Dual Chalcogen-Bonding Interaction for High-Performance Filterless Narrowband Organic Photodetectors.

A novel green-absorbing organic molecule featuring dual intramolecular chalcogen bonds is synthesized and characterized. This molecule incorporates two such bonds: one between a tellurium atom and the oxygen atom of a carbonyl moiety, and the other between the tellurium atom and the adjacent nitrogen atom within a pyridine moiety. The molecule, featuring dual intramolecular chalcogen bonds exhibits a narrow absorption spectrum and elevated absorption coefficients, closely aligned with a resonance parameter of approximately 0.5. This behavior is due to its cyanine-like characteristics and favorable electrical properties, which are a direct result of its rigid, planar molecular structure. Therefore, this organic molecule forming dual intramolecular chalcogen bonds achieves superior optoelectronic performance in green-selective photodetectors, boasting an external quantum efficiency of over 65% and a full-width at half maximum of less than 95 nm while maintaining the performance after 1000 h of heating aging at 85 °C. Such organic photodetectors are poised to enhance stacked organic photodetector-on-silicon hybrid image sensors, paving the way for the next-generation of high-resolution and high-sensitivity image sensors.

Catalytic Glycosylation for Minimally Protected Donors and Acceptors.

Oligosaccharides have myriad functions throughout biology.1,2 To investigate these functions requires multi-step chemical synthesis of these structurally complex molecules. With a dense concentration of stereocentres and hydroxyl groups, oligosaccharide assembly through O-glycosylation requires simultaneous control of site-, stereo-, and chemoselectivities3,4. Chemists have traditionally relied on protecting group manipulations for this purpose,5-8 adding a lot of synthetic work. Here, we report a glycosylation platform that enables selective coupling between unprotected or minimally protected donor and acceptor sugars, producing 1,2-cis-O-glycosides in a catalyst-controlled, site-selective manner. Radical-based activation9 of allyl glycosyl sulfones forms glycosyl bromides. A designed aminoboronic acid catalysts bring this reactive intermediate close to an acceptor through a network of noncovalent hydrogen bonding and reversible covalent B-O bonding interactions, allowing precise glycosyl transfer. The site of glycosylation can be switched with different aminoboronic acid catalysts by affecting their interaction modes with substrates. The method accommodates a wide range of sugar types, amenable to preparing naturally occurring sugar chains and pentasaccharides containing 11 free hydroxyls. Experimental and computational studies provide insights into the origin of selectivity outcomes.

Mechanism for Local-Atomic Structure Changes in Chalcogenide-based Threshold-Switching Devices.

Threshold-switching devices based on amorphous chalcogenides are considered for use as selector devices in 3D crossbar memories. However, the fundamental understanding of amorphous chalcogenide is hindered owing to the complexity of the local structures and difficulties in the trap analysis of multinary compounds. Furthermore, after threshold switching, the local structures gradually evolve to more stable energy states owing to the unstable homopolar bonds. Herein, based on trap analysis, DFT simulations, and operando XPS analysis, it is determined that the threshold switching mechanism is deeply related to the charged state of Se-Se homopolar defects. A threshold switching device is demonstrated with an excellent performance through the modification of the local structure via the addition of alloying elements and investigating the time-dependent trap evolution. The results concerning the trap dynamics of local atomic structures in threshold switching phenomena may be used to improve the design of amorphous chalcogenides.

Probability Density Reweighting of High-Temperature Molecular Dynamics.

Molecular dynamics (MD) simulation is a popular method for elucidating the structures and functions of biomolecules. However, exploring the conformational space, especially for large systems with slow transitions, often requires enhanced sampling methods. Although conducting MD at high temperatures provides a straightforward approach, resulting conformational ensembles diverge significantly from those at low temperatures. To address this discrepancy, we propose a novel probability density-based reweighting (PDR) method. PDR exhibits robust performance across four distinct systems, including a miniprotein, a cyclic peptide, a protein loop, and a protein-peptide complex. It accurately restores the conformational distributions at high temperatures to those at low temperatures. Additionally, we apply PDR to reweight previously studied high-T MD simulations of 12 protein-peptide complexes, enabling a comprehensive investigation of the conformational space of protein-peptide complexes.

Determination of Acetylamantadine by γ-Cyclodextrin-Assisted α-HL Nanopore for Potential Cancer Prediagnosis.

The high expression of Spermidine/spermine N1-acetyltransferase (SSAT-1) is an important indicator in early cancer diagnosis. Here, we developed a nanopore-based methodology with γ-cyclodextrin as an adaptor to detect and quantify acetylamantadine, the specific SSAT-1-catalyzed product from amantadine, to accordingly reflect the activity of SSAT-1. We employ γ-cyclodextrin and report that amantadine cannot cause any secondary signals in γ-cyclodextrin-assisted α-HL nanopore, while its acetylation product, acetylamantadine, does. This allows γ-cyclodextrin to practically detect acetylamantadine in the interference of excessive amantadine, superior to the previously reported ß-cyclodextrin. The quantification of acetylamantadine was not interfered with even a 50-fold amantadine and displayed no interference in artificial urine sample analysis, which indicates the good feasibility of this nanopore-based methodology in painless cancer prediagnosis. In addition, the discrimination mechanism is also explored by 2-D nuclear magnetic resonance (NMR) and nanopore experiments with a series of adamantane derivatives with different hydrophilic and hydrophobic groups. We found that both the hydrophobic region matching effect and hydrophilic interactions play a synergistic effect in forming a host-guest complex to further generate the characteristic signals, which may provide insights for the subsequent design and study of drug-cyclodextrin complexes.

Functionalized MXene ink enables environmentally stable printed electronics.

Establishing dependable, cost-effective electrical connections is vital for enhancing device performance and shrinking electronic circuits. MXenes, combining excellent electrical conductivity, high breakdown voltage, solution processability, and two-dimensional morphology, are promising candidates for contacts in microelectronics. However, their hydrophilic surfaces, which enable spontaneous environmental degradation and poor dispersion stability in organic solvents, have restricted certain electronic applications. Herein, electrohydrodynamic printing technique is used to fabricate fully solution-processed thin-film transistors with alkylated 3,4-dihydroxy-L-phenylalanine functionalized Ti3C2Tx (AD-MXene) as source, drain, and gate electrodes. The AD-MXene has excellent dispersion stability in ethanol, which is required for electrohydrodynamic printing, and maintains high electrical conductivity. It outperformed conventional vacuum-deposited Au and Al electrodes, providing thin-film transistors with good environmental stability due to its hydrophobicity. Further, thin-film transistors are integrated into logic gates and one-transistor-one-memory cells. This work, unveiling the ligand-functionalized MXenes' potential in printed electrical contacts, promotes environmentally robust MXene-based electronics (MXetronics).

Structure-Based Rational and General Strategy for Stabilizing Single-Chain T-Cell Receptors to Enhance Affinity.

The T-cell receptor (TCR) is a crucial molecule in cellular immunity. The single-chain T-cell receptor (scTCR) is a potential format in TCR therapeutics because it eliminates the possibility of αß-TCR mispairing. However, its poor stability and solubility impede the in vitro study and manufacturing of therapeutic applications. In this study, some conserved structural motifs are identified in variable domains regardless of germlines and species. Theoretical analysis helps to identify those unfavored factors and leads to a general strategy for stabilizing scTCRs by substituting residues at exact IMGT positions with beneficial propensities on the consensus sequence of germlines. Several representative scTCRs are displayed to achieve stability optimization and retain comparable binding affinities with the corresponding αß-TCRs in the range of µM to pM. These results demonstrate that our strategies for scTCR engineering are capable of providing the affinity-enhanced and specificity-retained format, which are of great value in facilitating the development of TCR-related therapeutics.

Mechanistic Insights into Sc(III)-Catalyzed Asymmetric Homologation of Ketones with Diazo Compounds: How Trans Influence Assists in Controlling Stereochemistry.

Asymmetric one-carbon homologation or ring expansion of ketones with formal insertion of carbene intermediate, is a challenging but useful strategy to construct a complex skeleton. Sc(III) and chiral ligands have been employed in this regard. However, due to flexible conformations and a variety of stereo models, the origin of stereochemistry remains ambiguous. Density functional theory (DFT) calculations were carried out to explore the interactions that control the stereoselectivity of a Sc(III)-catalyzed asymmetric homologation. The trans influence of counterions was found to affect the coordination mode of ketone to Sc(III), and consequently affect the stereoselectivity.

Functional outcomes of different surgical treatments for common peroneal nerve injuries: a retrospective comparative study.

BACKGROUND: This study aims to assess the recovery patterns and factors influencing outcomes in patients with common peroneal nerve (CPN) injury. METHODS: This retrospective study included 45 patients with CPN injuries treated between 2009 and 2019 in Jing'an District Central Hospital. The surgical interventions were categorized into three groups: neurolysis (group A; n = 34 patients), nerve repair (group B; n = 5 patients) and tendon transfer (group C; n = 6 patients). Preoperative and postoperative sensorimotor functions were evaluated using the British Medical Research Council grading system. The outcome of measures included the numeric rating scale, walking ability, numbness and satisfaction. Receiver operating characteristic (ROC) curve analysis was utilized to determine the optimal time interval between injury and surgery for predicting postoperative foot dorsiflexion function, toe dorsiflexion function, and sensory function. RESULTS: Surgical interventions led to improvements in foot dorsiflexion strength in all patient groups, enabling most to regain independent walking ability. Group A (underwent neurolysis) had significant sensory function restoration (P < 0.001), and three patients in Group B (underwent nerve repair) had sensory improvements. ROC analysis revealed that the optimal time interval for achieving M3 foot dorsiflexion recovery was 9.5 months, with an area under the curve (AUC) of 0.871 (95% CI = 0.661-1.000, P = 0.040). For M4 foot dorsiflexion recovery, the optimal cut-off was 5.5 months, with an AUC of 0.785 (95% CI = 0.575-0.995, P = 0.020). When using M3 toe dorsiflexion recovery or S4 sensory function recovery as the gold standard, the optimal cut-off remained at 5.5 months, with AUCs of 0.768 (95% CI = 0.582-0.953, P = 0.025) and 0.853 (95% CI = 0.693-1.000, P = 0.001), respectively. CONCLUSIONS: Our study highlights the importance of early surgical intervention in CPN injury recovery, with optimal outcomes achieved when surgery is performed within 5.5 to 9.5 months post-injury. These findings provide guidance for clinicians in tailoring treatment plans to the specific characteristics and requirements of CPN injury patients.

Mild Stereoselective Synthesis of Densely Substituted [3]Dendralenes via Ru-Catalyzed Intermolecular Dimerization of 1,1-Disubstituted Allenes.

Described here is a mild and stereoselective protocol for the synthesis of [3]dendralenes via the intermolecular dimerization of allenes. With the proper choice of a ruthenium catalyst, a range of unactivated 1,1-disubstituted allenes, without prefunctionalization in the allylic position, reacted efficiently to provide rapid access to densely substituted [3]dendralenes. An intermolecular C-C bond and three different types of C═C double bonds (di-, tri-, and tetrasubstituted) embedded in an acyclic structure were constructed with good to high E/Z stereocontrol. This is in contrast to the known catalytic protocols that focus on allenes with prefunctionalization at the allylic position and/or monosubstituted allenes, which would proceed by a different mechanism or require less stereocontrol. The silyl-substituted dendralene products are precursors of other useful dendralene molecules. Density functional theory (DFT) studies and control experiments supported a mechanism involving oxidative cyclometalation, ß-H elimination (the rate-determining step), and reductive elimination.

Uncertainty-guided cross learning via CNN and transformer for semi-supervised honeycomb lung lesion segmentation.

Objective. Deep learning networks such as convolutional neural networks (CNN) and Transformer have shown excellent performance on the task of medical image segmentation, however, the usual problem with medical images is the lack of large-scale, high-quality pixel-level annotations, which is a very time-consuming and laborious task, and its further leads to compromised the performance of medical image segmentation under limited annotation conditions.Approach. In this paper, we propose a new semi-supervised learning method, uncertainty-guided cross learning, which uses a limited number of annotated samples along with a large number of unlabeled images to train the network. Specifically, we use two networks with different learning paradigms, CNN and Transformer, for cross learning, and use the prediction of one of them as a pseudo label to supervise the other, so that they can learn from each other, fully extract the local and global features of the images, and combine explicit and implicit consistency regularization constraints with pseudo label methods. On the other hand, we use epistemic uncertainty as a guiding message to encourage the model to learn high-certainty pixel information in high-confidence regions, and minimize the impact of erroneous pseudo labels on the overall learning process to improve the performance of semi-supervised segmentation methods.Main results. We conducted honeycomb lung lesion segmentation experiments using a honeycomb lung CT image dataset, and designed several sets of comparison experiments and ablation experiments to validate the effectiveness of our method. The final experimental results show that the Dice coefficient of our proposed method reaches 88.49% on the test set, and our method achieves state-of-the-art performance in honeycomb lung lesion segmentation compared to other semi-supervised learning methods.Significance. Our proposed method can effectively improve the accuracy of segmentation of honeycomb lung lesions, which provides an important reference for physicians in the diagnosis and treatment of this disease.

Recognition of Oligonucleotide C by Polydopamine-Coated Solid-State Nanopores.

Selective recognition of short oligonucleotides at the single-molecule level is particularly important for early disease detection and treatment. In this work, polydopamine (PDA)-coated nanopores were prepared via self-polymerization as a solid-state nanopore sensing platform for the recognition of oligonucleotide C (PolyC). The PDA coating possesses abundant active sites, such as indole, amino, carboxyl, catechol, and quinone structures, which had interactions with short oligonucleotides to slow down the translocation rate. PDA-coated nanopores selectively interact with PolyC20 by virtue of differences in hydrogen bonding forces, generating a larger blocking current, while polyA and polyT demonstrated very small blockings. At the same time, PDA-coated nanopores can sensitively distinguish PolyC with different lengths, such as 20, 14, and 10 nt. The functionalization of PDA on the solid-state nanopore provides an opportunity for the rational design of the recognition surface for biomolecules.

Cadaveric feasibility study of modified contralateral C7 nerve transfer for targeted functional recovery in hemiplegic upper extremity.

BACKGROUND: Contralateral cervical seventh (cC7) nerve to C7 transfer has been proven effective for treating spastic upper limb. However, for those whose major impairment is not in the C7 area, cC7 nerve transfer to other nerve(s) may achieve a better outcome. The aim of this study was to explore the optimal surgical approach for transferring cC7 to one or two nerves by cadaveric study and to discuss the possible applications for hemiplegic patients. METHODS: Modified cC7 transfer to one (five procedures) or two nonadjacent (three procedures) nerve roots was proposed, and success rates of direct coaptation through two surgical approaches were compared: the superficial surface of longus colli (sLC) and the deep surface of longus colli (dLC) approaches. The length, diameter and distance of relevant nerves were also measured in 25 cadavers. RESULTS: Compared with the sLC approach, the distance of the dLC approach was 1.1 ± 0.3 cm shorter. The success rates for the sLC and dLC approaches were as follows, respectively: cC7-C5 surgery, 94% and reached 98%; cC7-C6 surgery, 54% and 96%; cC7-C7 surgery, 42% and 94%; cC7-C8 surgery, 34% and 94%; cC7-T1 surgery, 24% and 62%; cC7-C5C7 surgery, 74% and 98%; cC7-C6C8 surgery, 54% and 98%. cC7-C7T1 surgery, 42% and 88%. CONCLUSIONS: The dLC approach greatly improved direct coaptation rate for cC7 nerve transfer. The modified cC7 nerve transfer procedures are technically feasible for further application in clinic.

Solid-State Nanopore Distinguishes Ferritin and Apo-Ferritin with Identical Exteriors through Amplified Flexibility at Single-Molecule Level.

Protein identification and discrimination at the single-molecule level are big challenges. Solid-state nanopores as a sensitive biosensor have been used for protein analysis, although it is difficult to discriminate proteins with similar structures in the traditional discrimination method based on the current blockage fraction. Here, we select ferritin and apo-ferritin as the model proteins that exhibit identical exterior and different interior structures and verify the practicability of their discrimination with flexibility features by the strategy of gradually decreasing the nanopore size. We show that the larger nanopore (relative to the protein size) has no obvious effect on discriminating two proteins. Then, the comparable-sized nanopore plays a key role in discriminating two proteins based on the dwell time and fraction distribution, and the conformational changes of both proteins are also studied with this nanopore. Finally, in the smaller nanopore, the protein molecules are trapped rather than translocated, where two proteins are obviously discriminated through the current fluctuation caused by the vibration of proteins. This strategy has potential in the discrimination of other important similar proteins.

Enhanced catalysis of a vanadium-substituted Keggin-type polyoxomolybdate supported on the M3O4/C (M = Fe or Co) surface enables efficient and recyclable oxidation of HMF to DFF.

In the reaction of oxidizing 5-hydroxymethylfurfural (HMF), attaining high efficiency and selectivity in the conversion of HMF into DFF presents a challenge due to the possibility of forming multiple products. Polyoxometalates are considered highly active catalysts for HMF oxidation. However, the over-oxidation of products poses a challenge, leading to decreased purity and yield. In this work, metal-organic framework-derived Fe3O4/C and Co3O4/C were designed as carriers for the vanadium-substituted Keggin-type polyoxomolybdate H5PMo10V2O40·35H2O (PMo10V2). In this complex system, spinel oxides can effectively adsorb HMF molecules and cooperate with PMo10V2 to catalyze the aerobic oxidation of HMF. As a result, the as-prepared PMo10V2@Fe3O4/C and PMo10V2@Co3O4/C catalysts can achieve efficient conversion of HMF into DFF with almost 100% selectivity. Among them, PMo10V2@Fe3O4/C exhibits a higher conversion rate (99.1%) under milder reaction conditions (oxygen pressure of 0.8 MPa). Both catalysts exhibited exceptional stability and retained their activity and selectivity even after undergoing multiple cycles. Studies on mechanisms by in situ diffuse reflectance infrared Fourier transform spectroscopy and X-ray photoelectron spectroscopy revealed that the V5+ and Mo6+ in PMo10V2, together with the metal ions in the spinel oxides, act as active centers for the catalytic conversion of HMF. Therefore, it is proposed that PMo10V2 and M3O4/C (M = Fe, Co) cooperatively catalyze the transformation of HMF into DFF via a proton-coupled electron transfer mechanism. This study offers an innovative approach for designing highly selective and recyclable biomass oxidation catalysts.

Mitigating Age-Related Ovarian Dysfunction with the Anti-Inflammatory Agent MIT-001.

Ovarian aging is a major obstacle in assisted reproductive medicine because it leads to ovarian dysfunction in women of advanced age. Currently, there are no effective treatments to cure age-related ovarian dysfunction. In this study, we investigated the effect of MIT-001 on the function of aged ovaries. Young and old mice were utilized in this study. MIT-001 was intraperitoneally administered, and the number of follicles and oocytes was analyzed. Each group was then retrieved for RNA and protein isolation. Total RNA was subjected to mRNA next-generation sequencing. Protein extracts from ovarian lysates were used to evaluate various cytokine levels in the ovaries. MIT-001 enhanced follicles and the number of oocytes were compared with non-treated old mice. MIT-001 downregulated immune response-related transcripts and cytokines in the ovaries of old mice. MIT-001 modulates the immune complex responsible for generating inflammatory signals and has the potential to restore the function of old ovaries and improve female fertility.

Simultaneous sensing of strain and temperature based on the inline-MZI embedded point-shaped taper structure with low crosstalk.

An embedded spherical dot taper structure (EDT) based on the MZI principle is proposed in this paper, which is mainly fabricated by using two special arc discharges in the preparation process. The proposed structure involves two specialized arc discharge techniques. First, an oversaturated discharge fusion process creates a micro-arc spherical area on the fiber end face to form the first link type. Second, an unsaturated discharge-pulling taper fusion joint creates a local micro-extrusion operation on this micro-arc fiber end face to form the second link. The thermal stress from instantaneous discharge causes a reverse spherical expansion zone to form in the end face structure, similar to the micromachining of long-period fiber gratings that use local CO2 laser etching to create modulated zones. The study involves a mathematical and theoretical analysis of how geometric parameters in the spherical modulation zone impact the structure's characteristic spectrum. The research demonstrates the potential for this structure to function as a light-intensity modulated strain sensor device through both theoretical and experimental means. As per the experimental findings, the optimized structure displays a high level of strain sensing sensitivity at 0.03 dB/µÎµ and temperature sensing sensitivity of 73 pm/°C (20°C-75°C) and 169 pm/°C (75°C-120°C). Additionally, it possesses excellent cross-sensitivity at only ∼0.0015 µÎµ/°C. Therefore, this sensor presents a favorable option for strain and temperature synchronization sensing and monitoring components, and exhibits notable application prospects in precision engineering, which encompasses mechanical manufacturing, the power and electrical industry, healthcare domain, and certain specialized areas of small-scale precision engineering.

Effect of trifluoroacetic acid on InP/ZnSe/ZnS quantum dots: mimicking the surface trap and their effects on the photophysical properties.

Understanding the precise effects of defects on the photophysical properties of quantum dots (QDs) is essential to their development with near-unity luminescence. Because of the complicated nature of defects in QDs, the origins and detailed roles of the defects still remain rarely understood. In this regard, we used detailed chemical analysis to investigate the effect of surface defects on the optical properties of InP/ZnSe/ZnS QDs by introducing shell defects through controlled trifluoroacetic acid (TFA) etching. TFA treatment on the InP/ZnSe/ZnS QDs partially removed the ZnS shell as well as ligands and reduced the quantum yield by generating energetically deep surface traps. The surface defects of QDs by TFA cause charged trap sites inducing an Auger recombination process with a rate of ca. 200 ps. Based on these results, we proposed possible trap-assisted non-radiative decay pathways between the band-edge state and surface deep traps in InP/ZnSe/ZnS QDs.

New Insights into the Cooperativity and Dynamics of Dimeric Enzymes.

A survey of protein databases indicates that the majority of enzymes exist in oligomeric forms, with about half of those found in the UniProt database being homodimeric. Understanding why many enzymes are in their dimeric form is imperative. Recent developments in experimental and computational techniques have allowed for a deeper comprehension of the cooperative interactions between the subunits of dimeric enzymes. This review aims to succinctly summarize these recent advancements by providing an overview of experimental and theoretical methods, as well as an understanding of cooperativity in substrate binding and the molecular mechanisms of cooperative catalysis within homodimeric enzymes. Focus is set upon the beneficial effects of dimerization and cooperative catalysis. These advancements not only provide essential case studies and theoretical support for comprehending dimeric enzyme catalysis but also serve as a foundation for designing highly efficient catalysts, such as dimeric organic catalysts. Moreover, these developments have significant implications for drug design, as exemplified by Paxlovid, which was designed for the homodimeric main protease of SARS-CoV-2.

Propeptide-Mediated Allosteric Regulation of Xylanase Xyl-1: An Integrated Experimental and Computational Analysis.

Most GH11 family endo-ß-1,4-xylanases contain a propeptide region linked to the N-terminal region. The mechanistic basis of this region harboring key regulation information for enzyme function, however, remains poorly understood. We reported an investigation on the allosteric regulation mechanism of the propeptide based on biochemical characterization, molecular dynamics simulations, and evolutionary analysis. We discovered that the mutant of truncated propeptide shows a remarkably increased thermal stability (melting temperature increased by 11.5 °C) and catalytic efficiency (1.7-fold kcat/Km value of wild type). Molecular dynamics simulations reveal that long-range fluctuations in the propeptide lead to a conformational perturbation in the catalytic pocket and the thumb region. The probability of sampling the active conformation during the glycosylation step is reduced (i.e., catalytic efficiency). In-depth sequence analysis indicates that the propeptide has a strong plasticity and degeneration trend, and propeptide truncation experiments of the homologous enzyme XynB validated the feasibility of the truncation strategy. This work reveals the role of GH11 family propeptides in functional regulation and provides a straightforward and practical method to increase the robustness of GH11 family xylanases.