吖啶类衍生物的荧光性质

用比较法测得23种啶类衍生物的荧光量子效率（Φf)，以评估这些化合物的荧光性质，结果表明，N－烃基吖啶酮类化合物的荧光量子效率要比9－取代苯基吖啶类和9－取代苯亚甲基－10－甲基－9，10－二氢吖啶类化合物的荧光量子效率大，在非极性溶剂中，9－聚代苯亚甲基－9，10二氢吖啶分子内的强吸电子基NO2增强荧光量子效率，强推电子基OCH3降低荧光量子效率，这些测量结果与取代基的电子作用经验规律不相符，这种现象可以用分子内电荷转移理论进行解释。     

Determination of Aggregation Parameters of Hexadecyltrimethylammonium Bromide from Probe Absorption

The mean aggregation number (n) and the critical micelle concentrations (CMC) of reverse micelles formed by hexadecyltrimethylammonium bromide have been determined by means of an optical absorption probe (acridine orange). The procedure to obtain these quantities from absorption spectrophotometric measurements is described. The CMC and mean aggregation number are in satisfactory agreement with published results obtained from more sophisticated methods.     

Investigation of the interaction between acridine orange and bovine serum albumin

The results from the measurement of the fluorescence spectrum showing the binding characteristics of acridine orange (AO) and bovine serum albumin (BSA) are reported. It was found that the equilibrium constant k=4848.64 l mol⁻¹, and the number of binding sites n=0.82. Based on the mechanism of the Forster energy transference, the transfer efficiency of energy and distance between the acceptor AO and BSA were found. The interaction between AO and BSA have been verified as consistent with the static quenching procedure and the quenching mechanism is related to the energy transfer.     

Synthesis and photochromic properties of novel yellow developing photochromic compounds

Two 1-thiazolyl-2-thienylcyclopentene derivatives, 1a and 2a, and a 1-thiazolyl-2-vinylcyclopentene derivative 3a have been synthesized in an attempt to obtain photochromic compounds which change the color from colorless to yellow, and have low photocycloreversion quantum yields and high absorption coefficients of the colored isomers. All of these compounds underwent reversible photochromic reactions. Compounds 1a and 2a in toluene solutions changed the color upon 313 nm light irradiation from colorless to orange and pink, in which absorption maxima were observed at 494 nm (ε=10,000 M⁻¹ cm⁻¹) and 525 nm (ε=8500 M⁻¹ cm⁻¹), respectively. On the other hand, the colorless toluene solution of 3a turned yellow upon irradiation with 313 nm light, in which the absorption maximum was observed at 416 nm (ε=17,100 M⁻¹ cm⁻¹). The photocyclization/cycloreversion quantum yields of 3 were 0.19 and 0.0014, respectively. The conversion from the open- to the closed-ring isomer of 3 in the photostationary state under irradiation with 313 nm light was close to 100%.     

Analysis of the Chemical Composition of Red Pigments and Inks for the Characterization and Differentiation of Contemporary Prints

Prints are one of the most popular artistic forms. They consist of an original matrix that is printed on a paper support. The stamps are part of a series, and each series is composed of a particular number of prints. Many contemporary prints are made using oil inks and synthetic pigments (reds and yellows). Inks are mainly composed of pigments (organic or inorganic) and a binding medium. The analysis of inks has the potential to facilitate and complement the identification of stamps of different origins.

Fourier transform infrared spectroscopy (FTIR) and Scanning Electron Microscopy-Energy Dispersive X-ray (SEM-EDX) are techniques that are typically available in museums and centers related to the study of works of art. Both can be classified as micro-destructive and provide complementary information about the organic and some inorganic compounds (FTIR), and the elemental composition (SEM-EDX). In this article, the two techniques were used to analyze the composition of red ink in prints. As a result of these analyses, it was possible to distinguish among nearly all of the pigments and inks, indicating that the composition of the red ink can be reliably used to differentiate between stamps of different origins in a series of prints.     

The use of different dispersive Raman spectrometers for the analysis of uranium compounds

The performances of three different Raman spectrometers were compared and evaluated as a suitable tool for the analysis of a range of uranium compounds with a view to application in nuclear forensics. These included uranium ore concentrates of different chemical composition and uranium dioxide in the form of powder and sintered fuel pellet. The three spectrometers are termed as ‘portable’ or ‘hand-held’ from Ahura Scientific (785 nm), ‘Senterra’ from Bruker (532 and 785 nm), ‘T64000′ from HORIBA Jobin Yvon (488.0, 514.5, 647.1 and 752.5 nm). Figures of merit such as sensitivity, signal-to-noise ratio and detection capability were compared. The portable Raman displayed fairly good sensitivity and process related impurities could be detected despite the miniaturisation but it was unable to measure darkly coloured powders such as calcined ore concentrates or uranium dioxide powder. The bench-top spectrometer Senterra had the best sensitivity for all the seven measured uranium compounds and the best signal-to-noise ratio for six of the compounds. Laboratory T64000 had the best resolution and at the same time resulting in the poorest sensitivity among the three spectrometers for all compounds measured. However, T64000 has very low level of noise therefore leading to better signal-to-noise that were comparable, if not better than the portable or Senterra. All industrial compounds measured in this study could not be measured with higher frequency laser thus impeding the observation of N–H or O–H vibration bands, of which the latter could be observed with laboratory synthesized material.     

Highly sensitive inhibitory kinetics fluorescence method for determination of arsenic

A new and highly sensitive inhibitory kinetic fluorescence method for the determination of arsenic (III) has been established based on its inhibitory effect on the oxidation reaction of Acridine red (ADR) by KBrO₃ in sulphuric acid medium. The reaction has been followed by measuring the enhancement of fluorescence at 550?nm. It relies on the linear relationship where the change in the fluorescence (ΔF) versus added As(III) amounts in the range of 0–0.450?µg?mL^?1 is plotted, under the optimum conditions. The sensitivity of the proposed method, i.e. the limit of detection, is 2.1?×?10^?2?ng?mL^?1. The method is featured with good accuracy and reproducibility for arsenic (III) determination. This method was successfully applied for the quantitative determination of arsenic (III) in food products samples, and the relative standard deviations and the recoveries were in ranges of 2.31–2.83% and 90.0–107.2%, respectively. A review of recently published catalytic or inhibiting kinetic methods for the determination of arsenic (III) has also been presented for comparison. The mechanism of reaction was studied.     

Base mediated synthesis of α-aminated aroyl/acetylnaphthalenes through [4+2] annulations

We have developed a base promoted simple, efficient and alternative approach for the synthesis of 4-amino-3-aroyl//heteroaroyl/acetyl-2-methylsulfanyl-naphthalene-1-carbonitriles by reaction of easily accessible 3,3-bis(methylthio)-1-aryl/heteroaryl/acetylprop-2-en-1-one and 2-cyanomethyl-benzonitrile. Reaction of 1-(2-halo/methoxy-phenyl)-3,3-bis(methylthio)prop-2-en-1-one and 2-cyanomethyl-benzonitrile under basic conditions also afforded 6-(methylthio)-7-oxo-7,12-dihydrobenzo[c]acridine-5-carbonitrile along with usual product. Structure of the synthesized product has been confirmed by single X-ray crystallography.     

Effect of denaturation of DNA on the molecular organization of a fluorescent dye in ultra thin films

Acridine Orange (AO) forms H-dimer in solid state and in ultra thin films. However, H dimer of AO reduces its efficiency as a usefull material for fluorescence probe. In the present work detailed investigations has been done on the interaction of AO with different forms of DNA in order to check the effectiveness in controlling the dimeric sites of AO in the Layer by Layer (LbL) self assembled film. It was found that single stranded DNA (ssDNA) is most effective than the dsDNA and coil-shaped DNA in controlling the dimeric sites of AO in LbL film.     

Luminescence in GaN co-doped with carbon and silicon

GaN samples, containing various concentrations of carbon and doped intentionally with silicon, have been grown heteroepitaxially on sapphire using metal-organic-chemical-vapor deposition. Previous electrical and optical data, together with Density Functional calculations, have suggested that carbon is incorporated at acceptor and donor substitutional sites in this material; the relative importance of each is determined by the Fermi level position and the growth conditions. Here the luminescence behavior of these materials is examined in more detail, including spectral, temperature, and time dependences under ultraviolet light and electron beam excitation conditions. Particular attention is given to the commonly observed “yellow band” at , a blue luminescence at seen only in samples where carbon is the majority dopant, and ultraviolet bands near . Our data suggest that the latter two bands are both donor-acceptor related with the final state being the negatively charged state of a carbon atom substituting for nitrogen. In samples where carbon is the majority dopant, extended luminescence excitation at low temperatures results in large changes in the brightness of the yellow and blue luminescence bands. These effects are similar to other recent observations of luminescence metastability in high resistivity GaN, and we suggest that carbon plays a crucial role in this phenomenon.