Induced-fit binding of π-electron donor substrates to macrocyclic aromatic ether-imide-sulfones: a versatile approach to molecular assembly

Novel macrocyclic receptors which bind electron-donor aromatic substrates via π-stacking donor- acceptor interactions are obtained by cyclo-imidization of an amine-functionalized arylether-sulfone with pyromellitic- and 1,4,5,8-naphthalene-tetracarboxylic dianhydrides. These macrocycles complex with a wide variety of π-donor substrates including tetrathiafulvalene, naphthalene, anthracene, pyrene, perylene, and functional derivatives of these polycyclic hydrocarbons. The resulting supramolecular assemblies range from simple 1:1 complexes, to [2]- and [3]-pseudorotaxanes, and even (as a result of crystallographic disorder) an apparent polyrotaxane. Direct, five-component self-assembly of a metal-centred [3]pseudorotaxane is also observed, on complexation of a macrocyclic ether-imide with 8-hydroxyquinoline in the presence of palladium(II) ions. Binding studies in solution were carried out by 1H NMR and UV-visible spectroscopy, and the stoichiometries of binding were confirmed by Job plots based on charge-transfer absorption bands. The highest association constants are found for strong π-donor guests with large surface-areas, notably perylene and 1-hydroxypyrene, for which Ka values of 1.4 x 103 and 2.3 x 103 M-1 respectively are found. Single crystal X-ray analyses of the receptors and their derived complexes reveal large, induced-fit distortions of the macrocyclic frameworks as a result of complexation. These structures provide compelling evidence for the existence of strong, attractive forces between the electronically-complementary aromatic π-systems of host and guest.

Reactions of NO3 with the man-made emissions 2-methylpent-2-ene, (Z)-3-methylpent-2-ene, ethyl vinyl ether, and the stress-induced plant emission ethyl vinyl ketone

Rate coefficients for reactions of nitrate radicals (NO3) with the anthropogenic emissions 2-methylpent-2-ene, (Z)-3-methylpent-2-ene.. ethyl vinyl ether, and the stress-induced plant emission ethyl vinyl ketone (pent-1-en-3-one) were determined to be (9.3 +/- 1.1) x 10(-12), (9.3 +/- 3.2) x 10(-12), (1.7 +/- 1.3) x 10(-12) and (9.4 + 2.7) x 10(-17) cm(3) molecule(-1) s(-1). We performed kinetic experiments at room temperature and atmospheric pressure using a relative-rate technique with GC-FID analysis. Experiments with ethyl vinyl ether required a modification of our established procedure that might introduce additional uncertainties, and the errors suggested reflect these difficulties. Rate coefficients are discussed in terms of electronic and steric influences. Atmospheric lifetimes with respect to important oxidants in the troposphere were calculated. NO3-initiated oxidation is found to be the strongly dominating degradation route for 2-methylpent-2-ene, (Z)-3-methylpent-2-ene and ethyl vinyl ether. Atmospheric concentrations of the alkenes and their relative contribution to the total NMHC emissions from trucks can be expected to increase if plans for the introduction of particle filters for diesel engines are implemented on a global scale. Thus more kinetic data are required to better evaluate the impact of these emissions.

Synthesis of water-soluble and ether-soluble tetra-μ-acetatodiruthenium(II,III) complexes and X-ray crystal structure of [Ru2(μ-O2CC6H5)4(C2H5OH)2][Ru2(μ-O2CC6H5)4(HSO4)2]

[Ru2(μ-O2CCH3)4Cl] reacts readily with aqueous Ag2SO4 (2: 1 molar ratio) to give the sulphate salt [Ru2(μ-O2CCH3)4(H2O)2]2(SO4) (1). Addition of NaBPh4 to an aqueous solution of 1 produces the ether-soluble tetraphenylborate salt [Ru2(μ-O2CCH3)4(H2O)2][BPh4] (2). A methanolic solution of 1 reacts with Ba(C6H5CCCO2)2 · H2O to give the tetraacetatemonophenylpropynoate complex [Ru2(μ-O2CCH3)4(O2CCCC6H5)] · H2O (3). The reaction of an ethanolic suspension of [Ru2(μ-O2CC6H5)4Cl] with Ag2SO4 and H2SO4 (2 : 1 : 1 molar ratio) leads to the tetra-μ-benzoatodiruthenium(II,III) double complex salt [Ru2(μ-O2CC6H5)4(C2H5OH)2][Ru2(μ-O2CC6H5)4(HSO4)2] (4). Complex 4 is also obtained by reacting an ethanolic solution of 1 with an excess of benzoic acid in the presence of H2SO4. The X-ray crystal structure of 4 shows it to consist of [Ru2(μ-O2CC6H5)4(C2H5OH)2]+ and [Ru2(μ-O2CC6H5)4(HSO4)2]− ions, which are linked together by hydrogen bonds into an infinite polymeric chain. The RuRu distances in the cation and anion are very similar [2.265(2) and 2.272(2) Å, respectively]. Spectroscopic, magnetic, conductivity and cyclic voltammetry data are given for the complexes.

X-ray diffraction study of the influence of temperature on the structural correlations of poly(2-hydroxypropyl ether of bisphenol A)

The X-ray diffraction pattern of glassy poly(2-hydroxypropyl ether of bisphenol A) is studied at room temperature on oriented samples in order to associate its different peaks to different structural correlations. On the other hand, X-ray diffraction patterns have been obtained at different temperatures from Tg − 50 K up to Tg + 50 K for the above-mentioned polymer. Attention has been paid to the evolution with temperature of the position of the wide diffraction maximum corresponding to interchain correlations in the polymer. The temperature evolution of this parameter shows a marked discontinuity just at the glass transition temperature.

Synthesis of beaded poly(vinyl ether) solid supports with unique solvent compatibility

Poly(vinyl ether) gels SLURPS (Superior Liquid Uptake Resin for Polymer-supported synthesis) with low cross-linking levels have been synthesized for the first time in beaded form using a non-aqueous inverse suspension polymerisation approach. The synthetic protocol was optimized with regards to several parameters including reactions conditions, type and concentration of suspension stabilizer and controlled low temperature addition of co-initiator. Particle size measurements confirm the production of beads with average diameters of 700e950 mm. Optimization of the monomer composition of the poly (vinyl ether) gels resulted in a novel beaded polymer support with considerably improved as well as unique swelling characteristics in solvents ranging from hexane to water. The synthetic utility of the new gel was confirmed by carrying out a set of transformations with complete conversion leading to a useful amino and hydroxy terminated solid-phase precursor resin. Reaction progress could be monitored easily by 1H and 13C gel-phase NMR.

Controlled variation of monomer sequence-distribution in the synthesis of aromatic poly(ether ketone)s

The effects of varying the alkali metal cation in the high-temperature nucleophilic synthesis of a semi-crystalline, aromatic poly(ether ketone) have been systematically investigated, and striking variations in the sequence-distributions and thermal characteristics of the resulting polymers were found. Polycondensation of 4,4'-dihydroxybenzophenone with 1,3-bis(4-fluorobenzoyl)benzene in diphenylsulfone as solvent, in the presence of an alkali metal carbonate M2CO3 (M= Li, Na, K, or Rb) as base, affords a range of different polymers that vary in the distribution pattern of 2-ring and 3-ring monomer units along the chain. Lithium carbonate gives an essentially alternating and highly crystalline polymer, but the degree of sequence-randomisation increases progressively as the alkali metal series is descended, with rubidium carbonate giving a fully random and non-thermally-crystallisable polymer. Randomisation during polycondensation is shown to result from reversible cleavage of the ether linkages in the polymer by fluoride ions, and an isolated sample of alternating-sequence polymer is thus converted to a fully randomised material on heating with rubidium fluoride.

Effects of gamma radiation on the growth of Alternaria alternata and on the production of alternariol and alternariol monomethyl ether in sunflower seeds

The objective of the present study was to evaluate the effects of different gamma radiation doses on the growth of Alternaria alternata and on the production of toxins alternariol (AOH), and alternariol monomethyl ether (AME) in sunflower seed samples. After irradiation with 2, 5 and 7 kGy, the spore mass was resuspended in sterile distilled water and the suspension was inoculated into sunflower seeds. The number of colony-forming units per gram (CFU/g) was determined after culture on Dichloran Rose Bengal Chloramphenicol and Dichloran Chloramphenicol Malt Extract Agar. The presence of AOH and AME was investigated by liquid chromatography coupled to mass spectrometry. The radiation doses used resulted in a reduction of the number of A. alternata CFU/g and of AOH and AME levels when compared to the nonirradiated control group. Maximum reduction of the fungus (98.5%) and toxins (99.9%) was observed at a dose of 7 and 5 kGy, respectively. Under the present conditions, gamma radiation was found to be an alternative for the control of A. alternata and, consequently, of AOH and AME production in sunflower seeds. (C) 2009 Elsevier Ltd. All rights reserved.

Optimization of the ultrasound-assisted synthesis of allyl 1-naphthyl ether using response surface methodology

Allyl 1-naphthyl ethers are useful compounds for different purposes, but reported methods to synthesize them require long reaction times. In this work, we have obtained allyl 1-naphthyl ether in good yield using ultrasonic-assisted methodology in a 1-h reaction. A central composite design was used to obtain a statistical model and a response surface (p < 0.05; R(2) = 0.970; R(adj)(2) = 0.949; R(pred)(2) = 0.818) that can predict the optimal conditions to maximize the yield, validated experimentally. (C) 2010 Elsevier B.V. All rights reserved.

Ether-Bond-Containing Ionic Liquids and the Relevance of the Ether Bond Position to Transport Properties

The ionic liquids (ILs) 1-ethoxyethyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide, [EtO-(CH(2))(2)MMI][Tf(2)N], and N-(ethoxyethyl)-N-methylmorpholinium bis(trifluoromethanesulfonyl)imide, [EtO(CH(2))(2)MMor][Tf(2)N] were synthesized, and relevant properties, such as thermal stability, density, viscosity, electrochemical behavior, ionic conductivity, and self-diffusion coefficients for both ionic species, were measured and compared with those of their alkyl counterparts, 1-n-butyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide, [BMMI][Tf(2)N], and N-n-butyl-N-methylpiperidinium bis(trifluoromethanesulfonyl)imide,[BMP][Tf(2)N] and N-n-butyl-N-methylmorpholinium bis(trilfuoromethanesulfonyl)imide [BMMor][Tf(2)N][. This comparison was done to evaluate the effects caused by the presence of the ether bond in either the side chain or in the organic cation ring. The salt, LiTf(2)N, was added to the systems to estimate IL behavior with regard to lithium cation transport. Pure [EtO(CH(2))(2)MMI][Tf(2)N] and their LiTf(2)N solutions showed low viscosity and the highest conductivity among the ILs studied. The H(R) (AC conductivity/NMR calculated conductivity ratio) values showed that, after addition of LiTf(2)N, ILs containing the ether bond seemed to have a greater number of charged species. Structural reasons could explain these high observed HR values for [EtO(CH(2))(2)MMor][Tf(2)N].

Raman spectra of polymer electrolytes based on poly(ethylene glycol) dimethyl ether, lithium perchlorate, and the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate

Raman spectra of polymer electrolytes based on poly(ethylene glycol) dimethyl ether (PEGdME) with LiClO(4), PEGdME/LiClO(4), and the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate, PEGdME/[bmim]PF(6), are compared. Raman spectroscopy suggests stronger interactions in PEGdME/LiClO(4) than PEGdmE/[bmim]PF(6), thus corroborating previous results obtained by molecular dynamics simulations. Quantum Chemistry methods have been used to calculate vibrational frequencies and the equilibrium structure of segments of the polymer chain around the cation. A consistent picture has been obtained from Raman spectroscopy, density functional theory (DFT) calculations, and molecular dynamics simulations for these polymer electrolytes. (C) 2010 Elsevier B.V. All rights reserved.

Evaluation of Postpolymerization as a Function of the Storage Time of Triethylene Glycol Dimethacrylate/2,2-Bis[4-(2-Hydroxy-3-Methacryloxy-Prop-1-Oxy)-Phenyl]-propane Bisphenyl-alpha-Glycidyl Ether Dimethacrylate Copolymers Used in Dental Resins by Differential Scanning Calorimetry and Dynamic Mechanical Analysis

The aim of this work was to evaluate the effect of the storage time on the thermal properties of triethylene glycol dimethacrylate/2,2-bis[4-(2-hydroxy-3-methacryloxy-prop-1-oxy)-phenyl]propane bisphenyl-alpha-glycidyl ether dimethacrylate (TB) copolymers used in formulations of dental resins after photopolymerization. The TB copolymers were prepared by photopolymerization with an Ultrablue IS light-emitting diode, stored in the dark for 160 days at 37 degrees C, and characterized with differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and Fourier transform infrared spectroscopy with attenuated total reflection. DSC curves indicated the presence of an exothermic peak, confirming that the reaction was not completed during the photopolymerization process. This exothermic peak became smaller as a function of the storage time and was shifted at higher temperatures. In DMA studies, a plot of the loss tangent versus the temperature initially showed the presence of two well-defined peaks. The presence of both peaks confirmed the presence of residual monomers that were not converted during the photopolymerization process. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 112: 679-684, 2009

Fast dynamics in the optical storage with Langmuir-Blodgett films of a diazocrown ether molecule

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Study of optical properties and molecular structure of plasma polymerized diethylene glycol dimethyl ether

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Wettability, optical properties and molecular structure of plasma polymerized diethylene glycol dimethyl ether

Modern industry has frequently employed ethylene glycol ethers as monomers in plasma polymerization process to produce different types of coatings. In this work we used a stainless steel plasma reactor to grow thin polymeric films from low pressure RF excited plasma of diethylene glycol dimethyl ether. Plasmas were generated at 5W RF power in the range of 16 Pa to 60 Pa. The molecular structure of plasma polymerized films and their optical properties were analyzed by Fourier Transform Infrared Spectroscopy (FTIR) and UltravioletVisible Spectroscopy, respectively. The IR spectra show C-H stretching at 3000-2900 cm(-1), C=O stretching at 1730-1650 cm(-1), C-H bending at 1440-1380 cm(-1), C-O and C-O-C stretching at 1200-1000 cm(-1). The refraction index was around 1.5 and the optical gap calculated from absorption coefficient presented value near 3.8 eV. Water contact angle of the films ranged from 40 degrees to 35 degrees with corresponding surface energy from 66 to 73x10(-7) J. Because of its favorable optical and hydrophilic characteristics these films can be used in ophthalmic industries as glass lenses coatings.

Study of RF-excited Diethylene Glycol Dimethyl Ether Plasmas by Mass Spectrometry

This paper deals with the study of the fragmentation process of diethylene glycol dimethyl ether (CH3O(CH2CH2O)(2)CH3) (diglyme here in) molecule in low pressure RF excited plasma discharges. The study was carried out using mass spectrometry. The results showed that for a fixed pressure, the increase of the RF power coupled to the plasma chamber from 1 to 35 W produced a plasma environment much more reactive which increases the population of the ionized species like CH3+ (15 amu), C2H4+ (28 amu), CH3O+ (31 amu), C2H4O+ (44 amu), CH3OCH2CH2+ (59 amu) and CH3OCH2CH2O+ (75 amu). This fact may be attributed to the increase of the electronic temperature that makes predominant the occurrence of inelastic processes that promotes molecular fragmentation. For a fixed value of RF power the increase of pressure from 50 mTorr to 100 mTorr produces the decreasing of the above mentioned chemical species due the lower electronic mean free path. These results suggest that if one wants to keep the monomer's functionality within the plasma deposited films resulting from such kind of discharges one must operate in low power conditions.