Cluster Formation through Hydrogen Bond Bridges across Chloride Anions in a Hydroxyl-Functionalized Ionic Liquid

Several recent studies of hydroxyl-functionalized ionic liquids (ILs) have shown that cation-cation interactions can be dominating these materials at the molecular level when the anion involved is weakly interacting. The hydrogen bonds between the like ions led to the formation of interesting chain-like, ring-like, or distinct dimeric (i. e. two ion pairs) supermolecular clusters. In the present work, vibrational spectroscopy (ATR-IR and Raman) and density functional theory (DFT) calculations of the hydroxyl-functionalized imidazolium ionic liquid C₂OHmimCl indicate that anion-cation hydrogen bonding interactions are dominating, leading to the formation of distinct dimeric ion pair clusters. In this arrangement, the Cl⁻ anions function as a bridge between the cations by establishing bifurcated hydrogen bonds with the OH group of one cation and the C(2)-H of another cation. Cation–cation interactions, on the other hand, do not play a significant role in the observed clusters.     

Structure and Electrical Properties of Potassium-Doped Siloxane-Poly(oxypropylene) Ormolytes

The structure and the ionic conduction properties of siloxane-poly(oxypropylene) (PPO) hybrids doped with different potassium salts (KCF₃SO₃, KI, KClO₄ and KNO₂) are reported for two polymer molecular weights (300 and 4000 g/mol), labelled PPO₃₀₀ and PPO₄₀₀₀, respectively. The doping concentration, related to the concentration of the ether type oxygen of the PPO chain, is the same whatever the salt and verifies [O]/[K] = 20. Ionic room temperature conductivity shows the highest value for the KCF₃SO₃ doped PPO₄₀₀₀ hybrid (4 × 10^{–7 –1} cm^–1). The structure of these hybrids was investigated by X-ray powder diffraction (XRPD) and X-ray absorption spectroscopy (EXAFS and XANES) at the potassium K-edge (3607 eV). XRPD results show that the hybrid matrix is always amorphous and the formation of secondary potassium phases is observed for all the samples, except for the KCF₃SO₃ doped PPO₄₀₀₀ hybrid. EXAFS results evidence a good correlation between the ionic conductivity and the presence of oxygen atoms as first neighbours around potassium.     

Synthesis, structural and electrical characterizations of DySr5Ni2.4Cu0.6O12−δ

A new compound DySr₅Ni_2.4Cu_0.6O_12−δ has been prepared by sol gel method and annealed at 1473 K in 1 atm of Ar gas flow. The X-ray diffraction (XRD) is used for phase identification. The sample shows to adopt the K₂NiF₄-type structure based on tolerance factor calculation. XRD analysis using the Rietveld method was carried out and it was found that DySr₅Ni_2.4Cu_0.6O_12−δ (Dy_0.33Sr_1.67Ni_0.8Cu_0.2O_4−δ′) compound crystallizes in tetragonal symmetry with space group I4/mmm (Z=2). The lattice parameters are found to be at room temperature a=3.7696(5) Å and c=12.3747(2) Å. The final reliability indices were: R_B=5.219% and χ²=3.47. Four probe electrical resistivity measurements were performed versus temperature in the range 294–579 K. A semiconducting behaviour over the whole range of temperature, with a conductivity maximum of 0.4 S cm⁻¹ is observed at 510 K.     

Agriculture crop residues as a source for the production of nanofibrillated cellulose with low energy demand

Nanofibrillated cellulose (NFC) from three agricultural crop (rice straw, corn and rapeseed stalk) residues was isolated with high-yield production using either high pressure homogenisation or a high speed blender. The fibres were extracted from the neat biomass via an NaClO₂/acetic acid and alkali pulping process. TEMPO-mediated oxidation pretreatment at pH 7 and 10 was accomplished to facilitate the release of the cellulose microfibrils. The fibrillation yield, transparency degree and morphological characteristics of the ensuing NFC were analysed using the centrifugation method, transmittance measurement and SEM observation. The energy consumption during the disintegration process was also accessed. It was shown that the mode of lignin removal and the fibre pretreatment notably affected the nanofibrillation efficiency and energy demand. A successful production of NFC with yield exceeding 90 %, using a simple Waring blender, was achieved when the NaClO₂/acetic acid delignification followed by a TEMPO-NaBr–NaClO oxidation at pH 10 was adopted.     

Bioactive Electroconductive Hydrogels: The Effects of Electropolymerization Charge Density on the Storage Stability of an Enzyme-Based Biosensor

Electrode-supported hydrogels were conferred with the biospecificity of enzymes during the process of electropolymerization to give rise to a class of bioactive, stimuli-responsive co-joined interpenetrating networks of inherently conductive polymers and highly hydrated hydrogels. Glucose responsive biotransducers were prepared by potentiostatic electropolymerization [750 mV vs. Ag/AgCl (3 M KCl)] of pyrrole at Poly(hydoxyethyl methacrylate)-based hydrogel-coated Pt micro-electrodes (Φ = 100 μm) from aqueous solutions of pyrrole and glucose oxidase (GOx; 0.4 M pyrrole, 1.0 mg/ml GOx) to 1.0 and 10.0 mC/cm². Polypyrrole was them over-oxidized by cyclic voltammetry (0–1.2 V vs. Ag/AgCl, 40 cycles in PBKCl, pH = 7.0). Biotransducers were stored at 4 °C in PBKCl for up to 18 days. Amperometric dose–response at 0.4 V vs. Ag/AgCl followed by Lineweaver–Burk analysis produced enzyme kinetic parameters as a function of electropolymerization charge density and storage time. Apparent Michaelis constant (K _Mapp) increased from 18.6–152.0 mM (1.0 mC/cm²) and from 2.7–6.1 mM (10.0 mC/cm²). Biotransducer sensitivity increased to 21.2 nA/mM after 18 days and to 12.8 pA/mM after 10 days for the 1.0 and 10.0 mC/cm² membranes, respectively. Maximum current, I _max, also increased over time to 2.7 nA (1.0 mC/cm²) and to 170 pA (10.0 mC/cm²). Electropolymerization of polypyrrole is shown to be an effective means for imparting bioactivity to a hydrogel-coated microelectrode. GOx was shown to be stabilized and to increase activity over time within the electroconductive hydrogel.     

Synthesis, characterization, and DNA binding of new water-soluble cyclopentadienyl ruthenium(II) complexes incorporating phosphines

The new water-soluble ruthenium(II) chiral complexes [RuCpX(L)(L')](n+) (X = Cl, I. L = PPh3; L' = PTA, mPTA; L = L' = PTA, mPTA) (PTA = 1,3,5-triaza-7-phosphaadamantane; mPTA = N-methyl-1,3,5-triaza-7-phosphaadamantane) have been synthesized and characterized by NMR and IR spectroscopy and elemental analysis. The salt mPTA(OSO2CF3) was also prepared and fully characterized by spectroscopic techniques. X-ray crystal structures of [RuClCp(PPh3)(PTA)] (2), [RuCpI(PPh3)(PTA)] (3), and [RuCpI(mPTA)(PPh3)](OSO2CF3) (9) have been determined. The binding properties toward DNA of the new hydrosoluble complexes have been studied using the mobility shift assay. The ruthenium chloride complexes interact with DNA depending on the hydrosoluble phosphine bonded to the metal, while the corresponding compounds with iodide, [RuCpI(PTA)2] (1), [RuCpI(PPh3)(PTA)] (3), [RuCpI(mPTA)2](OSO2CF3)2 (6), and [RuCpI(mPTA)(PPh3)](OSO2CF3) (9), do not bind to DNA.