Element neighbourhoods in twofold triple systems

The method of differences is used to establish that every 2-regular multigraph onv– 10,2 (mod 3) points occurs as the neighbourhood graph of an element in a twofold triple system of orderv, with two exceptions: C₂C₃and C₃C₃.Dedicated to Professor Hanfried Lenz on the occasion of his seventieth birthday     

Unramified forcing preserving the law of double negation

Shoenfield's unramified version of Cohen's forcing is defined in two stages: one which does not preserve double negation and the other which modifies the former so as to preserve double negation. Here we express the unramified forcing, which preserves double negation, in a single stage. Surprisingly enough, the corresponding definition of forcing for equality acquires a rather simple form. In [2] forcing ∥- is expressed in terms of strong forcing \( \Vdash * \) viap∥-Q iffp \( \Vdash * \) ¬ ¬Q for every formulaQ ofZF set theory and every elementp of a partially ordered set (P, ≦). In its turn,p \( \Vdash * \) Q is defined by the following five clauses: (1) $$p \Vdash * a \in biff(\exists c)(\exists q \geqq p)((c,q) \in b \wedge p \Vdash * a = c)$$ (2) $$\begin{gathered} p \Vdash * a \ne biff(\exists c)(\exists q \geqq p)(((c,q) \in a \wedge p \Vdash * c \notin b) \hfill \\ ((c,q) \in b \wedge p \Vdash * c \notin a)) \hfill \\ \end{gathered} $$ (3) $$p \Vdash * \neg Qiff(\forall q)(q \leqq p \to \neg (q \Vdash * Q))$$ (4) $$p \Vdash * (Q \vee S)iff(p \Vdash * Q) \vee (p \Vdash * S)$$ (5) $$p \Vdash * (\exists x)Q(x)iff(\exists b)(p \Vdash * Q(b))$$ .     

Solution conformation of a nitrobenzoxadiazole derivative of the polyene antibiotic nystatin: a FRET study

Nystatin is a polyene antibiotic frequently applied in the treatment of topical fungal infections. In this work, a 7-nitrobenz-2-oxa-1,3-diazole (NBD) hexanoyl amide derivative of nystatin was synthesized and its detailed photophysical characterization is presented. The average conformation of the labelled antibiotic in tetrahydrofuran, ethanol and methanol was determined by intramolecular (tetraene to NBD) fluorescence resonance energy transfer measurements. At variance with the literature [Can. J. Chem. 63 (1985) 77-85], it was concluded that there is no need to invoke a solvent-dependent conformational equilibrium between extended and closed conformers of the antibiotic, because the mean tetraene-to-NBD separating distance was found to remain constant (approximately 18 A) in all the solvents studied. In addition, the large solvent dependence of the fluorescence anisotropy observed for the non-derivatized nystatin, was rationalized on the basis of the prolate ellipsoidal geometry of the molecule. It was concluded that the rod shaped and amphipathic antibiotic remains monomeric in different solvents within the concentration range studied (2-20 microM).     

Investigation of N-nitrohydrazines by the NMR method

Functionally substituted N-nitrohydrazines were studied by heteronuclear NMR. It was shown that all the investigated products from nitration of the trimethylsilyl derivatives of functionally substituted hydrazines contain the N-NO₂ fragment. The chemical shift of the nitrogen atoms of the hydrazine fragment in the¹⁵N NMR spectra and the spin-spin coupling constants were used as the main tests for structural identification. It was established that the number of recordable conformers decreases in the transition from the trimethylsilyl phenylhydrazine derivatives to the nitrohydrazines as a result of the conformational flexibility of the N(NO₂)CO fragment.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2024–2031, September, 1991.     

Characterization of the Fe(III)‐binding Site in Sepia Eumelanin by Resonance Raman Confocal Microspectroscopy¶

The resonance Raman spectrum of Sepia eumelanin is discussed by analogy to model compounds containing catechol (CAT)‐like structural units. These data are then compared with the analogous data on Fe(III)‐enriched Sepia eumelanin. In contrast to the natural eumelanin, the Fe(III)‐enriched samples exhibit absorption features in the visible and near‐IR spectral regions, which are attributed to ligand‐to‐metal charge‐transfer (LMCT) bands. Resonance Raman spectra collected by exciting these LMCT bands reveal bands at 580 and 1470 cm^?1; the intensity of these features increases wioth increasing Fe(III) content. The 580 and 1470 cm^?1 bands are assigned to Fe‐OR stretching and ring deformation modes, respectively. These data further substantiate that the Fe(III)‐ melanin‐binding site in melanin is composed of CAT‐like structural units.     

Nucleophilic substitution in benzo-1,2,3,4-tetrazine 1,3-dioxides

Nucleophilic substitution in nitro- and bromobenzo-1,2,3,4-tetrazine 1,3-dioxides (BTDOs) was studied. In most cases, the bromo and nitro groups are replaced by methylamino, dimethylamino, azido, and methoxy groups without opening of the tetrazine ring. It was illustrated with the reactions of dibromo-BTDOs with sodium methoxide that the reactivity of positions 5 to 8 in their benzene ring as regards nucleophilic substitution changes in the following order: 6 > 8 > 7 > 5. The structures of the BTDOs obtained were confirmed by ¹H, ¹³C, and ¹⁴N NMR data.     

On-line coupling of packed capillary electrochromatography with coordination ion spray-mass spectrometry for the separation of enantiomers

Pressure-supported packed capillary electrochromatography (CEC) and packed capillary high-performance liquid chromatography (pHPLC) have been coupled on-line to electrospray ionization-mass spectrometry (ESI-MS) and coordination ion spray-mass spectrometry (CIS-MS). Separation of enantiomers of barbiturates and chlorinated alkyl phenoxypropanoates were performed on a permethylated beta-cyclodextrin stationary phase by pressure-supported CEC. For on-line detection with ESI- and CIS-MS, a modified sheath-liquid interface was used. CIS-MS is a universal, novel ionization technique which improves the selectivity as well as the sensitivity. Charged complexes were formed through the addition of central complexing ions such as silver(I), cobalt(II), copper(II), and lithium(I) to the sheath flow. Advantages of CIS-MS detection compared to the ESI-MS mode are discussed. In the CIS-MS mode, increased sensitivity and high selectivity was attained through different possibilities of complexation. The superiority of pressure-supported CEC compared to pHPLC in the hyphenation with CIS-MS is demonstrated.     

A Study of the Uptake of Toluidine Blue O by Porphyromonas gingivalis and the Mechanism of Lethal Photosensitization

The purpose of the study was to determine the distribution of the photosensitizer toluidine blue O (TBO) within Porphyromonas gingivalis and the possible mechanism(s) involved in the lethal photosensitization of this organism. The distribution of TBO was determined by incubating P. gingivalis with tritiated TBO (³H-TBO) and fractionating the cells into outer membrane (OM), plasma membrane (PM), cytoplasmic proteins, other cytoplasmic constituents and DNA. The percentage of TBO in each of the fractions was found to be, 86.7, 5.4, 1.9, 5.7 and 0.3%, respectively. The involvement of cytotoxic species in the lethal photosensitization induced by light from a helium-neon (HeNe) laser and TBO was investigated by using deuterium oxide (D₂O), which prolongs the lifetime of singlet oxygen, and the free radical and singlet oxygen scavenger L-tryptophan. There were 9.0 log₁₀ and 2 log₁₀ reductions in the presence of D₂O and H₂O (saline solutions), respectively, at a light dose of 0.44 J (energy density = 0.22 J/cm²), suggesting the involvement of singlet oxygen. Decreased kills were attained in the presence of increasing concentrations of L-tryptophan. The effect of lethal photosensitization on whole cell proteins was determined by measuring tryptophan fluorescence, which decreased by 30% using 4.3 J (energy density = 4.3 J/ cm²) of light. Effects on the OM and PM proteins were determined by sodium dodecyl sulfate polyacrylamide gel electrophoresis. There was evidence of change in the molecular masses of several PM proteins and OM proteins compared to controls. There was evidence of damage to the DNA obtained from irradiated cells. Scanning electron microscopic studies showed that there was coaggre-gation of P. gingivalis cells when sensitized and then exposed to laser light. These results suggest that lethal photosensitization of P. gingivalis may involve changes in OM and/or PM proteins and DNA damage mediated by singlet oxygen.