A highly ordered 2D‐hexagonal mesoporous silica material is functionalized with 3‐aminopropyltriethoxysilane. This organically modified mesoporous material is grafted with a dialdehyde fluorescent chromophore, 4‐methyl‐2,6‐diformyl phenol. Powder X‐ray diffraction, transmission electron microscopy, N2 sorption, Fourier transform infrared spectroscopy, and UV‐visible absorption and emission have been employed to characterize the material. This material shows excellent selective Zn2+ sensing, which is due to the fluorophore moiety present at its surface. Fluorescence measurements reveal that the emission intensity of the Zn2+‐bound mesoporous material increases significantly upon addition of various concentrations of Zn2+, while the introduction of other biologically relevant (Ca2+, Mg2+, Na+, and K+) and environmentally hazardous transition‐metal ions results in either unchanged or weakened intensity. The enhancement of fluorescence is attributed to the strong covalent binding of Zn2+, evident from the large binding constant value (0.87 × 104 M−1). Thus, this functionalized mesoporous material grafted with the fluorescent chromophore could monitor or recognize Zn2+ from a mixture of ions that contains Zn2+ even in trace amounts and can be considered as a selective fluorescent probe. We have examined the application of this mesoporous zinc(II) sensor to cultured living cells (A375 human melanoma and human cervical cancer cell, HeLa) by fluorescence microscopy.
A Cd(ii) based 2D metal-organic framework (MOF), [Cd(4-bpd)(SCN)] (1) where 4-bpd = 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene, has been synthesized and characterized by standard methods including single crystal X-ray diffraction analysis. When it is sandwiched between ITO coated glass and Al, 1 shows interesting conduction properties. The I-V characteristics of the ITO/1/Al configuration measured in the dark and under illumination of incident light exhibit a highly non-linear rectifying behavior, which signifies its Schottky diode character. The conductivity of the configuration is 2.90 × 10 S m and 7.16 × 10 S m under dark and photoirradiation conditions, respectively. Different parameters have been analyzed and these indicate that 1 can be a promising candidate for light sensing electronic devices. This material has good sensitivity to the light source when switched on/off. Theoretical calculations have been performed to understand the reason for the enhancement of conductivity under illumination of incident light. It has been found that upon irradiation, slight changes in the bond distances of 4-bpd in 1 occur. These changes are related to the considerable decrease in the energy needed for the allowed electronic transition. This may influence the increase of conductivity along with other factors.
Highly ordered 2D-hexagonal mesoporous silica has been functionalized with 3-aminopropyltriethoxysilane (3-APTES). This is followed by its condensation with a dialdehyde, 4-methyl-2,6-diformylphenol to produce an immobilized Schiff-base ligand (I). This material is separately treated with methanolic solution of copper(II) chloride and nickel(II) chloride to obtain copper and nickel anchored mesoporous materials, designated as Cu-AMM and Ni-AMM, respectively. The materials have been characterized by Fourier transform infrared (FT-IR) and UV-vis diffuse reflectance (DRS) spectroscopy, powder X-ray diffraction (XRD), transmission electron microscopy (TEM), N(2) adsorption-desorption studies and (13)C CP MAS NMR spectroscopy. The metal-grafted mesoporous materials have been used as catalysts for the efficient and selective epoxidation of alkenes, viz. cyclohexene, trans-stilbene, styrene, α-methyl styrene, cyclooctene and norbornene to their corresponding epoxides in the presence of tert-butyl hydroperoxide (TBHP) as the oxidant under mild liquid phase conditions.
Three new Cu(ii) complexes, [Cu(4)(O)(L(n))(2)(CH(3)COO)(4)] where HL(1) = 4-methyl-2,6-bis(2-fluoroethyliminomethyl) phenol for complex , HL(2) = 4-methyl-2,6-bis(2-chloroethyliminomethyl) phenol for complex .0.25CH(3)CN and HL(3) = 4-methyl-2,6-bis(2-bromoethyliminomethyl) phenol for complex have been synthesized and characterized by elemental analysis, FTIR, UV-vis spectroscopy, and electrospray ionization mass spectroscopy. The structure of complex .0.25CH(3)CN has also been confirmed by single crystal X-ray diffraction analysis. These complexes have been found to be active catalysts for the oxidation of cyclohexane and toluene in the presence of hydrogen peroxide as the oxidant under mild conditions. Cyclohexane is oxidized to yield cyclohexanol and cyclohexanone, whereas toluene is oxidized to benzyl alcohol and benzaldehyde.
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