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Fluoride-based lanthanide-doped nanoparticles (LDNPs) featuring second near-infrared (NIR-II, 1000-1700 nm) downconversion emission for bioimaging have attracted extensive attention. However, conventional LDNPs cannot be degraded and eliminated from organisms because of an inert lattice, which obstructs bioimaging applications. Herein, the core-shell LDNPs of Na3HfF7:Yb,Er@CaF2:Ce,Zr(Hf) [labeled as Zr(Hf)Ce-HC] with pH-selective and tunable degradability were synthesized for dual-modal bioimaging. Notably, the "softening" lattice of the Na3HfF7 matrix and different Zr4+(Hf4+) doping amounts in the shell enable Zr(Hf)Ce-HC with acidity-dependent and tunable degradability. After coating of an optimized Ce3+-doped CaF2:Zr shell, the near-infrared-IIb (NIR-IIb, 1500-1700 nm) luminescence intensity of ZrCe-HC is enhanced by 5.2 times compared with that of Na3HfF7:Yb,Er. The Hf element with high X-ray attenuation allows ZrCe-HC as the contrast agent for computed tomography (CT) bioimaging. The modification of oxidized sodium alginate endows ZrCe-HC with satisfying biocompatibility for NIR-IIb/CT dual-modal bioimaging. These findings would benefit the bioimaging applications of degradable fluoride-based LDNPs.
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Fluoruros , Hafnio , Circonio , Circonio/química , Humanos , Hafnio/química , Fluoruros/química , Nanopartículas/química , Tomografía Computarizada por Rayos X/métodos , Animales , Medios de Contraste/químicaRESUMEN
Efficient data processing is heavily reliant on prioritizing specific stimuli and categorizing incoming information. Within human biological systems, dorsal root ganglions (particularly nociceptors situated in the skin) perform a pivotal role in detecting external stimuli. These neurons send warnings to our brain, priming it to anticipate potential harm and prevent injury. In this study, we explore the potential of using a ferroelectric memristor device structured as a metal-ferroelectric-insulator-semiconductor as an artificial nociceptor. The aim of this device is to electrically receive external damage and interpret signals of danger. The TiN/HfAlOx (HAO)/HfSiOx (HSO)/n+ Si configuration of this device replicates the key functions of a biological nociceptor. The emulation includes crucial aspects, such as threshold reactivity, relaxation, no adaptation, and sensitization phenomena known as "allodynia" and "hyperalgesia." Moreover, we propose establishing a connection between nociceptors and synapses by training the Hebbian learning rule. This involves exposing the device to injurious stimuli and using this experience to enhance its responsiveness, replicating synaptic plasticity.
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Nociceptores , Sinapsis , Sinapsis/fisiología , Nociceptores/fisiología , Humanos , Hafnio/química , SemiconductoresRESUMEN
Field-effect transistor (FET) biosensors based on two-dimensional (2D) materials are highly sought after for their high sensitivity, label-free detection, fast response, and ease of on-chip integration. However, the subthreshold swing (SS) of FETs is constrained by the Boltzmann limit and cannot fall below 60 mV/dec, hindering sensor sensitivity enhancement. Additionally, the gate-leakage current of 2D material biosensors in liquid environments significantly increases, adversely affecting the detection accuracy and stability. Based on the principle of negative capacitance, this paper presents for the first time a two-dimensional material WSe2 negative capacitance field-effect transistor (NCFET) with a minimum subthreshold swing of 56 mV/dec in aqueous solution. The NCFET shows a significantly improved biosensor function. The pH detection sensitivity of the NCFET biosensor reaches 994 pH-1, nearly an order of magnitude higher than that of the traditional two-dimensional WSe2 FET biosensor. The Al2O3/HfZrO (HZO) bilayer dielectric in the NCFET not only contributes to negative capacitance characteristics in solution but also significantly reduces the leakage in solution. Utilizing an enzyme catalysis method, the WSe2 NCFET biosensor demonstrates a specific detection of glucose molecules, achieving a high sensitivity of 4800 A/A in a 5 mM glucose solution and a low detection limit (10-9 M). Further experiments also exhibit the ability of the biosensor to detect glucose in sweat.
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Técnicas Biosensibles , Capacidad Eléctrica , Glucosa , Transistores Electrónicos , Técnicas Biosensibles/instrumentación , Glucosa/análisis , Óxido de Aluminio/química , Hafnio/química , Concentración de Iones de Hidrógeno , ÓxidosRESUMEN
Efficient separation of actinide elements from molten salts employed in pyroprocessing can significantly diminish the radiological hazards and oversight duration associated with spent nuclear fuel storage. The lanthanum content of waste salts is very high compared to actinides, leading to the co-electrodeposition of both groups of elements for conventional electrochemical techniques. Due to the difficulty in separating the two groups of elements, the feasibility of the density-based separation using liquid bismuth and intermetallics was explored. Hafnium was used as a stand-in for actinide elements with physical properties mirroring those of actinide-laden Bi-Hf intermetallics. Conversely, cerium was chosen to represent lanthanides. This study delved into the formation and spatial distribution of bismuth intermetallics under varying concentration ratios and cooling durations. Comprehensive characterization was achieved using scanning electron microscopy and energy-dispersive spectrometry. The analysis showed that Bi-Ce particles were formed and distributed in the upper layer of the Bi ingot, and Bi-(Ce, Hf) particles containing both Ce and Hf in the lower layer. The findings underscore the viability of density-based separation while highlighting the intricacies related to intermetallic coprecipitation. Continued investigations are essential to fully harness the potential of density-based separation.
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Bismuto , Cerio , Cerio/química , Bismuto/química , Hafnio/química , Estudios de Factibilidad , Microscopía Electrónica de RastreoRESUMEN
The artificial nervous system proves the great potential for the emulation of complex neural signal transduction. However, a more bionic system design for bio-signal transduction still lags behind that of physical signals, and relies on additional external sources. Here, this work presents a zero-voltage-writing artificial nervous system (ZANS) that integrates a bio-source-sensing device (BSSD) for ion-based sensing and power generation with a hafnium-zirconium oxide-ferroelectric tunnel junction (HZO-FTJ) for the continuously adjustable resistance state. The BSSD can use ion bio-source as both perception and energy source, and then output voltage signals varied with the change of ion concentrations to the HZO-FTJ, which completes the zero-voltage-writing neuromorphic bio-signal modulation. In view of in/ex vivo biocompatibility, this work shows the precise muscle control of a rabbit leg by integrating the ZANS with a flexible nerve stimulation electrode. The independence on external source enhances the application potential of ZANS in robotics and prosthetics.
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Técnicas Biosensibles , Circonio , Técnicas Biosensibles/instrumentación , Técnicas Biosensibles/métodos , Animales , Circonio/química , Conejos , Hafnio/química , Óxidos/química , Biónica/instrumentación , ElectrodosRESUMEN
Inspired by the favorable impact of heteroatom-containing groups in phenoxy-imine titanium and late transition metal catalysts, a series of novel pyridylamido hafnium catalysts bearing âOMe (Cat-OMe), âCF3 (Cat-CF3), and âC6F5 (Cat-C6F5) substituents are designed and synthesized. Together with the established hafnium catalysts Cat-H and Cat-iPr by Dow/Symyx, these catalysts are applied in the polymerization of α-olefins, including 1-hexene, 1-octene, and 4M1P, as well as in the copolymerization of these α-olefins with a specifically designed polar monomer. The enhancement of polymer molecular weight derived from catalyst modification and the incorporation of polar monomers is discussed in detail. Notably, the new catalysts are all highly active for α-olefins polymerization, with catalyst Cat-CF3 producing isotactic polymers with the highest molecular weight (Mw = 1649 kg mol-1); in copolymerization with polar monomers, catalyst Cat-OMe yields isotactic copolymer with the highest molecular weight (Mw = 2990 kg mol-1). Interestingly, catalyst Cat-C6F5 bearing a âC6F5 group in the N-aryl moiety gives rise to poly(α-olefin) with reduced stereoselectivity. The findings of this study underscore the potential of heteroatom-containing groups in the development of early transition metal catalysts and the synthesis of polymer with novel structures.
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Alquenos , Hafnio , Peso Molecular , Polimerizacion , Polímeros , Hafnio/química , Catálisis , Alquenos/química , Polímeros/química , Polímeros/síntesis química , Estructura MolecularRESUMEN
Herein, we successfully synthesized Hf/Zr co-doping on Fe2O3 nanorod photocatalyst by a hydrothermal process and quenching methods. The synergistic roles of Hf and Zr double-doping on the bacteria inactivation test and decomposition of organic pollutants were investigated in detail for the 1 wt% CoOx loaded Hf/Zr-Fe2O3 NRs and CuOx/CoOx loaded Hf/Zr-Fe2O3 NRs photocatalyst. Initially, the rod-like porous morphology of the Hf/Zr-doped Fe2O3 NRs was produced via a hydrothermal method at various Hf co-doping (0, 2, 4, 7 and 10)%. Further, CoOx and CuOx loaded by a wet impregnation approach on the Hf/Zr-Fe2O3 NRs and a highly photoactive Hf(4)/Zr-Fe2O3 [CoOx/CuOx] NRs photocatalyst were developed. After the Hf(4)/Zr-Fe2O3 [CoOx/CuOx] NRs photocatalyst treatment, the Bio-TEM imagery of bacterial cells showed extensive morphological deviations in cell membranes. Hf(4)/Zr-Fe2O3 NR achieved 84.1% orange II degradation upon 3 h illumination, which is higher than that of Hf-Fe2O3 and Zr-Fe2O3 (68.7 and 73.5%, respectively). Additionally, the optimum sample, Hf(4)/Zr-Fe2O3 [CoOx/CuOx] photocatalyst, exhibited 95.5% orange II dye degradation after light radiation for 3 h. Optimized Hf(4)/Zr-Fe2O3 [CoOx/CuOx] catalysts exhibited 99.9% and 99.7% inactivation of E. coli and S. aureus with 120 min, respectively. Further, scavenger experiments revealed that the electrons are the primary responsible species for photocatalytic kinetics. This work will provide a rapid method for the development of high photocatalytic performance materials for bacterial disinfection and organic degradation.
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Antibacterianos , Cobre , Compuestos Férricos , Nanotubos , Circonio , Circonio/química , Antibacterianos/química , Antibacterianos/farmacología , Catálisis , Nanotubos/química , Compuestos Férricos/química , Cobre/química , Cobre/farmacología , Hafnio/química , Óxidos/química , Cobalto/química , Procesos FotoquímicosRESUMEN
Metal-organic frameworks (MOFs) are porous materials with potential in biomedical applications such as sensing, drug delivery, and radiosensitization. However, how to tune the properties of the MOFs for such applications remains challenging. Herein, we synthesized two MOFs, Zr-PEB and Hf-PEB. Zr-PEB can be classified as porous interpenetrated zirconium frameworks (PIZOFs) and Hf-PEB is its analogue. We controlled their sizes while maintaining their crystal structure by employing a coordination modulation strategy. They were designed to serve as sensitizer for X-ray therapy and as potential drug carriers. Comprehensive characterizations of the MOFs' properties have been conducted, and the in vitro biological impacts have been studied. Since viability assay showed that Hf-PEB was more biocompatible compared to Zr-PEB, the cellular uptake of Hf-PEB by cells was evaluated using both fluorescence microscopy and soft X-ray tomography (SXT), and the three-dimensional structure of Hf-PEB in cells was observed. The results revealed the potential of Zr-PEB and Hf-PEB as nanomaterials for biomedical applications and demonstrated that SXT is an effective tool to assist the development of such materials.
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Estructuras Metalorgánicas , Circonio , Estructuras Metalorgánicas/química , Estructuras Metalorgánicas/síntesis química , Circonio/química , Humanos , Tomografía por Rayos X , Porosidad , Supervivencia Celular/efectos de los fármacos , Hafnio/química , Tamaño de la Partícula , Propiedades de Superficie , Materiales Biocompatibles/química , Materiales Biocompatibles/síntesis química , Materiales Biocompatibles/farmacologíaRESUMEN
BACKGROUND: An international multidisciplinary panel of experts aimed to provide consensus guidelines describing the optimal intratumoral and intranodal injection of NBTXR3 hafnium oxide nanoparticles in head and neck squamous cell carcinoma (HNSCC) of the oral cavity, oropharynx, and cervical lymph nodes and to review data concerning safety, feasibility, and procedural aspects of administration. METHODS: The Delphi method was used to determine consensus. A 4-member steering committee and a 10-member monitoring committee wrote and revised the guidelines, divided into eight sections. An independent 3-member reading committee reviewed the recommendations. RESULTS: After two rounds of voting, strong consensus was obtained on all recommendations. Intratumoral and intranodal injection was deemed feasible. NBTXR3 volume calculation, choice of patients, preparation and injection procedure, potential side effects, post injection, and post treatment follow-up were described in detail. CONCLUSIONS: Best practices for the injection of NBTXR3 were defined, thus enabling international standardization of intratumoral nanoparticle injection.
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Neoplasias de Cabeza y Cuello , Inyecciones Intralesiones , Carcinoma de Células Escamosas de Cabeza y Cuello , Humanos , Neoplasias de Cabeza y Cuello/terapia , Carcinoma de Células Escamosas de Cabeza y Cuello/terapia , Técnica Delphi , Hafnio/administración & dosificación , Óxidos/administración & dosificación , Nanopartículas/administración & dosificación , Masculino , Consenso , Femenino , Carcinoma de Células Escamosas/terapia , Carcinoma de Células Escamosas/patología , Guías de Práctica Clínica como AsuntoRESUMEN
This research aimed to compare the quantitative imaging attributes of synthesized hafnium oxide nanoparticles (NPs) derived from UiO-66-NH2(Hf) and two gadolinium- and iodine-based clinical contrast agents (CAs) using cylindrical phantom. Aqueous solutions of the studied CAs, containing 2.5, 5, and 10 mg/mL of HfO2NPs, gadolinium, and iodine, were prepared. Constructed within a cylindrical phantom, 15 cc small tubes were filled with CAs. Maintaining constant mAs, the phantom underwent scanning at tube voltage variations from 80 to 140 kVp. The CT numbers were quantified in Hounsfield units (HU), and the contrast-to-noise ratios (CNR) were calculated within delineated regions of interest (ROI) for all CAs. The HfO2NPs at 140 kVp and concentration of 2.5 mg/ml exhibited 2.3- and 1.3-times higher CT numbers than iodine and gadolinium, respectively. Notably, gadolinium consistently displayed higher CT numbers than iodine across all exposure techniques and concentrations. At the highest tube potential, the maximum amount of the CAs CT numbers was attained, and at 140 kVp and concentration of 2.5 mg/ml of HfO2NPs the CNR surpassed iodine by 114%, and gadolinium by 30%, respectively. HfO2NPs, as a contrast agent, demonstrated superior image quality in terms of contrast and noise in comparison to iodine- and gadolinium-based contrast media, particularly at higher energies of X-ray in computed tomography. Thus, its utilization is highly recommended in CT.
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Medios de Contraste , Hafnio , Nanopartículas , Óxidos , Fantasmas de Imagen , Tomografía Computarizada por Rayos X , Medios de Contraste/química , Óxidos/química , Hafnio/química , Nanopartículas/química , Gadolinio/química , Yodo/química , Relación Señal-RuidoRESUMEN
Precise diagnosis of complex and soft tumors is challenging, which limits appropriate treatment options to achieve desired therapeutic outcomes. However, multifunctional nano-sized contrast enhancement agents based on nanoparticles improve the diagnosis accuracy of various diseases such as cancer. Herein, a facile manganese-hafnium nanocomposites (Mn3O4-HfO2 NCs) system was designed for bimodal magnetic resonance imaging (MRI)/computed tomography (CT) contrast enhancement with a complimentary function of photodynamic therapy. The solvothermal method was used to fabricate NCs, and the average size of Mn3O4 NPs and Mn3O4-HfO2 NCs was about 7â¯nm and 15â¯nm, respectively, as estimated by TEM. Dynamic light scattering results showed good dispersion and high negative (-33â¯eV) zeta potential, indicating excellent stability in an aqueous medium. Mn3O4-HfO2 NCs revealed negligible toxic effects on the NCTC clone 929 (L929) and mouse colon cancer cell line (CT26), demonstrating promising biocompatibility. The synthesized Mn3O4-HfO2 NCs exhibit significant enhancement in T1-weighted magnetic resonance imaging (MRI) and X-ray computed tomography (CT), indicating the appropriateness for dual-modal MRI/CT molecular imaging probes. Moreover, ultra-small Mn3O4-HfO2 NCs show good relaxivities for MRI/CT. These nanoprobes Mn3O4-HfO2 NCs further possessed outstanding reactive oxygen species (ROS) generation ability under minute ultraviolet light (6â¯mW·cm-2) to ablate the colon cancer cells in vitro. Therefore, the designed multifunctional Mn3O4-HfO2 NCs were ideal candidates for cancer diagnosis and photodynamic therapy.
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Neoplasias del Colon , Nanocompuestos , Nanopartículas , Fotoquimioterapia , Ratones , Animales , Manganeso , Hafnio , Imagen por Resonancia Magnética , Tomografía Computarizada por Rayos X , Neoplasias del Colon/diagnóstico por imagen , Neoplasias del Colon/tratamiento farmacológicoRESUMEN
Upconversion (UC)/downconversion (DC)-luminescent lanthanide-doped nanocrystals (LDNCs) with near-infrared (NIR, 650-1700 nm) excitation have been gaining increasing popularity in bioimaging. However, conventional NIR-excited LDNCs cannot be degraded and eliminated eventually in vivo owing to intrinsic "rigid" lattices, thus constraining clinical applications. A biodegradability-tunable heterogeneous core-shell-shell luminescent LDNC of Na3HfF7:Yb,Er@Na3ZrF7:Yb,Er@CaF2:Yb,Zr (abbreviated as HZC) was developed and modified with oxidized sodium alginate (OSA) for multimode bioimaging. The dynamic "soft" lattice-Na3Hf(Zr)F7 host and the varying Zr4+ doping content in the outmoster CaF2 shell endowed HZC with tunable degradability. Through elaborated core-shell-shell coating, Yb3+/Er3+-coupled UC red and green and DC second near-infrared (NIR-II) emissions were, respectively, enhanced by 31.23-, 150.60-, and 19.42-fold when compared with core nanocrystals. HZC generated computed tomography (CT) imaging contrast effects, thus enabling NIR-II/CT/UC trimodal imaging. OSA modification not only ensured the exemplary biocompatibility of HZC but also enabled tumor-specific diagnosis. The findings would benefit the clinical imaging translation of LDNCs.
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Elementos de la Serie de los Lantanoides , Nanopartículas , Hafnio , Circonio , Nanopartículas/química , Tomografía Computarizada por Rayos XRESUMEN
cGAS-STING signaling plays a critical role in radiotherapy (RT)-mediated immunomodulation. However, RT alone is insufficient to sustain STING activation in tumors under a safe X-ray dose. Here, we propose a radiosensitization cooperated with cGAS stimulation strategy by engineering a core-shell structured nanosized radiosensitizer-based cGAS-STING agonist, which is constituted with the hafnium oxide (HfO2) core and the manganese oxide (MnO2) shell. HfO2-mediated radiosensitization enhances immunogenic cell death to afford tumor associated antigens and adequate cytosolic dsDNA, while the GSH-degradable MnO2 sustainably releases Mn2+ in tumors to improve the recognition sensitization of cGAS. The synchronization of sustained Mn2+ supply with cumulative cytosolic dsDNA damage synergistically augments the cGAS-STING activation in irradiated tumors, thereby enhancing RT-triggered local and system effects when combined with an immune checkpoint inhibitor. Therefore, the synchronous radiosensitization with sustained STING activation is demonstrated as a potent immunostimulation strategy to optimize cancer radio-immuotherapy.
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Hafnio , Compuestos de Manganeso , Neoplasias , Humanos , Compuestos de Manganeso/farmacología , Óxidos/farmacología , Óxidos/uso terapéutico , Inmunoterapia , Neoplasias/tratamiento farmacológico , Neoplasias/radioterapia , NucleotidiltransferasasRESUMEN
A significant amount of progress in nanotechnology has been made due to the development of engineered nanoparticles. The use of metallic nanoparticles for various biomedical applications has been extensively investigated. Biomedical research is highly focused on them because of their inert nature, nanoscale structure, and similar size to many biological molecules. The intrinsic characteristics of these particles, including electronic, optical, physicochemical, and surface plasmon resonance, that can be altered by altering their size, shape, environment, aspect ratio, ease of synthesis, and functionalization properties, have led to numerous biomedical applications. Targeted drug delivery, sensing, photothermal and photodynamic therapy, and imaging are some of these. The promising clinical results of NBTXR3, a high-Z radiosensitizing nanomaterial derived from hafnium, have demonstrated translational potential of this metal. This radiosensitization approach leverages the dependence of energy attenuation on atomic number to enhance energy-matter interactions conducive to radiation therapy. High-Z nanoparticle localization in tumor issue differentially increases the effect of ionizing radiation on cancer cells versus nearby healthy ones and mitigates adverse effects by reducing the overall radiation burden. This principle enables material multifunctionality as contrast agents in X-ray-based imaging. The physiochemical properties of hafnium (Z = 72) are particularly advantageous for these applications. A well-placed K-edge absorption energy and high mass attenuation coefficient compared to elements in human tissue across clinical energy ranges leads to significant attenuation. Chemical reactivity allows for variety in nanoparticle synthesis, composition, and functionalization. Nanoparticles such as hafnium oxide exhibit excellent biocompatibility due to physiochemical inertness prior to incidence with ionizing radiation. Additionally, the optical and electronic properties are applicable in biosensing, optical component coatings, and semiconductors. The wide interest has prompted extensive research in design and synthesis to facilitate property fine-tuning. This review summarizes synthetic methods for hafnium-based nanomaterials and applications in therapy, imaging, and biosensing with a mechanistic focus. A discussion and future perspective section highlights clinical progress and elaborates on current challenges. By focusing on factors impacting applicational effectiveness and examining limitations this review aims to support researchers and expedite clinical translation of future hafnium-based nanomedicine.
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Nanopartículas del Metal , Nanoestructuras , Neoplasias , Humanos , Hafnio/química , Nanoestructuras/uso terapéutico , Nanoestructuras/química , Nanopartículas del Metal/uso terapéutico , Nanopartículas del Metal/química , Neoplasias/tratamiento farmacológico , MetalesRESUMEN
Oligo-astheno-teratozoospermia (OAT) is a global public health problem, which affects 30% men of childbearing age. Meanwhile, with the rapid development of industry and economy, the contents of rare earth elements (REEs) in the environment are increasing. However, little is known about the associations between REEs levels and OAT risk. To evaluate the associations between the levels of four REEs (samarium (Sm), hafnium (Hf), tungsten (W), rhenium (Re)) in seminal plasma and OAT risk, from October 2021 to November 2022, semen samples from 924 men of childbearing age (460 controls and 464 cases) were collected from the reproductive center of the First Affiliated Hospital of Anhui Medical University. Inductively coupled plasma-mass spectrometry (ICP-MS) was used to measure the levels of Sm, Hf, Re and W in seminal plasma. Bayesian kernel machine regression (BKMR) was conducted to explore the joint effects of levels of four REEs in seminal plasma on the risk of OAT and select the one exerting a major role; generalized linear regression models (GLM) with log link function were employed to investigate the association of every REE level in seminal plasma and OAT risk; sankey diagram and linear regression models were utilized to describe the associations between the levels of four REEs and the indexes of sperm quality. The levels of four REEs in seminal plasma were higher in the case group than levels in the control group (pSm = 0.011, pHf = 0.040, pW = 0.062, pRe = 0.001, respectively). In BKMR analysis, the OAT risk increased when the overall levels of four REEs were higher than their 55th percentile compared to all of them at their 50th percentile, and Re level played a major role in the association. Additionally, Re level in seminal plasma was positively associated with the OAT risk in the single element model after adjustment of covariates (medium vs. low: OR (95% CI) = 1.55 (1.10, 2.18); high vs. low: OR (95% CI) = 1.69 (1.18, 2.42)). Lastly, the sankey diagram and linear regression models revealed that Sm level was negatively associated with the PR%, total sperm count and total progressively motile sperm count; Hf level was negatively associated with the PR%; W and Re levels were negatively associated with the PR% and total motility, and Re level was positively associated with abnormal morphology rate. Men of childbearing age with OAT had higher levels of Sm, Hf and Re in seminal plasma than those in the control group. An increasing trend for the OAT risk was observed with an increase in mixture levels of Sm, Hf, W and Re, and Re exposure level played a major role in the association whether in BKMR model or single element model. Additionally, the levels of these four REEs were negatively associated with the indexes of sperm quality.
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Metales de Tierras Raras , Renio , Humanos , Masculino , Femenino , Semen , Samario , Tungsteno , Hafnio/análisis , Hafnio/farmacología , Teorema de Bayes , Espermatozoides , Metales de Tierras Raras/análisis , Motilidad EspermáticaRESUMEN
X-ray-induced radiodynamic therapy (RDT) that can significantly reduce radiation dose with an improved anticancer effect has emerged as an attractive and promising therapeutic modality for tumors. However, it is highly significant to develop safe and efficient radiosensitizing agents for tumor radiation therapy. Herein, we present a smart nanotheranostic system FA-Au-CH that consists of gold nanoradiosensitizers, photosensitizer chlorin e6 (Ce6), and folic acid (FA) as a folate-receptor-targeting ligand for improved tumor specificity. FA-Au-CH nanoparticles have been demonstrated to be able to simultaneously serve as radiosensitizers and RDT agents for enhanced computed tomography (CT) imaging-guided radiotherapy (RT) of colon carcinoma, owing to the strong X-ray attenuation capability of high-Z elements Au and Hf, as well as the characteristics of Hf that can transfer radiation energy to Ce6 to generate ROS from Ce6 under X-ray irradiation. The integration of RT and RDT in this study demonstrates great efficacy and offers a promising therapeutic modality for the treatment of malignant tumors.
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Carcinoma , Neoplasias del Colon , Fotoquimioterapia , Porfirinas , Fármacos Sensibilizantes a Radiaciones , Humanos , Porfirinas/uso terapéutico , Hafnio , Oro , Neoplasias del Colon/diagnóstico por imagen , Neoplasias del Colon/radioterapia , Fármacos Sensibilizantes a Radiaciones/farmacología , Fármacos Sensibilizantes a Radiaciones/uso terapéutico , Línea Celular TumoralRESUMEN
In this study, novel stannous oxide@hafnium carbide (SnO@HfC) nanocomposite was successfully manufactured by an appropriate hydrothermal scheme which was utilized for the photocatalytic degradation of BPA by stimulation of peroxymonosulfate (PMS) and self-cleaning application. Numerous methods were applied for the characterization of photocatalyst and demonstrated the successful preparation of SnO@HfC nanocomposite. The crystal structures, band structures and density of states for SnO and HfC were explored by DFT analysis. The amazing PMS stimulation performance of SnO@HfC nanocomposite originated from the establishment of a heterojunction, which led to the enhancement of the light response aptitude and the electron conduction competence of the composite. BPA was degraded by 0.75 g/L PMS and SnO@HfC at neutral pH during the period of 60 min. In order to identify active groups in the reaction procedure, quenching experiments and electron paramagnetic resonance (EPR) approaches were also used. In the subsequent active species scavenging assays, where sulfate radicals, hydroxyl radicals, holes, and superoxide radicals were engaged in the degradation of BPA. While, liquid phase mass spectrometry (LC-MS) was used to pinpoint the intermediate metabolites in the course of degradation. SnO@HfC/PMS/light system delivered excellent TOC removal efficiency and less ions leaching. The SnO@HfC nanocomposite proved good durability and reusability in continuous cycle tests along with excellent self-cleaning function on the glass substrate. The SnO@HfC nanocomposite performs admirably in terms of self-cleaning application. The SnO@HfC nanocomposite is expected to be used in the future for the treatment of wastewater that contains pharmaceuticals due to its superior stability and reusability after five consecutive cycles.
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Hafnio , Peróxidos , SuperóxidosRESUMEN
Photothermal therapy (PTT) effectively suppresses tumor growth with high selectivity. Nevertheless, PTT may cause an inflammatory response that leads to tumor recurrence and treatment resistance, which are the main disadvantages of PTT. Herein, monodisperse hafnium carbide nanoparticles (HfC NPs) were successfully prepared for noninflammatory PTT of cancer. HfC NPs possessed satisfactory near-infrared (NIR) absorption, good photothermal conversion efficiency (PTCE, 36.8 %) and photothermal stability. Furthermore, holding large surface areas and intrinsic redox-active sites, HfC NPs exhibited excellent anti-inflammatory properties due to their antioxidant and superoxide dismutase (SOD) enzymatic activities. In vitro and in vivo experiments confirmed that HfC NPs converted light energy into heat energy upon NIR laser irradiation to kill cancer cells through PTT and achieved a better therapeutic effect by anti-inflammatory effects after PTT. This work highlights that multifunctional HfC NPs can be applied in noninflammatory PTT with outstanding safety and efficacy.
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Nanopartículas , Neoplasias , Humanos , Terapia Fototérmica , Hafnio , Fototerapia , Nanopartículas/química , Neoplasias/terapia , Línea Celular TumoralRESUMEN
When consumed, excess progesterone (P4)âfound in food and the environmentâcan lead to severe illnesses in humans. Therefore, quantitative analysis of P4 is critical for identifying its hazardous levels. In this study, a novel signal "on-amplified-off" P4 detection mode was proposed, which was based on the utilization of hafnium oxide (HfO2) as a unique electrochemiluminescence (ECL) emitter, produced by calcining UiO-66(Hf). This is the first time that HfO2 has been used as an ECL emitter. HfO2 displayed excellent conductivity and a high specific surface area, allowing it to connect with numerous aptamers and produce a "signal-on" effect. Ni-doped ZnO (Ni-ZnO) acted as a coreaction accelerator, enhancing the ECL strength of HfO2 by generating more tripropylamine radicals. cDNA was labeled with Ni-ZnO, and Ni-ZnO was linked to the aptamer via base complementary pairing, affording "signal-amplified". The presence of the target molecule P4 instigated a specific binding process with the aptamer, triggering the shedding of cDNA-Ni-ZnO and resulting in "signal-off". This novel "on-amplified-off" strategy effectively improved the sensitivity and specificity of P4 analysis, introducing a practical method for detecting biomolecules beyond the scope of this study, which holds immense potential for future applications.
Asunto(s)
Técnicas Biosensibles , Nanopartículas del Metal , Nanoestructuras , Óxido de Zinc , Humanos , Progesterona , Nanopartículas del Metal/química , ADN Complementario , Hafnio , Mediciones Luminiscentes/métodos , Nanoestructuras/química , Técnicas Biosensibles/métodos , Técnicas Electroquímicas/métodos , Límite de DetecciónRESUMEN
Radiotherapy (RT) is an extensively used strategy for cancer treatment, but its therapeutic effect is usually limited by the abnormal tumor microenvironment (TME) and it lacks the ability to control tumor metastases. In this work, a nanoscale coordination polymer, Hf-nIm@PEG (HNP), is prepared by the coordination of hafnium ions (Hf4+ ) with 2-nitroimidazole (2-nIm), and then modified with lipid bilayers containing poly(ethylene glycol) (PEG). Under low-dose X-ray irradiation, on the one hand, Hf4+ with high computed tomography signal enhancement ability can deposit radiation energy to induce DNA damage, and on the other hand, NO can be persistently released from 2-nIm, which can not only directly react with the radical DNA to prevent the repair of damaged DNA but also relieves the hypoxic immunosuppressive TME to sensitize radiotherapy. Additionally, NO can also react with superoxide ions to generate reactive nitrogen species (RNS) to induce cell apoptosis. More interestingly, it is discovered that Hf4+ can effectively activate the cyclic-di-GMP-AMP synthase (cGAS)-stimulator of interferon genes (STING) pathway to promote the immune responses induced by radiotherapy. Thus, this work presents a simple but multifunctional nanoscale coordination polymer to deposit radiation energy, trigger the release of NO, modulate the TME, activate the cGAS-STING pathway, and finally realize synergistic radio-immunotherapy.