A theoretical approach on the ability of functionalized gold nanoparticles for detection of Cd2+

Cadmium (Cd) as a toxic element that is widely present in water, soil, and air has important effects on human health, therefore proposing an accurate and selective method for detection of this element is of importance. In this article, by employing full atomistic molecular dynamics (MD) simulations and density functional theory dispersion corrected (DFT-D3) calculations, the effects of 6-mercaptonicotinic acid (MNA) and l-cysteine (CYS) on the stability of gold nanoparticles (AuNPs) and their sensitivity against Cd2+ were investigated. The obtained results indicate that pure AuNPs are not stable in water, while functionalized AuNPs with CYS and MNA groups have considerable stability without aggregation. In other words, the functional groups on the surface of AuNPs elevate their resistance against aggregation by an increase in the repulsive interactions between the gold nanoparticles. Moreover, functionalized AuNPs have considerable ability for selective detection of Cd2+ in the presence of different metal ions. Based on the MD simulation results, MNA-CYS-AuNPs (functionalized AuNPs with both functional groups) have the maximum sensitivity against Cd2+ in comparison with MNA-AuNPs and CYS-AuNPs due to the strong electrostatic interactions. DFT-D3 calculations reveal that the most probable interactions between the metal ions and functional groups are electrostatic, and Cd2+ can aggregate functionalized AuNPs due to strong electrostatic interactions with MNA and CYS groups. Moreover, charge transfer and donor–acceptor analyses show that molecular orbital interactions between the functional groups and Cd2+ can be considered as the driving force for AuNPs aggregation. A good agreement between the theoretical results and experimental data confirms the importance of the molecular modeling methods as a fast scientific protocol for designing new functionalized nanoparticles for application in different fields.

Synthesis and In Vitro Evaluation of Gold Nanoparticles Functionalized with Thiol Ligands for Robust Radiolabeling with 99mTc

Radiolabeled gold nanoparticles (AuNPs) have been widely used for cancer diagnosis and therapy over recent decades. In this study, we focused on the development and in vitro evaluation of four new Au nanoconjugates radiolabeled with technetium-99m (99mTc) via thiol-bearing ligands attached to the NP surface. More specifically, AuNPs of two different sizes (2 nm and 20 nm, referred to as Au(2) and Au(20), respectively) were functionalized with two bifunctional thiol ligands (referred to as L1H and L2H). The shape, size, and morphology of both bare and ligand-bearing AuNPs were characterized by transmission electron microscopy (TEM) and dynamic light scattering (DLS) techniques. In vitro cytotoxicity was assessed in 4T1 murine mammary cancer cells. The AuNPs were successfully radiolabeled with 99mTc-carbonyls at high radiochemical purity (>95%) and showed excellent in vitro stability in competition studies with cysteine and histidine. Moreover, lipophilicity studies were performed in order to determine the lipophilicity of the radiolabeled conjugates, while a hemolysis assay was performed to investigate the biocompatibility of the bare and functionalized AuNPs. We have shown that the functionalized AuNPs developed in this study lead to stable radiolabeled nanoconstructs with the potential to be applied in multimodality imaging or for in vivo tracking of drug-carrying AuNPs.

Validation and Optimization of Polyvinyl Alcohol-Functionalized Gold Nanoparticles for Producing Lactose-Free Dairy Products

The present study demonstrates the synthesis of lactose-free dairy items by Kluyveromyces lactis β-galactosidase bound to polyvinyl alcohol (PVA)-modified gold nanoparticles (AuNPs). The size of AuNPs was analyzed by dynamic light scattering experiment. The developed AuNPs served as a stable matrix for enzyme immobilization which was observed by obtaining 88% immobilization yield. Km and Vmax were determined for soluble and immobilized enzyme by incubating them with varying concentrations of substrate. Our findings demonstrated that immobilization leads to an increase of Km and a decline in Vmax values for the enzyme attached to PVA-functionalized AuNPs. Moreover, the enzyme conjugated to surface functionalized AuNPs displayed exceptional conversion of lactose hydrolysis in batch reactors at 40 oC in contrast to its hydrolysis at 50 oC. Hence, the developed nanosystem [β-galactosidase-(PVA-modified AuNPs)] serves as an excellent model for suggesting its application in other biomedical applications, particularly for constructing lactose based biosensors.

Optimally biosynthesized, PEGylated gold nanoparticles functionalized with quercetin and camptothecin enhance potential anti-inflammatory, anti-cancer and anti-angiogenic activities

Background The development of nano delivery systems is rapidly emerging area of nanotechnology applications where nanomaterials (NMs) are employed to deliver therapeutic agents to specific site in a controlled manner. To accomplish this, green synthesis of NMs is widely explored as an eco-friendly method for the development of smart drug delivery system. In the recent times, use of green synthesized NMs, especially metallic NMs have fascinated the scientific community as they are excellent carriers for drugs. This work demonstrates optimized green, biogenic synthesis of gold nanoparticles (AuNPs) for functionalization with quercetin (QT) and camptothecin (CPT) to enhance potential anti-inflammatory, anti-cancer and anti-angiogenic activities of these drugs. Results Gold nanoparticles were optimally synthesized in 8 min of reaction at 90 °C, pH 6, using 4 mM of HAuCl4 and 4:1 ratio of extract: HAuCl4. Among different capping agents tested, capping of AuNPs with polyethylene glycol 9000 (PG9) was found best suited prior to functionalization. PG9 capped AuNPs were optimally functionalized with QT in 1 h reaction at 70 °C, pH 7, using 1200 ppm of QT and 1:4 ratio of AuNPs-PG9:QT whereas, CPT was best functionalized at RT in 1 h, pH 12, AuNPs-PG9:CPT ratio of 1:1, and 0.5 mM of CPT. QT functionalized AuNPs showed good anti-cancer activity (IC50 687.44 µg/mL) against MCF-7 cell line whereas test of anti-inflammatory activity also showed excellent activity (IC50 287.177 mg/L). The CAM based assessment of anti-angiogenic activity of CPT functionalized AuNPs demonstrated the inhibition of blood vessel branching confirming the anti-angiogenic effect. Conclusions Thus, present study demonstrates that optimally synthesized biogenic AuNPs are best suited for the functionalization with drugs such as QT and CPT. The functionalization of these drugs with biogenic AuNPs enhances the potential anti-inflammatory, anti-cancer and anti-angiogenic activities of these drugs, therefore can be used in biomedical application.

Factors Influencing the Surface Functionalization of Citrate Stabilized Gold Nanoparticles with Cysteamine, 3-Mercaptopropionic Acid or l-Selenocystine for Sensor Applications

Thiols and selenides bind to the surface of gold nanoparticles (AuNPs) and thus provide suitable platforms for the fabrication of sensors. However, the co-existence of adsorbed citrate on the surface of the nanoparticles can influence their functionalization behavior and potentially their sensing performance measured by the extent of particle aggregation. In this study, the functionalization of purchased (7.3 ± 1.2 nm) and in-house prepared AuNPs (13.8 ± 1.2 nm), under the same experimental conditions with either cysteamine (Cys), 3-mercaptopropionic acid (3-MPA), or l-selenocystine (SeCyst) was investigated. 1H-NMR measurements showed distinct citrate signatures on the in-house synthesized citrate-stabilized AuNPs, while no citrate signals were detected on the purchased AuNPs other than evidence of the presence of α-ketoglutaric acid. Carboxylate-containing species attributed to either citrate or α-ketoglutaric acid were identified in all functionalized AuNPs. ATR-FTIR spectroscopy confirmed the functionalization of AuNPs with Cys and 3-MPA, and energy dispersive X-ray (EDX) spectroscopy measurements suggested the formation of SeCyst functionalized AuNPs. Co-adsorption rather than displacement by the functionalizing agents and carboxylate-containing molecules was indicated, which for Cys and SeCyst functionalized AuNPs was also the aggregation limiting factor. In contrast, the behavior of 3-MPA functionalized AuNPs could be attributed to electrostatic repulsions between the functionalized groups.