Rare-earth Doped Nanoparticles with Narrow NIR-II Emission for Optical Imaging with Reduced Autofluorescence

Fluorescence imaging in the second near-infrared region(900-1700 nm, NIR-II) with a high resolution and penetration depth due to the significantly reduced tissue scattering and autofluorescence has emerged as a useful tool in biomedical fields. Recently, many efforts have been devoted to the development of fluorophores with an emission band covering the long-wavelength end of NIR-II region(1500-1700 nm) to eliminate the autofluorescence. Alternatively, we believe imaging with a narrow bandwidth could also reduce the autofluorescence. As a proof of concept, NaYF₄:Yb,Nd@NaYF₄ downconversion nanoparticles(DCNPs) with sharp NIR-II emission were synthesized. The luminescence of DCNPs showed a half-peak width of 49 nm centered at 998 nm, which was perfectly matched with a (1000±25) nm bandpass filter. With this filter, we were able to retain most of the emissions from the nanoparticles, while the autofluorescence was largely reduced. After PEGylation, the DCNPs exhibited great performance for blood vessel and tumor imaging in living mice with significantly reduced autofluorescence and interference signals. This work provided an alternative way for the low-autofluorescence imaging and emphasized the importance of narrow emitting rare-earth doped nanoparticles for NIR-II imaging.     

A versatile A2 + B3 approach to hyperbranched polyacenaphthenequinones

A series of hyperbranched polyacenaphthenequinones has been prepared by superelectrophilic aromatic substitution of (substituted) acenaphthenequinone and 1,3,5‐tris‐(4‐phenoxybenzoyl)benzene via a facile A₂ + B₃ approach. Because of the strongly increased reactivity of the second A functionality, gelation was efficiently avoided during the polymerization. The structure of the resulting polymer was characterized by NMR spectroscopy and gel permeation chromatography. Further modification of the hyperbranched polyacenaphthenequinone was explored both on the acenaphthenequinone and aromatic moieties. Moreover, the polymer modified through sulfonation was investigated as a water‐soluble acid catalyst for the degradation of biomass resources. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2596‐2603     

Hydrogen Spillover Enhanced Hydroxyl Formation and Catalytic Activity Toward CO Oxidation at the Metal/Oxide Interface

H₂‐promoted catalytic activity of oxide‐supported metal catalysts in low‐temperature CO oxidation is of great interest but its origin remains unknown. Employing an FeO(111)/Pt(111) inverse model catalyst, we herewith report direct experimental evidence for the spillover of H(a) adatoms on the Pt surface formed by H₂ dissociation to the Pt?FeO interface to form hydroxyl groups that facilely oxidize CO(a) on the neighboring Pt surface to produce CO₂. Hydroxyl groups and coadsorbed water play a crucial role in the occurrence of hydrogen spillover. These results unambiguously identify the occurrence of hydrogen spillover from the metal surface to the noble metal/metal oxide interface and the resultant enhanced catalytic activity of the metal/oxide interface in low‐temperature CO oxidation, which provides a molecular‐level understanding of both H₂‐promoted catalytic activity of metal/oxide ensembles in low‐temperature CO oxidation and hydrogen spillover.     

Chemical Constituents of Corydalis saxicola

Chemistry of Natural Compounds -     

Helical Ullazine-Quinoxaline-Based Polycyclic Aromatic Hydrocarbons

Polycyclic aromatic azomethine ylides (PAMYs) are powerful building blocks in the bottom-up synthesis of internally nitrogen-containing polycyclic aromatic hydrocarbons (N-PAHs) through 1,3-cycloaddition reactions. In this work, the cycloaddition reaction of PAMYs to asymmetric ortho-quinones is presented, which, in contrast to the addition to symmetric para-quinones, facilitates subsequent condensation reactions and allows the synthesis of three helical N-PAHs with ullazine-quinoxaline ( UQ - 1 – 3 ) backbones. UQ - 1 and UQ - 2 possess two helical centers; however, single-crystal X-ray analysis together with the computational modeling of UQ - 3 elucidate the formation of only the thermodynamically most stable geometry with four helical centers in a (P,P,M,M) configuration. For the series UQ - 1 – 3 , the number of redox steps is directly correlated with the number of ullazine or quinoxaline units incorporated into the targeted molecular backbones. A detailed investigation of the spectroscopic and magnetic properties of the radical cation and anion as well as the dication and dianion species by in situ EPR/UV/Vis-NIR spectroelectrochemistry is provided. The excellent optical and redox properties combined with helical geometries render them possibly applicable as chiral emitter or ambipolar charge transport material in organic electronics.     

Efficient Syntheses of Traumatic Lactone and Rhizobialide

Herein, we report the total synthesis of traumatic lactone and rhizobialide by utilizing allenoic acid to construct the lactone ring. The key starting materials, allenoic acids, could be prepared by the ATA (allenation of terminal alkynes) of a terminal alkyne with an aldehyde that contained a protected hydroxyl group followed by hydrolysis. Importantly, the asymmetric synthesis could be realized just by replacing racemic diphenylprinol with (R)- or (S)-diphenylprinol to deliver the optically active allenoate.