Gold Uptake Research Articles

Unlocking the Power of Human Ferritin: Enhanced Drug Delivery of Aurothiomalate in A2780 Ovarian Cancer Cells.

Aurothiomalate (AuTM) is an FDA-approved antiarthritic gold drug with unique anticancer properties. To enhance its anticancer activity, we prepared a bioconjugate with human apoferritin (HuHf) by attaching some AuTM moieties to surface protein residues. The reaction of apoferritin with excess AuTM yielded a single adduct, that was characterized by ESI MS and ICP-OES analysis, using three mutant ferritins and trypsinization experiments. The adduct contains ~3 gold atoms per ferritin subunit, arranged in a small cluster bound to Cys90 and Cys102. MD simulations provided a plausible structural model for the cluster. The adduct was evaluated for its pharmacological properties and was found to be significantly more cytotoxic than free AuTM against A2780 cancer cells mainly due to higher gold uptake. NMR-metabolomics showed that AuTM bound to HuHf and free AuTM induced qualitatively similar changes in treated cancer cells, indicating that the effects on cell metabolism are approximately the same, in agreement with independent biochemical experiments. In conclusion, we have demonstrated here that a molecularly precise bioconjugate formed between AuTM and HuHf exhibits anticancer properties far superior to the free drug, while retaining its key mechanistic features. Evidence is provided that human ferritin can serve as an excellent carrier for this metallodrug.

Unlocking the Power of Human Ferritin: Enhanced Drug Delivery of Aurothiomalate in A2780 Ovarian Cancer Cells

Aurothiomalate (AuTM) is an FDA‐approved antiarthritic gold drug with unique anticancer properties. To enhance its anticancer activity, we prepared a bioconjugate with human apoferritin (HuHf) by attaching some AuTM moieties to surface protein residues. The reaction of apoferritin with excess AuTM yielded a single adduct, that was characterized by ESI MS and ICP‐OES analysis, using three mutant ferritins and trypsinization experiments. The adduct contains ~3 gold atoms per ferritin subunit, arranged in a small cluster bound to Cys90 and Cys102. MD simulations provide a plausible structural model for the cluster. The adduct was evaluated for its pharmacological properties and was found to be significantly more cytotoxic than free AuTM against A2780 cancer cells mainly due to higher gold uptake. NMR‐metabolomics showed that AuTM bound to HuHf and free AuTM induced qualitatively similar changes in treated cancer cells, indicating that the effects on cell metabolism are approximately the same, in agreement with independent biochemical experiments. In conclusion, we have demonstrated here that a molecularly precise bioconjugate formed between AuTM and HuHf exhibits anticancer properties far superior to the free drug, while retaining its key mechanistic features. Evidence is provided that human ferritin can serve as an excellent carrier for this metallodrug.

Porous Polypyrrolidines for Highly Efficient Recovery of Precious Metals through Reductive Adsorption Mechanism.

The recycling and utilization of precious metals have emerged as a critical research focus in advancing the development of the circular economy. Among numerous methods for recovering precious metals such as gold, adsorbents with both high adsorption selectivity and capacity have become key technologies. This article incorporated the N-phenylpyrrolidine into a flexible porous polynorbornene backbone to create a class of distinctive porous organic polymers, named BIT-POP-14-BIT-POP-17. Through a reductive capture mechanism, the reductive adsorption sites of N-phenylpyrrolidine coordinate selectively with precious metals, the reduced metal is captured by the hierarchically porous polymers with flexible backbone. This approach leads to remarkable gold recovery efficiency, achieving a record of 2321mgg-1 at ambient conditions, and 3020mgg-1 under UV light, surpassing the theoretical limit. The porous polymers are filled in a column for a continuous uptake of gold from waste printed circuit boards (PCBs), showing recovery efficiency toward gold as high as 95% after 84h. Overall, this work offers a new perspective on designing novel adsorbents for precious metal recovery, providing inspiration for researchers to explore novel adsorption modes and contribute to the advancement of the circular economy.

Effects of Gold Nanoparticles on Mentha spicata L., Soil Microbiota, and Human Health Risks: Impact of Exposure Routes.

Nanoparticles, due to their extensive production and application, can have significant consequences for the environment, including soil and plant pollution. Therefore, it is very important to assess how nanoparticles will affect plants depending on the exposure pathways. The effect of gold nanoparticles in a concentration range of 1-100 mg/L on Mentha spicata L. during a 28-day experiment was investigated. Two routes of nanoparticles exposure were applied: root and foliar. Transmission electron microscopy was used to characterize nanoparticles and their effect on plant leaves' ultrastructure. Gold content in soil and plant segments was determined using k0-neutron activation analysis. For root exposure, gold was mainly accumulated in soil (15.2-1769 mg/kg) followed by root systems (2.99-454 mg/kg). The maximum accumulation of gold in leaves (5.49 mg/kg) was attained at a nanoparticle concentration of 100 mg/L. Foliar exposure resulted in the maximum uptake of gold in leaves (552 mg/kg) and stems (18.4 mg/kg) at the highest applied nanoparticle concentration. The effect of nanoparticles on the Mentha spicata L. leaves' biochemical composition was assessed. Nanoparticles affected the content of chlorophyll and carotenoids and led to an increase in antioxidant activity. Root exposure to gold nanoparticles resulted in an increase in the number of starch grains in chloroplasts and also suppressed the activity of the soil microbiota. Gold extraction from mint leaves into herbal infusion varied from 2 to 90% depending on the concentration of nanoparticles in the solution and the exposure route. The health risk as a result of gold exposure via herbal tea intake was assessed through estimated daily intake. The hazard quotient values were found to be less than the cutoff, indicating that a cup of tea infusion should not cause a serious impact to human health.

Gold recovery from synthetic mine tailings leachate using chelating ion exchange resins with thiosulfate-thiourea lixiviant

Recovery of gold from mining tailings is important economically and environmentally in the mining industry. With a limited amount of mineable gold remaining, the process of recovering gold from mine tailings needs development. This paper will specifically investigate the recovery of gold using ion-exchange resins in a thiosulfate-thiourea lixiviant solution. A range of resins of different functionalities: Purolite® A200 (Type II quaternary ammonium), Lewatit® MonoPlus TP 214 and Puromet® MTS9140 (thiourea), Dowex™ M-4195 (bis-picolylamine) and Lewatit® VPOC 1026 (di(2-ethylhexyl)phosphate- D2EHPA) were assessed for their gold uptake capabilities via dynamic column experiments. A mixed-metal solution was used to accurately simulate the spent lixiviant from thiosulfate/thiourea leaching of mine tailings. All resins showed selectivity towards gold over the numerous other metals in solution, which was believed to be due to the stability of aqueous gold thiourea complexes. Puromet® MTS9140 had the highest gold capacity, with a calculated uptake capacity of 41.6 mg/L. Modified-Dose Response (MDR), Bohart-Adams and Yoon-Nelson models were used to describe the data; the MDR model being the most successful.

Self-Assembled Monolayers Derived from Positively Charged Adsorbates on Plasmonic Substrates for MicroRNA Delivery: A Review

MicroRNA (miRNA) has emerged as a promising alternative therapeutic treatment for cancer, but its delivery has been hindered by low cellular uptake and degradation during circulation. In this review, we discuss the various methods of delivering miRNA, including viral and non-viral delivery systems such as liposomes and nanoparticles. We also examine the use of nanoparticles for miRNA-based diagnostics. We focus specifically on non-viral delivery systems utilizing coinage metals in the form of nanoparticles and the use of self-assembled monolayers (SAMs) as a method of surface modification. We review the use of SAMs for the conjugation and delivery of small noncoding ribonucleic acid (ncRNA), particularly SAMs derived from positively charged adsorbates to generate charged surfaces that can interact electrostatically with negatively charged miRNA. We also discuss the effects of the cellular uptake of gold and other plasmonic nanoparticles, as well as the challenges associated with the degradation of oligonucleotides. Our review highlights the potential of SAM-based systems as versatile and robust tools for delivering miRNA and other RNAs in vitro and in vivo and the need for further research to address the challenges associated with miRNA delivery and diagnostics.

Porous Covalent Organic Framework Based Hydrogen-Bond Nanotrap for the Precise Recognition and Separation of Gold.

Utilizing weak interactions to effectively recover and separate precious metals in solution is of great importance but the practice remains a challenge. Herein, we report a novel strategy to achieve precise recognition and separation of gold by regulating the hydrogen-bond (H-bond) nanotrap within the pore of covalent organic frameworks (COFs). It is found that both COF-HNU25 and COF-HNU26 can efficiently capture AuIII with fast kinetics, high selectivity, and uptake capacity. In particular, the COF-HNU25 with the high density of H-bond nanotraps exhibits an excellent gold uptake capacity of 1725 mg g-1 , which is significantly higher than that (219 mg g-1 ) of its isostructural COF (COF-42) without H-bond nanostrap in the pores. Importantly, the uptake capacity is strongly correlated to the number of H-bonds between phenolic OH in the COF and [AuCl4 ]- in water, and multiple H-bond interactions are the key driving force for the excellent gold recovery and reusability of the adsorbent.

Porous Covalent Organic Framework Based Hydrogen‐Bond Nanotrap for the Precise Recognition and Separation of Gold

AbstractUtilizing weak interactions to effectively recover and separate precious metals in solution is of great importance but the practice remains a challenge. Herein, we report a novel strategy to achieve precise recognition and separation of gold by regulating the hydrogen‐bond (H‐bond) nanotrap within the pore of covalent organic frameworks (COFs). It is found that both COF‐HNU25 and COF‐HNU26 can efficiently capture AuIII with fast kinetics, high selectivity, and uptake capacity. In particular, the COF‐HNU25 with the high density of H‐bond nanotraps exhibits an excellent gold uptake capacity of 1725 mg g−1, which is significantly higher than that (219 mg g−1) of its isostructural COF (COF‐42) without H‐bond nanostrap in the pores. Importantly, the uptake capacity is strongly correlated to the number of H‐bonds between phenolic OH in the COF and [AuCl4]− in water, and multiple H‐bond interactions are the key driving force for the excellent gold recovery and reusability of the adsorbent.

Laser Ablated Albumin Functionalized Spherical Gold Nanoparticles Indicated for Stem Cell Tracking.

Cell tracking in cell-based therapy applications helps distinguish cell participation among paracrine effect, neovascularization, and matrix deposition. This preliminary study examined the cellular uptake of gold nanoparticles (AuNPs), observing cytotoxicity and uptake of different sizes and AuNPs concentrations in Adipose-derived stromal cells (ASCs). ASCs were incubated for 24 h with Laser ablated Albumin functionalized spherical AuNPs (LA-AuNPs), with average sizes of 2 nm and 53 nm in diameter, in four concentrations, 127 µM, 84 µM, 42 µM, and 23 µM. Cytotoxicity was examined by Live/Dead assay, and erythrocyte hemolysis, and the effect on the cytoskeleton was investigated by immunocytochemistry for β-actin. The LA-AuNPs were internalized by the ASCs in a size and concentration-dependent manner. Clusters were observed as dispersed small ones in the cytosol, and as a sizeable perinuclear cluster, without significant harmful effects on the cells for up to 2 weeks. The Live/Dead and hemolysis percentage results complemented the observations that the larger 53 nm LA-AuNPs in the highest concentrated solution significantly lowered cell viability. The demonstrated safety, cellular uptake, and labelling persistency with LA-AuNPs, synthesized without the combination of chemical solutions, support their use for cell tracking in tissue engineering applications.

Selective and rapid extraction of trace amount of gold from complex liquids with silver(I)-organic frameworks

The design of adsorbents for rapid, selective extraction of ultra-trace amounts of gold from complex liquids is desirable from both an environmental and economical point of view. However, the development of such materials remains challenging. Herein, we report the fabrication of two vinylene-linked two-dimensional silver(I)-organic frameworks prepared via Knoevenagel condensation. This material enables selective sensing of gold with a low limit of detection of 60 ppb, as well as selective uptake of ultra-trace gold from complex aqueous mixtures including distilled water with 15 competing metal ions, leaching solution of electronic waste (e-waste), wastewater, and seawater. The present adsorbent delivers a gold adsorption capacity of 954 mg g−1, excellent selectivity and reusability, and can rapidly and selectively extract ultra-trace gold from seawater down to ~20 ppb (94% removal in 10 minutes). In addition, the purity of recovered gold from e-waste reaches 23.8 Karat (99.17% pure).

Polyethyleneimine functionalized alginate composite fiber for fast recovery of gold from acidic aqueous solutions

In this paper, PEI-Alginate fibers were prepared using a more environmentally friendly method for the recovery of gold (Au (III)) from acidic wastewater. Adsorption results show that PEI plays a major role in the recovery of Au (III), and the maximum adsorption capacity of Au (III) was 644.92 ± 43.06 mg/g calculated by Langmuir model at pH 1, 25 °C. In addition, the constants k 1 and k 2 was 0.7044 ± 0.1038 L/min and 0.0025 ± 0.0002 g/mg min were calculated by pseudo-first-order and pseudo-second-order, which was outstanding compared to the most of the adsorbents reported in the literature. The mechanism of adsorbent preparation, characterization of adsorbents and adsorption-reduction mechanism of Au (III) were analyzed by Field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, Fourier-transform infrared spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The results showed that Au (III) was adsorbed by electrostatic attraction between protonated nitrogen-containing functional groups (=NH + -, and –NH 2 + -/-NH 3 + ) and AuCl 4 − . Furthermore, Au (III) was reduced to Au(I) and Au (0) during the adsorption process, and -NH-/-NH 2 , –NH 2 + -/-NH 3 + , and C–O provided electrons for Au (III) reduction and then they were oxidized to =N-, =NH + -, and C=O, respectively. • Polyethyleneimine functionalized alginate composite fiber were prepared by hydrothermal method. • The composite could recover 93 % of Au (III) at 20 min. • The maximum uptake of gold with the composite was 645 mg/g.

Selective recovery of gold from discarded cell phones by silk fibroin from Bombyx mori

Selectivity is a crucial factor for gold recovery from discarded cell phones. This is because discarded cell phones contain a large variety of metals. The use of biomaterials as gold adsorbents is attracting much attention because it is in accordance with sustainability goals. Here, we reported selective adsorption of gold on silk fibroin and its application to gold recovery from the actual leachate of discarded cell phones in a chloride medium. The experimental maximum gold-adsorption capacity of silk fibroin was 5.800 mg/g. Based on a kinetic study, the gold-adsorption mechanism followed the pseudo-second-order model with a rate constant (k2) of 0.077 g mg−1min−1. The adsorption fitted well with the Langmuir model, suggesting a monolayer adsorption mechanism. Despite the small adsorption capacity, silk fibroin showed remarkable selectivity toward gold in synthetic and actual leachate containing Pt4+, Pd2+, Al3+, Cu2+, Ni2+, Zn2+, Pb2+, and Fe3+ metal ions in 0.5 mol/L HCl. The gold uptake from the actual leachate of discarded cell phones was approximately 95 %. The gold loaded on the silk fibroin was completely desorbed by 0.1 mol/L thiourea.

Enhancing nanoparticle accumulation in two dimensional, three dimensional, and xenograft mouse cancer cell models in the presence of docetaxel

Recent clinical trials show docetaxel (DTX), given in conjunction with radiation therapy (RT) and androgen suppression, improves survival in high-risk prostate cancer. Addition of gold nanoparticles (GNPs) to this current DTX/RT protocol is expected to further improve therapeutic benefits remarkably. However, the foundation for the triple combination of RT, DTX, and GNPs must be elucidated to ensure quicker facilitation to the clinic. In this study, we explored the use of low concentrations of DTX combined with GNPs in two prostate cancer cell lines in a two-dimensional monolayer, a three-dimensional spheroid, and a mouse xenograft model. When used together, DTX and GNPs induced a nearly identical relative increase in uptake of gold in both the spheroid model and the mouse xenograft, which saw a 130% and 126% increase respectively after 24 h, showcasing the benefit of using spheroids as an in vitro model to better optimize in vivo experiments. Further, the benefits of using low concentrations of DTX combined with GNPs extended for over 72 h, allowing for less frequency in dosing when translating to the clinic. Overall, these results highlight the benefits of using DTX combined with GNPs and lays the groundwork for the translation of the triple combination of RT, GNPs, and DTX to the clinic.

Prospecting Cellular Gold Nanoparticle Biomineralization as a Viable Alternative to Prefabricated Gold Nanoparticles.

Gold nanoparticles (GNPs) have shown considerable potential in a vast number of biomedical applications. However, currently there are no clinically approved injectable GNP formulations. Conversely, gold salts have been used in the clinic for nearly a century. Further, there is evidence of GNP formation in patients treated with gold salts (i.e., chrysiasis). Recent reports evaluating this phenomenon in human cells and in murine models indicate that the use of gold ions for in situ formation of theranostic GNPs could greatly improve the delivery within dense biological tissues, increase efficiency of intracellular gold uptake, and specificity of GNP formation within cancer cells. These attributes in combination with safe clinical application of gold salts make this process a viable strategy for clinical translation. Here, the first summary of the current knowledge related to GNP biomineralization in mammalian cells is provided along with critical assessment of potential biomedical applications of this newly emergent field.

Crown ether-based hypercrosslinked porous polymers for gold adsorption

With the over-exploitation of global resources, the recycling of gold becomes an urgent task to be solved. In this regard, design of stable adsorbents with low cost and large capacity is meaningful for the secondary utilization of resources. Herein, to obtain the efficient adsorbents, dibenzo-18-crown-6 (DB18C6) and dibenzo-24-crown-8 (DB24C8) were cross-linked for the first time by Friedel–Crafts reaction to synthesize crown ether-based hypercrosslinked porous polymers, named DB18C6-HCP and DB24C8-HCP, respectively. These adsorbents exhibit high porosity, good stability, and outstanding gold adsorption selectivity. Notably, DB18C6-HCP exhibits a high gold uptake capacity with 1667 mg g−1. Furthermore, gold ions are in situ reduced into gold nanoparticles by DB18C6-HCP and DB24C8-HCP along with gold ion adsorption process. In short, we have confirmed the potential of porous organic polymers for the adsorption of gold, and provided a powerful reference for the recovery and reduction of gold.

Zwitterionic Polymer Coatings Enhance Gold Nanoparticle Stability and Uptake in Various Biological Environments.

Zwitterionic polymers are a class of materials that have demonstrated utility as non-fouling surfaces for medical devices and drug delivery vehicles. Here, we develop a synthesis protocol to produce zwitterionic polymers as coatings for gold nanoparticles and evaluate nanoparticle stability and biological function after exposure to various biological fluids. Thiol-functionalized polymethacryloyloxyethyl phosphorylcholine polymers (pMPC) were synthesized in nontoxic solvents via photoinitiated free radical polymerization with a radical addition-fragmentation chain transfer (RAFT) agent and coated onto gold nanoparticles. pMPC-coated nanoparticles exhibited reduced particle aggregation, improved suspension stability, and decreased protein adsorption upon exposure to serum and lung lavage fluid (BALF). Cell uptake in A549 cells was greater for pMPC-coated particles than uncoated particles after exposure to serum and BALF, with no observed cell toxicity, but pMPC-coated particles experienced higher levels of cell uptake after serum exposure than BALF exposure, suggesting that differences in the composition of the fluids result in differing impacts on particle fate. These zwitterionic polymers may serve as useful nanoparticle coatings to enhance particle stability and uptake in various biological environments.

Tuneable separation of gold by selective precipitation using a simple and recyclable diamide

The efficient separation of metals from ores and secondary sources such as electronic waste is necessary to realising circularity in metal supply. Precipitation processes are increasingly popular and are reliant on designing and understanding chemical recognition to achieve selectivity. Here we show that a simple tertiary diamide precipitates gold selectively from aqueous acidic solutions, including from aqua regia solutions of electronic waste. The X-ray crystal structure of the precipitate displays an infinite chain of diamide cations interleaved with tetrachloridoaurate. Gold is released from the precipitate on contact with water, enabling ligand recycling. The diamide is highly selective, with its addition to 29 metals in 2 M HCl resulting in 70% gold uptake and minimal removal of other metals. At 6 M HCl, complete collection of gold, iron, tin, and platinum occurs, demonstrating that adaptable selective metal precipitation is controlled by just one variable. This discovery could be exploited in metal refining and recycling processes due to its tuneable selectivity under different leaching conditions, the avoidance of organic solvents inherent to biphasic extraction, and the straightforward recycling of the precipitant.

Uptake and Recovery of Gold from Simulated Hydrometallurgical Liquors by Adsorption on Pine Bark Tannin Resin

The recovery of critical and precious metals from waste electrical and electronic equipment (WEEE) is an environmental and economic imperative. Biosorption has been considered a key technology for the selective extraction of gold from hydrometallurgical liquors obtained in the chemical leaching of e-waste. In this work, the potential of tannin resins prepared from Pinus pinaster bark to sequester and recover gold(III) from hydrochloric acid and aqua regia solutions was assessed. Equilibrium isotherms were experimentally determined and maximum adsorption capacities of 343 ± 38 and 270 ± 19 mg g−1 were found for Au uptake from HCl and HCl/HNO3 (3:1 v/v) solutions containing 1.0 mol L−1 H+. Higher levels of acidity (and chloride ligands) significantly impaired the adsorption of gold from both kinds of leaching solutions, especially in the aqua regia system, in which the adsorbent underperformed. Pseudo-first and pseudo-second order models successfully described the kinetic data. The adsorbent presented high selectivity towards gold. Actually, in simulated aqua regia WEEE liquors, Au(III) was extensively adsorbed, compared to Cu(II), Fe(III), Ni(II), Pd(II), and Zn(II). In three adsorption–desorption cycles, the adsorption capacity of the regenerated adsorbent moderately decreased (19%), although the gold elution in acidic thiourea solution had been quite limited. Future research is needed to examine more closely the elution of gold from the exhausted adsorbents. The results obtained in this work show good perspectives as regards the application of pine bark tannin resins for the selective extraction of Au from electronic waste leach liquors.

Uptake of silver, gold, and hybrids silver-iron, gold-iron and silver-gold aminolevulinic acid nanoparticles by MCF-7 breast cancer cells.

Nanoparticles show promise for theranostic applications in cancer. The metal-based nanoparticles can be used both as photosensitizers and delivery vehicles. In bimetallic particles based on gold or silver and iron, a combination of the plasmonic features of the gold or silver components with the magnetic properties of the iron makes these hybrid nanomaterials suitable for both imaging and therapeutic applications. Herein, we discuss toxicity and cell internalization of metallic (silver and gold) and bimetallic (silver-iron, gold-iron, and silver-gold) aminolevulinic acid (ALA) nanoparticles. ALA can control the production of an intracellular photosensitizer, protoporphyrin IX (PpIX), commonly used in photodynamic therapy. Nanoparticles were synthesized by photoreduction method and characterized by UV/Vis spectra, Zeta potential, FTIR, XRD, and transmission electron microscopy. The amount of singlet oxygen generation by a yellow LED, and ultrasound was studied for gold, gold-iron, and silver-gold nanoparticles. Cytotoxicity assays of MCF-7 in the presence of nanoparticles were performed, and PpIX fluorescence was quantified by high content screening (HCS). Red fluorescence observed after 24 h of nanoparticles incubation on MCF-7 cells, indicated that the ALA in surface of nanoparticles was efficiently converted to PpIX. The best results for singlet oxygen generation with LED or ultrasound irradiation were obtained with ALA:AgAuNPs. The studied nanoparticles present the potential to deliver aminolevulinic acid to breast cancer cells efficiently, generate singlet oxygen, and convert ALA into PpIX inside the cells allowing photodiagnosis and therapies such as photodynamic and sonodynamic therapies.

Triphosphonic acid modified multi-walled carbon nanotubes for gold ions adsorption

Triphosphonic acid modified multi-walled carbon nanotubes (TPA-MWCNTs) have been developed in a facile method and then characterized and used for gold ion adsorption. The adsorption behaviors of TPA-MWCNTs for Au(III), including the effect of pH, adsorption isotherm, adsorption kinetics, adsorption thermodynamics, and regeneration properties have been investigated, and the maximum adsorption capacity of TPA-MWCNTs obtained from the Langmuir isotherm is 980.39 mg/g at 35 °C. Moreover, the adsorption process optimization has been conducted by using response surface methodology (RSM) and the analysis of variance (ANOVA). Therefore, TPA-MWCNTs can be used as an efficient adsorbent in wastewater treatment and gold uptake.