Biosynthesis of Au nanoparticles using olive leaf extract: 1st Nano Updates

The biological synthesis of gold nanoparticles (AuNPs) of various shapes (triangle, hexagonal, and spherical) using hot water olive leaf extracts as reducing agent is reported. The size and the shape of Au nanoparticles are modulated by varying the ratio of metal salt and extract in the reaction medium. Only 20 min were required for the conversion into gold nanoparticles at room temperature, suggesting a reaction rate higher or comparable to those of nanoparticles synthesis by chemical methods. The variation of the pH of the reaction medium gives AuNPs nanoparticles of different shapes. The nanoparticles obtained are characterized by UV–Vis spectroscopy, photoluminescence, transmission electron microscopy (TEM), X-ray diffraction (XRD), FTIR spectroscopy and thermogravimetric analysis. The TEM images showed that a mixture of shapes (triangular, hexagonal and spherical) structures was formed at lower leaf broth concentration and high pH, while smaller spherical shapes were obtained at higher leaf broth concentration and low pH.     

Green synthesis of plant-stabilized Au nanoparticles for the treatment of gastric carcinoma

In this study, gold nanoparticles (AuNPs) were green synthesized using plant extract. The obtained nanoparticles (Au NPs) were characterized by advanced physical and chemical techniques like TEM, FTIR, UV–vis, SEM, XRD and EDX. SEM image displayed the quasi-spherical shaped nanoparticles of mean diameter 20–50 nm. All the particles were of uniform shape and texture. From the XRD pattern, four distinct diffraction peaks at 38.2°, 44.2°, 64.7° and 77.4° are indexed as (1 1 1), (2 0 0), (2 2 0) and (3 1 1) planes of fcc metallic gold. The in vitro cytotoxic and anti-gastric carcinoma effects of biologically synthesized Au NPs against cancer cell lines were assessed. The IC₅₀ of the Au NPs were 192, 149, 76 and 85 µg/mL against NCI-N87, MKN45, GC1401 and GC1436 gastric cancer cell lines. The anti-gastric carcinoma properties of the Au NPs could significantly remove the cancer cell lines in a time and concentration-dependent manner. So, the findings of the recent research show that biologically synthesized Au NPs might be used to cure cancer.     

Size and stability modulation of ionic liquid functionalized gold nanoparticles synthesized using Elaeis guineensis (oil palm) kernel extract

Bio-synthesis approach for gold nanoparticles (AuNPs) has received tremendous attention as an efficient and eco-friendly process. However, kinetic growth and colloidal stability of AuNPs synthesized by this process remained challenging. In this study, Elaeis guineensis (oil palm) kernel (OPK) extract prepared in an ionic liquid (IL)[EMIM][OAc] (1-ethyl-3-methylimidazolium acetate) was employed to control and tune the size and morphology of AuNPs. Synthesized AuNPs were characterized using UV-vis spectrophotometer, dynamic light scattering (DLS) and transmission electron microscopy (TEM) to observe any changes in absorbance, surface charge and particle size, respectively. IL mediated AuNPs were examined for 120 days and found well dispersed and stable at room temperature. UV-vis analysis demonstrated that volume of extract played an important role to control the stability of AuNPs. After 120 days, only 8.86% reduction from maximum absorbance was observed using 2 mL of volume of extract, which was elevated to 47.64% in case of 0.3 mL. TEM analysis was performed periodically after day 1, day 30, day 60, day 90 and day 120 and minor increase in the size was observed. Insignificant change in zeta potential value after 120 days supported enhanced stability of IL mediated AuNPs. Crystalline nature of AuNPs was confirmed by X-ray diffraction (XRD) pattern. The particles size and zeta potential of AuNPs was measured as 8.72 nm and −18.7 mV, respectively. However, the absence of [EMIM][OAc] from OPK extract resulted into larger particles size (9.64 nm), low zeta potential value (−13.9 mV) and enhanced aggregation of particles. Finally, experimental data were used to predict the theoretical and the experimental settling time for AuNPs to evaluate colloidal stability.     

CO oxidation over ceria supported Au22 nanoclusters: Shape effect of the support

CO oxidation over ceria-supported Au₂₂ nanoclusters shows strong dependence on the support shape: the lattice oxygen in CeO₂ rods is more reactive than in the cubes and thus make rods a superior support for Au nanoclusters in catalyzing low temperature CO oxidation.     

Theoretical study of Au/SAPO-11 catalyst and its potential use in thiophene HDS

Quantum chemistry calculations were carried out, using ONIOM2 methodology, in order to investigate the thiophene interaction with gold supported on silicoaluminophospates molecular sieves (Au/SAPO-11) catalysts. Two models were studied, one containing one Au atom per site, and the other with two Au atoms per site. Thiophene adsorption was found to be η¹ type. This adsorption presents a ΔH of ?13.2 and ?9.7 kcal/mol, for the models with one Au atom (Au/SAPO-11), and two Au atoms (Au₂/SAPO-11), respectively. The partial hydrogenation of the thiophene–Au/SAPO-11 and thiophene–Au₂/SAPO-11 complexes gives 2,5-dihydrothiophene (DHT), with a ΔH of ?23.0 and ?36.8 kcal/mol, respectively. 2-Butene production was found in both models with further hydrogenation. Likewise the direct butadiene elimination is achieved, but only with the separated Au dimer (ΔH = ?17.5 kcal/mol).     

Synthesis of Au/C and Au/Pani for anode electrodes in glucose microfluidic fuel cell

Gold nanoparticles have been prepared by two methods: chemical (ex-situ, Au/C) by two phase protocol, and electrochemical (in-situ, Au/Pani) by electroreduction of gold ions on a polyaniline film and compared as anode catalysts in a glucose microfluidic fuel cell. In this paper the structural characteristics and electrocatalytic properties were investigated by X-ray diffraction and electrochemical measurements. The catalytic behavior of both anodes was tested in a microfluidic fuel cell with a reference electrode incorporated, by means of linear sweep voltammetry (LSV), showing a cathodic shift in the glucose oxidation peak for Au/Pani. Results show a higher power density (0.5 mW cm^? 2) for Au/C anode compared with an already reported value, where a glucose microfluidic fuel cell was used in similar conditions.     

Flame atomic absorption spectrometry determination of trace amount of gold after separation and preconcentration onto ion-exchange polyethylenimine coated on Al2O3

The object of this work is to develop a simple and selective method for efficient extraction of Au(III) ions in aqueous solution using a new solid-phase extraction sorbent. Polyethylenimine (PEI) ion-exchange polymer was coated on alumina in the presence of NaNO₃. The method is based on sorption of Au³⁺ ions on 50 mg PEI/Al₂O₃. A solution of 0.5 M thiourea, then 1.0 M HCl effectively eluted the gold ion and then aspirated into flame atomic absorption spectroscopy (FAAS). The influence of flow rate of sample solution and eluent, the pH effect, eluent type and sorption capacity was investigated. The effects of various diverse ions for preconcentration and separation of the gold ion were investigated. Relative standard deviation of 4.0 μg mL⁻¹ of gold was 1.46% (n = 10). The detection limit was 26.2 ng L⁻¹ in original solution. The method has been applied successfully for the recovery of trace amount of Au(III) ions from water samples.     

Theoretical investigation of inclusion complex formation of Gold (III) – Dimethyldithiocarbamate anticancer agents with cucurbit[n = 5,6]urils

Gold (III)-N,N-dimethyldithiocarbamate [DMDT(Au)X₂] complexes have recently gained increasing attention as potential anticancer agents because of their strong tumor cell growth–inhibitory effects, generally achieved by exploiting non-cisplatin-like mechanisms of action. The goal of our research work is to encapsulate the gold(III) dimethyldithiocarbamate complexes as anticancer with cucurbit[n]urils (CB[n = 5, 6]) by accurate calculations, to predict the inclusion complex formation of gold(III) species with cucurbiturils (CB[n = 5, 6]). The calculations were carried out just for the 1:1 stoichiometric complexes. Upon encapsulation, binding energy, thermodynamic parameters, structural parameters and electronic structures of complexes are investigated. The results of the thermodynamic calculations and the binding energy show that the inclusion process is exothermic and the CB[6]/[DMDT(Au)Br₂] complex is more stable than other complexes. The final geometry of CB[n]/drugs indicates that the drugs were expelled from the cavity of CB[n]. NBO calculations reveal that the hydrogen bonding between CB[n] and drugs and electrostatic interactions are the major factors contributing to the overall stabilities of the complexes.     

Synthesis and structural characterisation of linear Au(I) N-heterocyclic carbene complexes: New analogues of the Au(I) phosphine drug Auranofin

The synthesis and characterisation of a series of neutral Au(I) N-heterocyclic carbene complexes [(NHC)AuX] (X = Cl and 2′,3′,4′,6′-tetra-O-acetyl-β-d-glucopyranosyl-1-thiolato) are reported. The chloro complexes were synthesised either by reaction of the appropriate 1,3-dialkylimidazol-2-ylidene with [(Me₂S)AuCl] or by transmetallation between the appropriate Ag(I)–NHC complex and [(Me₂S)AuCl]. The 2′,3′,4′,6′-tetra-O-acetyl-β-d-glucopyranosyl-1-thiolato complexes were prepared from the appropriate [(NHC)Au(I)Cl] complex and 2′,3′,4′,6′-tetra-O-acetyl-1-thio-β-d-glucopyranose under basic conditions. A cationic Au(I)–NHC triphenylphosphine adduct was also prepared. Structural studies (X-ray diffraction) of a number of the complexes show that in each case the gold atom is (quasi-) linearly two-coordinate, having C–Au–Cl, C–Au–S or C–Au–P coordination. In one case, a new phase of [(Cy₂Im)AuCl], the molecules pack pair-wise with a close Au⋯Au interaction (3.1566(6) Å). Preliminary studies show this complex is luminescent in the solid state.     

Controlled deposition of Pt on Au nanorods and their catalytic activity towards formic acid oxidation

Platinum submonolayer decorated gold nanorods with controlled coverage were prepared by the addition of Au nanorods into the growth solution of Pt in the presence of NH₂OH · HCl as the growth agent. The properties of Au nanorods decorated by Pt submonolayer were investigated by various techniques including transimission electron microscopy, X-ray diffraction, and electrochemical methods. The Pt decorated Au nanorods on carbon black showed significantly higher activity on formic acid electrooxidation than the conventional Pt/C catalysts. They showed different reaction path of formic acid electrooxidation by suppressing the formation of poisoning intermediate CO.     

Vibrational spectroscopic characterization of 4-acylamidobenzenethiol-stabilized gold nanoparticles

A simple preparation method of gold nanoparticles (AuNPs) with 4-acylamidobenzenethiol derivative (BD) was improved to obtain the larger size of AuNPs which exhibited localized surface plasmon resonance. The spectroscopic characterizations of two kinds of BD-stabilized AuNPs were carried out by means of ATR-FTIR and Raman spectroscopy in order to clarify the conformation and orientation of BDs adsorbed on AuNPs. The relation between the stability of AuNPs and the adsorbed states of BDs were also discussed. The average sizes of the resulting AuNPs were 18 nm for BD1 and 30 nm for BD2, respectively. It was found that the BD1-capped AuNPs formed large aggregates. The results of vibrational spectroscopy revealed that loosely packed self-assembled monolayer (SAM) of BD1 molecules was formed on the surface of the AuNPs; on the other hand, densely packed SAM was formed in the case of BD2. We concluded the difference behavior between the two types of molecules was caused by the functional groups. The sulfuryl groups of BD2 induced highly ordered SAM and suppressed aggregate formation of AuNPs.     

Quasi-reversible two-electron reduction of oxygen at gold electrodes modified with a self-assembled submonolayer of cysteine

The electrochemical reduction of molecular oxygen (O₂) has been performed at gold electrodes modified with a submonolayer of a self-assembly (sub-SAM/Au) of a thiol compound (typically cysteine (CYST)) in O₂-saturated 0.5 M KOH. At bare gold electrode O₂ reduction reaction proceeds irreversibly, while this reaction is totally hindered at gold electrodes with a compact structure of CYST over its surface. The partial reductive desorption of the compact CYST monolayer was achieved by controlling the potential of the CYST/Au electrode, leading to the formation of a submonolayer coverage of the thiol compound over the Au electrode surface (sub-SAM/Au), at which the CYST molecules selectively block the Au(1 0 0) and Au(1 1 0) fractions (the so-called rough domains) of the polycrystalline Au while the Au(1 1 1) component (the so-called smooth domains) remains bare (i.e., uncovered with CYST). This sub-SAM/Au electrode extraordinarily exhibits a quasi-reversible two-electron reduction of molecular oxygen (O₂) in alkaline medium with a peak separation (ΔE_p) between the cathodic and anodic peak potentials (E_p^c,E_p^a) of about 60 mV. The ratio of the anodic current to the cathodic one is close to unity. The formal potential (E^o′) of this reaction is found to equal −150 mV vs. Ag/AgCl/KCl(sat.).     

The influence of chloride on the initial anodic dissolution of Cu3Au(1 1 1)

We report a detailed in situ X-ray diffraction study of the influence of chloride on the atomic structure evolution at the solid-electrolyte interface during the selective dissolution of Cu from a Cu₃Au(1 1 1) surface immersed in 0.1 M H₂SO₄. We disclose that the formation of the initial ultrathin Au-rich (1 1 1) with an inverted stacking sequence, as recently observed at Cu₃Au(1 1 1) in contact with pure 0.1 M H₂SO₄, is strongly influenced by adding 5 mM HCl. The main finding is a negative shift of about 150 mV of the critical potential at which the ultra-thin Au-rich layer transforms into thicker Au islands. The presented results support the view that it is not a thermodynamic driving force, but rather the rate of surface diffusion that dominates the formation of the structures of the metallic layer.     

Synergistic contributions of multiwall carbon nanotubes and gold nanoparticles in a chitosan–ionic liquid matrix towards improved performance for a glucose sensor

We report an ingenious approach for the fabrication of a promising glucose sensor, GOx/Au/CS–IL–MWNT(SH), that exploits the synergistic beneficial characteristics of multiwalled-carbon nanotubes (MWNTs), gold nanoparticles (AuNPs), chitosan (CS) and room temperature ionic liquid (RTIL). Direct electron transfer between glucose oxidase (GOx) and electrode was achieved. Scanning electron microscopy and atomic force microscopy images of GOx/Au/CS–IL–MWNT(SH) reveal that MWNTs and AuNPs are dispersed in CS–IL matrix. Cyclic voltammetry, impedance spectroscopy and chronoamperometry were used to evaluate the performance of biosensor. The GOx/Au/CS–IL–MWNT(SH) biosensor exhibits a linear current response to glucose concentration (1–10 mM) at a low potential of 0.10 V and precludes interferences from uric acid and ascorbic acid. The GOx/Au/CS–IL–MWNT(SH) biosensor has superior performances over GOx/CS–IL–MWNT(SH).     

Electronic structure of the Au–Si(1 1 1) interface as a function of Au coverage

We have investigated the Au–Si(1 1 1) interface as a function of the Au coverage by the core-level photoemission spectroscopy. With increasing the Au coverage, the spectral features in the Si 2p core-level changed remarkably and some fine structures in both Si 2p and Au 4f spectra were observed. Based on the curve fitting analysis, the Si 2p and Au 4f spectra at more than 20 Å Au coverage were decomposed into three chemically different components, respectively. The assignments of their components were performed. In addition, we have compared these results for the Au–Si(1 1 1) interface with our previous study for the Au–Si(1 0 0) interface. It was found that the electronic structures for the Au–Si(1 1 1) interface is essentially identical to those of the Au–Si(1 0 0) interface except at the initial Au deposition.     

Spontaneous deposition of Sn on Au(1 1 1). An in situ STM study

The tin adlayer formed by spontaneous deposition on Au(1 1 1) was characterized by cyclic voltammetry and in situ scanning tunneling microscopy (STM) in sulphuric acid solution. Cyclic voltammetry measurements showed oxidation peaks in the potential range −0.60 ⩽ E/V vs SSE ⩽ 0, which can be ascribed to the dissolution of the Sn adsorbed layer. STM images of the Au(1 1 1)/Sn modified surface showed that tin nucleated both on step edges and on the flat terraces forming two-dimensional islands. The anodic polarization of this modified surface produced the gradual dissolution of the Sn adlayer which was evidenced by the formation of some holes and the reduction of the initial terraces to many small islands. STM images with atomic resolution obtained on these islands displayed an hexagonal expanded atomic structure. After the anodic stripping of this Sn adsorbed layer the images exhibited the typical Au(1 1 1) terraces with a (1 × 1) atomic structure. However, at more anodic potentials another dissolution process was observed producing noticeable changes on the surface morphology which could be ascribed to the dissolution of a Au–Sn surface alloy.     

High performance bioanode based on direct electron transfer of fructose dehydrogenase at gold nanoparticle-modified electrodes

The direct electron transfer reaction of fructose dehydrogenase (FDH) from Gluconobacter sp. on alkanethiol-modified gold nanoparticles (AuNPs) was examined. AuNP-modified electrodes were simply fabricated by depositing citrate-reduced gold nanoparticles onto a gold electrode and carbon fiber paper and then covering the surface with a self-assembled monolayer of alkanethiols. The immobilization of AuNPs provided a large effective surface area for the adsorption of FDH. Catalytic oxidation currents based on the direct electron transfer reaction of FDH were observed from a potential about ?100 mV (vs. Ag/AgCl, 3 M NaCl) in the presence of d-fructose without a mediator. The current density reached as high as 14.3 ± 0.93 mA/cm² (at +500 mV), which was achieved in the presence of 200 mM d-fructose by immobilization of FDH on 2-mercaptoethanol-modified AuNP/carbon fiber paper electrodes.     

Au-assisted visible laser MALDI

The excitation of UV-absorbing MALDI matrixes with visible laser (532 nm wavelength) and the desorption/ionization of biomolecules were performed by coating the analytes doped matrix with Au thin film (5–10 nm) using ion sputtering deposition. The Au film was first ablated with the laser of higher fluence, resulting in a crater/hole about the size of the laser beam spot on the target. After a few initial laser shots, analytes and matrix related ions were observed from the crater even at lower laser fluence. Electron microscopy inspection on the laser ablated region revealed the formation of nanoparticles with sizes ranging from <10 to 50 nm. Compared with the infra-red laser (1064 nm) excitation, the visible laser produced much higher abundance of matrix radical ions, and less heating effect as measured by the thermometer molecules. The results suggest the photo-excitation and photo-ionization of matrix molecules by the visible laser, possibly assisted by the gold nanoparticles and nanostructures left on the ablated crater.     

Amperometric sensor for hydrogen peroxide based on direct electron transfer of spinach ferredoxin on Au electrode

A protein-based electrochemical sensor for hydrogen peroxide (H₂O₂) was developed by an easy and effective film fabrication method where spinach ferredoxin (Fdx) containing [2Fe–2S] metal center was cross linked with 11-mercaptoundecanoic acid (MUA) on a gold (Au) surface. The surface morphology of Fdx molecules on Au electrodes was investigated by atomic force microscopy (AFM). Electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) were employed to study the electrochemical behavior of adsorbed Fdx on Au. The interfacial properties of the modified electrode were evaluated in the presence of Fe(CN)₆^3?/4? redox couple as a probe. From CV, a pair of well-defined and quasi-reversible redox peaks of Fdx was obtained in 10 mM, pH 7.0 Tris–HCl buffer solution at ?170 and ?120 mV respectively. One electron reduction of the [2Fe-2S]²⁺ cluster occurs at one of the iron atoms to give the reduced [2Fe-2S]⁺. The formal reduction potential of Fdx ca. ?150 mV (vs. Ag/AgCl electrode) at pH 7.0. The electron-transfer rate constant, k_s, for electron transfer between the Au electrode and Fdx was estimated to be 0.12 s^?1. From the electrochemical experiments, it is observed that Fdx/MUA/Au promoted direct electron transfer between Fdx and electrode and it catalyzes the reduction of H₂O₂. The Fdx/MUA/Au electrode displays a linear increase in amperometric current for increasing concentration of H₂O₂.The sensor calibration plot was linear with r² = 0.998 with sensitivity approximately 68.24 μAm M^?1 cm^?2. Further, the effect of nitrite on the developed sensor was examined which does not interfere with the detection of H₂O₂. Finally, the addition of H₂O₂ on MUA/Au electrode was observed which has no effect on amperometric current.     

CtrA gene based electrochemical DNA sensor for detection of meningitis

Electrochemical DNA sensor has been fabricated by immobilizing thiolated single stranded oligonucleotide (ssDNA) probe onto gold (Au) coated glass electrode for meningitis detection using hybridization with complementary DNA (CtrA) in presence of methylene blue (MB). These electrodes (ssDNA/Au and dsDNA/Au) have been characterized using atomic force microscopy (AFM), Fourier transform infrared spectroscopy (FT-IR), electrochemical impedance spectroscopy (EIS) and cyclic voltammetric (CV) technique. The DNA/Au electrode can detect the complementary DNA in the range of 7–42 ng/μl in 5 min (hybridization) with response time 60 s and electrode is stable for about 4 months when stored at 4 °C. The sensitivity of dsDNA/Au electrode is 115.8 μA/ng with 0.917 regression coefficient (R).