Four-Membered Ring-Embedded Cycloarene Enabling Anti-Aromaticity and Ultra-Narrowband Emission.

Synthesis of fully fused π-conjugated cycloarenes embedded nonbenzenoid aromatics is challenging. In this work, the first example of four-membered ring-embedded cycloarene (MF2) was designed and synthesized in single-crystal form by macrocyclization and ring fusion strategies. For comparison, single bond-linked chiral macrocycle MS2 without two fused four-membered rings and its linear-shaped polycyclic benzenoid monomer L1 were also synthesized. The pronounced anti-aromaticity of four-membered rings significantly adjusts the electronic structures and photophysical properties of cycloarene, resulting in an enhancement of the photoluminescence quantum yield (PLQY) from 10.66% and 10.74% for L1 and MS2, respectively, to 54.05% for MF2, which is the highest PLQY among the reported cycloarenes. Notably, owing to the embedded four-membered rings that reduce structural displacements, MF2 exhibits an ultra-narrowband emission with a single-digit full-width at half-maximum (FWHM) of only 7 nm (0.038 eV), which sets a new record among all reported organic narrowband luminescent molecules, and represents the first example of ultra-narrowband emission in conventional polycyclic aromatic hydrocarbons (PAHs) devoid of heteroatoms.

Photovoltaic nanocells for high-performance large-scale-integrated organic phototransistors.

A high-performance large-scale-integrated organic phototransistor needs a semiconductor layer that maintains its photoelectric conversion ability well during high-resolution pixelization. However, lacking a precise design for the nanoscale structure, a trade-off between photoelectric performance and device miniaturization greatly limits the success in commercial application. Here we demonstrate a photovoltaic-nanocell enhancement strategy, which overcomes the trade-off and enables high-performance organic phototransistors at a level beyond large-scale integration. Embedding a core-shell photovoltaic nanocell based on perovskite quantum dots in a photocrosslinkable organic semiconductor, ultralarge-scale-integrated (>221 units) imaging chips are manufactured using photolithography. 27 million pixels are interconnected and the pixel density is 3.1 × 106 units cm-2, at least two orders of magnitude higher than in existing organic imaging chips and equivalent to the latest commercial full-frame complementary metal-oxide-semiconductor camera chips. The embedded photovoltaic nanocells induce an in situ photogating modulation and enable photoresponsivity and detectivity of 6.8 × 106 A W-1 and 1.1 × 1013 Jones (at 1 Hz), respectively, achieving the highest values of organic imaging chips at large-scale or higher integration. In addition, a very-large-scale-integrated (>216 units) stretchable biomimetic retina based on photovoltaic nanocells is manufactured for neuromorphic imaging recognition with not only resolution but also photoresponsivity and power consumption approaching those of the biological counterpart.

One-base-mismatch CRISPR-based transistors for single nucleotide resolution assay.

An effective strategy for accurately detecting single nucleotide variants (SNVs) is of great significance for genetic research and diagnostics. However, strict amplification conditions, complex experimental instruments, and specialized personnel are required to obtain a satisfactory tradeoff between sensitivity and selectivity for SNV discrimination. In this study, we present a CRISPR-based transistor biosensor for the rapid and highly selective detection of SNVs in viral RNA. By introducing a synthetic mismatch in the crRNA, the CRISPR-Cas13a protein can be engineered to capture the target SNV RNA directly on the surface of the graphene channel. This process induces a fast electrical signal response in the transistor, obviating the need for amplification or reporter molecules. The biosensor exhibits a detection limit for target RNA as low as 5 copies in 100 µL, which is comparable to that of real-time quantitative polymerase chain reaction (PCR). Its operational range spans from 10 to 5 × 105 copy mL-1 in artificial saliva solution. This capability enables the biosensor to discriminate between wild-type and SNV RNA within 15 min. By introducing 10 µL of swab samples during clinical testing, the biosensor provides specific detection of respiratory viruses in 19 oropharyngeal specimens, including influenza A, influenza B, and variants of SARS-CoV-2. This study emphasizes the CRISPR-transistor technique as a highly accurate and sensitive approach for field-deployable nucleic acid screening or diagnostics.

Rational Molecular Design of Diketopyrrolopyrrole-Based n-Type and Ambipolar Polymer Semiconductors.

Diketopyrrolopyrrole (DPP)-based polymer semiconductors have drawn great attention in the field of organic electronics due to the planar structure, decent solubilizing capability, and high crystallinity. However, the electron-deficient capacity of DPP derivatives are not strong enough, leading to relatively high-lying lowest unoccupied molecular orbital (LUMO) energy levels of the corresponding polymers. As a result, n-type and ambipolar DPP-based polymers are rare and their electron mobilities also lag far behind the p-type counterparts, which limits the development of important p-n-junction-based electronic devices. Therefore, new design strategies have been proposed recent years to develop n-type/ambipolar DPP-based polymers with improved performances. In this view, these molecular design strategies are summarized, including copolymerization of DPP with different acceptors and weak donors, DPP flanked aromatic ring modification, DPP-core ring expansion and DPP dimerization. The relationship between the chemical structures and organic thin-film transistor performances is intensively discussed. Finally, a perspective on future trends in the molecular design of DPP-based n-type/ambipolar polymers is also proposed.

Design and synthesis of broadband absorption covalent organic framework for efficient artificial photocatalytic amine coupling.

Developing highly active materials that efficiently utilize solar spectra is crucial for photocatalysis, but still remains a challenge. Here, we report a new donor-acceptor (D-A) covalent organic framework (COF) with a wide absorption range from 200 nm to 900 nm (ultraviolet-visible-near infrared light). We find that the thiophene functional group is accurately introduced into the electron acceptor units of TpDPP-Py (TpDPP: 5,5'-(2,5-bis(2-ethylhexyl)-3,6-dioxo-2,3,5,6-tetrahydropyrrolo [3,4-c]pyrrole-1,4-diyl)bis(thiophene-2-carbaldehyde), Py: 1,3,6,8-tetrakis(4-aminophenyl)pyrene) COFs not only significantly extends its spectral absorption capacity but also endows them with two-photon and three-photon absorption effects, greatly enhancing the utilization rate of sunlight. The selective coupling of benzylamine as the target reactant is used to assess the photocatalytic activity of TpDPP-Py COFs, showing high photocatalytic conversion of 99% and selectivity of 98% in 20 min. Additionally, the TpDPP-Py COFs also exhibit the universality of photocatalytic selective coupling of other imine derivatives with ~100% conversion efficiency. Overall, this work brings a significant strategy for developing COFs with a wide absorption range to enhance photocatalytic activity.

Multi-order orbital angular momentum mode generators based on integrated long-period fiber gratings.

We propose integrated long-period fiber gratings (LPFGs) fabricated by a CO2 laser to realize a multi-channel and multi-order orbital angular momentum (OAM) mode generator. The integrated LPFG is inscribed on multiple surfaces of the few-mode fiber (FMF) by rotating the fiber in the opposite direction at an angle θ. By controlling the rotation angle, the number of integrated LPFGs can be set. The selected rotation angle is 43 ∘, which can integrate up to nine LPFGs, i.e., realizing that the number of channels for first-order orbital angular momentum (OAM) mode conversion is nine. The integrated LPFGs fabricated in this method allow a flexible design of channel spacing. In addition, the flexible selection of the integrated grating period achieves the simultaneous generation of multi-channel second-order and third-order OAM mode conversion. The multi-channel and multi-order OAM mode generators have important application in optical communication multiplexing systems and OAM sensing.

Electrically Oriented Antibodies on Transistor for Monitoring Several Copies of Methylated DNA.

An antibody transistor is a promising biosensing platform for the diagnosis and monitoring of various diseases. Nevertheless, the low concentration and short half-life of biomarkers require biodetection at the trace-molecule level, which remains a challenge for existing antibody transistors. Herein, we demonstrate a graphene field-effect transistor (gFET) with electrically oriented antibody probes (EOA-gFET) for monitoring several copies of methylated DNA. The electric field confines the orientation of antibody probes on graphene and diminishes the distance between graphene and methylated DNAs captured by antibodies, generating more induced charges on graphene and amplifying the electric signal. EOA-gFET realizes a limit of detection (LoD) of ∼0.12 copy µL-1, reaching the lowest LoD reported before. EOA-gFET shows a distinguishable signal for liver cancer clinical serum samples within ∼6 min, which proves its potential as a powerful tool for disease screening and diagnosis.

Tuning Molecular Packing and Boosting Self-Assembling Properties via Ring Fusion Strategy in Naphthalimide-Based A-D-A Conjugated Systems.

Two fully fused acceptor-donor-acceptor (A-D-A) architecture conjugated derivatives (NPF and NCF) comprising an electron-withdrawing naphthalimide (NMI) and two different electron-donating cores, phenanthrene and carbazole, respectively, were conveniently synthesized by bismuth(III)-catalyzed selective cyclization of vinyl ethers. Compared with their corresponding single bond-linked A-D-A molecules NPS and NCS, both having a moderately twisted aromatic configuration, the ring fusion strategy leads to fully coplanar conjugated skeletons and greatly changes the electronic structures, photophysical properties, self-assembling behaviors, and molecular packing motifs. In particular, the naphthalimide/carbazole derivative NCF exhibits intriguing 2D brickwork packing and significantly enhanced self-assembling properties.

The complete chloroplast genome of Illicium simonsii Maxim. (Illiciaceae), a species with important medicinal properties.

Illicium simonsii Maxim (1888) is a medicinal species of the genus Illicium in the Illiciaceae family. It is commonly used to cure gastro-frigid vomiting, cystic hernia, gas pains in the chest, and scabies as folk medicine. To utilize its resources efficiently, the complete chloroplast genome of I. simonsii was sequenced, assembled, and annotated by using high-throughput sequencing data. The complete chloroplast genome was 143,038 bp in length, with a large single-copy region (LSC) of 101,094 bp, a short single-copy region (SSC) of 20,070 bp, and a pair of inverted repeats (IRs) of 21,874 bp. A total of 113 genes were annotated, including 79 protein-coding genes, 30 tRNA genes, and four rRNA genes. The phylogenetic tree exhibited that I. simonsii and Illicium burmanicum form a sister group, and were nested in the monophyletic clade of the Illicium genus.

Effects of washing agents on the mechanical and biocompatibility properties of water-washable 3D printing crown and bridge resin.

Three-dimensional (3D) printing, otherwise known as additive manufacturing in a non-technical context, is becoming increasingly popular in the field of dentistry. As an essential step in the 3D printing process, postwashing with organic solvents can damage the printed resin polymer and possibly pose a risk to human health. The development of water-washable dental resins means that water can be used as a washing agent. However, the effects of washing agents and washing times on the mechanical and biocompatibility properties of water-washable resins remain unclear. This study investigated the impact of different washing agents (water, detergent, and alcohol) and washing time points (5, 10, 20, and 30 min) on the flexural strength, Vickers hardness, surface characterization, degree of conversion, biocompatibility, and monomer elution of 3D printed samples. Using water for long-term washing better preserved the mechanical properties, caused a smooth surface, and improved the degree of conversion, with 20 min of washing with water achieving the same biological performance as organic solvents. Water is an applicable agent option for washing the 3D printing water-washable temporary crown and bridge resin in the postwashing process. This advancement facilitates the development of other water-washable intraoral resins and the optimization of clinical standard washing guidelines.

Strain-insensitive viscoelastic perovskite film for intrinsically stretchable neuromorphic vision-adaptive transistors.

Stretchable neuromorphic optoelectronics present tantalizing opportunities for intelligent vision applications that necessitate high spatial resolution and multimodal interaction. Existing neuromorphic devices are either stretchable but not reconcilable with multifunctionality, or discrete but with low-end neurological function and limited flexibility. Herein, we propose a defect-tunable viscoelastic perovskite film that is assembled into strain-insensitive quasi-continuous microsphere morphologies for intrinsically stretchable neuromorphic vision-adaptive transistors. The resulting device achieves trichromatic photoadaptation and a rapid adaptive speed (<150 s) beyond human eyes (3 ~ 30 min) even under 100% mechanical strain. When acted as an artificial synapse, the device can operate at an ultra-low energy consumption (15 aJ) (far below the human brain of 1 ~ 10 fJ) with a high paired-pulse facilitation index of 270% (one of the best figures of merit in stretchable synaptic phototransistors). Furthermore, adaptive optical imaging is achieved by the strain-insensitive perovskite films, accelerating the implementation of next-generation neuromorphic vision systems.

Symplasmic and transmembrane zinc transport is modulated by cadmium in the Cd/Zn hyperaccumulator Sedum alfredii.

This study investigated the influence of Cd (25 µM) on Zn accumulation in a hyperaccumulating (HE) and a non-hyperaccumulating (NHE) ecotype of Sedum alfredii Hance at short-term supply of replete (Zn5, 5 µM) and excess (Zn400, 400 µM) Zn. Cd inhibited Zn accumulation in both ecotypes, especially under Zn400, in organs with active metal sequestration, i.e. roots of NHE and shoots of HE. Direct biochemical Cd/Zn competition at the metal-protein interaction and changes in transporter gene expression contributed to the observed accumulation patterns in the roots. Specifically, in HE, Cd stimulated SaZIP4 and SaPCR2 under Zn5, but downregulated SaIRT1 and SaZIP4 under Zn400. However, Cd downregulated related transporter genes, except for SaNRAMP1, in NHE, irrespective of Zn. Cadmium stimulated casparian strip (CSs) development in NHE, as part of the defense response, while it had a subtle effect on the (CS) in HE. Moreover, Cd delayed the initiation of the suberin lamellae (SL) in HE, but stimulated SL deposition in NHE under both Zn5 or Zn400. Changes in suberization were mainly ascribed to suberin-biosynthesis-related genes and hormonal signaling. Altogether, Cd regulated Zn accumulation mainly via symplasmic and transmembrane transport in HE, while Cd inhibited both symplasmic and apoplasmic Zn transport in NHE.

The Transfer Dehydrogenation Method Enables a Family of High Crystalline Benzimidazole-linked Cu (II)-phthalocyanine-based Covalent Organic Frameworks Films.

Heterocycle-linked phthalocyanine-based COFs with close-packed π-π conjugated structures are a kind of material with intrinsic electrical conductivity, and they are considered to be candidates for photoelectrical devices. Previous studies have revealed their applications for energy storage, gas sensors, and field-effect transistors. However, their potential application in photodetector is still not fully studied. The main difficulty is preparing high-quality films. In our study, we found that our newly designed benzimidazole-linked Cu (II)-phthalocyanine-based COFs (BICuPc-COFs) film can hardly formed with a regular aerobic oxidation method. Therefore, we developed a transfer dehydrogenation method with N-benzylideneaniline (BA) as a mild reagent. With this in hand, we successfully prepared a family of high crystalline BICuPc-COFs powders and films. Furthermore, both of these new BICuPc-COFs films showed high electrical conductivity (0.022-0.218 S/m), higher than most of the reported COFs materials. Due to the broad absorption and high conductivity of BICuPc-COFs, synaptic devices with small source-drain voltage (VDS=1 V) were fabricated with response light from visible to near-infrared. Based on these findings, we expect this study will provide a new perspective for the application of conducting heterocycle-linked COFs in synaptic devices.

Structural Design of Single-Atom Catalysts for Enhancing Petrochemical Catalytic Reaction Process.

Petroleum, as the "lifeblood" of industrial development, is the important energy source and raw material. The selective transformation of petroleum into high-end chemicals is of great significance, but still exists enormous challenges. Single-atom catalysts (SACs) with 100% atom utilization and homogeneous active sites, promise a broad application in petrochemical processes. Herein, the research systematically summarizes the recent research progress of SACs in petrochemical catalytic reaction, proposes the role of structural design of SACs in enhancing catalytic performance, elucidates the catalytic reaction mechanisms of SACs in the conversion of petrochemical processes, and reveals the high activity origins of SACs at the atomic scale. Finally, the key challenges are summarized and an outlook on the design, identification of active sites, and the appropriate application of artificial intelligence technology is provided for achieving scale-up application of SACs in petrochemical process.

From π-conjugated macrocycles to heterocycloarenes based on benzo[2,1-b:3,4-b']dithiophene (BDTh): size- and geometry-dependent host-guest properties.

π-Conjugated macrocycles have been highly attractive due to their challenging synthesis, fascinating aesthetic structure and unique physical and chemical properties. Although some progress has been made in synthesis, the study of π-macrocycles with different structural characteristics and supramolecular interactions still faces major challenges. In this paper, two new single-bond linked macrocycles (MS-4T/MS-6T) were reported, and the corresponding vinyl-bridged heterocycloarenes (MF-4T/MF-6T) were synthesized by the periphery fusion strategy. Further studies have indicated that the structure of these four macrocycles is determined by both size and curvature, showing unique variations from nearly planar to bowl and then to saddle. Interestingly, the nearly planar MS-4T with a small size and the rigid saddle-shaped MF-6T show no obvious response to fullerenes C60 or C70, while the bowl-shaped MS-6T and MF-4T demonstrate a strong binding affinity towards fullerenes C60 and C70. What's more, two kinds of co-crystals with capsule-like configurations, MS-6T@C60 and MS-6T@C70, have been successfully obtained, among which the former shows a loose columnar arrangement while the latter displays a unique three-dimensional honeycomb arrangement that is extremely rare in supramolecular complexes. This work systematically studies the π-conjugated macrocycles and provides a new idea for the development of novel host-guest systems and further multifunctional applications.

Bis(benzoselenadiazol)ethane: A π-Extended Acceptor-Dimeric Unit for Ambipolar Polymer Transistors with Hole and Electron Mobilities Exceeding 10†cm2 V-1 s-1.

The lack of ambipolar polymers with balanced hole (µh) and electron mobilities (µe) >10 cm2 V-1 s-1 is the main bottleneck for developing organic integrated circuits. Herein, we show the design and synthesis of a π-extended selenium-containing acceptor-dimeric unit, namely benzo[c][1,2,5]selenadiazol-4-yl)ethane (BBSeE), to address this dilemma. In comparison to its sulfur-counterpart, BBSeE demonstrates enlarged co-planarity, selective noncovalent interactions, polarized Se-N bond, and higher electron affinity. The successful stannylation of BBSeE offers a great opportunity to access acceptor-acceptor copolymer pN-BBSeE, which shows a narrower band gap, lower-lying lowest unoccupied molecular orbital level (-4.05 eV), and a higher degree of backbone planarity. Consequently, the pN-BBSeE-based organic transistors display an ideally balanced ambipolar transporting property with µh and µe of 10.65 and 10.72 cm2 V-1 s-1, respectively. To the best of our knowledge, the simultaneous µh/µe values >10.0 cm2 V-1 s-1 are the best performances ever reported for ambipolar polymers. In addition, pN-BBSeE shows an excellent shelf-storage stability, retaining over 85 % of the initial mobility values after two months storage. Our study demonstrates the π-extended acceptor-dimeric BBSeE is a promising acceptor building block for constructing high-performance ambipolar polymers applied in next-generation organic integrated circuit.

Antibody Nanotweezer Constructing Bivalent Transistor-Biomolecule Interface with Spatial Tolerance.

Establishing a multivalent interface between the biointerface of a living system and electronic device is vital to building intelligent bioelectronic systems. How to achieve multivalent binding with spatial tolerance at the nanoscale remains challenging. Here, we report an antibody nanotweezer that is a self-adaptive bivalent nanobody enabling strong and resilient binding between transistor and envelope proteins at biointerfaces. The antibody nanotweezer is constructed by a DNA framework, where the nanoscale patterning of nanobodies along with their local spatial adaptivity enables simultaneous recognition of target epitopes without binding stress. As such, effective binding affinity increases by 1 order of magnitude compared with monovalent antibody. The antibody nanotweezer operating on transistor offers enhanced signal transduction, which is implemented to detect clinical pathogens, showing ∼100% overall agreement with PCR results. This work provides a perspective of engineering multivalent interfaces between biosystems with solid-state devices, holding great potential for organoid intelligence on a chip.

Biomimetic nanocluster photoreceptors for adaptative circular polarization vision.

Nanoclusters with atomically precise structures and discrete energy levels are considered as nanoscale semiconductors for artificial intelligence. However, nanocluster electronic engineering and optoelectronic behavior have remained obscure and unexplored. Hence, we create nanocluster photoreceptors inspired by mantis shrimp visual systems to satisfy the needs of compact but multi-task vision hardware and explore the photo-induced electronic transport. Wafer-scale arrayed photoreceptors are constructed by a nanocluster-conjugated molecule heterostructure. Nanoclusters perform as an in-sensor charge reservoir to tune the conductance levels of artificial photoreceptors by a light valve mechanism. A ligand-assisted charge transfer process takes place at nanocluster interface and it features an integration of spectral-dependent visual adaptation and circular polarization recognition. This approach is further employed for developing concisely structured, multi-task, and compact artificial visual systems and provides valuable guidelines for nanocluster neuromorphic devices.

Inter-site structural heterogeneity induction of single atom Fe catalysts for robust oxygen reduction.

Metal-nitrogen-carbon catalysts with hierarchically dispersed porosity are deemed as efficient geometry for oxygen reduction reaction (ORR). However, catalytic performance determined by individual and interacting sites originating from structural heterogeneity is particularly elusive and yet remains to be understood. Here, an efficient hierarchically porous Fe single atom catalyst (Fe SAs-HP) is prepared with Fe atoms densely resided at micropores and mesopores. Fe SAs-HP exhibits robust ORR performance with half-wave potential of 0.94 V and turnover frequency of 5.99 e-1s-1site-1 at 0.80 V. Theoretical simulations unravel a structural heterogeneity induced optimization, where mesoporous Fe-N4 acts as real active centers as a result of long-range electron regulation by adjacent microporous sites, facilitating O2 activation and desorption of key intermediate *OH. Multilevel operando characterization results identify active Fe sites undergo a dynamic evolution from basic Fe-N4 to active Fe-N3 under working conditions. Our findings reveal the structural origin of enhanced intrinsic activity for hierarchically porous Fe-N4 sites.