Search results for "gold nanocluster"
showing 10 items of 29 documents
Exploring Strategies for Labeling Viruses with Gold Nanoclusters through Non-equilibrium Molecular Dynamics Simulations.
2017
Biocompatible gold nanoclusters can be utilized as contrast agents in virus imaging. The labeling of viruses can be achieved noncovalently but site-specifically by linking the cluster to the hydrophobic pocket of a virus via a lipid-like pocket factor. We have estimated the binding affinities of three different pocket factors of echovirus 1 (EV1) in molecular dynamics simulations combined with non-equilibrium free-energy calculations. We have also studied the effects on binding affinities with a pocket factor linked to the Au102pMBA44 nanocluster in different protonation states. Although the absolute binding affinities are over-estimated for all the systems, the trend is in agreement with r…
Core‐Selective Silver‐Doping of Gold Nanoclusters by Surface‐Bound Sulphates on Colloidal Templates: From Synthetic Mechanism to Relaxation Dynamics
2022
Funding Information: This work was carried out under the ERC Advanced grant (DRIVEN, ERC‐2016‐AdG‐742829), Academy of Finland's Centre of Excellence in Life‐Inspired Hybrid Materials (LIBER, 346108), Academy of Finland (No. 321443, 328942, 308647, and 318891) and Photonic Research and Innovation (PREIN) as well as FinnCERES flagships. L.F. and X.C. thanks for support from CSC (IT Center for Science, Finland) for providing computation resources. The authors acknowledge the provision of facilities and technical support by Aalto University OtaNano – Nanomicroscopy Center (Aalto‐NMC). | openaire: EC/H2020/742829/EU//DRIVEN Ultra-small luminescent gold nanoclusters (AuNCs) have gained substantia…
Highly Robust but Surface-Active : An N-Heterocyclic Carbene-Stabilized Au25 Nanocluster
2019
Surface organic ligands play a critical role in stabilizing atomically precise metal nanoclusters in solutions. However, it is still challenging to prepare highly robust ligated metal nanoclusters that are surface-active for liquid-phase catalysis without any pre-treatment. Now, an N-heterocyclic carbene-stabilized Au25 nanocluster with high thermal and air stabilities is presented as a homogenous catalyst for cycloisomerization of alkynyl amines to indoles. The nanocluster, characterized as [Au25(iPr2-bimy)10Br7]2+ (iPr2-bimy=1,3-diisopropylbenzimidazolin-2-ylidene) (1), was synthesized by direct reduction of AuSMe2Cl and iPr2-bimyAuBr with NaBH4 in one pot. X-ray crystallization analysis …
Acid–Base Properties and Surface Charge Distribution of the Water-Soluble Au102(pMBA)44 Nanocluster
2016
The pKa of the p-mercaptobenzoic acid (pMBA) ligands in the Au102(pMBA)44 nanocluster was measured by using acid–base and IR titration. The observed macroscopic pKa = 6.18 ± 0.05 is significantly more basic than that of free pMBA (pKa = 4.16), and the protonation behavior is anticooperative according to the Hill coefficient n = 0.64 ± 0.04. The cluster is truly water-soluble when more than 22 and insoluble when fewer than 7 ligands are in the deprotonated state. In order to obtain more insight into the anticooperative character, the cluster was modeled at pH ∼6.2 using constant pH molecular dynamics simulations. The pKa values of the individual pMBAs are in the range of 5.18–7.58, depending…
Dynamic Diglyme-Mediated Self-Assembly of Gold Nanoclusters
2015
We report the assembly of gold nanoclusters by the nonthiolate ligand diglyme into discrete and dynamic assemblies. To understand this surprising phenomenon, the assembly of Au20(SC2H4Ph)15-diglyme into Au20(SC2H4Ph)15-diglyme-Au20(SC2H4Ph)15 is explored in detail. The assembly is examined by high-angle annular dark field scanning transmission electron microscopy, size exclusion chromatography, mass spectrometry, IR spectroscopy, and calorimetry. We establish a dissociation constant for dimer to monomer conversion of 20.4 μM. Theoretical models validated by transient absorption spectroscopy predict a low-spin monomer and a high-spin dimer, with assembly enabled through weak diglyme oxygen-g…
Au25(SEt)18 a nearly naked thiolate-protected Au25 cluster Struct. analysis by single crystal X-ray crystallograp. and electron nuclear double res
2014
X-ray crystallography has been fundamental in discovering fine structural features of ultrasmall gold clusters capped by thiolated ligands. For still unknown structures, however, new tools capable of providing relevant structural information are sought. We prepared a 25-gold atom nanocluster protected by the smallest ligand ever used, ethanethiol. This cluster displays the electrochemistry, mass spectrometry, and UV-vis absorption spectroscopy features of similar Au25 clusters protected by 18 thiolated ligands. The anionic and the neutral form of Au25(SEt)18 were fully characterized by (1)H and (13)C NMR spectroscopy, which confirmed the monolayer's properties and the paramagnetism of neutr…
Jahn–Teller effects in Au25(SR)18
2016
The relationship between oxidation state, structure, and magnetism in many molecules is well described by first-order Jahn–Teller distortions. This relationship is not yet well defined for ligated nanoclusters and nanoparticles, especially the nano-technologically relevant gold-thiolate protected metal clusters. Here we interrogate the relationships between structure, magnetism, and oxidation state for the three stable oxidation states, 1, 0 and +1 of the thiolate protected nanocluster Au25(SR)18. We present the single crystal X-ray structures of the previously undetermined charge state Au25(SR)18+1, as well as a higher quality single crystal structure of the neutral compound Au25(SR)180 . …
Gold Nanowired: A Linear (Au25)n Polymer from Au25 Molecular Clusters
2014
Au25(SR)18 has provided fundamental insights into the properties of clusters protected by monolayers of thiolated ligands (SR). Because of its ultrasmall core, 1 nm, Au25(SR)18 displays molecular behavior. We prepared a Au25 cluster capped by n-butanethiolates (SBu), obtained its structure by single-crystal X-ray crystallography, and studied its properties both experimentally and theoretically. Whereas in solution Au25(SBu)18(0) is a paramagnetic molecule, in the crystal it becomes a linear polymer of Au25 clusters connected via single Au-Au bonds and stabilized by proper orientation of clusters and interdigitation of ligands. At low temperature, [Au25(SBu)18(0)]n has a nonmagnetic ground s…
Covalently linked multimers of gold nanoclusters Au102(p-MBA)44and Au∼250(p-MBA)n
2016
We present the synthesis, separation, and characterization of covalently-bound multimers of para-mercaptobenzoic acid (p-MBA) protected gold nanoclusters. The multimers were synthesized by performing a ligand-exchange reaction of a pre-characterized Au102(p-MBA)44 nanocluster with biphenyl-4,4′-dithiol (BPDT). The reaction products were separated using gel electrophoresis yielding several distinct bands. The bands were analyzed by transmission electron microscopy (TEM) revealing monomer, dimer, and trimer fractions of the nanocluster. TEM analysis of dimers in combination with molecular dynamics simulations suggest that the nanoclusters are covalently bound via a disulfide bridge between BP…
Template-Free Supracolloidal Self-Assembly of Atomically Precise Gold Nanoclusters : From 2D Colloidal Crystals to Spherical Capsids
2016
We report supracolloidal self-assembly of atomically precise and strictly monodisperse gold nanoclusters involving p-mercaptobenzoic acid ligands (Au102-pMBA44) under aqueous conditions into hexagonally packed monolayer-thick two-dimensional facetted colloidal crystals (thickness 2.7 nm) and their bending to closed shells leading to spherical capsids (d ca. 200 nm), as controlled by solvent conditions. The 2D colloidal assembly is driven in template-free manner by the spontaneous patchiness of the pMBA ligands around the Au102-pMBA44 nanoclusters preferably towards equatorial plane, thus promoting inter-nanocluster hydrogen bonds and high packing to planar sheets. More generally, the findin…