the SiO₂-C starting mixture involving the formation of a transparent gel and carbothermal synthesis under relatively soft conditions, namely, at temperatures of 1200–1500°C under a dynamic vacuum. The elemental and phase compositions of the products and their thermal behavior in air are studied. A relationship is found to exist between the microstructure of the product, on the one hand, and the temperature and time of heat treatment, on the other.     

Dilatometric study of phase transformations in advanced high-strength bainitic steel

The work deals with dilatometric studies of a new-developed advanced high-strength bainitic 3Mn–1.5Al steel. Ferritic, bainitic and martensitic phase transformations are investigated in detail in respect of their temperature range forming and microstructures produced under various conditions of both continuous and isothermal cooling. The equilibrium temperatures of A _e1 and A _e3 and phase composition of the investigated steel were initially calculated whereas critical temperatures of A _c1 and A _c3 as well as the decomposition of retained austenite were determined upon heating. The major tests consisted of controlled cooling of undeformed or plastically deformed austenite using the dilatometer within the cooling rate range of 2–0.5 °C s^?1. The effects of the cooling rate and deformation at temperatures of 900 and 1,050 °C on the phase transformation behaviour and microstructure were explained. The final experiment was carried out using a thermo-mechanical simulator under conditions of multi-step deformation and isothermal holding of the steel at 400 °C. Microstructural features were revealed using light microscopy and scanning electron microscopy techniques.     

Alkylation of ionic mercury to methylmercury and dimethylmercury by methylcobalamin: Simultaneous determination by purge-and-trap GC in line with FTIR

A new approach was used to determine the reaction products of methylcobalamin and ionic mercury: purge-and-trap gas chromatography in line with Fourier transform infrared spectroscopy (PT GC/FTIR). This technique simultaneously and specifically determines the spectrum of dimethylmercury (DMeHg) and methylmercury produced by the reaction. No interference from other known organic mercury species could be detected. The method is different from others because it does not require solvent extraction of the organomercurials from aqueous solution, but relies on immediate volatilization from the reaction vessel by addition of 100 μl of 10 mM NaBH₄. The sample was purged with nitrogen for 10 min. The volatile species of mercury were trapped in a column at ?120°C, injected into the gas chromatograph and detected by FTIR. The efficiency of DMeHg and MeHg formation depended on different parameters: pH, temperature, reaction time, and the methylcobalamin/ionic mercury ratio. The initial reaction product was MeHg which was further transformed to DMeHg. The first methylation rate was two times faster than the second. MeHg formed first, reaching a maximum at higher temperatures (28°C and 37°C) and later decreasing as DMeHg formed. At lower temperatures (20°C) the rate of MeHg formation was slower, being similar to the formation rate of DMeHg. Different species of inorganic mercury such as HgSO₄, Hg(NO₃)₂, Hg(SCN)₂, HgCl₂ and Hgl₂ were used to study differences in methylation by methylcobalamin under standard conditions of acidity, temperature and cofactor Hg(II) ratio.     

Chain-backbone motion in glassy polycarbonate studied by polarized infrared spectroscopy

Chain-backbone motion in glassy polycarbonate has been investigated both under isothermal stress, and also under zero stress during isothermal annealing of freely contracting film specimens. In both types of experiment, backbone motion was detected by measuring the change in infrared dichroism. The dichroism of absorption bands at 1364 and 2971 cm^?1, which have transition moment vectors directly related to the chain-backbone orientation, was studied. Under tensile stress in the homogeneous region of deformation, changes of up to 2.2° in the mean chain-backbone orientation angle were measured at 23°C. With the onset of cold drawing a total orientation change of some 8° was observed. For the isothermal annealing experiments, a film specimen holder employing conductive heating with radiative losses was employed. It enables infrared measurements to be made while the temperature of the contracting specimen is maintained constant to ± 0.5°C. Oriented specimens were prepared by isothermal stretching of polycarbonate films to strains of the order of 100%. Changes in the mean chain-backbone orientation angle were observed during annealing of these oriented films at temperatures between 80°C and the glass transition (149°C). Chain motion proceeded during annealing, and chain segments were observed to move cooperatively. The temperature at which the polymer is prestretched has a pronounced effect on its subsequent relaxation during annealing: when the sample was stretched at 23°C. motions were detected during annealing at temperatures as low as 81°C, while, if it was stretched at 154°C, no motion was detected at annealing temperatures below 127°C. The data are discussed in comparison with theories of the glassy state that predict the absence of chain-backbone motion at temperatures significantly below the glass transition. A shift in frequency of the ν_a (CH₃) absorption peak in stretched polycarbonate was measured by using polarized radiation. The effect was interpreted in terms of changes in the intermolecular bonding structure of the oriented polymer.     

Three-step macrokinetic model of butane and propane steam conversion to methane-rich gas

Low-temperature steam conversion (LTSC) of a methane-butane mixture (95% methane and 5% butane) into a methane-rich gas over an industrial Ni-based catalyst has been studied with the following reaction conditions: temperature 200–320°C, pressure 1 bar, gas hour space velocity 1200–3600 h^–1, and steam to carbon ratio 0.64. A three-step macrokinetic model has been suggested based on the kinetic parameters found. The model includes the following reactions: (1) irreversible steam reforming; (2) CO₂ methanation, which occurs in a quasi-equilibrium mode at temperatures above 260°C; (3) hydrogenolysis of propane and butane, which is essential at temperatures below 260°C. Steam reforming was shown to limit the overall reaction rate, whereas hydrogenolysis and CO₂ methanation determined the product distribution in low- and high-temperature regions, respectively. Temperature dependencies of the product distribution for the LTSC of a model ternary methane-propane-butane mixture (85% methane, 10% propane, and 5% butane) have been successfully simulated using the three-step model suggested.     

枯草杆菌α-淀粉酶在一些色谱体系中的热力学和超热力学研究

通过测定不同温度范围的热力学平衡常数、焓变、熵变、自由能变和补偿温度,研究了枯草杆菌α-淀粉酶在几种色谱介质上的热力学和超热力学。结果表明,在RP-C18反相介质、Zn2+螯合的Sepharose fast-flow亲和介质和WCX-1阳离子交换介质上,当温度分别在13-30和30-50℃范围时,它们的lnKSL分别随绝对温度的倒数线性变化;而在PEG-400和修饰的PEG-400疏水色谱介质上,当温度分别在13-40和13-30℃范围时,它们的lnKSL分别随绝对温度的倒数线性减小,但当温度分别高于40℃和30℃时,它们则随绝对温度的倒数剧烈减小。通过研究不同温度范围的焓变、熵变、自由能变和α-淀粉酶构象变化之间的关系,发现在RP-C18反相和Zn2+螯合的Sepharose fast-flow亲和介质上在30- 50 ℃温度范围内,在WCX-1阳离子交换介质上在13-30 ℃温度范围内,α-淀粉酶的吸附过程由焓变和熵变共同所支配,而在Zn2+螯合的Sepharose fast-flow亲和介质上在13- 30 ℃温度范围内,在WCX-1阳离子交换介质上在30-50 ℃温度范围和在PEG-400 和修饰的PEG-400疏水色谱介质上在13-65 ℃温度范围时,α-淀粉酶的吸附过程仅仅由熵变所控制。最后,通过α-淀粉酶在这些色谱体系中的补偿温度进一步发现,它们的焓变仅仅只能通过它们构象变化所引起的熵变所补偿。     

How xerogel carbonization conditions affect the reactivity of highly disperse SiO<Subscript>2</Subscript>–C composites in the sol–gel synthesis of nanocrystalline silicon carbide

A transparent silicon polymer gel was prepared by sol–gel technology to serve as the base in the preparation of highly disperse SiO₂–C composites at various temperatures (400, 600, 800, and 1000°C) and various exposure times (1, 3, and 6 h) via pyrolysis under a dynamic vacuum (at residual pressures of ~1 × 10^–1 to 1 × 10^–2 mmHg). These composites were X-ray amorphous; their thermal behavior in flowing air in the range 20–1200°C was studied. The encapsulation of nascent carbon, which kept it from oxidizing in air and reduced the reactivity of the system in SiC synthesis, was enhanced as the carbonization temperature and exposure time increased. How xerogel carbonization conditions affect the micro- and mesostructure of the xerogel was studied by ultra-small-angle neutron scattering (USANS). Both the carbonization temperature and the exposure time were found to considerably influence structure formation in highly disperse SiO₂–C composites. Dynamic DSC/DTA/TG experiments in an inert gas flow showed that the increasing xerogel pyrolysis temperatures significantly reduced silicon carbide yields upon subsequent heating of SiO₂–C systems to 1500°C, from 35–39 (400°C) to 10–21% (1000°C).     

Effect of temperature on growth of psychrophilic and psychrotrophic members of Rhodotorula aurantiaca

The thermodependence of growth kinetic parameters was investigated for the Antarctic psychrophilic strain Rhodotorula aurantiaca and a psychrotrophic strain of the same species isolated in Belgium (Ardennes area). Cell production, maximum growth rate (μ_max), and half-saturation constant for glucose uptake (Ks) of both yeasts were temperature dependent. For the two yeasts, a maximum cell production was observed at about 0°C, and cell production decreased when temperature increased. The μ_max values for both strains increased with temperature up to a maximum of 10°C for the psychrophilic strain and 17°C for the psychrotrophic strain. For both yeasts, Ks for glucose was relatively constant at low temperatures. It increased at temperatures above 10°C for the psychrophilic strain and 17°C for the psychrotrophic strain. Although its glucose affinity was lower, the psychrotrophic strain grew more rapidly than the psychrophilicone. The difference in growth rate and substrate affinity was related to the origin of the strain and the adaptation strategy of R. aurantiaca to environmental conditions.     

Cyclization of citronellal in a supercritical solvent in a flow reactor in the presence of Al2O3

The reactivity of citronellal under supercritical solvent conditions in a flow reactor in the presence of Al₂O₃ is examined. It is shown that at 160°C, the main transformation product of citronellal is isopulegol, and when the temperature is increased to 190°C, they are monoterpenes with a para-menthane framework and myrcene.