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1.
Small ; : e2310064, 2024 Apr 12.
Artigo em Inglês | MEDLINE | ID: mdl-38607265

RESUMO

Limited by the strong oxidation environment and sluggish reconstruction process in oxygen evolution reaction (OER), designing rapid self-reconstruction with high activity and stability electrocatalysts is crucial to promoting anion exchange membrane (AEM) water electrolyzer. Herein, trace Fe/S-modified Ni oxyhydroxide (Fe/S-NiOOH/NF) nanowires are constructed via a simple in situ electrochemical oxidation strategy based on precipitation-dissolution equilibrium. In situ characterization techniques reveal that the successful introduction of Fe and S leads to lattice disorder and boosts favorable hydroxyl capture, accelerating the formation of highly active γ-NiOOH. The Density Functional Theory (DFT) calculations have also verified that the incorporation of Fe and S optimizes the electrons redistribution and the d-band center, decreasing the energy barrier of the rate-determining step (*O→*OOH). Benefited from the unique electronic structure and intermediate adsorption, the Fe/S-NiOOH/NF catalyst only requires the overpotential of 345 mV to reach the industrial current density of 1000 mA cm-2 for 120 h. Meanwhile, assembled AEM water electrolyzer (Fe/S-NiOOH//Pt/C-60 °C) can deliver 1000 mA cm-2 at a cell voltage of 2.24 V, operating at the average energy efficiency of 71% for 100 h. In summary, this work presents a rapid self-reconstruction strategy for high-performance AEM electrocatalysts for future hydrogen economy.

2.
J Colloid Interface Sci ; 652(Pt B): 1588-1596, 2023 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-37666191

RESUMO

The poor conductivities and instabilities of accessible nickel oxyhydroxides hinder their use as oxygen evolution reaction (OER) electrocatalysts. Herein, we constructed Fe-NiOOH-OV-600, an Fe-doped nickel oxide hydroxide with abundant oxygen vacancies supported on nickel foam (NF), using a hydrothermal method and an electrochemical activation strategy involving 600 cycles of cyclic voltammetry, assisted by the precipitation/dissolution equilibrium of ferrous sulfide (FeS) in the electrolyte. This two-step method endows the catalyst with abundant Fe-containing active sites while maintaining the ordered structure of nickel oxide hydroxide (NiOOH). Characterization and density functional theory (DFT) calculations revealed that synergy between trace amounts of the Fe dopant and the oxygen vacancies not only promotes the generation of reconstructed active layers but also optimizes the electronic structure and adsorption capacity of the active sites. Consequently, the as-prepared Fe-NiOOH-OV-600 delivered large current densities of 100 and 1000 mA cm-2 for the OER at overpotentials of only 253 and 333 mV in 1 mol/L KOH. Moreover, the catalyst is stable for at least 100 h at 500 mA cm-2. This work provides insight into the design of efficient transition-metal-based electrocatalysts for the OER.

3.
J Am Chem Soc ; 145(27): 14686-14696, 2023 Jul 12.
Artigo em Inglês | MEDLINE | ID: mdl-37392183

RESUMO

The enantioconvergent C(sp3)-N cross-coupling of racemic alkyl halides with (hetero)aromatic amines represents an ideal means to afford enantioenriched N-alkyl (hetero)aromatic amines yet has remained unexplored due to the catalyst poisoning specifically for strong-coordinating heteroaromatic amines. Here, we demonstrate a copper-catalyzed enantioconvergent radical C(sp3)-N cross-coupling of activated racemic alkyl halides with (hetero)aromatic amines under ambient conditions. The key to success is the judicious selection of appropriate multidentate anionic ligands through readily fine-tuning both electronic and steric properties for the formation of a stable and rigid chelating Cu complex. Thus, this kind of ligand could not only enhance the reducing capability of a copper catalyst to provide an enantioconvergent radical pathway but also avoid the coordination with other coordinating heteroatoms, thereby overcoming catalyst poisoning and/or chiral ligand displacement. This protocol covers a wide range of coupling partners (89 examples for activated racemic secondary/tertiary alkyl bromides/chlorides and (hetero)aromatic amines) with high functional group compatibility. When allied with follow-up transformations, it provides a highly flexible platform to access synthetically useful enantioenriched amine building blocks.

4.
J Colloid Interface Sci ; 645: 410-419, 2023 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-37156149

RESUMO

Metal organic framework (MOF) is currently-one of the key catalysts for oxygen evolution reaction (OER), but its catalytic performance is severely limited by electronic configuration. In this study, cobalt oxide (CoO) on nickel foam (NF) was first prepared, which then wrapped it with FeBTC synthesized by ligating isophthalic acid (BTC) with iron ions by electrodeposition to obtain CoO@FeBTC/NF p-n heterojunction structure. The catalyst requires only 255 mV overpotential to reach a current density of 100 mA cm-2, and can maintain 100 h long time stability at 500 mA cm-2 high current density. The catalytic properties are mainly related to the strong induced modulation of electrons in FeBTC by holes in the p-type CoO, which results in stronger bonding and faster electron transfer between FeBTC and hydroxide. At the same time, the uncoordinated BTC at the solid-liquid interface ionizes acidic radicals which form hydrogen bonds with the hydroxyl radicals in solution, capturing them onto the catalyst surface for the catalytic reaction. In addition, CoO@FeBTC/NF also has strong application prospects in alkaline electrolyzers, which only needs 1.78 V to reach a current density of 1 A cm-2, and it can maintain long-term stability for 12 h at this current. This study provides a new convenient and efficient approach for the control design of the electronic structure of MOF, leading to a more efficient electrocatalytic process.

5.
Nature ; 618(7964): 294-300, 2023 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-36940729

RESUMO

Chiral amines are commonly used in the pharmaceutical and agrochemical industries1. The strong demand for unnatural chiral amines has driven the development of catalytic asymmetric methods1,2. Although the N-alkylation of aliphatic amines with alkyl halides has been widely adopted for over 100 years, catalyst poisoning and unfettered reactivity have been preventing the development of a catalyst-controlled enantioselective version3-5. Here we report the use of chiral tridentate anionic ligands to enable the copper-catalysed chemoselective and enantioconvergent N-alkylation of aliphatic amines with α-carbonyl alkyl chlorides. This method can directly convert feedstock chemicals, including ammonia and pharmaceutically relevant amines, into unnatural chiral α-amino amides under mild and robust conditions. Excellent enantioselectivity and functional-group tolerance were observed. The power of the method is demonstrated in a number of complex settings, including late-stage functionalization and in the expedited synthesis of diverse amine drug molecules. The current method indicates that multidentate anionic ligands are a general solution for overcoming transition-metal-catalyst poisoning.


Assuntos
Alquilação , Aminas , Catálise , Cobre , Amidas/química , Aminas/química , Cobre/química , Ligantes , Preparações Farmacêuticas/química
6.
Angew Chem Int Ed Engl ; 62(2): e202214709, 2023 01 09.
Artigo em Inglês | MEDLINE | ID: mdl-36357331

RESUMO

The copper-catalyzed enantioconvergent radical C(sp3 )-C(sp2 ) cross-coupling of tertiary α-bromo-ß-lactams with organoboronate esters could provide the synthetically valuable α-quaternary ß-lactams. The challenge arises mainly from the construction of sterically congested quaternary stereocenters between the tertiary alkyl radicals and chiral copper(II) species. Herein, we describe our success in achieving such transformations through the utilization of a copper/hemilabile N,N,N-ligand catalyst to forge the sterically congested chiral C(sp3 )-C(sp2 ) bond via a single-electron reduction/transmetalation/bond formation catalytic cycle. The synthetic potential of this approach is shown in the straightforward conversion of the corresponding products into many valuable building blocks. We hope that the developed catalytic cycle would open up new vistas for more enantioconvergent cross-coupling reactions.


Assuntos
Ésteres , beta-Lactamas , Cobre/química , Catálise , Elétrons
7.
Nat Chem ; 14(8): 949-957, 2022 08.
Artigo em Inglês | MEDLINE | ID: mdl-35618768

RESUMO

In contrast with the well-established enantioconvergent radical C(sp3)-C cross-coupling of racemic secondary alkyl electrophiles, the corresponding coupling of tertiary electrophiles to forge all-carbon quaternary stereocentres remains underexplored. The major challenge arises from the steric hindrance and the difficult enantio-differentiation of three distinct carbon substituents of prochiral tertiary radicals. Here we demonstrate a general copper-catalysed enantioconvergent C(sp3)-C(sp) cross-coupling of diverse racemic tertiary alkyl halides with terminal alkynes (87 examples). Key to the success is the rational design of chiral anionic N,N,N-ligands tailor-made for the computationally predicted outer-sphere radical group transfer pathway. This protocol provides a practical platform for the construction of chiral C(sp3)-C(sp/sp2/sp3) bonds, allowing for expedient access to an array of synthetically challenging quaternary carbon building blocks of interest in organic synthesis and related areas.


Assuntos
Alcinos , Cobre , Carbono/química , Ligantes , Níquel/química
8.
J Comput Chem ; 43(7): 465-476, 2022 03 15.
Artigo em Inglês | MEDLINE | ID: mdl-35023181

RESUMO

When the structures of 1342 molecules are optimized by 30 methods and 7 basis sets, there appear 289 (21.54%) problematic molecules and 112 (8.35%) failed ones. When 278 problematic molecules are compared, the best methods are BHandH and LC-wPBE, while B97D, BP86, HFS, VSXC, and HCTH are very unreliable. When 179 problematic molecules are computed with larger basis sets, the smallest mean absolute deviation (MAD) of bond angle (2.3°) is shown by QCISD(T)/cc-pVTZ, while the smallest MAD of bond length (0.021 Å), the best SUM1 (4.9 unit), and the best SUM2 (2.4 unit) are shown by DSDPBEP86(Full), DSDPBEP86, PBE1PBE-D3, MP2, and MP2(Full) in combination with aug-cc-pVQZ, cc-pVQZ, Def2QZVP, Def2TZVPP, and/or 6-311++G(3df,3pd). Very large basis sets, for example, larger than cc-pVTZ usually have to be used to obtain very good structures and the performances of many density-functional theory methods are encouraging. The best results may be the limit of modern computational chemistry.

9.
J Am Chem Soc ; 143(37): 15413-15419, 2021 09 22.
Artigo em Inglês | MEDLINE | ID: mdl-34505516

RESUMO

α-Chiral alkyl primary amines are virtually universal synthetic precursors for all other α-chiral N-containing compounds ubiquitous in biological, pharmaceutical, and material sciences. The enantioselective amination of common alkyl halides with ammonia is appealing for potential rapid access to α-chiral primary amines, but has hitherto remained rare due to the multifaceted difficulties in using ammonia and the underdeveloped C(sp3)-N coupling. Here we demonstrate sulfoximines as excellent ammonia surrogates for enantioconvergent radical C-N coupling with diverse racemic secondary alkyl halides (>60 examples) by copper catalysis under mild thermal conditions. The reaction efficiently provides highly enantioenriched N-alkyl sulfoximines (up to 99% yield and >99% ee) featuring secondary benzyl, propargyl, α-carbonyl alkyl, and α-cyano alkyl stereocenters. In addition, we have converted the masked α-chiral primary amines thus obtained to various synthetic building blocks, ligands, and drugs possessing α-chiral N-functionalities, such as carbamate, carboxylamide, secondary and tertiary amine, and oxazoline, with commonly seen α-substitution patterns. These results shine light on the potential of enantioconvergent radical cross-coupling as a general chiral carbon-heteroatom formation strategy.

10.
Nanoscale ; 13(31): 13463-13472, 2021 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-34477751

RESUMO

The oriented distribution and strong bonding of Fe active sites in multiple metal hydroxides are crucial to modulate activity and stability for efficient oxygen evolution reaction (OER). However, the dispersion and inevitable dissolution of Fe species still need to be addressed through deliberate design. Here, trace amounts of Fe chelated with tannic acid (TA) are precisely anchored to ultrathin Co hydroxides (TF@Co(OH)2-t) through a new anodic interfacial coordination assembly strategy: firstly, the ZIF-67@Co(OH)2 precursor with ultrathin Co(OH)2 nanosheets vertically grown on the shell, provides abundant active sites and sufficient anchoring regions for subsequent TA-Fe coating; secondly, the TA-Fe ligand network quickly and robustly coats the surface of the Co(OH)2via positive potential-driven chronopotentiometry, yielding TF@Co(OH)2-t with good dispersion and controllable Fe species. The TA-Fe network efficiently activates Co species and prevents the dissolution of Fe ions. Physical characterization and DFT simulations reveal that the optimized OER activity with 317 mV at 10 mA cm-2 for TF@Co(OH)2-500 can be attributed to the accelerated electron transfer, increased active sites, and the moderate fall in d-band center levels due to Fe integration. Moreover, prolonged stability is realized benefiting from the robust TA-Fe coating protecting the actives sites.

11.
ACS Appl Mater Interfaces ; 13(29): 34438-34446, 2021 Jul 28.
Artigo em Inglês | MEDLINE | ID: mdl-34264054

RESUMO

Promoting the reconstruction of electrocatalysts during the oxygen evolution reaction (OER) is generally regarded as a promising strategy for enhanced activity. F anions with strong electronegativity are predicted to enhance this transformation. Herein, a fluorine-anion doping route is proposed to convert the well-latticed NiMoO4@MNF to amorphous F-NiMoO4@MNF by a facile and versatile molten salt strategy. The well-defined nanorod arrays guarantee abundant exposed active sites, rapid mass transfer, and fast gas bubble release. Moreover, the emerged loose amorphous structure is conducive to the dynamic migration of F species and effective penetration of the electrolyte; therefore, the resulting exchange between F and hydroxide anions induces the formation of an active oxy(hydroxide) layer, thus finally optimizing the electronic structure and absorption/desorption energy on the surface of F-NiMoO4@MNF. The boosted OER performance of reconstructed F-NiMoO4@MNF is reliably confirmed by a low overpotential of 188 mV at 50 mA cm-2, a small Tafel slope of 33.8 mV dec-1, and favorable long-term stability. In addition, accelerated hydrogen evolution is observed, which is ascribed to the finely tuned electron distribution. This work would provide a new reconstruction route assisted by F-anion doping to the development of high-performance catalysts.

12.
J Opt Soc Am A Opt Image Sci Vis ; 38(6): 808-816, 2021 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-34143150

RESUMO

All-optical switch and multiple logic gates have been demonstrated using a hybrid-cavity semiconductor laser composed of a square microcavity and a Fabry-Perot cavity experimentally. In this paper, two-section tri-mode rate equations with optical injection terms are proposed and applied to study all-optical logic gates of NOT, NOR, and NAND operations utilizing the hybrid-cavity laser. Steady-state and dynamical characteristics of all-optical multiple logic gates are simulated, taking into account the influence of mode frequency detuning, gain suppression coefficients, mode Q factor, injection energy, and biasing current. All-optical logic NOT, NOR, and NAND gates up to 20, 15, and 20 Gbit/s are obtained numerically with dynamic extinction ratios of over 20, 20, and 10 dB, respectively, which are potential response speeds of the all-optical logic gates based on the hybrid-cavity semiconductor lasers.

13.
Sci Rep ; 11(1): 11835, 2021 06 04.
Artigo em Inglês | MEDLINE | ID: mdl-34088935

RESUMO

There is still a lack of competing risk analysis of patients with papillary renal cell carcinoma (pRCC) following surgery. We performed the cumulative incidence function (CIF) to estimate the absolute risks of cancer-specific mortality (CSM) and other-cause mortality (OCM) of pRCC over time, and constructed a nomogram predicting the probability of 2-, 3- and 5-year CSM based on competing risk regression. A total of 5993 pRCC patients who underwent nephrectomy between 2010 and 2016 were identified from the Surveillance, Epidemiology, and End Results (SEER) database. The 2-, 3-, 5-year CSM rates were 3.2%, 4.4% and 6.5%, respectively, and that of OCM were 3.2%, 5.0% and 9.3%, respectively. The estimates of 5-year cumulative mortality were most pronounced among patients aged > 75 years in OCM (17.0%). On multivariable analyses, age, tumor grade, T stage, N stage, and with or without bone, liver and lung metastases were identified as independent predictors of CSM following surgery and were integrated to generate the nomogram. The nomogram achieved a satisfactory discrimination with the AUCt of 0.730 at 5-year, and the calibration curves presented impressive agreements. Taken together, age-related OCM is a significant portion of all-cause mortality in elderly patients and our nomogram can be used for decision-making and patient counselling.


Assuntos
Carcinoma de Células Renais/mortalidade , Neoplasias Renais/mortalidade , Nomogramas , Análise de Sobrevida , Idoso , Área Sob a Curva , Calibragem , Carcinoma de Células Renais/epidemiologia , Tomada de Decisões , Feminino , Humanos , Incidência , Neoplasias Renais/epidemiologia , Masculino , Oncologia/métodos , Pessoa de Meia-Idade , Análise Multivariada , Metástase Neoplásica , Estadiamento de Neoplasias , Nefrectomia/métodos , Probabilidade , Curva ROC , Estudos Retrospectivos , Risco , Fatores de Risco , Programa de SEER , Software , Estados Unidos , Urologia/métodos
14.
ACS Appl Mater Interfaces ; 13(15): 17450-17458, 2021 Apr 21.
Artigo em Inglês | MEDLINE | ID: mdl-33822578

RESUMO

FeOOH on the real catalytic interface for the oxygen evolution reaction (OER) is chemically unstable to dissolve in alkaline media. Herein, based on the perspective of the dynamically stable interface, we purposely design the well-dispersed nanorod arrays of CoMoO4 as a host on activated iron foam (IF) to realize the optimal redeposition of FeOOH, constructing a self-sacrificial template rich in the FeOOH surface. Notably, at long-time oxidation potential, the precatalyst FeOOH-CoMoO4 can realize MoO42- dissolution and redeposition of Co oxyhydroxides on FeOOH host simultaneously, constructing a dynamically stable Fe(Co)OOH interface. The introduction of CoOOH improves conductivity and provides synergistic effect with FeOOH to lower the energy barrier for OER and maintain long-time stability, eventually exhibiting a low overpotential of 298 mV to reach the current density of 100 mA cm-2 and high stability over 60 h. This work demonstrates the feasibility of manipulating metal dissolution-redeposition process for a dynamically stable interface.

15.
Angew Chem Int Ed Engl ; 60(1): 380-384, 2021 01 04.
Artigo em Inglês | MEDLINE | ID: mdl-32949177

RESUMO

The development of enantioconvergent cross-coupling of racemic alkyl halides directly with heteroarene C(sp2 )-H bonds has been impeded by the use of a base at elevated temperature that leads to racemization. We herein report a copper(I)/cinchona-alkaloid-derived N,N,P-ligand catalytic system that enables oxidative addition with racemic alkyl bromides under mild conditions. Thus, coupling with azole C(sp2 )-H bonds has been achieved in high enantioselectivity, affording a number of potentially useful α-chiral alkylated azoles, such as 1,3,4-oxadiazoles, oxazoles, and benzo[d]oxazoles as well as 1,3,4-triazoles, for drug discovery. Mechanistic experiments indicated facile deprotonation of an azole C(sp2 )-H bond and the involvement of alkyl radical species under the reaction conditions.

16.
Sci Rep ; 10(1): 17675, 2020 10 19.
Artigo em Inglês | MEDLINE | ID: mdl-33077762

RESUMO

The roles played by several inflammatory factors in screening for prostate cancer (PCa) among gray area patients, namely those with serum prostate-specific antigen (PSA) levels between 4 and 10 ng/ml, have not been completely identified, and few effective diagnostic nomograms have been developed exclusively for these patients. We aimed to investigate new independent predictors of positive biopsy (PB) results and develop a novel diagnostic nomogram for this group of patients. The independent predictors of PB results were identified, and a nomogram was constructed using multivariate logistic regression analysis based on a cohort comprising 401 Gy area patients diagnosed at Xijing Hospital (Xi'an, China) between January 2016 and December 2019. The predictive accuracy of the nomogram was assessed using the receiver operating characteristic curve, and the nomogram was calibrated by comparing the prediction with the observation. The performance of the nomogram was further validated using an independent cohort. Finally, lymphocyte-to-monocyte ratio (LMR) > 4.11 and red blood cell distribution width (RDW)-standard deviation (SD) > 42.9 fl were identified as independent protective predictors of PB results, whereas PSA density (PSAD) > 0.141 was identified as an independent risk predictor. The nomogram established using PSAD, LMR, and RDW-SD was perfectly calibrated, and its predictive accuracy was superior to that of PSAD in both internal and external validations (0.827 vs 0.769 and 0.765 vs 0.713, respectively). This study is the first to report the importance of LMR and RDW-SD in screening for PCa among gray area patients and to construct an exclusive nomogram to predict the individual risk of positive 13-core biopsy results in this group of patients. With superior performance over PSAD, our nomogram will help increase the accuracy of PCa screening, thereby avoiding unnecessary biopsy.


Assuntos
Nomogramas , Neoplasias da Próstata/diagnóstico , Neoplasias da Próstata/patologia , Idoso , Biópsia , Estudos de Coortes , Humanos , Masculino , Pessoa de Meia-Idade , Antígeno Prostático Específico/sangue , Neoplasias da Próstata/sangue
17.
J Am Chem Soc ; 142(20): 9501-9509, 2020 05 20.
Artigo em Inglês | MEDLINE | ID: mdl-32338510

RESUMO

A copper-catalyzed intermolecular three-component asymmetric radical 1,2-carboalkynylation of alkenes has been developed, providing straightforward access to diverse chiral alkynes from readily available alkyl halides and terminal alkynes. The utilization of a cinchona alkaloid-derived multidentate N,N,P-ligand is crucial for the efficient radical generation from mildly oxidative precursors by copper and the effective inhibition of the undesired Glaser coupling side reaction. The substrate scope is broad, covering (hetero)aryl-, alkynyl-, and aminocarbonyl-substituted alkenes, (hetero)aryl and alkyl as well as silyl alkynes, and tertiary to primary alkyl radical precursors with excellent functional group compatibility. Facile transformations of the obtained chiral alkynes have also been demonstrated, highlighting the excellent complementarity of this protocol to direct 1,2-dicarbofunctionalization reactions with C(sp2/sp3)-based reagents.

18.
Nat Chem ; 11(12): 1158-1166, 2019 12.
Artigo em Inglês | MEDLINE | ID: mdl-31636393

RESUMO

Continued development of the Sonogashira coupling has made it a well established and versatile reaction for the straightforward formation of C-C bonds, forging the carbon skeletons of broadly useful functionalized molecules. However, asymmetric Sonogashira coupling, particularly for C(sp3)-C(sp) bond formation, has remained largely unexplored. Here we demonstrate a general stereoconvergent Sonogashira C(sp3)-C(sp) cross-coupling of a broad range of terminal alkynes and racemic alkyl halides (>120 examples) that are enabled by copper-catalysed radical-involved alkynylation using a chiral cinchona alkaloid-based P,N-ligand. Industrially relevant acetylene and propyne are successfully incorporated, laying the foundation for scalable and economic synthetic applications. The potential utility of this method is demonstrated in the facile synthesis of stereoenriched bioactive or functional molecule derivatives, medicinal compounds and natural products that feature a range of chiral C(sp3)-C(sp/sp2/sp3) bonds. This work emphasizes the importance of radical species for developing enantioconvergent transformations.

19.
Biochimie ; 163: 1-11, 2019 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-30998968

RESUMO

Osteosarcoma is an aggressive bone tumor characterized by a high level of genetic instability and recurring DNA deletions and amplifications. This study aims to investigate how microRNA-496 (miR-496) affects proliferation, invasion, and migration of human osteosarcoma (OS) cells and in vivo tumorigenicity by targeting eukaryotic translation initiation factor 4E (eIF4E). Microarray-based gene expression profiling involving OS was used in order to identify differentially expressed genes. After that, the interaction between miR-496 expression and OS patients' survival rate was determined. The expression pattern of miR-496 and eIF4E was determined in OS tissues and cells, and their potential relationship was further analyzed by using the dual luciferase reporter gene assay. With the purpose of identifying the functional role miR-496 in OS, cell proliferation, migration, and invasion were measured in cells treated with miR-496 mimic or inhibitor. A nude mouse model was constructed in order to investigate the regulatory effects of miR-496 on tumor growth in vivo by regulating eIF4E. OS cells exhibited a down-regulated expression of miR-496 and an up-regulated expression of eIF4E. miR-496 expression was positively correlated to OS patients' survival rate. Bioinformatics analysis suggested eIF4E would be a direct target of miR-496, and the expression of eIF4E was inhibited by overexpression of miR-496. miR-496 elevation was found to exert suppressive effects on OS cell proliferation, migration and invasion in vitro and tumor growth in vivo, with the effects being reversed using miR-496 depletion. Altogether, the above findings support a conclusion that miR-496 could work as a tumor suppressor in OS through down-regulation of eIF4E. This study may provide a novel target for treatment of OS.


Assuntos
Neoplasias Ósseas/metabolismo , Fator de Iniciação 4E em Eucariotos/genética , MicroRNAs/metabolismo , Osteossarcoma/metabolismo , Animais , Neoplasias Ósseas/genética , Neoplasias Ósseas/fisiopatologia , Linhagem Celular Tumoral , Movimento Celular , Proliferação de Células , Feminino , Perfilação da Expressão Gênica , Regulação Neoplásica da Expressão Gênica , Humanos , Masculino , Camundongos , Camundongos Nus , Invasividade Neoplásica , Osteossarcoma/genética , Osteossarcoma/fisiopatologia , RNA Mensageiro/metabolismo , Ensaios Antitumorais Modelo de Xenoenxerto
20.
Appl Opt ; 57(25): 7242-7248, 2018 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-30182985

RESUMO

AlGaInAs/InP waveguide-coupled deformed hexagonal resonator microlasers with enhanced mode quality (Q)-factors are demonstrated for realizing single-transverse-mode operation. A circular hole is introduced to the center of the hexagonal resonators with rounded corners to enhance the mode Q-factors and suppress high-order transverse modes simultaneously. Single-mode lasing with side-mode suppression ratios up to 40 dB is obtained for the 10-µm-sidelength hexagonal microlasers with a center hole. All the lasing spectra demonstrate pure single-transverse-mode properties within the whole tuning range of injection current, and mode hopping with one, two, and three longitudinal-mode intervals is observed due to the mode Q-factor modification by the center holes. To further reduce the device size and threshold current, the deformed hexagonal resonator microlasers with the flat sides replaced by circular arcs are analyzed and demonstrated experimentally. The Q-factors of the fundamental transverse modes can be enhanced by two orders of magnitude due to the convergence effect of the circular sides by optimizing the deformation amplitude, while the single-transverse-mode property is still maintained. A threshold current of 2.4 mA is realized for a circular-side hexagonal microlaser with the side length of 8.5 µm and the deformation amplitude of 0.55 µm.

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