Electron impact mass spectrometry of some 6-substituted tetrazolo[1,5-c]pyrimidin-5(6H)-ones

The electron impact mass spectra of 6-methyltetrazolo[1,5-c]pyrimidin-5(6H)-one, its 7- and 8-methyl derivatives, three 8-halo derivatives and two related nucleosides are reported. On the basis of the high-resolution data and detected metastable ions, the fragmentation routes of their molecular ions are proposed. Coexistence of the tautomeric forms of the title compounds of cyclic (tetrazole) or linear (azide) structure can be suggested owing to the fragmentation pathways identified for the bases. Decomposition of the related nucleosides lies in the breaking of nucleoside bonds to produce the appropriate base and sugar fragments.     

Solvent-modulated chemoselective deprotections of trialkylsilyl esters and chemoselective esterifications

A series of trialkylsilyl esters were deprotected or transesterificated into their corresponding carboxylic acids or methyl esters under a catalytic amount of CBr₄ in alcohol reaction system. This method enables to desilylate secondary sp³-carbon, sp²-carbon, sp-carbon and aryl tethered trialkylsilyl esters to carboxylic acids, whereas primary sp³-carbon tethered trialkylsilyl esters were further converted into their methyl esters under CBr₄/MeOH reaction conditions. The highly chemoselective deprotections can be modulated and achieved by the introduced protecting trialkylsilyl groups and the used alcohols such as MeOH and EtOH under this photochemically-induced reaction conditions.     

Group theoretic approach to the screened Coulomb problem

Perturbation method based on the group theory is developed for the radial solution of the Schrödinger equation with screened Coulomb potential. It may be treated as an alternative to the analytic perturbation theory proposed recently by McEnnan, Kissel, and Pratt (Phys. Rev. A, 2 (1976), 532) and is based on the expansion of the potential of the following form $\text{V(r) = ?(}\text{a}\text{r}\text{) × (1 + λV}{}_1\text{r + λ}{}^2\text{V}{}_2\text{r}{}^2\text{+ …)}$. Corrections to the point-Coulomb energy levels are given as series in λ and also the screened Coulomb eigenstates are given in the form of expansions in powers of λ. The method is applied also to the continuous spectrum and similar expansions are found. The problem of the normalization of both discrete and continuous spectrum eigenstates is discussed and we find some differences in the case of the scattering states. Origin of this discrepancy is explained.     

Rational design of an “all-in-one” phototheranostic

We report here porphodilactol derivatives and their corresponding metal complexes. These systems show promise as “all-in-one” phototheranostics and are predicated on a design strategy that involves controlling the relationship between intersystem crossing (ISC) and photothermal conversion efficiency following photoexcitation. The requisite balance was achieved by tuning the aromaticity of these porphyrinoid derivatives and forming complexes with one of two lanthanide cations, namely Gd³⁺ and Lu³⁺. The net result led to a metalloporphodilactol system, Gd-trans-2, with seemingly optimal ISC efficiency, photothermal conversion efficiency and fluorescence properties, as well as good chemical stability. Encapsulation of Gd-trans-2 within mesoporous silica nanoparticles (MSN) allowed its evaluation for tumour diagnosis and therapy. It was found to be effective as an “all-in-one” phototheranostic that allowed for NIR fluorescence/photoacoustic dual-modal imaging while providing an excellent combined PTT/PDT therapeutic efficacy in vitro and in vivo in 4T1-tumour-bearing mice.

We report here porphodilactol derivatives and their corresponding metal complexes as “all-in-one” phototheranostics by controlling the relationship between intersystem crossing (ISC) and photothermal conversion efficiency following photoexcitation.     

First experiments on transmutation studies of129I and237Np using relativistic protons of 3.7 GeV

First experiments on the transmutation of long-lived¹²⁹I and²³⁷Np using relativistic protons of 3.7 GeV are described. Relativistic protons generate in extended Pb-targets substancial neutron fluences. These neutrons get moderated in paraffin and are used for transmutation as follows:¹²⁹I(n,)¹³⁰I and²³⁷Np(n,)²³⁸Np. The isotopes¹³⁰I (T _1/2-12.36 h) and²³⁸Np (T _1/2=2.117 d) were identified radiochemically. One can estimate the transmutation cross-section (n,) in the given neutron field as (¹²⁹I(n,))=(10±2)b and (²³⁷Np(n,))=(140±30)b The experiments were carried out in November 1996 at the Synchrophasotron, LHE, Dubna, Russia. The investigation has been performed at the Laboratory of High Energies, JINR, Dubna.     

Stereochemical memory versus Curtin-Hammett behavior in the rearrangement of 1,3-cyclopentanediyl radical cations derived from housanes through structural effects on conformational control

The electron-transfer-catalyzed rearrangement of the housanes 1 affords regioselectively the two cyclopentenes 2 and 3 by 1,2-migration of a group at the methano bridge. Appropriate ring annelation in the intermediary cyclopentane-1,3-diyl radical cation 1(*+) changes the stereochemical course of the rearrangement from complete stereoselectivity (stereochemical memory) for the structurally simple housane 1b to partial loss of stereoselectivity through competing conformational interconversion for the tricyclic housane 1c. Additional cyclohexane annelation, as in the tetracyclic housane 1a, results in complete loss of stereocontrol through Curtin-Hammett behavior, as substantiated by the viscosity dependence on the product ratio of the rearrangement. Whereas in the radical cations 1b(*+) and 1c(*+) the 1,2-shifts (k(2) and k(3)) are faster than the conformational anti <==> syn change (k(1), k(-1)), the reverse applies for the radical cation 1a(*+). Such structural manipulation of conformational effects in radical cation rearrangements has hitherto not been documented.     

Dispersion relation approach to the anomaly in 2 dimensions

We calculate the chiral anomaly in 2 dimensions within a dispersion relation approach and we compare its features with then-dimensional regularization scheme.Supported by Fonds zur Förderung der wissenschaftlichen Forschung in Österreich, Projekt Nr. P8444-TEC     

Electroproduction of strangeness

Formalism for the electroproduction of strange particles based on the one photon exchange approximation and the Feynman diagrams representation of hadron current is reviewed. Different photoproduction models are compared with available photo and electroproduction data. New experiments are proposed that may resolve existing uncertainties and inconsistencies. The formation of hypernuclei via kaon electroproduction is investigated theoretically and compared with other reactions involving purely hadronic processes.     

On a class of atmospheres occurring in stellar hydrodynamic theory

Summary A derivation is given of the basic equation governing the behaviour of small disturbances in a stratified compressible atmosphere (with a locally unstable region bounded by semi-infinite stable regions) in which the time of radiative relaxation is constant.By means of a new independent variable that is a function of the equilibrium entropy stratification, various properties of such media can be established in a straightforward manner. A general expression for the wave energy flux is derived, and integral properties arising from this quantity are used to obtain in particular, results pertaining to the eigenfunctions and eigenvalues for strongly radiating systems. In addition, a model of an atmosphere with a strongly-radiating region embedded in a convective zone, and bounded by semi-infinite radiation-free layers is discussed in some detail. The paper is an approach towards providing some preliminary but unified results in the theory of stellar hydrodynamics.

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Résumé Nous donnons une dérivation de l'équation de base qui détermine la propagation des petites perturbations dans une atmosphère compressible stratifiée (présentant une zone d'instabilité locale entre des zones de stabilité semi-infinies) dont le temps de relaxation radiative est constant.Au moyen d'une nouvelle variable indépendante, fonction de la stratification de l'entropie en équilibre, diverses propriétés de tels milieux sont déterminées simplement. On donne une formulation du flux de l'énergie ondulative et on emploie les propriétés intégrales qui en résultent pour obtenir en particulier des résultats concernant les eigenfonctions et les eigenvalues pour des systèmes à forte radiation énergétique. En outre, on étudie en détail le modèle d'une amtosphère caractérisée par une zone à forte radiation insérée dans une zone convective entre des couches semi-infinies sans radiation.Ce travail présente quelques conclusions préliminaires mais cohérentes dans le domaine de la théorie de l'hydrodynamique stellaire.