Polymerization of lactides and lactones. III. Ring-opening polymerization of DL-lactide by the (η3-C3H5)2Sm(μ2-Cl)2(μ3-Cl)2Mg(tmed)(μ2-Cl)Mg(tmed) complex

Ring-opening polymerization of DL -lactide (LA) has been initiated with the (η³-C₃H₅)₂Sm(μ₂-Cl)₂(μ₃-Cl)₂Mg(tmed)(η₂-Cl)Mg(tmed) complex both in bulk and solution. The effects of reaction conditions, such as reaction time, reaction temperature, and monomer/initiator molar ratio on the polymerization has been discussed. The results showed that (η³-C₃H₅)₂Sm(μ₂-Cl)₂(μ₃-Cl)₂Mg(tmed)(μ₂-Cl)Mg(tmed) was more effective for the polymerization of LA, and high molecular weight of polylactide was obtained by this initiator. The solvent affected the polymerization significantly. The polymerization mechanism was in agreement with the coordination mechanism. The polymer was characterized by FTIR, ¹H-NMR, and DSC. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2857–2862, 1999     

Effect of substituents in the manganese μ-oxo porphyrins catalyzed oxidation of cyclooctane with molecular oxygen

Electron-donating or electron-withdrawing substituents at the porphyrin rings considerably increase the catalytic activity of the manganese monomeric and μ-oxo porphyrins in the oxidation of cyclooctane with molecular oxygen without the use of sacrificial co-reductant. The change in the catalytic activity is due to the nature and number of the substituents in the porphyrin ring.     

μ‐Gels as support materials for dinuclear olefin polymerization catalysts

μ‐Gels which consist of poly(organosilicon) networks can be employed as efficient support materials for ethylene polymerization catalyst precursors. Alkylaluminum cocatalysts can be fixed on the μ‐gel surfaces using the PHT (“partially hydrolyzed trimethylaluminum”) method. The influence of different aluminum/water ratios on the ethylene polymerization properties of these heterogeneous systems is investigated. Dinuclear silicon bridged zirconium complexes are used as catalyst precursors yielding polyethylenes with broad or bimodal molecular weight distributions. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Binuclear Iron(III) Phthalocyanine(μ‐Oxodimer)‐Catalyzed Oxygenation of Aromatic Hydrocarbons with Iodosylbenzene Sulfate and Iodosylbenzene as the Oxidants

Two binuclear iron(III) phthalocyanine‐(μ‐oxodimer) complexes were tested in catalytic oxygenation reactions of several aromatic hydrocarbons using iodosylbenzene (PhIO)_n or oligomeric iodosylbenzene sulfate [(PhIO)₃SO₃]_n as the oxidants. Results of this study demonstrate that [(PhIO)₃SO₃]_n is the most reactive oxygenating reagent that can be used as a safe and convenient alternative to the thermally unstable and potentially explosive iodosylbenzene. The pyridine‐containing binuclear μ‐oxobis{iron(III)‐pyridino[3,4]‐9(10),16(17),23(24)‐tri‐tert‐butyltribenzoporphyrazine} is significantly more active as compared to the traditional μ‐oxobis[iron(III)‐2,9(10),16(17),23(24)‐tetra‐tert‐butylphthalocyanine].     

Precisely Controlling Preparation of Ceria‐Stabilized Zirconia Microspheres of ~100 μm by External Gelation

Ceria‐stabilized zirconia (CSZ) microspheres of ~100 μm were prepared by external gelation process. The inner diameter of nozzle was 0.2 mm. The key process parameters including broth pH value, Zr concentration, flow rate, and vibration frequency were optimized for precise control of the diameter. The optimum parameters were found to be flow rate of 11.08 mL/min, Zr concentration of 0.72 mol/L, and vibration frequency of 2650 Hz. CSZ microspheres with an average diameter of 103.1 μm and standard deviation of 4.4 were prepared under these conditions. CSZ microspheres showed good monodispersity, good sphericity, and high density.     

一锅法从卟啉配体合成μ-氧代四苯基双核铁卟啉

A novel method for synthesis of substituted u-oxo-bis[tetraphenyl porphyrinatoiron] compotmds （[TRPPFe]20） based on the reaction among free base porphyrins （TRPPH2）, FeSO4·7H2O and H2O in one pot was proposed and investigated. Four kinds of [TRPPFe]2O were synthesized by this novel synthetic method, and their structures were characterized by elemental analysis, infrared spectra and UV-vis spectroscopy. The reaction conditions, including the effect of different iron salts on the formation of [TRPPFe]2O, the reaction time between FeSO4-7H2O and TRPPH2, the molar ratio of FeSO4-7H2O/TRPPH2 as well as the volume ratio of H2O/DMF, were investigated. The [TRPPFe]2O yield of 93% 98% could be obtained under the following optimal conditions： the reaction time of FeSOn-7H2O with TRPPH2 was about 10 h, the molar ratio of FeSOn-7H2O/TRPPH2 about 5 ： 1, and the volume ratio of H2O/DMF exceeded 2 ： 1. Further research indicated that only TRPPFeCI were formed once FeSOn-7H2O was replaced by FeCl2-4H2O, the reason of which might be that halogen ions in iron salts interfered the formation of [TRPPFe]2O, suggesting that halogen ions should be avoided in this novel synthetic method.     

Effect of nucleating duality on the formation of γ‐phase in a β‐nucleated isotactic polypropylene copolymer

BACKGROUND: It is a challenge for polymer processing to promote the formation of γ‐phase under atmospheric conditions in isotactic polypropylene (iPP) copolymer containing chain errors. Incorporation of an α‐nucleator in iPP copolymer seems reasonable since it can enhance non‐isothermal crystallization. Up to now, however, the issue regarding a β‐nucleated iPP copolymer still remains unclear, which is the subject of this study. RESULTS: The results indicate that the γ‐phase indeed occurs in a β‐nucleated random iPP copolymer with ethylene co‐unit (PPR) sample and becomes predominant at slow cooling rates (e.g. 1 °C min^?1) where the formation of the β‐form is suppressed to a large extent. With detailed morphological observations the formation of γ‐phase in the β‐nucleated PPR sample at slow cooling rate is unambiguously attributed to the nucleating duality of the β‐nucleator towards α‐ and β‐polymorphs. The α‐crystals, induced by the β‐nucleator, serve as seeds for the predominant growth of the γ‐phase. Moreover, the presence of the β‐nucleator, acting as heterogeneous nuclei, promotes the formation of γ‐phase in the nucleated PPR sample, at least to some extent. CONCLUSION: The findings in this study extend our insights into the formation of γ‐phase in β‐nucleated iPP copolymer and, most importantly, provide an alternative route to obtain iPP rich in γ‐phase. Copyright © 2008 Society of Chemical Industry     

An Analysis of Pressure Drop and Holdup for Liquid‐Liquid Upflow through Vertical Pipes

The present study has attempted to investigate pressure drop and holdup during simultaneous flow of two liquids through a vertical pipe. The liquids selected were kerosene and water. The measurements were made for phase velocities varying from 0.05–1.2 m/s for both liquids. The pressure drop was measured with a differential pressure transducer while the quick closing valve (QCV) technique was adopted for the measurement of liquid holdup. The measured holdup and pressure drop were analyzed with suitable theoretical models according to the existing flow patterns. The analysis reveals that the homogeneous model is suitable for dispersed bubbly flow whereas bubbly and churn‐turbulent flow pattern is better predicted by the drift flux model. On the other hand, the two fluid flow model accurately predicts the pressure drop in core annular flow.     

型板换热器的传热性能和阻力降特性研究

研究一种新型高效型板换热器 ,对型板换热器的传热特性及阻力降性能等进行了实验研究。通过研究发现 ,型板换热器的传热系数比列管式换热器的传热系数高 5 0 %～ 10 0 % ,阻力降值比传统的列管式换热器低 ,与型板内流体流速的 1 4 4次方成正比     

Regio‐ and Enantioselective Copper‐Catalyzed 1,4‐Conjugate Addition of Trimethylaluminium to Linear α,β,γ,δ‐Unsaturated Alkyl Ketones

A regio‐ and enantioselective copper‐catalyzed 1,4‐conjugate addition of trimethylaluminium to linear δ‐aryl‐substituted α,β,γ,δ‐unsaturated alkyl ketones was developed. A series of γ,δ‐unsaturated alkyl ketones were obtained in good yields with high regio‐ and enantioselectivity (up to 88% ee and 96:4 dr). Expansion of the reaction scope to substrates containing aromatic heterocycles also afforded good yields and enantioselectivities (up to 91% ee) with very high regioselectivities, exclusively providing the single 1,4‐products.

     

Ruthenium(II)‐Catalyzed Protocol for Preparation of Diverse α,β‐ and β,β‐Dihaloenones from Diazodicarbonyls

Efficient one‐step syntheses of α,β‐ and β,β‐dihaloenones were achieved by ruthenium(II)‐catalyzed reactions between cyclic or acyclic diazodicarbonyl compounds and oxalyl chloride or oxalyl bromide in moderate to good yields. This methodology offers several significant advantages, which include ease of handling, mild reaction conditions, one‐step reaction, and the use of an effective and non‐toxic catalyst. The synthesized compounds were further transformed into highly functionalized novel molecules bearing aromatic rings on the enone moiety using the Suzuki reaction.

     

Fabrication and Performance of Solid Oxide Fuel Cells with La0.2Sr0.7TiO3–δ as Anode Support and La2NiO4+δ as Cathode

A novel fabrication process for solid oxide fuel cells (SOFCs) with La_0.2Sr_0.7TiO_3–δ (LST_A–) as anode support and La₂NiO_4+δ (LNO) as cathode material, which avoids complicated impregnation process, is designed and investigated. The LST_A– anode‐supported half cells are reduced at 1,200 °C in hydrogen atmosphere. Subsequently, the LNO cathode is sintered on the YSZ electrolyte at 1,200 °C in nitrogen atmosphere and then annealed in situ at 850 °C in air. The results of XRD analysis and electrical conductivity measurement indicate that the structure and electrochemical characteristics of LNO appear similar before and after the sintering processes of the cathode. By using La_0.6Sr_0.4CoO_3–δ (LSC) as current collector, the cell with LNO cathode sintered in nitrogen atmosphere exhibits the power density at 0.7 V of 235 mW cm⁻² at 800 °C. The ohmic resistance (R_S) and polarization resistance (R_P) are 0.373 and 0.452 Ω cm², respectively. Compared to that of the cell with the LNO cathode sintered in air, the sintering processes of the cell with the LNO cathode sintered in nitrogen atmosphere can result in better electrochemical performance of the cell mainly due to the decrease in R_S. The microstructures of the cells reveal a good adhesion between each layer.     

Catalytic Hydrogenation of α‐Iminophosphonates as a Method for the Synthesis of Racemic and Optically Active α‐Aminophosphonates

It was shown that the catalytic hydrogenation of α‐iminophosphonates by molecular hydrogen can serve as a convenient method for the synthesis of racemic and optically active α‐aminophosphonates. Up to 94% ee was achieved in the rhodium‐catalyzed enantioselective hydrogenation using chiral ligand (R)‐BINAP.     

Friedel–Crafts Reaction of Indoles with Isatin‐Derived β,γ‐Unsaturated α‐Keto Esters Using a BINOL‐Derived Bisoxazoline (BOX)/Copper(II) Complex as Catalyst

Several chiral BINOL‐derived bisoxazoline (BOX)/copper(II) complexes were synthesized and evaluated as catalysts for the Friedel–Crafts reaction of indoles with isatin‐derived β,γ‐unsaturated α‐keto esters. The resulting bis‐indole products bearing a quaternary stereocenter were obtained in excellent yields and enantioselectivities. Additionally, the desired products were practically transformed to α‐amino esters, α‐hydroxy esters and α‐keto amides. It is noteworthy that this catalytic procedure was conducted with a catalyst loading of 0.5 mol% without any discernible decrease in the reactivity or enantioselectivity.

     

Structural characterization of α‐ and β‐nucleated isotactic polypropylene

Modification of isotactic polypropylene (iPP) with two nucleation agents, namely 1,3:24‐bis(3,4‐dimethylobenzylideno) sorbitol (DMDBS) (α‐nucleator) and N, N′‐dicyclohexylo‐2,6‐naphthaleno dicarboxy amide (NJ) (β‐nucleator), leads to significant changes of the structure, morphology and properties. Both nucleating agents cause an increase in the crystallization temperature. The efficiency determined in a self‐nucleation test is 73.4 % for DMDBS and 55.9 % for NJ. The modification with NJ induces the creation of the hexagonal β‐form of iPP. The addition of DMDBS lowers the haze of iPP while the presence of NJ increases the haze. Copyright © 2004 Society of Chemical Industry     

Peculiar sandwich-like π–π interaction regulating the nonplanarity of the model heme crystals

X-ray crystallographic analysis of bis(pyridine N-oxide) complexes of iron(III) porphyrinates has revealed that the two pyridine rings of the axial ligands correctly sandwich the porphyrin ring to induce the deformation of commonly observed S₄ saddled porphyrin ring.     

The Synthesis of trans‐Perhydroindolic Acids and their Application in Asymmetric Domino Reactions of Aldehyde Esters with β,γ‐Unsaturated α‐Keto Esters

(2S,3aR,7aS)‐Perhydroindolic acid, the key intermediate in the synthesis of trandolapril, and its trans‐isomers, were readily prepared. These proline‐like molecules are unique in that they contain a rigid bicyclic structure, with two hydrogen atoms trans to each other at the bridgehead carbon atoms. These molecules were used successfully as chiral organocatalysts in asymmetric domino Michael addition/cyclization reactions of aldehyde esters with β,γ‐unsaturated α‐keto esters. They proved to have excellent catalytic behavior, allowing for the synthesis of multi‐substituted, enantiomerically enriched hemiacetal esters. Under optimal conditions (using 10 mol% catalyst loading), a series of β,γ‐unsaturated α‐keto esters was examined with up to 99% de, ee and yield, respectively. Additionally, the enantiomerically enriched hemiacetal esters could be readily transformed into their corresponding bioactive pyrano[2,3‐b]pyrans (possessing a multi‐substituted bicyclic backbone).     

Synthesis and Pharmacological Evaluation of α4β2 Nicotinic Ligands with a 3‐Fluoropyrrolidine Nucleus

Nicotinic acetylcholine receptors (nAChRs) play an important role in many central nervous system disorders such as Alzheimer’s and Parkinson’s diseases, schizophrenia, and mood disorders. The α₄β₂ subtype has emerged as an important target for the early diagnosis and amelioration of Alzheimer’s disease symptoms. Herein we report a new class of α₄β₂ receptor ligands characterized by a basic pyrrolidine nucleus, the basicity of which was properly decreased through the insertion of a fluorine atom at the 3‐position, and a pyridine ring carrying at the 3‐position substituents known to positively affect affinity and selectivity toward the α₄β₂ subtype. Derivatives 3‐(((2S,4R)‐4‐fluoropyrrolidin‐2‐yl)methoxy)‐5‐(phenylethynyl)pyridine ( 11 ) and 3‐((4‐fluorophenyl)ethynyl)‐5‐(((2S,4R)‐4‐fluoropyrrolidin‐2‐yl)methoxy)pyridine ( 12 ) were found to be the most promising ligands identified in this study, showing good affinity and selectivity for the α₄β₂ subtype and physicochemical properties predictive of a relevant central nervous system penetration.     

Highly Enantioselective Michael Addition of Cyclic 1,3‐Dicarbonyl Compounds to β,γ‐Unsaturated α‐Keto Esters

A highly enantioselective Michael addition of cyclic 1,3‐dicarbonyl compounds to β,γ‐unsaturated α‐keto esters catalyzed by amino acid‐derived thiourea‐tertiary‐amine catalysts is presented. Using 5 mol% of a novel tyrosine‐derived thiourea catalyst, a series of chiral coumarin derivatives were obtained in excellent yields (up to 99%) and with up to 96% ee under very mild conditions within a short reaction time.