Excitation Energy-Transfer Processes in the Sensitization Luminescence of Europium in a Highly Luminescent Complex

The excitation energy transfer (EET) pathways in the sensitization luminescence of Eu^III and the excitation energy migration between the different ligands in [Eu(fod)₃dpbt] [where fod=6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione and dpbt=2-(N,N-diethylanilin-4-yl)-4,6-bis(3,5-dimethylpyrazol-1-yl)-1,3,5-triazine], exhibiting well-separated fluorescence excitation and phosphorescence bands of the different ligands, were investigated by using time-resolved luminescence spectroscopy for the first time. The data clearly revealed that upon the excitation of dpbt, the sensitization luminescence of Eu^III in [Eu(fod)₃dpbt] was dominated by the singlet EET pathway, whereas the triplet EET pathway involving T₁(dpbt) was inefficient. The energy migration from T₁(dpbt) to T₁(fod) in [Eu(fod)₃dpbt] was not observed. Moreover, upon the excitation of fod, a singlet EET pathway for the sensitization of Eu^III luminescence, including the energy migration from S₁(fod) to S₁(dpbt) was revealed, in addition to the triplet EET pathway involving T₁(fod). Under the excitation of dpbt at 410 nm, [Eu(fod)₃dpbt] exhibited an absolute quantum yield for Eu^III luminescence of 0.59 at 298 K. This work provides a solid and elegant example for the concept that singlet EET pathway could dominate the sensitization luminescence of Eu^III in some complexes.     

Singlet Biradical Versus Triplet Biradical/Zwitterion Characteristics in Isomers of C6−C5−C6−C7−C6-Fused Pentacyclic Aromatic Hydrocarbons Revealed through Reactivity Patterns

Among various polycyclic aromatic hydrocarbons, C₆−C₅−C₆−C₇−C₆ fused pentacyclic aromatic hydrocarbons have the unique potential to adopt quinonoid, zwitterion, singlet, or triplet biradical electronic configurations. Two such hybrid structures between pentacene and azulene were synthesized and their ground state electronic configurations were deduced from the reactivity patterns they exhibit respectively. Compound 6 , where the radicaloid carbons are linked through a para-phenylene, forms a head-to-head dimer like a singlet biradical. In contrast, isomer 7 , where the para-linkage was switched to meta, reacts readily with oxygen which resembles the reactivity of a triplet state. The oxidized intermediate(s) then undergoes rearrangement to furnish the C₆−C₅−C₆−C₆−C₆ ring contraction product 13 . Cation 14 , the protonated form of 7 , was synthesized, which implies 7 also reacts like a zwitterion. It was revealed the oxidative rearrangement takes place even with mesityl dibenzotropylium cation despite its perceived aromaticity. DFT calculations confirm the most stable forms of 6 and 7 are singlet and triplet diradical, which is consistent with the observed reactivity of respective molecules.     

The effect of CTAB on Na2SO4 nucleation in mixed Na2SO4/CTAB aerosols by FTIR-ATR technology

FTIR-ATR technology is used to study the efflorescence kinetic of Na_2SO_4 and mixed Na_2SO_4/CTAB aerosols.As the RH decreased linearly,the v_3-SO_4~2 band shifts from 1094 cm~1 to 1132 cm~1,suggesting the phase transition of Na_2SO_4 from solution to crystal phase(Ⅲ).For pure Na_2SO_4 aerosols,the ERH is 75.1%RH,whereas the efflorescence point of mixed Na_2SO_4/CTAB aerosols(74.2%) is lower.By further analysis of IR differential spectra,the ratio of Na_2SO_4 crystals in mixed aerosols is only 62.7%and the heterogeneous nucleation rate of Na_2SO_4 in Na_2SO_4/CTAB mixed aerosols is lower than that in pure Na_2SO_4 aerosols.They showed that CTAB assembled into reversed micelle and part Na_2SO_4 droplets are in the core to form core-shell structure,and CTAB shell prevents core Na_2SO_4 solutions from crystallizing.However,the counter ion Br for CTAB reversed micelle can interact with Na~+ ions,which decreases the crystallization rate of free Na_2SO_4 droplets and ERH is delayed.     

Temperature responsive methacrylamide polymers with antibacterial activity

<正>A new methacrylamide monomer,hexylamine methacrylamide(MAHA),was synthesized and used in polymerizations.The homopolymer of MAHA and its copolymers were synthesized by free radical polymerization techniques with N-isopropyl acrylamide(NIPAAm) in two different compositions.The quaternization of the homopolymer and copolymers were carried out using 1-bromopropane.The copolymers with NIPAAm and a low MAHA content showed temperature-responsive behavior in an aqueous environment.The lower critical solution temperatures(LCSTs) of these polymers varied between 32℃and 44℃.The LCSTs of quaternized copolymers were higher than those of neutral copolymers because they were more hydrophilic.The obtained homopolymers and copolymers were tested for antibacterial activities against S.aureus and E.coli.The quaternized water-soluble copolymers showed antibacterial activities against S.aureus.The quaternization resulted in the synthesis of both antibacterial and temperature-responsive copolymers.     

Stepwise ordering of imidazolium-based cationic surfactants during cooling-induced crystallization

Surfactants bearing imidazolium cations represent a new class of building blocks in molecular self-assembly. These imidazolium-based cationic surfactants can exhibit various morphologies during phase transformations. In this work, we studied the self-assembly and phase behavior of 1-hexadecyl-3-methylimidazolium chloride (C(16)mimCl) aqueous dispersions (0.5-10 wt %) by using isothermal titration calorimetry, differential scanning calorimetry, synchrotron small- and wide-angle X-ray scattering, freeze-fracture electron microscopy, optical microscopy, electrical conductance, and Fourier transform infrared spectroscopy. It was found that C(16)mimCl in aqueous solutions can form two different crystalline phases. At higher C(16)mimCl concentrations (>6 wt %), the initial spherical micelles convert directly to the stable crystalline phase upon cooling. At lower concentrations (0.5 or 1 wt %), the micelles first convert to a metastable crystalline phase upon cooling and then transform to the stable crystalline phase upon further incubation at low temperature. The electrical conductance measurement reveals that the two crystalline phases have similar surface charge densities and surface curvatures. Besides, the microscopic and spectroscopic investigations of the two crystalline phases suggest that the metastable crystalline phase has preassembled morphology and a preordered submolecular packing state that contribute to the final stable crystalline structure. The formation of a preordered structure prior to the final crystalline state deepens our understanding of the crystallization mechanisms of common surfactants and amphiphilic ionic liquids and should thus be widely recognized and explored.     

Micro-Raman observation on the HPO4(2-) association structures in an individual dipotassium hydrogen phosphate (K2HPO4) droplet

A single K(2)HPO(4) droplet with size of ～50 μm on a Teflon substrate was forced to enter into the supersaturated state by decreasing the relative humidity (RH), allowing accurate control over the concentration of the solute within a droplet of a nanogram. The K(2)HPO(4) solutions from dilute (0.1-1.0 mol·L(-1) bulk) to concentrated state (a droplet from RH 98.2% to 25.1%) were studied through micro-Raman spectroscopy in the spectral region of about 200-4000 cm(-1). The area ratio between the water stretching band to the sum of the ν(1)-PO(3), ν(2)-POH, and ν(4)-PO(3) bands of the HPO(4)(2-) at various RHs was used to describe the dehydration behavior of a microsized single K(2)HPO(4) droplet in dehumidifying process. The peak position of the v(1)-PO(3) band for the 1 mol·L(-1) bulk solution appeared at 991 cm(-1) and moved to 986 cm(-1) at 98.2% RH, to 978 cm(-1) at 70.2% RH, and then to 964 cm(-1) at 30.0% RH for a droplet, accompanying an increase of the full width at half-height (fwhh) of this peak from 16.3 to 17.2, 22.2, and then to 24.2 cm(-1), indicating transition of the HPO(4)(2-) anions from monomers to dimers/trimers/oligomers and then to polyanions with chain structures in the K(2)HPO(4) solutions. After 25.1% RH, the solid was proved to be K(2)HPO(4)·3H(2)O according to the Raman spectral features. Furthermore, the O-H stretching envelope of a K(2)HPO(4) droplet showed that the intensity ratios of the strong hydrogen bonding component (3255 cm(-1)) to the weak one (3417 cm(-1)) and the cage-like water (2925 cm(-1)) to the weak one (3417 cm(-1)) were sensitive to the HPO(4)(2-) association structures, which can be used to understand the effects of dimers/trimers/oligomers and chain structures of the HPO(4)(2-) associations on the hydrogen bonding of water molecules.     

浓香型烤烟矿质元素含量的测定及分析

测定了河南省主产烟区烤烟K、Cl、Ca、Mg、S、P的含量,结果表明K的含量偏低,其他矿质元素含量正常.元素间的相关性分析结果表明多种矿质元素间存在极显著或显著的相关;对6种矿质元素含量进行因子分析得到2个因子,2个因子的累积贡献率为80.710％.     

血浆中极长链脂肪酸的毛细管气相色谱分析

建立了血浆中极长链脂肪酸毛细管气相色谱法，并用于测定了１０例正常人和４例临床拟诊为肾上腺白质营养不良（ＡＬＤ）病人血浆中极长链脂肪酸，其中一例肯定了ＡＬＤ的临床诊断。     

Investigation of third-order nonlinear optical properties of two azo-nickel chelate compounds

This paper investigates the third-order nonlinear optical properties of two azo-nickel chelate compounds by the optical Kerr gate method at 830 nm wavelength with pulse duration of 120 fs. Both of the two compounds exhibited large third-order optical nonlinearity. The second-order hyperpolarizability,γ, of Compound 1 is of 1.0 × 10^-31 esu. Due to the charge transfer, the γ of Compound 2 with electron donor and acceptor group is 4.9 × 10^-31 esu, which is a four-time enhancement in comparison with Compound i. The absorption spectra show that the electron push-pull effect, which induces intramolecular charge transfer, leads to the increased optical nonlinearity.