Phenanthroline-fluorescein molecular hybrid as a ratiometric and selective fluorescent chemosensor for Cu2+ via FRET strategy: synthesis,computational studies and in vitro applications

A FRET-based chemosensor L containing donor phenanthroline and acceptor fluorescein moiety was designed, synthesised and characterised for the ratiometric fluorescent detection of Cu²⁺ in organo-aqueous solution. Probe L showed high selectivity and excellent sensitivity towards Cu²⁺ ions by exhibiting both colorimetric and fluorometric changes due to opening of the spirolactum ring of fluorescein upon complexation with Cu²⁺. In presence of Cu²⁺ ions, probe L formed L-Cu²⁺ complex in 1:1 stoichiometric fashion which is established on the basis of Job’s plot and mass spectroscopy. We also performed DFT computational studies to know the binding nature and coordination feature of the complex. Furthermore, fluorescence imaging studies revealed that probe L was cell permeable and could be used to detect intracellular Cu²⁺ in living cells.     

Reversible tunability of the near-infrared valence band plasmon resonance in Cu(2-x)Se nanocrystals

We demonstrate that colloidal Cu(2-x)Se nanocrystals exhibit a well-defined infrared absorption band due to the excitation of positive charge carrier oscillations (i.e., a valence band plasmon mode), which can be tuned reversibly in width and position by varying the copper stoichiometry. The value of x could be incrementally varied from 0 (no plasmon absorption, then a broad peak at 1700 nm) to 0.4 (narrow plasmon band at 1100 nm) by oxidizing Cu(2)Se nanocrystals (upon exposure either to oxygen or to a Ce(IV) complex), and it could be incrementally restored back to zero by the addition of a Cu(I) complex. The experimentally observed plasmonic behavior is in good agreement with calculations based on the electrostatic approximation.     

Effect of surface modes on the six-dimensional molecule-surface scattering dynamics of H2-Cu(100) and D2-Cu(111) systems

We include the phonon modes originating from the three layers of Cu(100)/Cu(111) surface atoms on the dynamics of molecular [H(2)(v,j)/D(2)(v,j)] degrees of freedom (DOFs) through a mean field approach, where the surface temperature is incorporated into the effective Hamiltonian (potential) either by considering Boltzmann probability (BP) or by including the Bose-Einstein probability (BEP) factor for the initial state distribution of the surface modes. The formulation of effective potential has been carried out by invoking the expression of transition probabilities for phonon modes known from the "stochastic" treatment of linearly forced harmonic oscillator (LFHO). We perform four-dimensional (4D?2D) as well as six-dimensional (6D) quantum dynamics on a parametrically time and temperature-dependent effective Hamiltonian to calculate elastic/inelastic scattering cross-section of the scattered molecule for the H(2)(v,j)-Cu(100) system, and dissociative chemisorption-physisorption for both H(2)(v,j)-Cu(100) and D(2)(v,j)-Cu(111) systems. Calculated sticking probabilities by either 4D?2D or 6D quantum dynamics on an effective potential constructed by using BP factor for the initial state distribution of the phonon modes could not show any surface temperature dependence. In the BEP case, (a) both 4D?2D and 6D quantum dynamics demonstrate that the phonon modes of the Cu(100) surface affect the state-to-state transition probabilities of the scattered H(2) molecule substantially, and (b) the sticking probabilities due to the collision of H(2) on Cu(100) and D(2) on Cu(111) surfaces show noticeable and substantial change, respectively, as function of surface temperature only when the quantum dynamics of all six molecular DOFs are treated in a fully correlated manner (6D).     

Steady-state photoinduced absorption of CdSe/CdS octapod shaped nanocrystals

Colloidal branched nanocrystals have been attracting increasing attention due to evidence of an interesting relationship between their complex shape and charge carrier dynamics. Herein, continuous wave photoinduced absorption (CW PIA) measurements of CdSe/CdS octapod-shaped nanocrystals are reported. CW PIA spectra show strong bleaching due to the one-dimensional (1D) CdS pod states (480 nm) and the zero-dimensional (0D) CdSe core states (690 nm). The agreement with previously reported ultrafast pump-probe experiments indicates that this strong bleaching signal may be assigned to state filling. Additional bleaching features at 520 and 560 nm are characterized by a longer lifetime and are thus ascribed to defect states, localized at the pod-core interface of the octapod, showing that some of the initially photogenerated carriers get quickly trapped into these long-lived defect states. However, we remark that a relevant part of electrons remain untrapped: this opens up the opportunity to exploit octapod shaped nanocrystals in photovoltaics applications, as electron acceptor materials, considering that several efficient hole extracting materials are already available for the realization of a composite bulk heterojunction.     

Fluorination suppresses thermal quenching in perovskite QLEDs

正Perovskite nanocrystals and quantum dots(QDs) have attracted great attention due to their potential in optical and optoelectronic applications, especially in ultra-high definition displays because of their high purity of photo/electroluminescence(PL/EL) [1,2]. Although the external quantum efficiency(EQE) of light-emitting diodes(LEDs) based on perovskite quantum dots(PeQDs) has been over 20% [3,4],another key problem, the PL/EL stability, still remains open.The thermal PL/EL quenching phenomenon, which is ubiquitously observed, has not aroused enough attention in this     

Invoking Pairwise Interactions in Water‐Promoted Diels–Alder Reactions by using Ionic Liquids as Cosolvents

Rate constants and derived activation parameters of organic reactions in aqueous media, in particular Diels–Alder reactions, are sensitive to the presence of cosolvents in water. To enhance the solubility window of water, we introduced ionic liquids as cosolvents in the aqueous Diels–Alder reaction between anthracene‐9‐carbinol and N‐ethylmaleimide. The reactive potentials of the organic compounds are parameterized by using semi‐empirical quantum chemical methods. The principle of Savage–Wood additivity of group interactions is used to quantify the pairwise group interactions among chemically inert ionic liquids and organic reactants, both at initial and transition states of the reaction. The present approach shows promise, as the use of simple calculations from easily available kinetic data can help researchers to understand the versatility of green ionic‐liquid alternatives to volatile organic solvents.     

Mathematical modeling of localized melting around graphite nodules during laser surface hardening of austempered ductile iron

An attempt has been made to mathematically predict the optimum conditions of laser surface hardening (LSH) of austempered ductile iron (ADI) that can ensure a predominantly martensitic microstructure and preclude partial/complete dissolution of graphite nodules in the laser hardened zone during laser irradiation. The exercise involves prediction of the thermal profile (using the Ashby and Easterling model), and consequently, the carbon diffusion profile around the graphite nodules at different depths from the surface for the given conditions of LSH. Microstructural investigations have been carried out by optical and scanning electron microscopy to study the morphology, shape and width of the partially/completely melted graphite nodules as a function of the LSH parameters. Finally, the predicted maximum width of the melted zone around the graphite nodules is compared with the relevant experimental data to validate the proposed model.     

Calorimetric investigation of the interaction between a macromolecular prodrug of diflunisal and human platelets

The thermal effect due to the interaction between human platelets and α,β poly(N-hydroxy-ethyl)-DL-aspartamide (PHEA) or the PHEA-Diflunisal conjugate was measured by the calorimetric technique at 25°C. The experimental data confirm that PHEA is a biocompatible macromolecule and that its conjugate influences the physiological activity of human platelets.