Distinctive p-d Orbital Hybridization in CuSb Porous Nanonetworks for Enhanced Nitrite Electroreduction to Ammonia.

Electrochemical nitrite reduction reaction ( NO 2 - RR ${\mathrm{NO}}_{\mathrm{2}}^{\mathrm{ - }}{\mathrm{RR}}$ ), as a green and sustainable ammonia synthesis technology, has broad application prospects and environmental friendliness. Herein, an unconventional p-d orbital hybridization strategy is reported to realize the fabrication of defect-rich CuSb porous nanonetwork (CuSb PNs) electrocatalyst for NO 2 - RR ${\mathrm{NO}}_{\mathrm{2}}^ - {\mathrm{RR}}$ . The crystalline/amorphous heterophase structure is cleverly introduced into the porous nanonetworks, and this defect-rich structure exposes more atoms and activated boundaries. CuSb PNs exhibit a large NH3 yield ( r N H 3 ${{r}_{{\mathrm{N}}{{{\mathrm{H}}}_{\mathrm{3}}}}}$ ) of 946.1 µg h-1 m cat - 1 ${\mathrm{m}}_{{\mathrm{cat}}}^{ - {\mathrm{1}}}$ and a high faradaic efficiency (FE) of 90.7%. Experimental and theoretical studies indicate that the excellent performance of CuSb PNs results from the defect-rich porous nanonetworks structure and the p-d hybridization of Cu and Sb elements. This work describes a powerful pathway for the fabrication of p-d orbital hybrid defect-rich porous nanonetworks catalysts, and provides hope for solving the problem of nitrogen oxide pollution in the field of environment and energy.

Simultaneously Strengthening and Toughening All-Natural Structural Materials via 3D Nanofiber Network Interfacial Design.

Constructing structural materials from sustainable raw materials is considered an efficient way to reduce the potential threat posed by plastics. Nevertheless, challenges remain regarding combining excellent mechanical and thermal properties, especially the balance of strength and toughness. Here, we report a 3D nanofiber network interfacial design strategy to strengthen and toughen all-natural structural materials simultaneously. The introduced protonated chitosan at the interface between the surface oxidized 3D nanonetwork of bacterial cellulose forms the interfacial interlocking structure of nanonetworks, achieving a robust physical connection and providing enough physical contact sites for chemical crosslinking. The obtained sustainable structural material successfully integrates excellent mechanical and thermal properties on the nanoscale of cellulose nanofibers, such as light weight, high strength, and superior thermal expansion coefficient. The relationship between structural design and comprehensive mechanical property improvement is analyzed in detail, providing a universal perspective to design sustainable high-performance structural materials from nanoscale building blocks.

Mesh size control in forming an Ag/AgO nano-network structure for transparent conducting application.

The variation behaviors of the morphology, transmission, and sheet resistance of the surface Ag/AgO nano-network (NNW) structures fabricated under different illumination conditions and with different Ag deposition thicknesses and thermal annealing temperatures in forming initial Ag nanoparticles (NPs) are studied. Generally, an NNW structure with a smaller mesh size or a denser branch distribution has a lower transmission and a lower sheet resistance level. Under the fabrication condition of a broader illumination spectrum, a lower thermal annealing temperature, or a thicker Ag deposition, we can obtain an NNW structure of a smaller mesh size. The mesh size of an NNW structure is basically controlled by the seed density of Brownian tree (BT) at the beginning of light illumination. A BT seed can be formed through a stronger local localized surface plasmon resonance for accelerating Ag oxidation in a certain region. Once an Ag/AgO BT seed is formed, the surrounding Ag NPs are reorganized to form the branches of a BT. Multiple BTs are connected to form a large-area NNW structure, which can serve as a transparent conductor. Under the fabrication conditions of a broader illumination spectrum, 3 nm Ag deposition, and 100 °C thermal annealing, we can implement an NNW structure to achieve ∼1.15µm in mesh size, ∼90 Ω sq-1in sheet resistance, and 93%-77% in transmittance within the wavelength range between 370 and 700 nm.

Nanonetwork Thermosets from Templated Polymerization for Enhanced Energy Dissipation.

Herein, we aim to develop a facile method for the fabrication of mechanical metamaterials from templated polymerization of thermosets including phenolic and epoxy resins using self-assembled block copolymer, polystyrene-polydimethylsiloxane with tripod network (gyroid), and tetrapod network (diamond) structures, as templates. Nanoindentation studies on the nanonetwork thermosets fabricated reveal enhanced energy dissipation from intrinsic brittle thermosets due to the deliberate structuring; the calculated energy dissipation for gyroid phenolic resins is 0.23 nJ whereas the one with diamond structure gives a value of 0.33 nJ. Consistently, the gyroid-structured epoxy gives a high energy dissipation value of 0.57 nJ, and the one with diamond structure could reach 0.78 nJ. These enhanced properties are attributed to the isotropic periodicity of the nanonetwork texture with plastic deformation, and the higher number of struts in the tetrapod diamond network in contrast to tripod gyroid, as confirmed by the finite element analysis.

Optimized Surface Characteristics and Enhanced in Vivo Osseointegration of Alkali-Treated Titanium with Nanonetwork Structures.

Alkali-treated titanium (Ti) with a porous, homogeneous, and uniform nanonetwork structure (TNS) that enables establishment of a more rapid and firmer osteointegration than titanium has recently been reported. However, the mechanisms underlying the enhanced osteogenic activity on TNS remains to be elucidated. This study aimed to evaluate the surface physicochemical properties of Ti and TNS, and investigate osteoinduction and osteointegration in vivo. Surface characteristics were evaluated using scanning electron microscopy (SEM), scanning probe microscopy (SPM), and X-ray photoelectron spectrometry (XPS), and the surface electrostatic force of TNS was determined using solid zeta potential. This study also evaluated the adsorption of bovine serum albumin (BSA) and human plasma fibronectin (HFN) on Ti and TNS surfaces using quartz crystal microbalance (QCM) sensors, and apatite formation on Ti and TNS surfaces was examined using a simulated body fluid (SBF) test. Compared with Ti, the newly developed TNS enhanced BSA and HFN absorbance capacity and promoted apatite formation. Furthermore, TNS held less negative charge than Ti. Notably, sequential fluorescence labeling and microcomputed tomography assessment indicated that TNS screws implanted into rat femurs exhibited remarkably enhanced osteointegration compared with Ti screws. These results indicate that alkali-treated titanium implant with a nanonetwork structure has considerable potential for future clinical applications in dentistry and orthopedics.

Co@Co3O4 core-shell three-dimensional nano-network for high-performance electrochemical energy storage.

An alternative routine is presented by constructing a novel architecture, conductive metal/transition oxide (Co@Co3O4) core-shell three-dimensional nano-network (3DN) by surface oxidating Co 3DN in situ, for high-performance electrochemical capacitors. It is found that the Co@Co3O4 core-shell 3DN consists of petal-like nanosheets with thickness of <10 nm interconnected forming a 3D porous nanostructure, which preserves the original morphology of Co 3DN well. X-ray photoelectron spectroscopy by polishing the specimen layer by layer reveals that the Co@Co3O4 nano-network is core-shell-like structure. In the application of electrochemical capacitors, the electrodes exhibit a high specific capacitance of 1049 F g(-1) at scan rate of 2 mV/s with capacitance retention of ~52.05% (546 F g(-1) at scan rate of 100 mV) and relative high areal mass density of 850 F g(-1) at areal mass of 3.52 mg/cm(2). It is believed that the good electrochemical behaviors mainly originate from its extremely high specific surface area and underneath core-Co "conductive network". The high specific surface area enables more electroactive sites for efficient Faradaic redox reactions and thus enhances ion and electron diffusion. The underneath core-Co "conductive network" enables an ultrafast electron transport.

Localization and Directionality of Surface Transport in Bi2Te3 Ordered 3D Nanonetworks.

The resistance of an ordered 3D-Bi2Te3 nanowire nanonetwork was studied at low temperatures. Below 50 K the increase in resistance was found to be compatible with the Anderson model for localization, considering that conduction takes place in individual parallel channels across the whole sample. Angle-dependent magnetoresistance measurements showed a distinctive weak antilocalization characteristic with a double feature that we could associate with transport along two perpendicular directions, dictated by the spatial arrangement of the nanowires. The coherence length obtained from the Hikami-Larkin-Nagaoka model was about 700 nm across transversal nanowires, which corresponded to approximately 10 nanowire junctions. Along the individual nanowires, the coherence length was greatly reduced to about 100 nm. The observed localization effects could be the reason for the enhancement of the Seebeck coefficient observed in the 3D-Bi2Te3 nanowire nanonetwork compared to individual nanowires.

Interconnected Vanadyl Pyrophosphate Nanonetworks as a Flexible Electrode for High-Voltage and Long-Life Li-Ion Supercapacitors.

Engineering vanadium-based materials with high conductivity, superior redox performance, and high operating voltage has attracted widespread attention in energy storage devices. Herein, we demonstrated a simple and feasible phosphorization technique to design three-dimensional (3D) network-like vanadyl pyrophosphate ((VO)2P2O7) nanowires on flexible carbon cloth (CC) (VP-CC). The phosphorization process enabled the VP-CC to increase the electronic conductivity, and the interconnected nano-network of VP-CC opens pathways for fast charge storage during the energy storage processes. Specifically, the 3D VP-CC electrodes and LiClO4 electrolyte designed as a Li-ion supercapacitor (LSC) demonstrate a maximum operating window of 2.0 V with a superior energy density (Ed) of 96 µWh cm-2, power density (Pd) of 10,028 µW cm-2, and outstanding cycling retention (98%) even after 10,000 cycles. In addition, a flexible LSC assembled utilizing VP-CC electrodes with a PVA/Li-based solid-state gel electrolyte exhibits a high capacitance value of 137 mF cm-2 and excellent cycling durability (86%) with a high Ed of 27 µWh cm-2 and Pd of 7237 µW cm-2. Considering excellent energy storage features, the highly conductive vanadium-based material has been utilized as an ideal electrode for various flexible/wearable energy storage devices with superior performance.

Block Copolymer Modified Nanonetwork Epoxy Resin for Superior Energy Dissipation.

Herein, this work aims to fabricate well-ordered nanonetwork epoxy resin modified with poly(butyl acrylate)-b-poly(methyl methacrylate) (PBA-b-PMMA) block copolymer (BCP) for enhanced energy dissipation using a self-assembled diblock copolymer of polystyrene-b-poly(dimethylsiloxane) (PS-b-PDMS) with gyroid and diamond structures as templates. A systematic study of mechanical properties using nanoindentation of epoxy resin with gyroid- and diamond-structures after modification revealed significant enhancement in energy dissipation, with the values of 0.36 ± 0.02 nJ (gyroid) and 0.43 ± 0.03 nJ (diamond), respectively, when compared to intrinsic epoxy resin (approximately 0.02 ± 0.002 nJ) with brittle characteristics. This enhanced property is attributed to the synergic effect of the deliberate structure with well-ordered nanonetwork texture and the toughening of BCP-based modifiers at the molecular level. In addition to the deliberate structural effect from the nanonetwork texture, the BCP modifier composed of epoxy-philic hard segment and epoxy-phobic soft segment led to dispersed soft-segment domains in the nanonetwork-structured epoxy matrix with superior interfacial strength for the enhancement of applied energy dissipation.

Bioinspired Nanonetwork Hydroxyapatite from Block Copolymer Templated Synthesis for Mechanical Metamaterials.

Inspired by Mantis shrimp, this work aims to suggest a bottom-up approach for the fabrication of nanonetwork hydroxyapatite (HAp) thin film using self-assembled polystyrene-block-polydimethylsiloxane (PS-b-PDMS) block copolymer (BCP) with a diamond nanostructure as a template for templated sol-gel reaction. By introducing poly(vinylpyrrolidone) (PVP) into precursors of calcium nitrate tetrahydrate and triethyl phosphite, which limits the growth of forming HAp nanoparticles, well-ordered nanonetwork HAp thin film can be fabricated. Based on nanoindentation results, the well-ordered nanonetwork HAp shows high energy dissipation compared to the intrinsic HAp. Moreover, the uniaxial microcompression test for the nanonetwork HAp shows high energy absorption per volume and high compression strength, outperforming many cellular materials due to the topologic effect of the well-ordered network at the nanoscale. This work highlights the potential of exploiting BCP templated synthesis to fabricate ionic solid materials with a well-ordered nanonetwork monolith, giving rise to the brittle-to-ductile transition, and thus appealing mechanical properties with the character of mechanical metamaterials.

Controlled Self-Assembly of Polystyrene-block-Polydimethylsiloxane for Fabrication of Nanonetwork Silica Monoliths.

Herein, this work aims to carry out controlled self-assembly of single-composition block copolymer for the fabrication of various nanonetwork silica monoliths. With the use of lamellae-forming polystyrene-block-polydimethylsiloxane (PS-b-PDMS), nanonetwork-structured films could be fabricated by solvent annealing using a PS-selective solvent (chloroform). By simply tuning the flow rate of nitrogen purge to the PS-selective solvent for the controlled self-assembly of the PS-b-PDMS, gyroid- and diamond-structured monoliths can be formed due to the difference in the effective volume of PS in the PS-b-PDMS during solvent annealing. As a result, well-ordered nanonetwork SiO2 (silica) monoliths can be fabricated by templated sol-gel reaction using hydrofluoric acid etched PS-b-PDMS film as a template followed by the removal of the PS. This bottom-up approach for the fabrication of nanonetwork materials through templated synthesis is appealing to create nanonetwork materials for various applications.

Facile Strategy for Constructing Highly Thermally Conductive Epoxy Composites Based on a Salt Template-Assisted 3D Carbonization Nanohybrid Network.

The construction of an interconnected nanofiller network is critical for the preparation of highly effective thermal management composites, though it remains a challenge to eliminate the anisotropic thermal conductivity of the nanofiller-induced defective interfacial heat-flow efficiency. In this work, a facile and novel approach is proposed to optimize phonon transport by building a salt template-assisted three-dimensional (3D) carbonization nanohybrid network in an epoxy system. The advantage of the salt template relied on green and scalable merits to construct a 3D nanofiller network and supporting abundant holes for the introduction of a polymer matrix after washing. Meanwhile, the contained carbonization materials contributed to reducing the interfacial phonon scattering issues of the filler/filler and filler/polymer for an efficient heat-flow pathway. As a result of this effect, the prepared epoxy nano-composites presented a high thermal conductivity of 4.27 W/m K, resulting in a 1841% increase compared to the thermal conductivity of the pure epoxy resin. In addition, the epoxy composites exhibited good mechanical properties and thermal conductive performance during heating and cooling. Therefore, this study may provide new insights into the design and preparation of thermal management polymers to meet the applicational requirements of electronics.

3D Carbon Nanonetwork Coated Composite Electrode with Multi-Heteroatom Doping for High-Rate Vanadium Redox Flow Batteries.

With the advantages of benign mechanical property, electrochemical stability, and low cost, graphite fibers (GFs) have been widely used as electrodes for vanadium redox flow batteries (VRFBs). However, GFs usually possess inferior electrochemical activity and ion diffusion kinetics for electrode reaction, vastly limiting their application in VRFBs. Here, a 3D carbon nanonetwork coated GFs with multi-heteroatom doping was constructed for application in VRFBs via low temperature polymerization between linear polymer monomer and phytic acid, and subsequent carbonization (900 °C) on the GFs (GF@PCNs-900). Benefiting from the 3D structural features and multi-heteroatom doping (O, N and P), the composite electrode displayed sufficient diffusion of vanadium ions, rapid electron conduction, and highly enhanced electrochemical activity of reactive site on the electrodes. As a result, the GF@PCNs-900 delivered a high discharge capacity of 21 Ah L-1 and energy efficiency of above 70% with extraordinary stability during 200 cycles at 200 mA cm-2. Even at a huge current density of 400 mA cm-2, the GF@PCNs-900 still maintained a discharge capacity of 5.0 Ah L-1, indicating an excellent rate of performance for VRFBs. Such design strategy opens up a clear view for further development of energy storage field.

Electrochemical Performance of Titania 3D Nanonetwork Electrodes Induced by Pulse Ionization at Varied Pulse Repetitions.

Pulse ionized titania 3D-nanonetworks (T3DN) are emerging materials for fabricating binder-free and carbon-free electrodes for electrochemical energy storage devices. In this article, we investigate the effect of the one of the most important fabrication parameters, pulse frequency, for optimizing supercapacitor efficiency. A series of coin cell batteries with laser-induced electrodes was fabricated; the effect of pulse frequency on oxidation levels and material properties was studied using both experimental and theoretical analysis. Also, detailed electrochemical tests including cyclic voltammetry (CV), charge/discharge, and electrochemical impedance spectroscopy (EIS) were conducted to better understand the effect of pulse frequency on the electrochemical performance of the fabricated devices. The results show that at a frequency of 600 kHz, more T3DN were observed due to the higher temperature and stabler formation of the plasma plume, which resulted in better performance of the fabricated supercapacitors; specific capacitances of samples fabricated at 600 kHz and 1200 kHz were calculated to be 59.85 and 54.39 mF/g at 500 mV/s, respectively.

Versatile photoelectrochemical and electrochemiluminescence biosensor based on 3D CdSe QDs-DNA nanonetwork-SnO2 nanoflower coupled with DNA walker amplification for HIV detection.

A novel 3D CdSe quantum dots (QDs)-DNA nanonetwork was assembled to sensitize the mesoporous SnO2 photoelectrochemical (PEC) substrate, which was coupled with a biped-DNA walker multiple amplification technique to design a versatile electrochemiluminescence (ECL) and PEC biosensor for dual detection of HIV. Firstly, the photosensitive CdSe QDs and SnO2 nanoflowers have well-matched band-edge energy level, thus their complex can promote effective transfer of the photogenerated carriers, and show better PEC and ECL property. Then, a novel 3D CdSe QDs-DNA nanonetwork was assembled and loaded with a large amount of QDs, which was used as multifunctional PEC and ECL probes. Moreover, the target-triggered biped DNA walker-cascade amplification method was introduced to generate a large amount of output DNA, which was used to link numerous 3D CdSe QDs-DNA nanonetwork probes to the electrode, generating greatly amplified signals for sensitive assay of HIV. The highly photosensitive 3D CdSe QDs-DNA reticulated nanomaterials have high stability and controllability, and display significantly improved PEC and ECL signals of the biosensor. This method opened a new photoelectric nanocomposite of QDs-sensitized SnO2 nanoflower, and developed a versatile biosensing strategy using the 3D CdSe QDS DNA sensitization probes for ultra-sensitive detection of biomolecules, which is important for the early diagnosis of diseases.

Efficient Framework Analysis for Targeted Drug Delivery Based on Internet of Bio-NanoThings.

The Internet of Bio-NanoThings (IoBNTs) is a novel paradigm that derives from synthetic biology and advances in nanotechnology for controlling the embedded nanodevices in various medical applications. However, numerous studies have focused on communication efficiency among the nanodevices in a given network, the challenges such as the design and the development of the nanodevices, and the coordination of molecular communication within the wireless body area network (BAN), and the interface connection between the BAN and the Internet are yet to be addressed. Therefore, in this study, we present a framework analysis comprising of the compartmental model, for studying the effects and variances in drug concentration that occur inside intra-body nanonetworks through IoBNT, while taking into account the properties of target cells as well as the ligand-receptor binding mechanism. A performance analysis of the proposed framework for the forward link (i.e., from the Internet to the intra-body nanonetwork) and reverse link (i.e., from the intra-body nanonetwork to the Internet) is presented. The simulation results of the developed framework reveal its ability to enhance the delivery of therapeutic drugs to the target cell while minimizing the side effects in healthy cells.

VIVID: In Vivo End-to-End Molecular Communication Model for COVID-19.

As an alternative to ongoing efforts for vaccine development, scientists are exploring novel approaches to provide innovative therapeutics, such as nanoparticle- and stem cell-based treatments. Thus, understanding the transmission and propagation dynamics of coronavirus inside the respiratory system has attracted researchers' attention. In this work, we model the transmission and propagation of coronavirus inside the respiratory tract, starting from the nasal area to alveoli using molecular communication theory. We performed experiments using COMSOL, a finite-element multiphysics simulation software, and Python-based simulations to analyze the end-to-end communication model in terms of path loss, delay, and gain. The analytical results show the correlation between the channel characteristics and pathophysiological properties of coronavirus. For the initial 50% of the maximum production rate of virus particles, the path loss increases more than 16 times than the remaining 50%. The delayed response of the immune system and increase in the absorption of virus particles inside the respiratory tract delay the arrival of virus particles at the alveoli. Furthermore, the results reveal that the virus load is more in case of asthmatic patients as compared to the normal subjects.

Thiol-sensitive probe enables dynamic electrochemical assembly of serum protein for detecting SARS-Cov-2 marker protease in clinical samples.

The poor situational awareness about the spreading of the virus especially in the underdeveloped regions calls for novel virus assays of low cost and simple operation. Currently, such assays are exclusively restricted to nucleic acid detection. In this investigation, a virus protein serum assay has been proposed in a one-step and reagent-less route. Specifically, in this assay, the main protease of the virus is targeted by a short probe mimicking its substrate. While the probe-protein interaction brings them together, a fluorescent thiol targeting molecule reacts with the free thiol groups on the target protein near the probe, generating a fluorescence signal proportional to the concentration of the target. This induces an electroactive 2D peptide nano-network on the sensing surface only in the presence of the target protein. The sensitivity of the method is enhanced through potential electrochemical scanning during incubation with serum samples. The successful detection of the virus marker protein in the serum of the infected patients encourages further development of incorporation of this method into clinical practice.

Enzyme-Initiated Assembly of an Extracellular-Like Two-Dimensional Nanonetwork as a Method to Detect Procancerous Activity.

Extracellular matrix (ECM) enzymes such as lysyl oxidase (LOX) provide a new possibility to contain the invasive progress of cancer. Unlike conventional enzymes, the activity of ECM enzymes is not simply the conversion of the substrate to the product; the amount of enzymes such as matrix metalloproteinases in the ECM changes the structural integrity and morphology of the ECM. These are all important aspects that must be monitored in a spatiotemporally coupled fashion to fully understand their procancerous effect. To achieve this goal, a new molecular probe is developed, which, unlike antibodies or aptamers, can interact with the target enzyme in a more interactive way: the probe can withdraw the metal ion cofactor of the enzyme and modulate its catalytic ability. This can lead to self-propagated cross-linking of the probes to form a network not dissimilar to the collagen and elastin network of the ECM, formed through LOX activity. Thus, the biosensing process itself is a biomimetic of what may occur in vivo in the ECM, and three distinct types of signal readouts can be simultaneously recorded on the sensing surface to provide a fuller picture of ECM enzyme activity, not achievable with traditional designs. Using this method, a parallel between the detected signal and the progress of colorectal cancer can be observed. These results may point to prospective application of this method in evaluating ECM-related tumor invasiveness in the future.

Multiwalled Carbon Nanotubes-CeO2 Nanorods: A "Nanonetwork" Modified Electrode for Detecting Trace Rifampicin.

Herein, a "nanonetwork" modified electrode was fabricated based on multiwalled carbon nanotubes and CeO2 nanorods. Scanning electron microscopy, X-ray powder diffraction and zeta potential were employed to characterize this electrode. Multiwalled carbon nanotubes negatively charged and CeO2 nanorods positively charged form "nanonetwork" via electrostatic interaction. The performance of the CeO2 nanorods-based electrode remarkably improved due to the introduction of multiwalled carbon nanotubes. The detection of rifampicin (RIF) was used as a model system to probe this novel electrode. The results showed a significant electrocatalytic activity for the redox reaction of RIF. Differential pulse voltammetry was used to detect rifampicin, the reduction peak current of rifampicin linear with the logarithm of their concentrations in the range of 1.0 × 10-13-1.0 × 10-6 mol/L, The linear equation is ip = 6.72 + 0. 46lgc, the detect limit is 3.4 × 10-14 mol/L (S/N = 3). Additionally, the modified electrode exhibits enduring stability, excellent reproducibility, and high selectivity. This strategy can be successfully used to detect trace rifampicin in samples with satisfactory results.