Ionic conductivity enhancement of PVA: carboxymethyl cellulose poly-blend electrolyte films through the doping of NaI salt

Cellulose - In this paper, we report the effect of doping sodium iodide (NaI) salt into a polymer blend matrix of sodium carboxymethyl cellulose (NaCMC) and poly(vinyl alcohol) (PVA). Solution...     

A metal-organic framework with highly polar pore surfaces: selective CO2 adsorption and guest-dependent on/off emission properties

A 3D porous Zn(II) metal-organic framework {[Zn(2)(H(2)dht)(dht)(0.5)(azpy)(0.5)(H(2)O)]·4H(2)O} (1; H(2)dht=dihydroxyterphthalate, azpy=4,4'-azobipyridine) has been synthesised by employing 2,5-dihydroxyterephthalic acid (H(4)dht), a multidentate ligand and 4,4'-azobipyridine by solvent-diffusion techniques at room temperature. The as-synthesised framework furnishes two different types of channels: one calyx-shaped along the [001] direction and another rectangle-shaped along the [101] direction occupied by guest water molecules. The dehydrated framework, {[Zn(2)(H(2)dht)(dht)(0.5)(azpy)(0.5)]} (1') provides 52.7% void volume to the total unit-cell volume. The pore surfaces of 1' are decorated with unsaturated Zn(II) sites and pendant hydroxyl groups of H(2)dht linker, thereby resulting in a highly polar pore surface. The dehydrated framework 1' shows highly selective adsorption of CO(2) over other gases, such as N(2), H(2), O(2) and Ar, at 195 K. Photoluminescence studies revealed that compound 1 exhibits green emission (λ(max)≈530 nm) on the basis of the excited-state intramolecular proton-transfer (ESIPT) process of the H(2)dht linker; no emission was observed in dehydrated solid 1'. Such guest-induced on/off emission has been correlated to the structural transformation and concomitant breaking and reforming of the OH···OCO hydrogen-bonding interaction in the H(2)dht linker in 1'/1.     

In situ Raman spectroscopy of surfaces modified by ion soft landing

The design and characterization of a system for in situ Raman analysis of surfaces prepared by ion soft landing (SL) is described. The performance of the new high vacuum compatible, low cost, surface analysis capability is demonstrated with surface enhanced Raman spectroscopy (SERS) of surfaces prepared by soft landing of ions of crystal violet, Rhodamine 6G, methyl orange and copper phthalocyanine. Complementary in situ mass spectrometric information is recorded for the same surfaces using a previously implemented secondary ion mass spectrometer (SIMS). Imaging of the modified surfaces is achieved using 2D Raman imaging as demonstrated for the case of Rhodamine 6G soft landing. The combination of the powerful molecular characterization tools of SERS and SIMS in a single instrument fitted with in-vacuum sample transport capabilities, facilitates in situ analysis of surfaces prepared by ion SL. In particular, information is provided on the charge state of the soft landed species. In the case of crystal violet the SERS data suggest that the positively charged ions being landed retain their charge state on the surface under vacuum. By contrast, in the case of methyl orange which is landed as an anion, the SERS spectra suggest that the SL species has been neutralized.     

A Conventient Synthesis of 3-Hydroxy-4-chromanone Using Iodobenzene Diacetate

A useful synthesis of 3-hydroxy-4-chromanone (6) is not currently available. Lead tetraacetate oxidation of 4-chromanone (4) yields the C(3) acetoxy derivative but this compound could not be deacetylated to 6.¹ Recently Donnelly and Maloney reported² that the Algar-Flynn-Oyamada reaction (H₂O₂/CH₃OH/NaOH), which is commonly used for the conversion of o-hydroxychalcones (1) into 3-hydroxyflavanone (2) and 3-hydroxyflavones (3), does not yield 6 when applied to o-hydroxya-crylophenone 1 (R = H). The authors found that under less basic conditions using K₂CO₃ some 6 is formed but the major product is catechol. These observations clearly indicate the necessity of developing a method for making 6. The present note describes a staightforward way of preparing 3-hydroxy-4-chromanone (6) in good yield.     

In situ SIMS analysis and reactions of surfaces prepared by soft landing of mass-selected cations and anions using an ion trap mass spectrometer

Mass-selected polyatomic cations and anions, produced by electrosonic spray ionization (ESSI), were deposited onto polycrystalline Au or fluorinated self-assembled monolayer (FSAM) surfaces by soft landing (SL), using a rectilinear ion trap (RIT) mass spectrometer. Protonated and deprotonated molecules, as well as intact cations and anions generated from such molecules as peptides, inorganic catalysts, and fluorescent dyes, were soft-landed onto the surfaces. Analysis of the modified surfaces was performed in situ by Cs⁺ secondary ion mass spectrometry (SIMS) using the same RIT mass analyzer to characterize the sputtered ions as that used to mass select the primary ions for SL. Soft-landing times as short as 30 s provided surfaces that yielded good quality SIMS spectra. Chemical reactions of the surfaces modified by SL were generated in an attached reaction chamber into which the surface was transferred under vacuum. For example, a surface on which protonated triethanolamine had been soft landed was silylated using vapor-phase chlorotrimethylsilane before being returned still under vacuum to the preparation chamber where SIMS analysis revealed the silyloxy functionalization. SL and vapor-phase reactions are complementary methods of surface modification and in situ surface analysis by SIMS is a simple way to characterize the products produced by either technique.     

The Role of Methoxy Group in the Nazarov Cyclization of 1,5-bis-(2-Methoxyphenyl)-1,4-Pentadien-3-one in the Gas Phase and Condensed Phase

ESI-protonated 1,5-bis-(2-methoxyphenyl)-1,4-pentadien-3-one (1) undergoes a gas-phase Nazarov cyclization and dissociates via expulsions of ketene and anisole. The dissociations of the [M + D]⁺ ions are accompanied by limited HD scrambling that supports the proposed cyclization. Solution cyclization of 1 was effected to yield the cyclic ketone, 2,3-bis-(2-methoxyphenyl)-cyclopent-2-ene-1-one, (2) on a time scale that is significantly shorter than the time for cyclization of dibenzalacetone. The dissociation characteristics of the ESI-generated [M + H]⁺ ion of the synthetic cyclic ketone closely resemble those of 1, suggesting that gas-phase and solution cyclization products are the same. Additional mechanistic studies by density functional theory (DFT) methods of the gas-phase reaction reveals that the initial cyclization is followed by two sequential 1,2-aryl migrations that account for the observed structure of the cyclic product in the gas phase and solution. Furthermore, the DFT calculations show that the methoxy group serves as a catalyst for the proton migrations necessary for both cyclization and fragmentation after aryl migration. An isomer formed by moving the 2-methoxy to the 4-position requires relatively higher collision energy for the elimination of anisole, as is consistent with DFT calculations. Replacement of the 2-methoxy group with an OH shows that the cyclization followed by aryl migration and elimination of phenol occurs from the [M + H]⁺ ion at low energy similar to that for 1.

Predicting extrusion instabilities of commercial polyethylene from non-linear rheology measurements

Processing at the highest possible throughput rates is essential from an economical point of view. However, various flow instabilities and extrudate distortions like sharkskin, stick slip, and gross melt fracture (GMF) may limit the production rate of high-quality products. Predicting the process conditions leading to the occurrence of rheological instabilities is the key for improving product quality, process control, and optimization. Large-amplitude oscillatory shear (LAOS) and FT-rheology were used to quantify the non-linear rheological behavior and instabilities of a series of well-characterized commercial polyethylene (PE). From the latter, we derive the critical non-linearity parameter, F _0,c, which corresponds to the normalized intensity of the third harmonic at the critical strain amplitude, γ _0,C (defined by the appearance of the second harmonic), normalized by γ _0,C . The F _0,c is correlated with the high molecular mass fraction of the polymers and with the Deborah numbers. Linear rheological parameters and molecular structures were related to F _0,c. An experimental correlation between F _0,c of commercial PE melts and pressure fluctuations associated with flow instabilities (sharkskin) was established both for capillary rheometry and extrusion.     

Positron annihilation spectroscopic studies of Mn substitution-induced cubic to tetragonal transformation in ZnFe2–xMnxO4 (x = 0.0–2.0) spinel nanocrystallites

The replacement of cations at the B-sites in the spinel ferrite ZnFe₂O₄ by Mn³⁺ ions brings in several interesting changes, the most striking among them being a transformation from the spinel cubic structure to a body-centered tetragonal one. Concomitantly, there are variations in the nanocrystallite sizes and also in the lattice parameters. These are examined through high-precision X-ray diffraction measurements and transmission electron microscopic analysis. A more interesting aspect is the success of positron annihilation spectroscopy comprising of the measurements of positron lifetime and coincidence Doppler broadening measurements in understanding the effects of cation replacement and the resultant generation of vacancy-type defects. There are definite changes in the positron lifetimes and intensities which show positron trapping in trivacancy-type defect clusters and the nanocrystallite surfaces. The presence of ortho-positronium atoms within the extended intercrystallite region is also identified, although in small concentrations. The cubic to tetragonal transformation is indicated through definite decrease in the values of the positron lifetimes. We also performed a model analysis to predict the expected effect of substitution on the positron lifetime in the bulk of the sample and the experimentally obtained positron lifetimes significantly differed, indirectly hinting at the possibility of a structural transformation. Finally, Mössbauer spectroscopic studies have indicated a ferromagnetic nature for one of the samples, i.e. the one with Mn³⁺ doping concentration x = 0.4, which incidentally had the lowest crystallite size ~10 nm.     

Renewable resource‐based poly (m‐phenylenevinylene)s and their statistical copolymers: Synthesis,characterization, and probing of molecular aggregation and Forster energy transfer processes

We report a novel poly (m‐phenylenevinylene)s and their copolymers based on renewable resource starting material 3‐pentadecylphenol to trace the Forster energy transfer process and molecular aggregation in the π‐conjugated polymers. The new bisylide monomer was polymerized with bisaldehyde (or benzaldehyde) under Wittig‐Horner reaction conditions to prepare poly [(4‐methoxy‐6‐pentadecyl‐1, 3‐phenylenevinylene)‐alt‐(1, 3‐phenylenevinylene)] (m‐PPV) and its para‐counterpart poly [(4‐methoxy‐6‐pentadecyl‐1, 3‐phenylenevinylene)‐alt‐(1, 4‐phenylenevinylene)] (p‐PPV) and oligo‐phenylenevinylene model compound 4‐methoxy‐6‐pentadecyl‐1, 3‐distyrylbenzene (OPV). A series of with m‐ or p‐conjugated segments were also prepared by varying the m‐ and p‐content from 0 to 100% in the feed. The selective excitation of m‐conjugated segments in the copolymer by 310 nm light showed emission properties of pure p‐conjugated segments indicating the efficient Forster energy transfer process in segmented copolymers. Both solution quantum yields and the emission intensities increase up to 75% of para‐content in the copolymers. In the solid state, the increase in the p‐incorporation in the copolymer decreases the photoluminescent intensity almost by four times as compared to that of pure meta‐substituted PPV. The excitation spectra of the polymers confirmed a new peak at 400 nm corresponding to the aggregated polymer chains in the film, which is absent in the solution. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3241–3256, 2008