Single-Ionic Conductivityin Poly(Sodium 2-Methacryloyl 3-[Ω-Methoxyl Oligo(Oxyethylene)]Propylsulfonate)

Abstract

Sodium 2-methacryloyl 3-[ω-methoxyl oligo(oxyethylene)] propylsulfonate was synthesized, from which homopolymer-based polyelectrolyte was prepared. The polyelectrolytes thus obtained show single Na⁺ionic conductivity at ambient temperature, neither adding plasticizer nor hybridizing small molecular salt. The conductivity depends considerably on the length of oligo(oxyethylene) side-chain. Optimally, the highest conductivity of 6.0 × 10^?6 S/cm at 25°C is obtained when the number of (CH₂CH₂O) repeating units equals 16. Results indicate that the conductivity data follow WLF and VTF equations. The WLF parameters are found to be comparable with “universal” values, and analysis of the configuration entropy model suggests that the conduction of Na⁺ ions is carried out by an association mechanism.     

Synthesis of α,ω‐Bis(oxazolidinone)polyoxyethylene via a Lithium Bromide–Catalyzed Reaction of Oligoethylene Glycol Diglycidyl Ethers with Isocyanates

The synthesis of bis(oxazolidinone)polyoxyethylene derivatives 2a–h from oligoethylene glycols diglycidyl ethers 1a–e and isocyanates is reported. The reaction was achieved by lithium bromide and tributylphosphine oxide. These bis‐oxazolidinones may have important antibacterial activity.     

Phase Behavior of Poly(Oxyethylene)–Poly(Oxypropylene)–Poly(Oxyethylene) Block Copolymer in Water and Water–C12EO5 Systems

Abstract

The binary phase diagram of a triblock copolymer poly(oxyethylene) (PEO) poly(oxypropylene) (PPO) poly(oxyethylene) (PEO), (PEO)₃₇(PPO)₅₈(PEO)₃₇ or P105 in water and the ternary system of P105, water, and pentaoxyethylene dodecyl ether (C₁₂EO₅) has been studied to understand the miscibility of a small amphiphile, C₁₂EO₅ and a copolymer, as well as the mixing effect on the formed liquid crystalline structures. Phase diagrams, small angle x‐ray scattering (SAXS) and differential scanning calorimetry (DSC) were used to characterize these systems. The phase diagram of the binary system is presented together with the characteristic parameters for founded phases, namely, cubic, hexagonal, and lamellar phases. In the ternary system it was found that the small amphiphile and the block copolymer, despite having very different chain lengths are essentially miscible forming single phases. A large amount of C₁₂EO₅ can be solubilized in the P105 aggregates whereas P105 is most difficult to dissolve in the C₁₂EO₅ aggregates because of the difference in the molecular size. The copolymer is practically insoluble in the lamellar phase of C₁₂EO₅ due to the packing constraint. Hence, two lamellar phases coexist in a surfactant‐rich region, at W _s  = 0.66, where W _s is the weight fraction of the total amphiphile in the system. This indicates that the thickness of the lipophilic part of the C₁₂EO₅ lamellar phase is too small to allocate the large lipophilic chain of the P105 triblock copolymer.     

Copolymerization of ω-Unsaturated Oligo(Methyl Methacrylate): New Macromonomers

Abstract

The free-radical copolymerization of ω-unsaturated oligo(methyl methacrylate) (1) with each of ethyl acrylate, styrene, methyl methacrylate, acrylonitrile, and vinyl acetate have been investigated. Incorporation of (1) into the polymer was observed in all cases although the molecular weights of the copolymers were substantially lower than those of the homopolymers obtained in the absence of (1) but under otherwise identical conditions. These experiments, together with a product study of the reactions of (1) with cyanoisopropyl radicals, have shown that the addition of free radicals to the double bond of (1) occurs readily. The sterically hindered radical so formed, however, undergoes facile β-scission, resulting in the termination of chains (chain transfer) in competition with chain propagation. The implications of these findings to the usefulness of (1) in the synthesis of graft copolymers and their relevance to the chemistry of free-radical polymerizations when methyl methacrylate is employed as a monomer or comonomer are discussed.     

Synthesis of Diaryl Ethers, Diaryl Sulfides, Heteroaryl Ethers and Heteroaryl Sulfides under Microwave Heating

Diaryl ether moiety is found in a pool of naturally occurring and medicinally important compounds.[1] As a consequent, considerable efforts have been devoted to the assembly of this framework.[2] Recently, we have developed a microwave heating version of the synthesis of diaryl ethers as well as aryl sulfides. Under our conditions, even the extremely electron-poor 4-nitrophenol works well and its reaction with 1-halo-4-nitrobenzenes produces 4-(nitrophenoxy)-benzonitriles in satisfactory yield. The scope of the present protocol has been expanded to hydroxylated six-membered heterocycles as well as 2-pyrimidinethiol with mildly activated aryl halides, affording heteroaryl ethers and respectively sulfides. The advantages of the present method include the wide substrate scope, no use of any metal catalysts, the ease of product isolation and high yields.     

Kinetics and Mechanism of the Oxidation of Glycol by Dihydroxyditelluratoargentate(Ⅲ) with Spectrophotometry

The kinetics of the oxidation of glycol by dihydroxyditelluratoargentate (Ⅲ) complex(DDA) was studied in alkaline medium with spectrophotometry(in a temperature range of 16.6-40 ℃).The first-order rates with respect to glycol and Ag(Ⅲ) were all found.The rates increased with the increase in [OH-] and decreased with the increase in [TeO2-4].No effect was found with the addition of KNO3 and no free radical was detected.In view of this,the dihydroxymonotelluratoargentate(Ⅲ) species(DMA) is assumed to be the active species.A plausible mechanism involving a two-electron transfer is proposed,and the rate equation derived from the mechanism can explain all experimental observations.Activation parameters of the rate-determining step and constants are evaluated.     

Optical Properties of Oligo(fluorene-vinylene) Functionalized Anthracene Linear Oligomers: Effect of π-extension

The photo-physical properties of oligo(fluorene-vinylene) functionalized anthracene linear oligomers (An-OFV_n (n=1-4)) have been systemically investigated through experimental and theoretical methods. The steady-state spectral measurement shows that the increas-ing of fluorene-vinylene (FV) group could lead to the red shift of absorption spectra and restrain the excimer formation between oligomers. Quantum chemical calculations exhibit that the energy levels of HOMO, LUMO, and the band gap gradually converge to a con-stant in accompany with the increasing of FV unit. Meanwhile, the electronic cloud which distributes on the branch arms, also gradually enhances and makes the absorption spectral shape of oligomers become similar to that of branch arms step by step. The time-resolved fluorescence tests exhibits that the lifetime of excimer emission would be almost invariable after the number of FV group in oligomer is ≥2. In nonlinear optical test, the two-photon photoluminescence efficiency and two-photon absorption cross-section will both gradually enhance and be close to an extremum after the number of FV unit is equal to 4. These results will provide a guideline for the design of novel photo-electronic materials.     

Synthesis of N-(4-Salicylideneiminoaryl)monoaza Crown Ethers and Dioxygen Affinities of Their Cobalt(II) Complexes

IntroductionSchiffbasesandtheirmetalcomplexeshavebeenap pliedwidelyinthefieldofcatalyticchemistry ,liquidcrystalsandphotochromism .1 3ManySchiffbaseligandscontainingcrownetherpossessdifferentrecognitionsitesforbothalkaliandtransitionmetalguestcations,4 forexample ,theNa(I)orK(I) /Co(II)hetero nuclearcomplexesofcrownedSchiffbasecanbindoxygenmolecule (O2 )toformstablesoliddioxygenadducts .5 7Gebbinkandco workershavereportedaK(I) /Cu(II)sandwichcomplexwhichcanacceleratethefor mationofdioxyg…     

Studies on Polymeric Crown Ethers (Ⅰ)——The Syntheses and Complexation Properties of Polymeric Thiacrown Ethers with Polyether Backbone

Four new polymeric oxa-thiacrown ethers were prepared by the intramolecular cy-clization of poly (2-chloroethylglycidyl ether) with dimercaptans, which is the most convenient method for synthesizing poly(thiacrownether)s. The poly(thiacrownether)s exhibited excellent complexation properties for noble metal ions such as Au ( Ⅲ ) , Pd ( Ⅱ ) and Ag( Ⅰ ) , except Pt( Ⅳ ). In addition, the XPS of polymeric thiacrown ether (PC3) and its complexes of Au( Ⅲ ) and Pd( Ⅱ ) were determined.     

Synthesis of α,α-Difluoroethyl Aryl and Heteroaryl Ethers

Fluorine plays a critical role in modern medicinal chemistry due to its unique properties, and new methods for its incorporation into target molecules are of high interest. An efficient new method for the preparation of aryl-α,α-difluoroethyl ethers (4) via addition of aryl and heteroaryl alcohols (1) to commercially available 2-bromo-1,1-difluoroethene (2) and subsequent hydrogenolysis is presented. This procedure is an attractive alternative to existing methods that employ harshly reactive fluorinating systems such as xenon difluoride and hydrogen fluoride.     

A Facile and Efficient synthesis for A Series of Bis(N-imidazolylethyl) Ethers

Multi-dentateligandssuchasopen-chainandcycliccrownethershavereceivedextensiveintCrestsandbeenmuchstudiedinhost-guestinteraction,supramolecularandbioorganicchemistry".Asabindingand/orcatalyticsiteintheactivecenterofmetalloenzymesandnon-metalloenzymes,imidazoleplaysaveryimportantroleinbiologicalsystem.Imidazole-basedbiomimeticmodelsandmacrocycles,especiallyrecentimidazoliumcyclophaneshavebeenpaidincreasingattention5-ll.Inspiteofthis,onlyoneliteratUre,toourknowledge,reportedthesynthesisofbis(N-i…     

Bis Crown Ethers( Ⅸ)——Caesium Selective PVC Membrane Electrodes Based on Schif f Base Type of Bis Crown Ethers

Recently, much attention has been focused on the use of neutral carrier species as membrane components to extract ions from aqueous solution into a hydrophobic membrane phase. Some potassium-or caesium-selective electrodes based on bis-benzo-15-crown-5 or bis-benzo-18-crown-6 containing ester or other linkage were prepared by K. Kimura and K. W. Fung. The selective coefficients K_(K,Na)~(pot), K_(Cs,Na)~(pot),or K_(Cs,K)~(pot), K were 2.6×10~(-4), 1.9×10~(-2) and 1.7×10~(-1), respectively.     

Reactions of Dicarbonyl(η5-Cyclopentadienyl)Iron(II)-Complexes of Two Cyclic Enol Ethers with Selected Nucleophiles

Dicarbonyl(η⁵-cyclopentadienyl)iron(II)-complexes of 2,3-dihydrofuran and 3,4-dihydro-2H-pyran rapidly react with carbanionic nucleophiles. The adducts of certain nucleophiles, such as the anion of diethyl malonate, readily isomerise to ring opened products. Ligand exchange reactions and polymerisation compete with the nucleophilic addition reactions of neutral nucleophiles such as enol ethers and indole.     

Dehydrogenative α-Oxygenation of Cyclic Ethers by a High-Valent Manganese(IV)-Oxo Species

High-valent metal-oxo species are typical catalytic cycle intermediates in mono-oxygenases and dioxygenases and commonly react through oxygen atom transfer to substrates. In this work we study a biomimetic model complex with a 1,1’-bis((3,5-dimethylpyridin-2-yl)methyl)-2,2’-bipiperidine ligand system bound to a manganese(IV)-oxo(hydroxo) species and study its formation from manganese(II)-hydroxo and H₂O₂ as well as its reaction with (S)-1-phenylisochromane through dehydrogenative α-oxygenation. The work utilizes density functional theory methods to explore its catalytic cycle and its reactivity patterns. We show that the manganese(IV)-oxo(hydroxo) species is an active oxidant and preferentially the oxo group abstracts a hydrogen atom from substrate with barriers well lower in energy than those found for hydrogen atom abstraction by the hydroxo group. Interestingly, the rate-determining step is the OH rebound rather than the hydrogen atom abstraction, which would imply they would have limited kinetic isotope effect for the replacement of the transferring hydrogen atom by deuterium.     

Kinetics and Mechanism of Oxidation of Glycol by Dihydroxydiperiodatonickelate ( Ⅳ )Complex in Aqueous Alkaline Medium

The kinetics of oxidation of glycol by dihydroxydiperiodato nickelate ( Ⅳ) complex (DDN) was studied by spectrophotometry in aqueous alkaline medium in a temperature range of 25-40℃. The reaction was found to be first order with respect to Ni( Ⅳ ) and also to be first order with respect to glycol. The rate increases with the increase in [OH ] and decreases with the increase in [IO-4], showing that dihydroxymonoperiodatonickelate ( Ⅳ )(DMN) is the reactive species of oxidant. Salt effect indicated that the reaction is of ion-dipole type. No free radical was detected. A mechanism of an inner-sphere two-electron transfer reaction involving a preequilibrium between DDN and DMN is proposed, and the rate equation derived from the mechanism can explain all experimental observations. Activation parameters of the rate-determing step and the equilibrium constants were calculated.     

Aluminium Chloride Hexahydrate (AlCl3 · 6H2O): An Efficient,Facile, Mild,And Highly Chemoselective Catalytic Deprotection of Tert-Butyldimethylsilyl (TBS) Ethers

tert-Butyldimethylsilyl (TBS) phenyl / alkyl ethers were cleaved to the corresponding efficiently parent hydroxyl compounds in good yields using catalytic amounts of AlCl₃ · 6H₂O by conventional or microwave-assisted heating in methanol or isopropanol solution. Intramolecular and competitive experiments demonstrated the chemoselective deprotection of TBS ethers in the presence of triisopropylsilyl and tert-butyldiphenylsilyl ethers.     

An Efficient Synthesis of Dicarbonyl (η5—Cyclopentadien—YL)Iron(II) Complexes of Two Cyclic Enol Ethers

An efficient synthesis of dicarbonyl(η⁵—cyclopentadienyl)iron—(II)—complexes of 2,3—dihydrofuran and 3,4—dihydro—2H—pyran from 3—bromo—2—methoxytetrahydrofuran and—pyran, respectively, is described.     

Novel Traceless Liquid‐Phase Synthesis of Coumarin Derivatives on Poly(Ethylene Glycol) Support

Coumarin derivatives were prepared by the von Pechmann reaction of PEG‐bound acetoacetate reagent with phenols in the presence of TiCl₄ in excellent yield and purity with a facile workup procedure. The polymer reagent could be recycled two to four times without diminishing the yield or purity.     

Thermal Decomposition Kinetics of Triethylene Glycol Dinitrate

Introduction Triethylene glycol dinitrate (TEGDN) is a novel en-ergetic material containing two groups of NO2, which can be used as an energetic plasticizer ingredient in propellants because of its excellent proformance.1 It exhibits lower impact sensitivity, better thermostability, weaker poisonousness and volatility, and stronger effec-tiveness of plasticizing cellulose nitrate than nitroglyc-erine (NG). As a new plasticizer TEGDN has good ap-plication prospects in the near future. The…     

Critical Behavior of Binary Mixtures of Nitrobenzene?+?n-Undecane and Nitrobenzene?+?n-Dodecane

Turbidities and isobaric heat capacities per unit volume, in a wide temperature range, have been measured for critical binary solutions of {nitrobenzene?+?n-undecane} and {nitrobenzene?+?n-dodecane}. The critical exponents and the system-dependent critical amplitudes were deduced. The non-critical and the critical-fluctuation induced contributions to the background heat capacities were determined. We also obtained the coupling constant $ \bar{u} $ by analyzing the coexistence curve data with crossover theory. These parameters were used to test some universal amplitude ratios and together with the coexistence-curve data to test the complete scaling theory. It is shown that the contribution from heat capacity plays an important role in describing the asymmetric criticality of the coexistence curve.