Surojit Pande

Dendrimer-encapsulated nanoparticles: New synthetic and characterization methods and catalytic applications

In this article we describe the synthesis, characterization, and applications of dendrimer-encapsulated nanoparticles (DENs). These materials are synthesized using a template approach in which metal ions are extracted into the interior of dendrimers and then subsequently reduced chemically to yield nearly size-monodisperse particles having diameters in the 1–2 nm range. Monometallic, bimetallic (alloy and core@shell), and semiconductor nanoparticles have been prepared by this route. The dendrimer component of these composites serves not only as a template for preparing the nanoparticle replica, but also as a stabilizer for the nanoparticle. In this perspective, we report on progress in the synthesis, characterization, and applications of these materials since our last review in 2005. Significant advances in the synthesis of core@shell DENs, characterization, and applications to homogeneous and heterogeneous catalysis (including electrocatalysis) are emphasized.

Synthesis of ZnO/Au and ZnO/Ag nanoparticles and their photocatalytic application using UV and visible light

We report a simple and convenient method for the synthesis of a ZnO/Au and ZnO/Ag heterostructure nanoflower by applying a surfactant mediated route. Initially, pure ZnO nanoflowers have been synthesized followed by Au and Ag deposition on ZnO surface using hydrazine hydrate as reducing agent. Structure, crystallinity, and morphology have been assessed by X-ray diffraction, X-ray photoelectron spectroscopy, and electron microscopy techniques. The influences of the deposited metal nanoparticles (Au and Ag) on the surface of ZnO have been emphasized by applying the as-synthesized nanostructure in dye degradation under illumination of UV and visible light. The basic motivation behind this work is to find a superior photocatalyst, which can work under UV as well as visible light i.e., to cover the whole range of the solar spectrum. Photocatalytic performances of bare ZnO, ZnO/Au, and ZnO/Ag have been studied thoroughly. Photodegradation results under UV and visible light demonstrated that the incorporation of noble metal nanoparticles significantly (or drastically) increases the catalytic efficiency by promoting the photogenerated charge carrier separation. The main advantage of the proposed ZnO/Au and ZnO/Ag semiconductor is that it delays the recombination process of the electron–hole pairs generated by the photon absorption, which in lieu increases the photocatalytic efficiency. It is a challenging issue to fabricate stable photocatalysts which can work under visible light as it covers 43% of sunlight. To investigate the role of photogenerated electrons and holes in dye degradation, scavenging experiments using different scavengers have also been performed.

Interaction of DNA bases with silver nanoparticles: Assembly quantified through SPRS and SERS

Colloidal silver nanoparticles were prepared by reducing silver nitrate with sodium borohydride. The synthesized silver particles show an intense surface plasmon band in the visible region. The work reported here describes the interaction between nanoscale silver particles and various DNA bases (adenine, guanine, cytosine, and thymine), which are used as molecular linkers because of their biological significance. In colloidal solutions, the color of silver nanoparticles may range from red to purple to orange to blue, depending on the degree of aggregation as well as the orientation of the individual particles within the aggregates. Transmission electron microscopy (TEM), X-ray diffraction (XRD), and absorption spectroscopy were used to characterize the assemblies. DNA base-induced differential silver nanoparticle aggregation was quantified from the peak separation (relates to color) of surface plasmon resonance spectroscopy (SPRS) and the signal intensity of surface-enhanced Raman scattering (SERS), which rationalize the extent of silver-nucleobase interactions.

Controlled interparticle spacing for surface-modified gold nanoparticle aggregates

Aggregation of gold nanoparticles of increasing size has been studied as a consequence of adsorption of 2-aminothiophenol (ATP) on gold nanoparticle surfaces. The capping property of ATP in the acidic pH range has been accounted from UV-vis absorption spectroscopy and surface-enhanced Raman scattering (SERS) studies. The effect of nanoparticle size (8-55 nm) on the nature of aggregation as well as the variation in the optical response due to variable degree of interparticle coupling effects among the gold particles have been critically examined. Various techniques such as transmission electron microscopy, X-ray diffraction, zeta-potential, and average particle size measurement were undertaken to characterize the nanoparticle aggregates. The aggregate size, interparticle distances, and absorption band wavelengths were found to be highly dependent on the pH of the medium and the concentration of the capping agent, ATP. The acquired SERS spectra of ATP relate the interparticle spacing. It has been observed that the SERS signal intensities are different for different sized gold nanoparticles.

Resin-Immobilized CuO and Cu Nanocomposites for Alcohol Oxidation

Resin immobilized stable, spherical CuO nanoparticles prepared in the presence of cyclodextrin (CD) act as catalysts for liquid phase alcohol oxidation in air. The catalytic activity of the CuO nanocomposites and its green chemistry approach make it superior to the related resin-bound Cu(0) nanocomposite. The effect of alcohol chain length and electron-donating or -withdrawing groups influence product yield. The nanocomposites exhibit good reusability, simple workup procedure, and a straightforward approach to aldehyde formation.

Analysis of poly(amidoamine) dendrimer structure by UV-vis spectroscopy.

We report a UV-vis spectroscopic study of four different types of poly(amidoamine) dendrimers. The results indicate that the degree of protonation of the interior tertiary amines of these dendrimers correlates directly to an absorption band with λ(max) in the range of 280-285 nm. Specifically, at low pH, the tertiary amines are protonated and the 280-285 nm band is absent. However, at elevated pH, when these groups are deprotonated, this band appears. Similar results were obtained for a simple model compound. The dependence of the 280-285 nm band on the chemical state of the tertiary amines of the dendrimers was confirmed by complexing them with Pd(2+) and Pt(2+). In this case the band disappears, and it only reappears when the metal ions are decomplexed following reduction with BH(4)(-). Finally, filtration experiments showed that the absorption band between 280-285 nm arises exclusively from intact, or nearly intact, dendrimers rather than low-molecular-weight fragments.

Cysteine functionalized copper organosol: synthesis, characterization and catalytic application

We herein report a facile one-pot synthesis, stabilization, redispersion and Cu–S interaction of L-cysteine and dodecanethiol (DDT) protected copper organosol in toluene from precursor copper stearate using sodium borohydride in toluene under a nitrogen atmosphere. Surface modification of the synthesized copper organosol with an amino acid L-cysteine and an alkanethiol (dodecanethiol, DDT) is accomplished by a thiolate bond between the used ligands and nanoparticle surface. The cysteine molecule binds the copper surface via a thiolate and amine linkage but not through electrostatic interaction with the carboxylate group due to the solvent polarity and dielectric medium. Fourier transform infrared (FTIR) analysis was performed to confirm the surface functionalization of the amino acid and DDT to the copper surface. Copper organosol has been characterized by optical spectroscopy (UV/vis), transmission electron microscopy (TEM), x-ray photoelectron spectroscopy (XPS) and x-ray diffraction (XRD). The as-synthesized particles are spherical in shape and exhibit a Mie scattering profile with an absorption maxima in the visible range. Copper nanoparticles capped by cysteine and/or DDT in non-aqueous media are found to represent an interesting catalytic approach for the synthesis of octylphenyl ether.

New hydrothermal process for hierarchical TiO2nanostructures

Hydrothermolysis of inorganic Ti(IV) compounds (peroxo or sulfate) yields hierarchical titania nanocrystals of controlled morphologies on either a glass or resin surface.

Synthesis, characterization, and electrocatalysis using Pt and Pd dendrimer-encapsulated nanoparticles prepared by galvanic exchange

In this report we present the synthesis and characterization of Pt and Pd dendrimer-encapsulated nanoparticles (DENs) using the method of galvanic exchange. Sixth-generation hydroxyl-terminated poly(amidoamine) dendrimers were used to prepare Cu DENs composed of 55 atoms. In the presence of either PtCl42− or PdCl42−, the less noble Cu DENs oxidize to Cu2+ leaving behind an equal-sized DEN of Pt or Pd, respectively. DENs prepared by direct reduction with BH4−, which is the common synthetic route, and those prepared by galvanic exchange have the same composition, structure, and properties as judged by UV-vis spectroscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, and electrochemical methods. However, the galvanic exchange synthesis is much faster (3 h vs. 96 h), and the yield of reduced DENs is significantly higher (nearly 100% in the case of galvanic exchange).

Synthesis of Superparamagnetic β-MnO2 Organosol : a Photocatalyst for the Oxidative Phenol Coupling Reaction

Superparamagnetic monodispersed spherical beta-MnO 2 nanoparticles of approximately 10 nm size with a band gap of 2.52 eV have been synthesized in toluene and support the oxidative phenol coupling reaction as a photocatalyst.