A Novel Biaryl Derivative from Hydrangea chinensis

Chemistry of Natural Compounds - A novel bibenzyl derivative, hydrangchinenin (1), was isolated from the stems of Hydrangea chinensis Maxim. (Hydrangeaceae). Its structure was determined on the...     

Secondary Metabolites of Litchi chinensis

Chemistry of Natural Compounds -     

Polymer nanoparticles with a sensitive CO2‐responsive hydrophilic/hydrophobic surface

Poly(methyl methacrylate) (PMMA) nanoparticles with a sensitive CO₂‐responsive hydrophilic/hydrophobic surface that confers controlled dispersion and aggregation in water were prepared by emulsion polymerization at 50 °C under CO₂ bubbling using amphiphilic diblock copolymers of 2‐dimethylaminoethyl methacrylate (DMAEMA) and N‐isopropyl acrylamide (NIPAAm) as an emulsifier. The amphiphilicity of the hydrophobic–hydrophilic diblock copolymer at 50 °C was triggered by CO₂ bubbling in water and enabled the copolymer to serve as an emulsifier. The resulting PMMA nanoparticles were spherical, approximately 100 nm in diameter and exhibited sensitive CO₂/N₂‐responsive dispersion/aggregation in water. Using copolymers with a longer PNIPAAm block length as an emulsifier resulted in smaller particles. A higher concentration of copolymer emulsifier led to particles with a stickier surface. Given its simple preparation and reversible CO₂‐triggered amphiphilic behavior, this newly developed block copolymer emulsifier offers a highly efficient route toward the fabrication of sensitive CO₂‐stimuli responsive polymeric nanoparticle dispersions. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2149–2156     

Bis-tridentate IrIII Phosphors Bearing Two Fused Five-Six-Membered Metallacycles: A Strategy to Improved Photostability of Blue Emitters

Iridium complexes bearing chelating cyclometalates are popular choices as dopant emitters in the fabrication of organic light-emitting diodes (OLEDs). In this contribution, we report a series of blue-emitting, bis-tridentate Ir^III complexes bearing chelates with two fused five-six-membered metallacycles, which are in sharp contrast to the traditional designs of tridentate chelates that form the alternative, fused five-five metallacycles. Five Ir^III complexes, Px-21 – 23 , Cz-4 , and Cz-5 , have been synthesized that contain a coordinated dicarbene pincer chelate incorporating a methylene spacer and a dianionic chromophoric chelate possessing either a phenoxy or carbazolyl appendage to tune the coordination arrangement. All these tridentate chelates afford peripheral ligand–metal–ligand bite angles of 166–170°, which are larger than the typical bite angle of 153–155° observed for their five-five-coordinated tridentate counterparts, thereby leading to reduced geometrical distortion in the octahedral frameworks. Photophysical measurements and TD-DFT studies verified the inherent transition characteristics that give rise to high emission efficiency, and photodegradation experiments confirmed the improved stability in comparison with the benchmark fac-[Ir(ppy)₃] in degassed toluene at room temperature. Phosphorescent OLED devices were also fabricated, among which the carbazolyl-functionalized emitter Cz-5 exhibited the best performance among all the studied bis-tridentate phosphors, showing a maximum external quantum efficiency (EQE_max) of 18.7 % and CIE_x,y coordinates of (0.145, 0.218), with a slightly reduced EQE of 13.7 % at 100 cd m⁻² due to efficiency roll-off.     

Construction algorithms for polynomial lattice rules for multivariate integration

We introduce a new construction algorithm for digital nets for integration in certain weighted tensor product Hilbert spaces. The first weighted Hilbert space we consider is based on Walsh functions. Dick and Pillichshammer calculated the worst-case error for integration using digital nets for this space. Here we extend this result to a special construction method for digital nets based on polynomials over finite fields. This result allows us to find polynomials which yield a small worst-case error by computer search. We prove an upper bound on the worst-case error for digital nets obtained by such a search algorithm which shows that the convergence rate is best possible and that strong tractability holds under some condition on the weights.

We extend the results for the weighted Hilbert space based on Walsh functions to weighted Sobolev spaces. In this case we use randomly digitally shifted digital nets. The construction principle is the same as before, only the worst-case error is slightly different. Again digital nets obtained from our search algorithm yield a worst-case error achieving the optimal rate of convergence and as before strong tractability holds under some condition on the weights. These results show that such a construction of digital nets yields the until now best known results of this kind and that our construction methods are comparable to the construction methods known for lattice rules.

We conclude the article with numerical results comparing the expected worst-case error for randomly digitally shifted digital nets with those for randomly shifted lattice rules.

     

Behavior and surface energies of polybenzoxazines formed by polymerization with argon,oxygen, and hydrogen plasmas

Polybenzoxazine (PBZZ) thin films can be fabricated by the plasma‐polymerization technique with, as the energy source, plasmas of argon, oxygen, or hydrogen atoms and ions. When benzoxazine (BZZ) films are polymerized through the use of high‐energy argon atoms, electronegative oxygen atoms, or excited hydrogen atoms, the PBZZ films that form possess different properties and morphologies in their surfaces. High‐energy argon atoms provide a thermodynamic factor to initiate the ring‐opening polymerization of BZZ and result in the polymer surface having a grid‐like structure. The ring‐opening polymerization of the BZZ film that is initiated by cationic species such as oxygen atoms in plasma, is propagated around nodule structures to form the PBZZ. The excited hydrogen atom plasma initiates both polymerization and decomposition reactions simultaneously in the BZZ film and results in the formation of a porous structure on the PBZZ surface. We evaluated the surface energies of the PBZZ films polymerized by the action of these three plasmas by measuring the contact angles of diiodomethane and water droplets. The surface roughness of the films range from 0.5 to 26 nm, depending on the type of carrier gas and the plasma‐polymerization time. By estimating changes in thickness, we found that the PBZZ film synthesized by the oxygen plasma‐polymerization process undergoes the slowest rate of etching in CF₄ plasma. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4063–4074, 2004     

Viscosity,particle size distribution,and structural investigation of tetramethyloxysilane/2‐hydroxyethyl methacrylate sols during the sol–gel process with acid and base catalysts

The tetramethoxysilane (TMOS)/2‐hydroxylethyl methacrylate (HEMA) hybrid gels were synthesized with acid and base catalysts, via the in situ polymerization of HEMA, with and without the cosolvent methanol. With methanol in the TMOS/HEMA sol, the enhanced esterification and depolymerization reactions of the silanols resulted in a slower growth of silica particles. The silica particles that were synthesized with an acid catalyst were less than 40 nm. The thermal resistance of the poly(2‐hydroxyethyl methacrylate) (PHEMA) chains was enhanced by the addition of colloidal silica. The Fourier transform infrared characterizations and the exothermal peaks on the differential scanning calorimetry traces of these hybrid gels indicated chemical hybridization occurring as a result of condensation of the colloid silica and PHEMA at higher temperatures. Hence, the residual weight content of the hybrid gel after its synthesis with the base catalyst was even higher than the content of TMOS in the hybrid sol. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3476–3486, 2004     

Production,Purification and Characterization of the Hen Egg-White Lysozyme Inhibitor from Enterobacter cloacae M-1002

Three hen egg-white lysozyme inhibitor producing strains, Enterobacter cloacae M-1002, E. sakazakii M-1204, and Erwinia rhapontici H-55, were isolated from the soils of Taiwan. E. cloacae M-1002 appeared to be a promising inhibitor producing strain. One inhibitor was isolated from the culture broth of this strain. Maximum lysozyme inhibitory activity was obtained when the bacterium was grown aerobically in a medium consisting of 0.75% glucose, 0.25% beef extract, 1.0% polypeptone, and 0.25% sodium L-glutamate (pH 70) at 37 °C after 36–48 hrs. A hen egg-white lysozyme inhibitor was isolated from the culture broth of this strain. The inhibitor was purified from the culture supernatant of E. cloacae M-1002 by ammonium sulfate fractionation, DEAE-Sepharose CL-6B column chromatography and Fractogel TSK HW-55 (S) gel chromatography. Molecular weight of the purified lysozyme inhibitor was estimated to be 18, 000–20, 000 by SDS-PAGE and HPLC, and was composed of 71% amino acid and 23% total sugar. Serine, glycine, and alanine in a 3:2:1 molar ratio were the major amino acids, calculated to be 32.8, 20.3, and 11.4% (mol%), respectively. Glucose and mannose were the major sugar components of the inhibitor. The inhibitor was stable at pH 5 to 8 and was stable under 50 °C. Only hen egg-white lysozyme was inhibited by the purified inhibitor but not the other tested enzymes such as lysozyme of celery, turnip; lytic enzyme of Pseudomonas aeruginosa M-1001; chitinase/lysozyme of P. aeruginosa K-187; or cellulase and xylanase of Streptomyces actuosus A-151 and Aspergillus sp. G-393. The inhibition of lysozyme to the bacterial cell lytic activity by the purified inhibitor was 100%.     

A delta white noise functional

The additive renormalization% MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXafv3ySLgzGmvETj2BSbqefm0B1jxALjhiov2D% aebbfv3ySLgzGueE0jxyaibaiGc9yrFr0xXdbba91rFfpec8Eeeu0x% Xdbba9frFj0-OqFfea0dXdd9vqaq-JfrVkFHe9pgea0dXdar-Jb9hs% 0dXdbPYxe9vr0-vr0-vqpWqaaeaabiGaciaacaqabeaadaqaaqGaaO% qaaiaabs7adaWgaaWcbaGaaeySdiaab6cacaqG0bqefeKCPfgBaGqb% diaa-bcaaeqaaOGaeyypa0Jaa8hiaiaacIcacaaIYaGaeqiWdaNaai% ykamaaCaaaleqabaGaeyOeI0IaaGymaiaac+cacaaIYaaaaGqadOGa% a4hiaiGacwgacaGG4bGaaiiCaiaacIcacqGHsislcaqGXoWaaWbaaS% qabeaacaqGYaaaaOGaai4laiaaikdacaGGPaGaa4hiaiaacQdaciGG% LbGaaiiEaiaacchacqGHXcqSdaWadiqaaiabgkHiTiaadkeacaGGNa% GaaiikaiaadshacaGGPaWaaWbaaSqabeaacaaIYaaaaOGaai4laiaa% ikdacaGFGaGaey4kaSIaa4hiaiaabg7acaWGcbGaai4jaiaacIcaca% WG0bGaaiykaaGaay5waiaaw2faaiaacQdaaaa!6C5C!\[{\rm{\delta }}_{{\rm{\alpha }}{\rm{.t}} } = (2\pi )^{ - 1/2} \exp ( - {\rm{\alpha }}^{\rm{2}} /2) :\exp \pm \left[ { - B'(t)^2 /2 + {\rm{\alpha }}B'(t)} \right]:\]is shown to be a generalized Brownian functional. Some of its properties are derived. is shown to be a generalized Brownian functional. Some of its properties are derived.On leave from Universidade do Minho, Area de Matematica, Largo Carlos Amarante, P-4700 Braga, Portugal.     

Ergodic theory and the Strong Law of Large Numbers on Riesz spaces

In [W.-C. Kuo, C.C.A. Labuschagne, B.A. Watson, Discrete-time stochastic processes on Riesz spaces, Indag. Math. (N.S.) 15 (3) (2004) 435-451], we introduced the concepts of conditional expectations, martingales and stopping times on Riesz spaces. Here we formulate and prove order theoretic analogues of the Birkhoff, Hopf and Wiener ergodic theorems and the Strong Law of Large Numbers on Riesz spaces (vector lattices).