磺化酞菁在甲醇-水溶液中的二聚作用研究(英文)

研究了不同磺化度的酞菁在甲醇－水混合溶剂中的聚集行为．通过紫外－可见光谱测定，发现磺化度在1．0以上时染料在稀溶液中主要以单体和二聚体的形式存在，并可用简便的方法计算出聚集平衡常数和平衡时单体所占的百分比，得到磺化度越低越易聚集的结论．有关激发态的实验表明，增加酞菁磺化度有助于提高表观荧光量子产率，但对荧光寿命影响较小．

Effect of Substitution Site on Two-Photon Absorption and Excited States Properties of Lipid Droplets Detection NAPBr Dyes:a Theoretical Perspective

Two-photon fluorescence dyes have shown promising applications in biomedical imaging.However,the substitution site effect on geometric structures and photophysical properties of fluorescence dyes is rarely illustrated in detail.In this work,a series of new lipid droplets detection dyes are designed and studied,molecular optical properties and non-radiative transitions are analyzed.The intramolecular weak interaction and electron-hole analysis reveal its inner mechanisms.All dyes are proven to possess excellent photophysical properties with high fluorescence quantum efficiency and large stokes shift as well as remarkable two-photon absorption cross section.Our work reasonably elucidates the experimental measurements and the effects of substitution site on two-photon absorption and excited states properties of lipid droplets detection NAPBr dyes are highlighted,which could provide a theoretical perspective for designing efficient organic dyes for lipid droplets detection in biology and medicine fields.

One-step synthesis of fluorescent hydroxyls-coated carbon dots with hydrothermal reaction and its application to optical sensing of metal ions

Carbon dots (CDs) with average diameter of 3.1 ± 0.5 nm were facilely synthesized with candle soot through hydrothermal reaction in sodium hydroxide aqueous solution. The as-prepared CDs were covered with a lot of hydroxyls, possessed properties of good water-solubility, anti-photobleaching, salt tolerance, and low cytotoxicity, and had a fluorescence quantum yield (QY) of about 5.5%. The fluorescence of the hydroxyls-coated CDs could be selectively quenched by metal ions such as Cr3+, Al3+ and Fe3+, which is because these metals can easily combine with the hydroxyl groups on the surface of CDs and induce aggregation of hydroxyls-coated CDs. Experiments showed that the quenching of Cr3+ had a Sterm-Volmer constant of 1.03 × 107 M-1 with a liner range of 1.0-25.0 μM and detection limit of 60 nM (3σ).

Simultaneous determination of Repaglinide and Irbesartan in biological plasmas using micellar enhanced excitation-emission matrix fluorescence coupled with ATLD method

A highly sensitive and selective 3D excitation-emission fluorescence method has been proposed to rapidly quantify the combined antidiabetics Repaglinide(Re) and Irbesartan(Ir) in rat and human plasmas with the aid of second-order calibration method based on alternating trilinear decomposition(ATLD) method. Re and Ir with weak fluorescence can be endowed with strong fluorescent property by changing the microenvironment in samples and improving the fluorescence quantum yield by using an appropriate micellar enhanced surfactant. The enhanced excitation-emission matrix fluorescence of Re and Ir can be accurately resolved and can simultaneously attain the optimal concentration even in the presence of a potentially strong intrinsic fluorescence from complex biological matrices, such as rat and human plasmas, by using the ATLD method, which completely exploits the "second-order advantage". The average recoveries of Re and Ir obtained from ATLD with the factor number of 3(N=3) were 101.0%±4.3% and 99.1%±4.1% for rat plasma and 100.5%±5.4% and 97.1%±3.6% for human plasma. Several statistical methods, including Student's t-test, figures of merit, and elliptical joint confidence region, have been utilized to evaluate the accuracy of the proposed method. Results show that the developed method can maintain second-order advantage in simultaneous determinations of the weak fluorescent analytes of interest in different biological plasma matrices.

Synthesis and luminescence properties of the europium quaternary complexes nanoparticles

In this paper,the nanometer-sized(200 nm)quaternary rare-earth complex Eu(BA)(TTA)2phen was successfully prepared by using the method of optimizing chemical precipitation.The characterizations of these nanoparticles were performed by using elemental analysis,thermogravimetric analysis,infrared spectroscopy,fluorescence spectroscopy,transmission electron microscopy and luminescence quantum-yield.The results indicate that they are better than common ternary complexes at light-emitting performance,luminescence properties,thermal stability,uniformity and particle size;they can also be further mixed with a suitable polymer to form functional rare earth polymers.Compared to the common solid materials,the quaternary complex has better and unique characteristics such as nanoparticle size effect and surface effect.A foundation had been laid for the further expansion of its application in the field of light-emitting and magnetic materials.

Tuning the optical properties of BODIPY dye through Cu(Ⅰ) catalyzed azide-alkyne cycloaddition(CuAAC) reaction

Borondipyrromethenes(BODIPY) are a class of fluorescent dyes whose fluorescence quantum yields are generally high and independent of the solvent.In this paper,we report the synthesis of a new type of BODIPY compound that carries an azido group on the 3-position of the pyrrole core.The azido group quenches the fluorescence of the dye due to its weak electron-donating effect.The fluorescence of the BODIPY dye can be switched on after reacting with alkynes via a Cu(Ⅰ) catalyzed azide-alkyne cycloaddition(CuAAC) reaction.We further demonstrate that this azido-BODIPY compound can be used in the cell imaging applications.

Tunable ultraviolet to deep blue light emission from sulfur nanodots fabricated by a controllable fission-aggregation strategy

Bright tunable light emission in the short wavelength range from sulfur nanodots was demonstrated with a photoluminescence quantum yield(PLQY)of up to 59.4%.A fission-aggregation mechanism was proposed for the formation of sulfur nanodots with desired performances.This synthetic strategy allowed for simultaneous size control from 3.2 to 5.6 nm,thus tuning the emission color from ultraviolet(UV)to deep blue(342±430 nm),and for the suppression of unwanted nonradiative recombination centers and deep level emission.The luminescence mechanism and quantum confinement effect of the synthesized sulfur nanodots were investigated by optical spectroscopy and theoretical calculations.These results show promise toward the application of sulfur nanodots in UV optoelectronics,biomedical treatments,and sterilization.

Spontaneously bundled nanotubes exhibit greatly enhanced emission via inter-nanotube energy transfer

Spontaneously bundled nanotubes assembled from chiral perylene diimide molecules exhibit greatly enhanced emission via inter-nanotube excitation energy transfer. The formation of densely packed superstructures is an effective approach for high fluorescence quantum yield in assembled nanomaterials without compromising optoelectronic properties.

Photophysical properties of heteroaromatic ring-fused(di)benzosiloles

Benzosiloles fused to heterocycles such as thiophene, benzothiophene, and benzofuran, and indole- and benzosilole-fused dibenzosiloles were prepared by palladium-catalyzed intramolecular coupling of the corresponding 2-（arylsilyl）aryl triflates in good to high yields. Molecular and crystal structures of 5,7-dihydro-5,5,7,7-tetrakis（1-methylethyl）bis[1]benzosilolo-[2,3-b：3＇, 2＇-d]thiophene, 6-methyl-12,12-diisopropyl-12H-indololo[3,2-b][1]silafluorene, and 5,5,11,11-tetraisopropyl-5,11H-benzosilolo[3,2-c]silafluorene were determined by X-ray diffraction analysis. The UV absorption spectra of the （di）benzosilole derivafives in cyclohexane red-shifted when compared to 1,1-diisopropyldibenzosilole, indicating that replacing a benzene ring of dibenzosilole by the heterocycles as well as fusion of indole and benzosilole moieties onto dibenzosilole narrowed the HOMO- LUMO gaps of the n-conjugation system. The thiophene-fused benzosiloles were faintly fluorescent in solution and in the solid state, whereas the dibenzosiloles exhibited luminescence with moderate and high quantum yields in cyclohexane and in microcrystals, respectively. In other words, aggregation-induced emission was observed for the dibenzosiloles. Notably, 5,5,11,1 1- tetraisopropyl-5,11H-benzosilolo[3,2-c]silafluorene in microcrystals exhibited violet fluorescence （λmax = 396 nm） with a quantum yield of 0.70. Density functional theory （DFT） calculations of the prepared （di）benzosiloles were also performed.