Halide-Driven Halogen-Hydrogen Bonding versus Chelation in Perovskite Nanocrystals: A Concept of Charge Transfer Bridging.

The choice of surface functionalized ligands to encapsulate semiconductor nanocrystals (NCs) is important for tailoring their optoelectronic properties. We use a small bidentate 8-hydroxyquinoline (HQ) molecule to surface functionalize CsPbX3 perovskite NCs (X = Cl, Br, I), along with traditional long-chain monodentate ligands. Our experimental results using optical and ultrafast spectroscopy depict a halogen-hydrogen bonding formation in the HQ functionalized CsPbCl3 and CsPbBr3 NCs, which act as a charge transfer (CT) bridging for the interfacial hole transfer from the NCs to the HQ molecule as fast as 540 fs. In contrast, weak chelation is observed for HQ-coupled CsPbI3 NCs without an active CT process. We explain two distinct surface coupling mechanisms via the polarizability of halides and larger PbI64- octahedral cage size. Control of two contrasting halide-dependent surface coupling phenomena of a small molecule that further regulate the CT process may have significant implications in their development in optoelectronics.

Simultaneous Sensing of H2 O, D2 O and HOD through Peroxo Vibrations.

Detection of HOD simultaneously in the presence of a mixture of H2 O and D2 O is still an experimental challenge. Till date, there is no literature report of simultaneous detection of H2 O, D2 O and HOD based on vibrational spectra. Herein we report simultaneous quantitative detection of H2 O, D2 O and HOD in the same reaction mixture with the help of bridged polynuclear peroxo complex in absence and presence of Au nanoparticles on the basis of a peroxide vibrational mode in resonance Raman and surface enhanced resonance Raman spectrum. We synthesize bridged polynuclear peroxo complex in different solvent mixture of H2 O and D2 O. Due to the formation of different nature of hydrogen bonding between peroxide and solvent molecules (H2 O, D2 O and HOD), vibrational frequency of peroxo bond is significantly affected. Mixtures of different H2 O and D2 O concentrations produce different HOD concentrations and that lead to different intensities of peaks positioned at 897, 823 and 867 cm-1 indicating H2 O, D2 O and HOD, respectively. The lowest detection limits (LODs) were 0.028 mole fraction of D2 O in H2 O and 0.046 mole faction of H2 O in D2 O. In addition, for the first time the results revealed that the cis-peroxide forms two hydrogen bonds with solvent molecules.

Enhanced solid-state plasmon catalyzed oxidation and SERS signal in the presence of transition metal cations at the surface of gold nanostructures.

The effect of several metal cations (Mn2+, Co2+, Ni2+, Cu2+ and Zn2+) on the photochemical conversion of 4-aminothiophenol (4-ATP) into 4,4'-dimercaptoazobenzene (DMAB) is probed using surface enhanced Raman scattering (SERS). The coupling reaction is carried out on the surface of Au nanoparticles and Au nanorods using 532 nm and 632.8 nm laser excitations, respectively, in the absence and presence of metal cations. Here, we report that DMAB formation on the surface of Au nanostructures - when carried out in the solid state - is augmented significantly (by a factor of 1.98 to 4.07 and 3.34 to 5.74 for Au nanoparticle and Au nanorod substrates, respectively, and depending on the metal). Furthermore, the SERS signal is also markedly enhanced. Thus, the results underpin a new way of carrying out a photochemical reaction with a higher yield along with a higher SERS signal.

One-pot synthesis of folic acid encapsulated upconversion nanoscale metal organic frameworks for targeting, imaging and pH responsive drug release.

In this work, a new theranostic nanoplatform is developed to construct an anticancer drug carrier by integrating the distinct advantages of upconversion nanoparticles (UCNPs) and metal organic frameworks (MOFs) encapsulated with a targeting ligand. Here NaYF4:Yb3+,Er3+ is chosen as an upconversion nanoparticle for its high luminescence properties. Then, folic acid encapsulated Zeolitic Imidazolate Framework-8 (ZIF-8) is directly coated on UCNPs in one step to form a monodispersed core-shell structured nanocomposite (labeled as UCNPs@ZIF-8/FA). The synthesized upconversion nanoscale MOFs (NMOFs) are simultaneously used as a targeted anticancer drug carrier and in cellular imaging. The UCNP@ZIF-8/FA nanocomposites are found to be nontoxic towards the human cervix adenocarcinoma (HeLa) and mouse fibroblast (L929) cell lines via a cell viability assay. It is worthwhile noting that, the anticancer drug 5-fluorouracil (5-FU) is absorbed into UCNP@ZIF-8/FA nanocomposites (loading amount 685 mg g-1) and also pH responsive drug release is observed. The as-prepared 5-FU loaded UCNP@ZIF-8/FA nanocomposites exhibited greater cytotoxicity towards HeLa cells due to the folate receptor-mediated endocytosis. Our study highlights the potential of developing multifunctional upconversion NMOFs for simultaneous targeted cellular imaging with delivery of anticancer drugs.

Neurocomputing model for computation of an approximate convex hull of a set of points and spheres.

In this letter, a two-layer neural network is proposed for computation of an approximate convex hull of a set of given points in 3-D or a set of spheres of different sizes. The algorithm is designed based on an elegant concept-shrinking of a spherical rubber balloon surrounding the set of objects in 3-D. Logically, a set of neurons is orderly placed on a spherical mesh i.e., on a rubber balloon surrounding the objects. Each neuron has a parameter vector associated with its current position. The resultant force of attraction between a neuron and each of the given points/objects, determines the direction of a movement of the neuron lying on the rubber balloon. As the network evolves, the neurons (parameter vectors) approximate the convex hull more and more accurately.

A novel connectionist framework for computation of an approximate convex-hull of a set of planar points, circles and ellipses.

We propose a two layer neural network for computation of an approximate convex-hull of a set of points or a set of circles/ellipses of different sizes. The algorithm is based on a very elegant concept - shrinking of a rubber band surrounding the set of planar objects. Logically, a set of neurons is placed on a circle (rubber band) surrounding the objects. Each neuron has a parameter vector associated with it. This may be viewed as the current position of the neuron. The given set of points/objects exerts a force of attraction on every neuron, which determines how its current position will be updated (as if, the force determines the direction of movement of the neuron lying on the rubber band). As the network evolves, the neurons (parameter vectors) approximate the convex-hull more and more accurately. The scheme can be applied to find the convex-hull of a planar set of circles or ellipses or a mixture of the two. Some properties related to the evolution of the algorithm are also presented.