A Hexagonally Ordered Nanoporous Silica-Based Fiber Coating for SPME of Polycyclic Aromatic Hydrocarbons from Water Followed by GC–MS

A highly porous fiber coating material was prepared and functionalized with 3-amino propyl triethoxysilane (APTES) on hexagonally ordered nanoporous silica (SBA-15). Applicability of this coating was assessed employing a laboratory made solid-phase microextraction (SPME) device and gas chromatography–mass spectrometry for the simultaneous sampling and determination of trace polycyclic aromatic hydrocarbons (PAHs) from aqueous sample solutions. A one at the time optimization strategy was applied to investigate and optimize important extraction parameters such as extraction temperature, extraction time, ionic strength and sonication time. In the optimum conditions, the relative standard deviations for deionized water, spiked with selected PAHs were between 3.3 and 7.7% (n = 3), and detection limits for the studied compounds were 4.2 and 26.1 pg mL⁻¹. No significant change was observed in the extraction efficiency of the new SPME fiber, over 50 extractions. The proposed method was successfully applied to the extraction and determination of PAHs in the waste water samples.

     

Synthesis of Dialkyl 2‐(Alkylamino)‐4,9‐dihydro‐9‐oxocyclohepta[b]pyran‐3,4‐dicarboxylates

Dialkyl 2‐(alkylamino)‐4,9‐dihydro‐9‐oxocyclohepta[b]pyran‐3,4‐dicarboxylates are prepared in a one‐pot three‐component reaction of alkyl isocyanide, dialkyl acetylenedicarboxylate, and α‐tropolone (=2‐hydroxycyclohepta‐2,4,6‐trienone). The reaction proceeds smoothly at room temperature and under neutral conditions to afford tropolone derivatives in high yield.     

A Simple One‐Pot Synthesis of N‐Alkyl‐2,5‐diaryl‐1,3‐dioxol‐4‐amines

An efficient procedure for the synthesis of N‐alkyl‐2,5‐diaryl‐1,3‐dioxol‐4‐amines 3 via a one‐pot reaction of aromatic aldehydes 2 and alkyl isocyanides 1 at room temperature in good yields is described (Scheme 1, Table).     

Fabrication of superhydrophobic polymethylsilsesquioxane nanostructures on cotton textiles by a solution-immersion process

Superhydrophobic cotton textiles are prepared by a simple, one-step and inexpensive phase separation method under ambient conditions by which a layer of polymethylsilsesquioxane (PMSQ) nanostructures is covered onto the cellulose fibers. By changing the silane precursor concentration, PMSQ nanostructures with various shapes, morphologies and sizes were fabricated. Nanostructures were characterized using SEM, EDS, and attenuated total reflectance FTIR. The wettability of the modified cellulose surfaces was characterized with contact-angle goniometry and sliding angle technique, respectively. The water contact angle of modified cotton is measured to be higher than 150°, which is high enough to exhibit the lotus effect as a result of the superhydrophobicity. Tunable water-repellent properties of the fabric are also demonstrated, with sliding contact angles varying from "sticky" to "slippery" depending upon different nanostructures on the surface of the fibers. It is expected that this simple technique will accelerate the large-scale production of superhydrophobic cellulosic materials with new industrial applications.     

The extent of molecular orientation at liquid/vapor interface of pyridine and its alkyl derivatives by molecular dynamics simulation

In this paper, molecular dynamics simulation was performed to investigate the liquid∕vapor interfacial structure of neat polar liquids. Large-scale ensembles of liquid pyridine and its alkyl derivatives, 4-methylpyridine and 4-ethylpyridine, were simulated by classical molecular dynamics at 298 K. For the liquid system of low polarity, the surface density profile of the atoms meet exactly at the middle of interfacial region, and atoms of hydrophobic nature can be hardly discriminated from hydrophilic ones in either vapor or liquid sides. For a liquid system of high polarity, the density profile of atoms with different nature is highly discriminated all over the interfacial region, and as the polarity increases, a dense region of atomic density is clearly developed in the subsurface region. The recognized bivariate method was also used to study the molecular orientational distribution quantitatively. Orientational analysis of the three liquid systems indicates that the pyridine ring plane in the outmost surface tends to be vertical. Its tendency in the innermost interfacial region is parallel. The orientational states available to 4-ethylpyridine and pyridine are discriminated by predicting the possibility of a bisector-wise tumbling for the ring plane in pyridine and a side-wise tumbling in 4-ethylpyridine. The orientational distribution maps explain the trend of experimental surface tension and surface entropy. As the dipole moment of these liquids increases with the alkyl chain length, the surface structural profile changes from a regular definite one to a surface of complex atomic structure involving a dense phase near the interface. The development of dense region in alkyl derivatives is the result of segregation of molecules due to the alkyl group, which is captured and discriminated by molecular dynamics simulation even when the length of a short alkyl chain is increased by one carbon atom.     

Cadmium sulfide and cadmium phosphide thin films from a single cadmium compound

Aerosol-assisted chemical vapor deposition of Cd[(SP(i)Pr(2))(2)N](2) leads to the growth of cadmium sulfide and/or phosphide thin films on glass. Decomposition of the precursor has been studied by pyrolysis-gas chromatography/mass spectrometry and modeled by density functional theory.     

Fluorescent zinc(II) complex exhibiting "on-off-on" switching toward Cu2+ and Ag+ ions

Binuclear zinc(II) and copper(II) complexes based on a new Schiff base ligand N,N'-bis(2-hydroxybenzilidene)-2,4,6-trimethylbenzene-1,3-diamine (H(2)L) have been synthesized. The ligand H(2)L and complexes under investigation have been characterized by elemental analyses, spectral (FT-IR, (1)H, (13)C NMR, ESI-MS, electronic absorption, emission), and electrochemical studies. The structures of H(2)L and complexes [{Zn(C(23)H(18)N(2)O(2))}(2)] (1) and [{Cu(C(23)H(18)N(2)O(2))}(2)]·H(2)O (2) have been determined crystallographically. Selective "On-Off-On" switching behavior of the fluorescent complex 1 has been studied. The fluorescence intensity of 1 quenches (turns-off) upon addition of Cu(2+), while enhances (turns-on) in the presence of Ag(+) ions. The mechanisms of "On-Off-On" signaling have been supported by (1)H NMR, ESI-MS, electronic absorption, and emission spectral studies. Job's plot analysis supported 1:1 and 1:2 stoichiometries for Cu(2+) and Ag(+) ions, respectively. Association and quenching constants have been estimated by the Benesi-Hildebrand method and Stern-Volmer plot. Moreover, 1 mimics a molecular keypad lock that follows correct chemical input order to give maximum output signal.     

Alkynylation of benzotriazole with silylethynyliodonium triflates. Regioselective synthesis of 2-ethynyl-2H-benzotriazole derivatives

Phenyl(trimethylsilylethynyl)iodonium and tert-butyldimethylsilylethynyl(phenyl)iodonium triflates were applied to alkynylation of benzotriazole. Treatment of the silylethynyliodonium triflates with the potassium salt of benzotriazole ion in (t)BuOH and CH(2)Cl(2) gave 2-(trimethylsilylethynyl)-2H-1,2,3-benzotriazole and 2-(tert-butyldimethylsilylethynyl)-2H-1,2,3-benzotriazole in 74% and 76% yields, respectively. The regioisomers, 1-silylethynyl-1H-1,2,3-benzotriazole derivatives, were minor. In both cases of the silyl-substitued ethynyliodonium salts, novel regioselective alkynylation of benzotriazole at the 2 position was observed.     

Solvent‐free synthesis of new 2,4,6‐triarylpyridines catalyzed by a Brønsted acidic ionic liquid as a green and reusable catalyst

Some new 4‐(aryl)‐2,6‐di‐2‐naphthylpyridines and 4‐(aryl)‐2,6‐di‐2‐thienylpyridines have been prepared through three‐component condensation of 2‐acetylnaphthalene or 2‐acetylthiophene, aromatic aldehydes, and ammonium acetate in presence of 1‐(4‐sulfonylbutyl) pyridinium hydrogensulfate [(CH₂)₄SO₃HPy][HSO₄], a Brønsted acidic ionic liquid as a green and reusable catalyst in solvent‐free conditions. Also some new 4,4'‐(1,4‐phenylene)‐bis‐(2,6‐di‐aryl pyridine) was prepared. J. Heterocyclic Chem., (2011).