Evolution of atomic and electronic structure of magnetic Gd-doped gold clusters

The evolution of atomic and electronic structure of small Au _n (n = 1–16, and 55) clusters doped with a Gd atom has been investigated using density functional theory within generalized gradient approximation for the exchange–correlation energy. Pure gold neutral clusters with n up to 15 are planar. However, with the doping of a Gd atom, the atomic structure of gold clusters changes, and there is a transition from planar-like structures to three dimensional structures at n = 10. The electronic structure of Gd-doped gold clusters shows a sharp increase in the highest occupied–lowest unoccupied molecular orbital (HOMO–LUMO) gap for certain sizes giving rise to their magic behavior. All clusters are magnetic with large magnetic moments ranging from 6 to 8 μ_B primarily due to the localized 4f electrons on Gd. This makes such clusters with large HOMO–LUMO gaps magnetic superatoms. The main interaction between gold and gadolinium atoms in the clusters is due to hybridization between Au-6s and Gd-5d6s orbitals. Our results indicate the emergence of a wheel structure for Gd@Au₇, a symmetric cage structure at n = 15 for Gd@Au₁₅ and n = 16 for Gd@Au₁₆ ⁺ and Eu@Au₁₆ corresponding to an electronic shell closing at 18 valence electrons leaving aside the f electrons on Gd while for Gd-doped Au₅₅ corresponding to 58 valence electrons, a Au₉Gd@Au₄₆ core–shell structure is obtained in which the Gd atom connects the core of Au₉ with the Au₄₆ shell. The binding energy shows odd–even oscillations with enhancement due to Gd doping compared with pure gold clusters. Such magnetic clusters of gold could have multifunctional biological applications in drug delivery, sensor, imaging, and cancer treatment.     

Atomic‐Precision Gold Clusters for NIR‐II Imaging

Near‐infrared II (NIR‐II) imaging at 1100–1700 nm shows great promise for medical diagnosis related to blood vessels because it possesses deep penetration and high resolution in biological tissue. Unfortunately, currently available NIR‐II fluorophores exhibit slow excretion and low brightness, which prevents their potential medical applications. An atomic‐precision gold (Au) cluster with 25 gold atoms and 18 peptide ligands is presented. The Au₂₅ clusters show emission at 1100–1350 nm and the fluorescence quantum yield is significantly increased by metal‐atom doping. Bright gold clusters can penetrate deep tissue and can be applied in in vivo brain vessel imaging and tumor metastasis. Time‐resolved brain blood‐flow imaging shows significant differences between healthy and injured mice with different brain diseases in vivo. High‐resolution imaging of cancer metastasis allows for the identification of the primary tumor, blood vessel, and lymphatic metastasis. In addition, gold clusters with NIR‐II fluorescence are used to monitor high‐resolution imaging of kidney at a depth of 0.61 cm, and the quantitative measurement shows 86% of the gold clusters are cleared from body without any acute or long‐term toxicity at a dose of 100 mg kg^?1.     

Two distinct fluorescent quantum clusters of gold starting from metallic nanoparticles by pH-dependent ligand etching

Two fluorescent quantum clusters of gold, namely Au₂₅ and Au₈, have been synthesized from mercaptosuccinic acid-protected gold nanoparticles of 4–5 nm core diameter by etching with excess glutathione. While etching at pH ∼3 yielded Au₂₅, that at pH 7–8 yielded Au₈. This is the first report of the synthesis of two quantum clusters starting from a single precursor. This simple method makes it possible to synthesize well-defined clusters in gram quantities. Since these clusters are highly fluorescent and are highly biocompatible due to their low metallic content, they can be used for diagnostic applications. Electronic Supplementary Material  Supplementary material is available for this article at and is accessible for authorized users. This article is published with open access at Springerlink.com     

Oxidation of Au4Al in gold ballbonds

Two different 4N (99.99% purity) gold wires were ballbonded on 1 μm thick Al-1 wt.% Si-0.5 wt.% Cu bondpad metallisation and subjected to high temperature storage (HTS) at 175 °C in air. Each wire type showed ball lift failures, Type A after 500 h and Type B after 1500 h, which in both cases was a result of Au₄Al oxidation. With wire Type A the dominant compound underneath the ball was Au₈Al₃. A thin layer of Au₄Al (≈ 1 μm thick) was observed between the Au₈Al₃ and the gold ball. Ball lift failures occurred in the Au₄Al layer, which appeared to disintegrate due to oxidation and the resulting by products of oxidation were deposited on the underlying and unoxidised Au₈Al₃. With wire Type B, a double layer Au₄Al was dominant after long term ageing and Au₈Al₃ was confined to the ball periphery. Consequently, because of the much greater volume of Au₄Al, compound oxidation resulted in the formation of a large amount of a completely new microstructure consisting of gold precipitates embedded in a dark oxide matrix. The Au₈Al₃ compound remained unoxidised. It is speculated that internal stress and contamination may accelerate the oxidation reaction.     

Advanced Catalyst for CO2 Photo-Reduction: From Controllable Product Selectivity by Architecture Engineering to Improving Charge Transfer Using Stabilized Au Clusters

Despite enormous progress and improvement in photocatalytic CO₂ reduction reaction (CO₂RR), the development of photocatalysts that suppress H₂ evolution reaction (HER), during CO₂RR, remains still a challenge. Here, new insight is presented for controllable CO₂RR selectivity by tuning the architecture of the photocatalyst. Au/carbon nitride with planar structure (p Au/CN) showed high activity for HER with 87% selectivity. In contrast, the same composition with a yolk@shell structure (Y@S Au@CN) exhibited high selectivity of carbon products by suppressing the HER to 26% under visible light irradiation. Further improvement for CO₂RR activity was achieved by a surface decoration of the yolk@shell structure with Au₂₅(PET)₁₈ clusters as favorable electron acceptors, resulting in longer charge separation in Au@CN/Au_c Y@S structure. Finally, by covering the structure with graphene layers, the designed catalyst maintained high photostability during light illumination and showed high photocatalytic efficiency. The optimized Au@CN/Au_c/G Y@S structure displays high photocatalytic CO₂RR selectivity of 88%, where the CO and CH₄ generations during 8 h are 494 and 198 µmol/gcat., respectively. This approach combining architecture engineering and composition modification provides a new strategy with improved activity and controllable selectivity toward targeting applications in energy conversion catalysis.     

Synthesis of Zn1 − xCdxO bramble-like nanostructures

Ternary Zn_1 − xCd_xO bramble-like nanostructures with a Cd incorporation of about 6.7 at.% were produced onto Au-catalyzed Si substrate by thermal evaporation of Zn and Cd. The X-ray diffraction (XRD) analysis showed that the existence of lattice expansion in the c-axis orientation. The ultra-violet (UV) near-band-edge (NBE) emission of the Zn_1 − xCd_xO nanobrambles was red-shifted from 369 nm (3.37 eV) to 397 nm (3.13 eV) due to Cd substitution. The oxygen partial pressure was deemed as the critical experimental parameter for the formation of the bramble-like Zn_1 − xCd_xO nanostructures.     

Promoted NIR-II Fluorescence by Heteroatom-Inserted Rigid-Planar Cores for Monitoring Cell Therapy of Acute Lung Injury

Fluorophores with emission in the second near-infrared (NIR-II) window have displayed salient advantages for biomedical applications. However, exploration of new luminogens with high NIR-II fluorescent brightness is still challenging. Herein, based on the “ring-fusion” strategy, a series of heteroatom-inserted rigid-planar cores is proposed to achieve the bathochromic NIR-II fluorophores with aggregation-induced emission (AIE) performance. Interestingly, one of the representative fluorophores, 4,4′-(5,5′-([1,2,5]thiadiazolo[3,4-i]dithieno[2,3-a:3′,2′-c]phenazine-8,12-diyl)bis(4-octylthiophene-5,2-diyl))bis(N,N-diphenylaniline) (TTQiT), enjoys a maximum emission beyond 1100 nm because of the efficiently narrowed energy bandgap by electron-rich sulfur-atom-inserted core, which is verified by theoretical calculation. Taking advantage of the bright NIR-II emission of TTQiT nanoparticles, the desirable in vivo NIR-II imaging with high signal-to-background ratios is successfully performed and a long-term stem cell tracking in the detection of acute lung injury is further realized. Therefore, it is anticipated that this work will provide a promising molecular engineering strategy to enrich the scope of NIR-II fluorophores for catering to diverse demands in biomedical applications.     

Physicochemical characterization of Au/CeO2 solids. Part 2: The impregnation preparation method

Au/CeO₂ solids with different gold contents were prepared using the impregnation method. Electron microscopy (SEM and TEM) studies indicated the formation of both nanoparticles and large gold particles on the surface of the ceria support. SEM and XRD analyses revealed that the number and size of large particles increases with the gold content in the solid. The XPS technique showed that 90% of the total gold is in the metallic form Au⁰ while the remaining 10% were cationic gold species Au⁺. These latter were formed following calcination under dry air at 400 °C and are located in the proximity of the O²⁻ and/or Cl⁻ present on the support. These Au⁺ species are present at the edge of gold particles and they were reduced into metallic gold when the solid was vacuum treated (5–7.10⁻⁴ mbar) at 400 °C for 1 h. When air was adsorbed at room temperature on the latter vacuum treated solids, two EPR signals were obtained. The first one was assigned to O₂⁻ species whereas attributing the second signal was difficult and required a more detailed investigation that will be presented in a forthcoming work.     

Quantum-chemical modeling of interaction between gold nanoclusters and thiols

Ab initio calculations are used to model small Au _n nanoclusters and Au _m SH clusters. The results for the Au₆, Au₈, and Au₂₀ clusters demonstrate that the substitution of a SH group for a Au atom gives a stable cluster of the same geometry if the Au atom has an acute bond angle and a negative effective charge. The example of the Au₁₀ cluster suggests that SH substitution for Au has a stabilizing effect. The modeling results are discussed with application to self-organizing thiol monolayers on gold clusters.     

Formation of Cd particles by UV laser irradiation

Formation of the metal particles of Cd has been studied by nanosecond laser flash photolysis using an ArF excimer laser with the oscillation wavelength of 193 nm. The sample was a 10% methanol solution of CdCl₂. The solvated electron, e_aq⁻, was generated by the excitation of charge transfer bands of Cl⁻ to solvent. The e_aq⁻ efficiently reduced Cd²⁺ to Cd⁺ during a laser pulse of 30 ns (FWHM). The Cd particles were produced by the reaction between Cd⁺ and Cd⁺. In the air saturated solution, the Cd⁺ was easily oxidized by dissolved oxygen. The concentration of the Cd particles formed in the degassed solution was approximately twice of that in the air saturated solution.     

Low-Dose NIR-II Preclinical Bioimaging Using Liposome-Encapsulated Cyanine Dyes

Fluorescence imaging in the second near-infrared window (NIR-II, 1000–1700 nm) provides a powerful tool for in vivo structural and functional imaging in deep tissue. However, the lack of biocompatible contrast agents with bright NIR-II emission has hindered its application in fundamental research and clinical trials. Herein, a liposome encapsulation strategy for generating ultrabright liposome-cyanine dyes by restricting dyes in the hydrophobic pockets of lipids and inhibiting the aggregation, as corroborated by computational modeling, is reported. Compared with free indocyanine green (ICG, an US Food and Drug Administration-approved cyanine dye), liposome-encapsulated ICG (S-Lipo-ICG) shows a 38.7-fold increase in NIR-II brightness and enables cerebrovascular imaging at only one-tenth dose over a long period (30 min). By adjusting the excitation wavelength, two liposome-encapsulated cyanine dyes (S-Lipo-ICG and S-Lipo-FD1080) enable NIR-II dual-color imaging. Moreover, small tumor nodules (2–5 mm) can be successfully distinguished and removed with S-Lipo-ICG image-guided tumor surgery in rabbit models. This liposome encapsulation maintains the metabolic pathway of ICG, promising for clinical implementation.     

Single‐Site AuI Catalyst for Silane Oxidation with Water

Single‐site Au anchored on mpg‐C₃N₄ (519 ppm Au loading) is developed as a highly active, selective, and stable catalyst for the oxidation of silanes with water with a turnover frequency as high as 50 200 h^?1, far exceeding most known catalysts based on total gold content. Other hydrosilanes bearing unsaturated functional groups also lead to corresponding silanols under mild reaction conditions without formation of any side products in good or excellent yields. The spherical aberration correction electron microscopy and extended X‐ray absorption fine structure measurements both confirm the atomic dispersion of Au atoms stabilized by mpg‐C₃N₄. The coordination of the catalytically active Au^I by three nitrogen or carbon atoms in the tri‐s‐triazine repeating units not only prevents the Au atoms from aggregation, but also renders the surface Au^I highly active, which is completely different than homogeneous Au^I species.     

Molecular Oligomerization and Donor Engineering Strategies for Achieving Superior NIR-II Fluorescence Imaging and Thermotherapy under 1064 nm Laser Irradiation

An enormous challenge still exists for designing molecules with the second near-infrared (NIR-II, 1000–1700 nm) window absorption, NIR-II fluorescence emission, and batch-to-batch reproducibility, which is the premise for high-performance NIR-II phototheranostics. Although organic small molecules and polymers have been largely explored for phototheranostics, it is difficult to satisfy the above three elements simultaneously. In this work, molecular oligomerization (the general structure is S-D-A-D′-A-D-S) and donor engineering (changing the donor linker D') strategies are applied to design phototheranostic agents. Such strategies are proved to be efficient in adjusting molecular configuration and energy level, affecting the optical and thermal properties. Three oligomers (O–T, O–DT, and O–Q) are further prepared into water-soluble nanoparticles (NPs). Particularly, the O-T NPs exhibit a higher molar extinction coefficient at 1064 nm (≈4.3-fold of O-DT NPs and ≈4.8-fold of O-Q NPs). Furthermore, the O–T NPs show the highest NIR-II fluorescence brightness and heating capacity (PCE = 73%) among the three NPs under 1064 nm laser irradiation and served as agents for NIR-II imaging guided in vivo photothermal therapy. Overall, by using molecular oligomerization and donor engineering strategies, a powerful example of constructing high-performance NIR-II phototheranostics for clinical translation is given.     

Surface nanostructures created by cluster-surface impact

This paper presents a review of the production of surface nanostructures from the controlled deposition of size-selected clusters on graphite. At high enough impact energies, the clusters can be implanted into the graphite surface to create open ‘well’ structures. Scanning tunnelling microscopy (STM) measurements, coupled with molecular dynamics (MD) simulations, for Au₇⁺, Ag₇⁺ and Si₇⁺ clusters exhibit scaling relations which reveal that the implantation depth scales linearly with the momentum of the clusters in all cases. At lower impact energies, the clusters can be pinned on the graphite surface when the impact energy exceeds a critical (threshold) value, thus allowing the fabrication of monodispersed cluster arrays which are stable at room temperature (and above). One application of such cluster arrays is to bind protein molecules; atomic force microscopy (AFM) measurements in buffer solution demonstrate dispersed arrays of both chaperonin and horseradish peroxidase molecules on graphite substrates decorated with size-selected Au_N⁺ clusters.     

Structural evolution of Aun (n = 29–35) clusters: A transition from hollow cage to amorphous packing

The structural evolution and competition between the hollow cage, amorphous, fcc-like and tubular structures for medium-sized Au_n (n = 29–35) clusters were investigated using density functional theory combined with empirical genetic algorithm search. Au_n (n = 29–32) clusters prefer the hollow cage structures. Amorphous core–shell configurations prevail over other kinds of structural motifs for Au_n (n = 33–35). A transition from hollow cage to amorphous packing occurs at n = 33. The size-dependent HOMO–LUMO gap, vertical ionization potential and electron density of states were discussed to illustrate the relationship between the electronic properties and the geometry structures.     

Sputtering deposited ternary Zn1−xCdxO crystal films on Si(111) substrates

Using the d.c. reactive magnetron sputtering method we have successfully deposited completely (002)-oriented ternary Zn_1−xCd_xO (0≤x≤0.6) alloy crystal films without Cd segregation on Si(111) substrates. X-Ray photoelectron spectroscopy measurements show that Cd/Zn ratios in the films are nearly consistent with those in the targets. The Zn and Cd exist only in oxidized states, no evidence of metallic Zn or Cd was observed. The O/(Cd+Zn) atomic ratios of the films are in the range of 0.89-0.98. Transmission electron microscopy measurements show that for the (002)-oriented films the grains are columnar structures with the c-axis perpendicular to the Si substrate. By post-annealing treatments in O₂ ambient, the crystal quality of the Zn_1−xCd_xO films can be improved. For the sample of x=0.2, the optimal annealing temperature is 500 °C.     

In Vivo NIR-II Fluorescence Lifetime Imaging of Whole-Body Vascular Using High Quantum Yield Lanthanide-Doped Nanoparticles

Second near infrared (NIR-II, 1000–1700 nm) fluorescence lifetime imaging is a powerful tool for biosensing, anti-counterfeiting, and multiplex imaging. However, the low photoluminescence quantum yield (PLQY) of fluorescence probes in NIR-II region limits its data collecting efficiency and accuracy, especially in multiplex molecular imaging in vivo. To solve this problem, lanthanide-doped nanoparticles (NPs) β-NaErF₄: 2%Ce@NaYbF₄@NaYF₄ with high PLQY and tunable PL lifetime through multi-ion doping and core–shell structural design, are presented. The obtained internal PLQY can reach up to 50.1% in cyclohexane and 9.2% in water under excitation at 980 nm. Inspired by the above results, a fast NIR-II fluorescence lifetime imaging of whole-body vascular in mice is successfully performed by using the homebuilt fluorescence lifetime imaging system, which reveals a murine abdominal capillary network with low background. A further demonstration of fluorescence lifetime multiplex imaging is carried out in molecular imaging of atherosclerosis cells and different organs in vivo through NPs conjugating with specific peptides and different injection modalities, respectively. These results demonstrate that the high PLQY NPs combined with the homebuilt fluorescence lifetime imaging system can realize a fast and high signal-to-noise fluorescence lifetime imaging; thus, opening a road for multiplex molecular imaging of atherosclerosis.     

Computational investigation of GanAl (n = 1–15) clusters by the density-functional theory

Low-lying equilibrium geometric structures of aluminum-doped gallium cluster Ga_nAl (n = 1–15) clusters obtained by an all-electron linear combination of atomic orbital approach, within spin-polarized density functional theory, are reported. The binding energy, dissociation energy, and stability of these clusters are studied with the three-parameter hybrid generalized gradient approximation (GGA) due to Becke-Lee–Yang–Parr (B3LYP). Ionization potentials, electron affinities, hardness, and static polarizabilities are calculated for the ground-state structures within the same method. The growth pattern for Ga_nAl (n = 1–15) clusters is Al-substituted Ga_n + 1 clusters and it keeps the similar frameworks of the most stable Ga_n + 1 clusters except for Ga₈Al and Ga₁₃ Al clusters. The Al atom substituted the surface atom of the Ga_n + 1 clusters for n < 12. Starting from n = 12, the Al atom completely falls into the center of the Ga-frame. The Al atom substituted the center atom of the Ga_n + 1 clusters to form the Al-encapsulated Ga_n geometries for n > 12. The odd−even oscillations from Ga_nAl (n = 5) in the dissociation energy, the second-order energy differences, the HOMO–LUMO gaps, the ionization potential, the electron affinity, and the hardness are more pronounced. The stability analysis based on the energies clearly shows the clusters from n = 5 with an even number of valence electrons are more stable than clusters with odd number of valence electrons.     

Oxidation of gold metal particles supported on TiO<Subscript>2</Subscript>: an FTIR study by means of low-temperature CO adsorption

Two Au/TiO₂ samples with different gold loadings (0.7 and 4.0 wt.% Au) were prepared by deposition-precipitation with urea and calcined at 673 K. TEM revealed gold particles of 3.2 and 3.9 nm for the 0.7 and 4.0 wt.% samples, respectively. The samples were subjected to different red-ox treatments and then the state of gold was determined by the FTIR spectra of CO adsorbed at low temperature. Several kinds of gold carbonyl species were detected during the experiments: (i) Au⁰–CO at around 2107 cm⁻¹; (ii) Au⁺–CO at ca. 2175 cm⁻¹; (iii) Au^δ+–CO in the region of 2140–2137 cm⁻¹ and (iv) Au^δ′+–CO (δ^′ > δ) at around 2155 cm⁻¹. The 4.0 wt.% sample contained mainly metallic gold after evacuation at 673 K. Subsequent interaction with oxygen at 373 K leads to oxidation of a fraction of the surface metallic gold sites to Au^δ+ sites. These sites were considered as cations located on the surface of the metal particles with a partially positive charge δ+ (0 < δ < 1) because of electron transfer from the gold bulk. Evacuation at 673 K leads to back reduction of the Au^δ+ sites to metallic gold. The oxidation of gold particles was more efficient when performed with a NO + O₂ mixture. It resulted in creation of Au^δ′+ sites with a higher positive charge than that of the Au^δ+ sites. In this case the oxidation involved a higher number of Au⁰ sites. A similar treatment of the 0.7 wt.% Au sample, however, resulted in formation of “isolated” Au⁺ species. The results indicate that small metal particles are more easily oxidized by a NO + O₂ mixture. A model of the formation of the different sites, explaining well the experimental results, is proposed.     

Loading path effect on the chemical expansion in substoichiometric LSF based perovskite

Density functional method has been used to study the structural features and energetics of Cd_mTe_n clusters (m + n  6). The results presented include the geometric structures, binding energies, Mulliken charges on atoms, vibrational frequencies and the corresponding non-zero infrared intensities, HOMO–LUMO energies and the frontier molecular orbital energy gaps, the most possible dissociation channels and their corresponding energies of the clusters.