Latest ArticlesA thickness-controllable method for preparing metal-organic framework hollow nanoflowers on magnetic cores (Fe3O4@MOFs HFs) was demonstrated for the first time. The petal of magnetic core with hollow nanoflower structure served as medium for assembling UiO-66-NH2 shell with different thickness. To further improve its performance, Zr4+ was immobilized on the surface of Fe3O4@UiO-66-NH2. Compared with conventional Fe3O4@UiO-66-NH2-Zr4+ nanospheres, the Fe3O4@UiO-66-NH2-Zr4+ HFs showed increased enrichment performance for phosphopeptides. The Fe3O4@UiO-66-NH2-Zr4+ HFs served as an attractive restricted-access adsorption material exhibited good selectivity (mβ-casein:mBSA=1:1000), high sensitivity (1.0 fmol) and excellent size-exclusion effect (mβ-casein digests:mBSA=1:200). Furthermore, the Fe3O4@UiO-66-NH2-Zr4+ HFs was successfully applied to the specific capture of ultratrace phosphopeptide from complex biological samples, revealing the great potential for the identification and analysis of trace phosphopeptides in clinical analysis. This work can be easily extended to the fabrication of diverse mag-MOF HFs with multifunctional and easy to post-modify properties, and open up a new avenue for the design and construction of new MOFs material.
Black phosphorus (BP), as a rising star of 2D nanomaterials has drawn considerable attention in cancer therapy. However, the poor stability under ambient conditions limits their practical applications. Herein, a multiple supramolecular assembly composed of adamantane-modified hyaluronic acid (HAADA), ferrocene-modified cinnamaldehyde (Fc-CA), guanidinium-functionalized β-cyclodextrin (Guano-CD), and black phosphorus (BP) nanosheets was successfully fabricated through cooperative host-guest and electrostatic interactions. Owing to the cooperative contribution of these building blocks, the obtained supramolecular assembly simultaneously possesses multiple functions including excellent stability, good biocompatibility and targeting property, and a high inhibition effect toward cancer cells. We believe that this work might provide new insights into designing a new generation of cancer theranostic protocols for potential clinical applications.
Aromatic nitro compounds present substantial health and environmental concerns due to their toxic nature and potential explosive properties. Consequently, the development of host–guest molecular recognition systems for these compounds serves a dual-purpose: enabling the fabrication of high-performance sensors for detection and guiding the design of efficient adsorbents for environmental remediation. This study investigated the host–guest recognition behavior of perethylated pillar[n]arenes toward two aromatic nitro molecules, 1-chloro-2,4-dinitrobenzene and picric acid. Various techniques including 1H NMR, 2D NOESY NMR, and UV-vis spectroscopy were employed to explore the binding behavior between pillararenes and aromatic nitro guests in solution. Moreover, valuable single crystal structures were obtained to elucidate the distinct solid-state assembly behaviors of these guests with different pillararenes. The assembled solid-state supramolecular structures observed encompassed a 1:1 host–guest inclusion complex, an external binding complex, and an exo-wall tessellation complex. Furthermore, based on the findings from these systems, a pillararene-based test paper was developed for efficient picric acid detection, and the removal of picric acid from solution was also achieved using pillararenes powder. This research provides novel insights into the development of diverse host–guest systems toward hazardous compounds, offering potential applications in environmental protection and explosive detection domains.
Visual assessment of tumor metastatic capacity is crucial for predicting hepatocellular carcinoma (HCC) prognosis and guiding clinical therapeutic approaches. In this study, we developed an enzyme-responsive probe based on the peptide GK10, which is selectively cleaved by matrix metalloproteinase-9 (MMP-9), a critical marker for metastasis in HCC. The GK10 peptide was conjugated with near-infrared fluorescent molecule IR783, fluorescent quencher black hole quencher 3 (BHQ3), and magnetic resonance (MR) contrast agent DOTA-Gd, forming the IR783-GK10-BHQ3-Gd probe. Upon MMP-9 cleavage of GK10, BHQ3 is released from the probe, thereby amplifying the previously quenched IR783 fluorescence signal. In vitro experiments demonstrate the probe’s impressive detection limit for MMP-9, as low as 1.84 ng/mL. Moreover, in vivo imaging results reveal that the probe can differentiate liver cancers with varying metastatic capacities. The fluorescence and MR imaging signal intensity of high metastatic HCC are approximately 1.2 times greater than that of low metastatic HCC. Thus, this engineered probe holds promise as a valuable tool for evaluating HCC metastatic capacity through fluorescence-MR dual-mode imaging.
With the rapid development of electric vehicles, hybrid electric vehicles and smart grids, people's demand for large-scale energy storage devices is increasingly intense. As a new type of secondary battery, potassium ion battery is promising to replace the lithium-ion battery in the field of large-scale energy storage by virtue of its low price and environmental friendliness. At present, the research on the anode materials of potassium ion batteries mainly focuses on carbon materials and the design of various nanostructured metal-based materials. Problems such as poor rate performance and inferior cycle life caused by electrode structure comminution during charge and discharge have not been solved. Quantum dots/nanodots materials are a new type of nanomaterials that can effectively improve the utilization of electrode materials and reduce production costs. In addition, quantum dots/nanodots materials can enhance the electrode reaction kinetics, reduce the stress generated in cycling, and effectively alleviate the agglomeration and crushing of electrode materials. In this review, we will systematically introduce the synthesis methods, K+ storage properties and K+ storage mechanisms of carbon quantum dots and carbon-based transition metal compound quantum dots composites. This review will have significant references for potassium ion battery researchers.
Polyetheretherketone (PEEK) is a desirable candidate to replace conventional metal implants owing to its excellent mechanical properties. However, the intrinsic bioinertness of PEEK results in inferior or delayed osseointegration, which limits its further clinical application. To address these challenges, one leading strategy is to construct a biofunctionalized surface on PEEK that provides a coordinated osteoblast-osteoclast interactions microenvironment. Herein, alendronate (ALN), a common bone absorption inhibitor, was loaded in biomedical inorganic/organic microspheres, consisting of bioactive inorganic nano-hydroxyapatite core, and chitosan (CS) shell. Polydopamine (PDA) modification was employed to ensure the adherence of the microspheres to the PEEK surface. The delivery of ALN and Ca2+ from these microspheres simultaneously suppressed osteoclastogenesis and promoted osteogenesis, resulting in a coordinated cascade of osteoblast-osteoclast interactions crucial for the per-implant osseointegration. In vitro experiments demonstrated that the PEEK surface exhibited satisfactory biocompatibility and enhanced the proliferation and osteogenic differentiation of rat bone mesenchymal stem cells while inhibiting the osteoclast differentiation. Moreover, the in vivo rat femoral drilling model demonstrated superior osseointegration three months after implantation. By considering the bone remodeling processes, this study proposes a novel biofunctionalized PEEK surface that regulates the activities of both osteoblasts and osteoclasts to promote osseointegration.
Cobalt sulfide has received widespread attention in the advanced oxidation treatment of wastewater, and its catalytic activity is influenced by crystal structure and exposed active sites. This work successfully constructed three types of cobalt sulfides, namely Co9S8, Co3S4 and CoS2, by changing the molar ratio of cobalt to sulfur. The results showed that the degradation efficiency of Co9S8, Co3S4 and CoS2 on chloroxylenol by activated peroxomonosulfate (PMS) were 100%, 88.70% and 67.73%, respectively. Combined with density functional theory (DFT), the structural properties and reaction energy barriers of different cobalt-sulfur ratios were calculated. As the ratio of cobalt to sulfur increases, the sulfur vacancies realized a fuller exposure of active sites (Co2+surf.) on the surface of the catalysts, with a highly linear relationship with the reaction rate constant (R2 = 0.945). This work explores the structure-activity relationship between cobalt sulfur ratio and degradation efficiency, which can guide new catalyst synthesis.
Designing carbon materials with ideal stable hierarchical porous structures and flexible functional properties for efficient and sustainable Zn2+ ion storage still faces great challenges. Herein, the three-dimensional carbon superstructures with spherical nanoflower-like structures were tailor-made by the self-assembly strategy. Specifically, organic polymer units (i.e., organic motifs) were formed by tetrachloro-p-benzoquinone (TBQ) and 2, 6-diamino anthraquinone (DAQ) via a noble-metal-free catalyzed coupling reaction. Subsequently, the organic motifs assemble into spherical nanoflower-like superstructures induced by intermolecular hydrogen bonding and aromatic π-π stacking interactions. Well-designed carbon superstructures can provide a stable backbone that effectively blocks structural stacking and collapse. Meanwhile, the hierarchical porous structures in 3D carbon superstructures provide continuous charge transport pathways to greatly shorten the ion diffusion distance, and as a result, the carbon superstructures-based zinc-ion hybrid capacitors (ZIHCs) provide a capacity of 245 mAh/g at 0.5 A/g, a high energy density of 152 Wh/kg and an ultra-long life of 300, 000 cycles at 20 A/g. The excellent electrochemical performance is also attributed to the corresponding charge storage mechanism, i.e., the alternate binding of Zn2+/CF3SO3− ions. Besides, the high-level N/O motifs improve the surface properties of the carbon superstructures and reduce the ion migration barriers for more efficient charge storage. This paper provides insights into the design of advanced carbon-based cathodes and presents a fundamental understanding of their charge storage mechanisms.
Agrochemicals, especially plant growth regulators (PGRs), are extensively used to modulate endogenous phytohormone signals in small quantities, significantly influencing plant growth and development. Plant hormones typically exhibit diverse chemical structures, with common examples including indole rings, terpenoid frameworks, adenine motifs, cyclic lactones, cyclopentanones, and steroidal compounds, which are extensively employed in pesticides. This article explores the interactions and biological activities of small molecules on proteins, enzymes, and other reactive sites involved in the biosynthesis, metabolism, transport, and signal transduction pathways of various plant hormones. Additionally, it analyzes the structure-activity relationships (SARs) of pesticides incorporating these structural motifs to elucidate the relationship between active fragments, pharmacophores, and targets, highlighting the characteristics of potent small molecules and their derivatives. This comprehensive review aims to provide novel perspectives for the development and design of pesticides, offering valuable insights for researchers in the field.
Carbon materials have long been a subject of study, offering diverse properties based on their hybridized structures. Except sp2-hybridized graphene and carbon nanotubes, the focus on sp1-hybridized carbon chains has garnered significant interest due to its unique predicted properties, despite limitations in research and development stemming from its high reactivity. This comprehensive review summaries recent advancements in synthetic methodologies and characterization of the sp1-hybridized carbon chains, encompassing linear carbon chains and cyclo[n]carbons. The review traces significant milestones in synthesis and offers a thorough overview of various properties on linear and cyclic carbon chains, from their initial discovery to recent development. The advancing synthetic methods have led to practical breakthroughs, transitioning theoretical concepts into tangible carbon-chain materials. However, challenges persist in achieving controlled and scalable preparation due to the high reactivity associated with sp1-hybridization. Future research prospects focus on fundamental studies, such as exploring the transition length from polyyne to carbyne and experimentally determining the properties of single carbon chains. This review underscores both the progress made and the compelling avenues for future exploration in the dynamic field of sp1-hybridized carbon chains.
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