Au Nanoclusters Research Articles

Tailoring sensitization properties and improving near-infrared photon upconversion performance through alloying in superatomic molecular Au25 nanoclusters.

Noble-metal nanoclusters (NCs) protected by organic ligands have recently come to the forefront as potent triplet sensitizers for photon upconversion (UC) via triplet-triplet annihilation (TTA), owing to their capacity for atomic-level photophysical property customization. Among these, the rod-shaped bi-icosahedral [Au25(PPh3)10(S-C2H4Ph)5Cl2]2+ (Au-rod) NC is a particularly iconic superatomic molecular NC, recently identified as a near-infrared (NIR)-absorbing sensitizer for TTA-UC. In this study, we synthesized Cu-doped NCs, [Au25-xCux(PPh3)10(S-C2H4Ph)5Cl2]2+ (AuCu-rod), and paired them with 9,10-bis(phenylethynyl)anthracene (BPEA) annihilator/emitter to explore the impact of Cu-doping on the triplet sensitization and NIR-UC performance. The triplet state of AuCu-rod, with lifetime of 3 μs, exhibited a modest blue shift compared to the Au-rod, resulting in the increment in the driving force for triplet energy transfer (TET) to the BPEA acceptor. The TET rate constant was determined to be 5.0 × 107 M-1 s-1, which is an order of magnitude higher than the rate constant for the Au-rod/BPEA pair. This improvement has led to a remarkable increase in the TET efficiency. Notably, the AuCu-rod/BPEA pair facilitated the efficient UC of 805 nm NIR light into 510 nm visible light, realizing a large anti-Stokes shift close to 0.9 eV. The UC internal quantum yield of this combination was determined to be 2.33 ± 0.05%, marking a fivefold enhancement over the Au-rod sensitizer (0.49%). Thus, alloying NC sensitizers offers a promising route to enhance UC performance by tuning the triplet state energy and optimizing the compatibility between the sensitizer and annihilator. Additionally, in this series of experiments, the formation of small amounts of BPEA microaggregates was observed. These aggregates did not undergo singlet fission and could retain multiple long-lived triplet excitons. This characteristic facilitated TTA among triplet excitons, resulting in efficient NIR-to-visible UC emission.

An Au25 nanocluster/MoS2 vdWaals heterojunction phototransistor for chromamorphic visual-afterimage emulation.

Color vision relies on three cone photoreceptors that are sensitive to different wavelengths of light. The interaction of three incident light wavelengths over time creates a fascinating color coupling perception, termed chromamorphic computing. However, the realization of this fascinating characteristic in semiconductor devices remains a great challenge. Herein, a mixed-dimensional optoelectronic transistor based on a novel metal nanocluster Au25(SC12H25)18 and two-dimensional MoS2 van der Waals (vdWaals) heterojunction is proposed for chromamorphic visual-afterimage emulation with red-green-blue three-color spatiotemporal coupling perception. This distinguished molecular-like electronic level of Au25 nanoclusters allows the transistor to have visible light-sensitive properties, endowing it with the ability to perceive color information. Moreover, the chromamorphic functions are realized using a color spatiotemporal coupling approach. By utilizing the photogating effect of light stimulus, the device exhibits visual experience-dependent plasticity in accordance with the Bienenstock-Cooper-Munro (BCM) learning rule. Most importantly, for the first time, intriguing visual afterimages could be implemented using a color sensitization approach based on a close relationship between visual persistence and negative afterimages. These results represent an important step towards a new generation of intelligent visual color perception systems for human-computer interaction, bionic robots, etc.

Tailoring two magic number Au13 nanoclusters with N-containing diphosphine ligands: a classical icosahedral core vs. an unprecedented UFO- shaped core

Two magic number Au13 nanoclusters were tailored using two N-containing multidentate phosphine ligands with a classical icosahedral core and an unprecedented “UFO”-shaped polyhedral core, respectively.

Na+ detection via brightening of synergistically originated noble metal nanoclusters.

Weakly fluorescent AuAg nanoclusters were obtained from glutathione, chloroauric acid, and silver nitrate aqueous solution under a modified hydrothermal method. Such glutathione-capped synergistically evolved clusters were obtained for the first time by employing our experimental conditions. Such weak fluorescence was made significantly brighter by employing Na+ and a Na+ sensor was obtained with a linear detection range of 10-5-5 × 10-9 M, while the limit of detection was 1.02 × 10-6 M. Na+ made the GSH matrix positively charged to stabilize AuAg clusters resulting in strong emissive properties. Furthermore, the effect of solvents, sunlight exposure, and temperature was gauged. Estimation of Na+ concentration was undertaken for natural water samples to demonstrate the practical utility of the designed nanosensor.

Trimetallic nanocomposites developed for efficient in vivo bimodal imaging via fluorescence and magnetic resonance.

Despite several attempts, in vivo bimodal imaging still represents a challenge. Generally, it is accepted that dual-modality in imaging can improve sensitivity and spatial resolution, namely, when exploiting fluorescence (FI) and magnetic resonance imaging (MRI), respectively. Here, a newly developed combination of (i) protein-protected luminescent Au-Ag nanoclusters (LGSN) manifesting themselves by fluorescent emission at 705 nm and (ii) superparamagnetic iron oxide nanoparticles (SPION) embedded within the same protein and creating contrast in MR images, has been investigated in phantoms and applied for in vivo bimodal imaging of a mouse as a proof of principle. Unique LGSN-SPION nanocomposites were synthesized in a specific sequential one-pot green preparation procedure and characterized thoroughly using many physicochemical experimental techniques. The influence of LGSN-SPION samples on the viability of healthy cells (RPE-1) was tested using a calcein assay. Despite the presence of Ag (0.12 mg mL-1), high content of Au (above 0.75 mg mL-1), and moderate concentrations of Fe (0.24 mg mL-1), LGSN-SPION samples (containing approx. 15 mg mL-1 of albumin) were revealed as biocompatible (cell viability above 80%). Simultaneously, these concentration values of all components in the LGSN-SPION nanocomposite were used for achieving both MRI and fluorescence signals in phantoms as well as in a living mouse with sufficiently high resolution. Thus, the LGSN-SPION samples can serve as new efficient bimodal FI and MRI probes for in vivo imaging.

Engineering in situ growth of Au nanoclusters on hydrophilic paper fibres for fluorescence calligraphy-based chemical logic gates and information encryption.

Gold nanoclusters (AuNCs) are a type of rising-star fluorescence nanomaterials, but their properties and applications are hindered by the multi-step synthesis and purification routes, as well as the lack of desired supporting substrates. To enhance optical performance and working efficiency, the synthesis and applications of AuNCs are suggested to be merged with emerging substrates. Herein, glutathione-modified hydrophilic rice papers are incubated in chloroauric acid aqueous solutions, and the oxidation-reduction reaction between glutathione and Au ions enables the in situ formation of fluorescent AuNCs on the solid fibres of rice papers. The in situ growth of fluorescent AuNCs on rice papers resulted in eye-catching fluorescence tracks, similar to traditional Chinese conventional calligraphy; thus, this fluoresence calligraphy is defined in this work. The entire process, including synthesis and signal responses, is extremely simple, rapid, and repeatable. Moreover, the diversity of additive chemical reagents in the studied rice papers resulted in responsive fluorescence calligraphy, and the as-synthesized AuNC materials exhibited high reliability and optical stability. Significantly, with the integration of synchronous formation and application of Au nanoclusters on hydrophilic paper substrates, high-performance logical gates and information encryption systems were constructed, remarkably facilitating the progress of molecular sensing and important information transmission.

Au9 nanocluster adsorption and agglomeration control through sulfur modification of mesoporous TiO2.

In the present work phenyl phosphine-protected Au9 nanoclusters were deposited onto (3-mercaptopropyl) trimethoxysilane (MPTMS) modified and unmodified mesoporous screen printed TiO2. The removal of the cluster ligands by annealing was applied to enhance the interaction between Au cluster cores and semiconductor surfaces in the creation of efficient photocatalytic systems. The heat treatment could lead to undesired agglomeration of Au clusters, affecting their unique properties as size specific clusters. To address this challenge, the semiconductor surfaces were modified by MPTMS. Characterization techniques confirm the effectiveness of the modification processes, and XPS demonstrates that S functionalized MTiO2 is more efficient than MTiO2 in increasing Au9 NCs adsorption by a factor of 10 and preventing Au cluster agglomeration even after annealing. Overall, this work contributes valuable insights into photocatalytic systems through controlled modification of semiconductor surfaces and Au nanocluster deposition.

Orchestration of ferro- and anti-ferromagnetic ordering in gold nanoclusters.

The unpaired electron in the gold clusters (Aun, n = no. of Au atoms) with an odd number of total electrons is solely responsible for the magnetic properties in the small-sized Au nano-clusters. However, no such unpaired electron is available due to pairing in the even number of atom gold clusters and behaving as a diamagnetic entity similar to bulk gold. In this work, we unveiled the spin-density distribution of odd Aun clusters with n = 1 to 19 that reveals that a single unpaired electron gets distributed non-uniformly among all Au-atoms depending on the cluster size and morphology. The delocalization of the unpaired electron leads to the spin dilution approaching a value of ∼1/n spin moments on each atom for the higher clusters. Interestingly, small odd-numbered gold clusters possess spin-magnetic moments similar to the delocalized spin moments as of organic radicals. Can cooperative magnetic properties be obtained by coupling these individual magnetic gold nanoparticles? In this work, by applying state-of-the-art computational methodologies, we have demonstrated ferromagnetic or anti-ferromagnetic couplings between such magnetic nanoclusters upon designing suitable organic spacers. These findings will open up a new avenue of nanoscale magnetic materials combining organic spacers and odd-electron nano-clusters.

Tailoring surface morphology on anatase TiO2 supported Au nanoclusters: implications for O2 activation.

Strong interaction between the support surface and metal clusters activates the adsorbed molecules at the metal cluster-support interface. Using plane-wave DFT calculations, we precisely model the interface between anatase TiO2 and small Au nanoclusters. Our study focusses on the adsorption and activation of oxygen molecules on anatase TiO2, considering the influence of oxygen vacancies and steps on the surface. We find that the plane (101) and the stepped (103) surfaces do not support O2 activation, but the presence of oxygen vacancies results in strong adsorption and O-O bond length elongation. Modifying the TiO2 surface with supported small Au n nanoclusters (n = 3-5) also significantly enhances O2 adsorption and stretches the O-O bond. We observe that manipulating the cluster orientation through discrete rotations results in improved O2 adsorption and promotes charge transfer from the surface to the molecule. We propose that the orientation of the supported cluster may be manipulated by making the cluster adsorb at the step-edge of (103) TiO2. This results in activated O2 at the cluster-support interface, with a peroxide-range bond length and a low barrier for dissociation. Our modeling demonstrates a straightforward means of exploiting the interface morphology for O2 activation under low precious metal loading, which has important implications for electrocatalytic oxidation reactions and the rational design of supported catalysts.

Copper doping boosts the catalase-like activity of atomically precise gold nanoclusters for cascade reactions combined with urate oxidase in the ZIF-8 matrix

A biocompatible cascade system was constructed by integrating the merits of urate oxidase and atomically precise Au nanoclusters with tunable catalase-like activity in ZIF-8 for constructing potential drug delivery systems.

Creation and plasmon anisotropy spectroscopy of wedge-shaped gold nanoclusters conditioned by GaAs(001) surface

Wedge-shaped nanoclusters of gold (Au2Ga) are fabricated by high-temperature annealing of a gold nanofilm deposited onto (001) surface of p-doped GaAs crystal with a very thin overlayer of natural oxide. The data of diagnostics confirm the presence in prepared Au/p-GaAs(001) structures of the wedge-shaped Au-intermetallic nanoclusters elongated in [110] direction at GaAs surface. A crystallographic model of the wedge-shaped Au (Au2Ga) nanoclusters conditioned by GaAs(001) surface is discussed in relation with their physicochemical nature. Anisotropic plasmons localized on equally oriented Au-based nanoclusters are detected optically with the reflectance anisotropy spectroscopy and investigated thoroughly with the spectroscopy of polarized light reflection. It is proved experimentally and theoretically that the inhomogeneously broadened infrared spectral peak at the energy about 1.1 eV is associated with plasmons polarized along the wedge-shaped clusters in [110] crystal direction. Another peak - at the energy approximately of 1.8 eV - is due to plasmons having orthogonal polarization in direction [11¯0].

Engineered protein-iron and/or gold-protein-iron nanocomposites in aqueous solutions upon UVA light: Photo-induced electron transfer possibilities and limitations

Occurrence/suppression of photo-induced electron transfer (PI-ET) process in solutions of nanocomposites represents a very hot topic in several photo-related research domains. In this work, this phenomenon is investigated in aqueous solutions using iron-containing mono-/bi-metallic nanocomposites that have been engineered through protein-templated syntheses, with the aim to potentially create new biocompatible imaging contrast agents for medical diagnostics. Two types of iron-containing nanocomposites, mono-metallic (protein-Fe) and bi-metallic (Au-protein-Fe), have been synthesized and characterized with the aid of several experimental techniques, such as high-resolution transmission electron microscopy (HR-TEM), steady-state fluorescence, electron paramagnetic resonance (EPR) and light-induced EPR (LEPR). Theoretical model of the N-terminal region of the bovine serum albumin protein interacting with Fe cations and simulations of the EPR spectral features upon UVA light irradiation complemented the material’s analysis. Two iron forms within the mono-/bi-metallic nanocomposites have been detected experimentally: (i)complexed iron cations (giving EPR signal at g = 4.29) and (ii)superparamagnetic iron oxide nanoparticles (SPIONs; expressing EPR resonances at g// = 2.21 and g⊥ = 2.09). Upon UVA-light irradiation (325 nm), PI-ET between the two iron forms have been observed in the protein-Fe nanocomposite; however, this electronic communication is suppressed in the Au-protein-Fe system. The presence of luminescent Au nanoclusters and dissimilar sizes of SPIONs in bi-metallic nanocomposites (around 5 nm vs. approx. 2 nm in the monometallic protein-Fe system) represent the two possible reasons underneath suppression of the PI-ET process in the former. Moreover, OH radicals were detected in aqueous solutions in both iron-containing nanocomposites (Fe and Au/Fe systems) when irradiated at 325 nm for 5 min at r.t. The reported evidence of PI-ET in iron-containing nanocomposite aqueous solutions can thus have a large impact on their potential medical and/or environmental applications.

Density Functional Theory and Raman Spectroscopy Studies of Adsorption Sites of Au Nanoparticles with Alectinib.

Alectinib is an ALK tyrosine kinase inhibitor, which is mainly used in patients with crizotinib-resistant nonsmall cell lung cancer. Alectinib has attracted much clinical attention for its longest progression-free survival time and the best therapeutic effect. The chemical adsorption of Au nanoclusters (AuNPs) with alectinib molecules is studied by density functional theory (DFT) and surface-enhanced Raman scattering spectroscopy (SERS) experiments. DFT/B3LYP-D3/6-311G** was used for optimization and vibration analysis of alectinib-Au6 complexes, as well as molecular electrostatic potential, frontier molecular orbital, and electro-optic-based charge transfer descriptors. Comparing the results of the DFT theory and SERS experiment, alectinib and AuNPs can form Au-N6 bonds primarily through chemical adsorption of N6 atoms, and the experimental results showed that the enhancement factor (EFCHEM) could reach 4.27. The results provide a theoretical basis for exploring the mechanism of chemical enhancement between AuNPs and alectinib.

In Situ Incorporation of Atomically Precise Au Nanoclusters within Zeolites for Ambient Temperature CO Oxidation.

Preserving ultrasmall sizes of metal particles is a key challenge in the study of heterogeneous metal-based catalysis. Confining the ultrasmall metal clusters in a well-defined crystalline porous zeolite has emerged as a promising approach to stabilize these metal species. Successful encapsulation can be achieved by the addition of ligated metal complexes to zeolite synthesis gel before hydrothermal synthesis. However, controlling the metal particle size during post-reduction treatment remains a major challenge in this approach. Herein, an in situ incorporation strategy of pre-made atomically precise gold clusters within Na-LTA zeolite was established for the first time. With the assistance of mercaptosilane ligands, the gold clusters were successfully incorporated within the Na-LTA without premature precipitation and metal aggregation during the synthesis. We have demonstrated that the confinement of gold clusters within the zeolite framework offers high stability against sintering, leading to superior CO oxidation catalytic performance (up to 12 h at 30 °C, with a space velocity of 3000 mL g-1 h-1).

Physicochemically modulated fluorescence-scattering ratiometric sensor for selective and visual detection of levodopa

In this study, a facile fluorescence-scattering ratiometric sensor was designed for visual and selective detection of levodopa (LD) via a clever physicochemical modulation scheme. The alkalized products of LD can rapidly react with polyethyleneimine (PEI) to exhibit an intense blue fluorescence and decrease the second-order scattering (SOS) signal of PEI. As the concentration of LD increased, the fluorescence intensity at 420 nm increased and the SOS intensity at 675 nm decreased synchronously. Thus the fluorescence-scattering ratiometric sensor was constructed by virtue of the two simultaneously changed signals. Furthermore, red light-emitting Au nanoclusters (AuNCs) were added into the above mixture solution to enlarge the SOS signal and provide a stable red background fluorescence. The intensity ratio of fluorescence to SOS (F/(S/Sblank)) is linear dependent on CLD in the wide range of 50.0–––30000.0 nM, and LD as low as 50.0 nM can be identified with the naked eye via change of fluorescence color. The developed ratiometric sensor is smart, simple and efficient, and has been applied to the convenient assay of LD in real samples. The proposed physicochemical modulation strategy provides a new and facile path for selectively and visually identifying the target from its analogues.

Very Low Temperature CO Oxidation over Atomically Precise Au25 Nanoclusters on MnO2.

Atomically precise Au25 nanoclusters have garnered significant interest in the field of heterogeneous catalysis due to their remarkable activity and selectivity. However, for the extensively studied reaction of low-temperature CO oxidation, their performance has not been competitive compared to other known gold nanocatalysts. To address this, we deposited Au25(SR)18 (R = CH2CH2Ph) nanoclusters onto a manganese oxide support (Au25/MnO2), resulting in a very stable and highly active catalyst. By optimizing the pretreatment temperature, we were able to significantly enhance the performance of the Au25/MnO2 catalyst, which outperformed most other gold catalysts. Impressively, 100% conversion of CO was achieved at temperatures as low as -50 °C, with 50% conversion being reached below -70 °C. Furthermore, the existence of ligands could also influence the negative apparent activation energy observed at intermediate temperatures. Analysis using X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), and X-ray diffraction (XRD) techniques indicated that the Au25 nanoclusters remained stable on the catalyst surface even after pretreatment at high temperatures. In-situ modulation excitation spectroscopy (MES) spectra also confirmed that the Au cluster was the active site for CO oxidation, highlighting the potential of atomically precise Au25 nanoclusters as primary active sites at very low temperatures.

Au Nanocluster Assisted Microstructural Reconstruction for Buried Interface Healing for Enhanced Perovskite Solar Cell Performance.

The heterogeneity of perovskite film crystallization along the vertical direction leads to voids and traps at the buried interfaces, hampering both efficiency and stability of perovskite solar cells. Here, bovine serum albumin-functionalized Au nanoclusters (ABSA), combined with heavy gravity, high surface charge density, and strong interactions with the electron transport layer, are designed to reconstruct the buried interfaces for not only high-quality crystallization, but also improved carrier transfer. The ABSA macromolecules with amine function groups and larger surface charge density interact with the perovskite to improve the crystallinity, and gradually migrate towards the buried interface, healing the defective voids, hence suppressing surface recombination velocity from 3075 to 452 cm s-1 . The healed buried interface and the higher surface potential of ABSA-modified TiO2 lead to improved carrier extraction at the interface. The resulting solar cell attains a power conversion efficiency of 25.0% with negligible hysteresis and remarkable stability, maintaining 92.9% of their initial efficiency after 3200 h of exposure to the ambient atmosphere, they also exhibit better continuous irradiation stability compared to control devices. These findings provide a new metal-protein complex to eliminate the deleterious voids and defects at the buried interface for improved photovoltaic performance and stability.

Electrochemical nonenzymatic glucose sensors catalyzed by Au nanoclusters on metallic nanotube arrays and polypyrrole nanowires

Monitoring blood glucose level is critical, since its abnormality leads to diabetes and causes death, even though glucose is essential for human living. Herein, the sensing study was performed on electrochemical nonenzymatic glucose sensors, which are composed of an Au nanocluster (AuNC) catalyst deposited on a metallic nanotube array (MeNTA) and polypyrrole nanowire (PPyNW). The AuNC was produced by irradiating a femtosecond pulse laser to the Au precursor solution, and it is a simple and facile method. The successful deposition of AuNC on both MeNTA and PPyNW was confirmed by means of the surface morphology and the Au content increase. On the exploration by cyclic voltammetry in alkaline condition, AuNC/MeNTA electrodes showed better performance than AuNC/PPyNW electrodes: The former was a remarkable electrocatalytic detector towards glucose oxidation with better sensitivity, lower detection limit, wider linear range, and longer-term stability without interference from potential interfering agents such as ascorbic acid, urea, NaCl, KCl, etc. Moreover, nonenzymatic AuNC/MeNTA electrodes exhibited high precision and accuracy in real human blood samples and, thus, can be a promising candidate in glucose sensing applications.

Directing the CdS nanosheet and nanowire to high efficiency for photocatalytic anaerobic dehydrogenation of benzyl alcohol to benzaldehyde by depositing Au25 nanoclusters

The photocatalysis of direct dehydrogenation of benzyl alcohol to benzaldehyde is an energy saving way to synthesize fine chemicals and pure hydrogen by using solar energy. The CdS-based catalysts were one of the typical kinds of photocatalysts for this reaction. The morphology of CdS could be easily tuned, which could greatly influence the photocatalytic performances. However, the morphology effect of CdS on the photocatalytic behaviour of the direct dehydrogenation of benzyl alcohol has not been investigated yet. In this work, we synthesized CdS with two different morphologies (nanosheet (NS) and nanowire (NW)) and found the CdS-NS showed much higher photocatalytic activity for converting the benzyl alcohol than the CdS-NW, but the selectivity to benzaldehyde over the two supports was very low. By depositing Au25 nanoclusters on the CdS-NW and CdS-NS, the morphology effect of the CdS support could be mitigated and their catalytic activity and selectivity could be greatly boosted for the photocatalytic anaerobic dehydrogenation of benzyl alcohol to benzaldehyde and H2. The results of this work would provide new insight into the design of efficient photocatalysts for synthesizing fine chemicals.

Dissecting the Triplet-State Properties and Intersystem Crossing Mechanism of the Ligand-Protected Au13 Superatom.

Icosahedral Au13 nanoclusters are among the most typical superatoms and are of great interest as promising building blocks for nanocluster-assembled materials. Herein, the key parameters involved in the intersystem crossing (ISC) process of [Au13(dppe)5Cl2]3+ (Au13; dppe = 1,2-bis(diphenylphosphino)ethane) were characterized. Quenching experiments using aromatic compounds revealed that the T1 energy of Au13 is 1.63 eV. An integrative interpretation of our experimental results and the relevant literature uncovered important facts concerning the Au13 superatom: the ISC quantum yield is unity due to the ultrafast ISC (∼1012 s-1), the lowest absorption band includes contributions of direct singlet-triplet transitions, and there exists a large S1-T1 gap of 0.73 eV. To explain the efficient ISC, the El-Sayed rule was applied to the superatomic orbitals corresponding to the excited-state hole/electron distributions obtained from theoretical calculations. The strong spin-orbit coupling between the S1 and T2-T4 states offers a reasonable explanation for the ultrafast ISC.