A New Emissive Chalcone-Based Chemosensor Armed by Coumarin and Naphthol with Fluorescence “Turn-on” Properties for Selective Detection of F<Superscript>−</Superscript> Ions

A new chalcone-based probe containing coumarin and naphthol at both ends has been synthesized via aldol condensation. The uniqueness of the newly derived probe can be ascribed to the presence of naphthol and coumarin units acting as binding site and signaling element, respectively. The fluorogenic behaviors toward various anions were investigated. The probe was characterized by various spectroscopic techniques and the in-depth study led to show excellent selectivity and sensitivity for fluoride ions. The hydrogen bonding thus formed with fluoride anion provides remarkable fluorometric responses. The interactions of the probe with fluoride ions were determined by fluorescence, FT-IR and NMR spectroscopic techniques. The exploratory studies by fluorescent spectral changes augur well for the naked-eye sensing applications.     

Adsorption of azacrown ethers at solid–liquid interface. Contact angle and neutron reflectivity study

Adsorption of two alkylated N,N′-diaza-18-crown-6 ethers (decyl- and hexadecyl-derivatives, ACE-10 and ACE-16, respectively) on solid surfaces was studied by using contact angle and neutron reflectivity measurements. The solid substrates used were (a) Si covered with a native oxide layer (Si/SiO₂) and (b) Si with sputtered Pt layer (Si/Pt). The sensitivity of neutron reflectivity was drastically improved by applying the intermediate Pt layer of 150 Å, which gave rise to several Kiessig fringes in the experimentally accessible q-range. The position of the fringes is very sensitive to slight changes of the interfacial composition induced by adsorption of a thin monolayer, otherwise very difficult to detect. Unfortunately, in the studied case this sensitivity is immediately lost due to undesired adsorption of a protonated material on the Pt surface exposed to the lab air. A decrease of surface energy (increase of contact angle) of both Si/SiO₂ and Si/Pt upon exposure to toluene solutions of ACEs suggests that the latter are attached to the surface via the hydrophilic azacrown ether head with alkyl chains standing upright towards the liquid phase.     

Preparation,Characterization and Drug Release Behavior of 5-Fluorouracil Loaded Carboxylic Poly(ε-caprolactone) Nanoparticles

In this paper, 5-Fluorouracil (5-FU) loaded carboxylic poly(ε-caprolactone) nanoparticles have been prepared by emulsification/solvent evaporation o/w method, and the drug release behaviors of 5-FU were investigated. The novel carboxylic poly (ε-caprolactone) (P(CL-OPD)-mal) was synthesized via conjugation of maleic anhydride to sodium borohydride (NaBH₄) reduced poly(ε-caprolactone-co -4- carbonyl -ε-caprolactone) (P(CL-OPD)), while P(CL-OPD) was synthesized in bulk by ring-opening polymerization of ε-caprolactone and 4-carbonyl-ε-caprolactone (OPD) with stannous octoate as a catalyst. Their structures were confirmed by ¹HNMR, FT-IR and GPC. Dynamic light scattering (DLS), transmission electron microscopy (TEM), zeta potential measurements were used for nanoparticle characterization. TEM and DLS showed the nanoparticles were with spherical shape and uniform size distribution (mean diameter 70～100 nm), respectively. Zeta potential analysis revealed that the nanoparticles had an increased negative surface with the increase of carboxyl group concentration. UV spectroscopy was adopted to study the entrapment and release behaviour. The maximum 5-FU loading efficiency was 14.39% with the entrapment efficiency be 42%. In vitro release studies were performed in PBS at 37°C. Results of the study showed that the release behavior can be well-controlled, and the balanced release was up to 96 h. P(CL-OPD)-mal nanoparticles would provide increased benefit in biomedical and pharmaceutical applications.     

Comparison of Oxidative Aromatic Coupling and the Scholl Reaction

Does the dehydrogenative coupling of aromatic compounds mediated by AlCl₃ at high temperatures and also by FeCl₃, MoCl₅, PIFA, or K₃[Fe(CN)₆] at room temperature proceed by the same mechanism in all cases? With the growing importance of the synthesis of aromatic compounds by double C? H activation to give various biaryl structures, this question becomes pressing. Since some of these reactions proceed only in the presence of non‐oxidizing Lewis acids and some only in the presence of certain oxidants, the authors venture the hypothesis that, depending on the electronic structure of the substrates and the nature of the “catalyst”, two different mechanisms can operate. One involves the intermediacy of a radical cation and the other the formation of a sigma complex between the acid and the substrate. The goal of this Review is to encourage further mechanistic studies hopefully leading to an in‐depth understanding of this phenomenon.     

SPE–HPLC–MS/MS method for the trace analysis of tobacco‐specific N‐nitrosamines and 4‐(methylnitrosamino)‐1‐(3‐pyridyl)‐1‐butanol in rabbit plasma using tetraazacalix[2]arene[2]triazine‐modified silica as a sorbent

Tobacco‐specific N‐nitrosamines (TSNAs), including N′‐nitrosonornicotine, 4‐(methylnitrosamino)‐1‐(3‐pyridyl)‐1‐butanone, N′‐nitrosoanatabine, and N′‐nitrosoanabasine, have been implicated as a source of carcinogenicity in tobacco and cigarette smoke. We present a rapid and effective method comprising SPE based on tetraazacalix[2]arene[2]triazine‐modified silica as sorbent and analysis with HPLC–MS/MS for the determination of TSNAs and 4‐(methylnitrosamino)‐1‐(3‐pyridyl)‐1‐butanol (NNAL), a metabolite of 4‐(methylnitrosamino)‐1‐(3‐pyridyl)‐1‐butanone, in rabbit plasma. The linear dynamic ranges were 10–2000 pg/mL for NNAL and 4–2000 pg/mL for the four TSNAs with good correlation coefficients (>0.9965). The LODs were in the range of 0.9–3.7 pg/mL, and the LOQs were between 2.9 and 12.3 pg/mL. The accuracies of the method were also evaluated and found to be in the range of 90.1–113.3%. This method is promising to be applied to the preconcentration and determination of TSNAs and NNAL in smoke and human body fluids.