Reactivity of the Hydroxy Groups in Melezitose and Their Selective Protection

The reactivity of melezitose hydroxy groups was studied by tritylation in pyridine with subsequent acetylation. After partial detritylation of the products, acetyl group transfer from position 4 to 6 was observed. The structure of the prepared melezitose derivatives was established on the basis of their IR, ¹H, ¹³C, and ¹H-¹H COSY NMR, and mass spectra (fast atom bombardment), as well as from the results of model calculations performed with the aid of SGI Indigo Molecule-Pattern-Work-Station software package (Biosym) where the potential energy function was approximated with the CVFF potential. The reactivity of primary hydroxy groups in melezitose was found to decrease in the following order: 6' > 6 6' > 1'.     

Photochemistry of ortho, ortho' dialkyl phenyl azides

Phenyl azide, 2,6-diethylphenyl azide, 2,6-diisopropylphenyl azide, and 2,4,6-tri-tert-butylphenyl azide were studied by laser flash photolysis (LFP) methods. LFP (266 nm) of the azides in glassy 3-methylpentane at 77 K produces the transient UV-vis absorption spectra of the corresponding singlet nitrenes. At 77 K, the singlet nitrenes relax to the corresponding triplet nitrenes. The triplet nitrenes are persistent at 77 K and their spectra were recorded. The rate constants of singlet to triplet intersystem crossing were determined at this temperature. LFP of 2,4,6-tri-tert-butyl phenyl azide in pentane at ambient temperature again produces a singlet nitrene, which is too short-lived to detect by nanosecond spectroscopy under these conditions. Unlike the other azides, the first detectable intermediate produced upon LFP of 2,4,6-tri-tert-butyl phenyl azide at ambient temperature is the benzazirine (285 nm) which has a lifetime of 62 ns controlled by ring opening to a didehydroazepine. The results are interpreted with the aid of Density Functional Theoretical and Molecular Orbital Calculations.     

Preparation of Zirconia Nanocrystals from Concentrated Zirconium Aqueous Solutions

A high concentration (0.8 M) zirconium solution turned into a stable aqueous colloid of about 60 nm in size upon low temperature (96^°C) incubation. Changing the acid concentration did not affect the colloidal growth rate nor the final colloid size much. However, the induction time before the rapid growth of colloidal particle could be altered. By limiting the incubation to just before the rapid growth of colloidal zirconia, and the addition of organic acids as surface modifiers, non-agglomerated primary crystallites (10 nm) of m-ZrO₂ could be recovered. These modified primary crystallites could then be repeatedly flocculated and redispersed in water by adjusting the pH.     

Rule of five cyclizations in 5‐hexenyl radicals and photocycloadditions of 1,5‐hexadienes: effect of 4‐oxa substitution

The effect of 4‐oxa substitution on the regiochemistry and rate of 5‐hexenyl radical cyclizations was investigated, as a potential model for [2 + 2] photocycloadditions of 2‐acyl‐4‐oxa‐1,5‐hexadienes. Increasing the electron density in the alkene decreases the rate of cyclization in the 4‐oxa‐hexenyl radicals, relative to the all carbon analogs, but has little effect on the regioselectivity of the cyclization. The radical model does not reproduce the high degree of 1,6 closure, observed in the [2 + 2] photocycloadditions for 4‐oxa‐1,5‐hexadiene 1a . However, the radical model does reinforce the interpretation that ground state conformational effects, engendered by substitution remote from the reacting centers have important rate consequences for cyclization reactions. Copyright © 2007 John Wiley & Sons, Ltd.     

Temperature field distribution in multi-layered solid media heated with multi-modes laser beam

In the present paper we want to develop an analytical model to study the thermal behavior of multi-layered solid media in interaction with a laser beam. We suppose that each layer has a constant thermal conductivity. We consider that the laser beam is formed by decoupled [Phys Rev A 1996; 53: 4435] multi-modes Hermite–Gauss beams. The model is applied using the classical heat equation which was solved using the integral transform method [Infrared Phys Technol 2002; 42: 31; Optics Laser Technol 2004; 36: 219–22; Optics Laser Technol 2004; 36: 677–9; Proc SPIE 2003; 5227: 323].     

Thermal fields in laser–multi-layer structures interaction

In the present paper, we are dealing with the thermal fields for laser–periodic multilayer structures interaction. Our point of view is originally that we consider any order transverse laser beams, like heating sources. We consider that the laser beam acts in IR (Nd:YAG or CO₂ laser beam) and it is in one transverse mode or in only a few decoupled modes. In order to solve this problem, we will use the Green function method. Specific results are presented for a laser beam (Nd:YAG laser) operating in the mode TEM₀₁ and a two-layer structure.     

Mass spectrometric studies of heterocyclic organophosphorus compounds: 1,3,2-benzodioxaphospholes

The mass spectral behaviour of a new type of organophosphorus compound, 1,3,2-benzodioxaphospholes, under 70 eV electron impact has been studied by means of high and low resolution mass spectrometry as well as by B/E and B²/E linked scans. The influence of different substituents in the molecule (O, S or N) on the mass spectra is investigated. The reason for isomerization between oxygen and sulphur within a molecule studied by mass spectrometry is discussed.     

Synthesis and characterization of three organic dyes with various donors and rhodanine ring acceptor for use in dye-sensitized solar cells

A series of new organic dyes comprising carbazole, iminodibenzyl, and phenothiazine moieties as the electron donors and rhodanine ring as the electron acceptor/anchoring groups were designed and developed for use in dye-sensitized solar cells. HOMO and LUMO energy level tuning was achieved by varying the carbazole, iminodibenzyls and phenothiazine donors. This was evidenced by spectral and electrochemical experiments and density functional theory calculations. Electrochemical studies indicated that the phenothiazine unit was much more effective in lowering the ionization potential than were the iminodibenzyl and carbazole units. The phenothiazine dye shows a solar-energy-to-electricity conversion efficiency (η) of 4.87%; the carbazole and iminodibenzyl dyes show η of 2.54% and 3.52%, respectively. These findings reveal that using carbazole, iminodibenzyl and phenothiazine donors as light-harvesting sensitizers are promising candidates for dye-sensitized solar cells.     

SYNTHESIS OF MELEZITOSE DERIVATIVES

The reactivity of melezitose hydroxyls is studied during tritylation in pyridine. Some novel derivatives of melezitose are prepared. An acetyl is transferred from the 4- to the 6-position after detritylation of 3 and 4. The structures of the products are proved by elemental analysis; ¹ H, ¹³ C, and ¹ H- ¹ H COSY NMR spectra;IR spectra; and fast-atom bombardment mass spectrometry.