Rapid Forming, Robust Adhesive Fungal-Sourced Chitosan Hydrogels Loaded with Deferoxamine for Sutureless Short-Gap Peripheral Nerve Repair.

Clinically, conventional sutures for repair of short-distance nerve injuries (< 5 mm) may contribute to uncontrolled inflammation and scar formation, thus negatively impacting nerve regeneration. To repair transected peripheral nerves with short distances, a rapid-forming, robust adhesive chitosan hydrogel is prepared by synthesizing maleic and dopamine bi-functionalized fungal-sourced chitosan (DM) and subsequently photopolymerizing DM precursor solution. The hydrogel rapidly polymerized under UV light irradiation (≈2 s) and possessed a strong adhesive strength (273.33 ± 55.07 kPa), facilitating a fast bonding of nerve stump. Especially, its tailored degradation profile over 28 days supported both early gap bridging and subsequent nerve regeneration. Furthermore, deferoxamine (DFO), a pro-angiogenic drug, is loaded into the hydrogel to reach sustainable release, accelerating axonal growth synergistically. A 3 mm long sciatic nerve defects model in rats is used to investigate the efficacy of DM@DFO hydrogel for repairing peripheral nerve defects. After 60 days, the DM@DFO hydrogel significantly outperformed conventional sutures and fibrin glue, improving motor and sensory recovery by reducing inflammation, inhibiting scar formation, and accelerating vascular regeneration within 14 days post-repair. This work highlights the DM@DFO hydrogel as a promising tissue adhesive for effective short-distance peripheral nerve repair.

Rapid start-up and stable operation of pilot scale denitrification-partial nitritation/anammox process for treating electroplating tail wastewater.

This study explored a novel economical and efficient process for treating actual low-ammonia nitrogen electroplating tail wastewater. A pilot scale system of denitrification-partial nitrification/anaerobic ammonium oxidation (DN-PN/A) was constructed and operated for 190 days. The partial nitrification (PN) reactor, filled with zeolite, increased free ammonia concentration beyond the nitrite oxidizing bacteria threshold and successfully supplied NO2--N, with nitrite accumulation rate exceeding 90 %. Over 109 days, the total nitrogen removal rate achieved was 80.2 ± 7.41 %, and the chemical oxygen demand removal rate reached 79.68 ± 9.53 %. The dominant functional bacteria were Nitrosomonas (5.45 %) and Candidatus Anammoxoglobus (28.84 %) in PN reactor and anaerobic ammonium oxidation (Anammox) reactor. This process, characterized by rapid start-up, strong shock resistance, and low cost, alleviates the pressure of ammonium pollution control, promotes the sustainable development of the electroplating industry and has the potential for application in the treatment of other industrial wastewater.

Minisci-Type Dehydrogenative Coupling of C(sp3)-H and N-Heteroaromatics Enabled by Photoelectrochemical Hydrogen Atom Transfer.

Minisci-type dehydrogenative coupling of C(sp3)-H and N-heteroaromatics was performed with N-hydroxysuccinimide as a hydrogen atom transfer catalyst in a photoelectrochemical cell composed of a mesoporous BiVO4 photoanode and a Pt electrode. In the absence of metal catalysts and chemical oxidants, a range of N-heteroarenes (e.g., quinolines, isoquinolines, and quinoxaline) can undergo coupling with various C(sp3)-H partners to form the corresponding products in excellent yields.

Enantioselective Aminosilylation of Alkenes by Palladium/Ming-Phos-Catalyzed Tandem Narasaka-Heck/Silylation Reaction.

A Pd-catalyzed enantioselective aminosilylation of alkenes via tandem Aza-Heck/silylation reaction under Pd/Sadphos catalysis is disclosed. A wide array of oxime esters and silicon reagents are tolerated, furnishing the chiral pyrrolines bearing one quaternary or two contiguous stereocenters in good yield with high enantioselectivity. Not only terminal alkenes but also tri-substituented internal alkenes successfully participate in the reaction, delivering vicinal stereocenters in complete diastereoselectivity and high enantioselectivity. DFT study is conducted to probe the reaction pathway and the origin of the enantioselectivity, which revealed that the stereoinduction arises from the weak interaction between the aromatic ring of the substrate fragment and naphthyl group in the ligand.

Fast Self-Healing Hyaluronic Acid Hydrogel with a Double-Dynamic Network for Skin Wound Repair.

Developing extracellular matrix-derived hydrogel with a fast self-healing capacity to provide a sustainable moist environment able to accelerate wound healing is highly desired for full-thickness skin wound repair. In this study, a fast self-healing hyaluronic acid hydrogel with a dual dynamic network was constructed through a primary reversible acylhydrazone bond formed between aldehyde-modified hyaluronic acid, 3,3'-dithiobis (propionyl hydrazide) (DTP), and secondary dynamic ionic interactions between κ-carrageenan (KC) and K+. Because of the presence of various dynamic covalent bonds such as the acylhydrazone bond, disulfide bond, and noncovalent bonds including hydrogen bonding and ionic interactions, as well as the notable thermoreversible nature of KC, the resultant hydrogel could be self-healed rapidly within 30 min under physiological temperature with a self-healing efficiency of 100%, which was significantly better than other hyaluronic acid hydrogels, as reported previously. Besides, the hydrogel displayed excellent cytocompatibility. According to this study, the hydrogel was administered into the wounds and achieved a superior performance of promoting full-thickness skin wound healing by increasing granulation tissue formation, deposition of collagen as well as the acceleration of re-epithelialization and neovascularization, compared to commercial products, e.g., gauze and 3 M hydrocolloid. We also anticipate that this strategy of double-dynamic network cross-linking can be adopted to fabricate self-healing materials for multiple applications.

Enantioselective Arylation of Sulfenamides to Access Sulfilimines Enabled by Palladium Catalysis.

Sulfur-containing functional groups have garnered considerable attention due to their common occurrence in ligands, pharmaceuticals, and insecticides. Nevertheless, enantioselective synthesis of sulfilimines, particularly diaryl sulfilimines remains a challenging and persistent goal. Herein we report a highly enantio- and chemoselective cross-coupling of sulfenamides with aryl diazonium salt to construct diverse S(IV) stereocenters by Pd catalysis. Bisphosphine ligands bearing sulfinamide groups play a crucial role in achieving high reactivity and selectivity. This approach provides a general, modular and divergent framework for quickly synthesizing chiral sulfilimines and sulfoximines that are otherwise challenging to access. In addition, the origins of the high chemoselectivity and enantioselectivity were extensively investigated using density functional theory calculations.

Inflammatory proteins mediate male erectile dysfunction via plasma metabolites.

Background: There are no clear conclusions as to whether inflammatory proteins and plasma metabolites influence erectile dysfunction (ED). Aim: In this research, we used Mendelian randomization (MR) analysis to discover a causal relationship between inflammatory proteins, plasma metabolites, and ED. Methods: Raw data with ED, inflammatory proteins, and plasma metabolites were obtained from the MRC IEU OpenGWAS and FinnGen database. After a series of screenings, the remaining single nucleotide polymorphisms were selected as instrumental variables or MR analysis to assess the relationship between genetically predicted inflammatory proteins or plasma metabolites and the pathogenesis of ED. Outcomes: The relationship between inflammatory factors and ED was fully analyzed and elaborated. Results: In the inverse variance-weighted method, there exists a significant causal relationship between 4 types of genetically predicted inflammatory proteins and 50 types of plasma metabolites with the incidence of ED. The primary discovery is that 3 inflammatory proteins, fibroblast growth factor 5, interleukin-22 receptor subunit alpha-1, and protein S100-A12, can impact the risk of ED through plasma metabolites. Clinical Implications: ED metabolites and inflammatory proteins are also closely associated with cardiovascular diseases, warranting further exploration. Strengths and Limitations: Our analysis is based on a European population, limiting its generalizability, the genome-wide association study dataset for ED has a relatively small number of cases, and we hope for larger genome-wide association study datasets for future validation. Conclusion: This study has identified that inflammatory proteins can influence ED through plasma metabolites.

Catalytic Asymmetric Synthesis of Sulfinamides via Cu-Catalyzed Asymmetric Addition of Aryl Boroxines to Sulfinylamines.

The application of sulfinamides has been witnessed in medicinal and agrochemistry with employment in asymmetric transformations. However, methods for their asymmetric catalytic synthesis have rarely been explored. Herein, the catalytic enantioselective addition of aryl boroxines to sulfinylamines via Cu catalyst and the newly developed Xuphos ligand were reported. A series of chiral aryl sulfinamides can be readily accessed in one step. This protocol enables the stereospecific transformation of sulfinamides to sulfonimidoyl fluorides, sulfonimidamides, and sulfonimidate esters. DFT calculations have revealed the reaction pathway, and the migratory insertion is the enantio-determining step. The noncovalent interaction between the oxygen atom of sulfinylamines and the C-H bonds in the ligand is crucial for enantioselectivity control.

Expansion-clotting chitosan fabrics based on unidirectional fast-absorption fibers for rapid hemorrhage control.

The rapid absorption of water from the blood to concentrate erythrocytes and platelets, thus triggering quick closure, is important for hemostasis. Herein, expansion-clotting chitosan fabrics are designed and fabricated by ring spinning of polylactic acid (PLA) filaments as the core layer and highly hydrophilic carboxyethyl chitosan (CECS) fibers as the sheath layer, and subsequent knitting of obtained PLA@CECS core spun yarns. Due to the unidirectional fast-absorption capacity of CECS fibers, the chitosan fabrics can achieve erythrocytes and platelets aggregate quickly by concentrating blood, thus promoting the formation of blood clots. Furthermore, the loop structure of coils formed in the knitted fabric can help them to expand by absorbing water to close their pores, providing effective sealing for bleeding. Besides, They have enough mechanical properties, anti-penetrating ability, and good tissue-adhesion ability in wet conditions, which can form a physical barrier to resist blood pressure during hemostasis and prevent them from falling off the wound, thus enhancing hemostasis synergistically. Therefore, the fabrics exhibit superior hemostatic performance in the rabbit liver, spleen, and femoral artery puncture injury model compared to the gauze group. This chitosan fabric is a promising hemostatic material for hemorrhage control.

Deep Red Light Driven Hydrogen Evolution by Heterojunction Polymer Dots for Diabetic Wound Healing.

We describe small heterojunction polymer dots (Pdots) with deep-red light catalyzed H2 generation for diabetic skin wound healing. The Pdots with donor/acceptor heterojunctions showed remarkably enhanced photocatalytic activity as compared to the donor or acceptor nanoparticles alone. We encapsulate the Pdots and ascorbic acid into liposomes to form Lipo-Pdots nanoreactors, which selectively scavenge ⋅OH radicals in live cells and tissues under 650 nm light illumination. The antioxidant capacity of the heterojunction Pdots is ~10 times higher than that of the single-component Pdots described previously. Under a total light dose of 360 J/cm2, the Lipo-Pdots nanoreactors effectively scavenged ⋅OH radicals and suppressed the expression of pro-inflammatory cytokines in skin tissues, thereby accelerating the healing of skin wounds in diabetic mice. This study provides a feasible solution for safe and effective treatment of diabetic foot ulcers.

A New Method for Bearing Fault Diagnosis across Machines Based on Envelope Spectrum and Conditional Metric Learning.

In recent years, most research on bearing fault diagnosis has assumed that the source domain and target domain data come from the same machine. The differences in equipment lead to a decrease in diagnostic accuracy. To address this issue, unsupervised domain adaptation techniques have been introduced. However, most cross-device fault diagnosis models overlook the discriminative information under the marginal distribution, which restricts the performance of the models. In this paper, we propose a bearing fault diagnosis method based on envelope spectrum and conditional metric learning. First, envelope spectral analysis is used to extract frequency domain features. Then, to fully utilize the discriminative information from the label distribution, we construct a deep Siamese convolutional neural network based on conditional metric learning to eliminate the data distribution differences and extract common features from the source and target domain data. Finally, dynamic weighting factors are employed to improve the convergence performance of the model and optimize the training process. Experimental analysis is conducted on 12 cross-device tasks and compared with other relevant methods. The results show that the proposed method achieves the best performance on all three evaluation metrics.

Medicago truncatula ß-glucosidase 17 contributes to drought and salt tolerance through antioxidant flavonoid accumulation.

Flavonoids are usually present in forms of glucosides in plants, which could be catabolized by ß-glucosidase (BGLU) to form their corresponding flavonoid aglycones. In this study, we isolated three abiotic-responsive BGLU genes (MtBGLU17, MtBGLU21 and MtBGLU22) from Medicago truncatula, and found only the recombinant MtBGLU17 protein could catalyse the hydrolysis of flavonoid glycosides. The recombinant MtBGLU17 protein is active towards a variety of flavonoid glucosides, including glucosides of flavones (apigenin and luteolin), flavonols (kaempferol and quercetin), isoflavones (genistein and daidzein) and flavanone (naringenin). In particular, the recombinant MtBGLU17 protein preferentially hydrolyses flavonoid-7-O-glucosides over their corresponding 3-O-glucosides. The content of luteoin-7-O-glucoside was reduced in the MtBGLU17 overexpression plants but increased in the Tnt-1 insertional mutant lines, whereas luteoin content was increased in the MtBGLU17 overexpression plants but reduced in the Tnt-1 insertional mutant lines. Under drought and salt (NaCl) treatment, the MtBGLU17 overexpression lines showed relatively higher DPPH content, and higher CAT and SOD activity than the wild type control. These results indicated that overexpression lines of MtBGLU17 possess higher antioxidant activity and thus confer drought and salt tolerance, implying MtBGLU17 could be potentially used as a candidate gene to improve plant abiotic stress tolerance.

Analysis of risk factors and development of predictive model for malnutrition in patients with traumatic brain injury.

Malnutrition is a highly prevalent complication in patients with traumatic brain injury (TBI), and it is closely related to the prognosis of patients. Accurate identification of patients at high risk of malnutrition is essential. Therefore, we analyzed the risk factors of malnutrition in patients with TBI and developed a model to predict the risk of malnutrition. A retrospective collection of 345 patients with TBI, and they were divided into malnutrition and comparison groups according to the occurrence of malnutrition. Univariate correlation and multifactor logistic regression analyses were performed to determine patients' malnutrition risk factors. We used univariate and logistic regression (forward stepwise method) analyses to identify significant predictors associated with malnutrition in patients with TBI and developed a predictive model for malnutrition prediction. The model's discrimination, calibration, and clinical utility were evaluated using the receiver operating characteristic (ROC) curve, calibration plots, and decision curve analysis (DCA). A total of 216 patients (62.6%) developed malnutrition. Multifactorial logistic regression analysis showed that pulmonary infection, urinary tract infection, dysphagia, application of NGT, GCS score ≤ 8, and low ADL score were independent risk factors for malnutrition in patients with TBI (P < 0.05). The area under the curve of the model was 0.947. Calibration plots showed good discrimination of model calibration. DCA showed that the column line plot models were all clinically meaningful when nutritional interventions were performed over a considerable range of threshold probabilities (0-0.98). Malnutrition is widespread in patients with TBI, and the nomogram is a good predictor of whether patients develop malnutrition.

Copper-Catalyzed Sulfur Alkylation of Sulfenamides with N-Sulfonylhydrazones.

Sulfilimines are valuable compounds in both organic synthesis and pharmaceuticals. In this study, we present a copper-catalyzed sulfur alkylation of sulfenamides with N-sulfonylhydrazones. In contrast to prior findings, hydrazones derived from aldehydes act as donor-type carbene precursors, effectively engaging in coupling with sulfenamides via a copper catalyst, demonstrating exclusive S selectivity. The utility of the protocol was highlighted in the rapid access to a wide range of sulfoximine derivatives.

Fabrication and Characterization of Silicon-Based Antimonene Thin Film via Electron Beam Evaporation.

Antimonene has attracted much attention due to its excellent characteristics of high carrier mobility, thermoelectric properties and high stability. It has great application prospects in Q-switched lasers, laser protection and spintronics. At present, the epitaxy growth of antimonene mainly depends on molecular beam epitaxy. We have successfully prepared antimonene films on silicon, germanium/silicon substrates for the first time using electron beam evaporation coating and studied the effects of the deposition rate and substrate on the preparation of antimonene; film characterization was performed via confocal microprobe Raman spectroscopy, via X-ray diffraction and using a scanning electron microscope. Raman spectroscopy showed that different deposition rates can lead to the formation of different structures of antimonene, such as α phase and ß phase. At the same time, it was found that the growth of antimonene is also affected by different substrates and ion beams.

Seasonal drought promotes citrate accumulation in citrus fruit through the CsABF3-activated CsAN1-CsPH8 pathway.

Plenty of rainfall but unevenly seasonal distribution happens regularly in southern China. Seasonal drought from summer to early autumn leads to citrus fruit acidification, but how seasonal drought regulates citrate accumulation remains unknown. Herein, we employed a set of physiological, biochemical, and molecular approaches to reveal that CsABF3 responds to seasonal drought stress and modulates citrate accumulation in citrus fruits by directly regulating CsAN1 and CsPH8. Here, we demonstrated that irreversible acidification of citrus fruits is caused by drought lasting for > 30 d during the fruit enlargement stage. We investigated the transcriptome characteristics of fruits affected by drought and corroborated the pivotal roles of a bHLH transcription factor (CsAN1) and a P3A-ATPase gene (CsPH8) in regulating citrate accumulation in response to drought. Abscisic acid (ABA)-responsive element binding factor 3 (CsABF3) was upregulated by drought in an ABA-dependent manner. CsABF3 activated CsAN1 and CsPH8 expression by directly and specifically binding to the ABA-responsive elements (ABREs) in the promoters and positively regulated citrate accumulation. Taken together, this study sheds new light on the regulatory module ABA-CsABF3-CsAN1-CsPH8 responsible for citrate accumulation under drought stress, which advances our understanding of quality formation of citrus fruit.

Minisci-Type Dehydrogenative Coupling of N-Heteroaromatic Rings with Inert C(sp3)-H Enabled by a Visible-Light-Catalyzed Intermolecular Hydrogen Atom Transfer Process.

The Minisci-type dehydrogenative coupling of N-heteroaromatic rings with inert C-H or Si-H partners via visible-light-catalyzed hydrogen atom transfer has been reported. This methodology allows the coupling reactions to be carried out in water as a solvent under air atmospheric conditions with visible-light illumination. A wide range of inert C-H and Si-H partners could be directly coupled with various N-aromatic heterocycles to deliver products in good to excellent yields.

Injectable, self-healing hyaluronic acid-based hydrogels for spinal cord injury repair.

The cystic cavity that develops following spinal cord injury is a major obstacle for repairing spinal cord injury (SCI). The injectable self-healing biomaterials treatment is a promising strategy to enhance tissue repair after traumatic spinal cord injury. Herein, a natural extracellular matrix (ECM) biopolymer hyaluronic acid-based hydrogel was developed based on multiple dynamic covalent bonds. The hydrogels exhibited excellent injectable and self-healing properties, could be effectively injected into the injury site, and filled the lesion cavity to accelerate the tissue repair of traumatic SCI. Moreover, the hydrogels were compatible with cells and various tissues and possessed proper stiffness matched with nervous tissue. Additionally, when implanted into the injured spinal cord site, the hyaluronic acid-based hydrogel promoted axonal regeneration and functional recovery by accelerating remyelination, axon regeneration, and angiogenesis. Overall, the injectable self-healing hyaluronic acid-based hydrogels are ideal biomaterials for treating traumatic SCI.

Pd-Catalyzed Asymmetric Larock Indole Synthesis to Access Axially Chiral N-Arylindoles.

Larock indole synthesis is one of the most straightforward and efficient methods for the synthesis of indoles; however, there has been no asymmetric version yet for the construction of indole-based axially chiral N-arylindoles since its initial report in 1991. Herein we report the first example of an asymmetric Larock indole synthesis by employing a chiral sulfinamide phosphine (SadPhos) ligand (Ming-Phos) with palladium. It allows rapid construction of a wide range of axially chiral N-arylindole compounds in good yields up to 98:2 er. The application of this unique chiral scaffold as an organocatalyst is promising. Furthermore, a kinetic study has revealed that the alkyne migratory insertion is the rate-determining step, which has been proven by the density functional theory (DFT) calculations. Additionally, DFT studies also suggest that the N-C dihedral difference caused by the steric hindrance of the ligand contributes to enantioselectivity control.

Self-Oxidated Hydrophilic Chitosan Fibrous Mats for Fatal Hemorrhage Control.

Enriching erythrocytes and platelets in seconds and providing a fast seal in bleeding sites is vital to fatal hemorrhage control. Herein, hydrophilic chitosan fibrous mats (CECS-D mats) are fabricated by introducing hydrophilic carboxyethyl groups and subsequent catechol groups onto chitosan fibers. Due to strong hydrophilicity, CECS-D mats exhibit rapid liquid-absorption capacity, especially instantaneous absorptivity to the rabbit blood, which can achieve erythrocyte and platelet aggregations quickly by concentrating blood, thus promoting the formation of blood clots. Furthermore, the mats are self-oxidated to form quinone-amine adducts or quinone multimers by adjusting pH conditions, which not only provides tissue adhesion but also induces erythrocyte aggregation and platelet adhesion, further enhancing the seal and triggering quick closure to achieve fast hemostasis. Therefore, the mats reveal superior hemostatic performance in rabbit liver and spleen models over CECS mats and gauze. Especially in the fatal femoral artery injury model of rabbits, the mats reduce the blood loss by ∼75% and shortened the bleeding time by ∼50% compared with CECS mats, which have been reported to have the same hemostatic effect as commercialized Celox products in a swine femoral artery injury model. Besides, the mats are cytocompatible and degradable as well as antibacterial. This chitosan mat is a promising hemostatic material for fatal hemorrhage control.