millifluidics-for-chemical-synthesis-time-resolved-mechanistic

Millifluidics for Chemical Synthesis and Time-resolved Mechanistic Studies

Procedures utilizing millifluidic devices for chemical synthesis and time-resolved mechanistic studies are described by taking three examples. In the ...

Louisiana State University

Form emerges from formless entities: temperature-induced self-assembly and growth of ZnO nanoparticles into zeptoliter bowls and troughs.

Unusual morphologies of silica, gold and carbon were obtained by using ZnO nanostructures as templates. Microdrums and pencil-shaped ZnO nanostructures are successfully replicated into silica, gold and carbon analogues which are otherwise difficult to make.

ZnO: a versatile template to obtain unusual morphologies of silica, gold and carbon nanostructures.

Here we report an instantaneous formation of high surface area metal nanosponges through a one-step inexpensive method in a completely green solvent, water. Merely by optimizing the concentration of the precursors and the reducing agent, we were able to generate a three-dimensional porous structure made up of nanowire networks. This is a general process, involves a simple, room temperature reduction of metal salts with sodium borohydride, and is therefore scalable to any amount. Further, these nanoporous metals because of their network structures show optical limiting behavior of a true broadband nature that would find applications in optoelectronic nanodevices.

Mixing does the magic: a rapid synthesis of high surface area noble metal nanosponges showing broadband nonlinear optical response.

Micronic cage structures of squarate based metal-organic coordination frameworks (MOCFs) have been fabricated for the first time by specific anion selective etching of metal squarate cubes. Time and stoichiometry dependent synthesis and the corresponding microscopic studies have provided mechanistic insight into the cage formation. Furthermore, a non-covalent post-synthetic strategy has been adopted to functionalize the micronic cubes or cages with chromophores rendering the resulting hybrids green fluorescent.

Shape assisted fabrication of fluorescent cages of squarate based metal-organic coordination frameworks.

Innovative in situ characterization tools are essential for understanding the reaction mechanisms leading to the growth of nanoscale materials. Though techniques, such as in situ transmission X-ray microscopy, fast single-particle spectroscopy, small-angle X-ray scattering, etc., are currently being developed, these tools are complex, not easily accessible, and do not necessarily provide the temporal resolution required to follow the formation of nanomaterials in real time. Here, we demonstrate for the first time the utility of a simple millifluidic chip for an in situ real time analysis of morphology and dimension-controlled growth of gold nano- and microstructures with a time resolution of 5 ms. The structures formed were characterized using synchrotron radiation-based in situ X-ray absorption spectroscopy, 3-D X-ray tomography, and high-resolution electron microscopy. These gold nanostructures were found to be catalytically active for conversion of 4-nitrophenol into 4-aminophenol, providing an example of the potential opportunities for time-resolved analysis of catalytic reactions. While the investigations reported here are focused on gold nanostructures, the technique can be applied to analyze the time-resolved growth of other types of nanostructured metals and metal oxides. With the ability to probe at least a 10-fold higher concentrations, in comparison with traditional microfluidics, the tool has potential to revolutionize a broad range of fields from catalysis, molecular analysis, biodefense, and molecular biology.

Millifluidics for time-resolved mapping of the growth of gold nanostructures.

The past two decades have seen a dramatic raise in the number of investigations leading to the development of Lab-on-a-Chip (LOC) devices for synthesis of nanomaterials. A majority of these investigations were focused on inorganic nanomaterials comprising of metals, metal oxides, nanocomposites and quantum dots. Herein, we provide an analysis of these findings, especially, considering the more recent developments in this new decade. We made an attempt to bring out the differences between chip-based as well as tubular continuous flow systems. We also cover, for the first time, various opportunities the tools from the field of computational fluid dynamics provide in designing LOC systems for synthesis inorganic nanomaterials. Particularly, we provide unique examples to demonstrate that there is a need for concerted effort to utilize LOC devices not only for synthesis of inorganic nanomaterials but also for carrying out superior in vitro studies thereby, paving the way for faster clinical translation. Even though LOC devices with the possibility to carry out multi-step syntheses have been designed, surprisingly, such systems have not been utilized for carrying out simultaneous synthesis and bio-functionalization of nanomaterials. While traditionally, LOC devices are primarily based on microfluidic systems, in this review article, we make a case for utilizing millifluidic systems for more efficient synthesis, bio-functionalization and in vitro studies of inorganic nanomaterials tailor-made for biomedical applications. Finally, recent advances in the field clearly point out the possibility for pushing the boundaries of current medical practices towards personalized health care with a vision to develop automated LOC-based instrumentation for carrying out simultaneous synthesis, bio-functionalization and in vitro evaluation of inorganic nanomaterials for biomedical applications.

Lab-on-a-chip synthesis of inorganic nanomaterials and quantum dots for biomedical applications.

Herein, we report a facile route for the synthesis of foam-like porous oxides using carbon spheres and polyvinylpyrrolidone (PVP) as sacrificial templates. The as-prepared porous structures were characterized by XRD, FESEM, TEM and BET methods. These foam-like macroporous oxides are formed through the fusion of oxide nanoparticles around the gas bubbles liberated during the combustion of composites and show good BET surface areas.

Carbon spheres assisted synthesis of porous oxides with foam-like architecture.

We present results from our investigations into correlating the styrene-oxidation catalysis of atomically precise mixed-ligand biicosahedral-structure [Au25(PPh3)10(SC12H25)5Cl2](2+) (Au25-bi) and thiol-stabilized icosahedral core-shell-structure [Au25(SCH2CH2Ph)18](-) (Au25-i) clusters with their electronic and atomic structure by using a combination of synchrotron radiation-based X-ray absorption fine-structure spectroscopy (XAFS) and ultraviolet photoemission spectroscopy (UPS). Compared to bulk Au, XAFS revealed low Au-Au coordination, Au-Au bond contraction and higher d-band vacancies in both the ligand-stabilized Au clusters. The ligands were found not only to act as colloidal stabilizers, but also as d-band electron acceptor for Au atoms. Au25-bi clusters have a higher first-shell Au coordination number than Au25-i, whereas Au25-bi and Au25-i clusters have the same number of Au atoms. The UPS revealed a trend of narrower d-band width, with apparent d-band spin-orbit splitting and higher binding energy of d-band center position for Au25-bi and Au25-i. We propose that the differences in their d-band unoccupied state population are likely to be responsible for differences in their catalytic activity and selectivity. The findings reported herein help to understand the catalysis of atomically precise ligand-stabilized metal clusters by correlating their atomic or electronic properties with catalytic activity.

Ligand-stabilized and atomically precise gold nanocluster catalysis: a case study for correlating fundamental electronic properties with catalysis.

Silver ions are widely used as antibacterial agents, but the basic molecular mechanism of this effect is still poorly understood. X-ray absorption near-edge structure (XANES) spectroscopy at the Ag LIII, S K, and P K edges reveals the chemical forms of silver in Staphylococcus aureus and Escherichia coli (Ag(+) treated). The Ag LIII-edge XANES spectra of the bacteria are all slightly different and very different from the spectra of silver ions (silver nitrate and silver acetate), which confirms that a reaction occurs. Death or inactivation of bacteria was observed by plate counting and light microscopy. Silver bonding to sulfhydryl groups (Ag-S) in cysteine and Ag-N or Ag-O bonding in histidine, alanine, and dl-aspartic acid was detected by using synthesized silver-amino acids. Significantly lower silver-cysteine content, coupled with higher silver-histidine content, in Gram-positive S. aureus and Listeria monocytogenes cells indicates that the peptidoglycan multilayer could be buffering the biocidal effect of silver on Gram-positive bacteria, at least in part. Bonding of silver to phosphate groups was not detected. Interaction with DNA or proteins can occur through Ag-N bonding. The formation of silver-cysteine can be confirmed for both bacterial cell types, which supports the hypothesis that enzyme-catalyzed reactions and the electron transport chain within the cell are disrupted.

X-Ray Absorption Near-Edge Structure (XANES) Spectroscopy Study of the Interaction of Silver Ions with Staphylococcus aureus, Listeria monocytogenes, and Escherichia coli.

Comparative theoretical and experimental investigations are reported into chemically induced magnetism in atomically-precise, ligand-stabilized gold clusters Au25 , Au38 and Au55 . The results indicate that [Au25 (PPh3 )10 (SC12 H25 )5 Cl2 ](2+) and Au38 (SC12 H25 )24 are diamagnetic, Au25 (SC2 H4 Ph)18 is paramagnetic, and Au55 (PPh3 )12 Cl6 , is ferromagnetic at room temperature. Understanding the magnetic properties resulting from quantum size effects in such atomically precise gold clusters could lead to new fundamental discoveries and applications.

Article	Year
Form emerges from formless entities: temperature-induced self-assembly and growth of ZnO nanoparticles into zeptoliter bowls and troughs. Angewandte Chemie (International ed. in English)\| PubMed ID: 17607675	2007
ZnO: a versatile template to obtain unusual morphologies of silica, gold and carbon nanostructures. Chemical communications (Cambridge, England)\| PubMed ID: 20376403	2010
Mixing does the magic: a rapid synthesis of high surface area noble metal nanosponges showing broadband nonlinear optical response. ACS nano\| PubMed ID: 20443580	2010
Shape assisted fabrication of fluorescent cages of squarate based metal-organic coordination frameworks. Chemical communications (Cambridge, England)\| PubMed ID: 23435584	2013
Millifluidics for time-resolved mapping of the growth of gold nanostructures. Journal of the American Chemical Society\| PubMed ID: 23496175	2013
Lab-on-a-chip synthesis of inorganic nanomaterials and quantum dots for biomedical applications. Advanced drug delivery reviews\| PubMed ID: 23726944	2013
Carbon spheres assisted synthesis of porous oxides with foam-like architecture. Journal of nanoscience and nanotechnology\| PubMed ID: 23763210	2013
Ligand-stabilized and atomically precise gold nanocluster catalysis: a case study for correlating fundamental electronic properties with catalysis. Chemistry (Weinheim an der Bergstrasse, Germany)\| PubMed ID: 23788381	2013
X-Ray Absorption Near-Edge Structure (XANES) Spectroscopy Study of the Interaction of Silver Ions with Staphylococcus aureus, Listeria monocytogenes, and Escherichia coli. Applied and environmental microbiology\| PubMed ID: 23934494	2013
Chemically Induced Magnetism in Atomically Precise Gold Clusters. Small (Weinheim an der Bergstrasse, Germany)\| PubMed ID: 24150895	2013

Katla Sai Krishna

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