Energy storage in Ce-doped LiCaAlF6 and LiSrAlF6 crystals

Absorption, emission and thermoluminescence (TL) of as-grown and X-irradiated pure and Ce-doped LiCaAlF₆ (LiCAF) and LiSrAlF₆ (LiSAF) crystals have been analyzed. It is shown that the energy storage is defined by the dissimilarity of basic matrix properties, intrinsic defect structure, preferred Ce³⁺ ion disposition and charge compensation defect type. This is the reason of higher colorability and TL efficiency of as-grown Ce:LiSAF compared to Ce:LiCAF. Pre-filling of ultra-deep traps leads to enormous increases in the TL response. Due to these properties Ce:LiSAF and Ce:LiCAF are promising thermoluminescent dosimetric materials.     

Fluorescence lifetime of Nile Red as a probe for the hydrogen bonding strength with its microenvironment

The fluorescence lifetime of Nile Red (NR) is not sensitive to dielectric solvent–solute interactions but markedly decreases with the increase of the hydrogen bond donating ability in alcohols because vibrations associated with hydrogen bonding are involved in the deactivation process. The negligible viscosity effect indicates that twisting of the diethylamino moiety of NR does not play significant role in the dissipation of the excitation energy.     

Interaction of 2-hydroxy-substituted Nile red fluorescent probe with organic nitrogen compounds

The fluorescent properties of 2-hydroxy Nile red dye (HONR) proved to be highly sensitive to the basicity of hydrogen bond acceptors. Fluorescence quantum yields and fluorescence decay profiles were measured as the function of the concentration of organic nitrogen compounds in solvents of various polarities. The detailed mechanism and the kinetics of the fluorescence quenching were revealed with the combined analysis of the steady-state and time-resolved spectroscopic data. The relative contribution of the competing reaction steps was found to be very sensitive to the basicity of the additive and to solvent polarity. The most profound change appeared in the unimolecular deactivation pathways of the excited hydrogen-bonded HONR, whereas the formation rate of this species varied to a lesser extent. The dissociation into excited HONR and ground-state base was able to compete with the energy dissipation only when 2,4,6-trimethylpyridine was used as hydrogen bond acceptor in toluene. The bimolecular quenching of the excited hydrogen-bonded complex played significant role in apolar solvents. Proton displacement along the hydrogen bond in the excited complex led to excited ion pairs in polar media.     

Formation and stability of N-heterocyclic carbenes in water: the carbon acid pKa of imidazolium cations in aqueous solution

We report second-order rate constants kDO (M-1 s-1) for exchange for deuterium of the C(2)-proton of a series of simple imidazolium cations to give the corresponding singlet imidazol-2-yl carbenes in D2O at 25 degrees C and I = 1.0 (KCl). Evidence is presented that the reverse protonation of imidazol-2-yl carbenes by solvent water is limited by solvent reorganization and occurs with a rate constant of kHOH = kreorg = 10(11) s-1. The data were used to calculate reliable carbon acid pK(a)s for ionization of imidazolium cations at C(2) to give the corresponding singlet imidazol-2-yl carbenes in water: pKa = 23.8 for the imidazolium cation, pKa = 23.0 for the 1,3-dimethylimidazolium cation, pKa = 21.6 for the 1,3-dimethylbenzimidazolium cation, and pKa = 21.2 for the 1,3-bis-((S)-1-phenylethyl)benzimidazolium cation. The data also provide the thermodynamic driving force for a 1,2-hydrogen shift at a singlet carbene: K12 = 5 x 10(16) for rearrangement of the parent imidazol-2-yl carbene to give neutral imidazole in water at 298 K, which corresponds to a favorable Gibbs free energy change of 23 kcal/mol. We present a simple rationale for the observed substituent effects on the thermodynamic stability of N-heterocyclic carbenes relative to a variety of neutral and cationic derivatives that emphasizes the importance of the choice of reference reaction when assessing the stability of N-heterocyclic carbenes.     

Kinetic study of the reaction of CH3O with Br and Br2

The title reactions have been studied at room temperature by applying the discharge flow method coupled with laser induced fluorescence detection of methoxy radicals and resonance fluorescence detection of bromine atoms. The following rate constants were determined: CH₃O + Br Õ products (1) k ₁ (298 K) = (3.4 ± 0.4 (1)) × 10¹³ cm³ mol^-1 s^-1, CH₃O + Br₂ Õ products (2) k ₂ (298 K) £ 5 × 10⁸ cm³ mol^-1 s^-1.     

Energy Dissipation Processes of singlet‐excited 1‐Hydroxyfluorenone and its Hydrogen‐bonded Complex with N‐methylimidazole¶

Effects of solvent, pH and hydrogen bonding with N‐methylimidazole (MIm) on the photophysical properties of 1‐hydroxyfluorenone (1HOF) have been studied. Fluorescence lifetime, fluorescence quantum yield and triplet yield measurements demonstrated that intersystem crossing was the dominant process in apolar media and its rate constant significantly diminished with increasing solvent polarity. The acceleration of internal conversion in alcohols paralleled the strength of intermolecular hydrogen bonding. The faster energy dissipation from the singlet‐excited state in cyclohexane was attributed to intramolecular hydrogen bonding. The pK_a of 1HOF decreased from 10.06 to 5.0 on light absorption, and H₃O⁺ quenched the singletexcited molecules in a practically diffusion‐controlled reaction. On addition of MIm in toluene, dual fluorescence was observed, which was attributed to reversible formation of excited hydrogen‐bonded ion pair. Rate constants for the various deactivation pathways were derived from the combined analysis of the steady‐state and the time‐resolved fluorescence results.     

Cinchona based squaramide catalysed enantioselective Michael addition of α-nitrophosphonates to aryl acrylates: enantioselective synthesis of quaternary α-aminophosphonates

Several cinchona based squaramide catalysts were applied to the asymmetric Michael addition of α-nitroethylphosphonates to acrylic acid aryl esters, resulting in high yields and enantioselectivities. The absolute configuration of one of the quaternary α-nitrophosphonate adducts was deduced from its experimental and calculated CD spectra. The adducts were reduced to their cyclic aminophosphonates by catalytic hydrogenation.     

Efficient syntheses of zoledronic acid as an active ingredient of a drug against osteoporosis

The reaction of 1H-imidazol-1-ylacetic acid and two equivalents of phosphorus trichloride/phosphorous acid at 75?°C in sulfolane, or in the presence of catalytic amounts of [bmim][BF₄] afforded zoledronic acid in yields up to 75%. The joint use of the ionic liquid additive and sulfolane as the solvent was synergetic affording highly valuable zoledronic acid in a record yield of 93%.     

Some Properties of Polycaprolactone Composites with Cellulose Nanocrystals

Russian Journal of General Chemistry - Composites of polycaprolactone with cellulose nanocrystals were produced, and their morphological, thermal, and strength characteristics were examined. It was...