Dialkyl (3-Aryl- 1,2,4-oxadiazol-5-yl)phosphonates: Synthesis and Thermal Behavior-Evidence for Monomeric Alkyl Metaphosphate

Dialkyl (3-aryl-l,2,4-oxadiazol-5-yl)phosphonate6sa -h have been obtained by 1,3-dipolar cycloaddition of arenenitrile oxides 5a-f to dialkyl phosphorocyanidates (4a and 4b) in yields ranging between 30% and 58%. A standardized method for obtaining cyanidates 4a and 4b has been established. The diethyl thiophosphorocyanidate (4c) is less reactive than 4a and 4b, only the 3-(4'-nitrophenyl) derivative 6i being obtainable. While the IR and NMFt spectra of 6a-i were unexceptional, their UV spectra showed evidence of conjugative interaction in high degrees between the phosphonate and heterocyclic moieties as well as a varying conjugative interaction between the heterocyclic and aryl moieties. The oxadiazoles 6a-h are thermally labile and yield trialkyl phosphates 7 as the only identifiable products. A mechanism based on the intermediacy of monomeric alkyl metaphosphate 11 in the formation of trialkyl phosphate was postulated, and supportive evidence in the form of trapping the metaphosphate with acetophenone has been obtained.

Effect of Prior Ultraviolet Irradiation on Thermal Decomposition and Ignition of Coal

Prior ultraviolet irradiation of coal results in catalysing the subsequent thermal decomposition and ignition of coal. Mechanically, it is shown that ultraviolet radiation brings about the catalysis by acting on the inorganic components of coal.

Thermal Analysis of Polypropylene Hydroperoxide

Studies on the low temperature oxidation of polyolefins have been the subject matter of several investigations because of interest in understanding the aging and weathering of polymers. One of the key steps in such an oxtdatton is the formation of hydroperoxide. Estimation of the hydroperoxide in oxidized samples, which is conventionally done by iodometric titrations, is quite important to gain knowledge about the kinetics and mechanism of the process. The present investigation is the first report of the thermal analysis of polypropylene hydroperoxide samples from two angles: (1) the thermal behavior of its decomposition and (2) whether such an analysis leads to knowledge of the concentration of hydroperoxide in the sample.

Thermal conductivity of a new carbon nanotube analog: The diamond nanothread

Based on the non-equilibrium molecular dynamics simulations, we have studied the thermal conductivities of a novel ultra-thin one-dimensional carbon nanomaterial - diamond nanothread (DNT). Unlike single-wall carbon nanotube (CNT), the existence of the Stone-Wales transformations in DNT endows it with richer thermal transport characteristics. There is a transition from wave-dominated to particle-dominated transport region, which depends on the length of poly-benzene rings. However, independent of the transport region, strong length dependence in thermal conductivity is observed in DNTs with different lengths of poly-benzene ring. The distinctive SW characteristic in DNT provides more degrees of freedom to tune the thermal conductivity not found in the homogeneous structure of CNT. Therefore, DNT is an ideal platform to investigate various thermal transport mechanisms at the nanoscale. Its high tunability raises the potential to design DNTs for different applications, such as thermal connection and temperature management.

The Great Gatsby and Ned Kelly: Telling national iconic stories through a transnational lens

This chapter will examine how transnational film making allows national and iconic stories to shift outside their imposed national boundaries, freeing them from “nation building” constraints and predetermined ideological motivations. Each interpretation creates one more dimension to the story’s complexity and hybridity assuring its continuance and relevance into the future. Each new film version, and in the case of iconic stories, each new transnational film version, breathes new energy and life into the stories and also stops monolithic ownership of them. What is also of interest in this chapter is the judgement cast upon each of the retelling and adaptations of these iconic stories. Every adaptation is weighed up and judged against a mythic ideal, and as such, each always falls short of imagined expectations. But in a paradoxical fashion, it is this failure to capture that provides the impetus for the story’s future retellings.

Thermal Stability of Polystyrene Peroxide

It has been observed that poly(styrene peroxide) with a high molecular weight is thermally less stable than the same polymer with a low molecular weight. This has been explained as being due to the strain on the O-O bond due to the greater polymer chain length.

Liquid Chromatography-Mass Spectrometry in Studies of Drug Metabolism and Permeability

Poor pharmacokinetics is one of the reasons for the withdrawal of drug candidates from clinical trials. There is an urgent need for investigating in vitro ADME (absorption, distribution, metabolism and excretion) properties and recognising unsuitable drug candidates as early as possible in the drug development process. Current throughput of in vitro ADME profiling is insufficient because effective new synthesis techniques, such as drug design in silico and combinatorial synthesis, have vastly increased the number of drug candidates. Assay technologies for larger sets of compounds than are currently feasible are critically needed. The first part of this work focused on the evaluation of cocktail strategy in studies of drug permeability and metabolic stability. N-in-one liquid chromatography-tandem mass spectrometry (LC/MS/MS) methods were developed and validated for the multiple component analysis of samples in cocktail experiments. Together, cocktail dosing and LC/MS/MS were found to form an effective tool for increasing throughput. First, cocktail dosing, i.e. the use of a mixture of many test compounds, was applied in permeability experiments with Caco-2 cell culture, which is a widely used in vitro model for small intestinal absorption. A cocktail of 7-10 reference compounds was successfully evaluated for standardization and routine testing of the performance of Caco-2 cell cultures. Secondly, cocktail strategy was used in metabolic stability studies of drugs with UGT isoenzymes, which are one of the most important phase II drug metabolizing enzymes. The study confirmed that the determination of intrinsic clearance (Clint) as a cocktail of seven substrates is possible. The LC/MS/MS methods that were developed were fast and reliable for the quantitative analysis of a heterogenous set of drugs from Caco-2 permeability experiments and the set of glucuronides from in vitro stability experiments. The performance of a new ionization technique, atmospheric pressure photoionization (APPI), was evaluated through comparison with electrospray ionization (ESI), where both techniques were used for the analysis of Caco-2 samples. Like ESI, also APPI proved to be a reliable technique for the analysis of Caco-2 samples and even more flexible than ESI because of the wider dynamic linear range. The second part of the experimental study focused on metabolite profiling. Different mass spectrometric instruments and commercially available software tools were investigated for profiling metabolites in urine and hepatocyte samples. All the instruments tested (triple quadrupole, quadrupole time-of-flight, ion trap) exhibited some good and some bad features in searching for and identifying of expected and non-expected metabolites. Although, current profiling software is helpful, it is still insufficient. Thus a time-consuming largely manual approach is still required for metabolite profiling from complex biological matrices.

Optimal scheduling of hydro-thermal power systems under shortage

The problem of optimal scheduling of the generation of a hydro-thermal power system that is faced with a shortage of energy is studied. The deterministic version of the problem is first analyzed, and the results are then extended to cases where the loads and the hydro inflows are random variables.

Kinetics of thermal decomposition of strontium zirconyl carbonate, Sr2Zr2O5CO3

The kinetics of decomposition of the carbonate Sr2Zr2O5CO3, are greatly influenced by the thermal effects during its formation. (α−t) curves are found to be sigmoidal and they could be analysed based on power law equations followed by first-order decay. The presence of carbon in the vacuum-prepared sample of carbonate has a strong deactivating effect. The carbonate is fairly crystalline and its decomposition leads to the formation of crystalline strontium zirconate.

Role of Melt Convection on the Thermal Performance of Heat Sinks with Phase Change Material

The role of melt convection oil the performance of beat sinks with Phase Change Material (PCM) is presented in this paper. The beat sink consists of aluminum plate fins embedded in PCM and heat flux is supplied from the bottom. The design of such a heat sink requires optimization with respect to its geometrical parameters. The objective of the optimization is to maximize the heat sink operation time for the prescribed heat flux and the critical chip temperature. The parameters considered for optimization are fin number and fill thickness. The height and base plate thickness of heat sink are kept constant in the present analysis. An enthalpy based CFD model is developed, which is capable Of Simulating phase change and associated melt convection. The CFD model is Coupled with Genetic Algorithm (GA) for carrying out the optimization. Two cases are considered, one without melt convection (conduction regime) and the other with convection. It is found that the geometrical optimizations of heat sinks are different for the two cases, indicating the importance of inch convection in the design of heat sinks with PCMs.

Thermal Overstability Of Hydromagnetic Surface-Waves

We investigate the effects of radiative heat losses and thermal conductivity on the hydromagnetic surface waves along a magnetic discontinuity in a plasma of infinite electrical conductivity. We show that the effects of radiative heat losses on such surface waves are appreciable only when values of the plasma pressure on the two sides of the discontinuity are substantially different. Overstability of a surface wave requires that the medium in which it gives larger first-order compression should satisfy the criterion of Field (1965). Possible applications of the study to magnetic discontinuities in solar corona are briefly discussed.