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.

Microchanneling and ultrasonic delivery of gold and platinum nanoparticles for selective photothermolysis of sebaceous follicles in the treatment of acne: a pilot study using porcine skin.

PURPOSE: Several treatment options for acne vulgaris are limited by their associated adverse effects. An innovative approach involves introducing light-absorbing nanoparticles into sebaceous follicles before destroying the follicles using selective photothermolysis. We aimed to investigate efficient methods for introducing gold and platinum nanoparticles into sebaceous follicles and to identify suitable laser equipment and parameters for the effective destruction of these follicles. METHODS: We used porcine skin as the experimental model. We compared the efficacies of a thulium laser, ultrasound, and manual massage and evaluated the optimal method for delivering nanoparticles in close proximity to sebaceous follicles. Subsequently, a 1064-nm-wavelength neodymium-doped yttrium aluminum garnet (Nd: YAG) laser was employed to induce selective photothermolysis. We compared different parameters to identify the optimal pulse duration and fluence of the Nd: YAG laser. The extent of penetration and destruction of sebaceous follicles was assessed using hematoxylin and eosin (H&E) staining, and a numerical evaluation was conducted. RESULTS: H&E staining showed that irradiation with a long-pulsed Nd: YAG laser following a combination of thulium laser and sonophoresis effectively destroyed sebaceous follicles, with destruction rates exceeding 50%. These results were valid with a long pulse duration and a high fluence of the Nd: YAG laser. CONCLUSION: This study demonstrated that sebaceous follicles can be effectively destroyed through a mixture of gold and platinum nanoparticle delivery by a combination of microchanneling and sonophoresis, followed by selective thermal damage induced by a 1064-nm long-pulsed high-fluence Nd: YAG laser.

Phytofabricated gold nanoparticles as modulators of salt stress responses in spinach: implications for redox homeostasis, biochemical and physiological adaptation.

Introduction: The utilization of plant material for synthesizing nanoparticles effectively triggers physiological and biochemical responses in plants to combat abiotic stresses. Salt stress, particularly caused by NaCl, significantly affects plant morphology and physiology, leading to reduced crop yields. Understanding the mechanisms of salt tolerance is crucial for maintaining crop productivity. Methods: In this study, we examined the effects of 150 µM spinach-assisted gold nanoparticles (S-AuNPs) on various parameters related to seed germination, growth attributes, photosynthetic pigments, stomatal traits, ion concentrations, stress markers, antioxidants, metabolites, and nutritional contents of spinach plants irrigated with 50 mM NaCl. Results: Results showed that S-AuNPs enhanced chlorophyll levels, leading to improved light absorption, increased photosynthates production, higher sugar content, and stimulated plant growth under NaCl stress. Stomatal traits were improved, and partially closed stomata were reopened with S-AuNPs treatment, possibly due to K+/Na+ modulation, resulting in enhanced relative water content and stomatal conductance. ABA content decreased under S-AuNPs application, possibly due to K+ ion accumulation. S-AuNPs supplementation increased proline and flavonoid contents while reducing ROS accumulation and lipid peroxidation via activation of both non-enzymatic and enzymatic antioxidants. S-AuNPs also regulated the ionic ratio of K+/Na+, leading to decreased Na+ accumulation and increased levels of essential ions in spinach plants under NaCl irrigation. Discussion: Overall, these findings suggest that S-AuNPs significantly contribute to salt stress endurance in spinach plants by modulating various physiological attributes.

Enantioseparation of six profenoid drugs by capillary electrophoresis with bovine serum albumin-modified gold nanoparticles as quasi-stationary phases.

Profenoid drugs are a kind of common non-steroidal anti-inflammatory drugs and their chiral enantiomers often have huge differences in pharmacological activities. In this work, a novel chiral separation system by capillary electrophoresis (CE) was constructed using gold nanoparticles (AuNPs) functionalized with bovine serum albumin (BSA) as a quasi-stationary phase (QSP), and the enantioseparation of six profenoid drugs was efficiently accomplished. Under optimal chromatographic conditions, the enantioseparation performance of the AuNP@BSA-based chiral separation system was greatly improved compared with that of free BSA (Resolutions, Ibuprofen: 0.89 â†’ 8.15; Ketoprofen: 0 â†’ 10.02; Flurbiprofen:0.56 â†’ 9.83; Indoprofen: 0.88 â†’ 13.83; Fenoprofen: 0 â†’ 15.21; Pyranoprofen: 0.59 â†’ 5.34). Such high Rs are exciting and satisfying and it is in the leading position in the reported papers. Finally, through molecular docking, it was also found that the difference in binding energy between BSA and enantiomers was closely related to the resolutions of CE systems, revealing the chiral selection mechanism of BSA. This work significantly improves the CE chiral separation performance through a simple strategy, providing a simple and efficient idea for the chiral separation method.

Optimization of e-beam lithography parameters for nanofabrication of sub-50 nm gold nanowires and nanogaps based on a bilayer lift-off process.

Electron beam lithography (EBL) stands out as a powerful direct-write tool offering nanometer-scale patterning capability and is especially useful in low-volume R&D prototyping when coupled with pattern transfer approaches like etching or lift-off. Among pattern transfer approaches, lift-off is preferred particularly in research settings, as it is cost-effective and safe and does not require tailored wet/dry etch chemistries, fume hoods, and/or complex dry etch tools; all-in-all offering convenient, "undercut-free" pattern transfer rendering it useful, especially for metallic layers and unique alloys with unknown etchant compatibility or low etch selectivity. Despite the widespread use of the lift-off technique and optical/electron-beam lithography for micron to even sub-micron scales, existing reports in the literature on nanofabrication of metallic structures with critical dimension (CD) in the 10-20 nm regime with lift-off-based EBL patterning are either scattered, incomplete, or vary significantly in terms of experimental conditions, which calls for systematic process optimization. To address this issue, beyond what can be found in a typical photoresist datasheet, this paper reports a comprehensive study to calibrate EBL patterning of sub-50 nm metallic nanostructures including gold nanowires and nanogaps based on a lift-off process using bilayer PMMA as the resist stack. The governing parameters in EBL, including exposure dose, soft-bake temperature, development time, developer solution, substrate type, and proximity effect (PE) are experimentally studied through more than 200 EBL runs, and optimal process conditions are determined by field emission scanning electron microscope (FE-SEM) imaging of the fabricated nanostructures reaching as small as 11 nm feature size. .

Highly Stable Carboranyl Ligated Gold Nano-catalysts for Regioselective Aromatic Bromination.

Achieving electronic/steric control and realizing selectivity regulation in nanocatalysis remains a formidable challenge, as the dynamic nature of metal-ligand interfaces, including dissolution (metal leaching) and structural reconstruction, poses significant obstacles. Herein, we disclose carboranyls (CBs) as unprecedented carbon-bonded functional ligands (Eads.CB-Au(111) = -2.90 eV) for gold nanoparticles (AuNPs), showcasing their exceptional stabilization capability that is attributed by strong Au-C bonds combined with B-H⋯Au interactions. The synthesized CB@AuNPs exhibit core(Aun)-satellite(CB2Au-) structure, showing high stability towards multiple stimuli (110oC, pH = 1-12, thiol etchants). In addition, different from conventional AuNP catalysts such as triphenylphosphine (PPh3) stabilized AuNPs, dissolution of catalytically active gold species was suppressed in CB@AuNPs under the reaction conditions. Leveraging these distinct features, CB@AuNPs realized outstanding p:o selectivities in aromatic bromination. Unbiased arenes including chlorobenzene (up to > 30:1), bromobenzene (15:1) and phenyl acrylate were examined using CB@AuNPs as catalysts to afford highly-selective p-products. Both carboranyl ligands and carboranyl derived counterions are crucial for such regioselective transformation. This work has provided valuable insights for AuNPs in realizing diverse regioselective transformations.

Diagnostic Value of High-Resolution Vessel Wall Imaging Technique in Intracranial Arterial Stenosis and Occlusion: A Comparative Analysis with Digital Subtraction Angiography.

Objective: To analyze the diagnostic value of HR-VWI in intracranial arterial stenosis and occlusion and compare it with DSA. Methods: A retrospective analysis of clinical data of 59 patients with intracranial arterial stenosis in our hospital was conducted to compare the diagnostic results of the two methods for different degrees of intracranial stenosis and various morphological plaques. Results: The diagnosis of stenosis and occlusion by both methods showed no significant difference (P > 0.05). Comparison of plaque morphology detected by HR-VWI with pathological examination results showed no significant difference (P > 0.05); however, there was a significant difference between plaque morphology detected by DSA and pathological examination results (P < 0.05). Additionally, there was a significant difference between plaque morphology detected by HR-VWI and DSA (P < 0.05). Conclusion: HR-VWI technique is comparable to DSA technique in diagnosing intracranial arterial stenosis and occlusion, but it is superior to DSA in plaque morphology diagnosis.

Enhancing Laser-Induced Graphene via Integration of Gold Nanoparticles and Titanium Dioxide for Sensing and Robotics Applications.

Laser-induced graphene (LIG) is a promising material for various applications due to its unique properties and facile fabrication. However, the electrochemical performance of LIG is significantly lower than that of pure graphene, limiting its practical use. Theoretically, integrating other conductive materials with LIG can enhance its performance. In this study, we investigated the effects of incorporating gold nanoparticles (AuNPs) and titanium dioxide (TiO2) into LIG on its electrochemical properties using ReaxFF molecular dynamics (MD) simulations and experimental validation. We found that both AuNPs and TiO2 improved the work function and surface potential of LIG, resulting in a remarkable increase in output voltage by up to 970.5% and output power density by 630% compared to that of pristine LIG. We demonstrated the practical utility of these performance-enhanced LIG by developing motion monitoring devices, self-powered sensing systems, and robotic hand platforms. Our work provides new insights into the design and optimization of LIG-based devices for wearable electronics and smart robotics, contributing to the advancement of sustainable technologies.

Tetraphenylethene-based mononuclear aggregation-induced emission (AIE)-active mechanofluorochromism gold(I) complexes with different auxiliary ligands.

In this study, a series of tetraphenylethene-containing gold(I) complexes with different auxiliary ligands have been synthesized. These complexes were characterized using a variety of techniques including nuclear magnetic resonance spectroscopy, mass spectrometry, and single crystal X-ray diffraction. Their aggregation-induced emission (AIE) behaviors were investigated through ultraviolet/visible and photoluminescence spectrum analyses, and dynamic light scattering measurements. Meanwhile, their mechanofluorochromic properties were also studied via solid-state photoluminescence spectroscopy. Intriguingly, all these mononuclear gold(I) molecules functionalized by tetraphenylethene group demonstrated AIE phenomena. Furthermore, five gold(I) complexes possessing diverse auxiliary ligands exhibited distinct fluorescence changes in response to mechanical grinding. For luminogens 2-5, their solids showed reversible mechanofluorochromic behaviors triggered by the mutual transformation of crystalline and amorphous states, while for luminogen 1, blue-green-cyan three-color solid fluorescence conversion was realized by sequential mechanical grinding and solvent fumigation. Based on this stimuli-responsive tricolored fluorescence feature of 1, an information encryption system was successfully constructed.

Colorimetric detection of neomycin sulfate in serum based on ultra-small gold nanoparticles with peroxidase-like activity.

Neomycin sulfate (NEO) is a kind of aminoglycoside antibiotics. Because of its strong ototoxicity, nephrotoxicity and other side effects, its content in the body should be strictly monitored during use. In this paper, a rapid colorimetric detection method for NEO based on ultrasmall polyvinylpyrrolidone modified gold nanoparticles (PVP/Au NPs) with peroxidase-like activity was developed. Firstly, ultra small PVP/Au NPs with weak peroxidase-like activity were synthetized. When they were mixed with NEO, strong hydrogen bonds were formed between NEO and PVP, resulting in the aggregation of PVP/Au NPs, and the aggregated PVP/Au NPs showed stronger peroxidase-like activity. Therefore, rapid colorimetric detection of NEO was achieved by utilizing the enhanced peroxidase-like activity mechanism caused by the aggregation of ultra small PVP/Au NPs. The naked eye detection limit of this method is 50 nM. Within the range of 1 nM-300 nM, there was a good linear relationship between NEO concentration and the change in absorbance intensity of PVP/Au NPs-H2O2-TMB solution at 652 nm, with the regression curve of y = 0.0045x + 0.0525 (R2 = 0.998), and the detection limit is 1 nM. In addition, this method was successfully applied to the detection of NEO in mouse serum. The recoveries were 104.4 % -107.6 % compared with HPLC assay results, indicating that this method for NEO detection based on PVP/Au NPs has great potential in actual detection of NEO in serum.

Delineation of the role of G6PD in Alzheimer's disease and potential enhancement through microfluidic and nanoparticle approaches.

Alzheimer's disease (AD) is a neurodegenerative pathologic entity characterized by the abnormal presence of tau and macromolecular Aß deposition that leads to the degeneration or death of neurons. In addition to that, glucose-6-phosphate dehydrogenase (G6PD) has a multifaceted role in the process of AD development, where it can be used as both a marker and a target. G6PD activity is dysregulated due to its contribution to oxidative stress, neuroinflammation, and neuronal death. In this context, the current review presents a vivid depiction of recent findings on the relationship between AD progression and changes in the expression or activity of G6PD. The efficacy of the proposed G6PD-based therapeutics has been demonstrated in multiple studies using AD mouse models as representative animal model systems for cognitive decline and neurodegeneration associated with this disease. Innovative therapeutic insights are made for the boosting of G6PD activity via novel innovative nanotechnology and microfluidics tools in drug administration technology. Such approaches provide innovative methods of surpassing the blood-brain barrier, targeting step-by-step specific neural pathways, and overcoming biochemical disturbances that accompany AD. Using different nanoparticles loaded with G6DP to target specific organs, e.g., G6DP-loaded liposomes, enhances BBB penetration and brain distribution of G6DP. Many nanoparticles, which are used for different purposes, are briefly discussed in the paper. Such methods to mimic BBB on organs on-chip offer precise disease modeling and drug testing using microfluidic chips, requiring lower sample amounts and producing faster findings compared to conventional techniques. There are other contributions to microfluid in AD that are discussed briefly. However, there are some limitations accompanying microfluidics that need to be worked on to be used for AD. This study aims to bridge the gap in understanding AD with the synergistic use of promising technologies; microfluid and nanotechnology for future advancements.

Au-decorated Ti3C2Tx/porous carbon immunoplatform for ECM1 breast cancer biomarker detection with machine learning computation for predictive accuracy.

Electrochemical immunosensors, surpassing conventional diagnostics, exhibit significant potential for cancer biomarker detection. However, achieving a delicate balance between signal sensitivity and operational stability, especially at the heterostructure interface, is crucial for practical immunosensors. Herein, porous carbon (PC) integration with Ti3C2Tx-MXene (MX) and gold nanoparticles (Au NPs) constructs a versatile immunosensing platform for detecting extracellular matrix protein-1 (ECM1), a breast cancer-associated biomarker. The inclusion of PC provided robust structural support, enhancing electrolytic diffusion with an expansive surface area while synergistically facilitating charge transfer with Ti3C2Tx. The biosensor optimized with 1.0 mg PC demonstrates a robust electrochemical redox response to the surface-bound thionine (th) redox probe, utilizing an inhibition-based strategy for ECM1 detection. The robust antibody-antigen interactions across the PC-integrated Ti3C2Tx-Au NPs platform (MX-Au-C-1) enabled robust ECM1 detection within 0.1-7.5 nM, with a low limit of detection (LOD) of 0.012 nM. The constructed biosensor shows improved operational stability with a 98.6 % current retention over 1 h, surpassing MXene-integrated (MX-Au) and pristine Au NPs (63.2 % and 44.3 %, respectively) electrodes. Moreover, the successful adaptation of the artificial neural network (ANN) model for predictive analysis of the generated DPV data further validates the accuracy of the biosensor, promising its future application in AI-powered remote health monitoring.

Redox cycling-based signal amplification at alkanethiol modified nanoporous gold interdigitated microelectrodes.

Interdigitated electrodes (IDEs) enable electrochemical signal enhancement through repeated reduction and oxidation of the analyte molecule. Porosity on these electrodes is often used to lower the impedance background. However, their high capacitive current and signal interferences with oxygen reduction limit electrochemical detection ability. We present utilization of alkanethiol modification on nanoporous gold (NPG) electrodes to lower their background capacitance and chemically passivate them from interferences due to oxygen reduction, while maintaining their fast electron transfer rates, as validated by lower separation between anodic and cathodic peaks (ΔE) and lower charge transfer resistance (Rct) values in comparison to planar gold electrodes. Redox amplification based on this modification enables sensitive detection of various small molecules, including pyocyanin, p-aminophenol, and selective detection of dopamine in the presence of ascorbic acid. Alkanethiol NPG arrays are applied as a multiplexed sensor testbed within a well plate to screen binding of various peptide receptors to the SARS COV2 S-protein by using a sandwich assay for conversion of PAPP (4-aminophenyl phosphate) to PAP (p-aminophenol), by the action of AP (alkaline phosphatase), which is validated against optical ELISA screens of the peptides. Such arrays are especially of interest in small volume analytical settings with complex samples, wherein optical methods are unsuitable.

A sensitive gold nanoflower-based lateral flow assay coupled with gold staining technique for the detection of SARS-CoV-2 antigen.

An enhanced lateral flow assay (LFA) is presented for rapid and highly sensitive detection of acute respiratory syndrome coronavirus-2 (SARS-CoV-2) antigens with gold nanoflowers (Au NFs) as signaling markers and gold enhancement to amplify the signal intensities. First, the effect of the morphology of gold nanomaterials on the sensitivity of LFA detection was investigated. The results showed that Au NFs prepared by the seed growth method showed a 5-fold higher detection sensitivity than gold nanoparticles (Au NPs) of the same particle size, which may benefit from the higher extinction coefficient and larger specific surface area of Au NFs. Under the optimized experimental conditions, the Au NFs-based LFA exhibited a detection limit (LOD) of 25 pg mL-1 for N protein using 135 nm Au NFs as the signaling probes. The signal was further amplified by using a gold enhancement strategy, and the LOD for the detection of N protein achieved was 5 pg mL-1. The established LFA also exhibited good repeatability and stability and showed applicability in the diagnosis of SARS-CoV-2 infection.

A ratiometric SERS aptasensor based on catalytic hairpin self-assembly mediated cyclic signal amplification strategy for the reliable determination of E. coli O157:H7.

A ratiometric SERS aptasensor based on catalytic hairpin self-assembly (CHA) mediated cyclic signal amplification strategy was developed for the rapid and reliable determination of Escherichia coli O157:H7. The recognition probe was synthesized by modifying magnetic beads with blocked aptamers, and the SERS probe was constructed by functionalizing gold nanoparticles (Au NPs) with hairpin structured DNA and 4-mercaptobenzonitrile (4-MBN). The recognition probe captured E. coli O157:H7 specifically and released the blocker DNA, which activated the CHA reaction on the SERS probe and turned on the SERS signal of 6-carboxyl-x-rhodamine (ROX). Meanwhile, 4-MBN was used as an internal reference to calibrate the matrix interference. Thus, sensitive and reliable determination and quantification of E. coli O157:H7 was established using the ratio of the SERS signal intensities of ROX to 4-MBN. This aptasensor enabled detection of 2.44 × 102 CFU/mL of E. coli O157:H7 in approximately 3 h without pre-culture and DNA extraction. In addition, good reliability and excellent reproducibility were observed for the determination of E. coli O157:H7 in spiked water and milk samples. This study offered a new solution for the design of rapid, sensitive, and reliable SERS aptasensors.

Gold Nanoparticles-Modified 2D Self-Assembled Amphiphilic Peptide Nanosheets with High Biocompatibility and Photothermal Therapy Efficiency.

Amphiphilic peptides have garnered significant attention due to their highly designable and self-assembling behaviors. Self-assembled peptides hold excellent potential in various fields such as biosensing, environmental monitoring, and drug delivery, owing to their remarkable biological, physical, and chemical properties. While nanomaterials formed by peptide self-assembly have found widespread use in biomedical applications, the development of 2D peptide nanosheets based on the self-assembly of amphiphilic peptides remains challenging in terms of rational design and morphology modulation. In this study, rationally designed amphiphilic peptide molecules are self-assembled into peptide nanosheets (PNS) under specific conditions to encapsulate gold nanoparticles (AuNPs), resulting in the formation of AuNPs/PNS hybrid materials with high photothermal conversion efficiency. The findings demonstrate that 2D PNS enhances the overall photothermal therapy effect of the nanohybrid materials due to their larger hosting area for AuNPs and higher biocompatibility. The well-designed amphiphilic peptides in this study offer insights into the structural design and functional modulation of self-assembled molecules. In addition, the constructed biomimetic-functional 2D inorganic/organic nanohybrid materials hold potential applications in biomedical engineering.

The formation of gold in woody biomass combustion ashes.

This paper investigates the enrichment of gold through combustion and ash-leaching techniques utilizing woody biomass as a fuel source. It delves into the formation of gold in ashes derived from the fixed grate combustion of pelletized woody biomass containing noble metals, conducted at a pilot-scale boiler. The biomass sample was gathered from a brownfield land at an abandoned mining area, avoiding induced phytoextraction. The fuel contained <0.05 mg/kg gold, while the bottom ash, after heat exchanger ash, deposited ash, and fly ash contained 1.52 mg/kg, 1.99 mg/kg, 2.64 mg/kg, and 3.52 mg/kg of gold, respectively. Although the amount of fly ash is lower compared to bottom ash, the concentration of gold is the highest in fly ash, which follows the after heat exchanger ash and bottom ash. The concentration of gold was enriched by a three-stage procedure of water leaching, acid leaching (10 % HCl), and alkaline leaching (5 % NaOH), after which 12.1 mg/kg and 12.6 mg/kg gold was found in the residues obtained from leached bottom ash and deposited ash, respectively. SEM was utilized to depict the morphology of gold, which appears in bottom ash as individual neat particles with a purity higher than 98 %. Pure gold particles in the size of 1-2 µm are presented in the after heat exchanger ash; meanwhile, gold in fly ash is primarily associated with potassium, sodium, sulfur, and oxygen. The findings in this study pave the way for reclaiming gold from bio-ores as well as assist in better understanding the formation of this precious metal in these secondary resources.

Development of a colloidal gold immunochromatographic strip for the simultaneous detection of porcine epidemic diarrhea virus and transmissible gastroenteritis virus.

In recent years, porcine diarrhea-associated viruses have caused significant economic losses globally. These viruses present similar clinical symptoms, such as watery diarrhea, dehydration, and vomiting. Co-infections with porcine epidemic diarrhea virus (PEDV) and transmissible gastroenteritis virus (TGEV) are common. For the rapid and on-site preliminary diagnosis on the pig farms, this study aimed to develop a colloidal gold immunochromatography assay (GICA) strip for the detection of PEDV and TGEV simultaneously. The GICA kit showed that there was no cross-reactivity with the other five common porcine viruses. With visual observation, the lower limits were approximately 104 TCID50/mL and 104 TCID50/mL for PEDV and TGEV, respectively. The GICA strip could be stored at 4°C or 25°C for 12 months without affecting its efficacy. To validate the GICA strip, 121 clinical samples were tested. The positive rates of PEDV and TGEV were 42.9 and 9.9%, respectively, and the co-infection rate of the two viruses was 5.8% based on the duplex GICA strip. Thus, the established GICA strip is a rapid, specific, and stable tool for on-site preliminary diagnosis of PEDV- and TGEV-associated diarrhea.

Study on adsorption of kaolinite and gold thiosulfate.

The adsorption behavior of gold thiosulfate ions on the surface of kaolinite was studied using a combination of experimental research and quantum chemical calculations. Under the condition of a stirring time of 30 min, a stirring speed of 500 r·min-1, and a mass ratio of 30% kaolinite in the slurry, when the initial gold concentration of 56.50 mg·L-1,the adsorption rate of gold-thiosulfate ions from a kaolinite-containing solution was 7.44%. The results of Fourier transform infrared spectroscopy (FTIR) and energy dispersive spectroscopy (EDS) showed that the physical and chemical adsorption of kaolinite and gold thiosulfate occurred in solution. Quantum chemical calculations were performed using the CASTEP module in Materials Studio. The adsorption energy of gold thiosulfate on the surface of kaolinite (001) was calculated as - 438.01 kJ·mol-1.The calculated H76-O289 distance was 1.615 Å. Mulliken Charge population analysis and bond population analysis showed that gold thiosulfate ions form relatively stable bonds on the kaolinite surface (001). In the process of thiosulfate immersion, part of gold is adsorbed by kaolinite, which affects the extraction of gold. These results indicate that during the leaching process of gold thiosulfate, kaolinite has the ability to "catch" gold, which affects the leaching efficiency.

4D Printed Protein-AuNR Nanocomposites with Photothermal Shape Recovery.

4D printing is the 3D printing of objects that change chemically or physically in response to an external stimulus over time. Photothermally responsive shape memory materials are attractive for their ability to undergo remote activation. While photothermal methods using gold nanorods (AuNRs) have been used for shape recovery, 3D patterning of these materials into objects with complex geometries using degradable materials has not been addressed. Here, we report on the fabrication of 3D printed shape memory bioplastics with photo-activated shape recovery. Protein-based nanocomposites based on bovine serum albumin (BSA), poly (ethylene glycol) diacrylate and gold nanorods were developed for vat photopolymerization. These 3D printed bioplastics were mechanically deformed under high loads, and the proteins served as mechanoactive elements that unfolded in an energy-dissipating mechanism that prevented fracture of the thermoset. The bioplastic object maintained its metastable shape-programmed state under ambient conditions. Subsequently, up to 99% shape recovery was achieved within 1 min of irradiation with near-infrared light. Mechanical characterization and small angle X-ray scattering (SAXS) analysis suggest that the proteins mechanically unfold during the shape programming step and may refold during shape recovery. These composites are promising materials for the fabrication of biodegradable shape-morphing devices for robotics and medicine.