A new methodology has been demonstrated for ultratrace detection of Hg2+, working at the limit of a few tens of metal ions. Bright, red luminescent atomically precise gold clusters, Au@BSA (BSA, bovine serum albumin), coated on Nylon-6 nanofibers were used for these measurements. A green emitting fluorophore, FITC (fluorescein isothiocyanate), whose luminescence is insensitive to Hg2+ was precoated on the fiber. Exposure to mercury quenched the red emission completely, and the green emission of the fiber appeared which was observed under dark field fluorescence microscopy. For the sensing experiment at the limit of sensitivity, we have used individual nanofibers. Quenching due to Hg2+ ions was fast and uniform. Adaptation of such sensors to pH paper-like test-strips would make affordable water quality sensors at ultralow concentrations a reality. © 2014 American Chemical Society.

C. Vijayan

Department Of Physics

Pradeep Thalappil

Department Of Chemistry

Atanu Ghosh

Vedhakkani Jeseentharani

Mohd Azhardin Ganayee

Rani Gopalakrishnan Hemalatha

Kamalesh Chaudhari

Body fluids

Dyes

Fluorescence microscopy

Gold coatings

Gold compounds

Luminescence

Mercury (metal)

Metal ions

METAL WORKING

Water quality

Bovine serum albumins

fluorescein isothiocyanate

Green emissions

INDIVIDUAL NANOFIBERS

NANOFIBER COMPOSITES

RED EMISSIONS

ULTRATRACE DETECTION

WATER QUALITY SENSORS

Nanofibers

IIT Madras is a public technical and research university located in Chennai, Tamil Nadu. Founded in 1959, it is recognised as an Institute of National Importance.

IIT Madras has been ranked as the top engineering institute in India for four years in a row by the National Institutional Ranking Framework of the MHRD

It currently offers undergraduate, postgraduate and research degrees across 16 disciplines in Engineering, Sciences, Humanities and Management. About 596 faculty belonging to science and engineering departments and centres of the Institute are engaged in teaching, research and industrial consultancy.

IIT Madras

Analytical Chemistry

We introduce a cluster coprotected by thiol and diphosphine ligands, [Ag22(dppe)4(2,5-DMBT)12Cl4]2+ (dppe = 1,2-bis(diphenylphosphino)ethane; 2,5-DMBT= 2,5-dimethylbenzenethiol), which has an Ag10 core encapsulated by an Ag12(dppe)4(2,5-DMBT)12Cl4 shell. The Ag10 core comprises two Ag5 distorted trigonal bipyramidal units and is uncommon in Au and Ag nanoclusters. The electrospray ionization mass spectrum reveals that the cluster is divalent and contains four free electrons. An uncommon crystallization-induced enhancement of emission is observed in the cluster. The emission is weak in the solution and amorphous states. However, it is enhanced 12 times in the crystalline state compared to the amorphous state. A detailed investigation of the crystal structure suggests that well-arranged C-H⋯πand π⋯πinteractions between the ligands are the major factors for this enhanced emission. Further, in-depth structural elucidation and density functional theory calculations suggest that the cluster is a superatom with four magic electrons. © 2019 American Chemical Society.

ACS Nano

Confining an Ag10 Core in an Ag12 Shell: A Four-Electron Superatom with Enhanced Photoluminescence upon Crystallization

Fulltext

Sustainable Nanoscale Engineering: From Materials Design to Chemical Processing

Challenges and directions for green chemical engineering-role of nanoscale materials

This article adds a new direction to the functional capability of protein-protected atomically precise gold clusters as sensors. Counting on the extensively researched intense luminescence of these clusters and considering the electron donating nature of select amino acids, we introduce a dual probe sensor capable of sensing changes in luminescence and conductivity, utilizing bovine serum albumin-protected atomically precise gold clusters hosted on nanofibers. To this end, we have also developed a hybrid nanofiber with a conducting core with a porous dielectric shell. We show that clusters in combination with nanofibers offer a highly selective and sensitive platform for the detection of trace quantities of trinitrotoluene, both in solution and in the vapor phase. In the solution phase, trinitrotoluene (TNT) can be detected down to 1 ppt at room temperature, whereas in vapor phase, 4.8 × 109 molecules of TNT can be sensed using a 1 mm fiber. Although the development in electrospinning techniques for fabricating nanofibers as sensors is quite substantial, a hybrid fiber with the dual properties of conductivity and luminescence has not been reported yet. © 2017 American Chemical Society.

ACS Omega

Dual Probe Sensors Using Atomically Precise Noble Metal Clusters

We report the synthesis and unique reactivity of a new green dithiol protected cluster (DTPC), Ag51(BDT)19(TPP)3 (BDT and TPP are 1,3-benzenedithiol and triphenylphosphine, respectively). The cluster composition was confirmed by electrospray ionization (ESI) and matrix-assisted laser desorption ionization (MALDI) mass spectrometric studies as well as by other supporting data. Surprisingly, the chemical reactivity between this DTPC and Au25(SR)18 involves only metal ion exchange in Au25(SR)18 without any ligand exchange, while reactions between monothiol protected clusters (MTPCs) show both metal and ligand exchange, an example being the reaction between Ag25DMBT18 and Au25PET18 (where DMBT and PET are 2,4-dimethylbenzenethiol and phenylethanethiol, respectively). The conclusions have been confirmed by the reaction of another DTPC, Ag29(BDT)12(TPP)4 with Au25BT18 (where BT corresponds to butanethiol) in which only metal exchange happens in Au25BT18. We also show the conversion of Ag51(BDT)19(TPP)3 to Ag29(BDT)12(TPP)4 in the presence of a second monothiol, DMBT which does not get integrated into the product cluster. This is completely different from the previous understanding wherein the reaction between MTPCs and a second thiol leads to either mixed thiol protected clusters with the same core composition or a completely new cluster core protected with the second thiol. The present study exposes a new avenue of research for monolayer protected clusters, which in turn will give additional impetus to explore the chemistry of DTPCs. © 2017 The Royal Society of Chemistry.

Nanoscale

Unusual reactivity of dithiol protected clusters in comparison to monothiol protected clusters: Studies using Ag51(BDT)19(TPP)3 and Ag29(BDT)12(TPP)4

Atomically precise gold and silver clusters are a new class of sensitizers which can be used as substitutes for dyes in the classical dye-sensitized solar cells (DSCs). Here noble metal clusters protected by proteins and thiols (Au30@BSA, Au25SBB18, and Ag44MBA30) have been used for photovoltaic studies. These metal clusters were used as sensitizers for the photoanodes fabricated using TiO2 nanotubes (NTs) and the commercial P25 TiO2 nanoparticles. The TiO2, clusters and the solar cells were characterized by spectroscopy, microscopy, current-voltage (I-V) and incident photon-to-current conversion efficiency (IPCE) measurements. A systematic I-V study revealed a conversion efficiency of 0.35 % for the Au30@BSA sensitized solar cell made from TiO2 NTs which showed an IPCE maximum of 3 % at ∼ 400 nm. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

ChemistrySelect

Atomically Precise Noble Metal Clusters Harvest Visible Light to Produce Energy

Sub-nanometer-sized metal clusters, having dimensions between metal atoms and nanoparticles, have attracted tremendous attention in the recent past due to their unique physical and chemical properties. As properties of such materials depend strongly on size, development of synthetic routes that allows precise tuning of the cluster cores with high monodispersity and purity is an area of intense research. Such materials are also interesting owing to their wide variety of applications. Novel sensing strategies based on these materials are emerging. Owing to their extremely small size, low toxicity, and biocompatibility, they are widely studied for biomedical applications. Primary focus of this review is to provide an account of the recent advances in their applications in areas such as environment, energy, and biology. With further experimental and theoretical advances aimed at understanding their novel properties and solving challenges in their synthesis, an almost unlimited field of applications can be foreseen. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Particle and Particle Systems Characterization

Noble metal clusters: Applications in energy, environment, and biology

How low can you go? The visual detection of 2,4,6-trinitrotoluene and Hg2+ at the sub-zeptomole level is demonstrated. This was achieved using a hybrid material that allowed for the development of a single-particle, single-molecule detection technique, which may be the ultimate in ultra-trace sensitivity with selectivity. Copyright © 2012 WILEY-VCH Verlag GmbH &amp; Co. KGaA, Weinheim.

Angewandte Chemie - International Edition

Selective visual detection of TNT at the sub-zeptomole level

A one-pot synthesis of extremely stable, water-soluble Cu quantum clusters (QCs) capped with a model protein, bovine serum albumin (BSA), is reported. From matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry, we assign the clusters to be composed of Cu 5 and Cu 13 cores. The QCs also show luminescence properties having excitation and emission maxima at 325 and 410 nm, respectively, with a quantum yield of 0.15, which are found to be different from that of protein alone in similar experimental conditions. The quenching of luminescence of the protein-capped Cu QCs in the presence of very low hydrogen peroxide concentration (approximately nanomolar, or less than part-per-billion) reflects the efficacy of the QCs as a potential sensing material in biological environments. Moreover, as-prepared Cu QCs can detect highly toxic Pb 2+ ions in water, even at the part-per-million level, without suffering any interference from other metal ions. © 2011 American Chemical Society.

Copper quantum clusters in protein matrix: Potential sensor of Pb 2+ ion

We have prepared Au15 quantum clusters anchored to α, β, and γcyclodextrin (CD) cavities. The synthesis process involves the core etching of larger clusters and the simultaneous trapping of the clusters formed inside the CD cavities. The clusters were characterized by various tools, such as optical absorption and luminescence spectroscopies, electrospray ionization-mass spectrometry (ESI-MS), X-ray photoelectron spectroscopy (XPS), circular dichroism spectroscopy, and two-dimensional nuclear magnetic resonance (2D NMR) spectroscopy. Trapping of the cluster in the CD cavity was proven by circular dichroism and also by rotational Overhauser effect spectroscopy (ROESY), in terms of the distinct cross peak between proton "e" of the glutathione (-SG) ligand and the ∼3 "e" proton of CD. Dynamic light scattering (DLS) studies showed a hydrodynamic diameter of ∼3-4 nm, indicating one CD molecule per cluster with an extension of one water of hydration. The clusters are intensely luminescent, with major lifetime components of 28, 71, and 24 ps for Au 15@ αCD, Au15atβCD, and Au 15atγCD, respectively. The clusters also are strongly luminescent in the solid state. Both in the solution and in the solid state, the luminescence is sensitive to solvents/vapors. The clusters adhere to glass plates, and the solvent dependency of luminescence was used to create patterns that are erased upon gradual evaporation of the solvent. This self-erasing property was further demonstrated with clusters supported on a thin layer chromatography (TLC) plate. Selective detection of metal ions using the luminescence of the clusters is reported. Evaporation of the cluster solutions leads to luminescent gel-like materials. © 2011 American Chemical Society.

Chemistry of Materials

Quantum clusters in cavities: Trapped Au15 in cyclodextrins

Fluorescence resonance energy transfer between the metal core and the ligand in Au25SG18 (SG-glutathione thiolate) is demonstrated using dansyl chromophores attached to the cluster core through glutathione linkers. The dansyl chromophore functionalization of the cluster has been carried out by two different routes. Efficient energy transfer from the dansyl donor to the Au25 core is manifested by way of the reduced lifetime of the excited state of the former and drastic quenching of its fluorescence. The donor-acceptor separation observed in the two synthetic routes reflects the asymmetry in the ligand binding on the cluster core, which is in agreement with the recent theoretical and experimental results on the structure of Au25. © 2008 American Chemical Society.

Journal of Physical Chemistry C

Quantum clusters of gold exhibiting FRET

Approaching sensitivity of tens of ions using atomically precise cluster-nanofiber composites

Journal	Data powered by TypesetAnalytical Chemistry
Publisher	Data powered by TypesetAmerican Chemical Society
ISSN	00032700
Open Access	No