The 1,2,4-triazolyl cation: thermolytic and photolytic studies

The generation of the 1,2,4-triazolyl cation (1) has been attempted by the thermolysis and photolysis of 1-(1,2,4-triazol-4-yl)-2,4,6-trimethylpyridinium tetrafluoroborate (2) and the thermolysis of 1- and 4-diazonium-1,2,4-triazoles, using mainly mesitylene as the trapping agent. Thermolysis of 2 gave mostly 1,2,4-triazole, together with 3-(1,2,4-triazol-4-yl)-2,4,6-trimethylpyridine, 4-(1,2,4-triazol-4-ylmethyl)-2,6-dimethylpyridine, and 4-(2,4,6-trimethylbenzyl)-2,6-dimethylpyridine. Thermolysis of each of the diazonium salts in the presence of mesitylene again gave mainly triazole together with very low yields of 1-(1,2,4-triazol-1-yl)-2,4,6-trimethylbenzene and the corresponding -4-yl isomer in about the same ratio. On the other hand, photolysis of 2 in mesitylene gave mainly 1-(1,2,4-triazol-1-yl)-2,4,6-trimethylbenzene. A photoinduced electron transfer from mesitylene to 2 has been observed and preliminary laser flash photolyses of 2 and the corresponding 2,4,6-triphenylpyridinium salt have been carried out. The observed transients are explained as arising from the first excited states of the pyridinium salts rather than from 1. Ab initio MO calculations are reported and indicate that the predicted electronic ground-state of the triazolyl cation is a triplet state of B1 symmetry with five pi electrons, which corresponds to a diradical cation (1c). Possible mechanisms for the formation of the various products are proposed.     

Effects of <Emphasis Type="Italic">L</Emphasis>-Carnitine on Sucrose-Induced Hyperlipidaemia

Summary. L-Carnitine, L-(−)-β-hydroxy-γ-trimethylaminobutyrate, plays an important role as a factor necessary for the transport of long-chain fatty acids into the mitochondria. In order to investigate the influence of L-carnitine on hyperlipidaemias, the experimental model of the sucrose-induced hypertriglyceridaemia of the rat was used. In these experiments L-carnitine in the dose of 11 mg per day and 100 g body weight (over the period of 1 week) was able to antagonize the sucrose-induced hypertriglyceridaemia and the increase of serum free fatty acid level in female rats of the Wistar strain. Carnitine administration did not change the activities of lipogenic enzymes and fatty acid synthesis in the liver. However, L-carnitine increases the rate of hepatic fatty acid oxidation. Our results indicate a hypotriglyceridemic and free fatty acid lowering effect of L-carnitine, and suggest the use of this compound in the therapy of hyperlipidaemias.     

A spectroscopic study of cobalt(III) furyldioximates

Summary The electronic properties of a series of cobalt(III)trans-furyldioximato-complexes of the type [CoB(FH)₂X] (B=NH₃, X=Cl, Br, I or NO₂; B=pyridine (py) or thiocarbamide (thio), X=Cl or Br; B=imidazole (imid), X=Br), [Co(FH₂)(FH)Cl₂] and [Co(thio)₂(FH)₂]NO₃ were studied by i.r., u.v. and¹H and¹³C n.m.r. spectra The results were compared with those from the corresponding dimethylglyoximato-complexes. It was concluded that -conjugation over the equatorial plane in the furyldioximates is greater than in the dimethylglyoximates. There is some evidence of thetrans-influence of the anionic ligands in the ammines which are in the order NO ₂ ^– >Br^–>Cl^–.     

Characterisation of fatty acids in biological oil samples using comprehensive multidimensional gas chromatography

Comprehensive multidimensional gas chromatography can adequately resolve very complex mixtures of analytes such as the fatty acid mixtures which are contained in, e.g., fish and vegetable oils. Well-ordered patterns are obtained in the two-dimensional separation plane which can be used to tentatively identify peaks when no standard is available. The technique which can also be used for quantification, i.e., quantitative ratio analysis, should be especially useful for fingerprinting purposes. Unravelling the composition of complex mixtures such as fish oils appears to be highly rewarding.     

Electronic detection of the enzymatic degradation of starch

[reaction: see text] The enzymatic degradation of starch can be monitored electronically using single-walled carbon nanotubes (SWNTs) as semiconducting probes in field-effect transistors (FETs). Incubation of these devices in aqueous buffer solutions of amyloglucosidase (AMG) results in the removal of the starch from both the silicon surfaces and the side walls of the SWNTs in the FETs, as evidenced by direct imaging and electronic measurements.     

Modified sampling and analysis method for large volatility range airborne polycyclic aromatic hydrocarbons (PAH) using gas chromatography-mass spectrometry

A sampling method has been developed for the measurement for polycyclic aromatic hydrocarbons in ambient air by gas chromatography isotope dilution mass spectrometry. The method has been designed to measure the largest possible volatility range of PAHs including the abundant naphthalenes. Sample volumes were approx. 500 m³ in size at a sampling rate of approx. 18 m³/h. The sampler contained three sorption stages for the simultaneous capturing of particle bound and low and high volatile gaseous PAH, respectivley. Recoveries of sampling spikes were on average 90%. The detection limit was approx. 5 pg/m³ for the high boiling range PAH. Results obtained showed a quite steady profile for most PAH in background air in The Netherlands. Comparison of abundance ratios with literature data indicate that traffic exhausts are the major source for the PAH in the area.     

PROFLAVINE MEDIATED PHOTOINACTIVATION OFBACTERIOPHAGE φX174 AND ITS ISOLATED DNA: EFFECTS OF AGENTS MODIFYING VARIOUS PHOTOCHEMICAL PATHWAYS

Abstract. Thiols and disulfides protect both φX174 phage and its isolated DNA from the lethal action of proflavine plus light. The protective ability of these compounds appears to be attributed to the -SH or the -S-S- group and the property to interact with the proflavine-phage DNA complex. The phage inactivation efficiency per proflavine bound to DNA is reduced by 50 to 30% upon addition of cysteine or cystamine. Substances that affect the lifetime of singlet oxygen modify the rate of phage photoinactivation in the presence of proflavine; the inactivation rate is decreased by N^-₃ and increased by D₂O. Irradiation under N₂ atmosphere markedly decreases the phage photosensitization by proflavine. Irradiation with monochromatic light of 440 nm is less efficient than irradiation with light of 440 nm plus 360 nm, and the difference is more pronounced in N₂ than in air. These results are discussed in relation to various possible photochemical pathways.     

Automated chemical separations in routine activation analysis

In recent years increased information is required about the distribution of elements at low concentration levels in the biosphere. Neutron activation analysis can play an important role if it can supply many data at relatively low cost. As some of the concentrations are too low for determination by non-destructive techniques, equipment for chemical separations on a routine basis is necessary. For environmental studies a separation scheme has been developed successfully for arsenic, antimony, cadmium, copper, mercury, selenium and zinc. It is based on a combination of distillation and ion-exchange. Special attention is paid to the prevention of interference from bromine and sodium. Additional information about chromium, cobalt, nickel and tungsten can easily be obtained. Experience gathered with an automated instrument for fifty samples a week is described.     

Static light scattering from microgel particles: model of variable dielectric permittivity

We perform static light scattering experiments on a dilute suspension of microgel particles and model the resultant form factors Pq by assuming an exponentially decaying dielectric permittivity. The result is that Pq is a Lorentzian function of the scattering wavevector q for length scales greater than the particle size; the width approximately corresponding to twice the particle radius. This simple model reasonably accounts for scattered light from both swollen and shrunken microgel phases.