Real-time fluorescent quantitative immuno-PCR method for determination of fluoranthene in water samples with a molecular beacon

A reliable and sensitive competitive real-time fluorescent quantitative immuno-PCR （RTFQ-IPCR） assay using a molecular beacon was developed for the determination of trace fluoranthene （FL） in the environment.Under optimized assay conditions,FL can be determined in the concentration range from 1 fg/mL to 100 ng/mL,with y=0.194x ＋ 7.859,and a correlation coefficient of 0.967 was identified,with a detection limit of 0.6 fg/mL.Environmental water samples were successfully analyzed,recovery was between 90% and 116%,with intra-day relative standard deviation （RSD） of 6.7%-12.8% and inter-day RSD of 8.4%-15.2%.The results obtained from RTFQ-IPCR were confirmed by ELISA,showing good accuracy and suitability to analyze FL in field samples.As a highly sensitive method,the molecular beacon-based RTFQ-IPCR is acceptable and promising for providing reliable test results to make environmental decisions.

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（Cv）,entropy（S）,standard enthalpy of formation（ΔfH） and standard Gibbs free energy of formation（ΔfG）.The relations of Cv,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.

Low-cost dopant-free fluoranthene-based branched hole transporting materials for efficient and stable n-i-p perovskite solar cells

It has been widely recognized that hole transporting materials(HTMs)play a key role in the rapid progress of perovskite solar cells(PVSCs).However,common organic HTMs such as spiro-OMe TAD not only suffer from high synthetic costs,but also usually require the additional chemical doping process to improve their hole transport ability,which unfortunately induces the terrible stability issue.Therefore,it is urgent to develop low-cost dopant-free HTMs for efficient and stable PVSCs.In this work,we have successfully developed a new class of efficient dopant-free fluoranthene-based HTMs(TPF1–5)with quite low lab synthetic costs by combining donor-acceptor and branched structure designs.The detailed structure-property study revealed that tuning the twisted arms at different substitution sites would regulate the intermolecular interactions and film-forming ability,thereby significantly affecting the performance of the HTMs.By applying these HTMs in conventional PVSCs,the dopant-free TPF1-based devices not only achieved the best efficiency of 21.76%,which is comparable to that of the doped spiro-OMeTAD control devices,but also showed much better operational stability,which maintained over 87%of the initial efficiency under maximum power point tracking after 1038 h.

Facile synthesis and functionalization of fluoranthenes via intramolecular[4+2]annulations between thiophenes and alkynes

Fluoranthenes have attracted tremendous attention due to their unique optoelectronic properties and extensive applications.Although several synthetic methodologies have been developed for the preparation of fluoranthene derivatives,it is still unfavorable to functionalize the fluoranthene framework at different positions due to the relatively low selectivity and reactivity.Herein,a catalyst-free intramolecular[4+2]annulation between thiophenes and alkynes is developed towards the synthesis of fluoranthenes.Altogether 20 examples have been demonstrated using this method.Various functional groups can be precisely introduced into the fluoranthene skeleton at different positions by simply tuning the substituents on the thiophenes and alkynes.The conjugation of the fluoranthene can be facilely extended through different directions.Furthermore,the feasibility of this[4+2]annulation reaction is also investigated by density functional theory calculations.Therefore,this protocol provides not only a synthetic methodology towards fluoranthenes with substituents functionalized at different positions,but also an effective pathway to construct large polycyclic aromatic hydrocarbons containing fluoranthene moieties.

Toxicity of Fluoranthene and Its Biodegradation by Cyclotella caspia Alga

Fluoranthene Is one of the polynuclear aromatic hydrocarbons with four benzene rings. Because of Its toxicity, mutagenlclty, and carclnogenlclty, fluoranthene Is on the black lists of 129 and 68 priority pollutants established by US Environmental Protection Agency and the People＇s Republic of China, respectively. In recent years, the amount of fluoranthene In the aquatic environment has been Increasing with Increases In anthropogenlc discharge. Based on the biological investigation of tidal water In the Futlan mangrove, Cycioteila ~aspla was selected as the dominant algal species to determine the toxicity of fluoranthene towards C. caspla alga and to Investigate the blodegradatlon of fluoranthene by C. caspla under pure culture. The toxicity experiment showed that the 96-h EC50 value for fluoranthene was 0.2 mg/mL. Four parameters, namely C. caspla algal growth rate, chlorophyll （Chl） a content, cell morphology, and superoxlde dlsmutase （SOD） activity, were chosen as Indices of toxicity and were measured at 6 d （144 h）. The results showed that： （Ⅰ） the toxicity of fluoranthene towards C. caspla alga was obvious; （Ⅱ） C. caspla algal growth rate and Chl a content decreased with Increasing concentrations of fluoranthene; and （Ⅲ） the rate of cell deformation and SOD activity Increased with Increasing concentrations of fluoranthene. The blodegradatlon experiment showed that： （Ⅰ） the rate of physical degradation of fluoranthene was only 5.86%; （Ⅱ） the rate of blodegradatlon of fluoranthene on the 1st and 6th days （l.e. at 24 and 144 h） was approximately 35% and 85%, respectively; and （Ⅲ） the blodegradatlon capability of C. caspla alga towards fluoranthene was high. It is suggested that further Investigations on the toxicity of fluoranthene towards algae, as well as on algal blodegradatlon mechanisms, are of great Importance to use C. caspla as a biological treatment species In an organic wastewater treatment system.

Synthesis, crystal structure, and application of an acenaphtho[1,2-k] fluoranthene diimide derivative

Organic electron acceptor materials play an important role in organic electronics.Recently,many organic electron acceptors have been developed,in which aromatic fused-imides have proved to be a promising family of excellent electron acceptors.We report the first synthesis of a novel aromatic fused-imide,acenaphtho[1,2-k]fluoranthene diimide derivative(AFI),using lithium-halogen exchange and Diels-Alder reactions.The construction of a large conjugated plane and the introduction of electron-withdrawing imide groups endow AFI with a low lowest unoccupied molecular orbital(LUMO)level of 3.80 e V.AFI exhibits a regular molecular arrangement and strong - interactions in the single-crystal structure,which indicates its potential application in organic electronic devices.Solar cell devices that were fabricated using AFI as the electron acceptor and P3HT as the electron donor achieved an energy conversion efficiency of 0.33%.

Accumulation of polycyclic aromatic hydrocarbons from contaminated soil by Kandelia candel

The purpose of this study was to investigate the accumulation behavior of two typical PAHs, phenanthrene （PHE） and fluoranthene （FLA）, uptaken by the mangrove Kandelia candel in various treated sandy soils. The experiment lasted for three months. Soil and plant samples were collected after 3, 6, 9 and 13 weeks of the incubation and the levels of PAHs were analyzed using a GC/MS （HP6890-5975B）. The results showed that the root accumulations of PHE and FLA were elevated with the increase of the PAH concentrations in the soil. With prolonged exposure time, PHE and FLA concentrations of the roots increased significantly in comparison with the control. PHE and FLA concentrations of root after 13 weeks of treatment ranged from 0.28 to 4.36 #g.g-1 and 0.79 to 35.76 pg.g 1 respectively. The calculated mean values of the root concentration factors were 0.58 for PHE and 0.71 for FLA. This indicated that root accumulation of FLA was greater than PHE, which would result from the higher octanol-water partition coefficient （Kow） of FLA. These results underline the ability of mangroves to remove PAHs from contaminated marine substrates and hence their potential use in bioremediation and the removal of PAHs from the marine food chain.

PAHs Sorption and Desorption on Soil Influenced by Pine Needle Litter-Derived Dissolved Organic Matter

Study of the relationship between plant litter-derived dissolved organic matter(DOM) and organic pollutant transport in soil is important for understanding the role of forest litter carbon cycling in influencing pollutant behaviour and fate in forest soil.With the aim of providing insight into the capacity of plant litter-derived DOM to influence sorption and desorption of selected polycyclic aromatic hydrocarbons(PAHs) on soil, batch experiments were carried out with application of a sorption-desorption model incorporating DOM effects. Freshly fallen pine(Pinus elliottii) needles were used as the source of organic matter. Input of the pine needle litter-derived DOM was found to significantly decrease desorption hysteresis as well as soil adsorption capacity of phenanthrene(PHE) and fluoranthene(FLA). Addition of 1 728 mg L-1dissolved organic carbon(DOC) lowered the organic carbon-normalized sorption distribution coefficient of PHE from 7 776 to 2 541 L kg-1C and of FLA from 11 503 to 4 368 L kg-1C. Decreases of the apparent sorption-desorption distribution coefficients of PHE and FLA with increased DOC concentration indicated that DOM favored desorption of PAHs from soil. Increases in the fraction of apparently dissolved PAHs were attributable to the dissolved PAH-DOM complexes, accounting for the dissolved proportions of 39% to 69% for PHE and 26% to 72% for FLA in the sorption and desorption processes as the concentration of the added DOM solution rose from 0 to 1 728 mg L-1. Our results suggest that pine needle litterderived DOM can have a substantial effect of inhibiting PAHs sorption and promoting PAHs desorption, thus leading to enhanced leaching in soil, which should be taken into account in risk assessment of PAHs accumulated in forest soil.