Cysteine-Induced Chirality Evolution of Molybdenum Disulfide Nanodots from a Bottom-Up Strategy.

The transfer of chirality from molecules to synthesized nanomaterials has recently attracted significant attention. Although most studies have focused on graphene and plasmonic metal nanostructures, layered transition metal dichalcogenides (TMDs), particularly MoS2, have recently garnered considerable attention due to their semiconducting and electrocatalytic characteristics. Herein, we report a new approach for the synthesis of chiral molybdenum sulfide nanomaterials based on a bottom-up synthesis method in the presence of chiral cysteine enantiomers. In the synthesis process, molybdenum trioxide and sodium hydrosulfide serve as molybdenum and sulfur sources, respectively. In addition, ascorbic acid acts as a reducing agent, resulting in the formation of zero-dimensional MoS2 nanodots. Moreover, the addition of cysteine enantiomers to the growth solutions contributes to the chirality evolution of the MoS2 nanostructures. The chirality is attributed to the cysteine enantiomer-induced preferential folding of the MoS2 planes. The growth mechanism and chiral structure of the nanomaterials are confirmed through a series of characterization techniques. This work combines chirality with the bottom-up synthesis of MoS2 nanodots, thereby expanding the synthetic methods for chiral nanomaterials. This simple synthesis approach provides new insights for the construction of other chiral TMD nanomaterials with emerging structures and properties. More significantly, the as-formed MoS2 nanodots exhibited highly defect-rich structures and chiroptical performance, thereby inspiring a high potential for emerging optical and electronic applications.

White light powered antimicrobial nanoagents for triple photothermal, chemodynamic and photodynamic based sterilization.

Antibacterial nanoagents have been increasingly developed due to their favorable biocompatibility, cost-effective raw materials, and alternative chemical or optical properties. Nevertheless, there is still a pressing need for antibacterial nanoagents that exhibit outstanding bacteria-binding capabilities and high antibacterial efficiency. In this study, we constructed a multifunctional cascade bioreactor (GCDCO) as a novel antibacterial agent. This involved incorporating carbon dots (CDs), cobalt sulfide quantum dots (CoSx QDs), and glucose oxidase (GOx) to enhance bacterial inhibition under sunlight irradiation. The GCDCO demonstrated highly efficient antibacterial capabilities attributed to its favorable photothermal properties, photodynamic activity, as well as the synergistic effects of hyperthermia, glucose-augmented chemodynamic action, and additional photodynamic activity. Within this cascade bioreactor, CDs played the role of a photosensitizer for photodynamic therapy (PDT), capable of generating ˙O2- even under solar light irradiation. The CoSx QDs not only functioned as a catalytic component to decompose hydrogen peroxide (H2O2) and generate hydroxyl radicals (˙OH), but they also served as heat generators to enhance the Fenton-like catalysis process. Furthermore, GOx was incorporated into this cascade bioreactor to internally supply H2O2 by consuming glucose for a Fenton-like reaction. As a result, GCDCO could generate a substantial amount of reactive oxygen species (ROS), leading to a significant synergistic effect that greatly induced bacterial death. Furthermore, the in vitro antibacterial experiment revealed that GCDCO displayed notably enhanced antibacterial activity against E. coli (99+ %) when combined with glucose under simulated sunlight, surpassing the efficacy of the individual components. This underscores its remarkable efficiency in combating bacterial growth. Taken together, our GCDCO demonstrates significant potential for use in the routine treatment of skin infections among diabetic patients.

An intelligent "chemical tongue" for high-order monitoring ATP-related physiological phosphates and ATP hydrolysis through diverse transduction principles.

For discriminating diverse analytes and monitoring a specific chemical reaction, the emerging multi-channel "chemical nose/tongue" is challenging multi-material "chemical nose/tongue". The former contributes greatly to integrating different transduction principles from a single sensing material, avoiding the need for complex design, high cost, and tedious operation involved with the latter. Therefore, this high-order sensing puts a particular emphasis on the effects of encapsulation. Herein, the plasmonic gold nanoparticles (Au NPs) are encapsulated as a core into the fluorescent guanine monophosphate-Tb3+ infinite coordination polymer nanoparticles (GMP-Tb ICPs) to obtain a core-shell nanocomposite named Au NPs@GMP-Tb ICPs. Hence, a dual-channel "chemical tongue" based on Au NPs@GMP-Tb ICPs is present to realize high-order sensing of adenosine triphosphate (ATP)-related physiological phosphates and the monitoring of ATP hydrolysis. Considering the affinity of Tb3+ towards P-O bonds, four inorganic phosphates and three nucleotide phosphates with different phosphate group numbers and steric hindrance effect directly regulate two stimulus responses (fluorescence intensity and UV-vis absorbance) of Au NPs@GMP-Tb ICPs. Robust statistical methods, such as linear discriminant analysis and hierarchical cluster analysis, are used to recognize each phosphate by the developed sensor array either in the aqueous solution or in complex media such as serum, together with efficiently monitored ATP hydrolysis at different intervals. These findings and blind test clarify that the designed "chemical tongue" guarantees interference resistance and strengthens analytical capacity, together with offering valuable insight into "lab-on-a-nanoparticle" development for monitoring specific chemical reactions.

Tracking the Growth of Chiral Plasmonic Nanocrystals at Molybdenum Disulfide Heterostructural Interfaces.

The way of accurately regulating the growth of chiral plasmonics is of great importance for exploring the chirality information and improving its potential values. Herein, cysteine enantiomers modulate the anisotropic and epitaxial growth of gold nanoplasmonics on seeds of exfoliated MoS2 nanosheets. The heterostructural Au and MoS2 hybrids induced by enantiomeric cysteine are presented with chiroptical characteristics, dendritic morphologies, and plasmonic performances. Moreover, the synthesis, condition optimization, formation mechanism, and plasmonic properties of Au and MoS2 dendritic nanostructures are studied. The chirality characteristics are identified using the circular dichroism spectra and scanning electron microscopy. Time-resolved transmission electron microscopy and UV-vis spectra of the intermediate products captured are analyzed to confirm the formation mechanism of dendritic plasmonic nanostructures at heterostructural surfaces. The specific dendritic morphologies originate from the synergistic impacts of heterostructural MoS2 interfaces and enantiomeric cysteine-induced anisotropic manipulation. Significantly, the developed synthesis strategy of chiral nanostructures at heterostructural interfaces is highly promising in promoting the understanding of the plasmonic function and crucial chirality bioinformation.

Chiral nanocrystals grown from MoS2 nanosheets enable photothermally modulated enantioselective release of antimicrobial drugs.

The transfer of the concept of chirality from molecules to synthesized nanomaterials has attracted attention amongst multidisciplinary teams. Here we demonstrate heterogeneous nucleation and anisotropic accumulation of Au nanoparticles on multilayer MoS2 planes to form chiroptically functional nanomaterials. Thiol amino acids with chiral conformations modulate asymmetric growth of gold nanoarchitectures on seeds of highly faceted Au/MoS2 heterostructures. Consequently, dendritic plasmonic nanocrystals with partial chiral morphologies are synthesized. The chirality of dendritic nanocrystals inherited from cysteine molecules refers to the structural characteristics and includes specific recognition of enantiomeric molecules. With integration of the intrinsic photothermal properties and inherited enantioselective characteristics, dendritic Au/MoS2 heterostructures exhibit chirality-dependent release of antimicrobial drugs from hydrogel substrates when activated by exogenous infrared irradiation. A three-in-one strategy involving synthesis of chiral dendritic heterostructures, enantioselective recognition, and controlled drug release system is presented, which improves nanomaterial synthetic technology and enhances our understanding of crucial chirality information.

Plasmonic Gold Nanoparticles Stain Hydrogels for the Portable and High-Throughput Monitoring of Mercury Ions.

The hybrid of l-cysteine and agarose can reduce HAuCl4 and support the rapid growth of plasmonic gold nanoparticles (Au NPs) in the hydrogel phase. The l-cysteine-doped agarose hydrogel (C-AGH) not only offers the substrate the capacity to reduce Au(III) ions but also stabilizes and precisely modulates the in situ grown Au NPs with high repeatability, easy operation, and anti-interference performance. Herein, before the incubation of HAuCl4, the improved hydrogel is preincubated in the aqueous solution containing mercury ions, and the cysteine can specifically conjugate with mercury via the thiol groups. Subsequently, the responsive allochroic bands from dark blue to red can be identified in the solid hydrogel after the incubation of HAuCl4, which is attributed to the formation of regulated Au-Hg nanoamalgams. As a proof-of-concept, toxic Hg2+ ions are exploited as targets for constructing novel sensing assays based on the improved C-AGH protocol. Based on naked-eye recognition, Hg2+ could be rapidly and simply measured. Additionally, the high-throughput and trace analysis with a low limit of detection (3.7 nM) is performed using a microplate reader. On the basis of the filtering technique and remodeling of hydrogels, C-AGH working as the filtering membrane can even achieve the integration of enrichment and measurement with enhanced sensitivity. Significantly, the strategy of using an allochroic hydrogel with the staining of Au NPs can promote the rapid and primary assessment of water quality in environmental analysis.

Assembling Defined DNA Nanostructure with Nitrogen-Enriched Carbon Dots for Theranostic Cancer Applications.

DNA nanostructures as scaffolds for drug delivery, biosensing, and bioimaging are hindered by its vulnerability in physiological settings, less favorable of incorporating arbitrary guest molecules and other desirable functionalities. Noncanonical self-assembly of DNA nanostructures with small molecules in an alternative system is an attractive strategy to expand their applications in multidisciplinary fields and is rarely explored. This work reports a nitrogen-enriched carbon dots (NCDs)-mediated DNA nanostructure self-assembly strategy. Given the excellent photoluminescence and photodynamic properties of NCDs, the obtained DNA/NCDs nanocomplex holds great potential for bioimaging and anticancer therapy. NCDs can mediate DNA nanoprism (NPNCD ) self-assembly isothermally at a large temperature and pH range in a magnesium-free manner. To explore the suitability of NPNCD in potential biomedical applications, the cytotoxicity and cellular uptake efficiency of NPNCD are evaluated. NPNCD with KRAS siRNA (NPNCD K) is further conjugated for KRAS-mutated nonsmall cell lung cancer therapy. The NPNCD K shows excellent gene knockdown efficiency and anticancer effect in vitro. The current study suggests that conjugating NCDs with programmable DNA nanostructures is a powerful strategy to endow DNA nanostructures with new functionalities, and NPNCD may be a potential theranostic platform with further fine-tuned properties of CDs such as near-red fluorescence or photothermal activities.

Layered Aggregation with Steric Effect: Morphology-Homogeneous Semiconductor MoS2 as an Alternative 2D Probe for Visual Immunoassay.

Liquid-phase exfoliation routes unavoidably generate 2D nanostructures with inhomogeneous morphologies. Herein, thickness-dependent sorting of exfoliated nanostructures is achieved via a treatment of differential-zone centrifugation in the surfactant aqueous phase. With this approach, homogeneous MoS2 nanosheets are obtained, and due to the intrinsic semiconducting characteristics, those 2D nanosheets are endowed with desired optical properties, rivaling classic gold nanoparticles in sensing applications. Furthermore, MoS2 nanosheets with high uniformity and chemical inertness are coupled with proteins, exhibiting high performance in stability and anti-interferences for bioanalysis. As a consequence of aggregation-induced steric effect, distinguishing running shifts of antibody-anchored conjugates in gel electrophoresis are visually responsive to those specific antigens. This assay enables the easy and fast monitoring of tumor biomarkers just according to "naked-eye" identification of band location in electrophoresis results, which are presented by an alternative visual probe of 2D MoS2 -protein conjugates. The developed visual immunoassay with the synergistic effect of gel electrophoresis techniques and 2D semiconductors pushes significant progress in "home-made" tests for disease early diagnosis.

Directing Assembly and Disassembly of 2D MoS2 Nanosheets with DNA for Drug Delivery.

Layer-by-layer (LbL) self-assembled stacked Testudo-like MoS2 superstructures carrying cancer drugs are formed from nanosheets controllably assembled with sequence-based DNA oligonucleotides. These superstructures can disassemble autonomously in response to cancer cells' heightened ATP metabolism. First, we functionalize MoS2 nanosheets (MoS2-NS) nanostructures with DNA oligonucleotides having thiol-terminated groups (DNA/MoS2-NS) via strong binding to sulfur atom defect vacancies on MoS2 surfaces. The driving force to assemble into a higher-order DNA/MoS2-NS superstructure is guided by a linker aptamer that induced interlayer assembly. In the presence of target ATP molecules, these multilayer superstructures disassembled as a consequence of stronger binding of ATP molecules with the linking aptamers. This design plays a dual role of protection and delivery by LbL stacked MoS2-NS similar in concept to a Greek Testudo. These superstructures present a protective armor-like shell of MoS2-NS, which still remains responsive to small and infiltrating ATP molecules diffusing through the protective MoS2-NS, contributing to an enhanced stimuli-responsive drug release system for targeted chemotherapy.

A potential fluorescent probe: Maillard reaction product from glutathione and ascorbic acid for rapid and label-free dual detection of Hg(2+) and biothiols.

Maillard reactions and their fluorescent products have drawn much attention in the fields of food and life science, however, the application of fluorescent products separated from the reaction as an indicator for detection of certain substances in sensor field has not been mentioned. In this article, we report on an easy-to-synthesize and water-soluble fluorescent probe separated from the typical Maillard reaction products of glutathione and ascorbic acid, with excellent stability and high quantum yield (18.2%). The further application of the probe has been explored for dual detection of Hg(2+) and biothiols including cysteine, homocysteine, and glutathione, which is based on Hg(2+)-induced fluorescence quenching of the Maillard reaction fluorescent products (MRFPs) and the fluorescence recovery as the introduction of biothiols. This sensing system exhibits a good selectivity and sensitivity, and the linear ranges for Hg(2+), cysteine, homocysteine, and glutathione are 0.05-12, 0.5-10, 0.3-20, and 0.3-20µM, respectively. The detection limits for Hg(2+), cysteine, homocysteine, and glutathione are 22, 47, 96, and 30nM at a signal-to-noise ratio of 3, respectively. Furthermore, the practical applications of this sensor for Hg(2+) and biothiols determination in water samples and human plasma sample have been demonstrated with satisfactory results.

A novel conducting poly(p-aminobenzene sulphonic acid)-based electrochemical sensor for sensitive determination of Sudan I and its application for detection in food stuffs.

In the present work, a new method for the determination of Sudan I has been developed based on a conducting poly(p-aminobenzene sulphonic acid) (poly(p-ABSA)) film modified electrode. The new electrochemical sensor showed strong accumulation ability and excellent electrocatalytic activity for Sudan I. Electrochemical oxidation signal of Sudan I at the poly(p-ABSA) modified glassy carbon electrode (poly(p-ABSA)/GCE) was significantly increased when compared to that at the bare GCE. The experimental conditions such as amount of alcohol, pH of buffer solution, accumulation time, and instrumental parameters for square wave anodic stripping voltammetry were optimised for the determination of Sudan I. Under optimum conditions, the linear regression equation of Sudan I was ip=1.868+0.1213c (ip: µA, c: µgL(-1), R=0.9981) from 1 to 500 µg L(-1) with a detection limit of 0.3 µg L(-1). Finally, this sensor was successfully employed to detect Sudan I in some hot chili and ketchup samples.

Anodic stripping voltammetric measurement of trace cadmium at tin-coated carbon paste electrode.

A carbon paste electrode modified with tin was used for the determination of trace cadmium by anodic stripping voltammetry. The electroanalytical performance for the determination of Cd(II) on the tin-coated carbon paste electrode(SnF-CPE) was better than that on the carbon paste electrode. The measuring conditions have been optimized. The measurement of trace cadmium on the SnF-CPE has the best response under the conditions of 0.10molL(-1) acetate buffer solution (pH 3.9), 3.5mgL(-1) Sn(II), deposition potential of -1.40V, and deposition time of 150s. The SnF-CPE revealed highly linear behavior in the concentration range of 2.0-90.0µgL(-1) with the detection limit of 1.13µgL(-1) for Cd(II). The developed sensor has been applied to the determination of Cd(II) in real water samples with satisfactory results.