3-Aryl-5-[(aryloxy)methyl]-3-[(1H-1,2,4-triazol-1-yl)methyl]-2-methylisoxazolidine derivatives. Synthesis and antifungal activity

The synthesis and antifungal activity of a novel series of 3-aryl-5-[(aryloxy)methyl]-3-[(1H-1,2,4-triazol-1-yl)-methyl]-2-methylisoxazolidines are described. The in vitro activity was evaluated in solid agar cultures against a variety of dermatophytes and yeast fungi, while in vivo activity was measured in an immune-compromised mouse model of systemic candidiasis. The activity of the title series was compared to that of ketoconazole and one derivative, the cis-3-(4-chlorophenyl)-5-(4-chlorophenyloxy)methyl analogue 5f was found to possess a similar potency in the in vivo assay. Structure-activity relationship correlations are also discussed.     

An analytical excitation model for an ionizing plasma

From an analytical model for the population of high-lying excited levels in ionizing plasmas it appears that the distribution is a superposition of the equilibrium (Saha) value and an overpopulation. This overpopulation takes the form of a Maxwell distribution for free electrons. Experiments for He II, Na I and Ar I confirm the general validity of the model.     

Some aspects of the winkler determination of oxygen in water

The reactions in the Winkler determination of oxygen have been examined with a rotating platinum electrode and a recording polarograph. In this manner the extent of the reaction has been determined over the pH range 7-10; at a pH of 7 only about 5% of the dissolved oxygen reacts; at a pH of 9 or above the reaction is essentially quantitative. The reaction of dissolved oxygen with manganese(II) is quite rapid. The sluggish response of the polarograph recorder prevented an accurate determination of the rate, but the reaction half-times were about 2 sec or less over the pH range used.     

Quasielastic gamma-ray scattering from glycerol

The Mössbauer scattering instrument at the Missouri University Research Reactor (MURR) has been used to study the liquid dynamics of glycerol as a function of temperature. The measurements were made by observing the Mössbauer gamma rays from the 46.5-keV level in¹⁸³W scattered in the direction corresponding to the first liquid structure peak atQ=1.36 Å^–1. The widths of the Mössbauer velocity spectra were found to be quasielastically broadened by 3.1 eV at 24 °C up to 55 eV at 113 °C. The broadening varied quadratically with temperature above the melting point, but showed a linear dependence when plotted versus the absolute temperature divided by the viscosity. As discussed by Singh and Mullen, this latter dependence is expected in the continuous diffusion limit. The original analysis by Singwi and Söjlander was carried out for a diffusing Mössbauer ion, where the observed cross section is the Fourier transform of the self-correlation function. Our case requires the use of the paircorrelation function. Quantitative calculations as well as further experiments are needed.This work was performed with the support of the US Department of Energy under Grant Nos. DE-FG02-85ER45200 and DE-FG02-85ER45199.     

An active spectroscopical study on the plasma parameters of an ICP

Various techniques to measure the electron density and temperature of a 100 MHz inductively coupled plasma (ICP) are compared with each other. Apart from passive spectroscopy of measuring the shape of (e.g. H) and the area under emission lines we explored the field of active spectroscopy. Non-intrusive and specific are the methods of diode laser absorption (DLA) of an argon 4s-4p transition and Thomson scattering (TS). Intrusive and global is the power interruption (PI) technique: the response of line (argon and analytes) and continuum emission is followed during PI. Finally, a combination of two active techniques, namely TS during PI, is studied. By using the different techniques on the same plasma condition (frequency, power and flows) this intercomparison will reveal the validity region of the various techniques. In this way a strong basis will be created for understanding plasma phenomena.     

Temperature dependence and kinetic isotope effects for the OH + HBr reaction and H/D isotopic variants at low temperatures (53-135 K) measured using a pulsed supersonic Laval nozzle flow reactor

The reactions of OH + HBr and all isotopic variants have been measured in a pulsed supersonic Laval nozzle flow reactor between 53 and 135 K, using a pulsed DC discharge to create the radical species and laser induced fluorescence on the A 2sigma <-- X 2pi (v' = 1 <-- v' = 0) transition. All reactions are found to possess an inverse temperature dependence, in accord with previous work, and are fit to the form k = A(T/298)(-n), with k1 (OH + HBr) = (10.84 +/- 0.31) x 10(-12) (T/298)(-0.67+/-0.02) cm3/s, k2 (OD + HBr) = (6.43 +/- 2.60) x 10(-12) (T/298)(-1.19+/-0.26) cm3/s, k3 (OH + DBr) = (5.89 +/- 1.93) x 10(-12) (T/298)(-0.76+/-0.22) cm3/s, and k4 (OD + DBr) = (4.71 +/- 1.56) x 10(-12) (T/298)(-1.09+/-0.21) cm3/s. A global fit of k vs T over the temperature range 23-360 K, including the new OH + HBr data, yields kT = (1.06 +/- 0.02) x 10(-11) (T/298)(-0.90+/-0.11) cm3/s, and (0.96 +/- 0.02) x 10(-11) (T/298)(-0.90+/-0.03) exp((-2.88+/-1.82 K)/T) cm3/s, in accord with previous fits. In addition, the primary and secondary kinetic isotope effects are found to be independent of temperature within experimental error over the range investigated and take on the value of (kH/kD)(AVG) = 1.64 for the primary effect and (kH/kD)(AVG) = 0.87 for the secondary effect. These results are discussed within the context of current experimental and theoretical work.     

Dynamics in physisorbed monolayers of 5-alkoxy-isophthalic acid derivatives at the liquid/solid interface investigated by scanning tunneling microscopy

Monolayers of isophthalic acid derivatives at the liquid/solid interface have been studied with scanning tunneling microscopy (STM). We have investigated the dynamics related to the phenomenon of solvent co-deposition, which was previously observed by our research group when using octan-1-ol or undecan-1-ol as solvents for 5-alkoxy-isophthalic acid derivatives. This solvent co-deposition has now been visualized in real-time (two frames per second) for the first time. Dynamics of individual molecules were investigated in mixtures of semi-fluorinated molecules with video-STM. The specific contrast arising from fluorine atoms in STM images allows us to use this functionality as a probe to analyze the data obtained for the mixtures under investigation. Upon imaging the same region of a monolayer for a period of time we observed that non-fluorinated molecules progressively substitute the fluorinated molecules. These findings illustrate the metastable equilibrium that exists at the liquid/solid interface, between the physisorbed molecules and the supernatant solution.     

Determination of agrochemical compounds in soya plants by imaging matrix-assisted laser desorption/ionisation mass spectrometry

Detection and imaging of the herbicide mesotrione (2-(4-mesyl-2-nitrobenzoyl)cyclohexane-1,3-dione) and the fungicide azoxystrobin (methyl (E)-2-{2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate), on the surface of the soya leaf, and the detection and imaging of azoxystrobin inside the stem of the soya plant, have been achieved using matrix-assisted laser desorption/ionisation quadrupole time-of-flight mass spectrometry. In leaf analysis experiments, the two pesticides were deposited onto the surface of individual soya leaves on growing plants. The soya leaves were removed and prepared for direct and indirect (following blotting onto matrix-coated cellulose membranes) imaging analysis at different periods after initial pesticide application. In stem analysis experiments, azoxystrobin was added to the nutrient solution of a soya plant growing in a hydroponics system. The plant was left for 48 h, and then horizontal and vertical stem sections were prepared for direct imaging analysis. The images obtained demonstrate the applicability of MALDI imaging to the detection and imaging of small organic compounds in plant tissue and further extend the analytical repertoire of the versatile MALDI technique.