Search

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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

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., (© 2024 Author(s). Published under an exclusive license by AIP Publishing.)

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 WSe 2 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 WSe 2 FET biosensor. The Al 2 O 3 /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 WSe 2 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.

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., (© 2024 Wiley‐VCH GmbH.)

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), ─CF 3 (Cat-CF 3 ), and ─C 6 F 5 (Cat-C 6 F 5 ) 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-CF 3 producing isotactic polymers with the highest molecular weight (M w = 1649 kg mol -1 ); in copolymerization with polar monomers, catalyst Cat-OMe yields isotactic copolymer with the highest molecular weight (M w = 2990 kg mol -1 ). Interestingly, catalyst Cat-C 6 F 5 bearing a ─C 6 F 5 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., (© 2024 Wiley‐VCH GmbH.)

Herein, we successfully synthesized Hf/Zr co-doping on Fe 2 O 3 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% CoO x loaded Hf/Zr-Fe 2 O 3 NRs and CuO x /CoO x loaded Hf/Zr-Fe 2 O 3 NRs photocatalyst. Initially, the rod-like porous morphology of the Hf/Zr-doped Fe 2 O 3 NRs was produced via a hydrothermal method at various Hf co-doping (0, 2, 4, 7 and 10)%. Further, CoO x and CuO x loaded by a wet impregnation approach on the Hf/Zr-Fe 2 O 3 NRs and a highly photoactive Hf(4)/Zr-Fe 2 O 3 [CoO x /CuO x ] NRs photocatalyst were developed. After the Hf(4)/Zr-Fe 2 O 3 [CoO x /CuO x ] NRs photocatalyst treatment, the Bio-TEM imagery of bacterial cells showed extensive morphological deviations in cell membranes. Hf(4)/Zr-Fe 2 O 3 NR achieved 84.1% orange II degradation upon 3 h illumination, which is higher than that of Hf-Fe 2 O 3 and Zr-Fe 2 O 3 (68.7 and 73.5%, respectively). Additionally, the optimum sample, Hf(4)/Zr-Fe 2 O 3 [CoO x /CuO x ] photocatalyst, exhibited 95.5% orange II dye degradation after light radiation for 3 h. Optimized Hf(4)/Zr-Fe 2 O 3 [CoO x /CuO x ] 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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

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.

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 HfO 2 NPs, 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 HfO 2 NPs 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 HfO 2 NPs the CNR surpassed iodine by 114%, and gadolinium by 30%, respectively. HfO 2 NPs, 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., (© 2024. The Author(s), under exclusive licence to Japanese Society of Radiological Technology and Japan Society of Medical Physics.)

Radioprotective agents hold clinical promises to counteract off-target adverse effects of radiation and benefit radiotherapeutic outcomes, yet the inability to control drug transport in human organs poses a leading limitation. Based upon a validated rank-based multigene signature model, radiosensitivity indices are evaluated of diverse normal organs as a genomic predictor of radiation susceptibility. Selective ORgan-Targeting (SORT) hafnium oxide nanoparticles (HfO 2 NPs) are rationally designed via modulated synthesis by α-lactalbumin, homing to top vulnerable organs. HfO 2 NPs like Hensify are commonly radioenhancers, but SORT HfO 2 NPs exhibit surprising radioprotective effects dictated by unfolded ligands and Hf(0)/Hf(IV) redox couples. Still, the X-ray attenuation patterns allow radiological confirmation in target organs by dual-beam spectral computed tomography. SORT HfO 2 NPs present potent antioxidant activities, catalytically scavenge reactive oxygen species, and mimic multienzyme catalytic activities. Consequently, SORT NPs rescue radiation-induced DNA damage in mouse and rabbit models and provide survival benefits upon lethal exposures. In addition to inhibiting radiation-induced mitochondrial apoptosis, SORT NPs impede DNA damage and inflammation by attenuating activated FoxO, Hippo, TNF, and MAPK interactive cascades. A universal methodology is proposed to reverse radioenhancers into radioprotectors. SORT radioprotective agents with image guidance are envisioned as compelling in personalized shielding from radiation deposition., (© 2024 Wiley‐VCH GmbH.)

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.

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 (HfO 2 ), 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 HfO 2 , HfO 2 -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., (© 2023 Wiley-VCH GmbH.)

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., (© 2023 Wiley-VCH GmbH.)

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 (HfO 2 ). Three layered versions of the proposed structure are studied; each configuration is built from alternating layers of HfO 2 , silica, Ge 2 Sb 2 Te 5 (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., (© 2023. The Author(s).)

In this work, we optimized the synthesis of HfO 2 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 HfO 2 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 V O3 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.

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.

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 (HfS 2 ) 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.

The colloidal stability, cytotoxicity, and cellular uptake of hafnium oxide (HfO 2 ) nanoparticles (NPs) were investigated in vitro to assess safety and efficacy for use as a deliverable theranostic in nanomedicine. Monoclinic HfO 2 NPs, ~60-90 nm in diameter and ellipsoidal in shape, were directly prepared without calcination by a hydrothermal synthesis at 83% yield. The as-prepared, bare HfO 2 NPs exhibited colloidal stability in cell culture media for at least 10 days without significant agglomeration or settling. The viability (live/dead assay) of human epithelial cells (HeLa) and monocyte-derived macrophages (THP-1) did not fall below 95% of untreated cells after up to 24 h exposure to HfO 2 NPs at concentrations up to 0.80 mg/ml. Similarly, the mitochondrial activity (MTT assay) of HeLa and THP-1 cells did not fall below 80% of untreated cells after up to 24 h exposure to HfO 2 NPs at concentrations up to 0.40 mg/ml. Cellular uptake was confirmed and visualized in both HeLa and THP-1 cells by fluorescence microscopy of HfO 2 NPs labeled with Cy5 and transmission electron microscopy (TEM) of bare HfO 2 NPs. TEM micrographs provided direct observation of macropinocytosis and endosomal compartmentalization within 4 h of exposure. Thus, the HfO 2 NPs in this study exhibited colloidal stability, cytocompatibility, and cellular uptake for potential use as a deliverable theranostic in nanomedicine., (© 2021 Wiley Periodicals LLC.)

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., Competing Interests: P. Zhang, J. Marill, A. Darmon, N. Mohamed Anesary, and S. Paris are full employees of Nanobiotix. The authors report no other conflicts of interest in this work., (© 2021 Zhang et al.)

Achieving direct imaging of the annihilation position of a positron on an event-by-event basis using an ultrafast detector would have a great impact on the field of nuclear medicine. Cherenkov emission is the most attractive physical phenomenon for realizing such an ultrafast timing performance. Moreover, a microchannel-plate photomultiplier tube (MCP-PMT) is one of the most promising photodetectors for fully exploiting the fast timing properties of Cherenkov emission owing to its excellent single photon time resolution of 25 ps full width at half maximum (FWHM). However, as the MCP structure generally contains a lead compound, the gamma rays frequently and directly interact with the MCP, resulting in the degradation of its timing performance and generation of undesirable side peaks in its coincidence timing histogram. To overcome this problem, we have developed a new MCP-PMT based on an MCP consisting of borosilicate glass, thus drastically reducing the probability of the photoelectric effect occurring in the MCP. To evaluate its insensitivity to gamma rays and its timing performance, a coincidence experiment was performed and showed that the probability of direct interactions was reduced by a factor of 3.4. Moreover, a coincidence time resolution of 35.4 ± 0.4 ps FWHM, which is equivalent to a position resolution of 5.31 mm, was obtained without any pulse height/area cut, improving to 28.7 ± 3.0 ps when selecting on the highest amplitude events by careful optimization of the voltage divider circuit of the new MCP-PMT. The timing performance of this new MCP-PMT presents an important step toward making direct imaging possible.

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 HfS 2 into native oxide, HfO x , which shows good insulating property and clean interface with HfS 2 . We then incorporate the HfO x /HfS 2 heterostructure into a flash memory device, achieving a high on/off current ratio of ∼10 5 , a large memory window over 60 V, good endurance, and a long retention time over 10 3 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.

Radiodynamic therapy (RDT), an emerging therapeutic approach for cancer treatment by employing ionizing irradiation to induce localized photodynamic therapy (PDT) can overcome the drawbacks of the limited penetration depth for traditional PDT and the unconcentrated energy in the tumor for traditional radiotherapy (RT). Taking advantage of aggregation-induced emission (AIE) photosensitizers with bright fluorescence and efficient singlet oxygen production in the aggregate state, Hf-AIE coordination polymer nanoparticles (CPNs), which show both strong RT and RDT effect under X-ray irradiation, are developed. Furthermore, to enhance the tumor accumulation and prolong the tumor retention of the CPNs, bioorthogonal click chemistry is applied in the system through coupling between dibenzocyclooctyne (DBCO)-modified CPNs (Hf-AIE-PEG-DBCO) (PEG: poly(ethylene glycol)) and azide groups on the cell membrane formed by metabolic glycoengineering. Thanks to the high penetration of X-ray irradiation, the bioorthogonal-assisted RT and RDT combination therapy realizes significant killing of cancer cells without showing noticeable biotoxicity after intravenous administration of CPNs., (© 2021 Wiley-VCH GmbH.)

The in situ spectroelectrochemical cyclic voltammetric studies of the antimony-monocapped nickel(II) and iron(II) tris-pyridineoximates with a labile triethylantimony cross-linking group and Zr(IV)/Hf(IV) phthalocyaninate complexes were performed in order to understand the nature of the redox events in the molecules of heterodinuclear zirconium(IV) and hafnium(IV) phthalocyaninate-capped derivatives. Electronic structures of their 1e-oxidized and 1e-electron-reduced forms were experimentally studied by electron paramagnetic resonance (EPR) spectroscopy and UV-vis-near-IR spectroelectrochemical experiments and supported by density functional theory (DFT) calculations. The investigated hybrid molecular systems that combine a transition metal (pseudo)clathrochelate and a Zr/Hf-phthalocyaninate moiety exhibit quite rich redox activity both in the cathodic and in the anodic region. These binuclear compounds and their precursors were tested as potential catalysts in oxidation reactions of cyclohexane and the results are discussed.

Structural evolution in functional materials is a physicochemical phenomenon, which is important from a fundamental study point of view and for its applications in magnetism, catalysis, and nuclear waste immobilization. In this study, we used x-ray diffraction and Raman spectroscopy to examine the Gd 2 Hf 2 O 7 (GHO) pyrochlore, and we showed that it underwent a thermally induced crystalline phase evolution. Superconducting quantum interference device measurements were carried out on both the weakly ordered pyrochlore and the fully ordered phases. These measurements suggest a weak magnetism for both pyrochlore phases. Spin density calculations showed that the Gd 3+ ion has a major contribution to the fully ordered pyrochlore magnetic behavior and its cation antisite. The origin of the Gd magnetism is due to the concomitant shift of its spin-up 4f orbital states above the Fermi energy and its spin-down states below the Fermi energy. This picture is in contrast to the familiar Stoner model used in magnetism. The ordered pyrochlore GHO is antiferromagnetic, whereas its antisite is ferromagnetic. The localization of the Gd-4f orbitals is also indicative of weak magnetism. Chemical bonding was analyzed via overlap population calculations: These analyses indicate that Hf-Gd and Gd-O covalent interactions are destabilizing, and thus, the stabilities of these bonds are due to ionic interactions. Our combined experimental and computational analyses on the technologically important pyrochlore materials provide a basic understanding of their structure, bonding properties, and magnetic behaviors.

Background: Recent studies have validated and confirmed the great potential of nanoscale metal-organic framework (NMOF) in the biomedical field, especially in improving the efficiency of cancer diagnosis and therapy. However, most previous studies only utilized either the metal cluster or the organic ligand of the NMOF for cancer treatments and merely reported limited theranostic functions, which may not be optimized. As a highly designable and easily functionalized material, prospective rational design offers a powerful way to extract the maximum benefit from NMOF for cancer theranostic applications., Materials and Methods: A NMOF based on hafnium (Hf) cluster and Mn(III)-porphyrin ligand was rational designed and synthesized as a high-performance multifunctional theranostic agent. The folic acid (FA) was modified on the NMOF surface to enhance the cancer targeting efficacy. The proposed "all-in-one" FA-Hf-Mn-NMOF (fHMNM) was characterized and identified using various analytical techniques. Then, in vitro and in vivo studies were performed to further explore the effects of fHMNM both as the magnetic resonance imaging (MRI)/computed tomography (CT)/photoacoustic imaging (PAI) contrast agent and as the photothermal therapy (PTT)/radiotherapy (RT) agent., Results: A tumour targeting multifunctional fHMNM was successfully synthesized with high performance for MRI/CT/PAI enhancements and image-guided PTT/RT synergistic therapy properties. Compared with the current clinical CT and MR contrast agents, the X-ray attenuation and T 1 relaxation rate of this integrated nanosystem increased 1.7-fold and 3-5-fold, respectively. More importantly, the catalase-like Mn(III)-porphyrin ligand can decompose H 2 O 2 into O 2 in tumour microenvironments to improve the synergistic treatment efficiency of PTT and RT. Significant tumour growth inhibition was achieved in mouse cancer models without obvious damage to the other organs., Conclusion: This work highlights the potential of fHMNM as an easily designable material for biomedical applications, could be an effective tool for in vivo detection and subsequent treatment of tumour., Competing Interests: The authors report no conflicts of interest in this work., (© 2020 Bao et al.)

Tridentate, bis-phenolate N -heterocyclic carbenes (NHCs) are among the ligands giving the most selective and active group 4-based catalysts for the copolymerization of cyclohexene oxide (CHO) with CO 2 . In particular, ligands based on imidazolidin-2-ylidene (saturated NHC) moieties have given catalysts which exclusively form polycarbonate in moderate-to-high yields even under low CO 2 pressure and at low copolymerization temperatures. Here, to evaluate the influence of the NHC moiety on the molecular structure of the catalyst and its performance in copolymerization, we extend this chemistry by synthesizing and characterizing titanium complexes bearing tridentate bis-phenolate imidazol-2-ylidene (unsaturated NHC) and benzimidazol-2-ylidene (benzannulated NHC) ligands. The electronic properties of the ligands and the nature of their bonds to titanium are studied using density functional theory (DFT) and natural bond orbital (NBO) analysis. The metal-NHC bond distances and bond strengths are governed by ligand-to-metal σ- and π-donation, whereas back-donation directly from the metal to the NHC ligand seems to be less important. The NHC π-acceptor orbitals are still involved in bonding, as they interact with THF and isopropoxide oxygen lone-pair donor orbitals. The new complexes are, when combined with [PPN]Cl co-catalyst, selective in polycarbonate formation. The highest activity, albeit lower than that of the previously reported Ti catalysts based on saturated NHC, was obtained with the benzannulated NHC-Ti catalyst. Attempts to synthesize unsaturated and benzannulated NHC analogues based on Hf invariably led, as in earlier work with Zr, to a mixture of products that include zwitterionic and homoleptic complexes. However, the benzannulated NHC-Hf complexes were obtained as the major products, allowing for isolation. Although these complexes selectively form polycarbonate, their catalytic performance is inferior to that of analogues based on saturated NHC.

Background: Due to increasing aging of population prevalence of age-related disorders including osteoporosis is rapidly growing. Due to health and economic impact of the disease, there is an urgent need to develop techniques supporting bone metabolism and bone regeneration after fracture. Due to imbalance between bone forming and bone resorbing cells, the healing process of osteoporotic bone is problematic and prolonged. Thus searching for agents able to restore the homeostasis between these cells is strongly desirable., Results: In the present study, using ALD technology, we obtained homogeneous, amorphous layer of hafnium (IV) oxide (HfO 2 ). Considering the specific growth rate (1.9Å/cycle) for the selected process at the temperature of 90 °C, we performed the 100 nm deposition process, which was confirmed by measuring film thickness using reflectometry. Then biological properties of the layer were investigated with pre-osteoblast (MC3T3), pre-osteoclasts (4B12) and macrophages (RAW 264.7) using immunofluorescence and RT-qPCR. We have shown, that HfO 2 (i) enhance osteogenesis, (ii) reduce osteoclastogenesis (iii) do not elicit immune response and (iv) exert anti-inflammatory effects., Conclusion: HfO 2 layer can be applied to cover the surface of metallic biomaterials in order to enhance the healing process of osteoporotic bone fracture.

The design and synthesis of a novel generation of a nanoscaled platform with imaging-guided therapy remain a real challenge. It can not only improve the imaging sensitivity of tumor tissues for guiding all kinds of treatments but also reduce the harm for healthy tissues. Here, polydopamine (PDA), polyethylene glycol (PEG), and c(RGDyK) peptide (RGD)-modified and cisplatin-loaded Gd 2 Hf 2 O 7 nanoparticles (Gd 2 Hf 2 O 7 @PDA@PEG-Pt-RGD NPs) are designed for magnetic resonance imaging (MRI)-guided combined chemo-/photothermal-/radiotherapy of resistant tumors. The as-prepared NPs display high relaxivity ( r 1 = 38.28 mM -1 s -1 ) as an MRI contrast agent because of their ultrasmall size and surface modification with polyacrylic acid and PDA. Gd 2 Hf 2 O 7 @PDA@PEG-Pt-RGD NPs exhibit pH and NIR dual-stimuli responsiveness for cisplatin release. Based on competent NIR absorption and high X-ray attenuation efficiency, Gd 2 Hf 2 O 7 @PDA@PEG-Pt-RGD NPs show potential photothermal effect by exposing to an 808 nm NIR laser and significantly improve the generation of reactive oxygen species after X-ray radiation. Combined chemo-/photothermal-/radiotherapy can effectively treat the resistant A549R cells, providing the enhanced therapeutic efficiency to cancer tissues and the reduced side effect to healthy tissues. Furthermore, Gd 2 Hf 2 O 7 @PDA@PEG-Pt-RGD NPs present no obvious toxicity during the treatment, which demonstrates the potential as an efficient MRI-guided combined chemo-/photothermal-/radiotherapy nanoplatform for drug-resistant tumors.

A new Hf(iv) based metal-organic framework with the UiO-66 (UiO = University of Oslo) topology was prepared via a standard modulated solvothermal reaction. The weakly emissive MOF material was well characterized via various analytical techniques. The parent MOF was then post-synthetically modified with a highly emissive pyrene based chemodosimeter probe without altering the parent framework structure. The incorporation of the chemodosimeter in the modified MOF material was successfully confirmed by using FT-IR and 1 H NMR spectroscopy. The emission behaviour of the parent MOF was changed drastically with a noticeable colour change after post-synthetic modification. After modification, the MOF material showed a very selective colorimetric and fluorometric dual-emissive response towards lethal cyanide ions. A large blue shift (Δλ = 127 nm) was observed in the emission spectra which can be also visualized with the naked eye under a hand held UV lamp. The presence of a vinyl functional group in the chemodosimeter can serve as a potential nucleophilic reaction centre, which was also confirmed by the DFT calculations. The reaction based sensing mechanism of the MOF material was successfully confirmed by 1 H NMR spectroscopy. Furthermore, to apply the modified MOF material in real life, the test strip based sensing of cyanide in drinking water was demonstrated.

The selective hydrolysis of proteins by non-enzymatic catalysis is difficult to achieve, yet it is crucial for applications in biotechnology and proteomics. Herein, we report that discrete hafnium metal-oxo cluster [Hf 18 O 10 (OH) 26 (SO 4 ) 13 ⋅(H 2 O) 33 ] (Hf 18 ), which is centred by the same hexamer motif found in many MOFs, acts as a heterogeneous catalyst for the efficient hydrolysis of horse heart myoglobin (HHM) in low buffer concentrations. Among 154 amino acids present in the sequence of HHM, strictly selective cleavage at only 6 solvent accessible aspartate residues was observed. Mechanistic experiments suggest that the hydrolytic activity is likely derived from the actuation of Hf IV Lewis acidic sites and the Brønsted acidic surface of Hf 18 . X-ray scattering and ESI-MS revealed that Hf 18 is completely insoluble in these conditions, confirming the HHM hydrolysis is caused by a heterogeneous reaction of the solid Hf 18 cluster, and not from smaller, soluble Hf species that could leach into solution., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Purpose: Despite tremendous results achieved by immune checkpoint inhibitors, most patients are not responders, mainly because of the lack of a pre-existing anti-tumor immune response. Thus, solutions to efficiently prime this immune response are currently under intensive investigations. Radiotherapy elicits cancer cell death, generating an antitumor-specific T cell response, turning tumors in personalized in situ vaccines, with potentially systemic effects (abscopal effect). Nonetheless, clinical evidence of sustained anti-tumor immunity as abscopal effect are rare., Methods: Hafnium oxide nanoparticles (NBTXR3) have been designed to increase energy dose deposit within cancer cells. We examined the effect of radiotherapy-activated NBTXR3 on anti-tumor immune response activation and abscopal effect production using a mouse colorectal cancer model., Results: We demonstrate that radiotherapy-activated NBTXR3 kill more cancer cells than radiotherapy alone, significantly increase immune cell infiltrates both in treated and in untreated distant tumors, generating an abscopal effect dependent on CD8+ lymphocyte T cells., Conclusion: These data show that radiotherapy-activated NBTXR3 could increase local and distant tumor control through immune system priming. Our results may have important implications for immunotherapeutic agent combination with radiotherapy., Competing Interests: P. Zhang, A. Darmon, J. Marill, N. Mohamed Anesary, and S. Paris are employees of Nanobiotix. The authors report no other conflicts of interest in this work., (© 2020 Zhang et al.)

Hf(OTf) 4 was identified as a highly potent catalyst (0.1-0.5 mol%) for three-component Mannich reaction under solvent-free conditions. Hf(OTf) 4 -catalyzed Mannich reaction exhibited excellent regioselectivity and diastereoselectivity when alkyl ketones were employed as substrates. 1 H NMR tracing of the H/D exchange reaction of ketones in MeOH- d 4 indicated that Hf(OTf) 4 could significantly promote the keto-enol tautomerization, thereby contributing to the acceleration of reaction rate.

This work utilized ultrathin metal-organic layer (MOL) to immobilize luminophores for effectively shortening the ion/electron-transport distance and relieving the diffusional constraints of ion/electron, which greatly enhanced the ECL efficiency and intensity. Moreover, the MOL's immobilization amount of luminophores should be higher than these of bulk MOFs because MOLs possess more accessible postmodification sites for the luminophores with minimal diffusion barriers. As expected, our proof-of-concept experiment indicated that the Hf-MOL's loading number of Ru(bpy) 2 (mcpbpy) 2+ was about 1.74 times that of a 3D mesoporous MOF (PCN-777), and the ECL efficiency and intensity of PEI@Ru-Hf-MOL were around 1.27 times and 14.5 times those of PEI@Ru-PCN-777, respectively. In view of these merits, this work utilized the prepared PEI@Ru-Hf-MOL as a highly efficient sensing platform for simple, rapid and sensitive detection of mucin 1, which exhibited a broad linearity from 1 fg/mL to 10 ng/mL and a low detection limit of 0.48 fg/mL. This work provided a practicable strategy to develop high-performance ECL materials, and therefore opened up a new avenue to design ultrasensitive ECL biosensors, which expanded the application potential of MOLs in ECL assays., (Copyright © 2019 Elsevier B.V. All rights reserved.)

We report here a new bimetallic ZrHf metal-organic framework (ZrHf-MOF) embedded with abundant carbon dots (CDs) (denoted as CDs@ZrHf-MOF), which exhibits strong fluorescence and rich-amino-functionalization. The CDs@ZrHf-MOF can be applied as the scaffold for anchoring aptamer strands to determine human epidermal growth factor receptor-2 (HER2) and living HER2-overexpressed MCF-7 cells. The basic characterizations reveal that the CDs are embedded within the interior cavities of ZrHf-MOF without varying the nanostructure, leading to good biocompatibility, strong fluorescence, and high electrochemical activity of CDs@ZrHf-MOF. As compared with the pristine ZrHf-MOF, the CDs@ZrHf-MOF-based electrochemical aptasensor displays better sensing performances toward both HER-2 and MCF-7 cells, giving an extremely low detection limit of 19 fg mL -1 (HER2 concentration range: 0.001-10 ng mL -1 ) and 23 cell mL -1 (cell concentration range: 1 × 10 2 ~1 × 10 5 cell mL -1 ), with good selectivity, stability, reproducibility, and acceptable applicability. The proposed strategy for developing CDs@ZrHf-MOF-based aptasensor is promising for the early and sensitive detection of cancer markers and living cancer cells., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Saliva has been reported to contain various cytokine biomarkers which are associated with some severe diseases such as cancers. Non-invasive saliva diagnosis using wearable or portable devices may pave a new avenue for monitoring conditions of the high risk population. Here, a graphene-based fully integrated portable nanosensing system, the entire size of which is smaller than a smart-phone and can be handheld, is presented for on-line detection of cytokine biomarkers in saliva. This miniaturized system employs an aptameric graphene-based field effect transistor (GFET) using a buried-gate geometry with HfO 2 as the dielectric layer and on-line signal processing circuits to realize the transduction and processing of signals which reflect cytokine concentrations. The signal can be wirelessly transmitted to a smart-phone or cloud sever through the Wi-Fi connection for visualizing the trend of the cytokine concentration change. Interleukin-6 (IL-6) is used as a representative to examine the sensing capability of the system. Experimental results demonstrate that the nanosensing system responds to the change of IL-6 concentration within 400s in saliva with a detection limit down to 12 pM. Therefore, this portable system offers the practicality to be potentially used for non-invasive saliva diagnosis of diseases at early stage., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Pincer-type [C naphthyl , N pyridine , N amido ]HfMe 2 complex is a flagship among the post-metallocene catalysts. In this work, various pincer-type Hf-complexes were prepared for olefin polymerization. Pincer-type [N amido , N pyridine , N amido ]HfMe 2 complexes were prepared by reacting in situ generated HfMe 4 with the corresponding ligand precursors, and the structure of a complex bearing 2,6-Et 2 C 6 H 3 N amido moieties was confirmed by X-ray crystallography. When the ligand precursors of [(CH 3 )R 2 Si-C 5 H 3 N-C(H)PhN(H)Ar (R = Me or Ph, Ar = 2,6-diisopropylphenyl) were treated with in situ generated HfMe 4 , pincer-type [C silylmethyl , N pyridine , N amido ]HfMe 2 complexes were afforded by formation of Hf-CH 2 Si bond. Pincer-type [C naphthyl , S thiophene , N amido ]HfMe 2 complex, where the pyridine moiety in the flagship catalyst was replaced with a thiophene unit, was not generated when the corresponding ligand precursor was treated with HfMe 4 . Instead, the [S thiophene , N amido ]HfMe 3 -type complex was obtained with no formation of the Hf-C naphthyl bond. A series of pincer-type [C naphthyl , N pyridine , N alkylamido ]HfMe 2 complexes was prepared where the arylamido moiety in the flagship catalyst was replaced with alkylamido moieties (alkyl = iPr, cyclohexyl, t Bu, adamantyl). Structures of the complexes bearing isopropylamido and adamantylamido moieties were confirmed by X-ray crystallography. Most of the complexes cleanly generated the desired ion-pair complexes when treated with an equivalent amount of [(C 18 H 37 ) 2 N(H)Me] + [B(C 6 F 5 ) 4 ] - , which showed negligible activity in olefin polymerization. Some complexes bearing bulky substituents showed moderate activities, even though the desired ion-pair complexes were not cleanly afforded.

Hafnium dioxide (HfO 2 ) is attracting attention for bio-related applications due to its good cytocompatibility, high density, and resistance to corrosion and mechanical damage. Here we synthesize two types of hafnium-oxide thin films on substrates via self-organized electrochemical anodization: (1) an array of hierarchically structured nanorods anchored to a thin oxide layer and (2) a microscopically flat oxide film. The nanostructured film is composed of a unique mixture of HfO 2 , suboxide Hf 2 O 3 , and oxide-hydroxide compound HfO 2 ·nH 2 O whereas the flat film is mainly HfO 2 . In vitro interaction of the two films with MG-63 osteoblast-like cells and Gram-negative E. coli bacteria is studied for the first time to assess the potential of the films for biomedical application. Both films reveal good cytocompatibility and affinity for proteins, represented by fibronectin and especially albumin, which is absorbed in a nine times larger amount. The morphology and specific surface chemistry of the nanostructured film cause a two-fold enhanced antibacterial effect, better cell attachment, significantly improved proliferation of cells, five-fold rise in the cellular Young's modulus, slightly stronger production of reactive oxygen species, and formation of cell clusters. Compared with the flat film, the nanostructured one features the weakening of AFM-measured adhesion force at the cell/surface interface, probably caused by partially lifting the nanorods from the substrate due to the strong contact with cells. The present findings deepen the understanding of biological processes at the living cell/metal-oxide interface, underlying the role of surface chemistry and the impact of nanostructuring at the nanoscale.

Hardware artificial neural network (ANN) systems with high density synapse array devices can perform massive parallel computing for pattern recognition with low power consumption. To implement a neuromorphic system with on-chip training capability, we need to develop an ideal synapse device with various device requirements, such as scalability, MLC characteristics, low power operation, data retention, and symmetric/linear conductance changes under potentiation/depression modes. Although various devices have been proposed for synapse applications, they have limitations for application in neuromorphic systems. In this paper, we will cover various RRAM synapse devices, such as filamentary switching RRAM (HfOx, TaOx, Cu-CBRAM) and analog RRAM devices, based on interface resistive switching (Pr0.7Ca0.3MnOx and TiOx) and ferroelectric polarization (HfZrOx). By optimizing potentiation/depression conditions, we could improve the conductance linearity and MLC characteristics of filamentary synapse devices. Interface RRAM has better MLC characteristics with limited retention and conductance linearity. By controlling the reactivity of metal electrodes and the oxygen concentration in oxides, we can modulate the synapse characteristics. Metal-Ferroelectric-Insulator-Semiconductor (MFIS) FET devices exhibit good retention characteristics and analog memory characteristics due to polarization. Based on various synapse device characteristics, we have estimated the pattern recognition accuracy of MNIST handwritten digits and CIFAR-10 datasets. We have confirmed that synapse device characteristics directly affect the pattern recognition accuracy of ANNs. In order to simultaneously satisfy all the requirements of synapse devices, it is necessary to develop new technology capable of controlling the movement of oxygen vacancies and metal ions at the atomic scale. Considering the limited synapse characteristics of current 2-terminal RRAM devices, hardware ANNs capable of only off-chip training can be constructed by optimizing the current RRAM devices by limiting the bit number. A 3-terminal synapse device or a device based on a new operation principle should be developed as an alternative for on-chip training applications.

In our studies on the catalytic activity of Group IVB transition metal Lewis acids, Hf(OTf)₄ was identified as a highly potent catalyst for "one-pot, three-component" Biginelli reaction. More importantly, it was found that solvent-free conditions, in contrast to solvent-based conditions, could dramatically promote the Hf(OTf)₄-catalyzed formation of 3,4-dihydro-pyrimidin-2-(1 H )-ones. To provide a mechanistic explanation, we closely examined the catalytic effects of Hf(OTf)₄ on all three potential reaction pathways in both "sequential bimolecular condensations" and "one-pot, three-component" manners. The experimental results showed that the synergistic effects of solvent-free conditions and Hf(OTf)₄ catalysis not only drastically accelerate Biginelli reaction by enhancing the imine route and activating the enamine route but also avoid the formation of Knoevenagel adduct, which may lead to an undesired byproduct. In addition, ¹H-MMR tracing of the H-D exchange reaction of methyl acetoacetate in MeOH- d ₄ indicated that Hf(IV) cation may significantly accelerate ketone-enol tautomerization and activate the β-ketone moiety, thereby contributing to the overall reaction rate.

High-Z metal oxide nanoparticles hold promise as imaging probes and radio-enhancers. Hafnium dioxide nanoparticles have recently entered clinical evaluation. Despite promising early clinical findings, the potential of HfO 2 as a matrix for multimodal theranostics is yet to be developed. Here, we investigate the physicochemical properties and the potential of HfO 2 -based nanoparticles for multimodal theranostic imaging. Undoped and lanthanide (Eu 3+ , Tb 3+ , and Gd 3+ )-doped HfO 2 nanoparticles were synthesized and functionalized with various moieties including poly(vinylpyrrolidone) (PVP), (3-aminopropyl)triethoxysilane (APTES), and folic acid (FA). We show that different synthesis routes, including direct precipitation, microwave-assisted synthesis, and sol-gel chemistry, allow preparation of hafnium dioxide particles with distinct physicochemical properties. Sol-gel based synthesis allows preparation of uniform nanoparticles with dopant incorporation efficiencies superior to the other two methods. Both luminescence and contrast properties can be tweaked by lanthanide doping. We show that MRI contrast can be unified with radio-enhancement by incorporating lanthanide dopants in the HfO 2 matrix. Importantly, ion leaching from the HfO 2 host matrix in lysosomal-like conditions was minimal. For Gd:HfO 2 nanoparticles, leaching was reduced >10× compared to Gd 2 O 3 , and no relevant cytotoxic effects have been observed in monocyte-derived macrophages for nanoparticle concentrations up to 250 μg/mL. Chemical surface modification allows further tailoring of the cyto- and hemocompatibility and enables functionalization with molecular targeting entities, which lead to enhanced cellular uptake. Taken together, the present study illustrates the manifold properties of HfO 2 -based nanomaterials with prospective clinical utility beyond radio-enhancement.

Background: Hafnium(IV) tetrachloride efficiently catalyzes the protection of a variety of aldehydes and ketones, including benzophenone, acetophenone, and cyclohexanone, to the corresponding dimethyl acetals and 1,3-dioxolanes, under microwave heating. Substrates possessing acid-labile protecting groups (TBDPS and Boc) chemoselectively generated the corresponding acetal/ketal in excellent yields., Aims and Objectives: In this study. the selective protection of aldehydes and ketones using a Hafnium(IV) chloride, which is a novel catalyst, under microwave heating was observed. Hence, it is imperative to find suitable conditions to promote the protection reaction in high yields and short reaction times. This study was undertaken not only to find a novel catalyst but also to perform the reaction with substrates bearing acid-labile protecting groups, and study the more challenging ketones as benzophenone., Materials and Methods: Using a microwave synthesis reactor Monowave 400 of Anton Paar, the protection reaction was performed on a raging temperature of 100°C ±1, a pressure of 2.9 bar, and an electric power of 50 W. More than 40 substrates have been screened and protected, not only the aldehydes were protected in high yields but also the more challenging ketones such as benzophenone were protected. All the products were purified by simple flash column chromatography, using silica gel and hexanes/ethyl acetate (90:10) as eluents. Finally, the protected substrates were characterized by NMR 1H, 13C and APCI-HRMS-QTOF., Results: Preliminary screening allowed us to find that 5 mol % of the catalyst is enough to furnish the protected aldehyde or ketone in up to 99% yield. Also it was found that substrates with a variety of substitutions on the aromatic ring (aldehyde or ketone), that include electron-withdrawing and electrondonating group, can be protected using this methodology in high yields. The more challenging cyclic ketones were also protected in up to 86% yield. It was found that trimethyl orthoformate is a very good additive to obtain the protected acetophenone. Finally, the protection of aldehydes with sensitive functional groups was performed. Indeed, it was found that substrates bearing acid labile groups such as Boc and TBDPS, chemoselectively generated the corresponding acetal/ketal compound while keeping the protective groups intact in up to 73% yield., Conclusion: Hafnium(IV) chloride as a catalyst provides a simple, highly efficient, and general chemoselective methodology for the protection of a variety of structurally diverse aldehydes and ketones. The major advantages offered by this method are: high yields, low catalyst loading, air-stability, and non-toxicity., (Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.net.)

We studied the pseudo-homeothermic synaptic behaviors by integrating complimentary metal-oxide-semiconductor-compatible materials (hafnium oxide, aluminum oxide, and silicon substrate). A wide range of temperatures, from 25 °C up to 145 °C, in neuronal dynamics was achieved owing to the homeothermic properties and the possibility of spike-induced synaptic behaviors was demonstrated, both presenting critical milestones for the use of emerging memristor-type neuromorphic computing systems in the near future. Biological synaptic behaviors, such as long-term potentiation, long-term depression, and spike-timing-dependent plasticity, are developed systematically, and comprehensive neural network analysis is used for temperature changes and to conform spike-induced neuronal dynamics, providing a new research regime of neurocomputing for potentially harsh environments to overcome the self-heating issue in neuromorphic chips.

Neuron is the basic computing unit in brain-inspired neural networks. Although a multitude of excellent artificial neurons realized with conventional transistors have been proposed, they might not be energy and area efficient in large-scale networks. The recent discovery of ferroelectricity in hafnium oxide (HfO2) and the related switching phenomena at the nanoscale might provide a solution. This study employs the newly reported accumulative polarization reversal in nanoscale HfO2-based ferroelectric field-effect transistors (FeFETs) to implement two key neuronal dynamics: the integration of action potentials and the subsequent firing according to the biologically plausible all-or-nothing law. We show that by carefully shaping electrical excitations based on the particular nucleation-limited switching kinetics of the ferroelectric layer further neuronal behaviors can be emulated, such as firing activity tuning, arbitrary refractory period and the leaky effect. Finally, we discuss the advantages of an FeFET-based neuron, highlighting its transferability to advanced scaling technologies and the beneficial impact it may have in reducing the complexity of neuromorphic circuits.

The development of feasible synthesis methods is critical for the successful exploration of novel properties and potential applications of nanomaterials. Here, we introduce the molten-salt synthesis (MSS) method for making metal oxide nanomaterials. Advantages over other methods include its simplicity, greenness, reliability, scalability, and generalizability. Using pyrochlore lanthanum hafnium oxide (La2Hf2O7) as a representative, we describe the MSS protocol for the successful synthesis of complex metal oxide nanoparticles (NPs). Furthermore, this method has the unique ability to produce NPs with different material features by changing various synthesis parameters such as pH, temperature, duration, and post-annealing. By fine-tuning these parameters, we are able to synthesize highly uniform, non-agglomerated, and highly crystalline NPs. As a specific example, we vary the particle size of the La2Hf2O7 NPs by changing the concentration of the ammonium hydroxide solution used in the MSS process, which allows us to further explore the effect of particle size on various properties. It is expected that the MSS method will become a more popular synthesis method for nanomaterials and more widely employed in the nanoscience and nanotechnology community in the upcoming years.

Biomedical implants that incorporate active electronics and offer the ability to operate in a safe, stable fashion for long periods of time must incorporate defect-free layers as barriers to biofluid penetration. This paper reports an engineered material approach to this challenge that combines ultrathin, physically transferred films of silicon dioxide (t-SiO 2 ) thermally grown on silicon wafers, with layers of hafnium oxide (HfO 2 ) formed by atomic layer deposition and coatings of parylene (Parylene C) created by chemical vapor deposition, as a dual-sided encapsulation structure for flexible bioelectronic systems. Accelerated aging tests on passive/active components in platforms that incorporate active, silicon-based transistors suggest that this trilayer construct can serve as a robust, long-lived, defect-free barrier to phosphate-buffered saline (PBS) solution at a physiological pH of 7.4. Reactive diffusion modeling and systematic immersion experiments highlight fundamental aspects of water diffusion and hydrolysis behaviors, with results that suggest lifetimes of many decades at physiological conditions. A combination of ion-diffusion tests under continuous electrical bias, measurements of elemental concentration profiles, and temperature-dependent simulations reveals that this encapsulation strategy can also block transport of ions that would otherwise degrade the performance of the underlying electronics. These findings suggest broad utility of this trilayer assembly as a reliable encapsulation strategy for the most demanding applications in chronic biomedical implants and high-performance flexible bioelectronic systems.

Hafnium (Hf) has attracted considerable attention as a component of biomedical titanium (Ti) alloys with low Young's moduli and/or shape-memory functionalities, because its cytotoxicity is as low as that of Ti. The drawback of metals is that their bone-bonding ability is generally low. It is known that apatite formation in the body is a prerequisite for bone-bonding. Although several chemical treatments have been proposed for preparing Ti for bone-bonding, there have been no similar investigations for Hf. In the present study, NaOH- and heat-treatments were applied to pure Hf and Ti-Hf alloys and their bone-bonding ability was assessed in vitro with the use of simulated body fluid (SBF). After NaOH- and heat-treatments, anatase formed on alloys with low Hf content (20-40% (atom%) Hf); mixtures of sodium titanate and hafnium titanate formed on alloys with similar Ti and Hf content (60% Hf); and hafnium oxide formed on alloys with high Hf content (80% Hf and pure Hf). Precipitates of apatite were observed on all the metals in SBF, except for the alloy with 60% Hf. We speculated that the hafnium titanate formed on this alloy had a low apatite-forming ability owing to its high negative surface charge, which inhibited P adsorption. The apatite-forming abilities of the Ti-Hf alloys strongly depended on their Hf content. The present results indicate that Hf-based materials have good potential for bone-bonding. © 2018 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 106B: 2519-2523, 2018., (© 2017 Wiley Periodicals, Inc.)

The removal of tenacious dental plaque is of paramount importance; however, early diagnosis can be a challenging task in dental clinics due to the limitations of current approaches, specifically X-ray-based techniques. We have approached this problem by integrating antibacterial properties and X-ray contrast enhancement in a single probe specific to colonies of Streptococcus mutans as the most predominant and carious oral bacteria. We report the synthesis of an inherently therapeutic polymeric silane conjugated hafnium oxide nanoparticles (Hf PS NPs). Using a high-affinity pathogen-selective peptide, the concept of molecularly targeted X-ray imaging of cariogenic pathogen S. mutans was demonstrated. Ex vivo studies using extracted human tooth demonstrated striking X-ray attenuation of NPs vs. tooth. Additionally, Hf PS NPs exhibited significant bactericidal properties against cariogenic pathogen. Electron microscopy revealed that the antibacterial activity occurred via a 'latch and kill' mechanism. Mechanistic studies determined that these NPs fragmented bacterial DNA components to exert their antimicrobial effect. Importantly, Hf PS NPs effectively inhibited the growth of a mature biofilm on an ex vivo human tooth model. Finally, the NPs were applied to the rodent model of dental biofilm. Topical administration of the Hf PS NPs for 8 days (1X daily) could effectively attenuate the S. mutans biofilm challenge. This report is the first of its kind to demonstrate that HfO 2 -based NPs can be used for simultaneous diagnosis and antibacterial treatment without requiring an additional drug., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Nuclear medicine with radioisotopes is extremely useful for clinical cancer diagnosis, prognosis, and treatment. Herein, polyethylene glycol (PEG)-modified nanoscale coordination polymers (NCPs) composed of hafnium (Hf 4+ ) and tetrakis (4-carboxyphenyl) porphyrin (TCPP) are prepared via a one-pot reaction. By chelation with the porphyrin structure of TCPP, such Hf-TCPP-PEG NCPs could be easily labeled with 99m Tc 4+ , an imaging radioisotope widely used for single-photon emission computed tomography (SPECT) in a clinical environment. Interestingly, Hf, as a high- Z element in such 99m Tc-Hf-TCPP-PEG NCPs, could endow nontherapeutic 99m Tc with the therapeutic function of killing cancer cells, likely owing to the interaction of Hf with γ rays emitted from 99m Tc to produce charged particles for radiosensitization. With efficient tumor retention, as revealed by SPECT imaging, our 99m Tc-Hf-TCPP-PEG NCPs offer exceptional therapeutic results in eliminating tumors with moderate doses of 99m Tc after either local or systemic administration. Importantly, those biodegradable NCPs could be rapidly excreted without much long-term body retention. Our work, showing the success of applying NCPs for radioisotope therapy (RIT), presents a potential concept for the realization of highly effective cancer treatment with 99m Tc, a short-half-life (6.0 h) diagnostic radioisotope, which is promising for cancer RIT with enhanced efficacy and reduced side effects.

The Resistive RAM (RRAM) technology is currently in a level of maturity that calls for its integration into CMOS compatible memory arrays. This CMOS integration requires a perfect understanding of the cells performance and reliability in relation to the deposition processes used for their manufacturing. In this paper, the impact of the precursor chemistries and process conditions on the performance of HfO 2 based memristive cells is studied. An extensive characterization of HfO 2 based 1T1R cells, a comparison of the cell-to-cell variability, and reliability study is performed. The cells' behaviors during forming, set, and reset operations are monitored in order to relate their features to conductive filament properties and process-induced variability of the switching parameters. The modeling of the high resistance state (HRS) is performed by applying the Quantum-Point Contact model to assess the link between the deposition condition and the precursor chemistry with the resulting physical cells characteristics.

Luminescent nanoparticles are researched for their potential impact in medical science, but no materials approved for parenteral use have been available so far. To overcome this issue, we demonstrate that Eu3+-doped hafnium dioxide nanocrystals can be used as non-toxic, highly stable probes for cellular optical imaging and as radiosensitive materials for clinical treatment. Furthermore, viability and biocompatibility tests on artificially stressed cell cultures reveal their ability to buffer reactive oxygen species, proposing an anti-cytotoxic feature interesting for biomedical applications.