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1.
Biochem Biophys Res Commun ; 522(3): 743-748, 2020 Feb 12.
Artigo em Inglês | MEDLINE | ID: mdl-31791581

RESUMO

Rheumatoid arthritis is a chronic and systemic autoimmune disease, which affects approximately 1% of the adult population worldwide. The present study investigated the therapeutic effect of theacrine (TC) on arthritis and its mechanisms in Freund's incomplete adjuvant (FIA)-induced SD rats. Rats were randomly divided into 5 groups: i) healthy control; ii) model; iii) positive control with methotrexate (MTX); iv) treatment with 12.5 mg/kg TC; and v) treatment with 25.0 mg/kg TC. The apparent scores, including changes in body weights, degree of paw swelling and arthritis indicators, were analyzed to evaluate the anti-chronic inflammatory effect of TC. The levels of interleukin (IL)-6 and transforming growth factor-ß (TGF-ß) in serum were measured by enzyme-linked immunosorbent assay. The protein and RNA expression levels of the critical factors in rats were measured to elucidate the mechanisms responsible for chronic inflammation and to verify molecular indexes of chronic inflammatory conditions. TC notably suppressed the severity of FIA-induced rat by attenuating the apparent scores, animal weight and inflammatory indexes in the 25 mg/kg TC group compared with the FIA rat model. Furthermore, TC significantly decreased the levels of IL-6 and increased the levels of TGF-ß. Histopathological examinations indicated that TC rescued the synovial hyperplasia and inflammatory cell infiltration in joint tissues. In addition, TC enhanced TGF-ß-mediated shifts in inflammatory marker expression in joint tissue. Overall, the present study demonstrated that TC exerted a superior anti-arthritic effect via the suppression of IL-6 and the activation of TGF-ß by the TGF-ß/SMAD pathway.

2.
Opt Express ; 27(21): 30798-30809, 2019 Oct 14.
Artigo em Inglês | MEDLINE | ID: mdl-31684323

RESUMO

Ultrashort laser pulses, featuring remarkable spectral tunability, are highly demanded for nonlinear light-matter interactions in a variety of molecules. Here, we report on the generation of soliton-plasma-driven ultrashort pulses with both bandwidth- and wavelength-tunability in the visible spectral region. Using He-filled single-ring photonic crystal fiber (SR-PCF), we demonstrate in the experiments that the spectral bandwidths of blueshifting solitons can be manipulated by adjusting the input pulse energy, gas pressure and core diameter of the SR-PCF, while the central wavelengths of these solitons can be continuously tuned over 200 nm. We found that in a large-core SR-PCF (24.6-µm core diameter), the bandwidths of blueshifting solitons can be effectively broaden to near 100 nm, pointing out the possibility of generating few-cycle, wavelength-tunable visible pulses using this set-up. In addition, we observed in the experiments that in a small-core SR-PCF (with a core diameter of 17 µm), the blueshifting solitons show little residual light near the pump wavelength, resulting in a high-efficiency frequency up-conversion process. These experimental results, confirmed by numerical simulations, pave the way to a new generation of compact, ultrashort light sources with excellent tunability at visible wavelengths, which may have many applications in the fields of time-resolved spectroscopy and ultrafast nonlinear optics.

3.
Opt Express ; 27(20): 27873-27881, 2019 Sep 30.
Artigo em Inglês | MEDLINE | ID: mdl-31684548

RESUMO

A common-path dual-wavelength phase demodulation technique for extrinsic Fabry-Perot interferometric (EFPI) sensors is proposed on the basis of a broadly tunable modulated grating Y-branch (MG-Y) laser. It can address the three main concerns of existing dual-wavelength phase interrogation methods: the imbalances and disturbances caused by two optical paths utilizing two lasers or two photodetectors, the restrictions between two operating wavelengths and the cavity length of EFPI, and the difficulty in eliminating the direct current (DC) component of the interferometric fringe. Dual-wavelength phase interrogation is achieved in a common optical path through high-speed wavelength switching. Taking advantage of the MG-Y laser's full spectrum scanning ability (1527 ∼ 1567 nm), initial cavity length and DC component can be directly measured by white light interferometry. Two quadrature wavelengths are then selected to perform high speed phase demodulation scheme. Three polyethylene terephthalate (PET) diaphragm based EFPI acoustic sensors with cavity lengths of 127.954 µm, 148.366 µm and 497.300 µm, are used to demonstrate the effectiveness.

4.
Artigo em Inglês | MEDLINE | ID: mdl-31725367

RESUMO

OBJECTIVE: This study investigated the performance of a dynamic orthodontic moment prediction model by analyzing orthodontic treatment processes with different utility archwires. METHOD: The prediction model was based on a wax resistance model, the combined load theory of beams and the lateral buckling theory of prisms. The experimental samples used herein comprised 12 different archwire configurations (3 different materials and 4 different diameters). The utility archwire was ligated to the 11th tooth of the wax mold, which was immersed in a constant temperature water environment at 75°C for 2 min. RESULT: As the archwire diameter increased, increasing the elastic modulus of the archwire produced greater increases in the change rate of the orthodontic moment with respect to the lateral arc length. A comparison of the orthodontic moment values from three common orthodontic archwire materials revealed the following trend: stainless steel wire>Australian wire>Ni-Ti wire. CONCLUSION: The accuracy of the utility archwire dynamic orthodontic moment prediction model was verified through a comparison of the experimental measurements and theoretical calculations. SIGNIFICANCE: The presented model can help make timely adjustments to orthodontic treatment schemes, improve the orthodontic effect, shorten the treatment cycle, and provide reference and guidance that enables orthodontists to carry out orthodontic treatment safely and efficiently.

5.
Opt Lett ; 44(22): 5402-5405, 2019 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-31730068

RESUMO

In this Letter, we propose a quadrature phase-stabilized three-wavelength demodulation technique for the interrogation of fiber-optic Fabry-Perot acoustic sensors. It is based on accurate and fast tuning of a monolithic modulated grating Y-branch laser. Three quadrature wavelengths are chosen to perform high-speed cavity length demodulation by wavelength switching, thereby avoiding imbalances and disturbances between the three optical paths in conventional three-wavelength quadrature phase-demodulation systems. A feedback-stabilization scheme for maintaining the quadrature phase condition is proposed for the first time, to the best of our knowledge, providing potential for long-term monitoring in harsh environments.

6.
J Vis Exp ; (150)2019 Aug 12.
Artigo em Inglês | MEDLINE | ID: mdl-31449244

RESUMO

aza-Michael adducts of tricarbonyl(tropone)iron are synthesized by two different methods. Primary aliphatic amines and cyclic secondary amines participate in a direct aza-Michael reaction with tricarbonyl(tropone)iron under solvent-free conditions. Less nucleophilic aniline derivatives and more hindered secondary amines add efficiently to the cationic tropone complex formed by protonation of tricarbonyl(tropone)iron. While the protocol utilizing the cationic complex is less efficient overall for accessing the aza-Michael adducts than the direct, solvent-free addition to the neutral complex, it allows the use of a broader range of amine nucleophiles. Following protection of the amine of the aza-Michael adduct as a tert-butyl carbamate, the diene is decomplexed from the iron tricarbonyl fragment upon treatment with cerium(IV) ammonium nitrate to provide derivatives of 6-aminocyclohepta-2,4-dien-1-one. These products can serve as precursors to diverse compounds containing a seven-membered carbocyclic ring. Because the demetallation requires protection of the amine as a carbamate, the aza-Michael adducts of secondary amines cannot be decomplexed using the protocol described here.

7.
J Am Chem Soc ; 141(25): 9769-9772, 2019 Jun 26.
Artigo em Inglês | MEDLINE | ID: mdl-31180212

RESUMO

Photon upconversion employing semiconductor nanocrystals (NCs) makes use of their large and tunable absorption to harvest light in the near-infrared (NIR) wavelengths as well as their small gap between singlet and triplet excited states to reduce energy losses. Here, we report the highest QY (11.8%) thus far for the conversion of NIR to yellow photons by improving the quality of the PbS NC. This high QY was achieved by using highly purified lead and thiourea precursors. This QY is 2.6 times higher than from NCs prepared with commercially available lead and sulfide precursors. Transient absorption spectroscopy reveals two reasons for the enhanced QY: longer intrinsic exciton lifetimes of PbS NCs and the ability to support a longer triplet lifetime for the surface-bound transmitter molecule. Overall, this results in a higher efficiency of triplet exciton transfer from the PbS NC light absorber to the emitter and thus a higher photon upconversion QY.

8.
Biomed Microdevices ; 21(1): 13, 2019 02 06.
Artigo em Inglês | MEDLINE | ID: mdl-30725200

RESUMO

Micro components processed by injection molding still have a defect of bad precision and short life. A Zr- based metallic glass was reported for injection mold insert which can solve the problem well. The microstructure of metallic glass mold insert can be fabricated by wire electrical discharge machining-low speed (WEDM-LS), WEDM-LS has higher machining accuracy than WEDM-high speed, and X-ray diffraction curves show that the processed sample still retained better amorphous characteristic, afterward, time-temperature-transformation diagram shows metallic glass has a long service life in production. Finally, under the observe of scanning electron microscope, it is found that the products after injection molding not only completely replicates the structure on metallic glass but also have a better surface morphology. These experiments show that processing a sophisticated and durable Zr-based metallic glass mold by WEDM-LS is good for getting micro structure injection of polymers. It also provides a good mold material and machining method for injection industry.


Assuntos
Sistemas de Liberação de Medicamentos/instrumentação , Sistemas de Liberação de Medicamentos/métodos , Vidro , Polímeros/farmacologia , Zircônio , Humanos , Propriedades de Superfície , Titânio
9.
J Phys Chem Lett ; 9(21): 6198-6206, 2018 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-30380890

RESUMO

Semiconductor nanocrystals (NCs) can initiate energy and charge transfer in multiple applications with their unique optical and electronic properties. In particular, NCs are excellent light absorbers for initiating triplet energy transfer (TET) to organic molecules, a key step in triplet-fusion-based photon upconversion. Triplet energy transfer across this inorganic-organic interface is one of the bottlenecks that currently limits the overall photon upconversion quantum yield. In this Perspective, we summarize the progress made in the past three years on this hybrid photon upconversion platform. We discuss the effects of NC size, composition, and surface states on TET. Nanocrystal surface engineering may address the loss mechanisms arising from defect states and exciton-phonon coupling. Alternative materials for NC triplet photosensitizers that do not contain toxic heavy metals will be especially useful for various biological applications.

10.
ACS Appl Mater Interfaces ; 10(31): 25930-25935, 2018 Aug 08.
Artigo em Inglês | MEDLINE | ID: mdl-30032615

RESUMO

Click chemistry has been widely used in bioconjugation, polymer synthesis, and the development of new anticancer drugs. Here, we report a nanoporous membrane made of AuCu alloy nanowires, which can effectively catalyze copper(I)-catalyzed 1,3-dipolar cycloaddition between azide and terminal alkyne (CuAAC) in flow condition with pressure less than one bar. Comparison studies of the nanowires before and after the reaction using X-ray photoelectron spectroscopy reveal Cu(0) and Cu(I) are main species that promote the reaction. This simple strategy can be used to synthesize a variety of compounds with triazole linkage and extended to gram level chemical production.


Assuntos
Nanoporos , Alquinos , Azidas , Catálise , Química Click , Cobre , Reação de Cicloadição , Pressão
11.
Opt Express ; 26(26): 34977-34993, 2018 Dec 24.
Artigo em Inglês | MEDLINE | ID: mdl-30650913

RESUMO

We numerically investigate the generation of wavelength-tunable few-cycle pulses in the visible spectral region through soliton-plasma interactions. We found that in a He-filled single-ring photonic crystal fiber (SR-PCF), soliton-plasma interactions could shift the optical spectra of pulses propagating in the fiber to shorter wavelengths. Through adjusting the single pulse energy launched into the fiber, the central wavelength of these blueshifting pulses could be continuously tuned over hundreds of nanometers, while maintaining a high energy conversion efficiency of >57%. Moreover, we observed that during the nonlinear pulse propagation in the SR-PCF, soliton self-compression effects enhanced the plasma density in the fiber at high pulse energies, which could modulate the phase-matching condition of ultraviolet (UV) dispersive wave (DW) generation. Furthermore, we employed the recently-developed model to study numerically the loss and dispersion of the SR-PCF in its resonant and anti-resonant spectral regions, and demonstrated the remarkable influence of the core-cladding resonance on the process of soliton-plasma interactions. The numerical results demonstrated here pave the way to develop wavelength-tunable, few-cycle light sources in the visible region, which may have considerable application potential in pump-probe spectroscopy and strong-field physics.

12.
ACS Appl Mater Interfaces ; 10(1): 635-641, 2018 Jan 10.
Artigo em Inglês | MEDLINE | ID: mdl-29278492

RESUMO

Two new UiO-68 type of Zr-MOFs featuring redox non-innocent catechol-based linkers of different redox activities have been synthesized through a de novo mixed-linker strategy. Metalation of the MOFs with Cu(II) precursors triggers the reduction of Cu(II) by the phenyl-catechol groups to Cu(I) with the concomitant formation of semiquinone radicals as evidenced by EPR and XPS characterization. The MOF-supported catalysts are selective toward the allylic oxidation of cyclohexene and it is found that the presence of in situ-generated Cu(I) species exhibits enhanced catalytic activity as compared to a similar MOF with Cu(II) metalated naphthalenyl-dihydroxy groups. This work unveils the importance of metal-support redox interactions in the catalytic activity of MOF-supported catalysts which are not easily accessible in traditional metal oxide supports.

13.
Angew Chem Int Ed Engl ; 56(52): 16583-16587, 2017 12 22.
Artigo em Inglês | MEDLINE | ID: mdl-29141118

RESUMO

A sub-monolayer CdS shell on PbS quantum dots (QDs) enhances triplet energy transfer (TET) by suppressing competitive charge transfer from QDs to molecules. The CdS shell increases the linear photon upconversion quantum yield (QY) from 3.5 % for PbS QDs to 5.0 % for PbS/CdS QDs when functionalized with a tetracene acceptor, 5-CT. While transient absorption spectroscopy reveals that both PbS and PbS/CdS QDs show the formation of the 5-CT triplet (with rates of 5.91±0.60 ns-1 and 1.03±0.09 ns-1 respectively), ultrafast hole transfer occurs only from PbS QDs to 5-CT. Although the CdS shell decreases the TET rate, it enhances TET efficiency from 60.3±6.1 % to 71.8±6.2 % by suppressing hole transfer. Furthermore, the CdS shell prolongs the lifetime of the 5-CT triplet and thus enhances TET from 5-CT to the rubrene emitter, further bolstering the upconverison QY.

14.
Chem Sci ; 8(8): 5488-5496, 2017 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-28970929

RESUMO

Herein we report the first example of nanocrystal (NC) sensitized triplet-triplet annihilation based photon upconversion from the visible to ultraviolet (vis-to-UV). Many photocatalyzed reactions, such as water splitting, require UV photons in order to function efficiently. Upconversion is one possible means of extending the usable range of photons into the visible. Vis-to-UV upconversion is achieved with CdS/ZnS core-shell NCs as the sensitizer and 2,5-diphenyloxazole (PPO) as annihilator and emitter. The ZnS shell was crucial in order to achieve any appreciable upconversion. From time resolved photoluminescence and transient absorption measurements we conclude that the ZnS shell affects the NC and triplet energy transfer (TET) from NC to PPO in two distinct ways. Upon ZnS growth the surface traps are passivated thus increasing the TET. The shell, however, also acts as a tunneling barrier for TET, reducing the efficiency. This leads to an optimal shell thickness where the upconversion quantum yield (Φ'UC) is maximized. Here the maximum Φ'UC was determined to be 5.2 ± 0.5% for 4 monolayers of ZnS shell on CdS NCs.

15.
Sci Rep ; 7(1): 10362, 2017 09 04.
Artigo em Inglês | MEDLINE | ID: mdl-28871108

RESUMO

In this study, the re-sequencing data from 3,000 rice genomes project (3 K RGP) was used to analyze the allelic variation at the rice blast resistance (R) Pid3 locus. A total of 40 haplotypes were identified based on 71 nucleotide polymorphic sites among 2621 Pid3 homozygous alleles in the 3k genomes. Pid3 alleles in most japonica rice accessions were pseudogenes due to premature stop mutations, while those in most indica rice accessions were identical to the functional haplotype Hap_6, which had a similar resistance spectrum as the previously reported Pid3 gene. By sequencing and CAPS marker analyzing the Pid3 alleles in widespread cultivars in China, we verified that Hap_6 had been widely deployed in indica rice breeding of China. Thus, we suggest that the priority for utilization of the Pid3 locus in rice breeding should be on introducing the functional Pid3 alleles into japonica rice cultivars and the functional alleles of non-Hap_6 haplotypes into indica rice cultivars for increasing genetic diversity.


Assuntos
Alelos , Resistência à Doença/genética , Variação Genética , Oryza/genética , Doenças das Plantas/genética , Proteínas de Plantas/genética , Substituição de Aminoácidos , China , Códon sem Sentido , Regulação da Expressão Gênica de Plantas , Haplótipos , Oryza/classificação , Fenótipo , Filogenia , Melhoramento Vegetal , Proteínas de Plantas/química , Polimorfismo de Nucleotídeo Único
16.
Chem Rev ; 117(13): 9016-9085, 2017 Jul 12.
Artigo em Inglês | MEDLINE | ID: mdl-28639787

RESUMO

Research and industrial interest in radical C-H activation/radical cross-coupling chemistry has continuously grown over the past few decades. These reactions offer fascinating and unconventional approaches toward connecting molecular fragments with high atom- and step-economy that are often complementary to traditional methods. Success in this area of research was made possible through the development of photocatalysis and first-row transition metal catalysis along with the use of peroxides as radical initiators. This Review provides a brief and concise overview of the current status and latest methodologies using radicals or radical cations as key intermediates produced via radical C-H activation. This Review includes radical addition, radical cascade cyclization, radical/radical cross-coupling, coupling of radicals with M-R groups, and coupling of radical cations with nucleophiles (Nu).

17.
J Am Chem Soc ; 139(28): 9412-9418, 2017 07 19.
Artigo em Inglês | MEDLINE | ID: mdl-28640637

RESUMO

Molecular control of energy transfer is an attractive proposition because it allows chemists to synthetically tweak various kinetic and thermodynamic factors. In this Perspective, we examine energy transfer between semiconductor nanocrystals (NCs) and π-conjugated molecules, focusing on the transmitter ligand at the organic-inorganic interface. Efficient transfer of triplet excitons across this interface allows photons to be directed for effective use of the entire solar spectrum. For example, a photon upconversion system composed of semiconductor NCs as sensitizers, bound organic ligands as transmitters, and molecular annihilators has the advantage of large, tunable absorption cross sections across the visible and near-infrared wavelengths. This may allow the near-infrared photons to be harnessed for photovoltaics and photocatalysis. Here we summarize the progress in this recently reported hybrid upconversion platform and point out the challenges. Since triplet energy transfer (TET) from NC donors to molecular transmitters is one of the bottlenecks, emphasis is on the design of transmitters in terms of molecular energetics, photophysics, binding affinity, stability, and energy offsets with respect to the NC donor. Increasing the efficiency of TET in this hybrid platform will increase both the up- and down-conversion quantum yields, potentially exceeding the Shockley-Queisser limit for photovoltaics and photocatalysis.

18.
Angew Chem Int Ed Engl ; 56(20): 5598-5602, 2017 05 08.
Artigo em Inglês | MEDLINE | ID: mdl-28402601

RESUMO

Owing to the difficulty in comprehensively characterizing nanocrystal (NC) surfaces, clear guidance for ligand design is lacking. In this work, a series of bidentate bis(pyridine) anthracene isomers (2,3-PyAn, 3,3-PyAn, 2,2-PyAn) that differ in their binding geometries were designed to find the best complementary fit to the NC surface. The efficiency of triplet energy transfer (TET) from the CdSe NC donor to a diphenylanthracene (DPA) acceptor mediated by these isomers was used as a proxy for the efficacy of orbital overlap and therefore ligand binding. 2,3-PyAn, with an intramolecular N-N distance of 8.2 Å, provided the best match to the surface of CdSe NCs. When serving as a transmitter for photon upconversion, 2,3-PyAn yielded the highest upconversion quantum yield (QY) of 12.1±1.3 %, followed by 3,3-PyAn and 2,2-PyAn. The TET quantum efficiencies determined by ultrafast transient absorption measurements showed the same trend.

19.
Org Lett ; 19(9): 2330-2333, 2017 05 05.
Artigo em Inglês | MEDLINE | ID: mdl-28421769

RESUMO

The first example of DMSO serving not only as a solvent but also as an oxidant to promote the oxidation of Cu(I) to Cu(II) has been demonstrated. X-ray absorption and electron paramagnetic resonance evidence revealed a single-electron redox process where DMSO could oxidize Cu(I) to Cu(II). The novel discovery guided the rational design of copper-catalyzed oxidative cyclization of aryl ketones with styrenes to furans, providing a new method for the synthesis of multiaryl-substituted furans from cheap and readily available starting materials.

20.
Chem Commun (Camb) ; 53(7): 1241-1244, 2017 Jan 19.
Artigo em Inglês | MEDLINE | ID: mdl-28067341

RESUMO

The effect of isomeric substitutions on the transmitter for triplet energy transfer (TET) between nanocrystal (NC) donor and molecular acceptor is investigated. Each isomeric acceptor is expected to bind in a unique orientation with respect to the NC donor. We see that this orbital overlap drastically affects the transmission of triplets. Here, two functional groups, the carboxylic acid and dithiocarbamate, were varied between the 1-, 2- and 9-positions of the anthracene ring to give three ACA and three ADTC isomers. These six anthracene isomers served as transmitters for triplets between CdSe NC sensitizers and 9,10-diphenylanthracene annihilators for photon upconversion. The photon upconversion quantum yield (QY) is the highest for 9-ACA (12%), lowest for 9-ADTC (0.1%), around 3% for both 1-ACA and 1-ADTC, and about 1% for the 2-isomers. These trends in QYs are reflected in the rates of TET given by ultrafast transient absorption spectroscopy where a maximum of 3.8 × 107 s-1 for 9-ACA was measured. Molecular excited state energy levels were measured both in solution and polymer hosts to correlate structure to TET. This work confirms that anthracene excited states levels are very sensitive to molecular substitution, which in combination with orbital overlap, critically affect Dexter-based TET.

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