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1.
BMC Anesthesiol ; 23(1): 213, 2023 06 20.
Artigo em Inglês | MEDLINE | ID: mdl-37340348

RESUMO

OBJECTIVES: General anesthesia results in a state of unconsciousness that is similar to sleep. In recent years, increasing evidence has reported that astrocytes play a crucial role in regulating sleep. However, whether astrocytes are involved in general anesthesia is unknown. METHODS: In the present study, the designer receptors exclusively activated by designer drugs (DREADDs) approach was utilized to specifically activate astrocytes in the basal forebrain (BF) and observed its effect on isoflurane anesthesia. One the other side, L-α-aminoadipic acid was used to selectively inhibit astrocytes in the BF and investigated its influence on isoflurane-induced hypnotic effect. During the anesthesia experiment, cortical electroencephalography (EEG) signals were recorded as well. RESULTS: The chemogenetic activation group had a significantly shorter isoflurane induction time, longer recovery time, and higher delta power of EEG during anesthesia maintenance and recovery periods than the control group. Inhibition of astrocytes in the BF delayed isoflurane-induced loss of consciousness, promoted recovery, decreased delta power and increased beta and gamma power during maintenance and recovery periods. CONCLUSIONS: The present study suggests that astrocytes in the BF region are involved in isoflurane anesthesia and may be a potential target for regulating the consciousness state of anesthesia.


Assuntos
Prosencéfalo Basal , Isoflurano , Camundongos , Animais , Isoflurano/farmacologia , Estado de Consciência , Astrócitos , Inconsciência , Anestesia Geral
2.
Immunopharmacol Immunotoxicol ; 43(1): 58-67, 2021 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-33285073

RESUMO

BACKGROUND: Glutathione is a potential therapy for systemic lupus erythematosus, but its role in allergic rhinitis (AR) has not been determined. This report probed into the actions of glutathione in AR, so as to supplement evidence for a therapeutical countermeasure for AR. METHODS: In this study, peripheral blood mononuclear cells (PBMCs) of patients were extracted and processed with glutathione. PBMCs and nasal mucosa tissues were collected from AR mouse models treated with or without glutathione. The proportions of Th17/Treg cell markers and autophagy-related molecules in the nasal mucosa, PBMCs or Th17/Treg cells were assessed by quantitative real-time polymerase chain reaction (qRT-PCR), Western blot (WB) or flow cytometry analysis, and serum contents of related factors were analyzed by enzyme-linked immunosorbent assay (ELISA). Hematoxylin-eosin (HE) staining was applied to observe the thickness of mouse mucosa. RESULTS: IL-17A, RORγt, Beclin1 and LC3-II/LC3-I levels were increased in AR patients, while Foxp3 and P62 were decreased. The serum contents of IL-17A and eosinophil cationic protein (ECP) in AR patients were elevated, but IL-10 level was reduced. In PBMCs of AR patients, the levels of IL-17A and LC3-II were increased, and the levels of Foxp3 and P62 were decreased, while these changes could be reversed by glutathione. In AR mouse models, glutathione could balance Th17/Treg cells, reduce autophagy, correct the levels of related cytokines in mouse serum, and shrunk mucosa thickness. CONCLUSION: Glutathione could rescue the imbalance of Treg/Th17 cells by suppressing intracellular autophagy, which might be beneficial to the treatment of AR patients.


Assuntos
Autofagia/imunologia , Glutationa/farmacologia , Líquido Intracelular/imunologia , Rinite Alérgica/imunologia , Linfócitos T Reguladores/imunologia , Células Th17/imunologia , Adulto , Animais , Autofagia/efeitos dos fármacos , Células Cultivadas , Feminino , Glutationa/uso terapêutico , Humanos , Líquido Intracelular/efeitos dos fármacos , Leucócitos Mononucleares/efeitos dos fármacos , Leucócitos Mononucleares/imunologia , Masculino , Camundongos , Camundongos Endogâmicos BALB C , Mucosa Nasal/efeitos dos fármacos , Mucosa Nasal/imunologia , Mucosa Nasal/patologia , Rinite Alérgica/tratamento farmacológico , Rinite Alérgica/patologia , Linfócitos T Reguladores/efeitos dos fármacos , Células Th17/efeitos dos fármacos
3.
Angew Chem Int Ed Engl ; 60(28): 15328-15334, 2021 Jul 05.
Artigo em Inglês | MEDLINE | ID: mdl-33885188

RESUMO

Organic electrical gas sensors have been developed for many decades because of their high sensitivity and selectivity. However, their industrialization is severely hindered by their intrinsic humidity susceptibility and poor recovery. Conventional organic sensory materials can only operate at room temperature owing to their weak intermolecular interactions. Herein, we demonstrate using a croconate polymer (poly-4,4'-biphenylcroconate) that the "ion-in-conjugation" concept enables organic gas sensors to operate at 100 °C and 70 % relative humidity with almost complete recovery. The fabricated sensor had a parts-per-billion (ppb) detection limit for NO2 and showed the highest sensitivity (2526 ppm-1 at 40 ppb) of all reported NO2 chemiresistive sensors. Furthermore, charge transfer increased with temperature. Theoretical calculations and in situ FTIR spectra confirmed the ion-in-conjugation-inspired hydrogen bond as key for excellent sensitivity. A NO2 alarm system was assembled to demonstrate the feasibility of this sensor.

4.
Small ; 15(49): e1905731, 2019 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-31668013

RESUMO

Memristors are emerging as a rising star of new computing and information storage techniques. However, the practical applications are severely challenged by their instability toward harsh conditions, including high moisture, high temperatures, fire, ionizing irradiation, and mechanical bending. In this work, for the first time, lead-free double perovskite Cs2 AgBiBr6 is utilized for environmentally robust memristors, enabling highly efficient information storage. The memory performance of the typical indium-tin-oxide/Cs2 AgBiBr6 /Au sandwich-like memristors is retained after 1000 switching cycles, 105 s of reading, and 104 times of mechanical bending, comparable to other halide perovskite memristors. Most importantly, the memristive behavior remains robust in harsh environments, including humidity up to 80%, temperatures as high as 453 K, an alcohol burner flame for 10 s, and 60 Co γ-ray irradiation for a dosage of 5 × 105 rad (SI), which is not achieved by any other memristors and commercial flash memory techniques. The realization of an environmentally robust memristor from Cs2 AgBiBr6 with a high memory performance will inspire further development of robust electronics using lead-free double perovskites.

5.
Small ; 15(2): e1803896, 2019 01.
Artigo em Inglês | MEDLINE | ID: mdl-30537175

RESUMO

Nitrogen dioxide (NO2 ) emission has severe impact on human health and the ecological environment and effective monitoring of NO2 requires the detection limit (limit of detection) of several parts-per-billion (ppb). All organic semiconductor-based NO2 sensors fail to reach such a level. In this work, using an ion-in-conjugation inspired-polymer (poly(3,3'-diaminobenzidine-squarine, noted as PDBS) as the sensory material, NO2 can be detected as low as 1 ppb, which is the lowest among all reported organic NO2 sensors. In addition, the sensor has high sensitivity, good reversibility, and long-time stability with a period longer than 120 d. Theoretical calculations reveal that PDBS offers unreacted amine and zwitterionic groups, which can offer both the H-bonding and ion-dipole interaction to NO2 . The moderate binding energies (≈0.6 eV) offer high sensitivity, selectivity as well as good reversibility. The results demonstrate that the ion-in-conjugation can be employed to greatly improve sensitivity and selectivity in organic gas sensors by inducing both H-bonding and ion-dipole attraction.

6.
Small ; 15(49): e1903188, 2019 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-31650707

RESUMO

Conjugated coordination polymers have become an emerging category of redox-active materials. Although recent studies heavily focus on the tailoring of metal centers in the complexes to achieve stable electrochemical performance, the effect on different substitutions of the bridging bonds has rarely been studied. An innovative tailoring strategy is presented toward the enhancement of the capacity storage and the stability of metal-organic conjugated coordination polymers. Two nanostructured d-π conjugated compounds, Ni[C6 H2 (NH)4 ]n (Ni-NH) and Ni[C6 H2 (NH)2 S2 ]n (Ni-S), are evaluated and demonstrated to exhibit hybrid electrochemical processes. In particular, Ni-S delivers a high reversible capacity of 1164 mAh g-1 , an ultralong stability up to 1500 cycles, and a fully recharge ability in 67 s. This tailoring strategy provides a guideline to design future effective conjugated coordination-polymer-based electrodes.

7.
Chemistry ; 25(18): 4808-4813, 2019 Mar 27.
Artigo em Inglês | MEDLINE | ID: mdl-30689240

RESUMO

Recently, resistance random access memories (RRAMs) have been studied extensively, because the demand for information storage is increasing. However, it remains challenging to obtain a flexible device because the active materials involved need to be nontoxic, nonpolluting, distortion-tolerable, and biodegradable as well adhesive to diverse flexible substrates. In this paper, tannic acid (TA) and an iron ion (FeIII ) coordination complex were employed as the active layer in a sandwich-like (Al/active layer/substrate) device to achieve memory performance. A nontoxic, biocompatible TA-FeIII coordination complex was synthesized by a one-step self-assembly solution method. The retention time of the TA-FeIII memory performance was up to 15 000 s, the yield up to 53 %. Furthermore, the TA-FeIII coordination complex can form a high-quality film and shows stable ternary memory behavior on various flexible substrates, such as polyethylene terephthalate (PET), polyimide (PI), printer paper, and leaf. The device can be degraded by immersing it in vinegar solution. Our work will broaden the application of organic coordination complexes in flexible memory devices with diverse substrates.


Assuntos
Materiais Biocompatíveis/química , Complexos de Coordenação/química , Alumínio/química , Ferro/química , Membranas Artificiais , Papel , Folhas de Planta/química , Maleabilidade , Polietilenotereftalatos/química , Resinas Sintéticas/química , Propriedades de Superfície , Taninos/química , Dispositivos Eletrônicos Vestíveis
8.
Small ; 14(12): e1703667, 2018 03.
Artigo em Inglês | MEDLINE | ID: mdl-29457377

RESUMO

Recently, organic-inorganic hybrid perovskites (OIHP) are studied in memory devices, but ternary resistive memory with three states based on OIHP is not achieved yet. In this work, ternary resistive memory based on hybrid perovskite is achieved with a high device yield (75%), much higher than most organic ternary resistive memories. The pseudohalide-induced 2D (CH3 NH3 )2 PbI2 (SCN)2 perovskite thin film is prepared by using a one-step solution method and fabricated into Al/perovskite film/indium-tin oxide (glass substrate as well as flexible polyethylene terephthalate substrate) random resistive access memory (RRAM) devices. The three states have a conductivity ratio of 1:103 :107 , long retention over 10 000 s, and good endurance properties. The electrode area variation, impedance test, and current-voltage plotting show that the two resistance switches are attributable to the charge trap filling due to the effect of unscreened defect in 2D nanosheets and the formation of conductive filaments, respectively. This work paves way for stable perovskite multilevel RRAMs in ambient atmosphere.

9.
Small ; 13(2)2017 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-27754595

RESUMO

An organic thin-film gas sensor based on squaraine detects ammonia as low as 40 ppb with impressive reversibility and stability. The resonance-stabilized zwitterionic characteristics offer squaraines high affinity and sensitivity toward electron-rich analytes without irreversible chemical binding, while the embedded squaric ring makes SA-CH3 highly sensitive. The symmetric molecular geometry and good crystallinity also contribute to the high performance.

10.
Chemistry ; 23(64): 16393-16400, 2017 Nov 16.
Artigo em Inglês | MEDLINE | ID: mdl-28925062

RESUMO

Recently, surface engineering of the indium tin oxide (ITO) electrode of sandwich-like organic electric memory devices was found to effectively improve their memory performances. However, there are few methods to modify the ITO substrates. In this paper, we have successfully prepared alkyltrichlorosilane self-assembled monolayers (SAMs) on ITO substrates, and resistive random access memory devices are fabricated on these surfaces. Compared to the unmodified ITO substrates, organic molecules (i.e., 2-((4-butylphenyl)amino)-4-((4-butylphenyl)iminio)-3-oxocyclobut-1-en-1-olate, SA-Bu) grown on these SAM-modified ITO substrates have rougher surface morphologies but a smaller mosaicity. The organic layer on the SAM-modified ITO further aged to eliminate the crystalline phase diversity. In consequence, the ternary memory yields are effectively improved to approximately 40-47 %. Our results suggest that the insertion of alkyltrichlorosilane self-assembled monolayers could be an efficient method to improve the performance of organic memory devices.

11.
Eur Arch Otorhinolaryngol ; 274(4): 1919-1924, 2017 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-28004261

RESUMO

The aim of this study is to evaluate the efficacy of ethosomes encapsulated with 5-fluorouracil (5-FU) in treatment of laryngotracheal stenosis in rabbit models. The 5-FU ethosome was prepared by the thin film hydration method, and the amorphous, size distribution and the encapsulation efficiency was investigated. The tracheal mucosa were scraped about 0.5 cm with a nylon brush to induce the scar in airway grow, then models were divided into three groups: 5-FU ethosome group, 5-FU group and saline group, drug were injected into scar of every group by paracentesis guided under endoscope, respectively. The stenosis states were observed under laryngo fiberscope immediate, 7, 14 and 21 days after administrated. Airway stenosis of 5-FU ethosome group has no significant difference when compared with 5-FU group at 7 days after administration, but 5-FU ethosome significantly reduced the airway stenosis after 21-day administration when compared with 5-FU group again and has no restenosis during the period under observation. The fact that ethosomes encapsulated with 5-FU were effective for laryngotracheal stenosis suggests that it has potential as a new method for ameliorating airway stenosis originating from granulation tissue.


Assuntos
Antimetabólitos/administração & dosagem , Fluoruracila/administração & dosagem , Laringoestenose/tratamento farmacológico , Estenose Traqueal/tratamento farmacológico , Animais , Antimetabólitos/uso terapêutico , Esquema de Medicação , Sistemas de Liberação de Medicamentos , Feminino , Fluoruracila/uso terapêutico , Injeções Intralesionais , Masculino , Coelhos , Distribuição Aleatória , Resultado do Tratamento
12.
Sci Rep ; 14(1): 20452, 2024 Sep 03.
Artigo em Inglês | MEDLINE | ID: mdl-39227661

RESUMO

This paper presents a novel 4D hyperchaotic system derived from a modified 3D Lorenz chaotic system. A key aspect of this system is the presence of a single equilibrium point, and its stability is carefully analyzed. The dynamic properties, including the Lyapunov exponent spectrum, bifurcation diagram, and chaotic attractors, are investigated using MATLAB simulations. The results reveal that the system displays hyperchaotic behavior across a wide range of the parameter d , with its chaotic attractor transitioning through four states: hyperchaotic, chaotic, periodic, and quasi-periodic, showcasing the system's complex dynamics. Experimental validation using STM32 embedded hardware successfully reproduces these four types of chaotic attractors, confirming the theoretical predictions. The proposed hyperchaotic system is then applied to image encryption, introducing a novel encryption method. The hyperchaotic key sequence generated by this system meets 15 tests of the NIST SP800-22 standard, and further experimental validation with STM32 hardware demonstrates the algorithm's effectiveness, simplicity, non-linearity, and high security. The encrypted images and sequences are rigorously tested key space analysis, histogram similarity analysis, information entropy analysis, statistical attack analysis, differential attack analysis, key sensitivity analysis, and correlation analysis, highlighting the robustness and reliability of the proposed system. This method is versatile and can be extended to various fields, including audio and video encryption, text encryption, IoT security, financial transaction security, and medical data protection.

13.
Materials (Basel) ; 17(7)2024 Mar 28.
Artigo em Inglês | MEDLINE | ID: mdl-38612050

RESUMO

As the central component in friction stir welding, the design and manufacture of welding tools for aluminum alloys have garnered substantial attention. However, the understanding of tool reliability during the welding process, especially in terms of fatigue performance, remains unclear. This paper focuses on the welding of AA2219-T4 as a case study to elucidate the predominant failure mode of the tool during the friction stir welding (FSW) of aluminum alloys. Experimental methods, including FSW welding and fracture morphology analysis of the failed tool, coupled with numerical simulation, confirm that high-cycle mechanical fatigue fracture is the primary mode of the tool failure. Failures predominantly occur at the tool pin's root and the shoulder end face with scroll concave grooves. The experimental and simulation results exhibit a noteworthy agreement, validating the reliability of the simulation model. The FSW Arbitrary Lagrangian-Eulerian (ALE) model developed in this study analyzes stress distribution and variation under the thermo-mechanical coupling effect of the tool. It reveals that stress concentration resulting from structural changes in the tool is the primary driver of fatigue crack initiation. This is attributed to exposure to alternating cyclic stresses such as bending, tension, and torsion at the tool pin's root, manifesting as multiaxial composite mechanical fatigue. Among these stresses, bending alternating cyclic stress exerts the most significant influence. The paper employs the Tool Life module in DEFORM software to predict the fatigue life of the tool. Results indicate that reducing welding speed or increasing rotation speed can enhance the tool's fatigue life to some extent. The methodology proposed in this paper serves as a valuable reference for optimizing FSW structures or processes to enhance the fatigue performance of welding tools.

14.
ACS Sens ; 9(1): 236-243, 2024 01 26.
Artigo em Inglês | MEDLINE | ID: mdl-38123468

RESUMO

Organic molecules are of great interest for gas sensing applications. However, achieving high-performance gas sensors with high sensitivity, fast response, low consumption, and workability in humid conditions is still challenging. Herein, we report the rational design and synthesis of an ion-in-conjugation polymer, PADC (poly-4,4'-azodianiline-croconamide), obtained by the condensation of croconic acid with 4-4'diaminoazobenzene for gas sensing under humid conditions. The as-fabricated PADC-based gas sensor exhibits ultrahigh sensitivity (802.7 ppm-1 at 1 ppm), subppb detection limit, and high selectivity under humid air with an 80% humidity effect at a temperature down to 350 K. PADC shows good planarity, excellent thermostability, and a narrow band gap of 1.2 eV because of azobenzene fragments spacing previously repulsed biphenyl rings. Compared to previous humidity immunity works, PADC-based sensors realized humidity immunity at a relatively lower temperature, resulting in lower energy consumption.


Assuntos
Dióxido de Nitrogênio , Poli A , Umidade , Polímeros , Temperatura
15.
Sci Rep ; 13(1): 19385, 2023 Nov 08.
Artigo em Inglês | MEDLINE | ID: mdl-37938603

RESUMO

In this study, a 4D hyperchaotic system is constructed based on the foundation of a 3D Lü chaotic system. The newly devised hyperchaotic system possesses a sole equilibrium point, showcasing a simplified system structure that reduces complexity. This simplification offers a clearer opportunity for in-depth analysis of dynamic behaviors in the realm of scientific research. The proposed hyperchaotic system undergoes an in-depth examination of its dynamical characteristics, including chaotic attractors, equilibrium point stability, Lyapunov exponents' spectrum, and bifurcation diagram. Numerical analysis results reveal that the attractor of this hyperchaotic system exhibits highly complex, non-periodic, and fractal structural dynamics. Its motion demonstrates extreme sensitivity and randomness, even within a wide range of variations in parameter d, affirming its hyperchaotic properties with two positive Lyapunov exponents. Hyperchaotic bifurcation diagrams typically exhibit highly intricate structures, such as fractals, branches, and period doubling characteristics, signifying that even minor parameter adjustments can lead to significant changes in system behavior, presenting diversity and unpredictability. Subsequently, to further investigate the practical utility of this hyperchaotic system, a linear feedback control strategy is implemented. Through linear feedback control, the hyperchaotic system is stabilized at its unique equilibrium point. Experimental validation is conducted using both computer software simulation Matlab, electronic circuit simulation Multisim, and embedded hardware STM32. The results of these experiments consistently align, providing theoretical support for the application of this hyperchaotic system in practical domains. Finally, leveraging the hyperchaotic keys generated by this hyperchaotic system, audio encryption is achieved using a cross-XOR algorithm, which is then realized on the embedded hardware platform STM32. The results show that the audio encryption scheme based on the hyperchaotic system is feasible, and the method is simple to implement, has nonlinear characteristics and certain algorithm complexity, which can be applied to audio encryption, image encryption, video encryption, and more.

16.
J Colloid Interface Sci ; 643: 403-408, 2023 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-37084620

RESUMO

Electrochemical oxidation of urea is of great importance in the removal and energy exchange and storage of urea from wastewater as well as of potential applications in potable dialysis of end-stage renal disease. However, the lack of economical electrocatalysts hinders its widespread application. In this study, we successfully fabricated ZnCo2O4 nanospheres with bifunctional catalysis on nickel foam (NF). The catalytic system has high catalytic activity and durability for urea overall electrolysis. The urea oxidation and hydrogen evolution reactions required only 1.32 V and -80.91 mV to obtain ± 10 mA cm-2. Only 1.39 V was needed to obtain 10 mA cm-2 for 40 h without noticeably declining activity. The excellent performance could be attributed to the fact that the material can provide multiple redox couplings and a three-dimensional porous structure to facilitate the release of gases from the surface.

17.
Laryngoscope Investig Otolaryngol ; 7(2): 592-598, 2022 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-35434316

RESUMO

Introduction: The aim of this study is to explore the potential factors in hearing outcomes and verify the role of oxidant-antioxidant equilibrium on the prognosis of sudden sensorineural hearing loss (SSNHL) treated with hyperbaric oxygen therapy (HBOT). Methods: Ninety-two patients who were diagnosed with SSNHL between January 2018 and December 2019 in our hearing clinic center were included in this study. All patients were treated with intravenous dexamethasone, and 72 cases were treated with additional HBOT for 10 consecutive days. Peripheral blood was collected prior to any treatment to determine the blood cell count and hemoglobin (HGB), hematocrit (HCT), and superoxide dismutase (SOD) levels. Pure tone audiometry was measured before and after treatment. Complete and overall recovery rate was evaluated. Multivariate logistic analysis was used to identify prognostic factors. Results: The rate of overall recovery was significantly higher in the patient with combined therapy compared to patients treated with steroids only (51.4% vs 25.0%, p = .036). The levels of HGB, HCT, and SOD were much higher in the patients with better hearing outcomes (p = .027, .033, and .011, respectively). Multivariate logistic analysis demonstrated that patients with higher initial hearing thresholds, or hearing loss at overall frequency, were more prone to have poor hearing gains after HBOT. Conclusion: HBOT is effective as an early adjuvant therapy for SSNHL. Hearing loss at low frequency, low initial hearing thresholds, as well as high HBG, HCT, and SOD levels are positive prognostic factors for SSNHL patients treated with HBOT.

18.
ACS Sens ; 7(12): 3782-3789, 2022 12 23.
Artigo em Inglês | MEDLINE | ID: mdl-36384296

RESUMO

As a common toxic gas, nitrogen dioxide (NO2) seriously threatens the environment and human respiratory system even at part per billion (ppb) level. Covalent organic frameworks (COFs) have gained widespread attention in sensing applications because of the benefits of designability, environmental stability, and a large number of active sites. However, the competitive adsorption of water molecules and the target gas molecules at room temperature as well as the weak interaction between COFs and gas molecules hinder their practical applications. Here, we introduce ion-in-conjugation (IIC) into a covalent organic framework (COF) by preparing a condensate of squaraine (SA) with 1,3,5-tris(4-aminophenyl)benzene (TAPB) to form a mesoporous macrocyclic material (SA-TAPB). Layers of SA-TAPB, drop cast onto interdigitated Ag-Pd alloy electrodes, show a statistically significant conductivity response to NO2 at concentrations as low as 30 ppb and a theoretical detection limit of 10.9 ppb. The sensor displays a lower sensitivity to variations in humidity when operated at 80 °C compared to room temperature. The density functional theory (DFT) calculations indicated that the main adsorption site of NO2 is dual hydrogen bonds formed between two amide hydrogen atoms of SA-TAPB and the NO2 molecule. Gas adsorption experiments revealed that SA-TAPB has the largest adsorption capacity of NO2 versus other interference gases, which were responsible for the excellent selectivity toward NO2.


Assuntos
Estruturas Metalorgânicas , Humanos , Dióxido de Nitrogênio , Adsorção , Ligação de Hidrogênio , Gases
19.
Adv Mater ; 34(36): e2205767, 2022 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-35841127

RESUMO

Nitrate electrocatalytic reduction (NO3 RR) for ammonia production is a promising strategy to close the N-cycle from nitration contamination, as well as an alternative to the Haber-Bosch process with less energy consumption and carbon dioxide release. However, current long-term stability of NO3 RR catalysts is usually tens of hours, far from the requirements for industrialization. Here, symmetry-broken Cusingle-atom catalysts are designed, and the catalytic activity is retained after operation for more than 2000 h, while an average ammonia production rate of 27.84 mg h-1 cm-2 at an industrial level current density of 366 mA cm-2 is achieved, obtaining a good balance between catalytic activity and long-term stability. Coordination symmetry breaking is achieved by embedding one Cu atom in graphene nanosheets with two N and two O atoms in the cis-configuration, effectively lowering the coordination symmetry, rendering the active site more polar, and accumulating more NO3 - near the electrocatalyst surface. Additionally, the cis-coordination splits the Cu 3d orbitals, which generates an orbital-symmetry-matched π-complex of the key intermediate *ONH and reduces the energy barrier, compared with the σ-complex generated with other catalysts. These results reveal the critical role of coordination symmetry in single-atom catalysts, prompting the design of more coordination-symmetry-broken electrocatalysts toward possible industrialization.

20.
Mol Neurobiol ; 58(10): 4802-4815, 2021 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-34176097

RESUMO

Bone cancer pain (BCP) was associated with microRNA dysregulation. In this study, we intended to clarify the potential role of miR-135-5p in a BCP mouse model, which was established by tumor cell implantation (TCI) in the medullary cavity of the mouse femur. The BCP-related behaviors were tested, including the paw withdrawal mechanical threshold (PWMT) and number of spontaneous flinches (NSF). The miRNA expression profiles in astrocytes of the sham and tumor groups were compared, and miRNA microarray and quantitative real-time PCR (qRT-PCR) assays confirmed that the amount of expression of miR-135-5p was significantly decreased in astrocytes of the tumor group. Gain- and loss-of-function studies showed that miR-135-5p could inhibit astrocyte activation and inflammation cytokine (TNF-α and IL-1ß) expression. The relation between miR-135-5p and JAK2 was detected by bioinformatic analysis and dual luciferase reporter gene assay. By conducting in vitro experiments, it was shown that the miR-135-5P mimics lowered the level of JAK2/STAT3 proteins and inflammatory factors in astrocytes. Moreover, in vivo analysis on BCP mice model indicated that the miR-135-5p agonist could sufficiently increase PWMT and decrease NSF. Meanwhile, reduced activation of astrocytes in the spinal cord, as well as decreased expression of JAK2/STAT3 and inflammatory mediators, were found after miR-135-5p agonist treatment. Collectively, the results showed that miR-135-5p could potentially reduce BCP in mice through inhibiting astrocyte-mediated neuroinflammation and blocking of the JAK2/STAT3 signaling pathway, indicating that the upregulation of miR-135-5P could be a therapeutic focus in BCP treatment.


Assuntos
Neoplasias Ósseas/metabolismo , Dor do Câncer/metabolismo , Janus Quinase 2/metabolismo , MicroRNAs/biossíntese , Doenças Neuroinflamatórias/metabolismo , Fator de Transcrição STAT3/metabolismo , Animais , Astrócitos/metabolismo , Astrócitos/patologia , Neoplasias Ósseas/patologia , Dor do Câncer/patologia , Dor do Câncer/prevenção & controle , Linhagem Celular Tumoral , Janus Quinase 2/antagonistas & inibidores , Masculino , Camundongos , Camundongos Endogâmicos C3H , Doenças Neuroinflamatórias/patologia , Fator de Transcrição STAT3/antagonistas & inibidores , Transdução de Sinais/fisiologia , Medula Espinal/metabolismo , Medula Espinal/patologia
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