Ligand effect in the synthesis of hyperbranched polymers via copper-catalyzed azide-alkyne cycloaddition polymerization (CuAACP)

Copper-catalyzed azide-alkyne cycloaddition polymerization (CuAACP) of AB₂ monomers demonstrated a chain-growth mechanism without any external ligand because of the complexation of in situ formed triazole groups with Cu catalysts. In this study, we explored the use of various ligands that affected the polymerization kinetics to tune the polymers’ molecular weights and the degree of branching (DB). Eight ligands were studied, including polyethylene glycol monomethyl ether (PEG₃₅₀, M_n = 350), tris(benzyltriazolylmethyl)amine (TBTA), 2,6-bis(1-undecyl-1H-benzo[d]imidazol-2-yl)pyridine (Py(DBim)₂), 2,2′-bipyridyl (bpy), 4,4′-di-n-nonyl-2,2′-bipyridine (dNbpy), N,N,N′,N″,N″-pentamethyldiethylenetriamine (PMDETA), N,N,N′,N″,N″-penta(n-butyl)diethylenetriamine (PBuDETA), and N,N,N′,N″,N″-pentabenzyldiethylenetriamine (PBnDETA). All ligands except PEG₃₅₀ exhibited stronger coordination with Cu(I) than the polytriazole polymer, which freed the Cu catalyst from polymers and resulted in dominant step-growth polymerization with simultaneous chain-growth feature. Meanwhile, the use of PEG₃₅₀ ligand retained the confined Cu in the polymer, demonstrating a chain-growth mechanism, but lower polymer molecular weights as compared with the no-external-ligand polymerization. Results indicated that aliphatic substituent groups on ligands had little effect on the molecular weights and DB of the polymers, but rigid aromatic substituent groups decreased both values. By varying the ligand species and amounts, hyperbranched polymers with DB value ranging from 0.53 ([TBTA]₀/[Cu]₀ = 5) to 0.98 ([PMDETA]₀/[Cu]₀ = 2) have been achieved. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2238–2244     

Condis Crystals of Small Molecules III. Thermal Analysis of Plastic and Condis Crystals of some Cyclosilanes

Three cyclic methyl and ethyl substituted silanes were synthesized and their thermal properties analyzed. All show a plastic crystalline state which permits also ring and/or side-chain conformational motion as judged from the enthalpies of transition to the isotropic state. Heat capacity data and entropies of disordering into the plastic crystal leave open the possibility of a condis (conformationally disordered) state below the plastic crystal state with a continuous, transitionless freezing of the conformational motion at lower temperature.     

Film-forming characteristics and thermal stability of low viscosity benzoxazines derived from melamine

A novel class of low-viscosity benzoxazines has been synthesized from melamine and formaldehyde with phenol or bisphenol A. The striking feature of the class of benzoxazines is the subtle combination of their inherently low viscosity at room temperature, good film-forming characteristics and high chemical and thermal stability mainly due to the introduction of melamine into the network of the polymers. The structure of the benzoxazines has been confirmed by proton nuclear magnetic resonance spectroscopy and fourier transform infrared spectroscopy. Thermal properties of polybenzoxazine have been studied by differential scanning calorimetry, dynamic mechanical analysis and thermogravimetric analysis. Transparent polybenzoxazine films were easily obtained under solvent-free conditions, exhibiting significantly improved toughness compared to the conventional polybenzoxazines. Our research may open a new path for overcoming the present drawbacks of polybenzoxazines such as high brittleness, the difficulties in preparing films and poor processibility via tailoring the structures and properties of amine in the benzoxazines.     

Cluster synchronization in nonlinearly coupled delayed networks of non-identical dynamic systems

In the real world, many networks show community structure, i.e., clusters of nodes, which have a high density of links within the same cluster but a lower density of links between different clusters. In this paper, nonlinearly coupled networks with community structure and non-identical nodes and with time-varying delay are considered. By applying pinning control to a fraction of network nodes, and using a suitable Lyapunov function, we obtain some new and useful synchronization criteria, which guarantee that various clusters are synchronized independently. An example is presented to show the application of the criteria obtained in this paper.     

Effects of monomer structure on the morphology of polymer networks and the electro-optical properties of polymer-dispersed liquid crystal films

Polymer-dispersed liquid crystal (PDLC) films were prepared by photochemical polymerisation with a series of (meth)acrylate monomers. The effects of monomer structure on the morphology of polymer networks in the PDLC films were studied. The acrylate monomers without sidegroup chain formed uniform polymer networks. The methacrylate monomers with methyl as their sidegroup chains formed lace-like networks. The size of the LC droplets increased with increasing the length of the flexible chain of both methacrylate and acrylate monomers. Meanwhile, the effects of the morphology of the polymer network on the electro-optical properties of PDLC films were also investigated.     

Synthesis of TiO2 based on hydrothermal methods using elevated pressures and microwave conditions

Titanium dioxide (TiO₂), especially in its anatase form, is an effective photocatalyst under ultraviolet (UV) light. The particle size of TiO₂ is a critical factor to determine its photoactivity based on its quantum effectiveness under light irradiations. Thus, nanocrystalline TiO₂ has been widely accepted to significantly enhance this effect. The sol–gel method is generally used to synthesize the anatase form of nanocrystalline TiO₂. In this study, we expanded the synthesis method of TiO₂ to high pressures under direct heating (hydrothermal method) and indirect heating (microwave-assisted method). It was found that pH value is one of the major factors to control nano-sizes of TiO₂ particles, and the neutral condition in all methods is preferable for controlling the sizes of the prepared TiO₂ particles. The microwave-assisted method further improves quality of synthesized nano-size TiO₂ below 10 nm. These results have been confirmed by both the direct size measurement using TEM images and indirect determination using XRD peaks. The collected samples are further analyzed using UV–Vis spectroscopy to identify the particle size-dependent photoreactivity and to confirm the effectiveness of microwave-assisting under neutral conditions. DSC is also a powerful tool to identify the crystalline transition of TiO₂.     

Screening of glycoside isomers in P. scrophulariiflora using ionic liquid‐based ultrasonic‐assisted extraction and ultra‐performance liquid chromatography/electrospray ionization quadrupole time‐of‐flight tandem mass spectrometry

A powerful ionic liquid‐based ultrasonic‐assisted extraction (ILUAE) method combined with ultra‐performance liquid chromatography coupled to electrospray ionization quadrupole time‐of‐flight tandem mass spectrometry (UPLC/ESI‐QTOFMSⁿ) was employed in the rapid simultaneous screening of iridoid glycosides, phenylethanoid glycosides, and cucurbitacin glycosides from P. scrophulariiflora. The ILUAE procedure was optimized over several ultrasonic parameters, including the ultrasonic power, concentration of the ionic liquid, and solid–liquid ratio. A comparison with conventional heat‐reflux extraction and regular UAE demonstrated that the optimized approach yielded a high extraction efficiency (Picroside I, 2.84%; Picroside II, 3.57%; 6‐O‐E‐feruloyl catalpol, 2.20%) within a short extraction time of 30 min. Negative ion mode ESI‐QTOFMS² analysis of the fragmentation reactions of the [M–H]^– ions was conducted to characterize the diagnostic ions related to the glycosyl moieties, aglycone units, and the type and substituted position of the ester groups. Interestingly, the positional isomers of the iridoid glycosides could be easily discriminated based on the characteristic ions. A total of 15 glycosides, including three groups of iridoid glycoside isomers and two groups of phenylethanoid glycoside isomers, were conveniently identified within 13.5 min. Moreover, 6'‐O‐vanilloyl catalpol was identified in P. scrophulariiflora for the first time. The method developed here was further validated by measuring the recovery, correlation coefficient (R²), and reproducibility (RSD, n = 5) of three iridoid glycosides: 89.60%–109.02%, 0.9991–0.9998, and 0.93%–1.44%, respectively. This study demonstrated the capabilities of ILUAE combined with UPLC/ESI‐QTOFMSⁿ for the rapid screening of glycosides in P. scrophulariiflora. This method offers an approach to similar studies on other natural plants. Copyright © 2012 John Wiley & Sons, Ltd.     

Rh-Catalyzed Decarbonylative Cross-Coupling between o-Carboranes and Twisted Amides: A Regioselective,Additive-Free,and Concise Late-Stage Carboranylation

The convenient cross-coupling of sp² or sp³ carbons with a specific boron vertex on carborane cage represents significant synthetic values and insurmountable challenges. In this work, we report an Rh-catalyzed reaction between o-carborane and N-acyl-glutarimides to construct various B_cage−C bonds. Under the optimized condition, the removable imine directing group (DG) leads to B(3)− or B(3,6)−C couplings, while the pyridyl DG leads to B(3,5)−Ar coupling. In particular, an unexpected rearrangement of amide reagent is observed in pyridyl directed B(4)−C(sp³) formation. This scalable protocol has many advantages, including easy access, the use of cheap and widely available coupling agents, no requirement of an external ligand, base or oxidant, high efficiency, and a broad substrate scope. Leveraging the Rh^I dimer and twisted amides, this method enables straightforward access to diversely substituted and therapeutically important carborane derivatives at boron site, and provides a highly valuable vista for carborane-based drug screening.