Additivity of the proton affinity of polysubstituted benzenes: the ipso position

It is shown, by the MP2(fc)/6-31G^{* *}/ /HF/6-31G^* +ZPE(HF/6-31G^*) theoretical model and concomitant use of homodesmic reactions, that the ipso proton affinities in polyfluorinated benzenes follow a simple additivity rule. Performance of the latter is good, as evidenced by a low average absolute deviation Δ_abs = 0.8 kcal/mol from the accurate ab initio results. Additional evidence supporting the additivity concept is provided by good accordance with the experimental proton affinity (PA) for perfluorobenzene. The present approach enables estimates of the ipso PAs of multiply substituted aromatics. It is particularly useful in those systems which involve or atomic groupings with lone pairs of electrons proximate to the aromatic π moiety. The additivity rule of thumb offers a simple rationalization of the ipso proton affinities. The origin of the PA additivity is briefly discussed.     

Structural Basis for Recognition of Guanosine by a Synthetic Tricyclic Cytosine Analogue: Guanidinium G‐Clamp

An oligonucleotide analogue containing a novel heterocyclic analogue, the guanidinium G‐clamp, was designed to allow formation of five H‐bonds to guanosine. The guanidinium group was introduced postsynthetically by treatment of the deprotected oligonucleotide containing a free amino group with a solution of 1H‐pyrazole‐1‐carboxamidine and purified by a combination of size‐exclusion chromatography and reversed‐phase HPLC. A single incorporation of this modification into an oligodeoxynucleotide sequence was found to increase duplex stability by 13° and 16° per modification to RNA and DNA, respectively. Crystals of a self‐complementary decamer sequence containing this modification were grown and diffracted to 1‐Å resolution. The structure was solved by molecular replacement and revealed that the modification forms additional H‐bonds to O(6) and N(7) of guanosine through the amino and imino N‐atoms, respectively. The origins of enhanced duplex stability are also attributed to increased stacking interactions mediated by the phenoxazine moiety of the G‐clamp and formation of H‐bond networks between the positively charged guanidinium group, H₂O molecules, and negatively charged O‐atoms from phosphates on the adjacent strand.     

New cationic aryldiazo,aryldiimine and arylhydrazine complexes of platinum

The preparation of some new cationic aryldiazo complexes of platinum of formula trans-[Pt(N₂Ar)(PEt₃)₂L]⁺, where N₂Ar = N₂C₆H₄F-m or -p and L = NH₃, Py, Et₃P or EtNC, is described. Protonation of these complexes gives the corresponding aryldiimide complexes trans-[Pt(NHNAr)(PEt₃)₂L]⁺, and reduction of the protonated complexes with molecular hydrogen in the presence of a catalyst gives the arylhydrazine complexes trans-[Pt(NH₂NHAr)(PEt₃)₂L]⁺. Some of the spectroscopic properties of these new complexes are reported and discussed.     

On an inconsistency connected with koopman's theorem

On the basis of Koopmans' theorem two methodically different ways to estimate the effect of a spin-orbit perturbation on the ionization potentials of I₂ have been proposed. In the present paper a model system is constructed to show the equivalence of both methods.     

Particle chaos in the Earth's magnetotail

Nonlinear particle dynamics is studied both in current sheets and near neutral lines. The parameter governing particle chaos in a current sheet with a constant normal component, B(n), is kappa=(R(min)/rho(max))(1/2), where R(min) is the minimum field line radius of curvature and rho(max) is the maximum gyroradius. In such a current sheet, motion can be viewed as a combination of a component normal to the current sheet and a tangential component. The parameter kappa represents the ratio of the characteristic time scale of the normal component to the tangential, and thus, particle chaos is maximized for kappa approximately 1. For kappa<1, the slow motion preserves the action integral of the fast motion, J(z), except near the separatrix, the phase space boundary separating motion that crosses the current sheet midplane from that which does not. Near a linear neutral line, it is found that the parameter b(n), which is the ratio of the characteristic vertical and horizontal field strengths, rather than kappa governs particle chaos. In the limit b(n)<1, the slow motion again preserves J(z), and J(z) has the same analytic form as in a constant B(n) current sheet. In the limit of b(n)<1, the structure of x-p(x) phase space is controlled by the stable and unstable manifolds associated with the unstable fixed point orbit at (x,p(x))=(0,0), and this structure lies along a contour of constant J(z).     

Aromatic hydrocarbon-carbonium ion molecular complexes

Molecular complexes of aromatic hydrocarbons and carbonium ions are described according to Mulliken's donor — acceptor theory. Estimations of electron affinities of several cations are deduced from charge-transfer transition energies and the indepently measured electron affinity of the tropylium ion.     

Ammoxidation of halogen-substituted toluenes on V-P-oxide catalysts

The ammoxidation of various halogen-substituted toluenes on crystalline vanadium phosphate catalysts was investigated. The monophosphates and the NH₄VOP₂O₇ are transformed into new NH₄-containing V-P-oxides. The (VO)₂P₂O₇ used is stable in time on stream. These structures are very active and selective ammoxidation catalysts.

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. NH₄VOP₂O₇ V-P , NH₄. (VO)₂P₂O₇ . .

     

Supercritical Propanol-Water Synthesis and Comprehensive Size Characterisation of Highly Crystalline anatase TiO2 Nanoparticles

Highly crystalline anatase TiO₂ nanoparticles have been synthesised in less than 1 min in a supercritical propanol-water mixture using a continuous flow reactor. The synthesis parameter space (T, P, concentration) has been explored and the average particle size can be accurately controlled within 10-18 nm with narrow size distributions (2-3 nm). At subcritical conditions amorphous products are obtained, whereas a broad range of T and P in the supercritical regime gives 11-14 nm particles. At high temperature and pressure, the particles size increase to 18 nm. The nanoparticles have been extensively characterised with powder X-ray diffraction (PXRD), transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) with excellent agreement on size and size distribution parameters. The SAXS analysis suggests disk-shaped particles with diameters that are approximately double the height. For comparison, a series of conventional autoclave sol-gel syntheses have been carried out. These also produce phase-pure anatase nanoparticles, but with much broader size distributions and at much longer synthesis times (hours). The study demonstrates that synthesis in supercritical fluids is a very promising method for manipulating the size and size distribution of nanoparticles, thus removing one of the key limitations in many applications of nanomaterials.     

The transverse hadronic energy accompanying weak bosons

We study the hadronic transverse energy (E _T ) accompanyingZ ⁰ events in \(p\bar p\) interactions and compare our result with the observedE _T distribution in minimum bias events. We expect excess transverse energy to accompanyZ ⁰'s. This effect can also be probed experimentally using Drell-Yan lepton pairs and represents an interesting way to probe the multi-gluon structure of QCD.