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1.
Nanomedicine (Lond) ; 19(13): 1133-1144, 2024.
Article in English | MEDLINE | ID: mdl-39302476

ABSTRACT

Aim: Radiotherapy employs high-energy ionizing radiation to inflict DNA damage on cancer cells, thereby causing their demise. However, this procedure can inadvertently harm healthy tissue. Thus, this study aimed to develop biodegradable radiosensitizers that counteract these adverse effects by enhancing the radiation sensitivity of tumor cells and safeguarding normal cells.Materials & methods: A biodegradable radiosensitizer was engineered by incorporating hafnium ions (Hf) into calcium carbonate (CaCO3) nanoparticles via a chemical precipitation technique, resulting in the formation of Hf:CaCO3 nanoparticles.Results & conclusion: Our findings demonstrate that Hf:CaCO3 nanoparticles exhibit pH-dependent solubility and can augment the efficacy of radiotherapy in treating cancer cells. This research underscores the potential of Hf:CaCO3 nanoparticles as a dual-modality radiosensitizer in radiotherapy.


Radiotherapy is a common cancer treatment that uses high-energy rays to kill cancer cells. However, it can also harm healthy cells. To protect healthy cells and make the treatment more effective, we use something called radiosensitizers. In our study, we made a new kind of radiosensitizer using hafnium ions (Hf) and CaCO3 nanoparticles. We made these nanoparticles using a method called chemical precipitation. Our tests showed that these nanoparticles are safe for the body and can make radiotherapy more effective against cancer cells, which could be a useful tool in cancer treatment.


Subject(s)
Calcium Carbonate , Hafnium , Nanoparticles , Radiation-Sensitizing Agents , Radiation-Sensitizing Agents/chemistry , Radiation-Sensitizing Agents/pharmacology , Calcium Carbonate/chemistry , Humans , Nanoparticles/chemistry , Hafnium/chemistry , Cell Line, Tumor , Cell Survival/drug effects , Hydrogen-Ion Concentration , Neoplasms/radiotherapy , Neoplasms/drug therapy
2.
Nanoscale ; 16(38): 17893-17907, 2024 Oct 03.
Article in English | MEDLINE | ID: mdl-39253754

ABSTRACT

Hafnium nitride nanoparticles (HfN NPs) can offer appealing plasmonic properties at the nanoscale, but the fabrication of stable water-dispersible solutions of non-toxic HfN NPs exhibiting plasmonic features in the window of relative biological transparency presents a great challenge. Here, we demonstrate a solution to this problem by employing ultrashort (femtosecond) laser ablation from a HfN target in organic solutions, followed by a coating of the formed NPs with polyethylene glycol (PEG) and subsequent dispersion in water. We show that the fabricated NPs exhibit plasmonic absorption bands with maxima around 590 nm, 620 nm, and 650 nm, depending on the synthesis environment (ethanol, acetone, and acetonitrile, respectively), which are largely red-shifted compared to what is expected from pure HfN NPs. The observed shift is explained by including nitrogen-deficient hafnium nitride and hafnium oxynitride phases inside the core and oxynitride coating of NPs, as follows from a series of structural characterization studies. We then show that the NPs can provide a strong photothermal effect under 808 nm excitation with a photothermal conversion coefficient of about 62%, which is comparable to the best values reported for plasmonic NPs. MTT and clonogenic assays evidenced very low cytotoxicity of PEG-coated HfN NPs to cancer cells from different tissues up to 100 µg mL-1 concentrations. We finally report a strong photothermal therapeutic effect of HfN NPs, as shown by 100% cell death under 808 nm light irradiation at NP concentrations lower than 25 µg mL-1. Combined with additional X-ray theranostic functionalities (CT scan and photon capture therapy) profiting from the high atomic number (Z = 72) of Hf, plasmonic HfN NPs promise the development of synergetically enhanced modalities for cancer treatment.


Subject(s)
Hafnium , Lasers , Nanoparticles , Photothermal Therapy , Polyethylene Glycols , Humans , Nanoparticles/chemistry , Nanoparticles/therapeutic use , Polyethylene Glycols/chemistry , Hafnium/chemistry , Cell Line, Tumor , Cell Survival/drug effects
3.
Nano Lett ; 24(37): 11738-11746, 2024 Sep 18.
Article in English | MEDLINE | ID: mdl-39229926

ABSTRACT

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.


Subject(s)
Fluorides , Hafnium , Zirconium , Zirconium/chemistry , Humans , Hafnium/chemistry , Fluorides/chemistry , Nanoparticles/chemistry , Tomography, X-Ray Computed/methods , Animals , Contrast Media/chemistry
4.
J Chem Phys ; 161(8)2024 Aug 28.
Article in English | MEDLINE | ID: mdl-39185849

ABSTRACT

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.


Subject(s)
Nociceptors , Synapses , Synapses/physiology , Nociceptors/physiology , Humans , Hafnium/chemistry , Semiconductors
5.
ACS Appl Mater Interfaces ; 16(32): 42597-42607, 2024 Aug 14.
Article in English | MEDLINE | ID: mdl-39102741

ABSTRACT

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.


Subject(s)
Biosensing Techniques , Electric Capacitance , Glucose , Transistors, Electronic , Biosensing Techniques/instrumentation , Glucose/analysis , Aluminum Oxide/chemistry , Hafnium/chemistry , Hydrogen-Ion Concentration , Oxides
6.
Chemosphere ; 363: 142882, 2024 Sep.
Article in English | MEDLINE | ID: mdl-39025315

ABSTRACT

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.


Subject(s)
Bismuth , Cerium , Cerium/chemistry , Bismuth/chemistry , Hafnium/chemistry , Feasibility Studies , Microscopy, Electron, Scanning
7.
Adv Mater ; 36(32): e2404026, 2024 Aug.
Article in English | MEDLINE | ID: mdl-38762756

ABSTRACT

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.


Subject(s)
Biosensing Techniques , Zirconium , Biosensing Techniques/instrumentation , Biosensing Techniques/methods , Animals , Zirconium/chemistry , Rabbits , Hafnium/chemistry , Oxides/chemistry , Bionics/instrumentation , Electrodes
8.
Macromol Rapid Commun ; 45(16): e2400204, 2024 Aug.
Article in English | MEDLINE | ID: mdl-38751341

ABSTRACT

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 ─OMe (Cat-OMe), ─CF3 (Cat-CF3), and ─C6F5 (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 ─C6F5 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.


Subject(s)
Alkenes , Hafnium , Molecular Weight , Polymerization , Polymers , Hafnium/chemistry , Catalysis , Alkenes/chemistry , Polymers/chemistry , Polymers/chemical synthesis , Molecular Structure
9.
J Mater Chem B ; 12(25): 6079-6090, 2024 Jun 27.
Article in English | MEDLINE | ID: mdl-38727406

ABSTRACT

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.


Subject(s)
Metal-Organic Frameworks , Zirconium , Metal-Organic Frameworks/chemistry , Metal-Organic Frameworks/chemical synthesis , Zirconium/chemistry , Humans , Tomography, X-Ray , Porosity , Cell Survival/drug effects , Hafnium/chemistry , Particle Size , Surface Properties , Biocompatible Materials/chemistry , Biocompatible Materials/chemical synthesis , Biocompatible Materials/pharmacology
10.
Chemosphere ; 360: 142450, 2024 Jul.
Article in English | MEDLINE | ID: mdl-38801902

ABSTRACT

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.


Subject(s)
Anti-Bacterial Agents , Copper , Ferric Compounds , Nanotubes , Zirconium , Zirconium/chemistry , Anti-Bacterial Agents/chemistry , Anti-Bacterial Agents/pharmacology , Catalysis , Nanotubes/chemistry , Ferric Compounds/chemistry , Copper/chemistry , Copper/pharmacology , Hafnium/chemistry , Oxides/chemistry , Cobalt/chemistry , Photochemical Processes
11.
Radiol Phys Technol ; 17(2): 441-450, 2024 Jun.
Article in English | MEDLINE | ID: mdl-38630390

ABSTRACT

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.


Subject(s)
Contrast Media , Hafnium , Nanoparticles , Oxides , Phantoms, Imaging , Tomography, X-Ray Computed , Contrast Media/chemistry , Oxides/chemistry , Hafnium/chemistry , Nanoparticles/chemistry , Gadolinium/chemistry , Iodine/chemistry , Signal-To-Noise Ratio
12.
ACS Nano ; 18(2): 1289-1324, 2024 Jan 16.
Article in English | MEDLINE | ID: mdl-38166377

ABSTRACT

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.


Subject(s)
Metal Nanoparticles , Nanostructures , Neoplasms , Humans , Hafnium/chemistry , Nanostructures/therapeutic use , Nanostructures/chemistry , Metal Nanoparticles/therapeutic use , Metal Nanoparticles/chemistry , Neoplasms/drug therapy , Metals
13.
Sci Rep ; 13(1): 7698, 2023 05 11.
Article in English | MEDLINE | ID: mdl-37169783

ABSTRACT

We report on the results of a numerical investigation into a phase transition material and hafnium (IV) oxide-based refractive index sensor with a wide spectral range, including both the visible and infrared regions of the electromagnetic spectrum. The sensor relies on hafnium (IV) oxide and a phase transition material (HfO2). Three layered versions of the proposed structure are studied; each configuration is built from alternating layers of HfO2, silica, Ge2Sb2Te5(GST), and silver. The three different arrangements have all been studied. The reflectance response of such multilayer structures is discussed in this manuscript for refractive indices ranging from 1 to 2.4. In addition, we have investigated how the varying heights of the materials affect the overall performance of the structure. Finally, we have supplied several formulae for resonating traces that may be used to calculate the sensing behaviour across a specific wavelength range and refractive index values. The corresponding equations are shown below. We have computed numerous equation traces throughout this inquiry to calculate the wavelength and refractive index values. Computational methods may be used to analyze the proposed structure, which might aid in creating biosensors for detecting a wide variety of biomolecules and biomarkers, such as saliva-cortisol, urine, glucose, cancerous and cancerous, and hemoglobin.


Subject(s)
Biosensing Techniques , Hafnium , Hafnium/chemistry , Oxides/chemistry , Hemoglobins
14.
Small ; 19(32): e2300341, 2023 08.
Article in English | MEDLINE | ID: mdl-37029564

ABSTRACT

With the rapid development of nanotechnology and nanomedicine, there are great interests in employing nanomaterials to improve the efficiency of disease diagnosis and treatment. The clinical translation of hafnium oxide (HfO2 ), commercially namedas NBTXR3, as a new kind of nanoradiosensitizer for radiotherapy (RT) of cancers has aroused extensive interest in researches on Hf-based nanomaterials for biomedical application. In the past 20 years, Hf-based nanomaterials have emerged as potential and important nanomedicine for computed tomography (CT)-involved bioimaging and RT-associated cancer treatment due to their excellent electronic structures and intrinsic physiochemical properties. In this review, a bibliometric analysis method is employed to summarize the progress on the synthesis technology of various Hf-based nanomaterials, including HfO2 , HfO2 -based compounds, and Hf-organic ligand coordination hybrids, such as metal-organic frameworks or nanoscaled coordination polymers. Moreover, current states in the application of Hf-based CT-involved contrasts for tissue imaging or cancer diagnosis are reviewed in detail. Importantly, the recent advances in Hf-based nanomaterials-mediated radiosensitization and synergistic RT with other current mainstream treatments are also generalized. Finally, current challenges and future perspectives of Hf-based nanomaterials with a view to maximize their great potential in the research of translational medicine are also discussed.


Subject(s)
Antineoplastic Agents , Nanostructures , Neoplasms , Humans , Hafnium/chemistry , Nanostructures/chemistry , Neoplasms/diagnostic imaging , Neoplasms/therapy , Nanotechnology/methods
15.
Angew Chem Int Ed Engl ; 62(22): e202217374, 2023 05 22.
Article in English | MEDLINE | ID: mdl-36988087

ABSTRACT

To increase the red blood cell (RBC) cryopreservation efficiency by metal-organic frameworks (MOFs), a dimensional reduction approach has been proposed. Namely, 3D MOF nanoparticles are progressively reduced to 2D ultra-thin metal-organic layers (MOLs). We found that 2D MOLs are beneficial for enhanced interactions of the interfacial hydrogen-bonded water network and increased utilization of inner ordered structures, due to the higher surface-to-volume ratio. Specifically, a series of hafnium (Hf)-based 2D MOLs with different thicknesses (monolayer to stacked multilayers) and densities of hydrogen bonding sites have been synthesized. Both ice recrystallization inhibition activity (IRI) and RBCs cryopreservation assay confirm the pronounced better IRI activity and excellent cell recovery efficiency (up to ≈63 % at a very low concentration of 0.7 mg mL-1 ) of thin-layered Hf-MOLs compared to their 3D counterparts, thereby verifying the dimensional reduction strategy to improved cryoprotectant behaviors.


Subject(s)
Metal-Organic Frameworks , Metal-Organic Frameworks/chemistry , Cryopreservation/methods , Cryoprotective Agents/pharmacology , Cryoprotective Agents/chemistry , Ice , Hafnium/chemistry , Erythrocytes
16.
Inorg Chem ; 61(17): 6508-6518, 2022 May 02.
Article in English | MEDLINE | ID: mdl-35438982

ABSTRACT

In this work, we optimized the synthesis of HfO2 nanoparticles (NPs) with a nonaqueous sol-gel method assisted by microwave heating, with a direct surfactant-free extraction and stabilization in water. To tune the structural, morphological, and photophysical properties, we explored the influence of reaction time, heating temperature, and type and concentration of a salt precursor. The controlled size, shape, crystallinity associated with high stability, a good yield of production, and stabilization in water without any surfactant modification of these HfO2 NPs open possibilities for future optoelectronic and biomedical applications. The investigation of their optical properties, revealed a high absorption in the UV range and the presence of a large band gap, originating in transparency at visible wavelengths. Under UV excitation, photoluminescence (PL) shows three emission bands centered at 305, 381, and 522 nm and are assigned to the vibronic transition of an excited OH•* radical or to a self-trapped exciton, to threefold oxygen vacancies VO3 with recombination to the valence band, and to defect level, respectively. The presence of oxygen vacancies associated with PL properties is particularly attractive for optoelectronic, photocatalysis, scintillator, and UV photosensor applications. Finally, by changing the nature of the hafnium precursor salt, using hafnium ethoxide or hafnium acetylacetonate, low-crystallized and aggregated NPs were obtained, which requires further investigation.


Subject(s)
Hafnium , Nanoparticles , Hafnium/chemistry , Microwaves , Nanoparticles/chemistry , Oxygen , Water/chemistry
17.
Chem Commun (Camb) ; 57(87): 11473-11476, 2021 Nov 02.
Article in English | MEDLINE | ID: mdl-34652356

ABSTRACT

Photothermal therapy (PTT) achieves substantive therapeutic progress in certain tumor types without exogenous agents but is hampered by the over-activated inflammatory response or tumor recurrence in some cases. Herein, we technically developed the metal-polyphenolic nanosystem with precise NIR-II fluorescence-imaging guidance for combining hafnium (Hf)-sensitized radiotherapy with PTT to regress tumor growth.


Subject(s)
Antineoplastic Agents/therapeutic use , Fluorescent Dyes/therapeutic use , Nanoparticles/therapeutic use , Neoplasms/drug therapy , Neoplasms/radiotherapy , Radiopharmaceuticals/therapeutic use , Animals , Antineoplastic Agents/chemistry , Cell Line, Tumor , Dopamine/analogs & derivatives , Female , Fluorescence , Fluorescent Dyes/chemistry , Hafnium/chemistry , Hafnium/therapeutic use , Mice, Inbred BALB C , Mice, Nude , Nanoparticles/chemistry , Neoplasms/diagnostic imaging , Photothermal Therapy , Poloxamer/chemistry , Radiopharmaceuticals/chemistry , Radiotherapy
18.
ACS Appl Mater Interfaces ; 13(42): 50132-50140, 2021 Oct 27.
Article in English | MEDLINE | ID: mdl-34662123

ABSTRACT

The simulation of human brain neurons by synaptic devices could be an effective strategy to break through the notorious "von Neumann Bottleneck" and "Memory Wall". Herein, opto-electronic synapses based on layered hafnium disulfide (HfS2) transistors have been investigated. The basic functions of biological synapses are realized and optimized by modifying pulsed light conditions. Furthermore, 2 × 2 pixel imaging chips have also been developed. Two-pixel visual information is illuminated on diagonal pixels of the imaging array by applying light pulses (λ = 405 nm) with different pulse frequencies, mimicking short-term memory and long-term memory characteristics of the human vision system. In addition, an optically/electrically driven neuromorphic computation is demonstrated by machine learning to classify hand-written numbers with an accuracy of about 88.5%. This work will be an important step toward an artificial neural network comprising neuromorphic vision sensing and training functions.


Subject(s)
Biomimetic Materials/metabolism , Disulfides/metabolism , Hafnium/metabolism , Neural Networks, Computer , Synapses/metabolism , Biomimetic Materials/chemical synthesis , Biomimetic Materials/chemistry , Disulfides/chemical synthesis , Disulfides/chemistry , Hafnium/chemistry , Humans , Light , Machine Learning , Materials Testing , Synapses/chemistry
19.
Int J Nanomedicine ; 16: 2761-2773, 2021.
Article in English | MEDLINE | ID: mdl-33880022

ABSTRACT

PURPOSE: The side effects of radiotherapy induced on healthy tissue limit its use. To overcome this issue and fully exploit the potential of radiotherapy to treat cancers, the first-in-class radioenhancer NBTXR3 (functionalized hafnium oxide nanoparticles) has been designed to amplify the effects of radiotherapy. PATIENTS AND METHODS: Thanks to its physical mode of action, NBTXR3 has the potential to be used to treat any type of solid tumor. Here we demonstrate that NBTXR3 can be used to treat a wide variety of solid cancers. For this, we evaluated different parameters on a large panel of human cancer models, such as nanoparticle endocytosis, in vitro cell death induction, dispersion, and retention of NBTXR3 in the tumor tissue and tumor growth control. RESULTS: Whatever the model considered, we show that NBTXR3 was internalized by cancer cells and persisted within the tumors throughout radiotherapy treatment. NBTXR3 activated by radiotherapy was also more effective in destroying cancer cells and in controlling tumor growth than radiotherapy alone. Beyond the effects of NBTXR3 as single agent, we show that the antitumor efficacy of cisplatin-based chemoradiotherapy treatment was improved when combined with NBTXR3. CONCLUSION: These data support that NBTXR3 could be universally used to treat solid cancers when radiotherapy is indicated, opening promising new therapeutic perspectives of treatment for the benefit of many patients.


Subject(s)
Antineoplastic Agents/therapeutic use , Hafnium/chemistry , Nanoparticles/chemistry , Neoplasms/radiotherapy , Oxides/chemistry , Animals , Antineoplastic Agents/pharmacology , Cell Line, Tumor , Cell Proliferation/drug effects , Cisplatin/pharmacology , Cisplatin/therapeutic use , Combined Modality Therapy , Endocytosis/drug effects , Humans , Mice, Nude , Nanoparticles/administration & dosage , Nanoparticles/ultrastructure , Neoplasms/drug therapy , Neoplasms/pathology , Tissue Distribution/drug effects , Treatment Outcome
20.
ACS Appl Mater Interfaces ; 13(8): 10639-10649, 2021 Mar 03.
Article in English | MEDLINE | ID: mdl-33606512

ABSTRACT

Two-dimensional (2D) materials based artificial synapses are important building blocks for the brain-inspired computing systems that are promising in handling large amounts of informational data with high energy-efficiency in the future. However, 2D devices usually rely on deposited or transferred insulators as the dielectric layer, resulting in various challenges in device compatibility and fabrication complexity. Here, we demonstrate a controllable and reliable oxidation process to turn 2D semiconductor HfS2 into native oxide, HfOx, which shows good insulating property and clean interface with HfS2. We then incorporate the HfOx/HfS2 heterostructure into a flash memory device, achieving a high on/off current ratio of ∼105, a large memory window over 60 V, good endurance, and a long retention time over 103 seconds. In particular, the memory device can work as an artificial synapse to emulate basic synaptic functions and feature good linearity and symmetry in conductance change during long-term potentiation/depression processes. A simulated artificial neural network based on our synaptic device achieves a high accuracy of ∼88% in MNIST pattern recognition. Our work provides a simple and effective approach for integrating high-k dielectrics into 2D material-based memory and synaptic devices.


Subject(s)
Computer Storage Devices , Hafnium/chemistry , Sulfides/chemistry , Biomimetics/methods , Electric Conductivity , Electronics , Neural Networks, Computer , Oxidation-Reduction , Semiconductors , Synapses/chemistry
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