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Nanomaterials, Volume 14, Issue 9 (May-1 2024) – 65 articles

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17 pages, 23851 KiB  
Review
Metal–Organic Framework Nanomaterials as a Medicine for Catalytic Tumor Therapy: Recent Advances
by Jiaojiao Zhang, Meiyu Li, Maosong Liu, Qian Yu, Dengfeng Ge and Jianming Zhang
Nanomaterials 2024, 14(9), 797; https://doi.org/10.3390/nano14090797 - 03 May 2024
Viewed by 119
Abstract
Nanomaterials, with unique physical, chemical, and biocompatible properties, have attracted significant attention as an emerging active platform in cancer diagnosis and treatment. Amongst them, metal–organic framework (MOF) nanostructures are particularly promising as a nanomedicine due to their exceptional surface functionalities, adsorption properties, and [...] Read more.
Nanomaterials, with unique physical, chemical, and biocompatible properties, have attracted significant attention as an emerging active platform in cancer diagnosis and treatment. Amongst them, metal–organic framework (MOF) nanostructures are particularly promising as a nanomedicine due to their exceptional surface functionalities, adsorption properties, and organo-inorganic hybrid characteristics. Furthermore, when bioactive substances are integrated into the structure of MOFs, these materials can be used as anti-tumor agents with superior performance compared to traditional nanomaterials. In this review, we highlight the most recent advances in MOFs-based materials for tumor therapy, including their application in cancer treatment and the underlying mechanisms. Full article
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11 pages, 1846 KiB  
Article
Redox-Modified Nanostructured Electrochemical Surfaces for Continuous Glucose Monitoring in Complex Biological Fluids
by Sajjad Janfaza, Nandhinee Radha Shanmugam, Pawan Jolly, Prashanthi Kovur, Upasana Singh, Scott Mackay, David Wishart and Donald E. Ingber
Nanomaterials 2024, 14(9), 796; https://doi.org/10.3390/nano14090796 - 03 May 2024
Viewed by 132
Abstract
Continuous glucose monitoring is valuable for people with diabetes but faces limitations due to enzyme–electrode interactions and biofouling from biological samples that reduce sensor sensitivity and the monitoring performance. We created an enzyme-based electrochemical system with a unique nanocomposite coating that incorporates the [...] Read more.
Continuous glucose monitoring is valuable for people with diabetes but faces limitations due to enzyme–electrode interactions and biofouling from biological samples that reduce sensor sensitivity and the monitoring performance. We created an enzyme-based electrochemical system with a unique nanocomposite coating that incorporates the redox molecule, aminoferrocene (NH2-Fc). This coating enhances stability via electroactivity and reduces nonspecific binding, as demonstrated through cyclic voltammetry. Our approach enables real-time glucose detection via chronoamperometry with a calculated linear range of 0.5 to 20 mM and a 1 mM detection limit. Validated with plasma and saliva, this platform shows promise for robust metabolite detection in clinical and research contexts. This versatile platform can be applied to accurately monitor a wide range of metabolites in various biological matrices, improving patient outcomes. Full article
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16 pages, 3896 KiB  
Article
Super-Suppression of Long-Wavelength Phonons in Constricted Nanoporous Geometries
by P. Alex Greaney, S. Aria Hosseini, Laura de Sousa Oliveira, Alathea Davies and Neophytos Neophytou
Nanomaterials 2024, 14(9), 795; https://doi.org/10.3390/nano14090795 - 03 May 2024
Viewed by 189
Abstract
In a typical semiconductor material, the majority of the heat is carried by long-wavelength, long-mean-free-path phonons. Nanostructuring strategies to reduce thermal conductivity, a promising direction in the field of thermoelectrics, place scattering centers of size and spatial separation comparable to the mean free [...] Read more.
In a typical semiconductor material, the majority of the heat is carried by long-wavelength, long-mean-free-path phonons. Nanostructuring strategies to reduce thermal conductivity, a promising direction in the field of thermoelectrics, place scattering centers of size and spatial separation comparable to the mean free paths of the dominant phonons to selectively scatter them. The resultant thermal conductivity is in most cases well predicted using Matthiessen’s rule. In general, however, long-wavelength phonons are not as effectively scattered as the rest of the phonon spectrum. In this work, using large-scale molecular-dynamics simulations, non-equilibrium Green’s function simulations, and Monte Carlo simulations, we show that specific nanoporous geometries that create narrow constrictions in the passage of phonons lead to anticorrelated heat currents in the phonon spectrum. This effect results in super-suppression of long-wavelength phonons due to heat trapping and reductions in the thermal conductivity to values well below those predicted by Matthiessen’s rule. Full article
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10 pages, 2513 KiB  
Article
CdSe/ZnS Quantum Rods (QRs) and Phenyl Boronic Acid BODIPY as Efficient Förster Resonance Energy Transfer (FRET) Donor–Acceptor Pair
by Gianluca Salerno, Pasquale Palladino, Marcello Marelli, Laura Polito, Maria Minunni, Debora Berti, Simona Scarano, Giacomo Biagiotti and Barbara Richichi
Nanomaterials 2024, 14(9), 794; https://doi.org/10.3390/nano14090794 - 03 May 2024
Viewed by 217
Abstract
The reversibility of the covalent interaction between boronic acids and 1,2- or 1,3-diols has put the spotlight on this reaction for its potential in the development of sensors and for the fishing of bioactive glycoconjugates. In this work, we describe the investigation of [...] Read more.
The reversibility of the covalent interaction between boronic acids and 1,2- or 1,3-diols has put the spotlight on this reaction for its potential in the development of sensors and for the fishing of bioactive glycoconjugates. In this work, we describe the investigation of this reaction for the reversible functionalization of the surface of CdSe/ZnS Quantum Rods (QRs). With this in mind, we have designed a turn-off Förster resonance energy transfer (FRET) system that ensures monitoring the extent of the reaction between the phenyl boronic residue at the meso position of a BODIPY probe and the solvent-exposed 1,2-diols on QRs’ surface. The reversibility of the corresponding boronate ester under oxidant conditions has also been assessed, thus envisioning the potential sensing ability of this system. Full article
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17 pages, 3574 KiB  
Article
Electrochemical Sensing Device for Carboplatin Monitoring in Proof-of-Concept Drug Delivery Nanosystems
by Alexandra Pusta, Mihaela Tertis, Catalina Ardusadan, Simona Mirel and Cecilia Cristea
Nanomaterials 2024, 14(9), 793; https://doi.org/10.3390/nano14090793 - 02 May 2024
Viewed by 324
Abstract
(1) Background: Carboplatin (CBP) is a chemotherapeutic drug widely used in the treatment of a variety of cancers. Despite its efficiency, CBP is associated with side effects that greatly limit its clinical use. To mitigate these effects, CBP can be encapsulated in targeted [...] Read more.
(1) Background: Carboplatin (CBP) is a chemotherapeutic drug widely used in the treatment of a variety of cancers. Despite its efficiency, CBP is associated with side effects that greatly limit its clinical use. To mitigate these effects, CBP can be encapsulated in targeted delivery systems, such as liposomes. Ensuring the adequate loading and release of CBP from these carriers requires strict control in pharmaceutical formulation development, demanding modern, rapid, and robust analytical methods. The aim of this study was the development of a sensor for the fast and accurate quantification of CBP and its application on proof-of-concept CBP-loaded nanosomes. (2) Methods: Screen-printed electrodes were obtained in-lab and the electrochemical behavior of CBP was tested on the obtained electrodes. (3) Results: The in-lab screen-printed electrodes demonstrated superior properties compared to commercial ones. The novel sensors demonstrated accurate detection of CBP on a dynamic range from 5 to 500 μg/mL (13.5–1350 μM). The method was successfully applied on CBP loaded and released from nanosomes, with strong correlations with a spectrophotometric method used as control. (4) Conclusions: This study demonstrates the viability of electrochemical techniques as alternative options during the initial phases of pharmaceutical formulation development. Full article
(This article belongs to the Special Issue Trends in Electrochemical Nanosensing)
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14 pages, 5060 KiB  
Article
Heat-Annealed Zinc Oxide on Flexible Carbon Nanotube Paper and Exposed to Gradient Light to Enhance Its Photoelectric Response
by Jih-Hsin Liu and Pi-Yu Shen
Nanomaterials 2024, 14(9), 792; https://doi.org/10.3390/nano14090792 - 02 May 2024
Viewed by 264
Abstract
Buckypaper (BP), a flexible and porous material, exhibits photovoltaic properties when exposed to light. In this study, we employed radio frequency (RF) sputtering of zinc oxide (ZnO) followed by rapid thermal annealing to enhance the photovoltaic response of BP. We investigated the impact [...] Read more.
Buckypaper (BP), a flexible and porous material, exhibits photovoltaic properties when exposed to light. In this study, we employed radio frequency (RF) sputtering of zinc oxide (ZnO) followed by rapid thermal annealing to enhance the photovoltaic response of BP. We investigated the impact of various sputtering parameters, such as the gas flow ratio of argon to oxygen and deposition time, on the morphology, composition, resistivity, and photovoltaic characteristics of ZnO-modified BP. Additionally, the photovoltaic performance of the samples under different illumination modes and wavelengths was compared. It was found that optimal sputtering conditions—argon to oxygen flow ratio of 1:2, deposition time of 20 min, and power of 100 watts—resulted in a ZnO film thickness of approximately 45 nanometers. After annealing at 400 °C for 10 min, the ZnO-modified BP demonstrated a significant increase in photocurrent and photovoltage, along with a reduction in resistivity, compared to unmodified BP. Moreover, under gradient illumination, the ZnO-modified BP exhibited a photovoltage enhancement of 14.70-fold and a photocurrent increase of 13.86-fold, compared to uniform illumination. Under blue light, it showed a higher photovoltaic response than under other colors. The enhancement in photovoltaic response is attributed to the formation of a Schottky junction between ZnO and BP, an increased carrier concentration gradient, and an expanded light absorption spectrum. Our results validate that ZnO sputtering followed by annealing is an effective method for modifying BP for photovoltaic applications such as solar cells and photodetectors. Full article
(This article belongs to the Special Issue Growth, Characterization and Applications of Nanotubes: Volume II)
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10 pages, 20028 KiB  
Article
UV/Ozone-Treated and Sol–Gel-Processed Y2O3 Insulators Prepared Using Gelation-Delaying Precursors
by Sangwoo Lee, Yoonjin Cho, Seongwon Heo, Jin-Hyuk Bae, In-Man Kang, Kwangeun Kim, Won-Yong Lee and Jaewon Jang
Nanomaterials 2024, 14(9), 791; https://doi.org/10.3390/nano14090791 - 01 May 2024
Viewed by 241
Abstract
In this study, a Y2O3 insulator was fabricated via the sol–gel process and the effect of precursors and annealing processes on its electrical performance was studied. Yttrium(III) acetate hydrate, yttrium(III) nitrate tetrahydrate, yttrium isopropoxide oxide, and yttrium(III) tris (isopropoxide) were [...] Read more.
In this study, a Y2O3 insulator was fabricated via the sol–gel process and the effect of precursors and annealing processes on its electrical performance was studied. Yttrium(III) acetate hydrate, yttrium(III) nitrate tetrahydrate, yttrium isopropoxide oxide, and yttrium(III) tris (isopropoxide) were used as precursors, and UV/ozone treatment and high-temperature annealing were performed to obtain Y2O3 films from the precursors. The structure and surface morphologies of the films were characterized via grazing-incidence X-ray diffraction and scanning probe microscopy. Chemical component analysis was performed via X-ray spectroscopy. Electrical insulator characteristics were analyzed based on current density versus electrical field data and frequency-dependent dielectric constants. The Y2O3 films fabricated using the acetate precursor and subjected to the UV/ozone treatment showed a uniform and flat surface morphology with the lowest number of oxygen vacancy defects and unwanted byproducts. The corresponding fabricated capacitors showed the lowest current density (Jg) value of 10−8 A/cm2 at 1 MV/cm and a stable dielectric constant in a frequency range of 20 Hz–100 KHz. At 20 Hz, the dielectric constant was 12.28, which decreased to 10.5 at 105 Hz. The results indicate that high-quality, high-k insulators can be fabricated for flexible electronics using suitable precursors and the suggested low-temperature fabrication methods. Full article
(This article belongs to the Special Issue Nano-Structured Thin Films: Growth, Characteristics, and Application)
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10 pages, 2877 KiB  
Article
Klein Tunneling in β12 Borophene
by Jinhao Lai, Lekang Wang, Fu Li, Hongbin Zhang and Qingtian Zhang
Nanomaterials 2024, 14(9), 790; https://doi.org/10.3390/nano14090790 - 01 May 2024
Viewed by 185
Abstract
Motivated by the recent observation of Klein tunneling in 8-Pmmn borophene, we delve into the phenomenon in β12 borophene by employing tight-binding approximation theory to establish a theoretical mode. The tight-binding model is a semi-empirical method for establishing the Hamiltonian based on [...] Read more.
Motivated by the recent observation of Klein tunneling in 8-Pmmn borophene, we delve into the phenomenon in β12 borophene by employing tight-binding approximation theory to establish a theoretical mode. The tight-binding model is a semi-empirical method for establishing the Hamiltonian based on atomic orbitals. A single cell of β12 borophene contains five atoms and multiple central bonds, so it creates the complexity of the tight-binding model Hamiltonian of β12 borophene. We investigate transmission across one potential barrier and two potential barriers by changing the width and height of barriers and the distance between two potential barriers. Regardless of the change in the barrier heights and widths, we find the interface to be perfectly transparent for normal incidence. For other angles of incidence, perfect transmission at certain angles can also be observed. Furthermore, perfect and all-angle transmission across a potential barrier takes place when the incident energy approaches the Dirac point. This is analogous to the “super”, all-angle transmission reported for the dice lattice for Klein tunneling across a potential barrier. These findings highlight the significance of our theoretical model in understanding the complex dynamics of Klein tunneling in borophene structures. Full article
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20 pages, 4960 KiB  
Article
Simultaneous Detection of Carbon Quantum Dots as Tracers for Interwell Connectivity Evaluation in a Pattern with Two Injection Wells
by Stephania Rosales, Karol Zapata, Farid B. Cortes, Benjamín Rojano, Carlos Diaz, Carlos Cortes, David Jaramillo, Adriana Vasquez, Diego Ramirez and Camilo A. Franco
Nanomaterials 2024, 14(9), 789; https://doi.org/10.3390/nano14090789 - 01 May 2024
Viewed by 221
Abstract
This study aimed to develop and implement a nanotechnology-based alternative to traditional tracers used in the oil and gas industry for assessing interwell connectivity. A simple and rapid hydrothermal protocol for synthesizing carbon quantum dots (CQDs) using agroindustry waste was implemented. Three commercial [...] Read more.
This study aimed to develop and implement a nanotechnology-based alternative to traditional tracers used in the oil and gas industry for assessing interwell connectivity. A simple and rapid hydrothermal protocol for synthesizing carbon quantum dots (CQDs) using agroindustry waste was implemented. Three commercial CQDs were employed (CQDblue, CQDgreen, and CQDred); the fourth was synthesized from orange peel (CQDop). The CQDs from waste and other commercials with spherical morphology, nanometric sizes less than 11 nm in diameter, and surface roughness less than 3.1 nm were used. These tracers demonstrated high colloidal stability with a negative zeta potential, containing carbonyl-type chemical groups and unsaturations in aromatic structures that influenced their optical behavior. All materials presented high colloidal stability with negative values of charge z potential between −17.8 and −49.1. Additionally, individual quantification of these tracers is feasible even in scenarios where multiple CQDs are present in the effluent with a maximum percentage of interference of 15.5% for CQDop in the presence of the other three nanotracers. The CQDs were injected into the field once the technology was insured under laboratory conditions. Monitoring the effluents allowed the determination of connectivity for five first-line producer wells. This study enables the application of CQDs in the industry, particularly in fields where the arrangement of injector and producer wells is intricate, requiring the use of multiple tracers for a comprehensive description of the system. Full article
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11 pages, 3437 KiB  
Article
Hydrogenation of Furfural over Biomass-Based Electron-Deficient Co-NC Nanotube Catalyst
by Zhu Zhu and Guangyue Xu
Nanomaterials 2024, 14(9), 788; https://doi.org/10.3390/nano14090788 - 01 May 2024
Viewed by 252
Abstract
The conversion of furfural to furfuryl alcohol is one of the most significant reactions from industrial-scale produced biomass platform molecules to value-added chemicals. In this work, biomass-based chitosan was used as both a carbon source and nitrogen source to synthesize nitrogen-doped carbon. With [...] Read more.
The conversion of furfural to furfuryl alcohol is one of the most significant reactions from industrial-scale produced biomass platform molecules to value-added chemicals. In this work, biomass-based chitosan was used as both a carbon source and nitrogen source to synthesize nitrogen-doped carbon. With the addition of cobalt, the optimized 7.5Co-NC-900 catalyst had the largest surface area and the graphite nanotube structure with the least defects. It was employed for the hydrogenation of furfural to furfuryl alcohol and reached a nearly full conversion and an equivalent yield at 130 °C in 4 MPa initial H2. The structure–function relationship study indicated that the N could interact with the neighbor Co in this catalyst and formed an electron-deficient Co center which was in favor of the adsorption of furfural in the nanotube and had high catalytic activity. The interactions between Co and N stabilized the catalyst so that it could remain stable in five runs of catalytic reactions. Full article
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17 pages, 12065 KiB  
Communication
Adjoint Algorithm Design of Selective Mode Reflecting Metastructure for BAL Applications
by Zean Li, Xunyu Zhang, Cheng Qiu, Yingshuai Xu, Zhipeng Zhou, Ziyuan Wei, Yiman Qiao, Yongyi Chen, Yubing Wang, Lei Liang, Yuxin Lei, Yue Song, Peng Jia, Yugang Zeng, Li Qin, Yongqiang Ning and Lijun Wang
Nanomaterials 2024, 14(9), 787; https://doi.org/10.3390/nano14090787 - 01 May 2024
Viewed by 205
Abstract
Broad-area lasers (BALs) have found applications in a variety of crucial fields on account of their high output power and high energy transfer efficiency. However, they suffer from poor spatial beam quality due to multi-mode behavior along the waveguide transverse direction. In this [...] Read more.
Broad-area lasers (BALs) have found applications in a variety of crucial fields on account of their high output power and high energy transfer efficiency. However, they suffer from poor spatial beam quality due to multi-mode behavior along the waveguide transverse direction. In this paper, we propose a novel metasurface waveguide structure acting as a transverse mode selective back-reflector for BALs. In order to effectively inverse design such a structure, a digital adjoint algorithm is introduced to adapt the considerably large design area and the high degree of freedom. As a proof of the concept, a device structure with a design area of 40 × 20 μm2 is investigated. The simulation results exhibit high fundamental mode reflection (above 90%), while higher-order transverse mode reflections are suppressed below 0.2%. This is, to our knowledge, the largest device structure designed based on the inverse method. We exploited such a device and the method and further investigated the device’s robustness and feasibility of the inverse method. The results are elaborately discussed. Full article
(This article belongs to the Section Theory and Simulation of Nanostructures)
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16 pages, 3376 KiB  
Article
Enhancement of Peroxydisulfate Activation for Complete Degradation of Refractory Tetracycline by 3D Self-Supported MoS2/MXene Nanocomplex
by Yuxia Song, Runhua Chen, Shihai Li, Shali Yu, Xiaoli Ni, Minglong Fang and Hanyun Xie
Nanomaterials 2024, 14(9), 786; https://doi.org/10.3390/nano14090786 - 30 Apr 2024
Viewed by 249
Abstract
Antibiotic abuse, particularly the excessive use of tetracycline (TC), a drug with significant environmental risk, has gravely harmed natural water bodies and even posed danger to human health. In this study, a three-dimensional self-supported MoS2/MXene nanohybrid with an expanded layer spacing [...] Read more.
Antibiotic abuse, particularly the excessive use of tetracycline (TC), a drug with significant environmental risk, has gravely harmed natural water bodies and even posed danger to human health. In this study, a three-dimensional self-supported MoS2/MXene nanohybrid with an expanded layer spacing was synthesized via a facile one-step hydrothermal method and used to activate peroxydisulfate (PDS) for the complete degradation of TC. The results showed that a stronger •OH signal was detected in the aqueous solution containing MoS2/MXene, demonstrating a superior PDS activation effect compared to MoS2 or Ti3C2TX MXene alone. Under the conditions of a catalyst dosage of 0.4 g/L, a PDS concentration of 0.4 mM, and pH = 5.0, the MoS2/MXene/PDS system was able to fully eliminate TC within one hour, which was probably due to the presence of several reactive oxygen species (ROS) (•OH, SO4•−, and O2•−) in the system. The high TC degradation efficiency could be maintained under the influence of various interfering ions and after five cycles, indicating that MoS2/MXene has good anti-interference and reusability performance. Furthermore, the possible degradation pathways were proposed by combining liquid chromatography–mass spectrometry (LC-MS) data and other findings, and the mechanism of the MoS2/MXene/PDS system on the degradation process of TC was elucidated by deducing the possible mechanism of ROS generation in the reaction process. All of these findings suggest that the MoS2/MXene composite catalyst has strong antibiotic removal capabilities with a wide range of application prospects. Full article
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20 pages, 4848 KiB  
Article
Pyroclastic Dust from Arequipa-Peru Decorated with Iron Oxide Nanoparticles and Their Ecotoxicological Properties in Water Flea D. magna
by Juan A. Ramos-Guivar, Yacu V. Alca-Ramos, Erich V. Manrique-Castillo, F. Mendoza-Villa, Noemi-Raquel Checca-Huaman, Renzo Rueda-Vellasmin and Edson C. Passamani
Nanomaterials 2024, 14(9), 785; https://doi.org/10.3390/nano14090785 - 30 Apr 2024
Viewed by 318
Abstract
A novel magnetic composite made of Peruvian pyroclastic dust material decorated with maghemite nanoparticles was synthesized and characterized using a variety of analytic techniques. The 13 nm maghemite nanoparticles were grown on the pyroclastic dust using the conventional coprecipitation chemical route. A short-term [...] Read more.
A novel magnetic composite made of Peruvian pyroclastic dust material decorated with maghemite nanoparticles was synthesized and characterized using a variety of analytic techniques. The 13 nm maghemite nanoparticles were grown on the pyroclastic dust using the conventional coprecipitation chemical route. A short-term acute assay was developed to study the ecotoxicological behavior of the water flea, Daphnia magna. A 24 h-lethal concentration (LC50) value equal to 123.6 mg L−1 was determined only for the magnetic composite. While the pyroclastic dust material did not exhibit a lethal concentration, it caused morphologically significant changes (p < 0.05) for heart and tail parameters at high concentrations. Morphologies exposed to the magnetic composite above the 24 h-LC50 revealed less tolerance and significant changes in the body, heart, antenna, and eye. Hence, it affects biomarker growth and swimming. The reproduction rate was not affected by the raw pyroclastic dust material. However, the number of individuals showed a decrease with increasing composite concentrations. The present study indicates the LC50 value, which can be used as a reference concentration for in-situ water cleaning with this material without damaging or changing the Daphnia magna ecosystem. Full article
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11 pages, 1173 KiB  
Article
Towards a More Efficient Breast Cancer Therapy Using Active Human Cell Membrane-Coated Metal–Organic Frameworks
by Pablo Graván, Sara Rojas, Darina Francesca Picchi, Francisco Galisteo-González, Patricia Horcajada and Juan Antonio Marchal
Nanomaterials 2024, 14(9), 784; https://doi.org/10.3390/nano14090784 - 30 Apr 2024
Viewed by 185
Abstract
The recent description of well-defined molecular subtypes of breast cancer has led to the clinical development of a number of successful molecular targets. Particularly, triple-negative breast cancer (TNBC) is an aggressive type of breast cancer with historically poor outcomes, mainly due to the [...] Read more.
The recent description of well-defined molecular subtypes of breast cancer has led to the clinical development of a number of successful molecular targets. Particularly, triple-negative breast cancer (TNBC) is an aggressive type of breast cancer with historically poor outcomes, mainly due to the lack of effective targeted therapies. Recent progresses in materials science have demonstrated the impressive properties of metal–organic framework nanoparticles (NPs) as antitumoral drug delivery systems. Here, in a way to achieve efficient bio-interfaces with cancer cells and improve their internalization, benchmarked MIL-100(Fe) NPs were coated with cell membranes (CMs) derived from the human TNBC cell line MDA-MB-468. The prepared CMs-coated metal–organic framework (CMs_MIL-100(Fe)) showed enhanced colloidal stability, cellular uptake, and cytotoxicity in MDA-MB-468 cells compared to non-coated NPs, paving the way for these human CMs-coated MIL-100(Fe) NPs as effective targeted therapies against the challenging TNBC. Full article
(This article belongs to the Section Inorganic Materials and Metal-Organic Frameworks)
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14 pages, 20281 KiB  
Article
Optimizing Josephson Junction Reproducibility in 30 kV E-Beam Lithography: An Analysis of Backscattered Electron Distribution
by Arthur M. Rebello, Lucas M. Ruela, Gustavo Moreto, Naiara Y. Klein, Eldues Martins, Ivan S. Oliveira, João P. Sinnecker and Francisco Rouxinol
Nanomaterials 2024, 14(9), 783; https://doi.org/10.3390/nano14090783 - 30 Apr 2024
Viewed by 203
Abstract
This paper explores methods to enhance the reproducibility of Josephson junctions, which are crucial elements in superconducting quantum technologies, when employing the Dolan technique in 30 kV e-beam processes. The study explores the influence of dose distribution along the bridge area on reproducibility, [...] Read more.
This paper explores methods to enhance the reproducibility of Josephson junctions, which are crucial elements in superconducting quantum technologies, when employing the Dolan technique in 30 kV e-beam processes. The study explores the influence of dose distribution along the bridge area on reproducibility, addressing challenges related to fabrication sensitivity. Experimental methods include e-beam lithography, with electron trajectory simulations shedding light on the behavior of backscattered electrons. Wedescribe the fabrication of various Josephson junction geometries and analyze the correlation between the success rates of different lithography patterns and the simulated distribution of backscattered electrons. Our findings demonstrate a success rate of up to 96.3% for the double-resist 1-step low-energy e-beam lithography process. As a means of implementation strategy, we provide a geometric example that takes advantage of simulated stability regions to administer a controlled, uniform dose across the junction area, introducing novel features to overcome the difficulties associated with fabricating bridge-like structures. Full article
(This article belongs to the Section Nanofabrication and Nanomanufacturing)
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15 pages, 2777 KiB  
Article
Synthesis, Surface Modification and Magnetic Properties Analysis of Heat-Generating Cobalt-Substituted Magnetite Nanoparticles
by Miloš Ognjanović, Marko Bošković, Hristo Kolev, Biljana Dojčinović, Sanja Vranješ-Đurić and Bratislav Antić
Nanomaterials 2024, 14(9), 782; https://doi.org/10.3390/nano14090782 - 30 Apr 2024
Viewed by 465
Abstract
Here, we present the results of the synthesis, surface modification, and properties analysis of magnetite-based nanoparticles, specifically Co0.047Fe2.953O4 (S1) and Co0.086Fe2.914O4 (S2). These nanoparticles were synthesized using the co-precipitation method at 80 °C [...] Read more.
Here, we present the results of the synthesis, surface modification, and properties analysis of magnetite-based nanoparticles, specifically Co0.047Fe2.953O4 (S1) and Co0.086Fe2.914O4 (S2). These nanoparticles were synthesized using the co-precipitation method at 80 °C for 2 h. They exhibit a single-phase nature and crystallize in a spinel-type structure (space group Fd3¯m). Transmission electron microscopy analysis reveals that the particles are quasi-spherical in shape and approximately 11 nm in size. An observed increase in saturation magnetization, coercivity, remanence, and blocking temperature in S2 compared to S1 can be attributed to an increase in magnetocrystalline anisotropy due to the incorporation of Co ions in the crystal lattice of the parent compound (Fe3O4). The heating efficiency of the samples was determined by fitting the Box-Lucas equation to the acquired temperature curves. The calculated Specific Loss Power (SLP) values were 46 W/g and 23 W/g (under HAC = 200 Oe and f = 252 kHz) for S1 and S2, respectively. Additionally, sample S1 was coated with citric acid (Co0.047Fe2.953O4@CA) and poly(acrylic acid) (Co0.047Fe2.953O4@PAA) to obtain stable colloids for further tests for magnetic hyperthermia applications in cancer therapy. Fits of the Box-Lucas equation provided SLP values of 21 W/g and 34 W/g for CA- and PAA-coated samples, respectively. On the other hand, X-ray photoelectron spectroscopy analysis points to the catalytically active centers Fe2+/Fe3+ and Co2+/Co3+ on the particle surface, suggesting possible applications of the samples as heterogeneous self-heating catalysts in advanced oxidation processes under an AC magnetic field. Full article
(This article belongs to the Collection Metallic and Metal Oxide Nanohybrids and Their Applications)
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15 pages, 2221 KiB  
Article
Field Emission from Carbon Nanotubes on Titanium Nitride-Coated Planar and 3D-Printed Substrates
by Stefanie Haugg, Luis-Felipe Mochalski, Carina Hedrich, Isabel González Díaz-Palacio, Kristian Deneke, Robert Zierold and Robert H. Blick
Nanomaterials 2024, 14(9), 781; https://doi.org/10.3390/nano14090781 - 30 Apr 2024
Viewed by 192
Abstract
Carbon nanotubes (CNTs) are well known for their outstanding field emission (FE) performance, facilitated by their unique combination of electrical, mechanical, and thermal properties. However, if the substrate of choice is a poor conductor, the electron supply towards the CNTs can be limited, [...] Read more.
Carbon nanotubes (CNTs) are well known for their outstanding field emission (FE) performance, facilitated by their unique combination of electrical, mechanical, and thermal properties. However, if the substrate of choice is a poor conductor, the electron supply towards the CNTs can be limited, restricting the FE current. Furthermore, ineffective heat dissipation can lead to emitter–substrate bond degradation, shortening the field emitters’ lifetime. Herein, temperature-stable titanium nitride (TiN) was deposited by plasma-enhanced atomic layer deposition (PEALD) on different substrate types prior to the CNT growth. A turn-on field reduction of up to 59% was found for the emitters that were generated on TiN-coated bulk substrates instead of on pristine ones. This observation was attributed exclusively to the TiN layer as no significant change in the emitter morphology could be identified. The fabrication route and, consequently, improved FE properties were transferred from bulk substrates to free-standing, electrically insulating nanomembranes. Moreover, 3D-printed, polymeric microstructures were overcoated by atomic layer deposition (ALD) employing its high conformality. The results of our approach by combining ALD with CNT growth could assist the future fabrication of highly efficient field emitters on 3D scaffold structures regardless of the substrate material. Full article
(This article belongs to the Special Issue The Research Related to Nanomaterial Cold Cathode II)
15 pages, 1208 KiB  
Article
Schottky Junctions with Bi@Bi2MoO6 Core-Shell Photocatalysts toward High-Efficiency Solar N2-to-Ammonnia Conversion in Aqueous Phase
by Meijiao Wang, Guosong Wei, Renjie Li, Meng Yu, Guangbo Liu and Yanhua Peng
Nanomaterials 2024, 14(9), 780; https://doi.org/10.3390/nano14090780 - 30 Apr 2024
Viewed by 153
Abstract
The photocatalytic nitrogen reduction reaction (NRR) in aqueous solution is a green and sustainable strategy for ammonia production. Nonetheless, the efficiency of the process still has a wide gap compared to that of the Haber–Bosch one due to the difficulty of N2 [...] Read more.
The photocatalytic nitrogen reduction reaction (NRR) in aqueous solution is a green and sustainable strategy for ammonia production. Nonetheless, the efficiency of the process still has a wide gap compared to that of the Haber–Bosch one due to the difficulty of N2 activation and the quick recombination of photo-generated carriers. Herein, a core-shell Bi@Bi2MoO6 microsphere through constructing Schottky junctions has been explored as a robust photocatalyst toward N2 reduction to NH3. Metal Bi self-reduced onto Bi2MoO6 not only spurs the photo-generated electron and hole separation owing to the Schottky junction at the interface of Bi and Bi2MoO6 but also promotes N2 adsorption and activation at Bi active sites synchronously. As a result, the yield of the photocatalytic N2-to-ammonia conversion reaches up to 173.40 μmol g1 on core-shell Bi@Bi2MoO6 photocatalysts, as much as two times of that of bare Bi2MoO6. This work provides a new design for the decarbonization of the nitrogen reduction reaction by the utilization of renewable energy sources. Full article
19 pages, 12359 KiB  
Review
Recent Advances in Self-Assembled Molecular Application in Solar Cells
by Linkun Zhong, Chuangping Liu, Shi Lai, Bing’e Li, Baihong Zheng and Xiaoli Zhang
Nanomaterials 2024, 14(9), 779; https://doi.org/10.3390/nano14090779 - 30 Apr 2024
Viewed by 255
Abstract
Perovskite solar cells (PSCs) have attracted much attention due to their low cost, high efficiency, and solution processability. With the development of various materials in perovskite solar cells, self-assembled monolayers (SAMs) have rapidly become an important factor in improving power conversion efficiency (PCE) [...] Read more.
Perovskite solar cells (PSCs) have attracted much attention due to their low cost, high efficiency, and solution processability. With the development of various materials in perovskite solar cells, self-assembled monolayers (SAMs) have rapidly become an important factor in improving power conversion efficiency (PCE) due to their unique physical and chemical properties and better energy level matching. In this topical review, we introduced important categories of self-assembled molecules, energy level modulation strategies, and various characteristics of self-assembled molecules. In addition, we focused on reviewing the application of self-assembled molecules in solar cells, and explained the changes that self-assembled molecules bring to PSCs by introducing the mechanism and effect of self-assembled molecules. Finally, we also elaborated on the challenges currently faced by self-assembled molecules and provided prospects for their applications in other optoelectronic devices. Full article
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14 pages, 2608 KiB  
Article
Long-Range Effects in Topologically Defective Arm-Chair Graphene Nanoribbons
by Enrique Louis, Guillermo Chiappe, José A. Vergés and Emilio San-Fabián
Nanomaterials 2024, 14(9), 778; https://doi.org/10.3390/nano14090778 - 30 Apr 2024
Viewed by 217
Abstract
The electronic structure of 7/9-AGNR superlattices with up to eight unit cells has been studied by means of state-of-the-art Density Functional Theory (DFT) and also by two model Hamiltonians, the first one including only local interactions (Hubbard model, Hu) while the second one [...] Read more.
The electronic structure of 7/9-AGNR superlattices with up to eight unit cells has been studied by means of state-of-the-art Density Functional Theory (DFT) and also by two model Hamiltonians, the first one including only local interactions (Hubbard model, Hu) while the second one is extended to allow long-range Coulomb interactions (Pariser, Parr and Pople model, PPP). Both are solved within mean field approximation. At this approximation level, our calculations show that 7/9 interfaces are better described by spin non-polarized solutions than by spin-polarized wavefunctions. Consequently, both Hu and PPP Hamiltonians lead to electronic structures characterized by a gap at the Fermi level that diminishes as the size of the system increases. DFT results show similar trends although a detailed analysis of the density of states around the Fermi level shows quantitative differences with both Hu and PPP models. Before improving model Hamiltonians, we interpret the electronic structure obtained by DFT in terms of bands of topological states: topological states localized at the system edges and extended bulk topological states that interact between them due to the long-range Coulomb terms of Hamiltonian. After careful analysis of the interaction among topological states, we find that the discrepancy between ab initio and model Hamiltonians can be resolved considering a screened long-range interaction that is implemented by adding an exponential cutoff to the interaction term of the PPP model. In this way, an adjusted cutoff distance λ=2 allows a good recovery of DFT results. In view of this, we conclude that the correct description of the density of states around the Fermi level (Dirac point) needs the inclusion of long-range interactions well beyond the Hubbard model but not completely unscreened as is the case for the PPP model. Full article
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15 pages, 3412 KiB  
Article
Modulation of the Effect of Cisplatin on Nicotine-Stimulated A549 Lung Cancer Cells Using Analog of Marine Sponge Toxin Loaded in Gelatin Nanoparticles
by Ahmad Joukhan, Veno Kononenko, Marija Sollner Dolenc, Matej Hočevar, Tom Turk and Damjana Drobne
Nanomaterials 2024, 14(9), 777; https://doi.org/10.3390/nano14090777 - 30 Apr 2024
Viewed by 221
Abstract
Nicotine activates nicotinic acetylcholine receptors (nAChRs), which are overexpressed in numerous cancer types, leading to signaling pathways that increase lung cancer invasiveness and resistance to chemotherapeutic agents. In this study, the effects of APS12-2, a synthetic analog of marine sponge toxin that acts [...] Read more.
Nicotine activates nicotinic acetylcholine receptors (nAChRs), which are overexpressed in numerous cancer types, leading to signaling pathways that increase lung cancer invasiveness and resistance to chemotherapeutic agents. In this study, the effects of APS12-2, a synthetic analog of marine sponge toxin that acts as an antagonist of nAChRs, was investigated in vitro on A549 human lung adenocarcinoma cells and non-tumorigenic human lung epithelial BEAS-2B cells. In addition, gelatin nanoparticles (GNPs) loaded with APS12-2 (APS12-2-GNPs) were prepared and their effects were compared with those of free APS12-2. Nicotine reduced cytotoxicity, the formation of reactive oxygen species, and the formation of lipid droplets caused by cisplatin on A549 cells. The effects of nicotine on the decreased efficacy of cisplatin were reduced by APS12-2 and APS12-2-GNPs. APS12-2-GNPs showed a substantial advantage compared with free APS12-2; the cytotoxicity of APS12-2 on BEAS-2B cells was greatly reduced when APS12-2 was loaded in GNPs, whereas the cytotoxicity on A549 cells was only slightly reduced. Our results suggest that both APS12-2 and APS12-2-GNPs hold promise as supportive agents in the cisplatin-based chemotherapy of lung cancer. Full article
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22 pages, 9304 KiB  
Article
The Time-Dependent Interfacial Adhesion between Artificial Rock and Fresh Mortar Modified by Nanoclay
by Xiaoyun Wang, Kim Van Tittelboom, Jiaolong Zhang, Yaxin Tao, Yao Rong, Luc Taerwe, Geert De Schutter and Yong Yuan
Nanomaterials 2024, 14(9), 776; https://doi.org/10.3390/nano14090776 - 30 Apr 2024
Viewed by 242
Abstract
The time-dependent interfacial adhesion between rock and fresh mortar is key for printing concrete linings in mountain tunnels. However, a scientific deficit exists in the time-dependent evolution of the interfacial adhesion, which can cause adhesion failure when printing tunnel lining. Nanoclay has the [...] Read more.
The time-dependent interfacial adhesion between rock and fresh mortar is key for printing concrete linings in mountain tunnels. However, a scientific deficit exists in the time-dependent evolution of the interfacial adhesion, which can cause adhesion failure when printing tunnel lining. Nanoclay has the potential to increase the interfacial adhesion and eliminate the adhesion failure. Before the actual printing of tunnel linings, the time-dependent interfacial adhesion between artificial rock and fresh mortar modified by nanoclay should be understood. This paper studied the time-dependent interfacial adhesion based on fast tack tests, fast shear tests, and isothermal calorimetry tests. With the addition of nanoclay, the maximum tensile stress and the maximum shear stress increased. Compared with a reference series, the maximum interfacial tensile stress in a 0.3% nanoclay series increased by 106% (resting time 1 min) and increased by 209% (resting time 32 min). A two-stage evolution of the interfacial adhesion was found with the addition of nanoclay. In the first stage, the time-dependent interfacial adhesion increased rapidly. A 0.3% NC series showed an increase rate six times higher than that of the reference series. As the matrices aged, the increase rate slowed down and followed a linear pattern of increase, still higher than that of the reference series. The stiffening of fresh matrices resulted in the interface failure mode transition from a ductile failure to a brittle failure. The effect of nanoclay on flocculation and on accelerating the hydration contributed to the time-dependent interfacial adhesion between artificial rock and fresh mortar. Full article
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11 pages, 1944 KiB  
Communication
Cytosine-Rich Oligonucleotide and Electrochemically Reduced Graphene Oxide Nanocomposite for Ultrasensitive Electrochemical Ag+ Sensing
by Nasir Abbas, Seung Joo Jang and Tae Hyun Kim
Nanomaterials 2024, 14(9), 775; https://doi.org/10.3390/nano14090775 - 29 Apr 2024
Viewed by 354
Abstract
Silver ions (Ag+) are crucial in various fields, but pose environmental and health risks at high concentrations. This study presents a straightforward approach for the ultra-trace detection of Ag+, utilizing a composite of a cytosine-rich oligonucleotide (CRO) and an [...] Read more.
Silver ions (Ag+) are crucial in various fields, but pose environmental and health risks at high concentrations. This study presents a straightforward approach for the ultra-trace detection of Ag+, utilizing a composite of a cytosine-rich oligonucleotide (CRO) and an electrochemically reduced graphene oxide (ERGO). Initially, ERGO was synthesized on a glassy carbon electrode (GCE) through the reduction of graphene oxide (GO) via cyclic voltammetry. A methylene blue-tagged CRO (MB-CRO) was then anchored to the ERGO surface through π–π interactions, resulting in the formation of an MB-CRO-modified ERGO electrode (MB-CRO/ERGO-GCE). The interaction with Ag+ ions induced the formation of silver-mediated C-Ag+-C coordination, prompting the MB-CRO to adopt a hairpin structure. This conformational change led to the desorption of the MB-CRO from the ERGO-GCE, causing a variation in the redox current of the methylene blue associated with the MB-CRO. Electrochemical assays revealed that the sensor exhibits extraordinary sensitivity to Ag+ ions, with a linear detection range from 1 femtomolar (fM) to 100 nanomolars (nM) and a detection limit of 0.83 fM. Moreover, the sensor demonstrated high selectivity for Ag+ ions and several other benefits, including stability, reproducibility, and straightforward fabrication and operational procedures. Additionally, real sample analyses were performed using the modified electrode to detect Ag+ in tap and pond water samples, yielding satisfactory recovery rates. Full article
(This article belongs to the Special Issue Advanced Nanocomposites for Sensing Applications)
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27 pages, 10894 KiB  
Article
Performance Prediction and Optimization of Nanofluid-Based PV/T Using Numerical Simulation and Response Surface Methodology
by Sreehari Sreekumar, Supriya Chakrabarti, Neil Hewitt, Jayanta Deb Mondol and Nikhilkumar Shah
Nanomaterials 2024, 14(9), 774; https://doi.org/10.3390/nano14090774 - 28 Apr 2024
Viewed by 253
Abstract
A numerical investigation was carried out in ANSYS Fluent® on a photovoltaic/thermal (PV/T) system with MXene/water nanofluid as heat transfer fluid (HTF). The interaction of different operating parameters (nanofluid mass fraction, mass flow rate, inlet temperature and incident radiation) on the output [...] Read more.
A numerical investigation was carried out in ANSYS Fluent® on a photovoltaic/thermal (PV/T) system with MXene/water nanofluid as heat transfer fluid (HTF). The interaction of different operating parameters (nanofluid mass fraction, mass flow rate, inlet temperature and incident radiation) on the output response of the system (thermal efficiency, electrical efficiency, thermal exergy efficiency, and electrical exergy efficiency) was studied using a predictive model generated using response surface methodology (RSM). The analysis of variance (ANOVA) method was used to evaluate the significance of input parameters affecting the energy and exergy efficiencies of the nanofluid-based PV/T system. The nanofluid mass flow rate was discovered to be having an impact on the thermal efficiency of the system. Electrical efficiency, thermal exergy efficiency, and electrical exergy efficiency were found to be greatly influenced by incident solar radiation. The percentage contribution of each factor on the output response was calculated. Input variables were optimized using the desirability function to maximize energy and exergy efficiency. The developed statistical model generated an optimum value for the mass flow rate (71.84 kgh−1), the mass fraction (0.2 wt%), incident radiation (581 Wm−2), and inlet temperature (20 °C). The highest overall energy and exergy efficiency predicted by the model were 81.67% and 18.6%, respectively. Full article
(This article belongs to the Special Issue Nano-Enabled Materials for Clean Water and Energy Generation)
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15 pages, 8158 KiB  
Article
Repeated Injection of Very Small Superparamagnetic Iron Oxide Particles (VSOPs) in Murine Atherosclerosis: A Safety Study
by Tobias Haase, Antje Ludwig, Anke Stach, Azadeh Mohtashamdolatshahi, Ralf Hauptmann, Lars Mundhenk, Harald Kratz, Susanne Metzkow, Avan Kader, Christian Freise, Susanne Mueller, Nicola Stolzenburg, Patricia Radon, Maik Liebl, Frank Wiekhorst, Bernd Hamm, Matthias Taupitz and Jörg Schnorr
Nanomaterials 2024, 14(9), 773; https://doi.org/10.3390/nano14090773 - 28 Apr 2024
Viewed by 271
Abstract
Citrate-coated electrostatically stabilized very small superparamagnetic iron oxide particles (VSOPs) have been successfully tested as magnetic resonance angiography (MRA) contrast agents and are promising tools for molecular imaging of atherosclerosis. Their repeated use in the background of pre-existing hyperlipidemia and atherosclerosis has not [...] Read more.
Citrate-coated electrostatically stabilized very small superparamagnetic iron oxide particles (VSOPs) have been successfully tested as magnetic resonance angiography (MRA) contrast agents and are promising tools for molecular imaging of atherosclerosis. Their repeated use in the background of pre-existing hyperlipidemia and atherosclerosis has not yet been studied. This study aimed to investigate the effect of multiple intravenous injections of VSOPs in atherosclerotic mice. Taurine-formulated VSOPs (VSOP-T) were repeatedly intravenously injected at 100 µmol Fe/kg in apolipoprotein E-deficient (ApoE KO) mice with diet-induced atherosclerosis. Angiographic imaging was carried out by in vivo MRI. Magnetic particle spectrometry was used to detect tissue VSOP content, and tissue iron content was quantified photometrically. Pathological changes in organs, atherosclerotic plaque development, and expression of hepatic iron-related proteins were evaluated. VSOP-T enabled the angiographic imaging of heart and blood vessels with a blood half-life of one hour. Repeated intravenous injection led to VSOP deposition and iron accumulation in the liver and spleen without affecting liver and spleen pathology, expression of hepatic iron metabolism proteins, serum lipids, or atherosclerotic lesion formation. Repeated injections of VSOP-T doses sufficient for MRA analyses had no significant effects on plaque burden, steatohepatitis, and iron homeostasis in atherosclerotic mice. These findings underscore the safety of VSOP-T and support its further development as a contrast agent and molecular imaging tool. Full article
(This article belongs to the Special Issue Advances in Nanotoxicology: Health and Safety)
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11 pages, 2465 KiB  
Article
Surface-Pore-Modified N-Doped Amorphous Carbon Nanospheres Tailored with Toluene as Anode Materials for Lithium-Ion Batteries
by Shiran Shan, Chunze Yuan, Guangsu Tan, Chao Xu, Lin Li, Guoqi Li, Jihao Zhang and Tsu-Chien Weng
Nanomaterials 2024, 14(9), 772; https://doi.org/10.3390/nano14090772 - 28 Apr 2024
Viewed by 291
Abstract
The surface modification of amorphous carbon nanospheres (ACNs) through templates has attracted great attention due to its great success in improving the electrochemical properties of lithium storage materials. Herein, a safe methodology with toluene as a soft template is employed to tailor the [...] Read more.
The surface modification of amorphous carbon nanospheres (ACNs) through templates has attracted great attention due to its great success in improving the electrochemical properties of lithium storage materials. Herein, a safe methodology with toluene as a soft template is employed to tailor the nanostructure, resulting in ACNs with tunable surface pores. Extensive characterizations through transmission electron microscopy (TEM), scanning electron microscopy (SEM), Raman spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption/desorption isotherms elucidate the impact of surface pore modifications on the external structure, morphology, and surface area. Electrochemical assessments reveal the enhanced performance of the surface-pore-modified carbon nanospheres, particularly ACNs-100 synthesized with the addition of 100 μL toluene, in terms of the initial discharge capacity, rate performance, and cycling stability. The interesting phenomenon of persistent capacity increase is ascribed to lithium ion movement within the graphite-like interlayer, resulting in ACNs-100 experiencing a capacity upswing from an initial 320 mAh g−1 to a zenith of 655 mAh g−1 over a thousand cycles at a rate of 2 C. The findings in this study highlight the pivotal role of tailored nanostructure engineering in optimizing energy storage materials. Full article
(This article belongs to the Topic Advanced Nanomaterials for Lithium-Ion Batteries)
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13 pages, 16041 KiB  
Article
Enhanced Nanotwinned Copper Bonding through Epoxy-Induced Copper Surface Modification
by Tsan-Feng Lu, Pei-Wen Wang, Yuan-Fu Cheng, Yu-Ting Yen and YewChung Sermon Wu
Nanomaterials 2024, 14(9), 771; https://doi.org/10.3390/nano14090771 - 27 Apr 2024
Viewed by 298
Abstract
For decades, Moore’s Law has neared its limits, posing significant challenges to further scaling it down. A promising avenue for extending Moore’s Law lies in three-dimensional integrated circuits (3D ICs), wherein multiple interconnected device layers are vertically bonded using Cu–Cu bonding. The primary [...] Read more.
For decades, Moore’s Law has neared its limits, posing significant challenges to further scaling it down. A promising avenue for extending Moore’s Law lies in three-dimensional integrated circuits (3D ICs), wherein multiple interconnected device layers are vertically bonded using Cu–Cu bonding. The primary bonding mechanism involves Cu solid diffusion bonding. However, the atomic diffusion rate is notably low at temperatures below 300 °C, maintaining a clear and distinct weak bonding interface, which, in turn, gives rise to reliability issues. In this study, a new method of surface modification using epoxy resin to form fine grains on a nanotwinned Cu film was proposed. When bonded at 250 °C, the interfacial grains grew significantly into both sides of the Cu film. When bonded at 300 °C, the interfacial grains extended extensively, eventually eliminating the original bonding interface. Full article
(This article belongs to the Special Issue Nano Surface Engineering)
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16 pages, 6928 KiB  
Article
Oxygen Defects Containing TiN Films for the Hydrogen Evolution Reaction: A Robust Thin-Film Electrocatalyst with Outstanding Performance
by Ayoub Laghrissi and Mohammed Es-Souni
Nanomaterials 2024, 14(9), 770; https://doi.org/10.3390/nano14090770 - 27 Apr 2024
Viewed by 217
Abstract
Density functional theory (DFT) calculations of hydrogen adsorption on titanium nitride had previously shown that hydrogen may adsorb on both titanium and nitrogen sites with a moderate adsorption energy. Further, the diffusion barrier was also found to be low. These findings may qualify [...] Read more.
Density functional theory (DFT) calculations of hydrogen adsorption on titanium nitride had previously shown that hydrogen may adsorb on both titanium and nitrogen sites with a moderate adsorption energy. Further, the diffusion barrier was also found to be low. These findings may qualify TiN, a versatile multifunctional material with electronic conductivity, as an electrode material for the hydrogen evolution reaction (HER). This was the main impetus of this study, which aims to experimentally and theoretically investigate the electrocatalytic properties of TiN layers that were processed on a Ti substrate using reactive ion sputtering. The properties are discussed, focusing on the role of oxygen defects introduced during the sputtering process on the HER. Based on DFT calculations, it is shown that these oxygen defects alter the electronic environment of the Ti atoms, which entails a low hydrogen adsorption energy in the range of −0.1 eV; this leads to HER performances that match those of Pt-NPs in acidic media. When a few nanometer-thick layers of Pd-NPs are sputtered on top of the TiN layer, the performance is drastically reduced. This is interpreted in terms of oxygen defects being scavenged by the Pd-NPs near the surface, which is thought to reduce the hydrogen adsorption sites. Full article
(This article belongs to the Section Synthesis, Interfaces and Nanostructures)
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21 pages, 6520 KiB  
Article
Gadolinium Doping Modulates the Enzyme-like Activity and Radical-Scavenging Properties of CeO2 Nanoparticles
by Madina M. Sozarukova, Taisiya O. Kozlova, Tatiana S. Beshkareva, Anton L. Popov, Danil D. Kolmanovich, Darya A. Vinnik, Olga S. Ivanova, Alexey V. Lukashin, Alexander E. Baranchikov and Vladimir K. Ivanov
Nanomaterials 2024, 14(9), 769; https://doi.org/10.3390/nano14090769 - 26 Apr 2024
Viewed by 459
Abstract
Their unique physicochemical properties and multi-enzymatic activity make CeO2 nanoparticles (CeO2 NPs) the most promising active component of the next generation of theranostic drugs. When doped with gadolinium ions, CeO2 NPs constitute a new type of contrast agent for magnetic [...] Read more.
Their unique physicochemical properties and multi-enzymatic activity make CeO2 nanoparticles (CeO2 NPs) the most promising active component of the next generation of theranostic drugs. When doped with gadolinium ions, CeO2 NPs constitute a new type of contrast agent for magnetic resonance imaging, possessing improved biocatalytic properties and a high level of biocompatibility. The present study is focused on an in-depth analysis of the enzyme-like properties of gadolinium-doped CeO2 NPs (CeO2:Gd NPs) and their antioxidant activity against superoxide anion radicals, hydrogen peroxide, and alkylperoxyl radicals. Using an anion-exchange method, CeO2:Gd NPs (~5 nm) with various Gd-doping levels (10 mol.% or 20 mol.%) were synthesized. The radical-scavenging properties and biomimetic activities (namely SOD- and peroxidase-like activities) of CeO2:Gd NPs were assessed using a chemiluminescent method with selective chemical probes: luminol, lucigenin, and L-012 (a highly sensitive luminol analogue). In particular, gadolinium doping has been shown to enhance the radical-scavenging properties of CeO2 NPs. Unexpectedly, both bare CeO2 NPs and CeO2:Gd NPs did not exhibit SOD-like activity, acting as pro-oxidants and contributing to the generation of reactive oxygen species. Gadolinium doping caused an increase in the pro-oxidant properties of nanoscale CeO2. At the same time, CeO2:Gd NPs did not significantly inhibit the intrinsic activity of the natural enzyme superoxide dismutase, and CeO2:Gd NPs conjugated with SOD demonstrated SOD-like activity. In contrast to SOD-like properties, peroxidase-like activity was observed for both bare CeO2 NPs and CeO2:Gd NPs. This type of enzyme-like activity was found to be pH-dependent. In a neutral medium (pH = 7.4), nanoscale CeO2 acted as a prooxidant enzyme (peroxidase), while in an alkaline medium (pH = 8.6), it lost its catalytic properties; thus, it cannot be regarded as a nanozyme. Both gadolinium doping and conjugation with a natural enzyme were shown to modulate the interaction of CeO2 NPs with the key components of redox homeostasis. Full article
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17 pages, 4410 KiB  
Article
Toxicological Characteristics of Bacterial Nanocellulose in an In Vivo Experiment—Part 1: The Systemic Effects
by Vladimir A. Shipelin, Ekaterina A. Skiba, Vera V. Budayeva, Antonina A. Shumakova, Alexey I. Kolobanov, Ilya E. Sokolov, Kirill Z. Maisaya, Galina V. Guseva, Nikita V. Trusov, Alexander G. Masyutin, Yanina A. Delegan, Yulia N. Kocharovskaya, Alexander G. Bogun, Ivan V. Gmoshinski, Sergey A. Khotimchenko and Dmitry B. Nikityuk
Nanomaterials 2024, 14(9), 768; https://doi.org/10.3390/nano14090768 - 26 Apr 2024
Viewed by 250
Abstract
Bacterial nanocellulose (BNC) is being considered as a potential replacement for microcrystalline cellulose as a food additive and a source of dietary fiber due to its unique properties. However, studies on the risks of consuming BNC in food are limited, and it is [...] Read more.
Bacterial nanocellulose (BNC) is being considered as a potential replacement for microcrystalline cellulose as a food additive and a source of dietary fiber due to its unique properties. However, studies on the risks of consuming BNC in food are limited, and it is not yet approved for use in food in the US, EU, and Russia. Aim: This study aims to perform a toxicological and hygienic assessment of the safety of BNC in a subacute 8-week administration in rats. Methods: BNC was administered to male Wistar rats in doses of 0, 1.0, 10.0, and 100 mg/kg body weight for 8 weeks. Various parameters such as anxiety levels, cognitive function, organ masses, blood serum and liver biochemistry, oxidative stress markers, vitamin levels, antioxidant gene expression, and liver and kidney histology were evaluated. Results: Low and medium doses of BNC increased anxiety levels and liver glutathione, while high doses led to elevated LDL cholesterol, creatinine, and uric acid levels. Liver tissue showed signs of degeneration at high doses. BNC did not significantly affect vitamin levels. Conclusion: The adverse effects of BNC are either not dose-dependent or fall within normal physiological ranges. Any effects on rats are likely due to micronutrient deficiencies or impacts on intestinal microbiota. Full article
(This article belongs to the Special Issue Nanosafety and Nanotoxicology: Current Opportunities and Challenges)
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