Flexible Printed Ultraviolet-to-Near-Infrared Broadband Optoelectronic Carbon Nanotube Synaptic Transistors for Fast and Energy-Efficient Neuromorphic Vision Systems.

To simulate biological visual systems and surpass their functions and performance, it is essential to develop high-performance optoelectronic neuromorphic electronics with broadband response, low power consumption, and fast response speed. Among these, optoelectronic synaptic transistors have emerged as promising candidates for constructing neuromorphic visual systems. In this work, flexible printed broadband (from 275 to 1050 nm) optoelectronic carbon nanotube synaptic transistors with good stability, high response speed (3.14 ms), and low-power consumption (as low as 0.1 fJ per event with the 1050 nm pulse illumination) using PbS quantum dots (QDs) modified semiconducting single-walled carbon nanotubes (sc-SWCNTs) as active layers are developed. In response to optical pulses within the ultraviolet to near-infrared wavelength range, the optoelectronic neuromorphic devices exhibit excitatory postsynaptic current, paired-pulse facilitation, and a transition from short-term plasticity to long-term plasticity, and other optical synaptic behaviors. Furthermore, a simplified neural morphology visual array is developed to simulate integrated functions such as image perception, memory, and preprocessing. More importantly, it can also emulate other complicated bionic functions, such as the infrared perception of salmon eyes and the warning behavior of reindeer in different environments. This work holds immense significance in advancing the development of artificial neural visual systems.

Construction of a sensitive SWCNTs integrated SPR biosensor for detecting PD-L1+ exosomes based on Fe3O4@TiO2 specific enrichment and signal amplification.

Programmed cell death-ligand 1 positive (PD-L1+) exosomes play a crucial role in the realm of cancer diagnosis and treatment. Nevertheless, due to the intricate nature of biological specimens, coupled with the heterogeneity, low refractive index (RI), and scant surface coverage density of exosomes, traditional surface plasmon resonance (SPR) sensors still do not meet clinical detection requirements. This study utilizes the exceptional electrical and optical attributes of single-walled carbon nanotubes (SWCNTs) as the substrate for SPR sensing, thereby markedly enhancing sensitivity. Furthermore, sp2 hybridized SWCNTs have the ability to load specific recognition elements. Additionally, through the coordination interaction of Ti with phosphate groups and the ferromagnetism of Fe3O4, efficient exosomes isolation and enrichment in complex samples are achievable with the aid of an external magnetic field. Owing to the high-quality and high-RI of Fe3O4@TiO2, the response signal experiences amplification, thus further improving the performance of the SPR biosensor. The linear range of the SPR biosensor constructed by this method is 1.0 × 103 to 1.0 × 107 particles/mL, with a limit of detection (LOD) of 31.9 particles/mL. In the analysis of clinical serum samples, cancer patients can be differentiated from healthy individuals with an Area Under Curve (AUC) of 0.9835. This study not only establishes a novel platform for exosomes direct detection but also offers new perspectives for the sensitive detection of other biomarkers.

Carbon nanowires made by the insertion-and-fusion method toward carbon-hydrogen nanoelectronics.

Carbon nanowires (CNWs), long linear carbon chains encapsulated inside carbon nanotubes, exhibit sp hybridization characteristics as one of one-dimensional nanocarbon materials. The research interests on CNWs are accelerated by the successful experimental syntheses from the multi-walled to double-walled until single-walled CNWs recently but the formation mechanisms and structure-property relationships of CNWs remain poorly understood. In this work, we studied the insertion-and-fusion formation process of CNWs at an atomistic level using ReaxFF reactive molecular dynamics (MD) and density functional theory (DFT) calculations with particular focus on the hydrogen (H) adatom effects on the configurations and properties of carbon chains. The constrained MD shows that short carbon chains can be inserted and fused into long carbon chains inside the CNTs due to the van der Waals interactions with little energy barriers. We found that the end-capped H atoms of carbon chains may still remain as adatoms on the fused chains without C-H bond breaking and could transfer along the carbon chains via thermal activation. Moreover, the H adatoms were found to have critical effects on the distribution of bond length alternation as well as the energy level gaps and magnetic moments depending on the varied positions of H adatoms on the carbon chains. The results of ReaxFF MD simulations were validated by the DFT calculations and ab initio MD simulations. The diameter effect of the CNTs on the binding energies suggest that multiple CNTs with a range of appropriate diameters can be used to stabilize the carbon chains. Different from the terminal H of carbon nanomaterials, this work demonstrated that the H adatoms could be used to tune the electronic and magnetic properties of carbon-based electronic devices, opening up the door toward rich carbon-hydrogen nanoelectronics.

Nickel-catalyzed asymmetric reductive arylation of α-chlorosulfones with aryl halides.

We report an asymmetric Ni-catalyzed reductive cross-coupling of aryl/heteroaryl halides with racemic α-chlorosulfones to afford enantioenriched sulfones. The reaction tolerates a variety of functional groups under mild reaction conditions, which complements the current methods. The utility of this work was demonstrated by facile late-stage functionalization of commercial drugs.

Green fabrication of Cu/rGO decorated SWCNT buckypaper as a flexible electrode for glucose detection.

As a paper-like membrane composed of single-walled carbon nanotube (SWCNT), buckypaper possesses high conductivity, ideal flexibility, large surface area, great thermal/chemical stability and biocompatibility, which has manifested its potential as an alternative support material. However, due to the lack of defects, high quality SWCNT synthesized by arc-discharge method is difficult to be modified with metal nanoparticles for electro-catalysis. In this paper, a novel green strategy has been developed to fabricate SWCNT buckypaper decorated with Cu/reduced graphene oxide (Cu/rGO-BP) for the first time, in which graphene oxide functions as the intermediate between SWCNT and Cu nanoparticles. The fabricated Cu/rGO-BP was applied as a flexible electrode for electrochemical glucose detection. The electrode exhibited excellent electro-catalytic activity for glucose oxidation. The sensor based on Cu/rGO-BP performed a high upper limit of linear range (25 mM), which is close to commercial glucose sensors. The proposed strategy for Cu/rGO-BP fabrication can be extended to modify buckypaper with other metal or metal oxide nanoparticles, and thus opens an innovative route to potential practical applications of flexible buckypaper in wearable bioelectronics.

Metal catalyst-free photo-induced alkyl C-O bond borylation.

Metal catalyst free, blue visible light-induced C-O bond borylation of unactivated tertiary alkyl methyl oxalates has been developed to furnish tertiary alkyl boronates. From the secondary alcohols activated with imidazolylthionyl, moderate yields of boronates were attained under standard photo-induced conditions. Preliminary mechanistic studies confirmed the involvement of a (DMF)2-B2cat2 adduct that weakly absorbs light at 437 nm so as to initiate a Bcat radical. A radical-chain process is proposed wherein the alkyl radical is engaged.

Radical Reactions in Cavitands Unveil the Effects of Affinity on Dynamic Supramolecular Systems.

Radical reduction of alkyl halides and aerobic oxidation of alkyl aromatics are reported using water-soluble container compounds (1 and 2). The reductions involve α,ω-dihalides (4-8 and 10) with radical initiators in cavitand hosts with varied binding affinities. Product distributions lead to general guidelines for the use of dynamic supramolecular systems with fast reactions. The binding of guest substrates in the hosts must show high affinities (Ka > 103 M-1) to ensure that the reactions take place under confinement in the containers.

Changing the Phosphorus Allotrope from a Square Columnar Structure to a Planar Zigzag Nanoribbon by Increasing the Diameter of Carbon Nanotube Nanoreactors.

Elemental phosphorus nanostructures are notorious for a large number of allotropes, which limits their usefulness as semiconductors. To limit this structural diversity, we synthesize selectively quasi-1D phosphorus nanostructures inside carbon nanotubes (CNTs) that act both as stable templates and nanoreactors. Whereas zigzag phosphorus nanoribbons form preferably in CNTs with an inner diameter exceeding 1.4 nm, a previously unknown square columnar structure of phosphorus is observed to form inside narrower nanotubes. Our findings are supported by electron microscopy and Raman spectroscopy observations as well as ab initio density functional theory calculations. Our computational results suggest that square columnar structures form preferably in CNTs with an inner diameter around 1.0 nm, whereas black phosphorus nanoribbons form preferably inside CNTs with a 4.1 nm inner diameter, with zigzag nanoribbons energetically favored over armchair nanoribbons. Our theoretical predictions agree with the experimental findings.

Facile Fabrication of NiO-Decorated Double-Layer Single-Walled Carbon Nanotube Buckypaper for Glucose Detection.

A novel NiO-decorated flexible buckypaper (NiO-BP) was fabricated by a simple and scalable vacuum filtration method for electrochemical detection of glucose. The NiO-BP consists of two layers: one side is composed of purified single-walled carbon nanotubes, serving as the supporting layer, whereas the other side comprises NiO-loaded single-walled carbon nanotubes, serving as the catalyst layer. The morphology and structure of NiO-BP were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction and Raman spectroscopy. The fabricated NiO-BP was applied to the electrochemical detection of glucose. Under optimized conditions, the sensor exhibited a wide linear range of 0.1-9 mM for the determination of glucose with high sensitivity (2701 µA mM-1 cm-2) and a short response time (<2.5 s). The present work reveals that the buckypaper with a unique double-layer structure is promising for wearable biosensors.

Rock-salt and helix structures of silver iodides under ambient conditions.

Many different phase structures have been discovered for silver iodides. The ß and γ phases were found to be the most common ones at ambient conditions, while the rock-salt phase was found to be stable under pressures between 400 MPa and 11.3 GPa. Recently, the α phase was demonstrated to be stable under ambient conditions when the particle sizes were reduced to below 10 nm. However, no other phase has been reported to be stable for silver iodides under ambient conditions. Rock-salt and helix structures have been found to be stable under ambient conditions in this study. The structures have been characterized by elemental mapping, Raman scattering, and high-resolution transmission electron microscopy. The stabilities of these structures were also confirmed by molecular dynamics and density functional theory.

Preparation of long linear carbon chain inside multi-walled carbon nanotubes by cooling enhanced hydrogen arc discharge method.

Long linear carbon chains with sp hybridization inside multi-walled carbon nanotubes (LLCC@MWCNTs) can be prepared in the cathode deposits obtained by hydrogen arc discharge. In this work, a cooling system was introduced into the hydrogen arc discharge method to improve the growth yield of LLCC@MWCNTs samples, as indicated by the corresponding stronger Raman peaks between 1780 cm-1 and 1880 cm-1, compared with conventional systems. Moreover, the cooling largely expanded the narrow scope of suitable conditions for the preparation of LLCC@MWCNTs, and high purity samples were easily produced. Qualitative analysis of arc discharge process helped conclude that cooling helps to increase the temperature of arc plasma, which is beneficial to improve both the growth yield of LLCC@MWCNTs and the purity of MWCNTs. This work provides a new approach to improve the growth yield of LLCC@MWCNTs and will benefit further studies and future applications of this new one-dimensional allotrope.

Single-walled carbon nanotubes assisted THz silicon grating modulator.

Single-walled carbon nanotubes (SWCNTs) are applied to realize an enhanced frequency modulation for a suspended THz silicon grating, which is fabricated by a nanosecond laser direct writing and coated with the synthetic SWCNTs/polyacrylic emulsion composite. With terahertz time domain spectroscopy system, the transmission spectra of the bare and SWCNTs coated silicon grating are measured and compared. The SWCNTs coated silicon grating can realize an improved extinction ratio and quality factor, which is due to the SWCNTs caused local field enhancement and can be explained by the theoretical simulation with finite element method. Besides the effective modulation of the grating transmittance, SWCNTs can also be integrated with other platforms and applied in future THz imaging and communication systems.

Flexible integrated diode-transistor logic (DTL) driving circuits based on printed carbon nanotube thin film transistors with low operation voltage.

Fabrication and application of hybrid functional circuits have become a hot research topic in the field of printed electronics. In this study, a novel flexible diode-transistor logic (DTL) driving circuit is proposed, which was fabricated based on a light emitting diode (LED) integrated with printed high-performance single-walled carbon nanotube (SWCNT) thin-film transistors (TFTs). The LED, which is made of AlGaInP on GaAs, is commercial off-the-shelf, which could generate free electrical charges upon white light illumination. Printed top-gate TFTs were made on a PET substrate by inkjet printing high purity semiconducting SWCNTs (sc-SWCNTs) ink as the semiconductor channel materials, together with printed silver ink as the top-gate electrode and printed poly(pyromellitic dianhydride-co-4,4'-oxydianiline) (PMDA/ODA) as gate dielectric layer. The LED, which is connected to the gate electrode of the TFT, generated electrical charge when illuminated, resulting in biased gate voltage to control the TFT from "ON" status to "OFF" status. The TFTs with a PMDA/ODA gate dielectric exhibited low operating voltages of ±1 V, a small subthreshold swing of 62-105 mV dec-1 and ON/OFF ratio of 106, which enabled DTL driving circuits to have high ON currents, high dark-to-bright current ratios (up to 105) and good stability under repeated white light illumination. As an application, the flexible DTL driving circuit was connected to external quantum dot LEDs (QLEDs), demonstrating its ability to drive and to control the QLED.

Origins of Dirac cone formation in AB3 and A3B (A, B = C, Si, and Ge) binary monolayers.

Compared to the pure two-dimensional (2D) graphene and silicene, the binary 2D system silagraphenes, consisting of both C and Si atoms, possess more diverse electronic structures depending on their various chemical stoichiometry and arrangement pattern of binary components. By performing calculations with both density functional theory and a Tight-binding model, we elucidated the formation of Dirac cone (DC) band structures in SiC3 and Si3C as well as their analogous binary monolayers including SiGe3, Si3Ge, GeC3, and Ge3C. A "ring coupling" mechanism, referring to the couplings among the six ring atoms, was proposed to explain the origin of DCs in AB3 and A3B binary systems, based on which we discussed the methods tuning the SiC3 systems into self-doped systems. The first-principles quantum transport calculations by non-equilibrium Green's function method combined with density functional theory showed that the electron conductance of SiC3 and Si3C lie between those of graphene and silicene, proportional to the carbon concentrations. Understanding the DC formation mechanism and electronic properties sheds light onto the design principles for novel Fermi Dirac systems used in nanoelectronic devices.

Origins of Dirac cones and parity dependent electronic structures of α-graphyne derivatives and silagraphynes.

Compared with graphene, graphyne and its derivatives possess more diversified atomic configurations and richer electronic structures including Dirac cones (DCs) and metallic features depending on the parity of the number of sp carbon atoms of graphynes. This report described conceptually the process of DC formation of α-graphyne within a tight-binding framework parameterized from density functional calculations. We propose a "triple coupling" mechanism elucidating the DC formation and some flat bands of α-graphynes where the couplings among the three sp carbon chain atoms are critical. The extension of this mechanism further explains the origins of DCs of silagraphynes and the parity dependent electronic structures of α-graphyne derivatives with extended sp carbon chains. Understanding these origins helps in tuning electronic properties in the design of C or C-Si based nanoelectronic devices.

All-Solid-State High-Energy Asymmetric Supercapacitors Enabled by Three-Dimensional Mixed-Valent MnOx Nanospike and Graphene Electrodes.

Three-dimensional (3D) nanostructures enable high-energy storage devices. Here we report a 3D manganese oxide nanospike (NSP) array electrode fabricated by anodization and subsequent electrodeposition. All-solid-state asymmetric supercapacitors were assembled with the 3D Al@Ni@MnOx NSP as the positive electrode, chemically converted graphene (CCG) as the negative electrode, and Na2SO4/poly(vinyl alcohol) (PVA) as the polymer gel electrolyte. Taking advantage of the different potential windows of Al@Ni@MnOx NSP and CCG electrodes, the asymmetric supercapacitor showed an ideal capacitive behavior with a cell voltage up to 1.8 V, capable of lighting up a red LED indicator (nominal voltage of 1.8 V). The device could deliver an energy density of 23.02 W h kg(-1) at a current density of 1 A g(-1). It could also preserve 96.3% of its initial capacitance at a current density of 2 A g(-1) after 10000 charging/discharging cycles. The remarkable performance is attributed to the unique 3D NSP array structure that could play an important role in increasing the effective electrode surface area, facilitating electrolyte permeation, and shortening the electron pathway in the active materials.

Origin of Dirac Cones in SiC Silagraphene: A Combined Density Functional and Tight-Binding Study.

The formation of Dirac cones in electronic band structures via isomorphous transformation is demonstrated in 2D planar SiC sheets. Our combined density functional and tight-binding calculations show that 2D SiC featuring C-C and Si-Si atom pairs possesses Dirac cones (DCs), whereas an alternative arrangement of C and Si leads to a finite band gap. The origin of Dirac points is attributed to bare interactions between Si-Si bonding states (valence bands, VBs) and C-C antibonding states (conduction bands, CBs), while the VB-CB coupling opens up band gaps elsewhere. A mechanism of atom pair coupling is proposed, and the conditions required for DC formation are discussed, enabling one to design a class of 2D binary Dirac fermion systems on the basis of DF calculations solely for pure and alternative binary structures.

Energetic stability, atomic and electronic structures of extended γ-graphyne: A density functional study.

The energetic stability, atomic and electronic structures of γ-graphyne and its derivatives (γ-GYs) with extended carbon chains were investigated as a function of chain length by density functional calculations in this work. The studied γ-GYs consist of hexagon carbon rings connected by linear chains with C atoms n = 0-22. We predict that the even-numbered C chains of γ-GYs consist of alternating single and triple C-C bonds (polyyne), energetically more stable than the odd-numbered C chains made of continuous C-C double bonds (polycumulene). The calculated electronic structures indicate that γ-GYs can be either metallic (odd n) or semiconductive (even n) depending on the parity of the number of C chain atoms. The semiconducting γ-GYs are predicted to have ~1.2 eV direct band gaps and 0.1-0.2 effective electron masses independent of the chain length. Thus introducing sp carbon atoms into sp (2)-based graphene provides a novel way to open up band gaps without doping and defects while maintaining small electron masses critical to good transport properties. Graphical Abstract The typical atomic model of graphyne (middle) as well as their band gaps (left) and electron density (right).

Fracture analysis for biological materials with an expanded cohesive zone model.

In this study, a theoretical framework for simulation of fracture of bone and bone-like materials is provided. An expanded cohesive zone model with thermodynamically consistent framework has been proposed and used to investigate the crack growth resistance of bone and bone-like materials. The reversible elastic deformation, irreversible plastic deformation caused by large deformation of soft protein matrix, and damage evidenced by the material separation and crack nucleation in the cohesive zone, were all taken into account in the model. Furthermore, the key mechanisms in deformation of biocomposites consisting of mineral platelets and protein interfacial layers were incorporated in the fracture process zone in this model, thereby overcoming the limitations of previous cohesive zone modeling of bone fracture. Finally, applications to fracture of cortical bone and human dentin were presented, which showed good agreement between numerical simulation and reported experiments and substantiated the effectiveness of the model in investigating the fracture behavior of bone-like materials.

On the mechanical behavior of bio-inspired materials with non-self-similar hierarchy.

Biological materials exhibiting non-self-similar hierarchical structures possess desirable mechanical properties. Motivated by their penetration resistance and fracture toughness, the mechanical performance of model materials with non-self-similar hierarchical structures was explored and the distinct advantages were identified. A numerical model was developed, based on microscopic observation of enamel prisms. Computational simulations showed that the systems with non-self-similar hierarchy displayed lateral expansion when subjected to longitudinal tensile loading, which reflected negative Poisson׳s ratio and potential for greater volume strain energies when compared with conventional materials with positive Poisson׳s ratio. Employing the non-self-similar hierarchical design, the capability of resilience can be improved. Additionally, the non-self-similar hierarchical structure exhibited larger toughness, resulting from the large pull-out work of the reinforcements. The findings of this study not only elucidate the deformation mechanisms of biological materials with non-self-similar hierarchical structure, but also provide a new path for bio-inspired materials design.