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Core-shell metal-organic frameworks with fluorescence switch to trigger an enhanced photodynamic therapy
摘要： The design of hybrid metal-organic framework (MOF) nanomaterials by integrating inorganic nanoparticle into MOF (NP@MOF) has demonstrated outstanding potential for obtaining enhanced, collective, and extended novel physiochemical properties. However, the reverse structure of MOF-integrated inorganic nanoparticle (MOF@NP) with multifunction has rarely been reported. Methods: We developed a facile in-situ growth method to integrate MOF nanoparticle into inorganic nanomaterial and designed a fluorescence switch to trigger enhanced photodynamic therapy. The influence of “switch” on the photodynamic activity was studied in vitro. The in vivo mice with tumor model was applied to evaluate the “switch”-triggered enhanced photodynamic therapy efficacy. Results: A core-satellites structure with fluorescence off and on function was obtained when growing MnO2 on the surface of fluorescent zeolitic imidazolate framework (ZIF-8) nanoparticles. Furthermore, A core-shell structure with photodynamic activity off and on function was achieved by growing MnO2 on the surface of porphyrinic ZrMOF nanoparticles (ZrMOF@MnO2). Both the fluorescence and photodynamic activities can be turned off by MnO2 and turned on by GSH. The GSH-responsive activation of photodynamic activity of ZrMOF@MnO2 significantly depleted the intracellular GSH via a MnO2 reduction reaction, thus triggering an enhanced photodynamic therapy efficacy. Finally, the GSH-reduced Mn2+ provided a platform for magnetic resonance imaging-guided tumor therapy. Conclusion: This work highlights the impact of inorganic nanomaterial on the MOF properties and provides insight to the rational design of multifunctional MOF-inorganic nanomaterial complexes.
关键词： Core-shell structure,Metal-organic frameworks,Fluorescence switch,Photodynamic therapy
更新于2025-11-21 11:08:12
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Highly sensitive and selective label-free detection of dopamine in human serum based on nitrogen-doped graphene quantum dots decorated on Au nanoparticles: Mechanistic insights through microscopic and spectroscopic studies
摘要： A rapid, facile and label-free sensing strategy is developed for the detection of dopamine (DA) in the real samples by exploiting nitrogen-doped graphene quantum dots (N-GQDs) decorated on Au nanoparticles (Au@N-GQD). The as-grown Au@N-GQD exhibits strong blue fluorescence at room temperature and the fluorescence intensity is drastically quenched in presence of DA in neutral medium. The mechanistic insight into the DA sensing by Au@N-GQDs is explored here by careful monitoring of the evolution of the interaction of Au NPs and N-GQDs with DA under different conditions through electron microscopic and spectroscopic studies. The highly sensitive and selective detection of DA over a wide range is attributed to the unique core-shell structure formation with Au@N-GQD hybrids. The quenching mechanism involves the ground state complex formation as well as electron transfer from N-GQDs. The presence of Au NPs in Au@N-GQD hybrids accelerates the quenching process (~14 fold higher than bare N-GQDs) by the formation of stable dopamine-o-quinone (DQ) in this present detection scheme. The fluorescence quenching follows the linear Stern-Volmer plot in the range 0-100 μM, establishing its efficacy as a fluorescence-based DA sensor with a limit of detection (LOD) 590 nM, which is ~27 fold lower than the lowest abnormal concentration of DA in serum (16 μM). This sensing scheme is also successively applied to trace DA in Brahmaputra river water sample with LOD 480 nM including its satisfactory recovery (95-112%). Our studies reveal a novel sensing pathway for DA through the core-shell structure formation and it is highly promising for the design of efficient biological and environmental sensor.
关键词： Dopamine,Fluorescence quenching,Nitrogen-doped graphene quantum dots,Colorimetric sensing,Core-shell structure,Gold nanoparticles
更新于2025-11-21 11:01:37
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Rapid gas-liquid detonation synthesis of core-shell structural graphite coated TiO2 nanoparticles
摘要： Here we demonstrate a simple, rapid for the controlled synthesis of core-shell structural graphite coated TiO2 nanoparticle (TiO2@G), which are directly prepared by detonation chemical decomposition of the gas-liquid mixture of CH4, O2, C6H6 and TiCl4 in milliseconds. Various techniques, including XPS, TEM, XRD and Raman were employed to investigate the products. It is found that the sphere, good disperse mixed crystal TiO2 nanoparticles with crystal size of 10–30 nm were coated with thick graphite layers. Based on Zeldovich Neuman-Doring (ZND) model, the detonation synthesis mechanism of core-shell structure TiO2@G is discussed. This rapid synthesis method can be extended to the preparation of other core-shell materials.
关键词： Gas-liquid detonation,Graphite coated TiO2,Core-shell structure,Composite materials,Formation mechanism
更新于2025-11-14 17:04:02
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Conductive electrodes based on Ni–graphite core–shell nanoparticles for heterojunction solar cells
摘要： Ni–graphite core–shell nanoparticles (CSNPs), which consisted of Ni nanoparticles (NPs) wrapped with several graphene layers, were grown by the thermal reduction of NiO NPs using H2. The effect of the synthesis temperature (800, 900, 1000, and 1100 °C) on the formation of multilayer graphene shells on the Ni core NPs was investigated to evaluate the structural and electrical characteristics of the particles. The proposed chemical reactions for the formation of Ni NPs can be summarized as follows: formation of liquid Ni by the reduction of NiO, thermal decomposition of the NiO phase, and formation of multilayer graphene shell because of the supersaturation of C in the liquid Ni phase. The resistivity of the electrode pattern fabricated with the Ni–graphite CSNP paste was found to be 6.75 × 10?3 ?·cm. Further, the power conversion efficiency of bulk heterojunction solar cells fabricated with the Ni–graphite CSNPs is higher than that of cells fabricated without the Ni- graphite CSNPs. Thus, our Ni–graphite CSNPs can be employed as a highly efficient electrode material in bulk heterojunction solar cells.
关键词： Thermal reduction,Core–shell structure,Nickel oxide nanoparticle,Graphite,Graphene
更新于2025-11-14 17:04:02
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How to unravel the chemical structure and component localization of individual drug-loaded polymeric nanoparticles by using tapping AFM-IR
摘要： AFM-IR is a photothermal technique that combines AFM and infrared (IR) spectroscopy to unambiguously identify the chemical composition of a sample with tens of nanometer spatial resolution. So far, it has been successfully used in contact mode in a variety of applications. However, the contact mode is unsuitable for soft or loosely adhesive samples such as polymeric nanoparticles (NPs) of less than 200 nm of wide interest for biomedical applications. We describe here the theoretical basis of the innovative tapping AFM-IR mode that can address novel challenges in imaging and chemical mapping. The new method enables gaining information not only on NP morphology and composition, but also reveals drug location and core–shell structures. Whereas up to now the locations of NP components could only be hypothesized, tapping AFM-IR allows accurately visualizing both the location of the NPs’ shells and that of the incorporated drug, pipemidic acid. The preferential accumulation of the drug in the NPs’ top layers was proved, despite its low concentration (<1 wt%). These studies pave the way towards the use of tapping AFM-IR as a powerful tool to control the quality of NP formulations based on individual NP detection and component quantification.
关键词： tapping mode,chemical mapping,core–shell structure,drug localization,polymeric nanoparticles,AFM-IR
更新于2025-11-14 15:18:02
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Efficient near-infrared photocatalysts based on NaYF4:Yb3+,Tm3+@NaYF4:Yb3+,Nd3+@TiO2 core@shell nanoparticles
摘要： In this work, we fabricated NaYF4:Yb3+,Tm3+@NaYF4:Yb3+,Nd3+@TiO2 (Tm@Nd@TiO2) core@shell nanoparticles and investigated their near-infrared (NIR) photocatalytic activities. Comparing to traditional TiO2 based upconversion (UC) photocatalysts (i.e., NaYF4:Yb3+,Tm3+@TiO2, named Tm@TiO2), Tm@Nd@TiO2 exhibits enhanced photocatalytic activity under NIR light irradiation. The photocatalytic activity of Tm@Nd@TiO2 under 980, 808, and 980+808 nm laser irradiation is 4.40, 5.84, and 9.83 times as high as that of Tm@TiO2 under only 980 nm irradiation, respectively. The ethylene degradation rate of Tm@Nd@TiO2 under 980+808 nm laser irradiation is 6.4 times as that of Tm@TiO2. The photocatalytic activity of Tm@Nd@TiO2 under visible+NIR irradiation is even comparable with (~2/3) that under UV light irradiation during Rhodamine B (RhB) degradation. The enhanced photocatalytic activity of Tm@Nd@TiO2 can be attributed to the stronger light absorption in NIR region ascribed to Nd3+, lower water absorption and the enhanced UC emission of Tm@Nd with unique core@shell nanostructures. This work can provide a possible route to improve the NIR photocatalytic activity and stimulate the applications in many other fields.
关键词： upconversion,near-infrared irradiation,photocatalyst,core@shell structure
更新于2025-09-23 15:23:52
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Nano-BaTiO3 phase transition behavior in coated BaTiO3-based dielectric ceramics
摘要： In this work, the phase structure of BaTiO3 nanopowders produced by the alkoxide-hydroxide and the hydrothermal method, respectively, was systemically investigated. BaTiO3 nanopowders with cubic phase produced by the alkoxide-hydroxide method could transform to tetragonal phase when heated to about 1100oC. Cubic to tetragonal phase transformation behavior of BaTiO3 nanopowders coated with 0.3BZT-0.7BT or 0.03Nb2O5-0.01Co2O3 was studied. The internal stress within core-shell structure was proposed to explain the BaTiO3 phase transformation behaviors. The mismatch of thermal expansion coefficient between core and shell plays a crucial role in cubic to tetragonal phase transformation of BaTiO3. By tuning the composition of shell and the ratio of the shell to the core, the cubic BaTiO3 core can transform to tetragonal phase successfully after sintering at 1100oC in BaTiO3 based ceramics with core-shell structure and it is mainly resulted by the reduced internal stress between the shell and core.
关键词： Phase transitions,BaTiO3 nanopowders,Internal stress.,Core-shell structure
更新于2025-09-23 15:23:52
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Core-shell structure of ZnO/Co3O4 composites derived from bimetallic-organic frameworks with superior sensing performance for ethanol gas
摘要： In recent years, metal-organic frameworks (MOFs), especially zeolite-imidazole frameworks (ZIFs), have been attracting widespread attention as templates for the synthesis of sensing materials. Limited researches, however, have been carried out to utilize bimetallic ZIFs in gas sensing, as the existing studies mostly involve mono-metallic ZIFs. Here in, the core-shell structure of ZnO and Co3O4 composite (CS-ZnO/Co3O4) was synthesized via chemical etched to Co/Zn based zeolitic imidazolate framework (Co/Zn-ZIF) with subsequent annealing. The morphology, composition and surface characteristics of the as-obtained samples were confirmed by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscope (TEM) and Brunauer-Emmett-Teller (BET). Moreover, the gas sensing measurements were implemented under various atmospheres. The response of CS-ZnO/Co3O4 sensor to 100 ppm ethanol at 200 °C achieves 38.87, which is 2.8 times that of single-shell ZnO/Co3O4 (SS-ZnO/Co3O4). The improved response is mainly attributed to the core-shell structure, which offers larger surface area, more active sites for gas diffusion and the formation of p-n heterojunction between ZnO and Co3O4.
关键词： Bimetallic-organic framework,Core-shell structure,ZnO/Co3O4,Ethanol gas sensor
更新于2025-09-23 15:23:52
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Enhanced upconversion luminescence intensity of core-shell NaYF4 nanocrystals guided by morphological control
摘要： How to further increase the upconversion luminescence (UCL) efficiency of core-shell upconversion nanoparticles (UCNPs) is highly desirable for their photoelectric and biological applications. Herein, a novel but facile strategy is proposed to substantially enhance the UCL intensity of NaYF4 based core-shell UCNPs by morphological control. The morphologies of core-shell UCNPs can be optimized from rod-like to spherical like by changing the ratio of oleic acid (OA) to 1-octadecene (ODE) during the shell growth process with other reaction conditions constant. The mechanism of shape control is further investigated based on the competitive absorption between OA molecules and lanthanide ions (Y3+, Yb3+, Er3+ or Tm3+) onto the different crystal axes (a, b and c) to guide their shell growth speed. The absolute quantum yields were up to 2.7 % and 1.8 % for spherical and rod like core-shell UCNPs under excitation of 980 nm laser (power density of 1.6 W/cm2), respectively. Moreover, the UCL intensity and effective lifetime (τeff) of Er3+ emission at 541 nm of spherical like core-shell UCNPs increased by 11.7 and 1.82 folds than rod like core-shell UCNPs. Therefore, our designed novel strategy can greatly improve the UCL efficiency of core-shell UCNPs and promote their development in diverse applications.
关键词： upconversion nanoparticles,upconversion luminescence,core-shell structure,morphological control
更新于2025-09-23 15:23:52
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Multifunctional BaTiO <sub/>3</sub> -(Bi <sub/>0.5</sub> Na <sub/>0.5</sub> )TiO <sub/>3</sub> -based MLCC with high energy storage properties and temperature stability
摘要： BaTiO3-(Bi0.5Na0.5)TiO3 (BTBNT)-based multilayer ceramic capacitor (MLCC) chips with the inner electrodes being Ag0.6/Pd0.4 are prepared by a roll-to-roll casting method. The BTBNT-based MLCC chips with ten-dielectric layers can be sintered very well at a low temperature of 1130°C via two step sintering (TSS). X-ray diffraction (XRD) and transmission electron microscope (TEM) results show that MLCC chips are a core-shell structure with two phases coexistence. The core exhibits a tetragonal phase at room temperature and then gradually changes into a cubic phase when the temperature increases above Tc (175°C). While, the shell exhibits a pseudocubic phase at all tested temperature from 25°C to 500°C. BTBNT-based MLCC chips exhibit a broad temperature stability and meet the requirement of Electronic Industries Association (EIA) X9R specifications. In terms of energy storage performance, a large discharge energy density of 3.33 J/cm3 can be obtained at 175°C under the applied electric field of 480 kV/cm. Among all tested temperature ranging from -50°C to 200°C, the energy efficiency of all chips is higher than 80%, even under a high applied electric field. The experimental results indicate that this novel BTBNT-based X9R MLCCs can be one of the most promising candidates for energy storage applications, especially operated in high temperature.
关键词： Energy storage,X9R,Two-step sintering (TSS),Core-shell structure,Multilayer ceramic capacitor (MLCC)
更新于2025-09-23 15:23:52