87 research outputs found

    Lithium and potassium heat pipes for thermionic converters

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    A prototypic heat pipe system for an out-of-core thermionic reactor was built and tested. The emitter of the concentric thermionic converter consists of the condenser of a tungsten heat pipe utilizing a lithium working fluid. The evaporator section of the emitter heat pipe is radiation heated to simulate the thermal input from the nuclear reactor. The emitter heat pipe thermal transport is matched to the thermionic converter input requirement. The collector heat pipe of niobium, 1% zirconium alloy uses potassium as the working fluid. The thermionic collector is coupled to the heat pipe by a tapered conical joint designed to minimize the temperature drop. The collector heat flux matches the design requirements of the thermionic converter

    Nanoparticle formation of chitosan induced by 4-sulfonatocalixarenes: utilization for alkaloid encapsulation

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    Spontaneous formation of positively charged nanoparticles was observed upon mixing more than stoichiometric amount of chitosan with 4-sulfonatocalix[8]arene (SCX8) in acidic solution. The particle size did not change with SCX8 concentration, polymer chain length, and the degree of deacetylation at 0.002 ≤ SCX8/chitosan ≤0.043 molar ratios in 0.01 M HCl. However, larger aggregates were produced when chitosan concentration was increased. The most stable nanoparticles with 160 nm diameter and narrow size distribution were obtained at pH 4 using low molecular weight chitosan. These particles encapsulated coralyne with more than 90 % entrapment efficiency and 15 % loading capacity. A loading ratio of [coralyne]/[SCX8] = 1.7 was achieved without any stability loss. 4-Sulfonatocalix[4]arene induced the formation of slightly smaller nanoparticles than its homologs comprising 6 or 8 phenol units. © 2016, Springer-Verlag Berlin Heidelberg

    Effect of host–guest complex formation on the fluorescence of 6-methoxy-1-methyl-quinolinium cation with 4-sulfonatocalix[4]arene: utilization as a fluorescent probe for the study of difenzoquat binding

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    The complexation of the highly fluorescent 6-methoxy-1-methyl-quinolinium (C1MQ) and the widely used herbicide, difenzoquat (DFQ), with 4-sulfonatocalix[4]arene (SCX4) macrocycle was studied by isothermal titration calorimetry, fluorescence and NMR spectroscopy in aqueous solutions at 298 K. Both guests produced 1:1 complexes with SCX4, but the binding affinity of C1MQ was more than one order of magnitude larger than that of DFQ in neutral medium. The higher stability of C1MQSCX4 complex originated from the significant enthalpy gain upon its formation. The encapsulation of C1MQ in SCX4 in the ground state resulted in an efficient fluorescence quenching due to electron transfer from the host to the excited guest. The marked difference in the fluorescence quantum yields for free and bound C1MQ was used to detect the competitive complexation of DFQ in SCX4

    Effect of Macrocycle Size on the Self-Assembly of Methylimidazolium Surfactant with Sulfonatocalix[n]arenes

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    The effect of macrocycle size on the association of supramolecular amphiphiles composed of 4-sulfonatocalix[n]arene and 1-methyl-3-tetradecylimidazolium (C14mim+) was studied in aqueous solutions at pH 7. When the cavitand contained four sulfonatophenol units (SCX4), spherical nanoparticle (NP) formation was observed. In contrast, both supramolecular micelle (SM) and NP formation could be attained in the presence of NaCl when the larger, more flexible 4-sulfonatocalix[8]arene (SCX8) served as host compound. The SCX8-promoted self-assembly into SM was enthalpically more favorable than NP production but the molar heat capacity changes in the two processes barely differed. Addition of 50 mM NaCl significantly increased the enthalpy of C14mim+−SCX8 NP formation making thereby the self-organization into SM more favorable. The transformation of SM into NP at high temperature was due to the substantial entropic contribution to the driving force of NP formation. The critical micelle concentration and the local polarity in the headgroup domain were considerably lower for SM compared to those of C14mim+Br conventional micelle

    Performance of a thermionic converter module utilizing emitter and collector heat pipes

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    A thermionic converter module simulating a configuration for an out-of-core thermionic nuclear reactor was designed, fabricated, and tested. The module consists of three cylindrical thermionic converters. The tungsten emitter of the converter is heated by a tungsten, lithium heat pipe. The emitter heat pipes are immersed in a furnace, insulated by MULTI-FOIL thermal insulation, and heated by tungsten radiation filaments. The performance of each thermionic converter was characterized before assembly into the module. Dynamic voltage, current curves were taken using a 60 Hz sweep and computerized data acquisition over a range of emitter, collector, and cesium-reservoir temperatures. An output power of 215 W was observed at an emitter temperature of 1750 K and a collector temperature of 855 K for a two diode module. With a three diode module, an output power of 270 W was observed at an average emitter temperature of 1800 K and a Collector temperature of 875 K

    Effect of Headgroup Variation on the Self-Assembly of Cationic Surfactants with Sulfonatocalix[6]arene

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    The effect of headgroup variation on the association of supramolecular amphiphiles composed of 4-sulfonatocalix[6]arene (SCX6) and cationic surfactant possessing tetradecyl substituent was studied in aqueous solutions at pH 7. When the surfactant contained hydrophilic trimethylammonium, pyridinium, or 1-methylimidazolium headgroup, highly reversible temperature-responsive nanoparticle-supramolecular micelle transformation could be attained at appropriately chosen component mixing ratios and NaCl concentrations. In these cases, the substantial negative molar heat capacity change (ΔCp) rendered nanoparticle formation strongly endothermic at low temperature, whereas the assembly to supramolecular micelle was always accompanied by enthalpy gain. The ΔCp values became less negative when the charge density and the hydrophilic character of the surfactant headgroup diminished. The association of the more hydrophobic 6-methoxyquinolinium and quinolinium surfactants with SCX6 did not lead to supramolecular micelle formation because the self-assembly into nanoparticles was highly exothermic

    Reversible Nanoparticle–Micelle Transformation of Ionic Liquid–Sulfonatocalix[6]arene Aggregates

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    The effect of temperature and NaCl concentration variations on the self-assembly of 1-methyl-3- tetradecylimidazolium (C14mim+) and 4-sulfonatocalix[6]- arene (SCX6) was studied by dynamic light scattering and isothermal calorimetric methods at pH 7. Inclusion complex formation promoted the self-assembly to spherical nanoparticles (NP), which transformed to supramolecular micelles (SM) in the presence of NaCl. Highly reversible, temperature-responsive behavior was observed, and the conditions of the NP−SM transition could be tuned by the alteration of C14mim+:SCX6 mixing ratio and NaCl concentration. The association to SM was always exothermic with enthalpy independent of the amount of NaCl. In contrast, NPs were produced in endothermic process at low temperature, and the enthalpy change became less favorable upon increase in NaCl concentration. The NP formation was accompanied by negative molar heat capacity change, which further diminished when NaCl concentration was raised

    Characterization of the thermal and photoinduced reactions of photochromic spiropyrans in aqueous solution

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    Six water-soluble spiropyran derivatives have been characterized with respect to the thermal and photoinduced reactions over a broad pH-interval. A comprehensive kinetic model was formulated including the spiro- and the merocyanine isomers, the respective protonated forms, and the hydrolysis products. The experimental studies on the hydrolysis reaction mechanism were supplemented by calculations using quantum mechanical (QM) models employing density functional theory. The results show that (1) the substitution pattern dramatically influences the pKa-values of the protonated forms as well as the rates of the thermal isomerization reactions, (2) water is the nucleophile in the hydrolysis reaction around neutral pH, (3) the phenolate oxygen of the merocyanine form plays a key role in the hydrolysis reaction. Hence, the nonprotonated merocyanine isomer is susceptible to hydrolysis, whereas the corresponding protonated form is stable toward hydrolytic degradation
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