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1.
Am J Hum Genet ; 110(5): 826-845, 2023 05 04.
Artículo en Inglés | MEDLINE | ID: mdl-37098352

RESUMEN

Alterations in cortical neurogenesis are implicated in neurodevelopmental disorders including autism spectrum disorders (ASDs). The contribution of genetic backgrounds, in addition to ASD risk genes, on cortical neurogenesis remains understudied. Here, using isogenic induced pluripotent stem cell (iPSC)-derived neural progenitor cells (NPCs) and cortical organoid models, we report that a heterozygous PTEN c.403A>C (p.Ile135Leu) variant found in an ASD-affected individual with macrocephaly dysregulates cortical neurogenesis in an ASD-genetic-background-dependent fashion. Transcriptome analysis at both bulk and single-cell level revealed that the PTEN c.403A>C variant and ASD genetic background affected genes involved in neurogenesis, neural development, and synapse signaling. We also found that this PTEN p.Ile135Leu variant led to overproduction of NPC subtypes as well as neuronal subtypes including both deep and upper layer neurons in its ASD background, but not when introduced into a control genetic background. These findings provide experimental evidence that both the PTEN p.Ile135Leu variant and ASD genetic background contribute to cellular features consistent with ASD associated with macrocephaly.


Asunto(s)
Trastorno del Espectro Autista , Trastorno Autístico , Células Madre Pluripotentes Inducidas , Megalencefalia , Células-Madre Neurales , Humanos , Trastorno del Espectro Autista/genética , Trastorno Autístico/genética , Megalencefalia/genética , Neurogénesis/genética , Neuronas , Fosfohidrolasa PTEN/genética
2.
Plant Cell ; 34(5): 1822-1843, 2022 04 26.
Artículo en Inglés | MEDLINE | ID: mdl-35171277

RESUMEN

Deployment of broad-spectrum disease resistance against multiple pathogen species is an efficient way to control plant diseases. Here, we identify a Microtubule-associated C4HC3-type E3 Ligase (MEL) in both Nicotiana benthamiana and Oryza sativa, and show that it is able to integrate and initiate a series of host immune signaling, conferring broad-spectrum resistance to viral, fungal, and bacterial pathogens. We demonstrate that MEL forms homodimer through intermolecular disulfide bonds between its cysteine residues in the SWIM domain, and interacts with its substrate serine hydroxymethyltrasferase 1 (SHMT1) through the YφNL motif. Ubiquitin ligase activity, homodimerization and YφNL motif are indispensable for MEL to regulate plant immunity by mediating SHMT1 degradation through the 26S proteasome pathway. Our findings provide a fundamental basis for utilizing the MEL-SHMT1 module to generate broad-spectrum-resistant rice to global destructive pathogens including rice stripe virus, Magnaporthe oryzae, and Xanthomonas oryzae pv. oryzae.


Asunto(s)
Magnaporthe , Oryza , Xanthomonas , Resistencia a la Enfermedad/genética , Regulación de la Expresión Génica de las Plantas , Interacciones Huésped-Patógeno/genética , Magnaporthe/fisiología , Oryza/metabolismo , Enfermedades de las Plantas/microbiología , Proteínas de Plantas/genética , Proteínas de Plantas/metabolismo , Ubiquitina-Proteína Ligasas/genética , Ubiquitina-Proteína Ligasas/metabolismo , Xanthomonas/fisiología
3.
Cell Mol Life Sci ; 81(1): 122, 2024 Mar 08.
Artículo en Inglés | MEDLINE | ID: mdl-38456997

RESUMEN

Doxorubicin-induced cardiotoxicity (DIC), which is a cardiovascular complication, has become the foremost determinant of decreased quality of life and mortality among survivors of malignant tumors, in addition to recurrence and metastasis. The limited ability to accurately predict the occurrence and severity of doxorubicin-induced injury has greatly hindered the prevention of DIC, but reducing the dose to mitigate side effects may compromise the effective treatment of primary malignancies. This has posed a longstanding clinical challenge for oncologists and cardiologists. Ferroptosis in cardiomyocytes has been shown to be a pivotal mechanism underlying cardiac dysfunction in DIC. Ferroptosis is influenced by multiple factors. The innate immune response, as exemplified by neutrophil extracellular traps (NETs), may play a significant role in the regulation of ferroptosis. Therefore, the objective of this study was to investigate the involvement of NETs in doxorubicin-induced cardiomyocyte ferroptosis and elucidate their regulatory role. This study confirmed the presence of NETs in DIC in vivo. Furthermore, we demonstrated that depleting neutrophils effectively reduced the occurrence of doxorubicin-induced ferroptosis and myocardial injury in DIC. Additionally, our findings showed the pivotal role of high mobility group box 1 (HMGB1) as a critical molecule implicated in DIC and emphasized its involvement in the modulation of ferroptosis subsequent to NETs inhibition. Mechanistically, we obtained preliminary evidence suggesting that doxorubicin-induced NETs could modulate yes-associated protein (YAP) activity by releasing HMGB1, which subsequently bound to toll like receptor 4 (TLR4) on the cardiomyocyte membrane, thereby influencing cardiomyocyte ferroptosis in vitro. Our findings suggest that doxorubicin-induced NETs modulate cardiomyocyte ferroptosis via the HMGB1/TLR4/YAP axis, thereby contributing to myocardial injury. This study offers a novel approach for preventing and alleviating DIC by targeting alterations in the immune microenvironment.


Asunto(s)
Trampas Extracelulares , Ferroptosis , Proteína HMGB1 , Cardiopatías , Humanos , Miocitos Cardíacos/metabolismo , Trampas Extracelulares/metabolismo , Proteína HMGB1/metabolismo , Receptor Toll-Like 4/metabolismo , Cardiotoxicidad/metabolismo , Calidad de Vida , Cardiopatías/metabolismo , Doxorrubicina/efectos adversos
4.
J Am Chem Soc ; 146(22): 15479-15487, 2024 Jun 05.
Artículo en Inglés | MEDLINE | ID: mdl-38780095

RESUMEN

The development of efficient and low-cost catalysts is essential for photocatalysis; however, the intrinsically low photocatalytic efficiency as well as the difficulty in using and recycling photocatalysts in powder morphology greatly limit their practical performance. Herein, we describe quasi-homogeneous photocatalysis to overcome these two limitations by constructing ultrastiff, hierarchically porous, and photoactive aerogels of conjugated microporous polymers (CMPs). The CMP aerogels exhibit low density but high stiffness beyond 105 m2 s-2, outperforming most low-density materials. Extraordinary stiffness ensures their use as robust scaffolds for scaled photocatalysis and recycling without damage at the macroscopic level. A challenging but desirable reaction for direct deaminative borylation is demonstrated using CMP aerogel-based quasi-homogeneous photocatalysis with gram-scale productivity and record-high efficiency under ambient conditions. Combined terahertz and transient absorption spectroscopic studies unveil the generation of high-mobility free carriers and long-lived excitonic species in the CMP aerogels, underlying the observed superior catalytic performance.

5.
J Am Chem Soc ; 146(4): 2574-2582, 2024 Jan 31.
Artículo en Inglés | MEDLINE | ID: mdl-38231138

RESUMEN

Two-dimensional conjugated metal-organic frameworks (2D c-MOFs) have attracted increasing interest in electronics due to their (semi)conducting properties. Charge-neutral 2D c-MOFs also possess persistent organic radicals that can be viewed as spin-concentrated arrays, affording new opportunities for spintronics. However, the strong π-interaction between neighboring layers of layer-stacked 2D c-MOFs annihilates active spin centers and significantly accelerates spin relaxation, severely limiting their potential as spin qubits. Herein, we report the precise tuning of the charge transport and spin dynamics in 2D c-MOFs via the control of interlayer stacking. The introduction of bulky side groups on the conjugated ligands enables a significant dislocation of the 2D c-MOFs layers from serrated stacking to staggered stacking, thereby spatially weakening the interlayer interactions. As a consequence, the electrical conductivity of 2D c-MOFs decreases by 6 orders of magnitude, while the spin density achieves more than a 30-fold increase and the spin-lattice relaxation time (T1) is increased up to ∼60 µs, hence being superior to the reference 2D c-MOFs with compact stackings whose spin relaxation is too fast to be detected. Spin dynamics results also reveal that spinless polaron pairs or bipolarons play critical roles in the charge transport of these 2D c-MOFs. Our strategy provides a bottom-up approach for enlarging spin dynamics in 2D c-MOFs, opening up pathways for developing MOF-based spintronics.

6.
Cancer Immunol Immunother ; 73(1): 15, 2024 Jan 18.
Artículo en Inglés | MEDLINE | ID: mdl-38236243

RESUMEN

PURPOSE: Immune checkpoint inhibitors (ICIs) have transformed traditional cancer treatments. Specifically, ICI-related myocarditis is an immune-related adverse event (irAE) with high mortality. ICIs activate CD4+ T-lymphocyte reprogramming, causing an imbalance between Th17 and Treg cell differentiation, ultimately leading to myocardial inflammatory damage. Low-intensity pulsed ultrasound (LIPUS) can limit inflammatory responses, with positive therapeutic effects across various cardiovascular inflammatory diseases; however, its role in the pathogenesis of ICI-related myocarditis and CD4+ T-cell dysfunction remains unclear. Accordingly, this study investigated whether LIPUS can alleviate ICI-related myocarditis inflammatory damage and, if so, aimed to elucidate the beneficial effects of LIPUS and its underlying molecular mechanisms. METHODS: An in vivo model of ICI-related myocarditis was obtained by intraperitonially injecting male A/J mice with an InVivoPlus anti-mouse PD-1 inhibitor. LIPUS treatment was performed via an ultrasound-guided application to the heart via the chest wall. The echocardiographic parameters were observed and cardiac function was assessed using an in vivo imaging system. The expression of core components of the HIPPO pathway was analyzed via western blotting. RESULTS: LIPUS treatment reduced cardiac immune responses and inflammatory cardiac injury. Further, LIPUS treatment alleviated the inflammatory response in mice with ICI-related myocarditis. Mechanistically, in the HIPPO pathway, the activation of Mst1-TAZ axis improved autoimmune inflammation by altering the interaction between the transcription factors FOXP3 and RORγt and regulating the differentiation of Treg and Th17 cells. CONCLUSION: LIPUS therapy was shown to reduce ICI-related myocarditis inflammatory damage and improve cardiac function, representing an exciting finding for irAEs treatment.


Asunto(s)
Miocarditis , Masculino , Animales , Ratones , Miocarditis/inducido químicamente , Miocarditis/diagnóstico por imagen , Miocarditis/terapia , Inhibidores de Puntos de Control Inmunológico , Diferenciación Celular , Activación de Linfocitos , Linfocitos T CD4-Positivos
7.
Nat Mater ; 22(7): 880-887, 2023 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-37337069

RESUMEN

Two-dimensional conjugated polymers (2DCPs), composed of multiple strands of linear conjugated polymers with extended in-plane π-conjugation, are emerging crystalline semiconducting polymers for organic (opto)electronics. They are represented by two-dimensional π-conjugated covalent organic frameworks, which typically suffer from poor π-conjugation and thus low charge carrier mobilities. Here we overcome this limitation by demonstrating two semiconducting phthalocyanine-based poly(benzimidazobenzophenanthroline)-ladder-type 2DCPs (2DCP-MPc, with M = Cu or Ni), which are constructed from octaaminophthalocyaninato metal(II) and naphthalenetetracarboxylic dianhydride by polycondensation under solvothermal conditions. The 2DCP-MPcs exhibit optical bandgaps of ~1.3 eV with highly delocalized π-electrons. Density functional theory calculations unveil strongly dispersive energy bands with small electron-hole reduced effective masses of ~0.15m0 for the layer-stacked 2DCP-MPcs. Terahertz spectroscopy reveals the band transport of Drude-type free carriers in 2DCP-MPcs with exceptionally high sum mobility of electrons and holes of ~970 cm2 V-1 s-1 at room temperature, surpassing that of the reported linear conjugated polymers and 2DCPs. This work highlights the critical role of effective conjugation in enhancing the charge transport properties of 2DCPs and the great potential of high-mobility 2DCPs for future (opto)electronics.


Asunto(s)
Estructuras Metalorgánicas , Polímeros , Electrónica , Electrones , Indoles
8.
Eur Radiol ; 34(3): 1948-1959, 2024 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-37670186

RESUMEN

OBJECTIVE: Uptake of the imaging tracers [18F]AlF-NOTA-FAPI-04 and [18F]FDG varies in some inflammatory lesions, which may result in false-positive findings for malignancy on PET/CT. Our aim was to compare the [18F]AlF-NOTA-FAPI-04 and [18F]FDG PET/CT imaging features of malignant and various inflammatory lung lesions and to analyze their value for differential diagnosis. METHODS: We retrospectively analyzed [18F]AlF-NOTA-FAPI-04 PET/CT scans from 67 cancer patients taken between December 2020 and January 2022, as well as the scans of 32 patients who also underwent [18F]FDG PET/CT imaging. The maximum and mean standardized uptake values (SUVmax and SUVmean, respectively) and lesion-to-background ratio (LBR) were calculated. The predictive capabilities of semiquantitative PET/CT parameters were analyzed by receiver operating characteristic curve analysis. RESULTS: A total of 70 inflammatory and 37 malignant lung lesions were evaluated by [18F]AlF­NOTA­FAPI­04 PET/CT, and 33 inflammatory and 26 malignant lung lesions also were evaluated by [18F]FDG PET/CT. Inflammatory lesions exhibited lower [18F]AlF-NOTA-FAPI-04 and [18F]FDG uptake compared to malignant lesions, with statistically significant differences in SUVmax, SUVmean, and LBR (all p < 0.001). [18F]AlF-NOTA-FAPI-04 uptake also varied among different types of inflammatory lesions (SUVmax, p = 0.005; SUVmean, p = 0.008; LBR, p < 0.001), with the highest uptake observed in bronchiectasis with infection, followed by postobstructive pneumonia, and the lowest in pneumonia. [18F]FDG uptake was higher in postobstructive pneumonia than in pneumonia (SUVmax, p = 0.009; SUVmean, p = 0.016; LBR, p = 0.004). CONCLUSION: [18F]AlF-NOTA-FAPI-04/[18F]FDG PET/CT showed significantly lower uptake in inflammatory lesions than malignancies as well as variation in different types of inflammatory lesions, and thus, may be valuable for distinguishing malignant and various inflammatory findings. CLINICAL RELEVANCE STATEMENT: Our study confirmed that the uptake of [18F]AlF-NOTA-FAPI-04/[18F]FDG PET/CT in inflammatory and malignant lung lesions is different, which is beneficial to distinguish inflammatory and malignant lung lesions in clinic. KEY POINTS: • Malignant and different inflammatory lung lesions showed varying degrees of uptake of [18F]AlF-NOTA-FAPI-04 and [18F]FDG. • Inflammatory lung lesions showed significantly less uptake than malignancies, and uptake varied among different types of inflammatory lesions. • Both types of PET/CT could differentiate malignant and various inflammatory lung findings.


Asunto(s)
Compuestos Heterocíclicos con 1 Anillo , Neoplasias , Neumonía , Quinolinas , Humanos , Tomografía Computarizada por Tomografía de Emisión de Positrones , Fluorodesoxiglucosa F18 , Diagnóstico Diferencial , Estudios Retrospectivos , Inflamación/diagnóstico por imagen , Pulmón/diagnóstico por imagen , Radioisótopos de Galio
9.
Phys Chem Chem Phys ; 26(20): 14613-14623, 2024 May 22.
Artículo en Inglés | MEDLINE | ID: mdl-38739028

RESUMEN

A Ru-containing complex shows good catalytic performance toward the hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) with the assistance of organic base ligands (OBLs) and CO2. Herein, we report the competitive mechanisms for the hydrogenation of LA to GVL, 4-oxopentanal (OT), and 2-methyltetrahydro-2,5-furandiol (MFD) with HCOOH or H2 as the H source catalyzed by RuCl3 in aqueous solution at the M06/def2-TZVP, 6-311++G(d,p) theoretical level. Kinetically, the hydrodehydration of LA to GVL is predominant, with OT and MFD as side products. With HCOOH as the H source, initially, the OBL (triethylamine, pyridine, or triphenylphosphine) is responsible for capturing H+ from HCOOH, leading to HCOO- and [HL]+. Next, the Ru3+ site is in charge of sieving H- from HCOO-, yielding [RuH]2+ hydride and CO2. Alternatively, with H2 as the H source, the OBL stimulates the heterolysis of H-H bond with the aid of Ru3+ active species, producing [RuH]2+ and [HL]+. Toward the [RuH]2+ formation, H2 as the H source exhibits higher activity than HCOOH as the H source in the presence of an OBL. Thereafter, H- in [RuH]2+ gets transferred to the unsaturated C site of ketone carbonyl in LA. Afterwards, the Ru3+ active species is capable of cleaving the C-OH bond in 4-hydroxyvaleric acid, yielding [RuOH]2+ hydroxide and GVL. Subsequently, CO2 promotes Ru-OH bond cleavage in [RuOH]2+, forming HCO3- and regenerating the Ru3+-active species owing to its Lewis acidity. Lastly, between the resultant HCO3- and [HL]+, a neutralization reaction occurs, generating H2O, CO2, and OBLs. Thus, the present study provides insights into the promotive roles of additives such as CO2 and OBLs in Ru-catalyzed hydrogenation.

10.
Artículo en Inglés | MEDLINE | ID: mdl-38330567

RESUMEN

Objective: To evaluate the effectiveness of urokinase and heparin in preventing catheter infection and dysfunction in permanent hemodialysis tunneled cuffed catheters. Methods: We randomized 153 cases of maintenance hemodialysis patients with newly implanted permanent hemodialysis tunneled cannula catheters from November 2018 to November 2021 for this single-center prospective randomized controlled trial The eligible patients were given one of two treatment plans: Patients in the control group (73 patients) were given heparin (6260 U/mL)three times a week after hemodialysis. The intervention group (80 cases) was administered urokinase(25000 U/mL) on the basis of heparin. After six months of maintenance hemodialysis with the above sealing protocols, the primary result was the frequency of catheter malfunction, and the secondary outcome was the frequency of catheter-associated infection. Results: In the final analysis of 153 patients, catheter malfunctions occurred in 29 of the 80 patients assigned to heparin alone, with an incidence of 36.3%, and 16 of the 73 subjects assigned to urokinase combined with heparin, with a rate of 21.9%. This represents an almost 2-fold increase in the risk of catheter malfunction among patients treated with heparin alone as compared to those treated with urokinase once weekly (hazard ratio, 1.85; 13 patients (16.3%) allocated to heparin alone experienced catheter-related bacteremia, compared to 4 patients (5.5%) assigned to urokinase (hazard ratio, 2.79; 95%CI, 1.08 to 7.22; P = .03). Baseline levels, and adverse events, including bleeding incidents, did not statistically differ between the two groups. Conclusion: Urokinase can be used as a secondary prevention drug for long-term catheter malfunction and infection based on its cheapness, efficacy, and safety, which can effectively save medical costs, and its sealing protocol is simple and suitable for promotion.

11.
J Clin Ultrasound ; 2024 Apr 10.
Artículo en Inglés | MEDLINE | ID: mdl-38597807

RESUMEN

Venous ultrasound is the primary, widely accepted diagnostic tool to assess deep vein thrombosis (DVT) in the lower extremities. However, other focal lesions in the lower extremities can be identified on ultrasound. The sonographic appearance of these abnormalities may overlap the thrombosis, which included vascular tumors, Baker's cyst, hematoma, cancer thrombosis, and peripheral nerve tumors. This essay derives from cases diagnosed in our centers and published literature, with images available for illustrations, which may help to improve the clinical management of these findings.

12.
Nano Lett ; 23(13): 5869-5876, 2023 Jul 12.
Artículo en Inglés | MEDLINE | ID: mdl-37338212

RESUMEN

Memristors are promising candidates for constructing neural networks. However, their dissimilar working mechanism to that of the addressing transistors can result in a scaling mismatch, which may hinder efficient integration. Here, we demonstrate two-terminal MoS2 memristors that work with a charge-based mechanism similar to that in transistors, which enables the homogeneous integration with MoS2 transistors to realize one-transistor-one-memristor addressable cells for assembling programmable networks. The homogenously integrated cells are implemented in a 2 × 2 network array to demonstrate the enabled addressability and programmability. The potential for assembling a scalable network is evaluated in a simulated neural network using obtained realistic device parameters, which achieves over 91% pattern recognition accuracy. This study also reveals a generic mechanism and strategy that can be applied to other semiconducting devices for the engineering and homogeneous integration of memristive systems.

13.
Nano Lett ; 23(5): 1850-1857, 2023 Mar 08.
Artículo en Inglés | MEDLINE | ID: mdl-36799492

RESUMEN

Bond-free integration of two-dimensional (2D) materials yields van der Waals (vdW) heterostructures with exotic optical and electronic properties. Manipulating the splitting and recombination of photogenerated electron-hole pairs across the vdW interface is essential for optoelectronic applications. Previous studies have unveiled the critical role of defects in trapping photogenerated charge carriers to modulate the photoconductive gain for photodetection. However, the nature and role of defects in tuning interfacial charge carrier dynamics have remained elusive. Here, we investigate the nonequilibrium charge dynamics at the graphene-WS2 vdW interface under electrochemical gating by operando optical-pump terahertz-probe spectroscopy. We report full control over charge separation states and thus photogating field direction by electrically tuning the defect occupancy. Our results show that electron occupancy of the two in-gap states, presumably originating from sulfur vacancies, can account for the observed rich interfacial charge transfer dynamics and electrically tunable photogating fields, providing microscopic insights for optimizing optoelectronic devices.

14.
Angew Chem Int Ed Engl ; 63(20): e202320091, 2024 May 13.
Artículo en Inglés | MEDLINE | ID: mdl-38488855

RESUMEN

Conjugated coordination polymers (c-CPs) are unique organic-inorganic hybrid semiconductors with intrinsically high electrical conductivity and excellent charge carrier mobility. However, it remains a challenge in tailoring electronic structures, due to the lack of clear guidelines. Here, we develop a strategy wherein controlling the redox state of hydroquinone/benzoquinone (HQ/BQ) ligands allows for the modulation of the electronic structure of c-CPs while maintaining the structural topology. The redox-state control is achieved by reacting the ligand TTHQ (TTHQ=1,2,4,5-tetrathiolhydroquinone) with silver acetate and silver nitrate, yielding Ag4TTHQ and Ag4TTBQ (TTBQ=1,2,4,5-tetrathiolbenzoquinone), respectively. In spite of sharing the same topology consisting of a two-dimensional Ag-S network and HQ/BQ layer, they exhibit different band gaps (1.5 eV for Ag4TTHQ and 0.5 eV for Ag4TTBQ) and conductivities (0.4 S/cm for Ag4TTHQ and 10 S/cm for Ag4TTBQ). DFT calculations reveal that these differences arise from the ligand oxidation state inhibiting energy band formation near the Fermi level in Ag4TTHQ. Consequently, Ag4TTHQ displays a high Seebeck coefficient of 330 µV/K and a power factor of 10 µW/m ⋅ K2, surpassing Ag4TTBQ and the other reported silver-based c-CPs. Furthermore, terahertz spectroscopy demonstrates high charge mobilities exceeding 130 cm2/V ⋅ s in both Ag4TTHQ and Ag4TTBQ.

15.
J Am Chem Soc ; 145(16): 8979-8987, 2023 Apr 26.
Artículo en Inglés | MEDLINE | ID: mdl-37067179

RESUMEN

Conductive metal-organic frameworks (c-MOFs) with outstanding electrical conductivities and high charge carrier mobilities are promising candidates for electronics and optoelectronics. However, the poor solubility of planar ligands greatly hinders the synthesis and widespread applications of c-MOFs. Nonplanar ligands with excellent solubility in organic solvents are ideal alternatives to construct c-MOFs. Herein, contorted hexabenzocoronene (c-HBC) derivatives with good solubility are adopted to synthesize c-MOFs. Three c-MOFs (c-HBC-6O-Cu, c-HBC-8O-Cu, and c-HBC-12O-Cu) with substantially different geometries and packing modes have been synthesized using three multitopic catechol-based c-HBC ligands with different symmetries and coordination numbers, respectively. With more metal coordination centers and increased charge transport pathways, c-HBC-12O-Cu exhibits the highest intrinsic electrical conductivity of 3.31 S m-1. Time-resolved terahertz spectroscopy reveals high charge carrier mobilities in c-HBC-based c-MOFs, ranging from 38 to 64 cm2 V-1 s-1. This work provides a systematic and modular approach to fine-tune the structure and enrich the c-MOF family with excellent charge transport properties using nonplanar and highly soluble ligands.

16.
J Am Chem Soc ; 145(4): 2430-2438, 2023 Feb 01.
Artículo en Inglés | MEDLINE | ID: mdl-36661343

RESUMEN

Electrically conductive coordination polymers and metal-organic frameworks are attractive emerging electroactive materials for (opto-)electronics. However, developing semiconducting coordination polymers with high charge carrier mobility for devices remains a major challenge, urgently requiring the rational design of ligands and topological networks with desired electronic structures. Herein, we demonstrate a strategy for synthesizing high-mobility semiconducting conjugated coordination polymers (c-CPs) utilizing novel conjugated ligands with D2h symmetry, namely, "4 + 2" phenyl ligands. Compared with the conventional phenyl ligands with C6h symmetry, the reduced symmetry of the "4 + 2" ligands leads to anisotropic coordination in the formation of c-CPs. Consequently, we successfully achieve a single-crystalline three-dimensional (3D) c-CP Cu4DHTTB (DHTTB = 2,5-dihydroxy-1,3,4,6-tetrathiolbenzene), containing orthogonal ribbon-like π-d conjugated chains rather than 2D conjugated layers. DFT calculation suggests that the resulting Cu4DHTTB exhibits a small band gap (∼0.2 eV), strongly dispersive energy bands near the Fermi level with a low electron-hole reduced effective mass (∼0.2m0*). Furthermore, the four-probe method reveals a semiconducting behavior with a decent conductivity of 0.2 S/cm. Thermopower measurement suggests that it is a p-type semiconductor. Ultrafast terahertz photoconductivity measurements confirm Cu4DHTTB's semiconducting nature and demonstrate the Drude-type transport with high charge carrier mobilities up to 88 ± 15 cm2 V-1 s-1, outperforming the conductive 3D coordination polymers reported till date. This molecular design strategy for constructing high-mobility semiconducting c-CPs lays the foundation for achieving high-performance c-CP-based (opto-)electronics.

17.
Small ; : e2306732, 2023 Dec 11.
Artículo en Inglés | MEDLINE | ID: mdl-38073322

RESUMEN

Currently, most reported 2D conjugated metal-organic frameworks (2D c-MOFs) are based on planar polycyclic aromatic hydrocarbons (PAHs) with symmetrical functional groups, limiting the possibility of introducing additional substituents to fine-tune the crystallinity and electrical properties. Herein, a novel class of wavy 2D c-MOFs with highly substituted, core-twisted hexahydroxy-hexa-cata-benzocoronenes (HH-cHBCs) as ligands is reported. By tailoring the substitution of the c-HBC ligands with electron-withdrawing groups (EWGs), such as fluorine, chlorine, and bromine, it is demonstrated that the crystallinity and electrical conductivity at the molecular level can be tuned. The theoretical calculations demonstrate that F-substitution leads to a more reversible coordination bonding between HH-cHBCs and copper metal center, due to smaller atomic size and stronger electron-withdrawing effect. As a result, the achieved F-substituted 2D c-MOF exhibits superior crystallinity, comprising ribbon-like single crystals up to tens of micrometers in length. Moreover, the F-substituted 2D c-MOF displays higher electrical conductivity (two orders of magnitude) and higher charge carrier mobility (almost three times) than the Cl-substituted one. This work provides a new molecular design strategy for the development of wavy 2D c-MOFs and opens a new route for tailoring the coordination reversibility by ligand substitution toward increased crystallinity and superior electric conductivity.

18.
PLoS Pathog ; 17(3): e1009370, 2021 03.
Artículo en Inglés | MEDLINE | ID: mdl-33662041

RESUMEN

The movement of plant viruses is a complex process that requires support by the virus-encoded movement protein and multiple host factors. The unfolded protein response (UPR) plays important roles in plant virus infection, while how UPR regulates viral infection remains to be elucidated. Here, we show that rice stripe virus (RSV) elicits the UPR in Nicotiana benthamiana. The RSV-induced UPR activates the host autophagy pathway by which the RSV-encoded movement protein, NSvc4, is targeted for autophagic degradation. As a counteract, we revealed that NSvc4 hijacks UPR-activated type-I J-domain proteins, NbMIP1s, to protect itself from autophagic degradation. Unexpectedly, we found NbMIP1 stabilizes NSvc4 in a non-canonical HSP70-independent manner. Silencing NbMIP1 family genes in N. benthamiana, delays RSV infection, while over-expressing NbMIP1.4b promotes viral cell-to-cell movement. Moreover, OsDjA5, the homologue of NbMIP1 family in rice, behaves in a similar manner toward facilitating RSV infection. This study exemplifies an arms race between RSV and the host plant, and reveals the dual roles of the UPR in RSV infection though fine-tuning the accumulation of viral movement protein.


Asunto(s)
Nicotiana/virología , Enfermedades de las Plantas/genética , Proteínas de Plantas/metabolismo , Tenuivirus/metabolismo , Silenciador del Gen , Oryza/genética , Oryza/metabolismo , Respuesta de Proteína Desplegada/genética , Respuesta de Proteína Desplegada/fisiología
19.
J Ultrasound Med ; 42(9): 2115-2123, 2023 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-37159482

RESUMEN

OBJECTIVE: To evaluate the feasibility of axillary nerve (AN) visualization in healthy volunteers and the diagnostic value of AN injury via high-resolution ultrasonography (HRUS). METHODS: AN was examined by HRUS on both sides of 48 healthy volunteers and oriented the transducer according to three anatomical landmarks: quadrilateral space, anterior to subscapular muscle, and posterior to axillary artery. The maximum short-axis diameter (SD) and cross-sectional area (CSA) of AN were measured at different levels, and AN visibility was graded by using a five-point scale. The patients suspected of having AN injury were assessed by HRUS, and the HRUS features of AN injury were observed. RESULTS: AN can be visualized on both sides in all volunteers. There was no significant difference in SD and CSA of AN at the three levels between the left and right sides or in SD between males and females. However, the CSA of males at different levels was slightly larger than those of females (P < .05). In most volunteers, AN visibility at different levels was excellent or good, and AN was best displayed anterior to subscapular muscle. Rank correlation analysis revealed that the degree of AN visibility had correlation with height, weight, and BMI. A total of 15 patients diagnosed with AN injury, 12 patients showed diffuse swelling or focal thickening in AN, and 3 patients showed AN discontinuity. CONCLUSION: HRUS is able to reliably visualize AN, and it could be considered as the first choice for diagnosing AN injury.


Asunto(s)
Plexo Braquial , Traumatismos de los Nervios Periféricos , Masculino , Femenino , Humanos , Ultrasonografía/métodos , Voluntarios Sanos
20.
Sensors (Basel) ; 23(19)2023 Sep 27.
Artículo en Inglés | MEDLINE | ID: mdl-37836954

RESUMEN

Prognostic and health management (PHM) plays a vital role in ensuring the safety and reliability of aircraft systems. The process entails the proactive surveillance and evaluation of the state and functional effectiveness of crucial subsystems. The principal aim of PHM is to predict the remaining useful life (RUL) of subsystems and proactively mitigate future breakdowns in order to minimize consequences. The achievement of this objective is helped by employing predictive modeling techniques and doing real-time data analysis. The incorporation of prognostic methodologies is of utmost importance in the execution of condition-based maintenance (CBM), a strategic approach that emphasizes the prioritization of repairing components that have experienced quantifiable damage. Multiple methodologies are employed to support the advancement of prognostics for aviation systems, encompassing physics-based modeling, data-driven techniques, and hybrid prognosis. These methodologies enable the prediction and mitigation of failures by identifying relevant health indicators. Despite the promising outcomes in the aviation sector pertaining to the implementation of PHM, there exists a deficiency in the research concerning the efficient integration of hybrid PHM applications. The primary aim of this paper is to provide a thorough analysis of the current state of research advancements in prognostics for aircraft systems, with a specific focus on prominent algorithms and their practical applications and challenges. The paper concludes by providing a detailed analysis of prospective directions for future research within the field.


Asunto(s)
Aeronaves , Aviación , Pronóstico , Estudios Prospectivos , Reproducibilidad de los Resultados
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