Syntheses and structural characterizations of 2-pyridyl(N/O)spirocyclotriphosphazene derivatives

The Cl exchange reaction of hexachlorocyclotriphosphazene, N₃P₃Cl₆ (1), with one equimolar amount of sodium salt of N/O donor type bidentate ligand containing a 2-pyridyl pendant arm (2) afforded, regioselectively, the partly substituted 2-pyridyl(N/O)spirocyclotriphosphazene (3; with a yield of 65%) in THF. The reactions of 3 with excess pyrrolidine, morpholine and 1,4-dioxa-8-azaspiro[4,5]decane (DASD) led to the formation of the tetraamino-2-pyridyl(N/O)spirocyclotriphosphazenes (3a-3c) in high yields. Compound 3 also gave both tetrapiperidino (3d) and gem-bispiperidino (3e) products with excess piperidine. The structures of all the compounds were determined by elemental analyses, ESI-MS, FTIR, HSQC, HMBC and ¹H, ¹³C, and ³¹P NMR techniques. The crystal structure of 3c was identified by single crystal X-ray crystallography. Besides, the compound 3e had one stereogenic P atom, and its chirality was verified by ³¹P NMR spectroscopy in the presence of (S)-(+)-2,2,2-trifluoro-1-(9’-anthryl)-ethanol (CSA).     

Design of multiple-target chemoprobe: “naked-eye” colorimetric recognition of Fe3+ and off–on fluorogenic detection for Hg2+ and its on-site applications

A novel multiple-target chemoprobe (E)-N′-((9-pentyl-9H-carbazole-3-yl)methylene)thiophene-2-carbohydrazide (CTH) was designed, successfully synthesized and employed for the detection of Hg²⁺ and Fe³⁺ ions as off–on fluorometric and colorimetric responses, respectively, in H₂O/DMF (10/90, v/v, Britton–Robinson buffer, pH 7) medium. The chemoprobe CTH demonstrated high sensitivity towards Hg²⁺ and Fe³⁺, among wide range of competitive cations with low recognition limits of 5.1 nM and 5.89 µM, respectively. The complexes of the chemoprobe CTH were synthesized and characterized by ¹H-NMR titration, FT-IR and MALDI-TOF MS techniques, which confirmed the binding stoichiometries and the possible sensing mechanisms, were suggested based on the hydrolysis reaction of C=N group. The practical utility of the chemoprobe CTH was revealed in quantification of the trace amounts of Hg²⁺ and Fe³⁺ in water samples. Also, a silica-coated test paper was used for the fluorescent monitoring of Hg²⁺, providing a novel approach for the quantitative and on-site detection in real samples. More excitingly, a smartphone application was employed for the visual detection of Fe³⁺ by recognizing the RGB (red/green/blue) of the chemoprobe CTH solution.

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Three Nematogen Azobenzene-Based Stationary Phases for Capillary GC: Synthesis and Comparative Study

In this paper, three laterally substituted liquid crystals termed LCC₁, LCC₃ and LCC₄ were synthesized. Characterization of these substances was carried out by ¹H NMR and ¹³C NMR; they possess similar core and differ in their lateral substituents. Their thermal stability was conducted by thermogravimetric analysis and showed decomposition beginning at 212, 233 and 264 °C related to LCC₁, LCC₃ and LCC₄, respectively. Thermal properties were determined by differential scanning calorimetry, thermomicroscopy and inverse gas chromatography. The three novel compounds exhibited a nematic mesophase at a defined range of temperatures, which varied from 81 to 55 °C. Lengthening of the lateral substituent seemed to affect the nematic range by decreasing it. Fused-silica capillary columns (30 m × 0.32 mm) were employed for the analytical study. Numerous mixtures of components of various properties were injected. Particular attention was given to the selectivity towards the close-boiling isomers. These investigations indicated that lateral attached groups had considerable effect on the thermal and chromatographic properties of the liquid crystal compounds. These interesting results may guide in improving the development of new type of liquid crystals with desired properties for a widespread application.     

A Novel Fluorescent Probe Based on Perylene Derivative for Hg2+ Ions and Biological Thiols and its Application in Live Cell Imaging and Theoretical Calculations

The selective and sensitive detection of biothiols; cysteine (Cys), homocysteine (Hcy) and glutathione (GSH) in aqueous solutions is of considerable importance because of their pivotal roles in maintaining the reducing environment in the cells. This study describes a strategy for the determination of biothiols based on the PDI/Met‐Hg²⁺complex platform. We designed and fabricated methionine modified perylene diimide molecule as a selective sensing probe for Hg²⁺ ions in aqueous solutions ( PDI/Met‐Hg ²⁺). The complex between perylene bisimide derivative ( PDI/Met) and Hg²⁺ was investigated and it demonstrated turn‐on fluorescence response for the detection of the biological thiols. Besides, PDI/Met displayed fluorescence quenching response in the presence of mercury ions and the emission intensity of PDI/Met‐Hg²⁺ was recovered after transferring biothiols (Cys, Hcy, and GSH). Thus, PDI/Met could be utilized as a fluorescent chemosensor for the sequential recognition of mercury ions and biological thiols.     

Investigation of Binding Properties of Umbelliferone (7Hydroxycoumarin) to Lysozyme

The binding interaction of lysozyme and umbelliferone (7hydroxcoumarin, 7HC) was investigated by UV–vis absorption and fluorescence quenching. It was obtained from fluorescence spectra that the fluorescence quenching of lysozyme by 7HC was probably a result of the formation of lysozyme-7HC complex and binding parameters were determined according to the Stern-Volmer equation. The effects of various common metal ions on the binding were also studied. The thermodynamic parameters were calculated at different temperatures which indicated that hydrophobic interaction. The binding distance (r) between the donor (lysozyme) and the acceptor (7HC) was 3.81 nm based on the Förster theory of non-radioactive resonance energy transfer.     

A novel amperometric inhibition biosensor based on HRP and gold sononanoparticles immobilised onto Sonogel-Carbon electrode for the determination of sulphides

A novel inhibition biosensor used for the detection of sulphides (Na₂S) has been developed. The biosensor is based on the immobilisation of horseradish peroxidase (HRP) on the Sonogel-Carbon (SNGC) electrode using glutaraldehyde, Poly(4-vinylpyridine) and gold sononanoparticles (AuSNPs). The Poly(4-vinylpyridine) was used due to its high affinity for sulphide anions, while the presence of gold sononanoparticles enhances the electron transfer reaction and improves the analytical performance of the biosensor. The amperometric measurements were performed at an applied potential of ?0.15 V vs. Ag/AgCl in 50 mM sodium acetate buffer solution pH = 6.0. The apparent kinetic parameters (K_mapp, V_max) of immobilised HRP were calculated in the absence of inhibitor (sulphide) using caffeic acid as substrate. Under the optimal experimental conditions, the determination of sulphide can be achieved in a dynamic range of 0.4–2.8 µM with a low limit of detection of 0.15 µM. The electrochemical impedance spectroscopy (EIS) was also used to characterise the interactions of substrate and inhibitor with the enzyme-modified electrode. The developed biosensor exhibited high sensitivity, selectivity and stability, and can be successfully applied to the detection of sulphide in water.     

Effect of current density on the microstructure and morphology of the electrodeposited nickel coatings

The aim of this research work was to study the effect of deposition current density on microstructure and surface morphology of electrodeposited nickel coatings. For this purpose, nickel deposits have been synthesized by direct current from Watts bath without additive, to limit the incorporation of pollutants resulting from surface adsorption or electro-activity of these compounds. Nickel deposits have been investigated by scanning electron microscopy and X-ray diffraction. Cyclic voltammetry was also used to gain information on the general behavior of the deposition. The optimum conditions of deposition were established and the influence of current density on the grain size, surface morphology, and crystal orientation was determined.     

Synthesis and characterization of oxime‐bearing hexakis(2‐formylphenoxy)‐phosphazene and its derivatives

Hexakis(2‐formylphenoxy)cyclotri‐phosphazene ( 2 ) was obtained from the reaction of hexachlorocylotriphosphazene ( 1 ) with 2‐hydroxy‐benzaldehyde. Hexakis(2‐[(hydroxyimino)methyl]‐phenoxy)cyclotriphosphazene (3) was synthesized from the reaction of 2 with hydroxlaminehydrochloride in pyridine. Hexasubstituted compounds 4, 5, 6, 8, 9 , and 10 were obtained from the reactions of 3 with methyl iodide, ethyl bromide, allyl bromide, propanoyl chloride, benzoyl chloride, and 4‐methoxybenzoyl chloride, respectively. Disubstituted product 7 was obtained from the reaction of 3 with chloroacetyl chloride. Pure and defined products could not be obtained from the reaction of 3 with acetyl chloride, benzyl chloride, and 2‐chlorobenzoyl chloride. The compounds were characterized by elemental analysis and IR, ¹H, ¹³C, and ³¹P NMR spectroscopy. © 2007 Wiley Periodicals, Inc. Heteroatom Chem 18:791–797, 2007; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20350