Surface Of Gold Nanoparticles Research Articles

Lateral Flow Immunoassay for the Rapid Detection of Thiamethoxam in Tea Based on a SERS Tag Constructed by Phenolic-Mediated Coating Engineering.

Sensitive and accurate detection of thiamethoxam in tea is significant to ensuring consumer health. In this study, surface-enhanced Raman scattering (SERS) tags were prepared by using a polyphenol-mediated coating engineering strategy. This approach involved the self-assembly of tannic acid (TA) and self-polymerization of benzene-1,4-dithiol (BDT) on the surface of gold nanoparticles, resulting in the formation of Au@pBDT-TA. The SERS tags possess high Raman signals and antibody adsorption properties, avoiding the complex decoration or label steps of SERS reporters. We discovered that Au@pBDT-TA, composed of gold nanoparticles at 40 nm and a pBDT-TA thickness of 10 nm, was optimal for the development of the SERS lateral flow immunoassay (LFIA). In comparison to the gold nanoparticle-based LFIA, the SERS-LFIA demonstrated 4-fold and 720-fold enhancements in visual and quantitative limits of detection in buffer solution. The SERS-LFIA demonstrated quantitative limits of detection of 0.06 and 0.1 ng/g for black and green tea, respectively, with a broader linear range spanning over 2 orders of magnitude and a short detection time of 20 min. The proposed SERS-LFIA not only offers a sensitive and reliable method for monitoring thiamethoxam in tea but also possesses a versatile potential that can be easily adapted for the trace detection of various other targets.

Synthesis and Characterization of Acacia-Stabilized Doxorubicin-Loaded Gold Nanoparticles for Breast Cancer Therapy.

The targeted delivery of drugs is vital in breast cancer treatment due to its ability to produce long-lasting therapeutic effects with minimal side effects. This study reports the successful development of doxorubicin hydrochloride (DOX)-loaded colloidal gold nanoparticles stabilized with acacia gum (AG). Optimization studies varied AG concentrations (0.25% to 3% w/v) to determine optimal conditions for nanoparticle synthesis. The resulting acacia stabilized gold nanoparticles (AGNPs) were characterized using various techniques including high-resolution transmission electron microscopy (HR-TEM), powder X-ray diffraction (PXRD), differential scanning calorimetry (DSC), ultraviolet-visible spectroscopy, Fourier-transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FE-SEM), and selected area electron diffraction (SAED). In vitro drug release studies demonstrated a higher release rate of DOX in sodium acetate buffer (pH 5.0) compared to phosphate buffer saline (pH 7.4), suggesting an enhanced therapeutic efficacy in acidic tumor environments. Cytotoxicity of DOX-AGNPs and free DOX was assessed in human breast cancer cells (MDA-MB-231). The DOX-AGNPs exhibited significantly greater cytotoxicity, indicating enhanced efficacy in targeting cancer cells. This enhancement suggests that adsorbing DOX on the surface of gold nanoparticles can improve drug delivery and effectiveness, potentially reducing side effects compared to pure DOX and traditional delivery methods. Stability tests conducted over six months at 25±1°C showed significant changes in particle size and PDI, suggesting limited stability under these conditions. Overall, the acacia-stabilized gold nanoparticles synthesized in this study exhibit promising characteristics for drug delivery applications, particularly in cancer therapy, with effective drug loading, controlled release, and favorable physicochemical properties.

Circularly Polarized Light-Induced Chiral Growth of Achiral Plasmonic Nanoparticles Dispersed in a Solution.

Plasmonic nanoparticles (NPs) with chiral geometries have wide applications from chiral molecular sensing to enantioselective catalysis. The synthesis of chiral plasmonic nanoparticles using circularly polarized light (CPL) has attracted a considerable amount of attention because it eliminates the need for chiral molecules. However, NPs need to be immobilized on a solid substrate during synthesis. Here, we successfully synthesized colloidal chiral plasmonic NPs by depositing silver on the surface of achiral gold nanoparticles dispersed in a solution using CPL. Circular dichroism (CD) signals corresponding to the handedness of the irradiated CPL were observed when gold nanorods or gold nanotriangles were used. In contrast, no clear CD signal was observed when gold nanospheres were used. The morphological anisotropy of the gold nanoparticles was a key factor in the synthesis of chiral plasmonic nanoparticles using CPL. Furthermore, we demonstrated the tuning of chiroptical properties according to the CPL wavelength.

The Adsorption of Chlorpromazine on the Surface of Gold Nanoparticles and Its Effect on the Toxicity to Selected Mammalian Cells

Chlorpromazine (CPZ) is a first-generation neuroleptic with well-established antitumor and antiviral properties. Currently, numerous studies are focused on developing new methods for CPZ delivery; however, the knowledge regarding its conjugates with metal nanoparticles remains limited. The aim of this study was to prepare CPZ conjugates with gold nanoparticles (AuNPs) and evaluate their biological activity on human lymphocytes (HUT-78 and COLO 720L), as well as human (COLO 679) and murine (B16-F0) melanoma cells, in comparison to the effects induced by unconjugated CPZ molecules and AuNPs with well-defined properties. During the treatment of cells with CPZ, AuNPs, and CPZ-AuNP conjugates, changes in mitochondrial activity, membrane integrity, and the secretion of lipid peroxidation mediators were studied using standard biological assays such as MTT, LDH, and MDA assays. It was found that positively charged CPZ-AuNP conjugates more effectively reduced cell viability compared to AuNPs alone. The dose-dependent membrane damage was correlated with oxidative stress resulting from exposure to CPZ-AuNP conjugates. The activity of the conjugates depended on their composition and the size of the AuNPs. It was concluded that conjugating CPZ to AuNPs reduced its biological activity, while the cellular response to the treatment varied depending on the specific cell type.

Surface-enhanced Raman scatting microfluidic chip based on the identification competition strategy were used for rapid and simultaneous detection of liver cancer related proteins

Biomarker testing plays a crucial role in the early detection of liver cancer. Herein, we developed a dual-signal amplification approach utilizing magnetic aggregation and a recognition competition strategy for the simultaneous detection of alpha-fetoprotein (AFP) and manganese superoxide dismutase (MnSOD) in serum. 4-MBA@AuNPs@H1 and DTNB@AuNPs@H2 were synthesized by functionalizing Raman signaling molecules and aptamer complementary chains onto the surface of gold nanoparticles (AuNPs). The detection complex Raman signal molecule@AuNPs@H-Fe3O4@cDNA was assembled by conjugating 4-MBA@AuNPs@H1 and DTNB@AuNPs@H2 with two nucleic acid aptamers (cDNA1 and cDNA2) modified with Fe3O4 through partial base complementary pairing. The target protein exhibited specific binding with the aptamer, leading to the competitive displacement of 4-MBA@AuNPs@H1 and DTNB@AuNPs@H2 from the Fe3O4 array surface, consequently resulting in a reduction of the Surface-Enhanced Raman Spectroscopy (SERS) signal. Through this approach, the limit of detection (LOD) for AFP and MnSOD in serum was achieved at remarkably low levels of 5.89 pg/mL and 6.23 pg/mL, respectively, with a reaction incubation period of only 5 min. Finally, the platform was utilized for the quantification of AFP and MnSOD in the serum of a nude mouse hepatocellular carcinoma model. The results obtained through SERS were consistent with those from enzyme-linked immunosorbent assay (ELISA), validating its accuracy. This methodology presents a novel approach for the swift and concurrent detection of proteins, holding significant clinical promise for the early diagnosis of hepatocellular carcinoma.

Osteo-modulatory potential of biologically synthesized cis-resveratrol passivated gold nanoparticles

Resveratrol, a stilbene, particularly trans-isomer, shows significant osteogenic potential but experiences high instability and poor bioavailability. However, cis-isomer (cRes) is not explored yet due to its instability. Our study investigates the osteoinductive potential of cRes for the first time by stabilizing it onto the surface of gold nanoparticles. cRes capped GNPs (cRGNPs) presented no toxic effects on the MC3T3-E1 cells with increased levels of alkaline phosphatase and calcium deposition. The nanoparticles presented a 2.6-fold increase in cell number compared to the control. The pro-migratory effect of the cRGNPs was also significantly higher (97.21 ± 0.99 % migration) in 4 days. The osteoinductivity was further confirmed by enhanced expression of osteoblastic genes like RUNX2, OPN, OCN, BMP, OPG, and Col1A. The stability provided to cRes upon conjugating to GNPs allowed exploration of its potential in aiding proliferation, migration, and differentiation of the pre-osteoblasts, which will be beneficial in repairing bone defects.

Label-Free Biosensor Based on Particle Plasmon Resonance Coupled with Diffraction Grating Waveguide.

Particle plasmon resonance (PPR), or localized surface plasmon resonance (LSPR), utilizes intrinsic resonance in metal nanoparticles for sensor fabrication. While diffraction grating waveguides monitor bioaffinity adsorption with out-of-plane illumination, integrating them with PPR for biomolecular detection schemes remains underexplored. This study introduces a label-free biosensing platform integrating PPR with a diffraction grating waveguide. Gold nanoparticles are immobilized on a glass slide in contact with a sample, while a UV-assisted embossed diffraction grating is positioned opposite. The setup utilizes diffraction in reflection to detect changes in the environment's refractive index, indicating biomolecular binding at the gold nanoparticle surface. The positional shift of the diffracted beam, measured with varying refractive indices of sucrose solutions, shows a sensitivity of 0.97 mm/RIU at 8 cm from a position-sensitive detector, highlighting enhanced sensitivity due to PPR-diffraction coupling near the gold nanoparticle surface. Furthermore, the sensor achieved a resolution of 3.1 × 10-4 refractive index unit and a detection limit of 4.4 pM for detection of anti-DNP. The sensitivity of the diffracted spot was confirmed using finite element method (FEM) simulations in COMSOL Multiphysics. This study presents a significant advancement in biosensing technology, offering practical solutions for sensitive, rapid, and label-free biomolecule detection.

Sensitive colorimetric detection of Escherichia coli in milk using Au@Ag core-shell nanoparticles

Escherichia coli (E. coli) is a prevalent pathogen that is frequently associated with the foodborne illness. It causes various infections and poses a significant threat to human health. A rapid and sensitive assay for detecting E. coli is essential for timely diagnosis. Herein, a simple and sensitive colorimetric analysis method for detecting E. coli was developed based on the formation of Au@Ag core-shell nanoparticles facilitated by p-benzoquinone (BQ). E. coli reduced p-benzoquinone to generate hydroquinone (HQ), which could reduce the added Tollens’ reagent to silver elemental and grow on the surface of gold nanoparticles (AuNPs). As the E. coli concentration increased, the silver layer thickess on the AuNPs surface growed, resulting in a stronger silver absorption peak observed at 390 nm. The color of the solution changed from red to orange, which could be used to detect E. coli by the naked eye. As a result, E. coli was detected with a linear range from 1.0 × 101 to 1.0 × 107 CFU/mL based on the absorbance intensity. In addition, this method accurately detected E. coli in real milk sample, demonstrating promising applications in foodborne pathogen detection. With satisfactory accuracy, the proposed colorimetric method holds excellent prospects in detecting pathogens in actual food samples.

Localized Cas12a-based cascade amplification for sensitive and robust detection of APE1

APE1, an essential enzyme for DNA repair, is overexpressed in various cancers and has been identified as a potential biomarker for cancer diagnosis. However, detecting APE1 at low expression levels in the early stage of cancer presents a significant obstacle. Here, we introduced a novel localized Cas12a-based cascade amplification (LCas12a-CA) method. This method confined both the terminal deoxynucleotidyl transferase and the crRNA/Cas12a complex onto the surfaces of gold nanoparticles (AuNPs). This confinement not only boosts the stability of the multiple enzymes but also induces a substrate channeling effect. As a result, it significantly accelerates the reaction rate and enhances the sensitivity of APE1 detection. Upon the addition of APE1, the AP sites within the APE1 primer can be recognized and cleaved by APE1, exposing the 3′-OH ends. In the presence of LCas12a-CA, polyA sequences are generated at 3′-OH ends with the help of TdT and dATP. The sequences directly enter the Cas12a system, activating the trans-cleavage activity of Cas12a, thereby cutting the reporters on the surface of AuNPs and releasing fluorescence. Our platform demonstrates a detection limit (LOD) as low as 2.51 × 10−6 U/mL, which is more than 60 times lower than that of free Cas12a-CA. Furthermore, the LCas12a-CA exhibits enhanced resistance ability in extreme environments and has been proven effective for the detection of APE1 in clinical samples. Overall, this work offers a promising platform for robust biosensing in cancer diagnosis and prognosis.

A quantitative method for aquaporin-1 protein using magnetic preconcentration and probe-based immunoassay coupling to inductively coupled plasma mass spectrometry in urine analysis

BackgroundAquaporin-1 (AQP1) protein plays a crucial role in intracellular and extracellular water homeostasis and fluid transport in organs and tissues associated with diverse life activities and is extremely abundant in the kidney. Accurate detection of AQP1 in urine can be applied as screening of early-stage disease. Application of magnetic preconcentration and probe-based signal amplification strategy coupling to inductively coupled plasma mass spectrometry (ICP-MS) is a more accurate, sensitive and specific detection method for AQP1 in complex biological samples compared to conventional methods. ResultsWe described an element-labelling strategy based on magnetic preconcentration and probe-based immunoassay coupling to ICP-MS detection. The magnetic beads (MBs) modified with epoxy groups were capable of enriching AQP1 proteins and separating them from complex matrices. The probe constructed by conjugating anti-AQP1 antibody molecules on the surface of gold nanoparticles could specifically recognize AQP1 proteins attached on MBs and be analyzed by ICP-MS. The concentration of AQP1 protein could be precisely quantified and amplified by 14,000 times through the corresponding signal of Au atoms. This assay for AQP1 protein quantification achieved a detection limit down to 0.023 ng mL−1, a broad linear calibration curve between 0.3 ng mL−1 and 30 ng mL−1, as well as outstanding specificity. SignificanceThe proposed method was successfully applied to detect AQP1 protein in human urine samples, showing the potential for its applications concerning accurate AQP1 quantification. It can also screen a wide range of proteins provided the antibodies specific to these target proteins are available.

A Multimode Detection Platform for Biothiols Using BODIPY Dye-Conjugated Gold Nanoparticles

This study explored the synthesis and application of BODIPY-functionalized gold nanoparticles (AuNPs) for the sensitive detection of biothiols via an indicator displacement assay coupled with surface-enhanced Raman scattering (SERS) techniques, alongside their efficacy for in vitro cancer cell imaging. Moreover, the assay allowed for the visible colorimetric detection of biothiols under normal and ultraviolet light conditions. The BODIPY (boron-dipyrromethene) fluorophores were strategically conjugated to the surface of gold nanoparticles, forming a robust nanohybrid that leverages the plasmonic properties of AuNPs for enhanced spectroscopic sensitivity. The detection mechanism exploited the displacement of the BODIPY indicator upon interaction with biothiols, triggering a measurable change in fluorescence and SERS signals. This dual-mode sensing approach provides high selectivity and sensitivity for biothiol detection, with detection limits reaching nanomolar concentrations using fluorescence and femtomolar concentration for cysteine using SERS. Furthermore, the BODIPY-AuNP complexes demonstrated excellent biocompatibility and photostability, facilitating their use in the fluorescence imaging of biothiol presence within cellular environments and highlighting their potential for diagnostic and therapeutic applications in biomedical research.

Phenylboronic Acid-Functionalized Ratiometric Surface-Enhanced Raman Scattering Nanoprobe for Selective Tracking of Hg2+ and CH3Hg+ in Aqueous Media and Living Cells.

The development of appropriate molecular tools to monitor different mercury speciation, especially CH3Hg+, in living organisms is attractive because its persistent accumulation and toxicity are very harmful to human health. Herein, we develop a novel activity-based ratiometric SERS nanoprobe to selectively monitor Hg2+ and CH3Hg+ in aqueous media and in vivo. In this nanoprobe, a new bifunctional Raman probe bis-s-s'-[(s)-(4-(ethylcarbamoyl)phenyl)boronic acid] (b-(s)-EPBA) was synthesized and immobilized on the surface of gold nanoparticles via a Au-S bond, in which the phenylboronic acid group was employed as the recognition unit for Hg2+ and CH3Hg+ based on the Hg-promoted transmetalation reaction. In the presence of Hg2+ and CH3Hg+, a new surface-enhanced Raman scattering (SERS) peak aroused from of C-Hg appeared at 1080 cm-1, and the SERS intensity at 1002 cm-1 belonged to the B-O symmetric stretching decreased simultaneously. The quantitative tracking of Hg2+ and CH3Hg+ was realized based on the SERS intensity ratio (I1080/I1303) with rapid response (∼4 min) and high sensitivity, with detection limits of 10.05 and 25.13 nM, respectively. Moreover, the SERS sensor was used for the quantitative detection of Hg2+ and CH3Hg+ in four actual water samples with a high accuracy and excellent recovery. More importantly, cell imaging experiments showed that AuNPs@b-(s)-EPBA could quantitatively detect intracellular CH3Hg+ and had a good concentration dependence in ratiometric SERS imaging. Meanwhile, we demonstrated that AuNPs@b-(s)-EPBA could detect and image CH3Hg+ in zebrafish. We anticipate that AuNPs@b-(s)-EPBA could potentially be used to study the physiological functions related to CH3Hg+ in the future.

Determination of ammonia nitrogen by surface-enhanced Raman spectroscopy and DFT studies

Ammonia nitrogen is one of the most important indicators for evaluating the quality of water bodies. It is very difficult to determine ammonia nitrogen directly by Surface-enhanced Raman spectroscopy (SERS) in practice. In order to realize SERS determination of ammonia nitrogen, in this paper, SERS combined with density functional theory (DFT) was used to investigate why ammonia nitrogen needs to be derivatized to hexamethylenetetramine (HMTA) and why HMTA can be determined using SERS. The molecular electrostatic potential (MEP) results exhibit that there was no adsorption site on the surface of ammonia nitrogen, whereas its derivate HMTA had four available adsorption sites. This provides a basic guarantee for the SERS detection of HMTA. The molecular adsorption state of HMTA on the gold nanoparticles surface was concluded from the binding energies, the bond length, and the Raman activity spectra. Among them, the HMTA-Au4 complex has the lowest bond energy (−586.873 Kcal/mol) and the shortest bond length (2.161 Å), which is the most stable state and its Raman activity spectrum is the closest to the experimental data. Calculations results of frontier molecular orbital (FMO) demonstrate that the energy gap of HMTA and HMTA-Au4 complex are 0.30258 eV and 0.10947 eV, respectively, with a really obvious difference between them, which indicates that the HMAT-Au4 complex possessed higher chemical reactivity. In addition, charge transfer phenomenon on the MEP of HMTA-Au4 complex was deduced due to the change in the symmetry of its charge distribution, which can be explained the mechanism of chemical enhancement in the detection of HMTA by SERS. The selective enhancement at 1048 cm−1 peaks in theoretical spectrum and at 1044 peaks cm−1 in experimental spectrum provided theoretical and practical basis for indirect determination of ammonia nitrogen by SERS. The obtained results will help to better understand the reasons why some components are difficult to be directly determined by SERS, and why these components need to be derivatized. It provides a new method for components that are difficult to detect by SERS.

Inhalable explosive nanosensor for real-time visual monitoring of therapeutic effects of lung cancer

Lung cancer, as one of the major diseases that endanger human health, has a very high fatality rate. Consequently, effective evaluation of clinical treatment outcomes for lung cancer is crucial for the formulation of subsequent treatment plans for patients. In this work, we utilized amorphous calcium carbonate nanoparticles (CaCO3 NPs) as sources of calcium ions (Ca2+) to develop CPs (CaCO3@PDA) core–shell nanoprobes. Concurrently, we functionalized the surface of gold nanoparticles with Cy5.5-peptide, AS1411, and (4-aminosulfonylphenyl) boronic acid (4-APBA) to produce APAAs (Au NPs@pep-AS1411-(4-APBA)), which were further assembled with CPs using PEG to construct an innovative explosive nanosensor, CPAs (CaCO3@PDA-APAAs). The CPs component of the nanosensor could cause the release of a substantial amount of Ca2+ in response to the tumor microenvironment (TME), which in turn induced cellular Ca2+ overload and subsequent apoptosis. This event triggers caspase-3 activation, causing the cleavage of a specific peptide sequence (DEVD), resulting in the fluorescence signal being reinstated. Additionally, the 4-APBA moiety on the probe interacted with H2O2 resulting in alterations in surface-enhanced Raman spectroscopy (SERS) signals, which aided in the detection of reactive oxygen species (ROS) during the physiological processes. By utilizing atomization, the nanoprobes were strategically deposited in the affected lung regions to enhance the fluorescence imaging capabilities and effectively mirror the therapeutic outcomes. Overall, the CPAs explosive nanosensor has a potential in advancing the non-invasive visual monitoring of lung cancer prognosis and can be a valuable tool in ongoing efforts to improve the management of this challenging disease.

Rapid intracellular pH measurement based on electroporation- surface-enhanced Raman scattering

In this study, electroporation-surface-enhanced Raman scattering (SERS) was applied to rapidly measure intracellular pH. The generation of a sensitive SERS probe for measuring pH in the range of 6.0–8.0 was accomplished through the conjugation of the pH-sensitive molecule 4-mercaptobenzoic acid (4-MBA) to the surface of gold nanoparticles (Au NPs) through its thiol functional group. This bioprobe was then rapidly introduced into nasopharyngeal carcinoma CNE-1 cells by electroporation, followed by SERS scanning and the fitting of intensity ratios of each detection point’s Raman peaks at 1423 cm−1 and 1072 cm−1, to create the pH distribution map of CNE-1 cells. The electroporation-SERS assay introduces pH bioprobes into a living cell in a very short time and disperses the nanoprobe throughout the cytoplasm, ultimately enabling rapid and comprehensive pH analysis of the entire cell. Our work demonstrates the potential of electroporation-SERS for the biochemical analysis of live cells.

Development and validation of colorimetric-assisted chemometrics methods based on the localized gold nanoparticles surface plasmon resonance for fast simultaneous estimation of anti-hepatitis C virus drugs in their combined dosage form: A comparative study with HPLC method

The present work describes a developed analytical method based on a colorimetric assay using gold nanoparticles (AuNPs) along with chemometric techniques for the simultaneous estimation of sofosbuvir (SOF) and ledipasvir (LED) in their synthetic mixtures and tablet dosage form. The applied chemometric approaches were continuous wavelet transform (CWT) and least squares support vector machine (LS-SVM). Characterization of AuNPs and AuNPs in combination with the drug was performed by UV–vis spectrophotometer, transmission electron microscopy (TEM), dynamic light scattering (DLS), and Fourier transform infrared (FTIR) spectroscopy. In the CWT method, the zero amplitudes were determined at 427 nm with Daubechies wavelet family for SOF (zero crossing point of LED) and 440 nm with Symlet wavelet family for LED (zero crossing point of SOF) over the concentration range of 7.5–90.0 μg/L and 40.0–100.0 μg/L with coefficients of determination (R2) of 0.9974 and 0.9907 for SOF and LED, respectively. The limit of detection (LOD) and limit of quantification (LOQ) of this method were found to be 7.92, 9.96 μg/L and 12.02, 30.2 μg/L for SOF and LED, respectively. In the LS-SVM model, the mean percentage recovery of SOF and LED in synthetic mixtures was 98.29 % and 99.25 % with root mean square error of 2.392 and 1.034, which were obtained by the optimization of regularization parameter (γ) and width of the function (σ) based on the cross-validation method. The proposed methods were also applied for the determination concentration of SOF and LED in the combined dosage form, recoveries were higher than 95 %, and relative standard deviation (RSD) values were lower than 0.4 %. The achieved results were statistically compared with those obtained from the high-performance liquid chromatography (HPLC) technique for the concurrent estimation of components through one-way analysis of variance (ANOVA), and no significant difference was found between the suggested approaches and the reference one. According to these results, simplicity, high speed, lack of time-consuming process, and cost savings are considerable benefits of colorimetry along with chemometrics methods compared to other ways.

Chiral electrochemical sensing of propranolol enantiomers on D/L-Cys modified gold nanoparticles

The present study aims to explore the interaction mechanisms between propranolol (PRNL) enantiomers and bare and L/D-Cysteine modified gold nanoparticles (L/D-Cys−AuNPs) surfaces, using electrochemical (cyclic voltammetry, differential pulse voltammetry, electrochemical impedance spectroscopy) and microcalorimetric (isothermal titration calorimetry) techniques. In the absence of a chiral environment, PRNL enantiomers are strongly physisorbed on the AuNPs modified surface, yet no significant difference was recorded in the oxidation peak potential (+0.778 V R(+)-PRNL versus +0.78 V for S(-)-PRNL). Upon decorating AuNPs with l-Cys, an ∼40 mV anodic shift is recorded for S(-)-PRNL due to a more favored orientation of its diastereoisomer on the electrode's surface towards electron transfer. Interestingly, by altering the conformation of the diastereoisomeric chiral selector (replacing l-Cys with d-Cys), the enantioselective nature of the recorded electrochemical signals fades out. Additionally, the potential synergistic effects of a dual chiral system, based on the covalently bound l-/D-Cys−AuNPs and β-cyclodextrin (β-CD), a free, host-guest type chiral selector, added to the electrolyte, has also been studied.

The Self-Assembly of Cationic Metal Complexes on Gold Nanoparticle Surface.

This work aims to study the interaction between cationic metal complexes (M z +) and gold nanoparticles (AuNPs z- ). The M z + complexes were chosen from previous works described in the literature and were synthesized as defined. For example, they are as follows: 1 = [RuCl(dppb)(bipy)(py)](PF6); 2 = [RuCl(dppb)(bipy)(vpy)](PF6); 3 = [RuCl(dppb)(bipy)(mepy)](PF6); 4 = [RuCl(dppb)(bipy)(tbpy)](PF6); 5 = [RuCl2(dppb)(bipy)](PF6); 6 = [Fe(bipy)3]Cl2; 7 = [Ru(bipy)3](PF6)2; 8 = [TPyP{RuCl(dppb)(bipy)}4](PF6)4; and 9 = [RuCl(p-cymene)(Diipmp)](PF6). The interactions between M z + and AuNPs z- were carried out using conductometry and UV-vis spectroscopy. These experiments allowed determination of kinetic parameters, revealing three different steps in the interaction process: induction time, flocculation, and agglomeration. The self-assembly between M z + and AuNPs z- was investigated using three different models of binding site, namely, Langmuir or direct plot, Benesi-Hildebrand, and Scatchard. These models provide the fraction of total binding sites occupied (θ), the formation constant (K f), which is dependent on the temperature and geometric structure of each group of M z +, and the Gibbs free energy of reaction (ΔG r ), which was negative for each pair of M z + and AuNPs z- , revealing a spontaneous agglomeration process. The Hill coefficient (n) was 1 for almost all complexes, indicating that agglomeration is an independent process, except for 5, where n = 2, suggesting a positive propensity to bind onto the AuNPs z- surface. The models have confirmed a noncovalent interaction between these species. The relative error in site binding does not show any variation with changes in the temperature, but a fine-tuning of the n value to 1.00 was observed with the increase of the temperature. Finally, the reduction reaction of the 4-nitrophenolate anion (4-NP-) by NaBH4 catalyzed by AuNPs z- was used in the presence of M z + as an evaluation test to show how the M z + species will disturb the 4-NP- binding site on the surface of gold nanoparticles.

Adsorption and disproportionation of carbon monoxide on faceted-gold surfaces and edges

Localized surface plasmons (LSP) on faceted surfaces of gold nanoparticles enable carbon monoxide disproportionation to be driven at room temperature. In order to expand the known surfaces that catalyze this reaction, we explore the adsorption of carbon monoxide at top, long bridge, short bridge, and hole sites on gold (100), (110), (111), (211), and (311) faceted surfaces, as well as the reaction barriers for disproportionation at the lowest energy adsorption site on each surface and edges between two (311) surfaces and (100) and (110) surfaces. Generally, the less atomically dense, higher index facets promote both good adsorption and reactivity, and the edges show lower barriers for disproportionation. For most of the explored surfaces, adsorption directly on top of a gold atom is most favorable. The lowest activation energy for carbon monoxide disproportionation to amorphous carbon and carbon dioxide is predicted for two carbon monoxides adsorbed on top of atoms on the (311)/(311) edge.

Mechanistic Insights Behind the Self-Assembly of Human Insulin under the Influence of Surface-Engineered Gold Nanoparticles.

Elucidating the underlying principles of amyloid protein self-assembly at nanobio interfaces is extremely challenging due to the diversity in physicochemical properties of nanomaterials and their physical interactions with biological systems. It is, therefore, important to develop nanoscale materials with dynamic features and heterogeneities. In this work, through engineering of hierarchical polyethylene glycol (PEG) structures on gold nanoparticle (GNP) surfaces, tailored nanomaterials with different surface properties and conformations (GNPs-PEG) are created for modulating the self-assembly of a widely studied protein, insulin, under amyloidogenic conditions. Important biophysical studies including thioflavin T (ThT) binding, circular dichroism (CD), surface plasmon resonance (SPR), and atomic force microscopy (AFM) showed that higher-molecular weight GNPs-PEG triggered the formation of amyloid fibrils by promoting adsorption of proteins at nanoparticle surfaces and favoring primary nucleation rate. Moreover, the modulation of fibrillation kinetics reduces the overall toxicity of insulin oligomers and fibrils. In addition, the interaction between the PEG polymer and amyloidogenic insulin examined using MD simulations revealed major changes in the secondary structural elements of the B chain of insulin. The experimental findings provide molecular-level descriptions of how the PEGylated nanoparticle surface modulates protein adsorption and drives the self-assembly of insulin. This facile approach provides a new avenue for systematically altering the binding affinities on nanoscale surfaces by tailoring their topologies for examining adsorption-induced fibrillogenesis phenomena of amyloid proteins. Together, this study suggests the role of nanobio interfaces during surface-induced heterogeneous nucleation as a primary target for designing therapeutic interventions for amyloid-related neurodegenerative disorders.