Symmetries of BLT-Sets

We do the tentative beginnings of a study of BLT-sets of generalised quadrangles via their symmetries. In particular, the study of whorls about a line leads us to hyperbolic reflections preserving a BLT-set of Q(4, q).     

Autoxidation of terpenic aldehydes—II

The influence of steric factors on the autoxidation of aldehydes having tertiary formyl groups has been investigated. These afford nor-derivatives by loss of carbon monoxide, and carboxylic acids. Steric interactions have been shown to affect strongly the ratio between carboxylic acid and nor-derivatives and, in addition, to increase the autoxidation rate. For the first time, formation of formates from aldehydes by autoxidation conditions, has been demonstrated.     

Collective dynamics in molten potassium: an inelastic x-ray scattering study

The high-frequency collective dynamics of molten potassium has been investigated by inelastic x-ray scattering, disclosing an energy/momentum transfer region unreachable by previous inelastic neutron scattering (INS) experiments. We find that a two-step relaxation scenario, similar to that found in other liquid metals, applies to liquid potassium. In particular, we show how the sound velocity determined by INS experiments, exceeding the hydrodynamic value by approximately 30%, is the higher limit of a speedup, located in the momentum region 1 < Q < 3 nm(-1), which marks the departure from the isothermal value. We point out how this phenomenology is the consequence of a microscopic relaxation process that, in turn, can be traced back to the presence of "instantaneous" disorder, rather than to the crossover from a liquid to solidlike response.     

Grafting of monosaccharide derivatives to cellulose acetate

Grafting of 1,2-O-isopropylidene-α-D -xylofuranose to commercial cellulose diacetate has been accomplished by using a boron trifluoride catalyst. The reaction proceeds quickly at 25 and 40°C, resulting in degrees of molar substitution (MS) of 0.37 and 0.34, respectively. If monomer and catalyst are added over an extended period of time to maintain low concentrations, MS values as high as 0.89 and 0.85 are obtained at 25 and 40°C, respectively. Major side reactions are depolymerization of the cellulose acetate backbone and grafted D -xylose and the homopolymerization of the monomer. These side reactions may be minimized by conducting the reaction at 40°C for a short time or by adding monomer and catalyst over an extended period of time. Grafting has also been accomplished by using D -xylose derivatives with various reactive groups at the anomeric carbon atom. The grafted material of MS greater than 0.7 is insoluble in acetone and after deacetylation is soluble in water under alkaline, neutral and acidic conditions. Oxalic acid hydrolysis of the deacetylated material indicates that most of the grafted D -xylose units are in the furanose form. Methylation and hydrolysis of the methylated material shows that 75% of the D -xylose residues are terminal units and indicates the presence of many singly grafted D -xylose residues and a few di-and trisaccharide grafts.     

Two new polyhydroxylated sterols from Ruppia maritima

Two new sterols have been isolated from the aquatic plant Ruppia maritima and their structures were established as (24R) ergosta-8,22-diene-3 beta,6 beta,7 alpha-triol (1) and (24R) ergosta-8(14),22-diene-3 beta,6 beta,7 alpha-triol (2) on the basis of spectroscopic analysis.     

Anil-Synthese. 23. Mitteilung. Über die Herstellung von Styryl- und Stilbenyl-Derivaten des Pyrimidins

Preparation of Styryl and Stilbenyl Derivatives of Pyrimidines 2- and 4-(p-Tolyl)-substituted pyrimidines react with anils of hetero-aromatic aldehydes in the presence of dimethylformamide and potassium hydroxide or potassium t-butoxide to yield the corresponding 2- and 4-[4″-(heteroaryl)stilben-4′-yl]pyrimidines or the 2- and 4-[a-(heteroaryl)-4′-styryl]pyrimidines respectively (‘Anil synthesis’). Furthermore, the Schiff′s bases derived from p-chloroaniline and 4-(pyrimidine-2-yl and 4-yl)benzaldehydes give, with methyl- and with p-tolyl-substituted heterocycles, the corresponding heterocyclic substituted styryl and stilbenyl derivatives. Alkyl-, alkoxy- or phenyl-substituted pyrimidines undergo also the ‘Anil synthesis’.     

Reversal of Clar's Aromatic-Sextet Rule in Ultrashort Single-End-Capped [5,5] Carbon Nanotubes

The three-fold HOMO-LUMO gap oscillation, typical of finite length armchair carbon nanotubes (CNT), has a major effect on the magnetic response of ultrashort, single-end-capped [5,5] carbon nanotubes to a perturbing magnetic field parallel to the main symmetry axis. For the CNT's containing 40, 70, and 100 carbon atoms, for which 100 % of the C=C double bonds can be grouped into aromatic-sextets, i. e., fully or complete Clar networks, large paratropic (antiaromatic) global circulations around the cylindrical axis are predicted at the DFT level of calculation. Local and semi-global diatropic (aromatic) currents of strengths not larger than that of the benzene molecule are determined for a perpendicular perturbing magnetic field. CNTs of intermediate lengths do not display this enhanced antiaromatic response. The paratropic current flow clearly shows that these complete Clar networks can be viewed as stacked cycloparaphenylene belts, each providing a double annulene circuit as a consequence of the quinoidal resonance structure that results from their closure. Paradoxically, the fully aromatic Clar structure itself is responsible for the enhanced global antiaromaticity.     

Luminescence Properties of Platinum(II) Dithiooxamide Compounds

Tight contact ion pairs of general formula {Pt(H(2)-R(2)-dto)(2)(2+),(X(-))(2)} have been prepared, and their absorption spectra and luminescence properties (at room temperature in dichloromethane fluid solution and at 77 K in butyronitrile rigid matrix) have been studied (dto = dithiooxamide; R = methyl, X = Cl (1); R = butyl, X = Cl (2); R = benzyl, X = Cl (3); R = cyclohexyl, X = Cl (4); R = cyclohexyl, X = Br (5); R = cyclohexyl, X = I (6)). The absorption spectra of all the compounds are dominated by moderately strong Pt(dpi)/S(p) to dithiooxamide (pi) charge transfer (Pt/S --> dto CT) bands in the visible region (epsilon in the 10(4)-10(5) M(-)(1) cm(-)(1) range). Absorption features are also present at higher energies, due to pi-pi transitions centered in the dto ligands (ligand centered, LC). All the compounds exhibit a unstructured luminescence band in fluid solution at room temperature, with the maximum centered in the 700-730 nm range. The luminescence bands are blue-shifted about 4000 cm(-)(1) on passing to the rigid matrix at 77 K. Luminescence lifetimes are on the 10(-)(8)-10(-)(7) s time scale at room temperature and 1 order of magnitude longer at 77 K. Luminescence is assigned to triplet Pt/S --> dto CT excited states in all cases. Compounds 3-6 also exhibit a second higher-energy luminescence band at room temperature, centered at about 610 nm, attributed to a LC excited state. Charge transfer interactions between halides and dto ligands destabilize dto-centered orbitals, affecting the energy of Pt/S --> dto CT transitions and states. The X counterions and X --> dto CT levels are proposed to play a role in promoting excited state conversion between LC and Pt/S --> dto CT levels. The R substituents on the nitrogen atoms of the dto ligands influence the absorption and photophysical properties of the compounds, by affecting proximity of the ion pairs. The possibility to functionalize the R substituents may open the way to interface these luminescent compounds with desired substrates and to construct supramolecular assemblies.     

Enantioselective Synthesis of Phenylpropanetriols

The four stereomer 1-(4-hydroxy-3-methoxy)-phenyl-1,2,3-propanetriols were obtained in about 30% yields starting from ferulic acid by a synthesis based on osmium catalyzed asymmetric dihydroxylation.