Synthesis of lariat organochalcogenoethers based on azacalix[3]arenes for the potentiometric detection of [UO2] ions

The syntheses of organochalcogen-supported azacalix[3]arenes are described in a one-pot manner in satisfactory yields. A remarkably selective potentiometric response was accomplished for uranyl ions over a variety of other metal ions, including alkali (Na⁺, K⁺), alkaline-earth (Mg²⁺, Ca²⁺, Ba²⁺), transition and heavy metal ions (Co²⁺, Ni²⁺, Cu²⁺, Ag⁺, Fe³⁺, Zn²⁺, Cd²⁺ and Pb²⁺) using an ion-selective electrode based on compound 3 incorporated into a polymeric (PVC) membrane.     

Sc(OTf)3-catalyzed alkylation of indoles with propargyl alcohols: an expeditious synthesis of 3-substituted indoles

Indoles undergo smooth alkylation with propargylic alcohols in the presence of 10 mol % of scandium triflate under mild conditions to produce 3-propargylated indoles in excellent yields with high selectivity.     

Lewis acid mediated SN2-type nucleophilic ring opening followed by [4+2] cycloaddition of N-tosylazetidines with aldehydes and ketones: synthesis of chiral 1,3-oxazinanes and 1,3-amino alcohols

A highly efficient strategy for Cu(OTf)₂ mediated S_N2-type nucleophilic ring opening followed by [4+2] cycloaddition reactions of enantiopure 2-phenyl-N-tosylazetidines with various aldehydes and ketones afforded a variety of substituted 1,3-oxazinanes and 1,3-amino alcohols in excellent yields, excellent de and good to excellent ee. The proposed S_N2-type mechanism of the cycloaddition reaction is supported by experimental evidence.     

An efficient synthesis of 2-(1-methyl-1,2,5,6-tetrahydropyridin-3-yl)morpholine: a potent M1 selective muscarinic agonist

2-(1-Methyl-1,2,5,6-tetrahydropyridin-3-yl)morpholine is useful for synthesizing potent antimicrobials including the arecoline derivatives, phendimetrazine and polygonapholine and was synthesised in nine steps with an overall yield of 36%. Bromination of 3-acetylpyridine and dehydration of a diol with cyclization were pivotal to the success of the strategy.     

Indium-mediated allylation/propargylation of α-diazoketones: a facile synthesis of 1-bromo-2-alkyl- or 2-arylpent-4-en-2-ols

α-Diazoketones undergo smooth allylation with successive bromide insertion with allylindium bromide generated in situ from allyl bromide and indium metal to produce 1-bromo-2-alkyl- or 2-arylpent-4-en-2-ols in high yields. Addition of propargylindium bromide produces 1-bromo-2-alkyl-or 2-arylpent-4-yn-2-ols under similar conditions.     

A cross-metathesis approach for the synthesis of tedanolide and 13-deoxytedanolide: stereoselective synthesis of the C3-C16 segment

A unified synthetic strategy has been devised for the synthesis of both tedanolide and 13-deoxytedanolide, which involves a cross-metathesis reaction as the key step. We report herein the stereoselective synthesis of the C3-C16 segment (+)-5b and subsequent manipulation of the C12-C13 double bond leading to the preparation of both tedanolides.     

One-pot general synthesis of metalloporphyrins

A new general one-pot method for the synthesis of various metalloporphyrins has been developed from pyrrole and substituted aldehydes using transition metal salts. This method allows higher working concentrations than those previously reported. Along with the reported metalloporphyrins, some new metalloporphyrins were synthesized in good yield.     

Fabrication and characterization of Meldola's blue/zinc oxide hybrid electrodes for efficient detection of the reduced form of nicotinamide adenine dinucleotide at low potential

We report the synthesis and the electrochemical properties of hybrid films made of zinc oxide (ZnO) and Meldola's blue dye (MB) using cyclic voltammetry (CV). MB/ZnO hybrid films were electrochemically deposited onto glassy carbon, gold and indium tin oxide-coated glass (ITO) electrodes at room temperature (25 ± 2 °C) from the bath solution containing 0.1 M Zn(NO₃)₂, 0.1 M KNO₃ and 1 × 10⁻⁴ M MB. The surface morphology and deposition kinetics of MB/ZnO hybrid films were studied by means of scanning electron microscopy (SEM), atomic force microscopy (AFM) and electrochemical quartz crystal microbalance (EQCM) techniques, respectively. SEM and AFM images of MB/ZnO hybrid films have revealed that the surfaces are well crystallized, porous and micro structured. MB molecules were immobilized and strongly fixed in a transparent inorganic matrix. MB/ZnO hybrid films modified glassy carbon electrode (MB/ZnO/GC) showed one reversible redox couple centered at formal potential (E⁰′) −0.12 V (pH 6.9). The surface coverage (Γ) of the MB immobilized on ZnO/GC was about 9.86 × 10⁻¹² mol cm⁻² and the electron transfer rate constant (ks) was determined to be 38.9 s⁻¹. The MB/ZnO/GC electrode acted as a sensor and displayed an excellent specific electrocatalytic response to the oxidation of nicotinamide adenine dinucleotide (NADH). The linear response range between 50 and 300 μM NADH concentration at pH 6.9 was observed with a detection limit of 10 μM (S/N = 3). The electrode was stable during the time it was used for the full study (about 1 month) without a notable decrease in current. Indeed, dopamine (DA), ascorbic acid (AA), acetaminophen (AP) and uric acid (UA) did not show any interference during the detection of NADH at this modified electrode.     

Physico-mechanical and free volume behaviour of guar gum filled polyurethane/polyacrylonitrile biodegradable composites

A series of different weight ratios of guar gum viz. 5, 10, 20 and 30 were incorporated into polyurethane/polyacrylonitrile (PU/PAN, 50/50) semi interpenetrating polymer networks (SIPNs) using polyethylene glycol-400, 4,4′-diphenyl methane diisocyanate, acrylonitrile, benzoyl peroxide and new metallic catalyst. The obtained polymer composites were subjected to biodegradation studies using specific fungi Aspergillus niger. The composites are characterized for physico-mechanical properties like density and tensile behaviour of the specimens before and after biodegradation. The positron annihilation lifetime spectroscopy (PALS) was used to monitor the content of free volume before and after biodegradation. The extent of degradation was examined by change in tensile behaviour and surface morphology. The influences of fungi on mechanical and morphological behaviour of filled IPNs are found to be interesting. The free volume changes in the composite systems correlates well with the mechanical properties.     

A p‐Hydroxyphenacyl–Benzothiazole–Chlorambucil Conjugate as a Real‐Time‐Monitoring Drug‐Delivery System Assisted by Excited‐State Intramolecular Proton Transfer

Among the well‐known phototriggers, the p‐hydroxyphenacyl (pHP) group has consistently enabled the very fast, efficient, and high‐conversion release of active molecules. Despite this unique behavior, the pHP group has been ignored as a delivery agent, particularly in the area of theranostics, because of two major limitations: Its excitation wavelength is below 400 nm, and it is nonfluorescent. We have overcome these limitations by incorporating a 2‐(2′‐hydroxyphenyl)benzothiazole (HBT) appendage capable of rapid excited‐state intramolecular proton transfer (ESIPT). The ESIPT effect also provided two unique advantages: It assisted the deprotonation of the pHP group for faster release, and it was accompanied by a distinct fluorescence color change upon photorelease. In vitro studies showed that the p‐hydroxyphenacyl–benzothiazole–chlorambucil conjugate presents excellent properties, such as real‐time monitoring, photoregulated drug delivery, and biocompatibility.