Gold Monolayer Research Articles

Influence of Aliphatic versus Aromatic Ligand Passivation on Intersystem Crossing in Au25(SR)18.

The electronic relaxation dynamics of gold monolayer protected clusters (MPCs) are influenced by the hydrocarbon structure of thiolate protecting ligands. Here, we present ligand-dependent electronic relaxation for a series of Au25(SR)18- (SR = SC8H9, SC6H13, SC12H25) MPCs using femtosecond time-resolved transient absorption spectroscopy. Relaxation pathways included a ligand-independent femtosecond internal conversion and a competing ligand-dependent picosecond intersystem crossing process. Intersystem crossing was accelerated for the aliphatic (SC6H13, SC12H25) thiolate MPCs compared to the aromatic (SC8H9) thiolate MPCs. Additionally, a 1.2 THz quadrupolar acoustic mode and a 2.4 THz breathing acoustic mode was identified in each cluster, which indicated that differences in ligand structure did not result in significant structural changes to the metal core of the MPCs. Considering that the difference in relaxation rates did not result from ligand-induced core deformation, the accelerated intersystem crossing was attributed to greater electron-vibrational coupling to Au-S vibrational modes. The results suggested that the organometallic semiring was less rigid for the aliphatic thiolate MPCs due to reduced steric effects, and in turn, increases in nonradiative decay rates were observed. Overall, these results imply that the protecting ligand structure can be used to modify carrier relaxation in MPCs.

Highly sensitive near-field leakage-enhanced optical fiber SPR sensor based on gold nanoarrays modulation

A novel near-field leakage-enhanced optical fiber surface plasmon resonance (NLF-SPR) sensor based on the synergistic sensitization of cuboid gold nanoarrays and WSe2 film is proposed for the first time to our knowledge. The sensor is composed of a side-polished multimode fiber, a continuous gold film, a continuous tungsten selenide (WSe2) film, and well-arranged cuboid gold nanoarrays. The sensor leverages the high carrier mobility characteristic of the WSe2 film, the near-field leakage enhancement arising from the nanoarrays structure, and the localized electric field enhancement property introduced by nanotips to enhance the refractive index sensitivity. In order to optimize the spectral characteristic, the modulation of electric field distribution and spectral characteristic by the structural parameters of gold nanoarrays is investigated through three-dimensional (3D) finite element simulation. Results show that in the refractive index range of 1.3332–1.3432 refractive index unit (RIU), the average sensitivity of the NLF-SPR sensor can reach up to 10108 nm/RIU, and the highest sensitivity can reach up to 14692.46 nm/RIU. The average sensitivity and the highest sensitivity are 1.87 times and 2.56 times higher, respectively, than those of the side-polished fiber SPR sensor with a monolayer gold film. Furthermore, the experimental results demonstrate that the near-field leakage enhancement introduced by gold nanoarrays improves the performance of the fiber SPR sensor, resulting in a 49.3 % increment in sensitivity. The experimental results are in agreement with the trend of the simulation results. Even better performance improvements have been achieved compared to existing methods and a more flexible approach to performance tuning is provided. With the maturity and development of various nanoarray processing techniques such as focused ion beam, electron beam lithography, and nanoimprint lithography, the proposed NLF-SPR sensor has the potential to be fabricated on a large scale and is expected to be widely employed in biomedical, clinical applications, and other fields.

Surface Plasmon Resonance Sensor Based on Fe2O3/Au for Alcohol Concentration Detection.

Hematite (α-Fe2O3) is widely used in sensor sensitization due to its excellent optical properties. In this study, we present a sensitivity-enhanced surface plasmon resonance alcohol sensor based on Fe2O3/Au. We describe the fabrication process of the sensor and characterize its structure. We conduct performance testing on sensors coated multiple times and use solutions with the same gradient of refractive indices as the sensing medium. Within the refractive index range of 1.3335-1.3635, the sensor that was coated twice achieved the highest sensitivity, reaching 2933.2 nm/RIU. This represents a 30.26% enhancement in sensitivity compared to a sensor with a pure gold monolayer film structure. Additionally, we demonstrated the application of this sensor in alcohol concentration detection by testing the alcohol content of common beverages, showing excellent agreement with theoretical values and highlighting the sensor's potential in food testing.

Dual-band and spectrally selective infrared absorbers based on hybrid gold-graphene metasurfaces

In this paper, we propose a dual-band and spectrally selective infrared (IR) absorber based on a hybrid structure comprising a patterned graphene monolayer and cross-shaped gold resonators within a metasurface. Rooted in full-wave numerical simulations, our study shows that the fundamental absorption mode of the gold metasurface hybridizes with the graphene pattern, leading to a second absorptive mode whose properties depend on graphene’s electrical properties and physical geometry. Specifically, the central operation band of the absorber is defined by the gold resonators whereas the relative absorption level and spectral separation between the two modes can be controlled by graphene’s chemical potential and its pattern, respectively. We analyze this platform using coupled-mode theory to understand the coupling mechanism between these modes and to elucidate the emergence and tuning of the dual band response. The proposed dual-band device can operate at different bands across the IR spectrum and may open new possibilities for tailored sensing applications in spectroscopy, thermal imaging, and environmental monitoring.

Synthesis of goldene comprising single-atom layer gold

The synthesis of monolayer gold has so far been limited to free-standing several-atoms-thick layers, or monolayers confined on or inside templates. Here we report the exfoliation of single-atom-thick gold achieved through wet-chemically etching away Ti3C2 from nanolaminated Ti3AuC2, initially formed by substituting Si in Ti3SiC2 with Au. Ti3SiC2 is a renown MAX phase, where M is a transition metal, A is a group A element, and X is C or N. Our developed synthetic route is by a facile, scalable and hydrofluoric acid-free method. The two-dimensional layers are termed goldene. Goldene layers with roughly 9% lattice contraction compared to bulk gold are observed by electron microscopy. While ab initio molecular dynamics simulations show that two-dimensional goldene is inherently stable, experiments show some curling and agglomeration, which can be mitigated by surfactants. X-ray photoelectron spectroscopy reveals an Au 4f binding energy increase of 0.88 eV. Prospects for preparing goldene from other non-van der Waals Au-intercalated phases, including developing etching schemes, are presented.

Biomimetic Chiral Nanotopography for Manipulating Immunological Response

AbstractImmune response regulates implanted biomaterial−tissue integration and tissue regeneration, in which macrophages play a key role due to their plasticity and polarization. Chirality, an inherent property of carbon‐based life, can also exist in biomaterials such as gold monolayer. Constructing chiral nanostructured surfaces of implants can imitate the chirality of extracellular environment in a biomimetic manner, but the manipulation and mechanism of chiral nanotopography on macrophages remain poorly understood. Here, highly ordered gold nanoparticle arrays with 300 or 900 nm spacing are fabricated and modified with L‐ or D‐chirality. The D‐nanoarrays can promote M2 polarization and related cytokine secretion of macrophages, thus facilitating the reduction of inflammatory reaction and promoting tissue healing and regeneration. The mechanistic analysis further suggests that D‐nanoarrays proceeded these regulations through enhancing the expression of integrin αv/α8/β3‐p‐FAK pathway in macrophages, which may be largely attributed to its higher stereo‐affinity for fibronectin as revealed by quantitative experiments and molecular dynamics simulations. Overall, this study demonstrates that biomimetic chiral nanotopography can promote biomaterial−tissue integration by manipulating macrophage phenotype, bringing a novel strategy for immunomodulation.

A two-fold SPR-SERS sensor utilizing gold nanoparticles and graphene thin membrane as a spacer in a 3D composite structure

Localized surface plasmonic resonance (LSPR) biosensing using optical fibers has gained popularity due to its label-free approach and high sensitivity to changes in the nanoparticle surface's local index of refraction. However, improving sensitivity remains a challenge. In this study, a two-step approach was employed to fabricate a composite structure using gold nanoparticles and monolayer graphene (Gr-AuNPs). The combination of AuNPs and graphene membrane demonstrated high potential for Surface-enhanced Raman scattering (SERS) and surface plasmonic resonance (SPR) fiber sensors. The Gr-AuNPs sensor successfully detected R6G molecules with a low detection limit of 10−12 M, indicating promising SERS activity. Numerical simulations confirmed that the graphene generated densely hot spots in the nanogap region between plasmonic layers. It's interesting that the proposed SPR-SERS Sensor can detect both glucose and thiram. This demonstrates the sensors practicality and can help with a basic environmental need to find leftover pesticides in the soil. The combination of SPR-SERS dual-mode detection provides more options for detecting and verifying data, increasing the precision and repeatability of experiments.

Gold nanoparticles engineered nanoporous membrane with sandwich structure for sensitive electrochemical quantification of exosome

Exosome has been identified as an excellent potential biomarker for tumor diagnosis. Herein, electrochemical aptasensor for exosome detection was developed via a sandwich-structured nanoporous membrane which was fabricated by assembling multilayer gold nanoparticles (mulAu) and monolayer gold nanoparticles (monAu) on the opposite side of a nanoporous alumina membrane (NAM). The tumor-derived exosomes can be efficiently captured by the specific probes confined on the monAu side of the membrane. And the mulAu side that was tightly attached with a Si wafer allowed the electrochemical exosome detection by monitoring the amperometric signal of ferricyanide that transported across the nanochannel array of the membrane. After optimization of pore diameter of the NAM, base sequence of the capture probe and incubation temperature as well as incubation time for exosomes, this NAM-based electrochemical aptasensor was applied to the quantification of the MCF-7 cells-derived exosomes. The steady state current displayed linearity relationship with the concentration of the exosomes in a broad range of 103 to 107 particles μL−1, along with a detection limit of 2.8 × 102 particles μL−1. By changing capture probe, this sandwich-structured membrane could be further extended to label-free, sensitive and rapid quantification of other tumor-associated vesicles.

Tunable Subnanometer Gaps in Self-Assembled Monolayer Gold Nanoparticle Superlattices Enabling Strong Plasmonic Field Confinement.

Nanoparticle superlattices produced with controllable interparticle gap distances down to the subnanometer range are of superior significance for applications in electronic and plasmonic devices as well as in optical metasurfaces. In this work, a method to fabricate large-area (∼1 cm2) gold nanoparticle (GNP) superlattices with a typical size of single domains at several micrometers and high-density nanogaps of tunable distances (from 2.3 to 0.1 nm) as well as variable constituents (from organothiols to inorganic S2-) is demonstrated. Our approach is based on the combination of interfacial nanoparticle self-assembly, subphase exchange, and free-floating ligand exchange. Electrical transport measurements on our GNP superlattices reveal variations in the nanogap conductance of more than 6 orders of magnitude. Meanwhile, nanoscopic modifications in the surface potential landscape of active GNP devices have been observed following engineered nanogaps. In situ optical reflectance measurements during free-floating ligand exchange show a gradual enhancement of plasmonic capacitive coupling with a diminishing average interparticle gap distance down to 0.1 nm, as continuously red-shifted localized surface plasmon resonances with increasing intensity have been observed. Optical metasurfaces consisting of such GNP superlattices exhibit tunable effective refractive index over a broad wavelength range. Maximal real part of the effective refractive index, nmax, reaching 5.4 is obtained as a result of the extreme field confinement in the high-density subnanometer plasmonic gaps.

A surface plasmon resonance haemoglobin concentration sensor based on D‐type optical fibre with a graphene‐gold surface architecture

AbstractIn this study, a surface plasmon resonance sensor for detecting haemoglobin concentration based on a D‐type optical fibre with a graphene‐gold surface architecture is proposed. The graphene‐gold surface architecture included a 50 nm thick gold film and monolayer graphene film, which were decorated on a 10 mm long D‐type sensing region. The proposed sensor worked in wavelength interrogation mode, with the light wavelength ranging from 400 to 1100 nm. The authors realised the D‐type optical fibre surface polishing process, the gold film vacuum coating process, and the chemical‐vapour‐deposited graphene's wet transfer process. Furthermore, the fabricated sensors were used to detect the refractive index (RI) of haemoglobin samples, which varied from 1.331 to 1.346. Experiment results show that the fitted RI sensitivity of the sensor decorated with gold and graphene reaches 1874.41 nm/RIU, 4.995% higher than that of the sensor decorated only with gold. The concentration sensitivity of the sensor coated with gold and graphene film is 4.96 nm/(g/dL), and the proposed sensor can provide a resolution of 20.2 mg/dL for haemoglobin concentration detection.

Wafer-scale fibrous SERS substrates allow label-free, portable detection of food adulteration and diagnosis of pesticide poisoning

Herein, a method for constructing three-dimensional (3D) fibrous surface-enhanced Raman scattering (SERS) substrates was developed. This strategy enables the wafer-scale, direct formation of monolayer gold nanoparticles (Au NPs) on filter paper. The process begins with coating of the fiber surface with perfluorooctyltrichlorosilane (FOS) to manipulate the surface energy. During subsequent sputter deposition, the large difference in surface energy between the Au atoms and the FOS-modified fibers leads to the thermodynamically driven formation of discrete Au NPs, thereby generating an abundance of hotspots. Moreover, the Au NP–decorated paper maintained its great hydrophobicity, condensing the analyte molecules nearby hot spots after solvent evaporation. In addition, the 3D fibrous structure provided a large detection space to efficiently utilize the large depth of field of a portable Raman spectrometer. These features resulted in the as-designed SERS paper having high sensitivity, with the enhancement factor reaching 1.63 × 108 and the detection limit reaching the nanomolar level when using a portable 785-nm Raman spectrometer. We used this approach for the trace-level, label-free detection of a diverse range of substances as well as their practical on-site detection in multiple-component systems, including illegal rhodamine B in commercial beverages and lethal paraquat in poisoning patients.

Optimization of immersion direction and time of covalently self-assembled monolayer gold nanourchins on glass as SERS substrate

Optimization of immersion direction and time of covalently self-assembled monolayer gold nanourchins on glass as SERS substrate

Optical characteristics of a monolayer of identical spherical particles in an absorbing host medium.

The problem of light interaction with a 2D ensemble of homogeneous spherical particles embedded into an unbounded homogeneous absorbing host medium is considered. Based on the statistical approach, the equations are derived to characterize optical response of such a system with taking into account multiple scattering of light. Numerical data are presented for the spectral behavior of coherent transmission and reflection, incoherent scattering, and absorption coefficients of thin dielectric, semiconductor, and metal films containing a monolayer of particles with various spatial organization. The results are compared with the characteristics of the inverse structure: particles consist of the host medium material and vice versa. Data for the redshift of the surface plasmon resonance of the monolayer of gold (Au) nanoparticles in the fullerene (C 60) matrix are presented as a function of the monolayer filling factor. They are in qualitative agreement with the known experimental results. The findings have potential applications in the development of new electro-optical and photonic devices.

Substrate mediated properties of gold monolayers on SiC.

In light of their unique physicochemical properties two-dimensional metals are of interest in the development of next-generation sustainable sensing and catalytic applications. Here we showcase results of the investigation of the substrate effect on the formation and the catalytic activity of representative 2D gold layers supported by non-graphenized and graphenized SiC substrates. By performing comprehensive density functional theory (DFT) calculations, we revealed the epitaxial alignment of gold monolayer with the underlying SiC substrate, regardless of the presence of zero-layer graphene or epitaxial graphene. This is explained by a strong binding energy (∼4.7 eV) of 2D Au/SiC and a pronounced charge transfer at the interface, which create preconditions for the penetration of the related electric attraction through graphene layers. We then link the changes in catalytic activity of substrate-supported 2D Au layer in hydrogen evolution reaction to the formation of a charge accumulation region above graphenized layers. Gold intercalation beneath zero-layer graphene followed by its transformation to quasi-free-standing epitaxial graphene is found to be an effective approach to tune the interfacial charge transfer and catalytic activity of 2D Au. The sensing potential of substrate-supported 2D Au was also tested through exploring the adsorption behaviour of NH3, NO2 and NO gas molecules. The present results can be helpful for the experimental design of substrate-supported 2D Au layers with targeted catalytic activity and sensing performance.

Development of a coarse-grained model for surface-functionalized gold nanoparticles: towards an accurate description of their aggregation behavior.

Understanding the dispersion stability and aggregation propensity of self-assembled monolayer gold NPs at a molecular level is crucial to guide their rational design and to inform about the optimal surface functionalization for specific applications. To reach this goal, in silico modeling via coarse-grained (CG) molecular dynamics (MD) simulations is a fundamental tool to complement the information acquired from experimental studies since CG modeling allows to get a deep knowledge of the molecular interactions that take place at the nanoscale in this kind of systems. Unfortunately, current CG models of monolayer-protected AuNPs present several drawbacks that limit their accuracy in certain scenarios. We here develop a CG model that is fully compatible and extends the SPICA/SDK (Shinoda-DeVane-Klein) force field. Our model allows reproducing the behavior of AuNPs functionalized with hydrophobic as well as charged and more hydrophilic ligands. This model improves upon results obtained with previously derived CG force fields and successfully describes NPs aggregation and self-assembly in aqueous solution.

Chronoamperometry-based controllable fabrication of gold nanoparticle monolayers and their hydrophobic force-induced movement on indium tin oxide glass substrate

Owing to their unique plasmonic properties, noble metals have been the materials of choice for photovoltaics, photocatalysis and sensors. Here, we demonstrate novel gold(Au) monolayers with tailorable particle diameters and optical property on transparent indium tin oxide (ITO) using a simple electrochemical deposition. The nanoparticles on ITO are spherical and isolated, and are identified as Au0 nanoparticles. The gold nanoparticles are uniformly distributed on ITO surface, but the gold nanoparticle sizes increase and the particle population densities decrease at lower current densities, resulting in higher light scattering. There is a positive correlation between mean particle size and maximum extinction wavelength of gold nanoparticles prepared with different current densities under a fixed total charge, whereas the maximum extinction wavelength of gold nanoparticles does not change with the total charge under the fixed current densities. The localized surface plasmon resonance change of Au nanoparticles on ITO can be effectively tuned by regulating deposition current density. With the existence of alkanethiols on Au monolayers surface, the original pink color of gold monolayers changed to blue after immersion in toluene for 30 min, indicating hydrophobic force produced by oil-in-water (O/W) or water-in-oil (W/O) phenomenon caused gold nanoparticles to migrate and produce a color change.

Machine Learning Aided Interpretable Approach for Single Nucleotide-Based DNA Sequencing using a Model Nanopore

Solid-state nanopore-based electrical detection of DNA nucleotides with the quantum tunneling technique has emerged as a powerful strategy to be the next-generation sequencing technology. However, experimental complexity has been a foremost obstacle in achieving a more accurate high-throughput analysis with industrial scalability. Here, with one of the nucleotide training data sets of a model monolayer gold nanopore, we have predicted the transmission function for all other nucleotides with root-mean-square error scores as low as 0.12 using the optimized eXtreme Gradient Boosting Regression (XGBR) model. Further, the SHapley Additive exPlanations (SHAP) analysis helped in exploring the interpretability of the XGBR model prediction and revealed the complex relationship between the molecular properties of nucleotides and their transmission functions by both global and local interpretable explanations. Hence, experimental integration of our proposed machine-learning-assisted transmission function prediction method can offer a new direction for the realization of cheap, accurate, and ultrafast DNA sequencing.

Variation in gold monolayer properties on interaction with DNA/RNA nucleobases useful for DNA sensing

Interfacing DNA/RNA nucleobases with gold nanoparticles (AuNPs) has been thoroughly investigated for several biomedical and diagnostic applications because of its numerous advantages. In this work, the interaction of DNA/RNA nucleobases with recently reported pristine gold monolayer in HCP structure, has been explored by utilizing the Ab-initio calculations. The binding characteristics between the two entities, the charge transfer, and the optical and electronic properties of the nucleobase–gold monolayer system, show distinct results for each nucleobase. The binding energies of the nucleobase-Au monolayer system vary as: G > A ∼ C > T ∼ U. The density of states of the nucleobase-gold monolayer system clearly reveals the modulation in electronic properties owing its origin to the presence of nucleobase atoms. The changes in optical properties (plasmon frequencies, reflection cofficient and refractive index), and tunneling current characteristic of gold monolayer are observed due to gold-nucleobase interactions. On adsorption of nucleobase on gold monolayer, additional peaks appear in the EELS spectra and imaginary part of dielectric function and the values of refractive index, static dielectric constant and reflectance increase. We observe higher tunnel current and enhanced negative resistance region for nucleobase adsorbed systems. The results indicate that pristine Au-monolayer in HCP structure is a good candidate for DNA/RNA sequencing devices. Results from our current study are helpful in understanding experimental findings and may be beneficial for advancements in biosensing technology.

Self-assembly of anisotropy gold nanocubes into large area two-dimensional monolayer superlattices

The spontaneous self-assembly of metal nanocrystals into two-dimensional (2D) monolayer superlattices with highly ordered symmetry and configuration paves the way towards the fabrication of functional materials. However, there remains great challenge for anisotropic nanocrystals to self-assembly into high quality superlattice because of the orientation and configuration consistency. Here, a facile yet universal solvent annealing driven 2D interfacial assembly of synthetic dried metal nanocrystals is firstly developed to realize the construction of the non-close-packing 2D monolayer gold nanocube (AuNC) superlattice with tunable interparticle distance and internal configurations (i.e. face-to-face and hexagonally-packed arrangement), which is achieved by precisely controlling molecular weight of polymer ligands tethered on AuNCs and the van der Waals forces between the adjacent AuNCs. In addition, the scale of the generated 2D monolayer AuNC superlattice with highly ordered internal arrangement and orientation can reach up to hundreds of micrometers, thus acquiring significant surface-enhanced Raman scattering performance of the large scale superlattice due to the strong plasma coupling effect. This strategy not only provides a robust route to fabricate nanocrystal superlattice structures but also offers a promising platform for preparing diverse functional materials with potential applications in electronics, photonics, detections, and others.

Electronic phase transitions in quasi-one-dimensional atomic chains: Au wires on Si(553)

The Si(553) surface, covered with half a monolayer of gold, forms a double strand of well-ordered atomic Au chains in each miniterrace. It represents one of the smallest possible realizations of quasi-one-dimensional (1D) systems. In this prototype system, by combining DC conductance and low-energy electron diffraction measurements with density functional calculations and ab initio Monte Carlo simulations, we demonstrate that nonlocal electronic correlations, together with thermal excitations, lead to peculiar phase transitions without long-range order. They are characterized by marginal (average) geometric relaxations, but with huge variations of the electronic band structure and concomitant strong temperature-dependent modifications of the density of states close to the Fermi level. Similar phenomena are expected in the large class of quasi-1D conductors and open a wide range of possibilities for their controlled manipulation. It is the increasing hybridization between spin-polarized Au and Si edge states that makes the Si dangling bond states at the step edge conducting, first as a transient between two insulating phases and finally opening a permanent new 1D conduction channel at high temperatures.