Reversible Microscale Assembly of Nanoparticles Driven by the Phase Transition of a Thermotropic Liquid Crystal.

The arrangement of nanoscale building blocks into patterns with microscale periodicity is challenging to achieve via self-assembly processes. Here, we report on the phase-transition-driven collective assembly of gold nanoparticles in a thermotropic liquid crystal. A temperature-induced transition from the isotropic to the nematic phase under anchoring-driven planar alignment leads to the assembly of individual nanometer-sized particles into arrays of micrometer-sized agglomerates, whose size and characteristic spacing can be tuned by varying the cooling rate.

High-resolution scanning tunneling microscopy characterization of mixed monolayer protected gold nanoparticles.

Gold nanoparticles protected by a binary mixture of thiolate molecules have a ligand shell that can spontaneously separate into nanoscale domains. Complex morphologies arise in such ligand shells, including striped, patchy, and Janus domains. Characterization of these morphologies remains a challenge.

Ag44(SR)30(4-): a silver-thiolate superatom complex.

Intensely and broadly absorbing nanoparticles (IBANs) of silver protected by arylthiolates were recently synthesized and showed unique optical properties, yet question of their dispersity and their molecular formulas remained. Here IBANs are identified as a superatom complex with a molecular formula of Ag(44)(SR)(30)(4-) and an electron count of 18. This molecular character is shared by IBANs protected by 4-fluorothiophenol or 2-naphthalenethiol.

Biomimetic monolayer-protected gold nanoparticles for immunorecognition.

Gold nanoparticles (AuNPs) protected by self-assembled monolayers (SAMs) are capable of presenting precisely engineered surfaces at the nanoscale, allowing the mimicry of biomacromolecules on an artificial platform. Here we review the generation, characterization, and applications of monolayer-protected AuNPs that have been designed for immunorecognition by the integration of an oligopeptide epitope into the protecting monolayer. The resulting peptide-AuNP conjugate is an effective platform for biomimesis, as demonstrated by multiple studies.

Nanoscale phase segregation of mixed thiolates on gold nanoparticles.

Phase segregation and domain formation is observed within the protecting monolayer of gold nanoparticles (AuNPs) using ion mobility-mass spectrometry, a two-dimensional gas-phase separation technique. Experimental data is compared to a theoretical model that represents a randomly distributed ligand mixture. Deviations from this model provide evidence for nanophase separation resulting in anisotropic AuNPs.

Short-chain PEG mixed monolayer protected gold clusters increase clearance and red blood cell counts.

Monolayer-protected gold nanoparticles have great potential as novel building blocks for the design of new drugs and therapeutics based on the easy ability to multifunctionalize them for biological targeting and drug activity. In order to create nanoparticles that are biocompatible in vivo, polyethylene glycol functional groups have been added to many previous multifunctionalized particles to eliminate nonspecific binding. Recently, monolayer-protected gold nanoparticles with mercaptoglycine functionalities were shown to elicit deleterious effects on the kidney in vivo that were eliminated by incorporating a long-chain, mercapto-undecyl-tetraethylene glycol at very high loadings into a mixed monolayer.

Tiopronin gold nanoparticle precursor forms aurophilic ring tetramer.

In the two step synthesis of thiolate-monolayer protected clusters (MPCs), the first step of the reaction is a mild reduction of gold(III) by thiols that generates gold(I) thiolate complexes as intermediates. Using tiopronin (Tio) as the thiol reductant, the characterization of the intermediate Au(4)Tio(4) complex was accomplished with various analytical and structural techniques. Nuclear magnetic resonance (NMR), elemental analysis, thermogravimetric analysis (TGA), and matrix-assisted laser desorption/ionization-mass spectrometry (MALDI-MS) were all consistent with a cyclic gold(I)-thiol tetramer structure, and final structural analysis was gathered through the use of powder diffraction and pair distribution functions (PDF).

A structural mass spectrometry strategy for the relative quantitation of ligands on mixed monolayer-protected gold nanoparticles.

It is becoming increasingly common to use gold nanoparticles (AuNPs) protected by a heterogeneous mixture of thiolate ligands, but many ligand mixtures on AuNPs cannot be properly characterized due to the inherent limitations of commonly used spectroscopic techniques. Using ion mobility-mass spectrometry (IM-MS), we have developed a strategy that allows measurement of the relative quantity of ligands on AuNP surfaces. This strategy is used for the characterization of three samples of mixed-ligand AuNPs: tiopronin:glutathione (av diameter 2.

Characterization of thiolate-protected gold nanoparticles by mass spectrometry.

Thiolate-protected gold nanoparticles (AuNPs) are a highly versatile nanomaterial, with wide-ranging physical properties dependent upon the protecting thiolate ligands and gold core size. These nanoparticles serve as a scaffold for a diverse and rapidly increasing number of applications, extending from molecular electronics to vaccine development. Key to the development of such applications is the ability to quickly and precisely characterize synthesized AuNPs.

Surface fragmentation of complexes from thiolate protected gold nanoparticles by ion mobility-mass spectrometry.

Matrix-assisted laser desorption/ionization-ion mobility-mass spectrometry (MALDI-IM-MS) was used to analyze low mass gold-thiolate fragments generated from thiolate-protected gold nanoparticles (AuNPs). This is the first report of using gas-phase structural separations by IM-MS for the characterization of AuNPs, revealing significant structural variation between organic and gold-thiolate ionic species. Through the separation of background chemical noise, gold-thiolate ion species corresponding to fragments from the AuNP surface can be isolated.