A simple route to derivatives of benzo[j]fluoranthene

3,6,8,11-Tetramethoxybenzo[j]fluoranthene can be made from 1,6-dimethoxynaphthalene in a one-pot ferric chloride oxidation/methanol reduction procedure. The reaction is tolerant of the presence of substituents in the 7-position of the naphthalene nucleus and provides a quick and easy route to these particular benzo[j]fluoranthenes. The reactions presumably proceed through initial formation of a bond between the 4-positions of two naphthalene molecules followed by closure of the five-membered ring. Indeed in one case some 4,4′-binaphthyl was isolated from the reaction mixture and it was generally found that better yields of the benzo[j]fluoranthrenes were obtained starting from the 4,4′-binaphthyl rather than by using the naphthalene as the starting material. In an analogous manner to the ring-closure of the 4,4′-binaphthyls, starting from a hexakisalkoxyphenylnaphthalene, a hexakisalkoxyfluoranthene could be obtained.     

Highly Curved Bowl‐Shaped Fragments of Fullerenes: Synthesis,Structural Analysis,and Physical Properties

Highly curved buckybowls 3 , 4 , and 5 were synthesized from planar precursors, fluoranthenes 8 , benzo[k]fluoranthenes 10 and naphtho[1,2‐k]‐cyclopenta[cd]fluoranthenes 12 , respectively, using straightforward palladium‐catalyzed cyclization reactions. These fluoranthene‐based starting materials were easily prepared from 1,8‐bis(arylethynyl)naphthalenes 6 . Both buckybowls 3 and 4 are fragments of C₆₀, whereas 5 is a unique subunit of C₇₀. The curved structures were identified by X‐ray crystallography, and they are deep bowls. The maximum π‐orbital axis vector (POAV) pyramidalization angle in both 3 and 4 is 12.8°. Such a high curvature is very rarely obtained. Buckybowls 5 are less curved than the others because they have a lower density of five‐membered rings, analogous to the tube portion of C₇₀. Cyclopentaannulation increases the bowl depths of 3 and 4 , but not the maximum POAV pyramidalization angle. Among the eight buckybowls studied herein, five form polar crystals. The bowl‐to‐bowl inversion dynamics of these buckybowls can be classified into two types; one has a planar transition structure, whereas the other has an S‐shaped transition structure. A larger longitudinal length of these buckybowls corresponds to a stronger preference for the latter. The photophysical properties of these buckybowls were examined and compared with those of C₆₀ and C₇₀. Buckybowls 5 have absorption bands at wavelengths greater than 450 nm, which are similar to those of C₇₀. The chiral resolution of the mono‐substituted buckybowl 4 ac was also studied by using HPLC with a chiral column.     

SERS signal response and SERS/SERDS spectra of fluoranthene in water on naturally grown Ag nanoparticle ensembles

We present experimental results of the time‐dependent Raman signal response of fluoranthene adsorbed on a naturally grown Ag nanoparticle ensemble, which serves as surface enhanced Raman scattering (SERS) substrate. In addition, SERS characteristics such as the concentration‐dependent calibration curves and the limit of detection (LOD) for fluoranthene in distilled water will be shown. The SERS substrate was prepared by Volmer–Weber growth under ultrahigh vacuum condition and exhibits a plasmon resonance wavelength at 491 nm. For the measurement of SERS signal response and SERS/shifted excitation Raman difference spectroscopy spectra of fluoranthene in water, experimental Raman setup containing a microsystem light source with two emission wavelengths (487.61 nm and 487.91 nm) was used. We experimentally demonstrate that the maximum SERS intensity is achieved 9 min after changing the analyte concentration from 0 nmol/l to 600 nmol/l. This response time is explained by a time‐dependent adsorption of the probe molecules onto the nanoparticles. The LOD for fluoranthene in water was evaluated applying shifted excitation Raman difference spectroscopy (SERDS) at different molecule concentrations. For SERDS, two emission wavelengths of a prototype microsystem light source have been used for Raman excitation. The experimental results reveal that the LOD for the probe molecules is very low. Experimentally, we have detected a fluoranthene concentration of only 4 nmol/l, which is very close to our estimated LOD of 2 nmol/l. Thus, the presented Raman setup, with a SERS substrate, whose plasmon resonance coincides with the excitation wavelength for SERS measurements, is well suited for in‐situ trace detection of pollutant chemicals in water. Copyright © 2013 John Wiley & Sons, Ltd.     

宽时域宽频域分子荧光寿命测试系统

设计组装了宽时域和宽频域的激光光源分子荧光寿命测试系统。系统中配置了Ｎ２分子激光，Ｎｄ：ＹＡＧ激光及其泵浦的染料激光和美国ＥＧ＆Ｇ公司的４４００型信号检测和分析系统，通过对硫酸奎宁，荧蒽和稀土络合物典型样品的检测表明该仪器系统性能稳定，结果可靠。     

A Reinvestigatton of the 13C-NMR Chemical Shift Assignments of Fluoranthene

Disparities in the protonated carbon NMR chemical shift assignments of the polynuclear aromatic molecule, fluoranthene, have been noted. Using two-dimensional ¹³C- ¹³C double quantum coherence, the ¹³C-NMR chemical shift assignments were reinvestigated and a set of unequivocal assignments obtained.     

聚二甲基硅氧烷溶胶凝胶气相毛细管柱与传统毛细管柱的柱容量比较

 将十一烷和荧蒽分别注入溶胶 凝胶法涂渍的聚二甲基硅氧烷气相毛细管柱和传统的聚二甲基硅氧烷毛细管柱并测量柱效率。在注射量增加到一定程度以后,柱效率迅速下降。能引起柱效率下降10%的注射量称之为柱容量。实验结果表明溶胶 凝胶聚二甲基硅氧烷柱的柱容量远高于传统聚二甲基硅氧烷柱的柱容量。对溶胶 凝胶聚二甲基硅氧烷柱有较高柱容量的原因进行了探讨。     

Electrochemical Properties of the Sandwich and Carbonyl π-Complexes of Chromium with Fluoranthene

Redox properties of mono- and binuclear -complexes of Cr with fluoranthene with the composition of (⁶-C₁₆H₁₀)Cr(⁶-C₆H₆), (⁶-C₁₆H₁₀)Cr(CO)₃ and (-⁶,⁶-C₁₆H₁₀)Cr₂(⁶-C₆H₆)(CO)₃ are studied by cyclic voltammetry. Relations between half-wave potentials of redox processes and coordination sites of fragments Cr(⁶-C₆H₆)- and Cr(CO)₃ with the ligand and their nature are found.     

荧蒽修饰的四苯基乙烯衍生物:分子合成、聚集增强荧光特性及其对苦味酸的高灵敏度检测

由于聚集体和固态发光量子效率高等优点,因此聚集诱导发光（AIE）材料成为光电功能材料研究领域的热点,拓展AIE分子体系始终是这一领域中的关键和基础的科学问题.通过Suzuki-Miyaura偶联这一条件较为温和的反应,将AIE生色团四苯基乙烯（TPE）与荧蒽直接共轭键接,制备得到单荧蒽和双荧蒽修饰的TPE衍生物TPE-FA与TPE-DFA,它们具有聚集增强荧光（AEE）行为,聚集体发射峰值波长分别在477和494 nm,固体薄膜的绝对荧光量子产率高达74.1%和40.4%.它们可以高灵敏地检测苦味酸,荧光猝灭常数大,检出限低于1 μg·g^-1.这两种AEE分子可望用于其它多硝基取代的芳香类吸电子分子的检测.     

光纤荧光法对吸附于红树叶片表面上荧蒽的测定

利用光纤荧光法实现了吸附于白骨壤(Am)、海漆(Ea)、秋茄(Kc)、桐花树(Ac)和老鼠簕(Ai)叶片表面上荧蒽(Fla)的定量测定.所建方法测定吸附于Am、Ea、Kc、Ac和Ai叶片表面上Fla的线性范围分别为2.5 ～500、2.0 ～600、4.5 ～1 100、15 ～600、3.5 ～450 ng/spot,相应的检出限分别为0.91、0.63、1.12、3.52、1.40 ng/spot,方法的相对标准偏差小于7.8%(n=15),加标回收率分别为97% ～108%、78% ～95%、77% ～90%、84% ～108%和78% ～102%.利用所建方法考察了5种红树叶片正反面吸附不同量Fla的信号强度随时间的变化情况.结果表明:在200 min内,叶片正反面上Fla的信号均发生不同程度的衰减,且反面的信号衰减率大于正面;5种红树叶片正反面对Fla的吸附特性均不同;吸附于叶片正面的Fla多残留在叶片表面,而吸附于叶片反面的Fla易向叶片内部迁移.     

Theoretical Studies on the Molecular Structures and Thermodynamic Properties of Polychlorinated Fluoranthenes

DFT-B3LYP/6-311G** method has been used to optimize molecular geometric structures of 527 polychlorinated fluoranthene(PCFRT) congeners and calculate their thermo-dynamic properties in the ideal gas state,such as heat capacity at constant volume(Cv),entropy(S),standard enthalpy of formation(ΔfH) and standard Gibbs free energy of formation(ΔfG).The relations of Cv,S,ΔfH and ΔfG with the number and position of chlorine atoms have also been explored,from which the relative stability of PCFRT congeners was theoretically proposed according to the magnitude of the relative standard Gibbs free energy of formation(Δr,fG).It was found that some of the PCFRT isomers are in a nonplanar configuration and there are intramolecular Cl…Cl weak interactions in some of the isomers.With increasing the number of chlorine atoms,the values of ΔfH and ΔfG of the most stable PCFRT isomers decrease initially and then increase.The values of ΔfH and ΔfG of PCFRT congeners with the same number of chlorine atoms show a strong dependence on the positions of chlorine atoms.The relative thermodynamic stability of PCFRT isomers is determined mainly by intramolecular adjacent Cl…Cl nuclear repulsive interaction between Cl atoms at two different six-membered rings.Most PCFRT congeners are easier to form thermodynamically than their parent compound.