Anirban Som

Ambient solid-state mechano-chemical reactions between functionalized carbon nanotubes

Carbon nanotubes can be chemically modified by attaching various functionalities to their surfaces, although harsh chemical treatments can lead to their break-up into graphene nanostructures. On the other hand, direct coupling between functionalities bound on individual nanotubes could lead to, as yet unexplored, spontaneous chemical reactions. Here we report an ambient mechano-chemical reaction between two varieties of nanotubes, carrying predominantly carboxyl and hydroxyl functionalities, respectively, facilitated by simple mechanical grinding of the reactants. The purely solid-state reaction between the chemically differentiated nanotube species produces condensation products and unzipping of nanotubes due to local energy release, as confirmed by spectroscopic measurements, thermal analysis and molecular dynamic simulations.

Anisotropic Molecular Ionization at 1 V from Tellurium Nanowires (Te NWs)

Ionization of molecular species from one-dimensional (1D) tellurium nanowires (Te NWs) has been achieved at 1 V. Molecules with a range of chemical functional groups gave quality mass spectra with high signal/noise ratios and no fragment ions. Experiments suggest the possibility of emission of microdroplets of solution due to the intense fields at the ends or interfaces of nanostructures. It appears that electrolytic conduction of the solution wetting of the nanostructures and not the electronic conduction of the nanostructures themselves is involved in the ionization event. Anisotropy was seen when two-dimensionally aligned Te NWs were used for ionization. The orientation effect of aligned Te NWs on molecular ion intensity is demonstrated for many analytes including organic molecules and amino acids with experiments done using a silicon substrate having aligned Te NWs. These measurements suggest the possibility of creating a MS source that extends the applicability of mass spectrometry. Analysis of a variety of analytes, including amino acids, pesticides, and drugs, in pure form and in complex mixtures, is reported. These experiments suggest that 1D nanostructures in general could be excellent ionization sources.

Interparticle Reactions: An Emerging Direction in Nanomaterials Chemistry

Nanoparticles exhibit a rich variety in terms of structure, composition, and properties. However, reactions between them remain largely unexplored. In this Account, we discuss an emerging aspect of nanomaterials chemistry, namely, interparticle reactions in solution phase, similar to reactions between molecules, involving atomically precise noble metal clusters. A brief historical account of the developments, starting from the bare, gas phase clusters, which led to the synthesis of atomically precise monolayer protected clusters in solution, is presented first. Then a reaction between two thiolate-protected, atomically precise noble metal clusters, [Au25(PET)18]- and [Ag44(FTP)30]4- (PET = 2-phenylethanethiol, FTP = 4-fluorothiophenol), is presented wherein these clusters spontaneously exchange metal atoms, ligands, and metal-ligand fragments between them under ambient conditions. The number of exchanged species could be controlled by varying the initial compositions of the reactant clusters. Next, a reaction of [Au25(PET)18]- with its structural analogue [Ag25(DMBT)18]- (DMBT = 2,4-dimethylbenzenethiol) is presented, which shows that atom-exchange reactions happen with structures conserved. We detected a transient dianionic adduct, [Ag25Au25(DMBT)18(PET)18]2-, formed between the two clusters indicating that this adduct could be a possible intermediate of the reaction. A reaction involving a dithiolate-protected cluster, [Ag29(BDT)12]3- (BDT = 1,3-benzenedithiol), is also presented wherein metal atom exchange alone occurs, but with no ligand and fragment exchanges. These examples demonstrate that the nature of the metal-thiolate interface, that is, its bonding network and dynamics, play crucial roles in dictating the type of exchange processes and overall rates. We also discuss a recently proposed structural model of these clusters, namely, the Borromean ring model, to understand the dynamics of the metal-ligand interfaces and to address the site specificity and selectivity in these reactions. In the subsequent sections, reactions involving atomically precise noble metal clusters and one- and two-dimensional nanosystems are presented. We show that highly protected, stable clusters such as [Au25(PET)18]- undergo chemical transformation on graphenic surfaces to form a bigger cluster, Au135(PET)57. Finally, we present the transformation of tellurium nanowires (Te NWs) to Ag-Te-Ag dumbbell nanostructures through a reaction with an atomically precise silver cluster, Ag32(SG)19 (SG = glutathione thiolate). The starting materials and the products were characterized using high resolution electrospray ionization mass spectrometry, matrix assisted laser desorption ionization mass spectrometry, UV/vis absorption, luminescence spectroscopies, etc. We have analyzed principally mass spectrometric data to understand these reactions. In summary, we present the emergence of a new branch of chemistry involving the reactions of atomically precise cluster systems, which are prototypical nanoparticles. We demonstrate that such interparticle chemistry is not limited to metal clusters; it occurs across zero-, one-, and two-dimensional nanosystems leading to specific transformations. We conclude this Account with a discussion of the limitations in understanding of these reactions and future directions in this area of nanomaterials chemistry.

Cluster-Mediated Crossed Bilayer Precision Assemblies of 1D Nanowires

Highly organized crossed bilayer assemblies of nanowires (NWs) are made using directed hydrogen bonding between the protecting ligand shells of atomically precise cluster molecules anchored on NWs. Layers of quantum clusters remain sandwiched between two neighboring NWs at a defined distance, dictated by the core-size of the cluster, while the orientation of the ligands in space dictates the interlayer geometry.

Metallic Nanobrushes Made using Ambient Droplet Sprays

An ambient solution-state method for making uniform nanobrushes composed of oriented 1D silver nanowires (NWs) with aspect ratios of 10(2) -10(4) is reported. These structures are grown over cm(2) areas on conducting surfaces. Assemblies of NWs form uniform nanobrush structures, which can capture micrometer-sized objects, such as bacteria and particulate matter. Variation in composition produces unique structures with catalytic properties.

Confined Metastable 2-Line Ferrihydrite for Affordable Point-of-Use Arsenic-Free Drinking Water.

Arsenic-free drinking water, independent of electrical power and piped water supply, is possible only through advanced and affordable materials with large uptake capacities. Confined metastable 2-line ferrihydrite, stable at ambient temperature, shows continuous arsenic uptake in the presence of other complex species in natural drinking water and an affordable water-purification device is made using the same.

Atomically Precise Nanocluster Assemblies Encapsulating Plasmonic Gold Nanorods

The self-assembled structures of atomically precise, ligand-protected noble metal nanoclusters leading to encapsulation of plasmonic gold nanorods (GNRs) is presented. Unlike highly sophisticated DNA nanotechnology, this strategically simple hydrogen bonding-directed self-assembly of nanoclusters leads to octahedral nanocrystals encapsulating GNRs. Specifically, the p-mercaptobenzoic acid (pMBA)-protected atomically precise silver nanocluster, Na4 [Ag44 (pMBA)30 ], and pMBA-functionalized GNRs were used. High-resolution transmission and scanning transmission electron tomographic reconstructions suggest that the geometry of the GNR surface is responsible for directing the assembly of silver nanoclusters via H-bonding, leading to octahedral symmetry. The use of water-dispersible gold nanoclusters, Au≈250 (pMBA)n and Au102 (pMBA)44 , also formed layered shells encapsulating GNRs. Such cluster assemblies on colloidal particles are a new category of precision hybrids with diverse possibilities.

Catalytic Paper Spray Ionization Mass Spectrometry with Metal Nanotubes and the Detection of 2,4,6-Trinitrotoluene

Materials are making inroads into mass spectrometry, and an example is the use of advanced materials for enhanced ionization by transformation of a less-ionizable molecule to an easily ionizable one. Here we show the use of Pt nanoparticle-decorated nanotubes as highly active catalysts for the reduction of 2,4,6-trinitrotoluene to 2,4,6-triaminotoluene and subsequent easy detection of the product by in situ ambient ionization mass spectrometry.

Nanoscience in India: a perspective

India has emerged as a leading player in the field of nanoscience and nanotechnology over the last decade. The Indian nano-endeavor got its initial push through the Nano Science and Nano Technology (NS&NT) initiative (now the Nano Mission) of the Department of Science and Technology (DST), Government of India in 2002 and has accelerated very fast since then. This article is intended to sketch a brief picture of the recent nanoscience and technology activities in India with special emphasis on synthesis of nanomaterials and emergence of new properties in them. Application of nanomateials into the very basic needs of India like water purification and energy creation along with the recent developments at the bio-nano interface will be discussed. State of nanoscience education at educational institutions in India and nanoscience based industrial initiatives will be touched upon.

Holey MoS2 Nanosheets with Photocatalytic Metal Rich Edges by Ambient Electrospray Deposition for Solar Water Disinfection

Abstract A new method for creating nanopores in single‐layer molybdenum disulfide (MoS2) nanosheets (NSs) by the electrospray deposition of silver ions on a water suspension of the former is introduced. Electrospray‐deposited silver ions react with the MoS2 NSs at the liquid–air interface, resulting in Ag2S nanoparticles which enter the solution, leaving the NSs with holes of 3–5 nm diameter. Specific reaction with the S of MoS2 NSs leads to Mo‐rich edges. Such Mo‐rich defects are highly efficient for the generation of active oxygen species such as H2O2 under visible light which causes efficient disinfection of water. 105 times higher efficiency in disinfection for the holey MoS2 NSs in comparison to normal MoS2 NSs is shown. Experiments are performed with multiple bacterial strains and a virus strain, demonstrating the utility of the method for practical applications. A conceptual prototype is also presented.