A multi-cation responsive Ni(II)-supramolecular metallogel mimics a molecular keypad lock via reversible fluorescence switching.

Synthesis of a bidentate N,O-donor Schiff base fluorescent ligand 5-(diethylamino-2-((4-(diethylamino-2-((4-(diethylamino)phenylimino)ethyl)phenol) (HL) adopting a new preparation procedure and its complexes with Ni(II) (1) and Zn(II) (2) has been illustrated. Structures of HL and 1 have been elucidated using X-ray single crystal analysis. Moreover, HL leads to the formation of a mechanically stable Ni(II)-gel (MG) upon treatment with Ni(NO3)2·6H2O in the presence of triethylamine (TEA) using THF/MeOH (1 : 1) solvents at rt. The gelator HL, complexes 1-2 and MG have been characterized by different spectroscopic and microscopic techniques including NMR (1H & 13C), FT-IR, ESI-MS, SEM, powder-XRD, rheology, UV/vis and fluorescence analysis. Rheological studies suggested good mechanical and thermal stability, whereas SEM analysis reveals a porous earth crust-like morphology of MG. Notably, 1 : 1 complexation between HL and Ni(II) forms a stable gel (MG), whereas 2 : 1 (HL : Ni2+) complexation leads to partial gelation. Formation of the Ni(II)-MG leads to slight "Turn-OFF" fluorescence relative to HL with a limit of detection (LOD) of 7.76 × 10-9 M; however, MG is considered as the "ON" state due to moderate emission. Remarkably, Ni(II)-MG further displayed reversible "ON-OFF-ON" fluorescence switching behavior through detection of Zn2+, Cu2+ and Hg2+. The emission intensity of MG is quenched with Cu2+/Hg2+ but enhances with Zn2+ in 1 : 1 (MG : M2+) stoichiometry. Therefore, MG mimics a sequence dependent molecular keypad lock for Cu2+ (C), Hg2+ (H) and Zn2+ (Z) to give the maximum output. Association and quenching constants were calculated by the Benesi-Hildebrand method, and from the Stern-Volmer plot the LOD was determined to be 4.2 × 10-6 M, 5.8 × 10-6 M and 7.8 × 10-6 M for MG with Zn(II), Cu(II) and Hg(II), respectively. To date, Ni(II) based MGs have been explored only toward electrochemical, thermal and conduction studies; however, the present work demonstrates the fluorescent reversible cation detection behavior of Ni(II)-MG to act as a molecular keypad lock for development of password protection devices.

Metal-semiconductor pair nanoparticles by a physical route based on bipolar mixing.

In this report a methodology is described and demonstrated for preparing Au-Ge pair nanoparticles with known compositions by extending and modifying the basic steps normally used to synthesize nanoparticles in carrier gas. For the formation of pair nanoparticles by bipolar mixing, two oppositely charged aerosols of nanoparticles having the desired size are produced with the help of two differential mobility analyzers. Then both are allowed to pass through a tube, which provides sufficient residence time to result in nanoparticle pair formation due to Brownian collisions influenced by Coulomb forces. The effect of residence time on the formation of nanoparticle pairs as well as the influence of diffusion and discharging is described. Subsequently, necessary modifications to the experimental setup are demonstrated systematically. The kinetics of nanoparticles pair formation in a carrier gas is also calculated and compared with measurements made with the help of an online aerosol size analysis technique. This synthesis of nanoparticle pairs can be seen as a possible route towards Janus-type nanoparticles.

Concentration-specific hydrogen sensing behavior in monosized Pd nanoparticle layers.

In this study, H2 sensing behavior of monosized and monocrystalline Pd nanoparticles has been studied as a function of H2 concentration and measurement temperature. A unique concentration-specific H2 sensing behavior with a 'pulsed' response at larger H2 concentrations and 'saturated' response at lower concentrations has been observed. The threshold concentration required for transition from 'saturated' to 'pulsed' response is very sensitive to measurement temperature. The characteristic change in the sensing behavior can be used to develop a novel sensor capable of determining H2 concentration level having high sensitivity and fast response. This study demonstrates that electrical and gas sensing properties of the nanoparticle layer depend critically on interparticle gaps.

XPS and AFM studies of monodispersed Pb/PbO core-shell nanostructures.

A probe of the core-shell formation and the interfacial properties of monodispersed 30 nm Pb nanoparticles are presented. A direct correlation between the structures of the particle to its chemical states is done, by a careful Ar+ ion depth profiling followed by X-ray Photoelectron Spectroscopy and Atomic Force Microscopy. The study provides a unique insight into the structure of the nanoparticles. A PbO shell of 4 nm is observed to cover a 15-nm core, with a 5 nm interfacial region. The valence band spectra show the movement of the valence band maxima towards and beyond the Fermi-level during the insulator to metal transition along the particle depth. Evidence is also provided for an enhanced preferential sputtering of the PbO shell and an ion induced penetration of PbO into the Pb core.