Three-dimensional Nanostructures Research Articles

Nanomaterials revolutionize biosensing: 0D-3D designs for ultrasensitive detection of microorganisms and viruses.

Various diseases caused by harmful microorganisms and viruses have caused serious harm and huge economic losses to society. Thus, rapid detection of harmful microorganisms and viruses is necessary for disease prevention and treatment. Nanomaterials have unique properties that other materials do not possess, such as a small size effect and quantum size effect. Introducing nanomaterials into biosensors improves the performance of biosensors for faster and more accurate detection of microorganisms and viruses. This review aims to introduce the different kinds of biosensors and the latest advances in the application of nanomaterials in biosensors. In particular, this review focuses on describing the physicochemical properties of zero-, one-, two-, and three-dimensional nanostructures as well as nanoenzymes. Finally, this review discusses the applications of nanobiosensors in the detection of microorganisms and viruses and the future directions of nanobiosensors.

Three-dimensional Au-MnO2 nanostructure as an agent of synergistic cancer therapy: chemo-/photodynamic and photothermal approaches.

The design of multimodal cancer therapy was focused on reaching an efficient process and minimizing harmful effects on patients. In the present study, the Au-MnO2 nanostructures have been successfully constructed and produced as novel multipurpose photosensitive agents simultaneously for photodynamic therapy (PDT), photothermal therapy (PTT), and chemodynamic therapy (CDT). The prepared AuNPs were conjugated with MnO2 NPs by its participation in the thermal decomposition process of KMnO4 confirmed by X-ray diffraction (XRD), transmission electron microscopy (TEM), and Fourier transform infrared (FTIR) spectroscopy (FT-IR). The 16.5 nm Au-MnO2 nanostructure exhibited an absorbance at 438 nm, which is beneficial for application in light induction therapy due to the NIR band, as well as its properties of generating reactive oxygen species (ROS) associated with the 808 nm laser light for PDT. The photothermal transduction efficiency was calculated and compared with that of the non-irradiated nanostructure, in which it was found that the 808 nm laser induced a high efficiency of 83%, 41.5%, and 37.5% for PDT, PTT, and CDT, respectively. The results of DPBF and TMB assays showed that the efficiency of PDT and PTT was higher than that of CDT. The nanostructure also confirmed the time-dependent peroxidase properties at different H2O2, TMB, and H2TMB concentrations, promising good potency in applying nanomedicine in clinical cancer therapy.

Strategy for predicting catalytic activity of catalysts with hierarchical nanostructures.

Three-dimensional hierarchical nanostructures have been employed as electrodes of solid oxide fuel cells (SOFCs) to notably improve the catalytic performance. Hierarchical nanoscale porous electrodes face a trade-off: macroscale pores enhance mass transfer but reduce the number of active sites, while microscale pores increase the number of active sites at the cost of higher transport resistance. Careful design of these structures is crucial for balancing mass transfer and reaction dynamics. A three-dimensional multiphysics model is developed in this paper to examine the influence of different hierarchical geometrical nanostructures on catalytic performance. Additionally, the effects of different diffusion coefficients are also investigated in this study to present the changes in catalytic activity in diffusion, mixed, and reaction-controlled regimes. The model shows good alignment with the experimentally obtained data. An improved Thiele modulus is formulated to quantitatively evaluate the efficiencies of complex hierarchical nanostructures by considering the detailed characteristics of the main and secondary structures.

Advancements in DNA computing: exploring DNA logic systems and their biomedical applications.

DNA computing is regarded as one of the most promising candidates for the next generation of molecular computers, utilizing DNA to execute Boolean logic operations. In recent decades, DNA computing has garnered widespread attention due to its powerful programmable and parallel computing capabilities, demonstrating significant potential in intelligent biological analysis. This review summarizes the latest advancements in DNA logic systems and their biomedical applications. Firstly, it introduces recent DNA logic systems based on various materials such as functional DNA sequences, nanomaterials, and three-dimensional DNA nanostructures. The material innovations driving DNA computing have been summarized, highlighting novel molecular reactions and analytical performance metrics like efficiency, sensitivity, and selectivity. Subsequently, it outlines the biomedical applications of DNA computing-based multi-biomarker analysis in cellular imaging, clinical diagnosis, and disease treatment. Additionally, it discusses the existing challenges and future research directions for the development of DNA computing.

Exploring the chemical dynamics of phenanthrene (C14H10) formation via the bimolecular gas-phase reaction of the phenylethynyl radical (C6H5CC) with benzene (C6H6).

The exploration of the fundamental formation mechanisms of polycyclic aromatic hydrocarbons (PAHs) is crucial for the understanding of molecular mass growth processes leading to two- and three-dimensional carbonaceous nanostructures (nanosheets, graphenes, nanotubes, buckyballs) in extraterrestrial environments (circumstellar envelopes, planetary nebulae, molecular clouds) and combustion systems. While key studies have been conducted exploiting traditional, high-temperature mechanisms such as the hydrogen abstraction-acetylene addition (HACA) and phenyl addition-dehydrocyclization (PAC) pathways, the complexity of extreme environments highlights the necessity of investigating chemically diverse mass growth reaction mechanisms leading to PAHs. Employing the crossed molecular beams technique coupled with electronic structure calculations, we report on the gas-phase synthesis of phenanthrene (C14H10)-a three-ring, 14π benzenoid PAH-via a phenylethynyl addition-cyclization-aromatization mechanism, featuring bimolecular reactions of the phenylethynyl radical (C6H5CC, X2A1) with benzene (C6H6) under single collision conditions. The dynamics involve a phenylethynyl radical addition to benzene without entrance barrier leading eventually to phenanthrene via indirect scattering dynamics through C14H11 intermediates. The barrierless nature of reaction allows rapid access to phenanthrene in low-temperature environments such as cold molecular clouds which can reach temperatures as low as 10 K. This mechanism constitutes a unique, low-temperature framework for the formation of PAHs as building blocks in molecular mass growth processes to carbonaceous nanostructures in extraterrestrial environments thus affording critical insight into the low-temperature hydrocarbon chemistry in our universe.

Spontaneous formation of liquid-crystalline nuclei in blue-phase liquid crystals based on different chirality

The self-assembly of three-dimensional nanostructures of blue-phase liquid crystals is becoming the spotlight of soft matter research and has potential applications in photonic crystals, sensors, electro-optic devices, and others.

Scalable nano-integration strategy: Controllable three-dimensional monocrystalline GaN nanostructures from nanobelts to nanonetwork

The effective and scalable assembly of 1D nano-units into ordered 3D monocrystalline networks remains a challenge. Based on the crystal structure and growth characteristics of GaN, we have designed a specific epitaxy strategy and successfully achieved large area self-networking of 3D monocrystalline nanostructure on Au-coated β-LiGaO2 (100) substrate formed by the interconnection of GaN nanobelts grown along three equivalent directions of the m-axis [011̅0], [101̅0] and [11̅00]. This well-aligned 3D GaN nanostructure grown by simple CVD method has good reproducibility and the yield of cross-linked junctions are quite high. The mono-crystallinity of this structure were proved by X-ray diffraction (XRD) and transmission electron microscope (TEM) results, especially at the crosslinked junctions. The overall epitaxial relationships between GaN and LiGaO2 was analyzed and the defect-mediated anisotropic VS growth mechanism was deduced from thorough characterization of individual nanobelts. Besides, the morphology of 3D GaN nanostructure including length, width and height was found to be controllable. The E2 (high) phonon peak at 567.4 cm−1 in the Raman spectrum and the strong ultraviolet emission peak centered at 363.3 nm (3.41 eV) in the photoluminescence (PL) spectrum indicate that the 3D GaN nanostructures are nearly strain-less and have high crystalline quality. This large-scale 3D monocrystalline network not only retains the advantage of 1D nanomaterials, but also become easier to operate compared with individual nanowire. The epitaxy assembly strategy is expected to ensure the property homogeneity of chip-scale devices for their real applications and provide a reference for further growth of tunable 3D structures of other materials.

Designing a square periodic racemic helix photonic metamaterial using phase-controlled interference lithography for tailored chiral response

In this study, we propose a double exposure phase-controlled laser interference lithography (DE-PCLIL) approach in 4 + 1 beams interference to design a three-dimensional (3D) racemic helical periodic nanostructure. The explicit azimuthal rotation of each beam by π/2 between the two exposures and the resultant intensity distribution discover the racemic 3D helix structure arranged in the square unit cell. The proof of concept is experimentally demonstrated by recording a series of cross-sectional images at different z-planes of the volumetric interference pattern on a CMOS camera using a spatial light modulator (SLM). Additionally, we propose an approach to realize tapering in such a geometry through a slight variation of the interference angle in both exposures. We numerically investigated optical modes and circular dichroism (CD) characteristics of the racemic helix metamaterial. The racemic helix metamaterial structure offers an angle of incidence and polarization-insensitive coupled mode. Through numerical studies, we propose an alternative way to bring 3.4-fold CD signal enhancement by varying the phase of a particular handed helix only through modulating the local chiral field. Such 3D structure is profound with perfect absorption in broad spectral regions, potentially suited for plasmonic absorber-based photovoltaic and photo-catalysis applications.

Bimetallic-Coordinated Covalent Triazine Framework-Derived FeNi Alloy Nanoparticle-Decorated Coral-Like Nanocarbons for Oxygen Electrocatalysis.

It is highly desirable to fabricate transition bimetallic alloy-embedded porous nanocarbons with a unique nanoarchitecture for the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) in rechargeable zinc-air batteries. In this work, we introduce a template-assisted in situ alloying synthesis of FeNi alloy nanoparticle-decorated coral-like nanocarbons (FeNi-CNCs) as efficient OER/ORR dual-functional electrocatalysts. The present materials are produced through polycondensation of a covalent triazine framework (CTF), the coordination of Ni and Fe ions, and sequential pyrolytic treatment. Through the pyrolysis process, the nanolamellar FeNi-CTF precursors can be facilely converted into FeNi alloy nanoparticle-decorated nanocarbons. These nanocarbons possess a distinctive three-dimensional (3D) coral-like nanostructure, which is favorable for the transport of oxygen and the diffusion of electrolyte. As a result, FeNi-CNC-800 with the highest efficiency exhibited remarkable electrocatalytic performance and great durability. Additionally, it also can be assembled into rechargeable zinc-air batteries that can be assembled in both liquid and solid forms, offering a superior peak power density, large specific capacity, and outstanding reusability during charging/discharging cycles (e.g., 5160 charging-and-discharging cycles at 10 mA cm-2 for the liquid forms). These traits make it a highly promising option in the burgeoning field of wearable energy conversion.

Three-dimensional nanoscale vortex line visualization and chiral nanostructure fabrication of tightly focused multi-vortex beams via direct laser writing

Optical singularity is pivotal in nature and has attracted wide interest from many disciplines nowadays, including optical communication, quantum optics, and biomedical imaging. Visualizing vortex lines formed by phase singularities and fabricating chiral nanostructures using the evolution of vortex lines are of great significance. In this paper, we introduce a promising method based on two-photon polymerization direct laser writing (2PP-DLW) to record the morphology of vortex lines generated by tightly focused multi-vortex beams (MVBs) at the nanoscale. Due to Gouy phase, the singularities of the MVBs rotate around the optical axis and move towards each other when approaching the focal plane. The propagation dynamics of vortex lines are recorded by 2PP-DLW, which explicitly exhibits the evolution of the phase singularities. Additionally, the MVBs are employed to fabricate stable three-dimensional chiral nanostructures due to the spiral-forward property of the vortex line. Because of the obvious chiral features of the manufactured nanostructures, a strong vortical dichroism is observed when excited by the light carrying orbital angular momentum. A number of applications can be envisioned with these chiral nanostructures, such as optical sensing, chiral separation, and information storage.

Acoustic Shock Wave-Induced Solid-State Fusion of Nanoparticles: A Case Study of the Conversion of One-Dimensional Rod Shape into Three-Dimensional Honeycomb Nanostructures of CdO for High-Performance Energy Storage Materials.

Herein, we describe the solid-state fusion of rod-shaped to honeycomb-shaped cadmium oxide particles (CdO NPs) caused by the process of repeated exposure to acoustic shock waves. Significant changes have been observed in structurally and morphologically dependent properties. For instance, at the 200-shocked condition, the high-pressure CdO-B2 phase is present as a secondary phase wherein all of the rod-shaped particles have been transformed into honeycomb-shaped CdO particles which possess comparatively higher specific-capacitance than CdO nanorods (NRs). The computed specific capacitance values for the 0, 100, and 200 shocked samples at a scan rate of 100 m V s-1 are computed to be 433, 415, and 583 F g-1, respectively. The second-stage decomposition temperature points of the CdO NPs have significantly increased in accordance with the morphological changes from rod to honeycomb patterns such that the values are 343, 526, and 534 °C, respectively, for 0, 100, and 200 shocked conditions. Note that such honeycomb nanostructured CdO particles by shock-wave processing have never been observed, to date. Due to the superior energy storage abilities as well as the spectacular high thermal stability of the honeycomb CdO nanostructures compared to CdO NRs, shocked CdO with honeycomb nanostructures can be considered as energy storage materials.

Crystallization kinetics of Al2O3-28mol%Lu2O3 glass and full crystallized transparent Lu3Al5O12-based nanoceramics

Transparent Lu3Al5O12 (LuAG) ceramics have become very promising phosphor matrix materials due to their high doping concentration and luminous efficiency, thermal conductivity and thermal stability. However, LuAG transparent ceramics prepared by traditional powder sintering method are facing several problems, such as time-consuming and energy-consuming, complex preparation process, high quality of raw material powders and large crystalline grain size. Here we report facile elaboration of transparent LuAG-Al2O3 two-phase nanocrystalline ceramics through pressureless crystallization (1000 °C, 2 h) of 72 mol.% Al2O3-28 mol.% Lu2O3 (ALu28) bulk glasses combined with the crystallization kinetics analysis. The results of the crystallization kinetics analysis show that the ALu28 bulk glasses have a low activation energy (<750 kJ mol−1) and a crystallization mechanism of three-dimensional crystal growth mode accompanied by volume nucleation. The resulting LuAG-Al2O3 ceramics with nanosized grains and dense three-dimensional network nanostructures present good transmittance (80.6 %@780 nm) and excellent mechanical properties (hardness is 24 GPa).

A Facilely Synthesized NiCo2S4 with Two Mutually Reinforcing Active Sites for High-Performance Lithium-Sulfur Batteries.

The shuttle effect and slow conversion kinetics of soluble polysulfides hinder the commercial application of lithium-sulfur batteries (LSBs). In this context, we propose a three-dimensional lamellar-stacked nanostructure of nickel cobalt sulfide (D-NiCo2S4) enriched with lattice defects by manipulating the cations in spinel sulfides. It has an obvious synergistic promotion mechanism for the adsorption and catalysis of lithium sulfides. Specifically, Ni3+ on tetrahedral (Td) sites with strong Ni-S covalency anchors LiPSs, whereas Co3+ on octahedral (Oh) sites promotes a highly efficient catalytic conversion of LiPSs, which is confirmed by experimental results and density functional theory (DFT) calculations. Besides, the crystal defects and distortions in the lamellar region could expose more active sites and enhance the redox reaction kinetics of polysulfides. Hence, Li-S batteries with D-NiCo2S4@S as the cathode show outstanding cycle stability; upon cycling at 1 A/g, the battery achieves a high initial specific capacity of 1001.12 and 655.31 mAh g-1 after 1000 cycles (decay rate as low as 0.05% per cycle), as well as a high initial areal capacity of 3.15 mAh cm-2 under high S loading (4.2 mg cm-2). This work provides a viable scheme for designing efficient bimetal sulfide catalysts and furnishes a rational strategy for constructing LSB cathodes with high specific capacity and high area capacity.

Advances in three dimensional metal enhanced fluorescence based biosensors using metal nanomaterial and nano-patterned surfaces.

Metal enhanced fluorescence (MEF) is a phenomenon that increases fluorescence signal through placement of metal near a fluorophore. For biosensing applications, MEF-based biosensors are becoming increasingly popular as it enables highly sensitive detection of molecules, important for early diagnosis. The structure and size of the metal influence the optical properties through enhancing the fluorophore photostability and light absorption and emission. In recent years, many metal nanostructures have been fabricated and examined for their effectiveness in developing MEF-based biosensors. This review focuses on the latest applications of three-dimensional nanostructures and nano-patterned surfaces used to develop and improve fluorescence sensing via MEF. Current reviews mostly discussed the applications of two dimensional MEF and metal-nanoparticles-based MEF with a focus on fabrication of nanoparticles and metal substrates. In this article, we focused more on the effect of the metal nanostructure and size on MEF and then provided an in-depth summary of the performance of the state-of-the-art three dimensional MEF-based biosensors. While more work is needed to demonstrate applicability for complex samples, it is evident that with the use of metal nanoparticles and three dimensional nano-patterns, the assay sensitivity of fluorescence-based detection can be greatly improved, making it suitable for use in early disease diagnostics.

Conducting polymers/oxygen vacancies WO3 vertically nanowire arrays supported on carbon cloth as advanced electrodes for high-performance supercapacitors

The low energy density of supercapacitors (SCs) is one of the main factors restricting their development. WO3 with high theoretical capacitance is an ideal n-type material for anode electrode, but its narrow potential window and low conductivity are not conducive to the application of high-energy-density SCs. Herein, a high electrochemical activity poly(indole-5-carboxylic acid) (P5-ICA) as p-type material wrapping n-type oxygen vacancies WO3 vertically nanowire arrays supported on carbon cloth is prepared by hydrothermal method and subsequent electrodeposition method. This adhesive free flexible p/n-type hetero-structural P5-ICA@WO3 vertical nanowire array electrode has a three-dimensional porous nanostructure that not only provides a large surface area, but also promotes the penetration of electrolyte ions and the transmission of electrons. It is found that the P5-ICA@WO3 nanowire array with high areal specific capacitance (1430 mF cm−2 at 4 mA cm−2) and long cycle stability (94 % after 6000 cycles) exhibits a widened electrochemical activity window compared to individual material. The symmetrical SCs assembled using P5-ICA@WO3 can provide a high areal energy density of 137.6 μWh cm−2 at the power density of 1.4 mW cm−2, which is significantly higher than the SCs performance of previously used WO3-based electrode materials.

3D plasmonic hexaplex paper sensor for label-free human saliva sensing and machine learning-assisted early-stage lung cancer screening

A label-free detection method for noninvasive biofluids enables rapid on-site disease screening and early-stage cancer diagnosis by analyzing metabolic alterations. Herein, we develop three-dimensional plasmonic hexaplex nanostructures coated on a paper substrate (3D-PHP). This flexible and highly absorptive 3D-PHP sensor is integrated with commercial saliva collection tube to create an efficient on-site sensing platform for lung cancer screening via surface-enhanced Raman scattering (SERS) measurement of human saliva. The multispike hexaplex-shaped gold nanostructure enhances contact with saliva viscosity, enabling effective sampling and SERS enhancement. Through testing patient salivary samples, the 3D-PHP sensor demonstrates successful lung cancer detection and diagnosis. A logistic regression-based machine learning model successfully classifies benign and malignant patients, exhibiting high clinical sensitivity and specificity. Additionally, important Raman peak positions related to different lung cancer stages are investigated, suggesting insights for early-stage cancer diagnosis. Integrating 3D-PHP senor with the conventional saliva collection tube platform is expected to offer promising practicality for rapid on-site disease screening and diagnosis, and significant advancements in cancer detection and patient care.

Recent advances in DNA nanomaterials for cancer diagnosis and treatment

Abstract The elucidation of the structural characteristics of deoxyribonucleic acid (DNA) by Watson and Crick, the advent of polymerase chain reaction technology, and the development of primer-synthesis methods, enable DNA to be replicated and transformed in an increasingly easy manner, such that it is among the most directed and evolving nanomaterials in molecular biology. Traditional cancer diagnosis methods are somewhat limited and are unable to meet existing needs; consequently, DNA nanostructures with wide ranging properties are receiving increasingly more attention because a number of DNA materials have been shown to exhibit diagnostic properties. Some DNA materials can functionally alter the biological behavior of cells, such as cell migration, cell proliferation, cell differentiation, autophagy, and anti-inflammatory effects. Some single-stranded DNA or ribonucleic acid with secondary structure through self-pairing, called aptamer, systematic evolution of ligands by exponential enrichment (SELEX), have targeting capabilities and can be applied to tumor targeted diagnosis and therapy. Several DNA nanomaterials with three-dimensional nanostructures and stable structures are being investigated as drug carrier systems to act on a variety of antitumor drugs or gene therapy agents. This article reviews the use of functionalized DNA nanostructures in cancer diagnosis and treatment applications. Various biosensors and carriers based on DNA nanostructures are introduced and chemical reactions related to the preparation of the carrier and the signal transduction mechanism of the sensor are discussed. Efficient carrier/biosensor platforms based on various structural developments and current DNA nanomaterial developments are also presented.

Cactus-like (Ni,Co)Se2 nanosheets with 3D structure decorated on the conductive substrate for efficient hydrogen evolution reaction

Transition metal selenides are a fascinating class of substitute for traditional noble metal electrocatalysts for hydrogen evolution reaction (HER). However, the monometallic selenides still have the disadvantages of low electroactive sites and electrical conductivity. To address such drawbacks, three-dimensional (3D) hierarchical nanostructures composed of bimetallic compounds have aroused great attention. In this study, cactus-like bimetallic nickel–cobalt nanosheets with a 3D nanostructure are successfully prepared on the surface of conductive substrate by a one-step hydrothermal reaction. Then a high-efficiency bimetallic catalyst ((Ni,Co)Se2/CFP) is obtained by a facile chemical vapor deposition. Benefiting from bimetallic components and the unique 3D structure, the cactus-like (Ni,Co)Se2/CFP only requires a low overpotential of 154 mV to reach the current density of 10 mA cm−2. The Tafel slope of (Ni,Co)Se2/CFP (67 mV dec−1) further shows that (Ni,Co)Se2/CFP has faster HER kinetics. Besides, the long-term stability test demonstrates the excellent durability of (Ni,Co)Se2/CFP in 0.5 M H2SO4. This research offers a useful technique and guide for improving the structure of bimetallic selenides based on transition metals to design high-efficient HER electrocatalysts.

Characterization of porosity in periodic 3D nanostructures using spectroscopic scatterometry

Periodic nanostructures have important applications in nanophotonics and nanostructured materials as they provide various properties that are advantageous compared to conventional solid materials. However, there is a lack of metrology techniques that are suitable for large-scale manufacturing, as the traditional tools used in nanotechnology have limited throughput and depth resolution. In this work, we use spectroscopic scatterometry as a fast and low-cost alternative to characterize the porosity of three-dimensional (3D) periodic nanostructures. In this technique, the broadband reflectance of the structure is measured and fitted with physical models to predict the structure porosity. The process is demonstrated using 3D periodic nanostructures fabricated using colloidal phase lithography at various exposure dosages. The measured reflectance data are compared with an optical model based on finite-difference time-domain and transfer-matrix methods, which show qualitative agreement with the structure porosity. We found that this technique has the potential to further develop into an effective method to effectively predict the porosity of 3D nanostructures and can lead to real-time process control in roll-to-roll nanomanufacturing.

Engineering Mn–Nx sites on porous carbon via molecular assembly strategy for long-life zinc-air batteries

Nitrogen-coordinated manganese atoms on carbon materials denoted as MnNC, serve as the highly active non-precious metal electrocatalysts for oxygen reduction reaction (ORR) in zinc-air batteries (ZABs). Nonetheless, a significant challenge arises from the tendency of Mn atoms to aggregate during heat treatment, thereby compromising ORR performance in ZABs. In this work, the molecular assembly strategy based on the hydrogen bond interaction was employed to fabricate the MnNC electrocatalyst. This approach promotes the dispersion of Mn atoms, creating abundant Mn–Nx active sites. Furthermore, the resulting three-dimensional porous nanostructure, formed by molecular assembly, significantly enhances accessibility to the Mn–Nx active sites. The porous nanostructure not only shortens the diffusion path of reactants and charges but also improves mass transfer. The MnNC exhibits impressive ORR catalytic performance with a half-wave potential of 0.90 V (vs. RHE). The liquid-type ZAB based on MnNC displays a high specific capacity of 816.6 mAh/g and an extended charge–discharge cycle life of 1000 h. Quasi-solid-state ZAB based on MnNC can operate stably for 24 h. This work presents an effective strategy to synthesize transition metal-nitrogen-carbon (MNC) electrocatalysts tailored for long-life zinc-air battery.