Formation of Azulene-Embedded Nanographene: Naphthalene to Azulene Rearrangement During the Scholl Reaction

Incorporation of a non-hexagonal ring into a nanographene framework can lead to new electronic properties. During the attempted synthesis of naphthalene-bridged double [6]helicene and heptagon-containing nanographene by the Scholl reaction, an unexpected azulene-embedded nanographene and its triflyloxylated product were obtained, as confirmed by X-ray crystallographic analysis and 2D NMR spectroscopy. A 5/7/7/5 ring-fused substructure containing two formal azulene units is formed, but only one of them shows an azulene-like electronic structure. The formation of this unique structure is explained by arenium ion mediated 1,2-phenyl migration and a naphthalene to azulene rearrangement reaction according to an in-silico study. This report represents the first experimental example of the thermodynamically unfavorable naphthalene to azulene rearrangement and may lead to new azulene-based molecular materials.     

Conversion of Methanol to Aromatic-Rich Gasoline over High-Efficiency Bifunctional Catalysts: Green Synthesis of GaZSM-5 Zeolites via Dry-Gel Conversion Strategy

Russian Journal of Applied Chemistry - Nanoscale ZSM-5 (AlZ5-D) and Ga-substituted ZSM-5 zeolites ((Al,Ga)Z5-D and GaZ5-D) were synthesized by a green dry-gel conversion strategy. For comparison,...     

Malononitrile-involved Michael addition polymerization: An efficient and facile route for cyano-rich polyesters with programmable thermal and mechanical properties

An efficient, atom-economic, oxygen-tolerant, and water-tolerant strategy has been established to synthesize cyano-rich polyesters. Four kinds of organic bases, 1,1,3,3-tetramethylguanidine (TMG), 4-dimethylaminopyridine, triethylamine, and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) were explored for accelerating Michael addition polymerization of malononitrile and 1,4-butandiol diacrylate. TMG can promote the polymerization efficiently under mild conditions to quantitatively afford polyester with high-molecular weight and moderate polydispersity. The comparison of the kinetic studies of TMG and TBD reveals that TMG shows better catalytic performance, while the catalysis of TBD brings about oligomers in spite of the higher efficiency at early age of the polymerization. Moreover, other diacrylate compounds could also be quantitatively polymerized to afford polyesters with high molecular weight. When dimethacrylate is chose as the monomer, the polymerization becomes sluggish. All the afforded polyesters display programmable thermal and mechanical properties that are closely related to their chemical structures.     

Thermal decomposed behavior and kinetic study for untreated and flame retardant treated regenerated cellulose fibers using thermogravimetric analysis

Journal of Thermal Analysis and Calorimetry - In the present work, pyrolysis kinetic mechanism was studied for regenerated cellulosic fiber (RCF) and composite RCF containing silicon/nitrogen flame...     

Direct Transformation of Arenols Based on C—O Activation

In the view of substrate availability, atomic efficiency and cost, directly using arenols as coupling partners in cross‐coupling, would be one of the most attractive goals. Up to date, many efforts have been made to activate the C—O bond of phenols with different strategies, for example, through in‐situ formed intermediates, through a catalytic reductive dearomatization‐condensation‐rearomatization sequence or catalytic deoxygenation. In this review, we summarized recent advances in cross‐couplings of arenols as the electrophiles via C—O activation.     

Polypyrrole Shell@3D‐Ni Metal Core Structured Electrodes for High‐Performance Supercapacitors

Three‐dimensional (3D) nanometal films serving as current collectors have attracted much interest recently owing to their promising application in high‐performance supercapacitors. In the process of the electrochemical reaction, the 3D structure can provide a short diffusion path for fast ion transport, and the highly conductive nanometal may serve as a backbone for facile electron transfer. In this work, a novel polypyrrole (PPy) shell@3D‐Ni‐core composite is developed to enhance the electrochemical performance of conventional PPy. With the introduction of a Ni metal core, the as‐prepared material exhibits a high specific capacitance (726 F g^?1 at a charge/discharge rate of 1 A g^?1), good rate capability (a decay of 33 % in C_sp with charge/discharge rates increasing from 1 to 20 A g^?1), and high cycle stability (only a small decrease of 4.2 % in C_sp after 1000 cycles at a scan rate of 100 mV s^?1). Furthermore, an aqueous symmetric supercapacitor device is fabricated by using the as‐prepared composite as electrodes; the device demonstrates a high energy density (≈21.2 Wh kg^?1) and superior long‐term cycle ability (only 4.4 % and 18.6 % loss in C_sp after 2000 and 5000 cycles, respectively).     

Photons can hide where they have been

Recently,the nested Mach–Zehnder interferometer[Phys.Rev.Lett.111,240402(2013)]was modified by adding Dove prisms in a paper[Quantum Stud.:Math.Found.2,255(2015)],and an interesting result is that,after the Dove prisms were inserted,a signal at the first mirror of the nested interferometer was obtained.But,according to the former original paper,the photons have never been present near that mirror.In this work,we interpret this result naturally by resorting to the three-path interference method.Moreover,we find that even though the photons have been somewhere,they can hide the trace of being there.     

A Ru(II)-Based Nanoassembly Exhibiting Theranostic PACT Activity in NIR Region

Photoactivated chemotherapy (PACT) has appealing merits over traditional chemotherapy as well as photodynamic therapy (PDT) by virtue of its spatial and temporal control on drug activity and oxygen-independent mechanisms of action. However, the short photoactivation wavelengths, e.g., visible light–activated Ru(II)-based PACT agents, limit the clinical application severely. In this work, a facile construction of supramolecular nanoparticles from a poly(ethylene glycol) (PEG)-modified [Ru(dip)₂(py-SO₃)]⁺ (abbreviated as Ru-PEG, dip = 4,7-diphenyl-1,10-phenanthroline, py-SO₃ = pyridine-2-sulfonate) and 1,3-phenylenebis(pyren-1-ylmethanone) (BP) is shown. While Ru-PEG may undergo photoinduced ligand dissociation and release anticancer species of [Ru(dip)₂(H₂O)₂]²⁺, BP has extremely large two-photon absorption cross sections (δ₂) in the NIR region and intense fluorescence over the wavelengths where Ru-PEG has strong absorption. Thus, two-photon excitation of BP followed by an efficient Förster resonance energy transfer (FRET) from BP to Ru-PEG may lead to a potent inactivation against cisplatin-resistant cancer cells and 3D multicellular tumor spheroids (MCTSs). The residue fluorescence of BP also allows the cellular uptake of the particles to be visualized. This work provides a universal and convenient strategy to realize theranostic PACT in the ideal phototherapeutic window of 650–900 nm.