Gold Surface Research Articles

Interactions involved in the adsorption of ethylene glycol and 2-hydroxyethoxide on the Au(111) surface: a Density Functional Theory study.

The monolayers of ethylene glycol and 2-hydroxyethoxide on gold surfaces have been used in hybrid materials as biosensors. In this article, the adsorption of ethylene glycol and 2-hydroxyethoxide on the Au(111) surface was analyzed. For the first system, ethylene glycol on Au(111), there are Au O and Au H interactions. To the best of our knowledge, the Au H interaction has been overlooked until now. However, in this work, there is strong evidence that this interaction is important to stabilize the system. For the second system, the atomic interactions mentioned previously are also predicted, although there is an additional interaction between 2-hydroxyethoxide molecules. Such an interaction induces the link -O-H-O-, with high values of the electron density at the critical points of the corresponding bond path of the O-H interaction. These links suggest the forming of ethylene glycol chains. The calculations were performed using two exchange-correlation functionals: BEEF-vdW and C09 -vdW; both functionals incorporate dispersion effects within the Kohn-Sham approach in Density Functional Theory as implemented in GPAW code and ASE computational packages. The contacts between the molecules considered in this article and the Au(111) surface were analyzed through the Quantum Theory of Atoms in Molecules implemented in GPUAM code.

Engineering DNA Nanocube SAM Scaffolds for FRET-Based Biosensing: Interfacial Characterization and Sensor Demonstration.

Decorating a gold surface with molecular-level control over the positioning of DNA probes was demonstrated using a self-assembled monolayer (SAM) of wireframe DNA nanocube structures. The DNA nanocubes were specifically adsorbed and oriented using thiol-modified DNA on one face of the cube. The DNA nanocube SAM had a uniform coverage over the gold single crystal bead electrode with a separation of 20-30 nm measured by AFM. The face of the nanocube furthest from the gold surface was designed to hybridize with two different sequences of a 50 base single-stranded DNA probe that was modified with a fluorophore. The first 20 bases were hybridized with the DNA nanocube. One of a pair of FRET fluorophores was used for each probe strand. The dimensions of the nanocube controlled the relative spacing between these fluorophores. When the DNA probes were single-stranded, a FRET signal was observed. FRET decreased to background levels when a complementary DNA target was hybridized to either probe, resulting in a turn-off sensor with little cross-talk between the individual hybridization events. Hybridization isotherms for one target gave KA = 170 pM and a detection limit <50 pM. In addition, the DNA nanocube SAM was configured to be used as a turn-on NeutrAvidin sensor using biotinylated DNA targets hybridized to each probe resulting in an increase in FRET. We show that the wireframe DNA nanocube can be an effective scaffold for preparing biosensors with controlled separation between surface-bound probes facilitating precise sensor surface design and enabling a wide range of sensing modalities with more than one signal available for correlative confirmation of the target binding.

Making Mobile Nanotechnology Accessible: Is the Explicit Preparation of Janus Nanoparticle Necessary to Achieve Mobility?

This study compares the mobility behaviour, in a H2O2 environment, of three different geometries of hybrid particle made of silica core functionalized by gold (nanoparticles or layer). It is known that the decomposition of H2O2 on gold surfaces drives mobility; however, the link between mobility orientation and the organization of gold on silica surfaces is still questionable. While conventional wisdom posits that asymmetric designs are crucial for generating phoretic forces or localized bubble propulsion, recent research suggests that symmetrical particles may also exhibit motility. To address this debate, we developed a robust workflow for synthesizing gold grafted silica nanoparticles with precise control over size and shape, enabling the direct comparison of their motile behaviour by dynamic light scattering and particle tracking velocimetry. Our results indicate, first, that a combination of techniques is necessary to overcome their intrinsic limitation and, second, that the inherent asymmetry generated by isotropic gold nanoparticle deposition onto silica surfaces may enable particle motility.

Interfacial reaction on different solder composition after laser soldering

AbstractThis study used electroless nickel‐immersion gold surface finish. The lead free solder used are tin‐silver‐copper 305 and tin‐silver‐copper 307 solder alloys. The difference in copper composition will affect the intermetallic compound′s microstructure after the laser soldering process. The intermetallic compound formation analysis reveals that only (Cu, Ni)6Sn5 was observed at the solder joint interface for both solders after laser soldering. The grain microstructure of tin‐silver‐copper 305 formed is rounded‐shaped and bar‐shaped, while tin‐silver‐copper 307 shapes are oval‐shaped and flake‐like. However, for cross‐sectioned analysis, the intermetallic compound grain microstructure formed at the solder joint formation was (Ni, Cu)3Sn4 and (Cu, Ni)6Sn5 presented in dendrite‐like and scale‐like shapes. This result shows that copper content in solder composition is directly affected the intermetallic compound grain microstructure. When exposed to the ageing process, the intermetallic compound thickness will increase directly with ageing time. The intermetallic compound thickness for tin‐silver‐copper 305 was increased from 0.98 μm to 8.34 μm while tin‐silver‐copper 307 was increased from 1.54 μm to 8.76 μm. The result also shows that nano‐sized of Ag3Sn grain particle was formed on the intermetallic compound surface after an ageing process for both samples, tin‐silver‐copper 305 and tin‐silver‐copper 307.

Polarization modulated spectroscopic ellipsometry-based surface plasmon resonance biosensor for E. coli K12 detection

In this work, we report on the application of the polarization modulated spectroscopic ellipsometry-based surface plasmon resonance method for sensitive detection of microorganisms in Kretschmann configuration. So far, rotating analyzer and single wavelength polarization modulation methods have widely been investigated for phase sensitive surface plasmon resonance measurement. In this study, a much simpler optical setup relying on fast electro-optic phase modulator crystals is introduced for bacteria detection. A beta barium borate crystal connected to a function generator is adapted for generating phase shifts in the millisecond regime to extract the ellipsometric angles (Ψ\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\Psi$$\\end{document} and Δ\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\Delta$$\\end{document}) under the surface plasmon resonance condition. For detection, the gold surface was functionalized with anti-Escherichia coli antibodies, and E. coli K12 was attached to them. We show that polarization modulated spectroscopic ellipsometry achieves a refractive index resolution in the order of 10-5\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$10^{-5}$$\\end{document} RIU, and a limit of detection of 102\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$10^{2}$$\\end{document} CFU/mL for E. coli K12 which is compatible with other surface plasmon resonance based phase sensitive methods with more complex detection concepts. As a follow-up step, an optical model can be developed to enhance this biosensor’s performance, and applications for sorting and detecting other biological targets will be investigated.

A Supramolecular Wire Able to Self‐Assemble on Gold Surface: Controlling the Film Length to Optimize the Device Lifetime and Electron Transfer Efficiency

AbstractA chemical “lego nanoset” has been used to realize different structures on gold surfaces. Three building blocks have been designed, in order to chemically link the surface and self‐assemble in an ordered manner. Self‐assembled films are arranged on a gold surface into 3D suprastructures via consecutive deposition of different mono‐layers, taken together by thymine‐adenine hydrogen bonds. Three films, composed of one, two, and three helical peptide layers, both containing a zinc‐tetraphenylporphyrin dye as an external sheet, are built and characterized by spectro‐electrochemical and spectroscopic techniques. All films are found to generate current under illumination, and their photoresponse and stability are studied as a function of the number of peptide layers. The efficiency of the photoconversion process has been correlated to the molecular organization of the porphyrin dyes in the film and to the templating role of the bridge between the porphyrin and the gold surface.

Integrating theoretical and experimental insights into nanoporous gold electrochemistry for enhanced baicalein sensing performance

We introduce an innovative electrochemical sensing method for the sensitive detection of Baicalein (BAI), emphasizing a simple surface modification process. The study encompasses both practical and theoretical investigations into the electrochemical behavior of nanoporous gold. Our theoretical analysis, based on advanced quantum-mechanical calculations, demonstrates that the adsorption of BAI molecule on gold-based substrates is energetically favorable, with adsorption energy increasing from an unmodified surface to a more porous substrate. BAI physisorbs on unmodified regions in a horizontal alignment, while it chemisorbs more strongly on nanoporous regions by penetrating the pores. On less modified surfaces, interaction energy predominates, whereas on heavily modified surfaces, distortion energies become more significant due to increased substrate reactivity. These results align with physicochemical characterizations, which reveal that nanoscale modifications, induced by different anodization times, explain the variations in electrode performance. Experimentally, cyclic voltammetry (CV) and differential pulse voltammetry (DPV) were employed using both a gold electrode (GE) and a nanoporous gold electrode (NPGE). The GE was subjected to surface treatment by immersion in H2SO4 and potential control at ca. +2.0 V for 40 seconds, resulting in a nanoporous configuration. Following optimizations, Adsorptive Stripping Voltammetry (AdSV) was used to determine BAI. The method achieved detection (LOD) and quantification (LOQ) limits of 0.015 µmol L-1 and 0.045 µmol L-1, respectively (Edeposition=-0.25 V; tdeposition=50 s). Additionally, the standard addition method was applied to the NPGE for recovering BAI from spiked synthetic human plasma and urine, with success rates ranging from 93.4% to 106%. This approach exhibited excellent stability, precision, and accuracy, with minimal interference from other substances. Moreover, the theoretical findings provided deeper insights into the selective electrochemical detection of BAI on nanoporous gold surfaces, offering new perspectives on this field.

Evaluation of the interactions between human stratum corneum and liposome formulations using QCM-D

The interactions between human stratum corneum (SC) and two liposomal formulations, azithromycin (AZM)- and nisin-loaded liposomal formulations designed for topical/intradermal application, were investigated using quartz crystal microbalance with dissipation (QCM-D) using. SC isolated from cadaver skin was affixed onto the QCM sensor’s surface. The liposome formulations were prepared using the thin film rehydration method. The particle sizes of the blank liposome, nisin-loaded, AZM-loaded, and combined-loaded liposomes were measured as 90.7 ± 0.58 nm, 100.8 ± 2.5 nm, 136.9 ± 6.5 nm, and 174.3 ± 9.8 nm, respectively. The frequency shifts when blank and drug-loaded liposomes were passed over the gold surface were ∼20 and ∼25 Hz, respectively as a result of the formation of bilayers in a two-step process, adsorption of intact vesicles followed by the formation of the bilayer upon rinsing with water. The frequency shifts for blank and drug-loaded liposomes on SC were ∼8 and ∼15 Hz, respectively. These results show that the liposomes are deposited as bilayers on SC with both the blank and drug-loaded liposomes. The increase in frequency shifts with drug-loaded liposomes indicate the deposition of drug along with lipids onto both the gold and SC surfaces. More significantly, the data showed much slower kinetics of liposome component spreading onto the SC than on gold. The changes in dissipation that accompanies these differences in frequency shifts show transformation of vesicle onto rigid bilayer on gold upon rinsing with water, but direct formation of lipid bilayers on SC. The findings of this study contribute to a better understanding of the interaction between SC and liposomes, such as adsorption, deformation, and rupture of liposomes on different substrates, paving the way for investigating topical and intradermal mechanisms of drug delivery and cosmetic products developed based on liposome formulations.

Investigation of the modification of gold electrodes by electrochemical molecularly imprinted polymers as a selective layer for the trace level electroanalysis of PAH

Electrochemical molecularly imprinted polymers (e-MIPs) were grafted for the first time as a thin layer to the surface of a gold electrode to perform trace level electroanalysis of benzo(a)pyrene (BaP). This was achieved by controlled/living radical photopolymerization of a redox tracer monomer (ferrocenylmethyl methacrylate, FcMMA) with ethylene glycol dimethacrylate in the presence of benzo(a)pyrene as the template molecule. For that purpose, a novel photoiniferter-derived SAM was first deposited on the gold surface. The SAM formation was monitored by cyclic voltammetry and electrochemical impedance spectroscopy. Then, the “grafting from” of the e-MIP was achieved upon photoirradiation during a controlled time. Differential pulse voltammetry was used to quantify BaP in aqueous solution by following the modification of the signal of FcMMA. A limit of detection of 0.19 nM in water and a linear range of 0.66 nM to 4.30 nM, were determined, thus validating the enhancement of sensitivity induced by the close contact between the e-MIP and the electrode, and the improved transfer electron.

Dielectric Surface-Based Biosensors for Enhanced Detection of Biomolecular Interactions: Advances and Applications

Surface plasmon resonance (SPR) biosensors are extensively utilized for analyzing molecular interactions due to their high sensitivity and label-free detection capabilities. Recent innovations in surface-sensitive biosensors with dielectric surfaces address the inherent limitations associated with traditional gold surfaces, such as thermal effects and biocompatibility issues, which can impede broader applications. This review examines state-of-the-art biosensor configurations, including total internal reflection, optical waveguide, photonic crystal resonators, Bloch surface wave biosensors, and surface electrochemical biosensors, which can enhance analyte signals and augment the molecular detection efficiency at the sensor interface. These technological advancements not only improve the resolution of binding kinetics analysis and single-molecule detection but also extend the analytical capabilities of these systems. Additionally, this review explores prospective advancements in augmenting field enhancement and incorporating multimodal sensing functionalities, emphasizing the significant potential of these sophisticated biosensing technologies to profoundly enhance our understanding of molecular interactions.

Quantification of the Surface Coverage of Gold Nanoparticles with Mercaptosulfonates Using Isothermal Titration Calorimetry (ITC).

This manuscript presents a comprehensive study on the quantification of modifier molecules adsorbed on gold nanoparticles (AuNPs) using two complementary techniques Ellman's method (UV-vis spectroscopy) and isothermal titration calorimetry (ITC). In this paper, we compare the feasibility of using the ITC technique and Ellman's method to study the interactions of mercaptosulfonate compounds (sodium mercaptoethanesulfonate, MES, and sodium mercaptoundecanesulfonate, MUS) with the surface of AuNPs of various sizes. The thermodynamic functions of the attachment of mercaptosulfonates to AuNPs were determined, revealing a linear relationship between the number of adsorbed molecules and the surface area of the nanoparticles. The amount of MES and MUS determined by Ellman's method (7 and 11 molecules per square nm, respectively) is more than twice that measured by the ITC technique (3 and 4 molecules per square nm, respectively). The slight differences in the adsorption of MES and MUS on the gold surface are due to differences in the carbon chain length of the ligand molecules. In the case of MES, the formation of the Au-S bond is the dominant stage of the adsorption process, whereas for MUS, the ordering process and self-assembly of molecules on the gold surface are dominant.

Glucose oxidation on gold in alkaline solution: A DEMS and microkinetic modeling study

The mechanism and kinetics of the electrochemical oxidation of glucose on gold surfaces in 0.1 M NaOH solution are investigated by rotating disk electrode and differential electrochemical mass spectrometry coupled to microkinetic modeling. For this purpose, the glucose mass-transport parameters (solution viscosity and density, glucose diffusion coefficient) were determined in the relevant conditions. Koutecký–Levich analysis of rotating disk electrode current-potential curves revealed that the glucose oxidation reaction (GOR) follows a one-electron mechanism at 0.6 V vs RHE, while H2 production could be evidenced by DEMS in this potential range. This suggests that the glucose oxidation selectively produces gluconate at 0.6 V vs RHE through an electrochemical oxidative dehydrogenation (EOD) mechanism. A microkinetic model of the current-potential curves was developed, taking into account the hydrogen electrode reactions kinetics, the dissociative adsorption/desorption of glucose, and the glucose electrooxidation on gold surfaces. The dissociative adsorption of glucose was found to be the rate-determining step of the reaction. It is also revealed that the release of anodic H2 through the Tafel step is triggered by the consumption of the adsorbed reaction intermediates. The gluconate electrooxidation into further products has to be considered for potential above 0.7 V vs RHE.

Non‐Fouling Multi‐Azide Polyoxazoline Brush‐co‐Polymers for Sensing Applications

Abstract One of the key parameters of an artificial biosensor is a high signal‐to‐noise ratio. This is achieved by limiting non‐specific interactions while simultaneously maximizing the targeted specific interaction. Here, it is combined non‐fouling characteristics of poly(2‐methyl‐2‐oxazoline) (PMOXA) coatings with an abundance of azide groups to create a multi‐azide containing poly(2‐methyl‐2‐oxazoline‐co‐2‐(3‐azidopropyl)‐2‐oxazoline) (PMCA) that can participate in bioorthogonal strain‐promoted azide‐alkyne cycloaddition (SPAAC) for functionalization. This functional polymer is made surface‐active using the PAcrAm™ technology to obtain well‐defined spontaneously adsorbed monolayers on gold surfaces. The resistance to non‐specific interactions is tested against full human serum (HS), analyzed via variable angle spectroscopic ellipsometry (VASE), and compared to equivalent coatings based on PMOXA and azido‐poly(ethylene glycol) (PEG‐N3). The specific interactions are investigated via VASE and quartz crystal microbalance with dissipation (QCM‐D) by immobilization of dibenzocyclooctyne‐PEG4‐biotin conjugate (DBCO‐biotin) and streptavidin. The new PMCA‐based coating shows superior resistance to non‐specific protein adhesion than equivalent coatings based on commercially available PEG‐N3 and significantly increases capacity for SPAAC. A proof of principle assay (biotin‐streptavidin/biotin‐BSA/anti‐BSA) shows improved binding for the new PMCA polymer compared with single azide PEG.

Uptake of Magnetite Nanoparticles on Polydopamine Films Deposited on Gold Surfaces: A Study by AFM and XPS.

Polydopamine has the capacity to adhere to a large variety of materials and this property offers the possibility to bind nanoparticles to solid surfaces. In this work, magnetite nanoparticles were deposited on gold substrates coated with polydopamine films. The aim of this work was to investigate the effects of the composition and morphology of the PDA layers on the sticking of magnetite nanoparticles. The polydopamine coating of gold surfaces was achieved by the oxidation of alkaline solutions of dopamine with various reaction times. The length of the reaction time to form PDA was expected to influence the composition and surface roughness of the PDA films. Magnetite nanoparticles were deposited on these polydopamine films by immersing the samples in aqueous dispersions of nanoparticles. The morphology at the nanometric scale and the composition of the surfaces before and after the deposition of magnetite nanoparticles were investigated by means of AFM and XPS. We found that the amount of magnetite nanoparticles on the surface did not vary monotonically with the reaction time of PDA formation, but it was at the minimum after 20 min of reaction. This behavior may be attributed to changes in the chemical composition of the coating layer with reaction time.

Gold-enhanced aptasensors for highly sensitive dengue detection: a cost-effective approach

The reemergence of diseases such as Dengue has spurred the development of efficient biosensing devices. This study aims to establish a rapid, cost-effective, and efficient platform for Dengue detection. The surface of the sensor was constructed by sputtering gold onto fluorine-doped tin oxide thin films, that were previously deposited on glass substrates. Varied sputtering deposition times were used. Results obtained from X-Ray Diffraction analysis showed that the films with 4-minute deposition time had the best gold surface coverage and the best cost-benefit ratio for sensor fabrication. Subsequently, the gold thin films were functionalized with the co-immobilization of a self-organized monolayer of aptamers and 6-mercapto-1-hexanol (MCH). The monolayer was analysed using the electrochemical impedance spectroscopy technique, and the ratio of 1:25 (aptamer: total thiol) was determined for surface optimization. The performance of the aptasensor was tested for the detection of the non-structural protein 1 of Dengue serotype 4 (NS1-S4). A good sensitivity of 40.2 ± 3.7 % per decade and a low detection limit of 1.25 pg/mL were obtained. The development of this platform represents an advance in the fast fabrication of aptasensors for the detection of emerging diseases such as Dengue, contributing also to the miniaturization process of point-of-care devices.

Modification Of a Screen-Printed Carbon Electrode with Nanoporous Gold by Electrodeposition and Dealloying of a Gold-Copper Alloy

In this study, a three-dimensional structure of nanoporous gold (NPG) was made by selectively corroding copper (Cu) from gold-copper (Au-Cu) alloys using a two-step electrochemical method. Given its large surface area and interconnected porous network, nanoporous gold is a suitable material for the advancement of electrochemical sensors. The screen-printed carbon electrode (SPCE) modified with nanoporous gold (NPG/SPCE) was fabricated by electrodepositing a gold-copper alloy from gold ion (Au3+) and copper ion (Cu2+) solution via cyclic voltammetry (CV) by scanning from -0.3 V to -0.8 V for 80 cycles. The copper is then removed via a dealloying process in 3M HNO3 using the cyclic voltammogram (CV) method by scanning potential from 0 V to +1.0 V for 100 cycles at 100 mV/s. The morphology, elemental composition, and electrochemical active surface area (ECSA) of NPG/SPCE electrodes were characterized using FESEM, EDX, and CV analysis, respectively. The electrochemical performance of the NPG/SPCE was compared with bare SPCE in a 10 mM potassium ferrocyanide (K4FeCN6) solution using cyclic voltammetry. The morphological study using FESEM revealed that the NPG/SPCE had an average pore diameter of 53 nm. The quantification of elements using EDX shows that 84 % of the copper in the electrodeposited gold-copper alloy electrode was successfully removed by the dealloying process. The higher number of cycles during the dealloying process led to producing NPG with higher ECSA electrodes. The ECSA of NPG/SPCE is 12 times greater than that of bare or unmodified SPCE in an equivalent geometrical area. NPG/SPCE has a much better electron transfer surface than bare SPCE due to its high surface area and gold surface properties, making it a potential sensing material for biosensing applications.

Bioreceptors’ immobilization by hydrogen bonding interactions and differential pulse voltammetry for completely label-free electrochemical biosensors

Label-free electrochemical biosensors show great potential for the development of point-of-care devices (POCDs) for environmental and clinical applications. These sensors operate with shorter analysis times and are more economic than the labelled ones. Here, four completely label-free biosensors without electron transfer mediators were developed for hepatitis B virus (HBV) detection. The approach consisted in (i) the modification of gold surfaces with cysteamine (CT) or cysteine (CS) linkers, (ii) the subsequent antibody (Ab) immobilization, either directly by hydrogen bonding (HB) interactions or by covalent bonds (CB) using additional reagents, and (iii) measuring the biosensor response by electrochemical impedance spectroscopy (EIS) and differential pulse voltammetry (DPV). The electrode surfaces at each stage of the modification process were characterised by X-ray photo-electron spectroscopy (XPS) and atomic force microscopy (AFM). The combination of Ab immobilization by HB with the DPV analysis displayed improved repeatability, lower interference to serum matrix and similar limits of detection and quantification than the traditional biosensors that immobilize the Ab via CB and use EIS as readout technique. The Ab immobilization by HB is shown as a simple, efficient and low-cost alternative to CB ones, while DPV was faster and showed better performance than EIS. The CT-HB biosensor displayed the lowest limits of detection and quantification of 0.14 and 0.46 ng/mL, respectively, a 0.46–12.5 ng/mL linear analytical range, and 100% of recovery for 1/10 human serum media during HBV surface antigen detection by DPV. Even, it preserved the initial sensing capability after 7 days of its fabrication.Graphical abstract

Paper-Based DNA Biosensor for Rapid and Selective Detection of miR-21.

Cancer is the second leading cause of death globally, with 9.7 million fatalities in 2022. While routine screenings are vital for early detection, healthcare disparities persist, highlighting the need for equitable solutions. Recent advancements in cancer biomarker identification, particularly microRNAs (miRs), have improved early detection. MiR-21 is notably overexpressed in various cancers and can be a valuable diagnostic tool. Traditional detection methods, though accurate, are costly and complex, limiting their use in resource-limited settings. Paper-based electrochemical biosensors offer a promising alternative, providing cost-effective, sensitive, and rapid diagnostics suitable for point-of-care use. This study introduces an innovative electrochemical paper-based biosensor that leverages gold inkjet printing for the quantitative detection of miR-21. The biosensor, aimed at developing cost-effective point-of-care devices for low-resource settings, uses thiolated self-assembled monolayers to immobilize single-stranded DNA-21 (ssDNA-21) on electrodeposited gold nanoparticles (AuNPs) on the printed gold surface, facilitating specific miR-21 capture. The hybridization of ssDNA-21 with miR-21 increases the anionic barrier density, impeding electron transfer from the redox probe and resulting in a current suppression that correlates with miR-21 concentration. The biosensor exhibited a linear detection range from 1 fM to 1 nM miR-21 with a sensitivity of 7.69 fM µA-1 cm2 and a rapid response time (15 min). With a low detection limit of 0.35 fM miR-21 in serum, the biosensor also demonstrates excellent selectivity against interferent species. This study introduces an electrochemical paper-based biosensor that uses gold inkjet printing to precisely detect miR-21, a key biomarker overexpressed in various cancers. This innovative device highlights the potential for cost-effective, accessible cancer diagnostics in underserved areas.

The combined leaching of copper, gold and uranium in chloride solutions. II. Concentrate leach tests

This study of the simultaneous leaching of copper, gold and uranium from a flotation concentrate is aimed at establishing the conditions that could be applied in a possible heap leach process that would recover all three metals (plus silver, if present) in a single step. The results obtained in this study confirm the results obtained in Part I (Nicol et al., 2024) that enhanced rates for leaching of chalcopyrite from flotation concentrates from two different sources can be obtained in acidic chloride solutions in the presence of chlorate ions. The measurements of the solution potentials during leaching with chlorate are similar to those obtained previously and confirm that chlorine generated by the chlorate-chloride reaction is the active oxidant.Uranium is dissolved even in the absence of chlorate by iron(III) as the oxidant. The latter is re-generated by reaction of iron(II) with chlorate. The dissolution of gold requires higher potentials, and it is only leached when the potential approaches 1.0 V in concentrated chloride solutions. At low chloride concentrations (1 M), gold is not dissolved because of apparent passivation.An electrochemical study of the behaviour of gold in chloride solutions in the presence of sulfide ions has shown that the passivation is probably the result of the formation of a layer of Au2S on the gold surface at low potentials before the addition of chlorate to the leach solutions i.e., before the generation of sufficient chlorine concentrations. At potentials above about 0.95 V Au2S is unstable being oxidised to AuCl2− and elemental sulfur thereby eliminating passivation.

Tailored functional monolayers made from mesoionic carbenes

Significant progress has been made over the last decades in surface functionalization of coinage metals using thiols and more recently N-heterocyclic carbenes. As shown in this work, mesoionic carbenes (MICs) provide straightforward access to a novel class of surface ligands including electroactive ones and thus materials. Importantly, MICs are easily accessed from triazolium salts (TS) onto which functional groups may be attached with little synthetic effort. Here, we present a library of TS that were further converted, in situ, into MICs and grafted onto gold surfaces. The modified surfaces were thoroughly characterized by advanced spectroscopic methods such as XPS, infrared and Tip-Enhanced Raman Spectroscopy. Through cyclic voltammetry at 100 Vs-1, we could evaluate the surfacic concentration of the grafted molecules for electroactive MICs. We also prepared mixed MIC/thiol self-assembled monolayers, which opens the route to multifunctional surfaces.