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1.
Small ; : e2311509, 2024 Apr 08.
Article in English | MEDLINE | ID: mdl-38587968

ABSTRACT

Developing robust non-platinum electrocatalysts with multifunctional active sites for pH-universal hydrogen evolution reaction (HER) is crucial for scalable hydrogen production through electrochemical water splitting. Here ultra-small ruthenium-nickel alloy nanoparticles steadily anchored on reduced graphene oxide papers (Ru-Ni/rGOPs) as versatile electrocatalytic materials for acidic and alkaline HER are reported. These Ru-Ni alloy nanoparticles serve as pH self-adaptive electroactive species by making use of in situ surface reconstruction, where surface Ni atoms are hydroxylated to produce bifunctional active sites of Ru-Ni(OH)2 for alkaline HER, and selectively etched to form monometallic Ru active sites for acidic HER, respectively. Owing to the presence of Ru-Ni(OH)2 multi-site surface, which not only accelerates water dissociation to generate reactive hydrogen intermediates but also facilitates their recombination into hydrogen molecules, the self-supported Ru90Ni10/rGOP hybrid electrode only takes overpotential of as low as ≈106 mV to deliver current density of 1000 mA cm-2, and maintains exceptional stability for over 1000 h in 1 m KOH. While in 0.5 m H2SO4, the Ru90Ni10/rGOP hybrid electrode exhibits acidic HER catalytic behavior comparable to commercially available Pt/C catalyst due to the formation of monometallic Ru shell. These electrochemical behaviors outperform some of the best Ru-based catalysts and make it attractive alternative to Pt-based catalysts toward highly efficient HER.

2.
Adv Mater ; : e2403803, 2024 Apr 10.
Article in English | MEDLINE | ID: mdl-38598181

ABSTRACT

Aqueous zinc-ion batteries are attractive post-lithium battery technologies for grid-scale energy storage because of their inherent safety, low cost and high theoretical capacity. However, their practical implementation in wide-temperature surroundings persistently confronts irregular zinc electrodeposits and parasitic side reactions on metal anode, which leads to poor rechargeability, low Coulombic efficiency and short lifespan. Here, this work reports lamellar nanoporous Cu/Al2Cu heterostructure electrode as a promising anode host material to regulate high-efficiency and dendrite-free zinc electrodeposition and stripping for wide-temperatures aqueous zinc-ion batteries. In this unique electrode, the interconnective Cu/Al2Cu heterostructure ligaments not only facilitate fast electron transfer but work as highly zincophilic sites for zinc nucleation and deposition by virtue of local galvanic couples while the interpenetrative lamellar channels serving as mass transport pathways. As a result, it exhibits exceptional zinc plating/stripping behaviors in aqueous hybrid electrolyte of diethylene glycol dimethyl ether and zinc trifluoromethanesulfonate at wide temperatures ranging from 25 to -30 °C, with ultralow voltage polarizations at various current densities and ultralong lifespan of >4000 h. The outstanding electrochemical properties enlist full cell of zinc-ion batteries constructed with nanoporous Cu/Al2Cu and ZnxV2O5/C to maintain high capacity and excellent stability for >5000 cycles at 25 and -30 °C.

3.
Angew Chem Int Ed Engl ; 63(18): e202402327, 2024 Apr 24.
Article in English | MEDLINE | ID: mdl-38467561

ABSTRACT

Metallic zinc is a promising anode material for rechargeable aqueous multivalent metal-ion batteries due to its high capacity and low cost. However, the practical use is always beset by severe dendrite growth and parasitic side reactions occurring at anode/electrolyte interface. Here we demonstrate dynamic molecular interphases caused by trace dual electrolyte additives of D-mannose and sodium lignosulfonate for ultralong-lifespan and dendrite-free zinc anode. Triggered by plating and stripping electric fields, the D-mannose and lignosulfonate species are alternately and reversibly (de-)adsorbed on Zn metal, respectively, to accelerate Zn2+ transportation for uniform Zn nucleation and deposition and inhibit side reactions for high Coulombic efficiency. As a result, Zn anode in such dual-additive electrolyte exhibits highly reversible and dendrite-free Zn stripping/plating behaviors for >6400 hours at 1 mA cm-2, which enables long-term cycling stability of Zn||ZnxMnO2 full cell for more than 2000 cycles.

4.
Small ; : e2310722, 2024 Jan 17.
Article in English | MEDLINE | ID: mdl-38229525

ABSTRACT

Aqueous aluminum-ion batteries are attractive post-lithium battery technologies for large-scale energy storage in virtue of abundant and low-cost Al metal anode offering ultrahigh capacity via a three-electron redox reaction. However, state-of-the-art cathode materials are of low practical capacity, poor rate capability, and inadequate cycle life, substantially impeding their practical use. Here layered manganese oxide that is pre-intercalated with benzoquinone-coordinated aluminum ions (BQ-Alx MnO2 ) as a high-performance cathode material of rechargeable aqueous aluminum-ion batteries is reported. The coordination of benzoquinone with aluminum ions not only extends interlayer spacing of layered MnO2 framework but reduces the effective charge of trivalent aluminum ions to diminish their electrostatic interactions, substantially boosting intercalation/deintercalation kinetics of guest aluminum ions and improving structural reversibility and stability. When coupled with Zn50 Al50 alloy anode in 2 m Al(OTf)3 aqueous electrolyte, the BQ-Alx MnO2 exhibits superior rate capability and cycling stability. At 1 A g-1 , the specific capacity of BQ-Alx MnO2 reaches ≈300 mAh g-1 and retains ≈90% of the initial value for more than 800 cycles, along with the Coulombic efficiency of as high as ≈99%, outperforming the Alx MnO2 without BQ co-incorporation.

5.
Angew Chem Int Ed Engl ; 63(10): e202319116, 2024 Mar 04.
Article in English | MEDLINE | ID: mdl-38225920

ABSTRACT

Enhanced bioenergy anabolism through transmembrane redox reactions in artificial systems remains a great challenge. Here, we explore synthetic electron shuttle to activate transmembrane chemo-enzymatic cascade reactions in a mitochondria-like nanoarchitecture for augmenting bioenergy anabolism. In this nanoarchitecture, a dendritic mesoporous silica microparticle as inner compartment possesses higher load capacity of NADH as proton source and allows faster mass transfer. In addition, the outer compartment ATP synthase-reconstituted proteoliposomes. Like natural enzymes in the mitochondrion respiratory chain, a small synthetic electron shuttle embedded in the lipid bilayer facilely mediates transmembrane redox reactions to convert NADH into NAD+ and a proton. These facilitate an enhanced outward proton gradient to drive ATP synthase to rotate for catalytic ATP synthesis with improved performance in a sustainable manner. This work opens a new avenue to achieve enhanced bioenergy anabolism by utilizing a synthetic electron shuttle and tuning inner nanostructures, holding great promise in wide-range ATP-powered bioapplications.


Subject(s)
NAD , Protons , NAD/metabolism , Electrons , Adenosine Triphosphate/metabolism , Mitochondria/metabolism , Electron Transport
6.
Angew Chem Int Ed Engl ; 62(45): e202312020, 2023 Nov 06.
Article in English | MEDLINE | ID: mdl-37728941

ABSTRACT

Single-ion conductive electrolytes can largely eliminate electrode polarization, reduce the proportion of anion migration and inhibit side reactions in batteries. However, they usually suffer from insufficient ion conductivity due to the strong interaction between cations and cationic receptors. Here we report an ultrafast light-responsive covalent organic frameworks (COF) with sulfonic acid groups modification as the acrylamide polymerization initiator. Benefiting from the reduced electrostatic interaction between Zn2+ and sulfonic acid groups through solvation effects, the as-prepared COF-based hydrogel electrolyte (TCOF-S-Gel) receives an ion conductivity of up to 27.2 mS/cm and Zn2+ transference number of up to 0.89. In addition, sufficient hydrogen bonds endow the single-ion conductive TCOF-S-Gel electrolyte to have good water retention and superb mechanical properties. The assembled Zn||TCOF-S-Gel||MnO2 full zinc-ion battery exhibits high discharge capacity (248 mAh/g at 1C), excellent rate capability (90 mAh/g at 10C) and superior cycling performance. These enviable results enlist the instantaneously photocured TCOF-S-Gel electrolyte to be qualified to large-scaled flexible high-performance quasi-solid-state zinc-ion batteries.

7.
J Am Chem Soc ; 145(38): 20907-20912, 2023 09 27.
Article in English | MEDLINE | ID: mdl-37606591

ABSTRACT

We demonstrate that ATP synthase-reconstituted proteoliposome coatings on the surface of microcapsules can realize photozyme-catalyzed oxidative phosphorylation. The microcapsules were assembled through layer-by-layer deposition of semiconducting graphitic carbon nitride (g-C3N4) nanosheets and polyelectrolytes. It is found that electrons from polyelectrolytes are transferred to g-C3N4 nanosheets, which enhances the separation of photogenerated electron-hole pairs. Thus, the encapsulated g-C3N4 nanosheets as the photozyme accelerate oxidation of glucose into gluconic acid to yield protons under light illumination. The outward transmembrane proton gradient is established to drive ATP synthase to synthesize adenosine triphosphate. With such an assembled system, light-driven oxidative phosphorylation is achieved. This indicates that an assembled photozyme can be used for oxidative phosphorylation, which creates an unusual way for chemical-to-biological energy conversion. Compared to conventional oxidative phosphorylation systems, such an artificial design enables higher energy conversion efficiency.


Subject(s)
Adenosine Triphosphate , Protons , Polyelectrolytes , Capsules , Catalysis
8.
Science ; 381(6654): 209-215, 2023 Jul 14.
Article in English | MEDLINE | ID: mdl-37440655

ABSTRACT

Perovskite solar cells (PSCs) consisting of interfacial two- and three-dimensional heterostructures that incorporate ammonium ligand intercalation have enabled rapid progress toward the goal of uniting performance with stability. However, as the field continues to seek ever-higher durability, additional tools that avoid progressive ligand intercalation are needed to minimize degradation at high temperatures. We used ammonium ligands that are nonreactive with the bulk of perovskites and investigated a library that varies ligand molecular structure systematically. We found that fluorinated aniliniums offer interfacial passivation and simultaneously minimize reactivity with perovskites. Using this approach, we report a certified quasi-steady-state power-conversion efficiency of 24.09% for inverted-structure PSCs. In an encapsulated device operating at 85°C and 50% relative humidity, we document a 1560-hour T85 at maximum power point under 1-sun illumination.

9.
Proc Natl Acad Sci U S A ; 120(23): e2301118120, 2023 Jun 06.
Article in English | MEDLINE | ID: mdl-37252984

ABSTRACT

For organic photovoltaic (OPV) devices to achieve consistent performance and long operational lifetimes, organic semiconductors must be processed with precise control over their purity, composition, and structure. This is particularly important for high volume solar cell manufacturing where control of materials quality has a direct impact on yield and cost. Ternary-blend OPVs containing two acceptor-donor-acceptor (A-D-A)-type nonfullerene acceptors (NFAs) and a donor have proven to be an effective strategy to improve solar spectral coverage and reduce energy losses beyond that of binary-blend OPVs. Here, we show that the purity of such a ternary is compromised during blending to form a homogeneously mixed bulk heterojunction thin film. We find that the impurities originate from end-capping C=C/C=C exchange reactions of A-D-A-type NFAs, and that their presence influences both device reproducibility and long-term reliability. The end-capping exchange results in generation of up to four impurity constituents with strong dipolar character that interfere with the photoinduced charge transfer process, leading to reduced charge generation efficiency, morphological instabilities, and an increased vulnerability to photodegradation. As a consequence, the OPV efficiency falls to less than 65% of its initial value within 265 h when exposed to up to 10 suns intensity illumination. We propose potential molecular design strategies critical to enhancing the reproducibility as well as reliability of ternary OPVs by avoiding end-capping reactions.

10.
Nat Commun ; 14(1): 1834, 2023 Apr 01.
Article in English | MEDLINE | ID: mdl-37005408

ABSTRACT

Hybrid magnonic systems are a newcomer for pursuing coherent information processing owing to their rich quantum engineering functionalities. One prototypical example is hybrid magnonics in antiferromagnets with an easy-plane anisotropy that resembles a quantum-mechanically mixed two-level spin system through the coupling of acoustic and optical magnons. Generally, the coupling between these orthogonal modes is forbidden due to their opposite parity. Here we show that the Dzyaloshinskii-Moriya-Interaction (DMI), a chiral antisymmetric interaction that occurs in magnetic systems with low symmetry, can lift this restriction. We report that layered hybrid perovskite antiferromagnets with an interlayer DMI can lead to a strong intrinsic magnon-magnon coupling strength up to 0.24 GHz, which is four times greater than the dissipation rates of the acoustic/optical modes. Our work shows that the DMI in these hybrid antiferromagnets holds promise for leveraging magnon-magnon coupling by harnessing symmetry breaking in a highly tunable, solution-processable layered magnetic platform.

11.
Nat Commun ; 14(1): 1811, 2023 Mar 31.
Article in English | MEDLINE | ID: mdl-37002220

ABSTRACT

Developing robust nonprecious-metal electrocatalysts with high activity towards sluggish oxygen-evolution reaction is paramount for large-scale hydrogen production via electrochemical water splitting. Here we report that self-supported laminate composite electrodes composed of alternating nanoporous bimetallic iron-cobalt alloy/oxyhydroxide and cerium oxynitride (FeCo/CeO2-xNx) heterolamellas hold great promise as highly efficient electrocatalysts for alkaline oxygen-evolution reaction. By virtue of three-dimensional nanoporous architecture to offer abundant and accessible electroactive CoFeOOH/CeO2-xNx heterostructure interfaces through facilitating electron transfer and mass transport, nanoporous FeCo/CeO2-xNx composite electrodes exhibit superior oxygen-evolution electrocatalysis in 1 M KOH, with ultralow Tafel slope of ~33 mV dec-1. At overpotential of as low as 360 mV, they reach >3900 mA cm-2 and retain exceptional stability at ~1900 mA cm-2 for >1000 h, outperforming commercial RuO2 and some representative oxygen-evolution-reaction catalysts recently reported. These electrochemical properties make them attractive candidates as oxygen-evolution-reaction electrocatalysts in electrolysis of water for large-scale hydrogen generation.

12.
Nat Mater ; 22(3): 329-337, 2023 Mar.
Article in English | MEDLINE | ID: mdl-36849816

ABSTRACT

Stability and current-voltage hysteresis stand as major obstacles to the commercialization of metal halide perovskites. Both phenomena have been associated with ion migration, with anecdotal evidence that stable devices yield low hysteresis. However, the underlying mechanisms of the complex stability-hysteresis link remain elusive. Here we present a multiscale diffusion framework that describes vacancy-mediated halide diffusion in polycrystalline metal halide perovskites, differentiating fast grain boundary diffusivity from volume diffusivity that is two to four orders of magnitude slower. Our results reveal an inverse relationship between the activation energies of grain boundary and volume diffusions, such that stable metal halide perovskites exhibiting smaller volume diffusivities are associated with larger grain boundary diffusivities and reduced hysteresis. The elucidation of multiscale halide diffusion in metal halide perovskites reveals complex inner couplings between ion migration in the volume of grains versus grain boundaries, which in turn can predict the stability and hysteresis of metal halide perovskites, providing a clearer path to addressing the outstanding challenges of the field.

13.
J Colloid Interface Sci ; 638: 76-83, 2023 May 15.
Article in English | MEDLINE | ID: mdl-36736120

ABSTRACT

Herein, we develop a strategy of matched spectral and temporal light management to improve photosynthetic efficiency by co-assembling natural thylakoid membrane (TM) with artificial long afterglow particle (LAP). To be specific, LAP with excellent stability and biocompatibility possesses the capabilities of light conversion and storage, optically-matched with the absorption of TM. These favorable features permit LAP as an additional well-functioned light source of photosynthesis performed by TM. As a consequence, enhanced photosynthesis is achieved after co-assembly, compared with pure TM. Under light, the rates of electron transfer, oxygen yield and adenosine triphosphate (ATP) production in this biohybrid architecture are boosted owing to down-conversion fluorescence emission from LAP. Under dark, persistent phosphorescence emission in charged LAP facilitates continual photosynthesis of TM, while that of pure TM almost stops immediately. This proof-of-concept work opens a new route to augment the photosynthetic efficiency of green plants by utilizing precise light-managed materials.


Subject(s)
Photosynthesis , Thylakoids , Electron Transport , Thylakoids/metabolism , Fluorescence
14.
Gynecol Oncol Rep ; 44(Suppl 1): 101110, 2022 Dec.
Article in English | MEDLINE | ID: mdl-36506036

ABSTRACT

Objectives: To investigate the clinical characteristics and prognosis of primary vaginal sarcoma. Methods: A retrospective analysis of patients with primary vaginal sarcoma treated at our center from 2000 to 2020 was conducted. Results: Fifteen patients were identified, among which 9 (60.0 %) patients had leiomyosarcoma, 2 (13.3 %) patients had Ewing's sarcoma, 2 (13.3 %) patients had rhabdomyosarcoma, 1 (6.7 %) patient had undifferentiated sarcoma, and 1 (6.7 %) patient had malignant peripheral schwannoma. Nine patients presented with vaginal mass that was the most common primary symptoms. Eleven patients received their primary surgery, and 7 of them received postoperative adjuvant chemotherapy or radiation therapy. The remaining 4 patients received initial chemotherapy and/or radiotherapy because of advanced stage. The distribution by stage was as follows: stage I in 10 patients, stage II in 1 patient, stage III in 2 patients and stage IV in 2 patients. The median follow-up was 43.7 months (10.1-137.5 months). Thirteen patients (86.7 %) had disease extent during follow-up, and among them, 11 patients (11/13, 84.6 %) developed local relapse or adjacent organ metastases, 1 patient (1/13, 7.7 %) developed liver metastases, and the remaining 1 patient (1/13, 7.7 %) developed lung metastases and local relapse during follow-up. Ten (10/13, 76.9 %) patients relapsed within 2 years after diagnosis. Eight patients (8/11, 72.7 %) with local recurrence or adjacent organ metastases received a secondary surgery treatment, and only 2 of them relapsed again. Two-year overall survival (OS) and 5-year OS were 80.0 % and 66.7 %, respectively. Patients with leiomyosarcoma had a tendency toward a better 5-year OS than those with other sarcomas (74.1 % vs 66.7 %, P = 0.307). Conclusions: Primary vaginal sarcomas are aggressive neoplasms with different presenting characteristics. Surgery is the main treatment for primary vaginal sarcoma and for local relapse vaginal sarcoma.

15.
Nat Commun ; 13(1): 2598, 2022 May 11.
Article in English | MEDLINE | ID: mdl-35545620

ABSTRACT

Enhancing the luminescence property without sacrificing the charge collection is one key to high-performance organic solar cells (OSCs), while limited by the severe non-radiative charge recombination. Here, we demonstrate efficient OSCs with high luminescence via the design and synthesis of an asymmetric non-fullerene acceptor, BO-5Cl. Blending BO-5Cl with the PM6 donor leads to a record-high electroluminescence external quantum efficiency of 0.1%, which results in a low non-radiative voltage loss of 0.178 eV and a power conversion efficiency (PCE) over 15%. Importantly, incorporating BO-5Cl as the third component into a widely-studied donor:acceptor (D:A) blend, PM6:BO-4Cl, allows device displaying a high certified PCE of 18.2%. Our joint experimental and theoretical studies unveil that more diverse D:A interfacial conformations formed by asymmetric acceptor induce optimized blend interfacial energetics, which contributes to the improved device performance via balancing charge generation and recombination.

16.
Adv Mater ; 34(9): e2109862, 2022 Mar.
Article in English | MEDLINE | ID: mdl-35007377

ABSTRACT

Solution-processed metal halide perovskite (MHP) single crystals (SCs) are in high demand for a growing number of printed electronic applications due to their superior optoelectronic properties compared to polycrystalline thin films. There is an urgent need to make SC fabrication facile, scalable, and compatible with the printed electronic manufacturing infrastructure. Here, a universal cosolvent evaporation (CSE) strategy is presented by which perovskite SCs and arrays are produced directly on substrates via printing and coating methods within minutes at room temperature from drying droplets. The CSE strategy successfully guides the supersaturation via controlled drying of droplets to suppress all crystallization pathways but one, and is shown to produce SCs of a wide variety of 3D, 2D, and mixed-cation/halide perovskites with consistency. This approach works with commonly used precursors and solvents, making it universal. Importantly, the SC consumes the precursor in the droplet, which enables the large-scale fabrication of SC arrays with minimal residue. Direct on-chip fabrication of 3D and 2D perovskite photodetector devices with outstanding performance is demonstrated. The approach shows that any MHP SC can now be manufactured on substrates using precision printing and scalable, high-throughput coating methods.

17.
Gynecol Oncol Rep ; 44: 101122, 2022 Dec.
Article in English | MEDLINE | ID: mdl-36589507

ABSTRACT

Objectives: To investigate the clinical characteristics and prognosis of primary vaginal sarcoma. Methods: A retrospective analysis of patients with primary vaginal sarcoma treated at our center from 2000 to 2020 was conducted. Results: Fifteen patients were identified, among which 9 (60.0 %) patients had leiomyosarcoma, 2 (13.3 %) patients had Ewing's sarcoma, 2 (13.3 %) patients had rhabdomyosarcoma, 1 (6.7 %) patient had undifferentiated sarcoma, and 1 (6.7 %) patient had malignant peripheral schwannoma. Nine patients presented with vaginal mass that was the most common primary symptoms. Eleven patients received their primary surgery, and 7 of them received postoperative adjuvant chemotherapy or radiation therapy. The remaining 4 patients received initial chemotherapy and/or radiotherapy because of advanced stage. The distribution by stage was as follows: stage I in 10 patients, stage II in 1 patient, stage III in 2 patients and stage IV in 2 patients. The median follow-up was 43.7 months (10.1-137.5 months). Thirteen patients (86.7 %) had disease extent during follow-up, and among them, 11 patients (11/13, 84.6 %) developed local relapse or adjacent organ metastases, 1 patient (1/13, 7.7 %) developed liver metastases, and the remaining 1 patient (1/13, 7.7 %) developed lung metastases and local relapse during follow-up. Ten (10/13, 76.9 %) patients relapsed within 2 years after diagnosis. Eight patients (8/11, 72.7 %) with local recurrence or adjacent organ metastases received a secondary surgery treatment, and only 2 of them relapsed again. Two-year overall survival (OS) and 5-year OS were 80.0 % and 66.7 %, respectively. Patients with leiomyosarcoma had a tendency toward a better 5-year OS than those with other sarcomas (74.1 % vs 66.7 %, P = 0.307). Conclusions: Primary vaginal sarcomas are aggressive neoplasms with different presenting characteristics. Surgery is the main treatment for primary vaginal sarcoma and for local relapse vaginal sarcoma.

18.
Adv Mater ; 34(6): e2105943, 2022 Feb.
Article in English | MEDLINE | ID: mdl-34818688

ABSTRACT

Fused-ring core nonfullerene acceptors (NFAs), designated "Y-series," have enabled high-performance organic solar cells (OSCs) achieving over 18% power conversion efficiency (PCE). Since the introduction of these NFAs, much effort has been expended to understand the reasons for their exceptional performance. While several studies have identified key optoelectronic properties that govern high PCEs, little is known about the molecular level origins of large variations in performance, spanning from 5% to 18% PCE, for example, in the case of PM6:Y6 OSCs. Here, a combined solid-state NMR, crystallography, and molecular modeling approach to elucidate the atomic-scale interactions in Y6 crystals, thin films, and PM6:Y6 bulk heterojunction (BHJ) blends is introduced. It is shown that the Y6 morphologies in BHJ blends are not governed by the morphology in neat films or single crystals. Notably, PM6:Y6 blends processed from different solvents self-assemble into different structures and morphologies, whereby the relative orientations of the sidechains and end groups of the Y6 molecules to their fused-ring cores play a crucial role in determining the resulting morphology and overall performance of the solar cells. The molecular-level understanding of BHJs enabled by this approach will guide the engineering of next-generation NFAs for stable and efficient OSCs.

19.
Article in Chinese | WPRIM (Western Pacific) | ID: wpr-934971

ABSTRACT

@#[摘 要] 目的:探究miR-323a-3p、四次穿膜蛋白超家族成员1(TM4SF1)在NSCLC组织和细胞中的表达及两者间的靶向调控关系,观察两者表达对A549细胞增殖、迁移、侵袭和裸鼠移植瘤生长的影响。方法:收集2014年1月至12月间青海省人民医院手术切除的20例NSCLC组织及其相应的癌旁组织,qPCR和WB法检测癌组织中miR-323a-3p、TM4SF1 mRNA 和TM4SF1蛋白的表达。向A549细胞转染miR-323a-3p mimic,采用MTT法、Transwell法、WB法检测miR-323a-3p过表达对细胞的增殖、迁移和侵袭以及TM4SF1、细胞周期蛋白D1(cyclin D1)、p21、MMP-2、MMP-9蛋白表达的影响。采用生物信息学预测工具StarBase和双荧光素酶报告基因实验分析miR-323a-3p与TM4SF1靶向关系。将si-TM4SF1转染至A549细胞,以及分别将miR-323a-3p mimic与pcDNA或pcDNA-TM4SF1共转染A549细胞,评估细胞增殖、迁移和侵袭能力的变化;同时建立各组细胞的BALB/c裸鼠移植瘤模型,在14、21和28 d时测量并计算移植瘤体积。结果:与癌旁组织相比,NSCLC组织中miR-323a-3p表达水平明显下调,TM4SF1 mRNA和蛋白表达水平显著上调(均P<0.01)。miR-323a-3p过表达或抑制TM4SF1表达都会降低A549 细胞的增殖、迁移、侵袭能力及cyclin D1、MMP-2、MMP-9蛋白表达而促进p21蛋白表达,并且抑制A549细胞裸鼠移植瘤的生长(均P<0.01)。生物信息学StarBase工具预测和双荧光素酶基因报告实验结果显示miR-323a-3p能够靶向结合TM4SF1基因并调控 TM4SF1的表达。上调TM4SF1表达后,miR-323a-3p过表达对A549细胞恶性生物学行为及cyclin D1、MMP-2、MMP-9蛋白表达、移植瘤生长的抑制作用均被部分逆转(均P<0.01),对p21蛋白表达的促进作用也被逆转(P<0.01)。结论:miR-323a-3p 通过靶向下调肺癌A549细胞中TM4SF1的表达抑制细胞的增殖、迁移、侵袭和裸鼠移植瘤生长。

20.
J Am Chem Soc ; 143(4): 1822-1835, 2021 02 03.
Article in English | MEDLINE | ID: mdl-33492129

ABSTRACT

In bulk-heterojunction organic solar cells, it is well established that the active-layer morphology significantly impacts device performance. However, morphology control remains very challenging. An interesting step in that direction was recently provided by the development of polymer donors that display a temperature-dependent aggregation behavior in solution; the aggregation characteristics were found indeed to play a determining role in the eventual active-layer morphology. Here, a combination of thermodynamic analyses, molecular dynamics simulations, and long-range corrected density functional theory calculations enables us (i) to establish the Flory-Huggins interaction parameter, χ, as a useful figure of merit that allows us to integrate the contributions from all inter-related molecular interactions and to describe the extent of polymer preaggregation in solution at room temperature; (ii) to correlate the χ values for various polymer solutions to the extent of polymer aggregation and the morphological characteristics of the active layers; and (iii) to assess how polymer-polymer and polymer-solvent intermolecular interactions contribute to the variations in χ values among different polymer solutions. We have chosen to examine four representative polymer donors (PBT4T-2OD, PBTff4T-2OD, PffBT4T-2OD, and PffBTff4T-2DT) in solution in chlorobenzene or dichlorobenzene. With χ as a robust bridge, our results provide an unprecedented, detailed description of the relationships among intermolecular interactions, extent of polymer solution aggregation, and morphological features of the active layers.

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