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Dual–mode detection of H2S by CD and FL based on the novel CuxOS‐Cy3@ZIF‐8 nanoprobe: A) CD spectra of the nanoprobe responding to different Na2S (the common H2S donor). B) The linear relationship between the concentration of Na2S and the corresponding ΔCD intensity (ΔCD = CD488 − CD560). C) Fluorescence spectra of CuxOS‐Cy3@ZIF‐8 reacting with different Na2S. λex = 488 nm, λem = 560 nm. D) The standard curve of fluorescence peak intensities at 560 nm at the various Na2S concentrations.
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In this study, a CuxOS@ZIF‐8 nanostructure is fabricated to quantify the levels of hydrogen sulfide (H2S) in living cells and in vivo. Zeolitic lmidazolate framework‐8 (ZIF‐8) is chosen as an encapsulation shell to improve the selectivity of this probe. Using this unique nanostructure, ultrasensitive quantification and bioimaging of H2S in living c...
Citations
... Chiral Cu x OS@ZIF-8 core-shell nanostructure was developed to enable ultra-sensitive quantification of H 2 S in living cells and in vivo. [154] This sensor operates in both CD and fluorescence modes with a limit of detection of 0.8 and 5.3 nmol per 10 6 cells, respectively (Figure 7d). Li et al. [155] constructed DNA-driven self-assembled gold-up-conversion (Au-UCNP) NPs, whose chirality originates from their pyramid-like geometry. ...
Chirality represents a fundamental characteristic inherent in nature, playing a pivotal role in the emergence of homochirality and the origin of life. While the principles of chirality in organic chemistry are well‐documented, the exploration of chirality within inorganic crystal structures continues to evolve. This ongoing development is primarily due to the diverse nature of crystal/amorphous structures in inorganic materials, along with the intricate symmetrical and asymmetrical relationships in the geometry of their constituent atoms. In this review, we commence with a summary of the foundational concept of chirality in molecules and solid states matters. This is followed by an introduction of structural chirality and electronic chirality in three‐dimensional and two‐dimensional inorganic materials. The construction of chirality in inorganic materials is classified into physical photolithography, wet‐chemistry method, self‐assembly, and chiral imprinting. Highlighting the significance of this field, we also summarize the research progress of chiral inorganic materials for applications in optical activity, enantiomeric recognition and chiral sensing, selective adsorption and enantioselective separation, asymmetric synthesis and catalysis, and chirality‐induced spin polarization. This review aims to provide a reference for ongoing research in chiral inorganic materials and potentially stimulate innovative strategies and novel applications in the realm of chirality.
... The synthesis of the D-/L-Cu x OS@Fe-MOF nanoplatform is illustrated in Scheme 1. Chiral D-/L-Cu x OS nanoparticles were first prepared using the chirality transfer strategy, [56] and had a mean diameter of ≈5 nm based on transmission electron microscopy (TEM) observations ( Figure 1A). D-/L-Cu x OS nanoparticles showed CD bands at 400-800 nm with opposite signs but similar amplitudes ( Figure S1, Supporting Information). ...
Here, the development of chiral D‐/L‐CuxOS nanoparticle‐engineered metal–organic frameworks (Fe‐MIL‐88B‐NH2), denoted as D‐/L‐CuxOS@Fe‐MOFs, for cuproptosis and ferroptosis synergistic therapy is described. The D‐/L‐CuxOS@Fe‐MOF displayed intense circular dichroism (CD) bands at 488 nm due to the chirality transfer from chiral penicillamine ligands. Chiral D‐/L‐CuxOS@Fe‐MOF showed tumor microenvironment‐triggered catalytic therapeutic activity by simultaneously depleting L‐glutathione (GSH) and generating potent reactive oxygen species in cancer cells. In vivo experimental results synchronously demonstrated D‐CuxOS@Fe‐MOF with higher efficiency of cancer therapy. The findings revealed that copper/iron ions released from chiral D‐CuxOS@Fe‐MOF induced augmented oxidative stress and potent ferroptosis, which synergizes with cuproptosis for enhanced cancer therapy. The synergistic index for D‐CuxOS@Fe‐MOF is determined to be 1.94, while L‐CuxOS@Fe‐MOF and D,L‐CuxOS@Fe‐MOF with 1.75 and 1.84, respectively. To the best of the knowledge, this is the first report of a chiral nanomaterial capable of inducing synergistic ferroptosis‐cuproptosis therapy for cancers. The results should invigorate studies pursuing the rational design of chiral nanomaterials for efficacious cancer therapy based on cuproptosis and ferroptosis.
... Additionally, the introduction of ZIF-8 can preconcentrate sulfide around the nanoprobe through surface adsorption and also be selectively degraded in the presence of sulfide ions, both of which can enhance the sensitivity and selectivity of the Au@4-MBN@Ag@ZIF-8 nanoprobe for sulfide detection. In the presence of sulfide, the ZIF-8 shell of the nanoprobe was degraded owing to the strong affinity between sulfide and the zinc nodes of ZIF-8, which disrupted the metal-ligand coordination bonds in ZIF-8 [34,35]. Subsequently, sulfide accessed the exposed Ag sensitive layer, etching the Ag layer and forming Ag 2 S. ...
A surface-enhanced Raman scattering nanoprobe has been developed for sulfide detection and applied to complex bacterial biofilms. The nanoprobe, Au@4-MBN@Ag@ZIF-8, comprised a gold core modified with 4-mercaptobenzonitrile (4-MBN) as signaling source, a layer of silver shell as the sulfide sensitization material, and a zeolitic imidazolate framework-8 (ZIF-8) as surface barrier. ZIF-8, with its high surface area and mesoporous structure, was applied to preconcentrate sulfide around the nanoprobe with its excellent adsorption capacity. Besides, the external wrapping of ZIF-8 can not only prevent the interference of biomolecules, such as proteins, with the Au@4-MBN@Ag assay but also enhance the detection specificity through the sulfide cleavage function towards ZIF-8. These properties are critical for the application of this nanoprobe to complex environmental scenarios. In the presence of sulfide, it was first enriched through adsorption by the outer ZIF-8 layer, then destroyed the barrier layer, and subsequently reacted with the Ag shell, leading to changes in the Raman signal. Through this rational design, the Au@4-MBN@Ag@ZIF-8 nanoprobe exhibited excellent detection sensitivity, with a sulfide detection limit in the nanomolar range and strong linearity in the concentration range 50 nM to 500 μM. Furthermore, the proposed Au@4-MBN@Ag@ZIF-8 nanoprobe was effectively utilized for sulfide detection in intricate biofilm matrices, demonstrating its robust selectivity and reproducibility.
Graphical Abstract
... Chair nanostructures have garnered substantial levels of attention over the last decade due to their potential application in DNA cleavage, [135] drug delivery, [136] chiral sensing, [137] oxidation prevention [138] and the treatment of Alzheimer's disease, [139] and so on. [140] Among these chiral nanomaterials, core-shell chiral nanostructures have shown advantageous optical properties because of their robust optical activity and distinctive surface plasmon resonance. ...
Unprecedented advances in metal nanoparticle synthesis have paved the way for broad applications in sensing, imaging, catalysis, diagnosis and therapy by tuning optical properties, enhancing catalytic performance, and improving chemical and biological properties of metal nanoparticles. The central guiding concept for regulating the size and morphology of metal nanoparticles has been identified as the precise manipulation of nucleation and subsequent growth, often known as seed‐mediated growth methods. However, since the growth process is sensitive not only to the metal seeds but also to capping agents, metal precursors, growth solution, growth/incubation time, reductant and other influencing factors, the precise control of metal nanoparticle morphology is multifactorial. Further, multiple reaction parameters are entangled with each other, so it is necessary to clarify the mechanism by which each factor precisely regulates the morphology of metal nanoparticles. In this review, to exploit the generality and extendibility of metal nanoparticle synthesis, we systematically summarized the mechanism of growth influencing factors in seed‐mediated growth methods. Second, we focus on a variety of critical properties and applications enabled by grown metal nanoparticles. Finally, we review the current progress and offer insights on the challenges, opportunities, and future directions for the growth and applications of grown metal nanoparticles.
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... Such effects in HOCNs have been utilized in potential applications over various fields, starting from ultrasensitive biosensing to enantioselective catalysis. [3][4][5] Recently, the transfer of chirality in such hierarchical biological structures has been widely addressed in the literature through self-assembled chiral fibrillar networks, 6 aggregates, 7 nanostructured chiral molecular gels, 8 and helical ribbons of the chiral lipid bilayer. 9 However, unlike in the biological system, transferring handedness from NP building blocks to higher-order inorganic structures has remained elusive. ...
Optical asymmetry and structural complexity across different length scales were realized in flower-shaped CuO nanostructures, prepared through refluxing an aqueous solution of copper acetate, sodium hydroxide, and D-tartaric acid, as well as in their toroid-like forms obtained on calcination at 600°C. Atomic scale chirality in the flower morphology could be visualized as putative Boerdijk-Coexter-Bernal like tetrahelical fragments, while that in the toroid form could be identified as screw dislocation-driven helicity. The fraction of asymmetry in the nanostructures has been evaluated from their chiroptical responses based on Kuhn asymmetry factor (g) from circular dichroism (CD) spectroscopy in the entire UV−vis range. The origin of chirality in the two CuO nanostructures has been assigned to the helical arrangement of the Cu−O−Cu network in accordance with their microscopic and spectroscopic observations. Attempts have been made to interpret the crystallographic and geometric chiralities in the two CuO nanostructures based on the redshift and augmented intensity of the CD signal along with an increase in their corresponding anisotropic factor on calcination. Further, the diverse interaction of the toroid-shaped CuO nanostructures with enantiomeric tryptophan moieties has been illustrated from the measurement of their corresponding thermodynamic parameters.
... 21,22 We sought to employ zeolitic imidazolate frameworks-8 (ZIF-8) as precursors to substitute ZIF-67 for synthesis of LDHs and their hybrids using a similar synthetic strategy in the research since ZIF-8 with good biocompatibility is extensively applied to studies of nanoparticle-based drug delivery platforms. 23,24 On the basis, to investigate the roles of mesopores and micropores respectively originated from LDH nanosheet assemblies and ZIF-8 in the drug delivery process, the small molecular weight drugs of doxorubicin hydrochloride (DOX) and 5-uorouracil (5-FU) with different sizes to match these porous structures were used separately as therapeutic agents. 25 Finally, in comparison to ZIF-8@LDHs core-shell structures, LDH nanosheets assembled porous cages demonstrate better drug loading performance towards DOX; during the 5-FU loading process, ZIF-8@LDHs core-shell structures were gradually transformed into porous cages of LDHs (PC-LDHs); drug carriers with porous structures exhibit better drug sustained release performance. ...
As one of the important types of two-dimensional materials, layered double hydroxides (LDHs) have been widely used in the biomedical field as carriers for drug delivery. In this case, we propose a facile synthetic method for preparing LDH-based self-assembly structures via a metal ions-mediated zeolitic imidazolate framework-8 (ZIF-8) transformation process. The as-made hierarchical porous ZIF-8@LDHs core-shell structures and porous cages of LDHs (PC-LDHs) in drug delivery systems are used to study the loading and release of small molecular weight drugs such as doxorubicin hydrochloride (DOX) and 5-fluorouracil (5-FU). The intrinsic properties and assembly structures of both carriers are investigated in depth for their impact on slow drug release. Finally, PC-LDHs outperform ZIF-8@LDHs core-shell structures in terms of drug delivery performance under various conditions, indicating that LDH nanosheets would play a decisive role in the drug delivery process. In the drug release system, scattered LDH nanosheets with smaller sizes than their assemblies are gradually produced, allowing nanodrugs to enter cancer tissues more easily across biological barriers. This study provides the preliminary preparation for an LDH-based nanomedicine platform in the field of cancer therapy.
... Synthesis of UR: CR was prepared according to a previous method [24] with few innovative adaptations. First, CuCl 2 ·2H 2 O (100 µL, 2 m) and NaOH (100 µL, 4 m) were mixed, and added deionized water to final volume of 5 mL under magnetic stirring at room temperature. ...
Intestinal milieu disorders are strongly related to the occurrence of inflammatory bowel diseases (IBDs), which results from mucosa destruction, epithelium disruption and tight junction (TJ) proteins loss. Excess of H2 S in the intestinal milieu produced by sulfate-reducing bacteria metabolism contributes to IBDs development via epithelial barrier breakdown. Conventional interventions, such as surgery and anti-inflammatory medications, are considered not completely effective because of frequent recurrence and other complications. Herein, a novel oral delivery system, a hydroxypropyl methylcellulose acetate succinate (HPMCAS)-based polymer-coated Zr-based metal-organic framework (UiO-66) with a Cux -rhodamine B (CR) probe (hereinafter referred to as HUR), was produced via co-flow microfluidic assistance with ability to reduce H2 S levels, thus restoring the intestinal lumen milieu. HPMCAS serves as an enteric coating that exposes UiO-66@CR at the pH of the intestine but not the acidic pH of the stomach. The synthesized HUR exhibits notable therapeutic efficacy, including mucosa recovery, epithelium integrity restoration and TJ proteins up-regulation via H2 S scavenging to protect against intestinal barrier damage and microbiome dysbiosis. Thus, HUR has been verified to be a promising theranostic platform able to decrease the H2 S content for intestinal milieu disorder treatment. The presented study therefore opens the door for further exploitation for IBDs therapy. This article is protected by copyright. All rights reserved.
... www.advancedsciencenews.com spectrum; it indicates the quenching of fluorescence emitted from Cy3 ( Figure 2C). [40] Thus, in the presence of H 2 O 2 , the chiral MoSe 2 NPs reacted with ROS and then gradually oxidated to form achiral MoO 3 NPs. Excitingly, after reacting chiral MoSe 2 NPs with H 2 O 2 , the emission spectra of Cy3 fluorescent molecules and the absorbance spectra of MoO 3 NPs had almost no overlapping area, resulting in fluorescence recovery by FRET, thus showing an "OFF-ON" fluorescent signal, which could be used for ROS detection ( Figure 2D). ...
Reactive oxygen species (ROS) are involved in neurodegenerative diseases, cancer, and acute hepatitis, and the early diagnosis of these diseases by quantification of ROS is critical for the curable treatment of patients. Here, a novel probe was developed based on chiral molybdenum diselenide (MoSe2) nanoparticles (NPs) modified by the fluorescence molecule, cyanine 3 (Cy3). Chiral MoSe2 NPs showed intensive circular dichroism (CD) signals at 390 nm and 550 nm, whereas the fluorescence signal of Cy3 at 560 nm was quenched by MoSe2 NPs. With the presence of ROS, the novel probe reacted with ROS and then oxidated rapidly, resulting in decreased CD signals and the recovery of Cy3 fluorescence signals. With the help of ROS‐related CD and fluorescent dual‐mode signals, the limit of detection (LOD) of CD signals and fluorescence signals in living cells was 0.0093 nmol/106 cells and 0.024 nmol/106 cells, respectively. The high selectivity and sensitivity to ROS in complex biological environments was attributed to the Mo4+ and Se2− oxidation reaction on the surface of the NPs. Furthermore, chiral MoSe2 NPs was able to monitor the levels of ROS in vivo by fluorescence signals. Collectively, this strategy offers a new approach for ROS detection and has the potential to inspire others to explore chiral nanomaterials as potential biosensors to investigate biological events. This article is protected by copyright. All rights reserved
... 13 They also have antimicrobial properties 14 by the following mechanisms: (1) metal ions and ligands have antimicrobial activity, and slow release in the environment can make them have long-lasting antimicrobial activity; 15 (2) loading antimicrobial drugs in their pores can make active substances slowly released into the environment; 16 (3) using MOFs with catalytic activity, active substances such as reactive oxygen species (ROS) are produced under certain conditions and released into the environment, thus kill microorganisms. 17 As one kind of MOFs, ZIF-8 has good biocompatibility 18 and is receiving increasing attention for applications in bioimaging, 19 drug controlled-release, 20 photothermal therapy 21 and photodynamic therapy. 22 According to the study of Taheri et al., 23,24 ZIF-8 can release zinc ions slowly into the environment, giving it good antimicrobial activity and superiority over zinc oxide. ...
Textiles modified with antimicrobial nanomaterials have excellent comprehensive performance. However, the shedding of nanoparticles often occurs in actual use. This not only reduces the service life of antimicrobial textiles, but also causes potential harm. Here, we report a new method to covalently immobilize a zinc-imidazolate MOF (ZIF-8) onto cotton fabric by electron beam irradiation to prepare antimicrobial textiles with excellent durability. A series of characterization analysis showed the electron beam irradiation did not damage the structure of the ZIF-8 nanoparticles and the particles were successfully introduced onto cotton fibers via poly hydroxyethyl acrylate (PHEA). The modified cotton fabric exhibited >99% inhibition of Escherichia coli, Staphylococcus aureus and Candida albicans. The results of dry cleaning and rub resistance tests showed that the prepared antimicrobial cotton fabric had significant durability which was attributed to the strong covalent binding between the MOF and textile.
... The variation in CD signals caused by the construction and destruction of chiral nanostructures using DNA origami technology [30, 36−38] provides a new method for detecting molecules such as reactive oxygen species [39] , bovine serum albumin (BSA) [40] , hydrogen sulfide [41] , microRNA [36] , and mycotoxin [42] both in vitro and in vivo. Structures are built through specific connections of biological molecules (such as chiral pyramids [36−38] , propeller-like NRs [30] , and core-satellite superstructures with Au NPs as the core [42] ). ...
Inorganic chiral nanomaterials have attracted wide attention because of their superior physical properties and chiroptical activities. Great progress in chiral nanostructure preparation has been made, such as noble metals and semiconductors. In this review, we introduce several chiral nanomaterials with feasible biocompatibility and low cytotoxicity that are promising candidates for biological applications, and we focus on their preparation in terms of their circular dichroism (CD) effects and circular luminescence properties. Additionally, we summarize the working function of chiral nanostructures toward some common diseases with high prevalence, such as Alzheimer’s disease (AD), Parkinson’s disease (PD), diabetes and even cancers. The introduction of inorganic chirality will provide a novel way to diagnose and treat these diseases.
