Synthesis and properties of conjugated copolycondensates consisting of carbazole‐2,7‐diyl and fluorene‐2,7‐diyl

Carbazole and fluorene‐based random and alternating copolycondensates were synthesized to develop high‐performance blue light‐emitting polymers by improving electron injection ability of poly(N‐aryl‐2,7‐carbazole)s that showed intense blue electroluminescence (EL) with good hole‐injection and ‐transport ability. These copolycondensates absorbed light energy at about λ_max = 390 nm in CHCl₃ and 400 nm in film state, and fluoresced at about λ_max = 417 nm in CHCl₃ and 430 nm in the thin film state. Energy gaps between highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of them were about 2.9 eV, and the energy levels of LUMO situated lower than that of corresponding polycarbazole. Polymer light‐emitting diode devices having configuration of indium tin oxide/poly(3,4‐ethylenedioxythiophene)‐poly(styrenesulfonate)/polymer/CsF/Al using the copolycondensates, poly(N‐arylcarbazole‐2,7‐diyl), and poly(9,9‐dialkylfluorene‐2,7‐diyl), emitted bluish EL at operating voltages lower than 7 V. The device embedded the random copolycondensate showed notably higher performance with maximum luminance of 31,200 cd m^?2 at 11.0 V, and the current efficiencies observed under operating voltages lower than 7 V were higher than those of the other devices. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis of π‐conjugated polymer containing both thiophene and phosphole sulfide in the main chain by simultaneous post‐element transformation of organotitanium polymer

The synthesis and unique optoelectronic features of a π‐conjugated polymer containing both thiophene and 1‐phenylphosphole sulfide units (multiple heteroles) in the main chain by the post‐element transformation of a regioregular organometallic polymer possessing titanacyclopentadiene‐2,5‐diyl unit are described. The π‐conjugated polymer containing multiple heteroles was obtained in 73% yield by the simultaneous reaction of the organotitanium polymer with sulfur monochloride and dichlorophenylphosphine (0.6 equiv each), whose number‐average molecular weight (M_n) and the molecular‐weight distribution (M_w/M_n) were estimated to be 11,000 and 3.4, respectively, by the size exclusion chromatography (SEC). The π‐conjugated polymer thus obtained was found to have the high HOMO and the low LUMO energy levels due to the electron‐rich thiophene and electron‐deficient phosphole sulfide units, respectively, as supported by its cyclic voltammetry (CV) analysis. Compared to a mixture of a polymer containing sole thiophene‐unit and that containing sole phosphole sulfide units, the π‐conjugated polymer‐containing multiple heteroles proved to exhibit interesting optical properties. For example, a specific emission peak was observed at 608 nm in the photoluminescence spectrum, which was not observed in the case of the thiophene‐containing polymer, the phosphole‐containing polymer, and their mixture. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2519–2525     

Self‐Supported Chiral Titanium Cluster (SCTC) as a Robust Catalyst for the Asymmetric Cyanation of Imines under Batch and Continuous Flow at Room Temperature

A robust heterogeneous self‐supported chiral titanium cluster (SCTC) catalyst and its application in the enantioselective imine‐cyanation/Strecker reaction is described under batch and continuous processes. One of the major hurdles in the asymmetric Strecker reaction is the lack of availability of efficient and reusable heterogeneous catalysts that work at room temperature. We exploited the readily hydrolyzable nature of titanium alkoxide to synthesize a self‐supported chiral titanium cluster (SCTC) catalyst by the controlled hydrolysis of a preformed chiral titanium‐alkoxide complex. The isolated SCTC catalysts were remarkably stable and showed up to 98 % enantioselectivity (ee) with complete conversion of the imine within 2 h for a wide variety of imines at room temperature. The heterogeneous catalysts were recyclable more than 10 times without any loss in activity or selectivity. The robustness, high performance, and recyclability of the catalyst enabled it to be used in a packed‐bed reactor to carry out the cyanation under continuous flow. Up to 97 % ee and quantitative conversion with a throughput of 45 mg h^?1 were achieved under optimized flow conditions at room temperature in the case of benzhydryl imine. Furthermore, a three‐component Strecker reaction was performed under continuous flow by using the corresponding aldehydes and amines instead of the preformed imines. A good product distribution was obtained for the formation of amino nitriles with ee values of up to 98 %. Synthetically useful ee values were also obtained for challenging α‐branched aliphatic aldehyde by using the three‐component continuous Strecker reaction.     

亲水作用色谱柱与阳离子交换树脂柱结合分离无机离子（英文）

A combination of hydrophilic interaction chromatographic(HILIC) column and a weakly acidic cation-exchange resin(WCX) column was used for simultaneous separation of inorganic anions and cations by ion chromatography(IC).Firstly,the capability of HILIC column for the separation of analyte ions was evaluated under acidic eluent conditions.The columns used were SeQuant ZIC-HILIC(ZIC-HILIC) with a sulfobetaine-zwitterion stationary phase(ZIC-HILIC) and Acclaim HILIC-10 with a diol stationary phase(HILIC-10).When using tartaric acid as the eluent,the HILIC columns indicated strong retentions for anions,based on ion-pair interaction.Especially,HILIC-10 could strongly retain anions compared with ZIC-HILIC.The selectivity for analyte anions of HILIC-10 with 5 mmol/L tartaric acid eluent was in the order of I-> NO-3 > Br-> Cl-> H2PO-4.However,since HILIC-10 could not separate analyte cations,a WCX column(TSKgel Super IC-A/C) was connected after the HILIC column in series.The combination column system of HILIC and WCX columns could successfully separate ten ions(Na+,NH+4,K+,Mg2+,Ca2+,H2PO-4,Cl-,Br-,NO-3 and I-) with elution of 4 mmol/L tartaric acid plus 8 mmol/L 18-crown-6.The relative standard deviations(RSDs) of analyte ions by the system were in the ranges of 0.02%-0.05% in retention times and 0.18%-5.3% in peak areas through three-time successive injections.The limits of detection at signal-to-noise ratio of 3 were 0.24-0.30 μmol/L for the cations and 0.31-1.2 μmol/L for the anions.This system was applied for the simultaneous determination of the cations and the anions in a vegetable juice sample with satisfactory results.     

Preparation of thin plate-like calcium phosphate particles with slit-shaped micropores and their molecular sieve effect

The formation of plate-like calcium phosphate particles with slit-shaped micropores produced from the forced hydrolysis reaction of 10?mM Ca(OH)₂, 3.2?mM triphosphate(tripolyphosphate, tpp; $ {{\text{P}}_3}{\text{O}}_{{10}}^{{5 - }} $ ) and 20?mM HCl mixed solution at 100?°C for 2?h were investigated. The molecular sieve effect of produced particles was also explored by using five kinds of adsorptives with various molecular diameters. The large thin plate-like particles as prepared exhibited a large and sharp peak at 2θ?=?6.929° with small diffraction patterns of β-Ca₂P₂O₇. This characteristic peaks at 2θ?=?6.929° suggested that the particles possess a layer structure with ordered basal plane and the large thin plate-like particles are made up of thin sheets. However, the large peak at 2θ?=?6.929° shifted to higher 2θ value after evacuated the particles at 50～200?°C, and these characteristic peak was diminished after treated over 300?°C. The interlayer distances of basal plane were estimated to be 1.280 to 0.980?nm. TG and FTIR measurements disclosed that large amounts of water molecules exist in the particles. It was also revealed that tpp molecules are not completely hydrolyzed to phosphate (orthophosphate, op; $ {\text{PO}}_4^{{3 - }} $ ) ions but still remain tpp and diphosphate (pyrophosphate, pp: $ {{\text{P}}_2}{\text{O}}_7^{{4 - }} $ ) ones, and are adsorbed in slit-shaped micropores. The N₂ adsorption isotherms for the particles were of Type II and they did not change significantly by changing the evacuation temperature from 25?°C to 300?°C. On the contrary, the amount of adsorbed H₂O molecules on the particles after evacuated at 25 and 50?°C steeply increased at ca. 0.3?<?p/p ⁰ ?<?0.6 to provide a step-like adsorption isotherm, but it disappeared after evacuated over 75?°C. From the molecular adsorption experiments employing adsorptives with different molecular diameters, it was indicated that the slit-shaped micropores possess a width less than 0.353?nm being exhibits a high selective adsorption of H₂O molecules into slit-shaped ultramicropores that are accessible to H₂O molecules but not to N₂ and other adsorptive ones. It was indicated that ultramicropores can be formed by the narrowing effect of residual tpp and pp ions unhydrolyzed in the slit-shaped micropores. The residual tpp and pp ions may serve for the adsorption of H₂O molecules by their strong hydrogen bonding nature.     

Nucleation behaviour and anomalous eutectic formation in highly undercooled Fe2O3-La2O3 eutectic melts

Employing an aero-acoustic levitator, the Fe₂O₃-16.5 mol% La₂O₃ eutectic alloy was levitated, melted, undercooled and then solidified under a containerless condition when a continuous laser beam heating system was incorporated. By revealing the surface and cross-sectional microstructures, copious nucleation is confirmed to take place in the undercooled melts solidified by either an external seeding or spontaneous crystallization. The nucleation behaviour of eutectic alloys is summarized, indicating that copious nucleation may be an intrinsic attribute of a eutectic system with the exact eutectic composition in unconstrained solidification. Considering the complexity level of crystal structures of eutectic oxide phases in the Fe₂O₃-La₂O₃ alloy, the linear kinetic constants are approximately estimated and the growth kinetics are discussed. The sluggish growth kinetics of the perovskite-type phase, that is LaFeO₃ with a higher complexity level in a unit cell leads to a decoupled growth within a single eutectic colony when the melt is undercooled to exceed the critical undercooling ΔT = 125 K. It is the decoupled growth that results in the formation of anomalous eutectics. The present concept based on the kinetic constant of different phases can also be applicable to account for the growth behaviour of other oxide eutectics when considering the stable and metastable eutectic reactions in different solidification conditions. The nucleation behaviour and growth modes in some oxide eutectic systems have been predicted in the free solidification from an undercooled state.     

Gorenstein Isolated Quotient Singularities of Odd Prime Dimension are Cyclic

In this article, we shall prove that Gorenstein isolated quotient singularities of odd prime dimension are cyclic. In the case where the dimension is bigger than 1 and is not an odd prime number, then there exist Gorenstein isolated noncyclic quotient singularities.     

Decomposition mechanism of methylene blue caused by metallic iron-maghemite mixture

Decomposition mechanism of methylene blue (MB) caused by a mixture of metallic iron-maghemite (Fe⁰-γFe₂O₃) was investigated by means of ⁵⁷Fe-Mössbauer spectroscopy, X-ray diffractometry (XRD), Ultraviolet-Visible Absorption Spectroscopy (UV-vis) and electrospray-ionization mass spectroscopy (ESI-MS). Ten day-leaching test of 10 μmol L^???1 MB aqueous solution and Fe⁰-γFe₂O₃ mixture (mass ratio 3:7) showed a decrease in the concentration from 10.5 to 4.45 μmol L^???1 with first-order rate constant (k) of $1.5_{7} \times 10^{-1}$  day^???1. An ESI-MS study of Fe⁰-γFe₂O₃ mixture (3:7) after the leaching test revealed new peaks at m/z of 100, 110 and 137 due to fragmentation of MB, in addition to those observed at m/z of 284, 270 and 256 which were ascribed to MB, Azure B and Azure A, respectively. ⁵⁷Fe-Mössbauer spectra of Fe⁰-γFe₂O₃ mixture (3:7) resulted in a decrease in absorption area (A) for Fe⁰ (δ?=?0.00_±0.01 mm s^???1, H _int?=?33.0_±0.1 T) from 37.5 to 21.3, 9.7, 7.9, 7.0 and 4.5_±0.5 %, together with an increase in A from 0.0 to 5.0, 13.8, 17.2, 21.0 and 22.4_±0.5 % for octahedral (O _h) iron (Fe^II?+?Fe^III) of Fe₃O₄. XRD study of these samples indicated that the peak intensity at 2Θ of 44.7° being ascribed to Fe⁰ was decreased, while that of 35.6° due to Fe₃O₄ was almost constant; relative peak ratio of Fe $^{0}/\mathrm{Fe}_{3}$ O₄ was decreased from 26.3 to 2.76 after the leaching, indicating that Fe⁰ in the Fe⁰-γFe₂O₃ mixture was oxidized to Fe₃O₄. These experimental results suggest that Fe⁰-γFe₂O₃ mixture could be utilized for the cleaning or decomposition of toxic organic compounds like trichloroethylene.     

In situ generation of active sites in olefin metathesis

The depth of our understanding in catalysis is governed by the information we have about the number of active sites and their molecular structure. The nature of an active center on the surface of a working heterogeneous catalyst is, however, extremely difficult to identify and precise quantification of active species is generally missing. In metathesis of propene over dispersed molybdenum oxide supported on silica, only 1.5% of all Mo atoms in the catalyst are captured to form the active centers. Here we combine infrared spectroscopy in operando with microcalorimetry and reactivity studies using isotopic labeling to monitor catalyst formation. We show that the active Mo(VI)-alkylidene moieties are generated in situ by surface reaction of grafted molybdenum oxide precursor species with the substrate molecule itself gaining insight into the pathways limiting the number of active centers on the surface of a heterogeneous catalyst. The active site formation involves sequential steps requiring multiple catalyst functions: protonation of propene to surface Mo(VI)-isopropoxide species driven by surface Br?nsted acid sites, subsequent oxidation of isopropoxide to acetone in the adsorbed state owing to the red-ox capability of molybdenum leaving naked Mo(IV) sites after desorption of acetone, and oxidative addition of another propene molecule yielding finally the active Mo(VI)-alkylidene species. This view is quite different from the one-step mechanism, which has been accepted in the community for three decades, however, fully consistent with the empirically recognized importance of acidity, reducibility, and strict dehydration of the catalyst. The knowledge acquired in the present work has been successfully implemented for catalyst improvement. Simple heat treatment after the initial propene adsorption doubled the catalytic activity by accelerating the oxidation and desorption-capturing steps, demonstrating the merit of knowledge-based strategies in heterogeneous catalysis. Molecular structure of active Mo(VI)-alkylidene sites derived from surface molybdena is discussed in the context of similarity to the highly active Schrock-type homogeneous catalysts.