In Situ Facile Synthesis of Ru‐Based Core–Shell Nanoparticles Supported on Carbon Black and Their High Catalytic Activity in the Dehydrogenation of Amine‐Boranes

Well‐dispersed core–shell Ru@M (M=Co, Ni, Fe) nanoparticles (NPs) supported on carbon black have been synthesized via a facile in situ one‐step procedure under ambient condition. Core‐shell Ru@Co NPs were synthesized and characterized for the first time. The as‐synthesized Ru@Co and Ru@Ni NPs exhibit superior catalytic activity in the hydrolysis of ammonia borane compared with their monometallic and alloy counterparts. The Ru@Co/C NPs are the most reactive, with a turnover frequency (TOF) value of 320 (mol min^?1) mol_Ru^?1 and activation energy (E_a) of 21.16 kJ mol^?1. Ru@Ni/C NPs are the next most active, whereas Ru@Fe/C NPs are almost inactive. Additionally, the as‐synthesized NPs supported on carbon black exhibit higher catalytic activity than catalysts on other conventional supports, such as SiO₂ and γ‐Al₂O₃.     

Extraction of coal-tar pitch using NMP/ILs mixed solvents

Coal-tar pitch(CP)is a promising carbon raw material for producing needle coke,carbon fiber etc.During processing,the H/C ratio,ash content,and quinoline insoluble(QI)in the CP are the key factors that influence the material preparation.In this study,NMP was selected to extract CP first;then[BMIM]Cl/NMP mixed solvent was used;and finally a series of ionic liquids(ILs)mixtures with NMP were developed for the extraction of CP to obtain the refined pitch.The extracts were analyzed via elemental analysis,TGA,FT-IR,and 13C-NMR.Results indicate that different NMP/IL mass ratios or different kinds of ILs have impact on the extraction yield.The relationship of the hydrogen to carbon(H/C)ratio changed with different solvents and QI extracts were obtained.Results showed that the H/C ratios changed little between NMP extracts and could be adjusted by changing the NMP/ILs mass ratio or using different ILs.The extracts are suitable for preparation mesophase pitch because of no ash content,low QI,and appropriate H/C ratios.As a result,NMP can be used to refine pitch.In addition,[BMIM]Cl is good mixed with NMP for CP extraction,because it can obtain a relatively high yield under the same extraction conditions.     

Phosphorescent Cyclometalated Iridium(III) Complexes That Contain Substituted 2‐Acetylbenzo[b]thiophen‐3‐olate Ligand for Red Organic Light‐Emitting Devices

We report the synthesis of a new class of thermally stable and strongly luminescent cyclometalated iridium(III) complexes 1 – 6 , which contain the 2‐acetylbenzo[b]thiophene‐3‐olate (bt) ligand, and their application in organic light‐emitting diodes (OLEDs). These heteroleptic iridium(III) complexes with bt as the ancillary ligand have a decomposition temperature that is 10–20 % higher and lower emission self‐quenching constants than those of their corresponding complexes with acetylacetonate (acac). The luminescent color of these iridium(III) complexes could be fine‐tuned from orange (e.g., 2‐phenyl‐6‐(trifluoromethyl)benzo[d]thiazole (cf₃bta) for 4 ) to pure red (e.g., lpt (Hlpt=4‐methyl‐2‐(thiophen‐2‐yl)quinolone) for 6 ) by varying the cyclometalating ligands (C‐deprotonated C^N). In particular, highly efficient OLEDs based on 6 as dopant (emitter) and 1,3‐bis(carbazol‐9‐yl)benzene (mCP) as host that exhibit stable red emission over a wide range of brightness with CIE chromaticity coordinates of (0.67, 0.33) well matched to the National Television System Committee (NTSC) standard have been fabricated along with an external quantum efficiency (EQE) and current efficiency of 9 % and 10 cd A^?1, respectively. A further 50 % increase in EQE (>13 %) by replacing mCP with bis[4‐(6H‐indolo[2,3‐b]quinoxalin‐6‐yl)phenyl]diphenylsilane (BIQS) as host for 6 in the red OLED is demonstrated. The performance of OLEDs fabricated with 6 (i.e., [(lpt)₂Ir(bt)]) was comparable to that of the analogous iridium(III) complex that bore acac (i.e., [(lpt)₂Ir(acac)]; 6 a in this work) [Adv. Mater.­ 2011 , 23, 2981] fabricated under similar conditions. By using ntt (Hnnt=3‐hydroxynaphtho[2,3‐b]thiophen‐2‐yl)(thiophen‐2‐yl)methanone) ligand, a substituted derivative of bt, the [(cf₃bta)₂Ir(ntt)] was prepared and found to display deep red emission at around 700 nm with a quantum yield of 12 % in mCP thin film.     

o‐Fluorination of Aromatic Azides Yields Improved Azido‐Based Fluorescent Probes for Hydrogen Sulfide: Synthesis,Spectra, and Bioimaging

Hydrogen sulfide (H₂S) is an endogenously produced gaseous signaling molecule with multiple biological functions. To visualize the endogenous in situ production of H₂S in real time, new coumarin‐ and boron‐dipyrromethene‐based fluorescent turn‐on probes were developed for fast sensing of H₂S in aqueous buffer and in living cells. Introduction of a fluoro group in the ortho position of the aromatic azide can lead to a greater than twofold increase in the rate of reaction with H₂S. On the basis of o‐fluorinated aromatic azides, fluorescent probes with high sensitivity and selectivity toward H₂S over other biologically relevant species were designed and synthesized. The probes can be used to in situ to visualize exogenous H₂S and D ‐cysteine‐dependent endogenously produced H₂S in living cells, which makes them promising tools for potential applications in H₂S biology.     

Recent Progress on Transition Metal Catalyst Separation and Recycling in ATRP

Atom transfer radical polymerization (ATRP) is a versatile and robust tool to synthesize a wide spectrum of monomers with various designable structures. However, it usually needs large amounts of transition metal as the catalyst to mediate the equilibrium between the dormant and propagating species. Unfortunately, the catalyst residue may contaminate or color the resultant polymers, which limits its application, especially in biomedical and electronic materials. How to efficiently and economically remove or reduce the catalyst residue from its products is a challenging and encouraging task. Herein, recent advances in catalyst separation and recycling are highlighted with a focus on (1) highly active ppm level transition metal or metal free catalyzed ATRP; (2) post‐purification method; (3) various soluble, insoluble, immobilized/soluble, and reversible supported catalyst systems; and (4) liquid‐liquid biphasic catalyzed systems, especially thermo‐regulated catalysis systems.

     

Topologically protected interface mode in plasmonic waveguide arrays

Recent realization of nontrivial topological phases in photonic systems has provided unprecedented opportunities in steering light flow in novel manners. Based on the Su–Schriffer–Heeger (SSH) model, a topologically protected optical mode was successfully demonstrated in a plasmonic waveguide array with a kinked interface that exhibits a robust nonspreading feature. However, under the same excitation conditions, another antikinked structure seemingly cannot support such a topological interface mode, which appears to be inconsistent with the SSH model. Theoretical calculations are carried out based on the coupled‐mode theory, in which the mode properties, excitation conditions, and the robustness are studied in detail. It is revealed that under the exact eigenstate excitations, both kinked and antikinked structures do support such robust topological interface modes; however, for a realistic single‐waveguide input only the kinked structure does so. It is concluded that the symmetry of interface eigenmodes plays a crucial role, and the odd eigenmode in a kinked structure offers the capacity to excite the nonspreading interface mode in the realistic excitation of a one‐waveguide input. Our finding deepens the understanding of mode excitation and propagation in coupled waveguide systems, and could open a new avenue in optical simulations and photonic designs.

     

Broadband spin‐controlled focusing via logarithmic‐spiral nanoslits of varying width

This work presents analytical, numerical and experimental demonstrations of light diffracted through a logarithmic spiral (LS) nanoslit, which forms a type of switchable and focus‐tunable structure. Owing to a strong dependence on the incident photon spin, the proposed LS‐nanoslit converges incoming light of opposite handedness (to that of the LS‐nanoslit) into a confined subwavelength spot, while it shapes light with similar chirality into a donut‐like intensity profile. Benefitting from the varying width of the LS‐nanoslit, different incident wavelengths interfere constructively at different positions, i.e., the focal length shifts from 7.5 μm (at λ = 632.8 nm) to 10 μm (at λ = 488 nm), which opens up new opportunities for tuning and spatially separating broadband light at the micrometer scale.

     

Unveiling the correlation between non‐diffracting tractor beam and its singularity in Poynting vector

This paper investigates the singular optics of nonparaxial light beams in the near field when the light behaves as a tractor beam. New insights into the optical pulling force, which is usually represented by integrating the stress tensor at a black box enclosing the object, are interpreted by the optical singularity of the Poynting vector. The negative nonconservative pulling force originates from the transfer of the azimuthal Poynting vector to the longitudinal component partly owing to the presence of a scatterer. The separatrice pattern and singularity shifts of the Poynting vector unanimously exhibit a differentiable near‐field distribution in the presence of optical pulling force. A new method is established to calculate the near‐field optical force using the differential Poynting vector in the far field. The results obtained provide a clear physical interpretation of the light–matter interaction and manifest the significance of singular optics in manipulating objects.

     

Recent research advances of the biomimetic tumor microenvironment and regulatory factors on microfluidic devices: A systematic review

Tumor microenvironment is a multicomponent system consisting of tumor cells, noncancer cells, extracellular matrix, and signaling molecules, which hosts tumor cells with integrated biophysical and biochemical elements. Because of its critical involvement in tumor genesis, invasion, metastasis, and resistance, the tumor microenvironment is emerging as a hot topic of tumor biology and a prospective therapeutic target. Unfortunately, the complex of microenvironment modeling in vitro is technically challenging and does not effectively generalize the local tumor tissue milieu. Recently, significant advances in microfluidic technologies have provided us with an approach to imitate physiological systems that can be utilized to mimic the characterization of tumor responses with pathophysiological relevance in vitro. In this review, we highlight the recent progress and innovations in microfluidic technology that facilitates the tumor microenvironment study. We also discuss the progress and future perspective of microfluidic bionic approaches with high efficiency for the study of tumor microenvironment and the challenges encountered in cancer research, drug discovery, and personalized therapy.     

Secondary Metabolites of Clinacanthus nutans

Chemistry of Natural Compounds -