Dynamic rheology studies of in situ polymerization process of polyacrylamide–cellulose nanocrystal composite hydrogels

A series of dynamic small-amplitude oscillatory shear experiments for in situ polymerization process of polyacrylamide–cellulose nanocrystal (PAM–CNC) nanocomposite hydrogels were performed to investigate the relationship between rheological properties and synthesis parameters including chemical cross-linker concentration, polymerization temperature, initiator concentration, and CNC aspect ratios. The results showed that CNCs accelerated the onset of gelation (t _onset) and acted as a multifunctional cross-linker during the gelation reaction. The composite hydrogels exhibited enhanced steady-state elastic modulus ( G_￥￠ ) \left( {G_\infty^\prime } \right) and plateau loss factor (tanδ) compared to these of the pure PAM hydrogels, indicating that adding CNCs not only reinforced but also toughened PAM hydrogels. ( G_￥￠ ) \left( {G_\infty^\prime } \right) and the effective network junction density (N) increased with increased cross-linker concentration, polymerization temperature, and CNC aspect ratios, but decreased with increased initiator concentration. The changes of plateau tanδ were opposite to that of G_￥￠ G_\infty^\prime . The sol–gel transition kinetics of PAM–CNC hydrogels accelerated with increased cross-linker concentration and polymerization temperature and, however, reached optimization at 0.25 wt% of initiator concentration. CNCs with lower aspect ratios promoted t _onset and the sol–gel transition of PAM–CNC hydrogels, suggesting the fact that CNCs with lower aspect ratios further facilitated the formation of network of PAM–CNC nanocomposite hydrogels.     

Synthesis,characterisation and ion exchange properties of hybrid organic–inorganic composite material: polyacrylamide zirconium (IV) iodosulphosalicylate

ABSTRACT

Contamination of groundwater by heavy metal is one of the most emerging and serious environmental problems. There are so many methods which are available to overcome these problems. Among various available methods, hybrid organic–inorganic ion exchange resin has become more popular due to certain advantages over other available conventional methods; hence, in the present proposed work, we synthesised a hybrid organic–inorganic composite material polyacrylamide zirconium (IV) iodosulphosalicylate by using the sol-gel technique. Synthesised resin was characterised by various methods like Infrared spectroscopy and Thermogravimetric analysis-Differential thermal analysis. Various samples of this ion exchange resin are prepared by changing the condition of synthesis, i.e. concentration of acrylamide to rationalise the ion exchange capacity of the synthesise hybrid organic–inorganic ion exchange resins. A mixture of 0.1 M potassium iodate, 0.1 M sulphosalicylic acid and 0.1 M acrylamide was added dropwise to 0.4 M zirconium oxychloride accompanied by constant stirring for 8 h using magnetic stirrer at 70°C to yield polyacrylamide zirconium (IV) iodosulphosalicylate with maximum ion exchange capacity. Ion exchange capacity of synthesised resin was determined by column method and the maximum ion exchange capacity was found for Pb(II). Determination of k_d values shows that the resin was highly selective for Pb (II).The selectivity for Pb was also evaluated by using certain binary mixture separation such as Ni (II)-Pb(II), Cu(II)-Pb(II), Cd(II)-Pb(II), Sr(II)-Pb(II), Ba(II)-Pb(II),Zn(II)-Pb(II) and Mg(II)-Pb(II).     

Gram scale synthesis of the C(1)–C(9) fragment of amphidinolide C

An allylic cis-epoxide prepared by Sharpless asymmetric epoxidation was transformed in nine steps and 41% overall yield to the cyclization precursor 4 via a key one carbon homologation. Cobalt-catalyzed aerobic oxidative cyclization of 4 gave the trans-THF in 94% yield at gram scale. Subsequent manipulations, including a Still–Gennari olefination, Sharpless asymmetric dihydroxylation, Corey–Fuchs alkynylation, and Kazmaier hydrostannylation provided the fully functionalized C(1)–C(9) fragment 2 suitable for cross-coupling. The sequence is readily scalable and provides gram quantities of 2.     

Iron-catalyzed alkenylation of cyclic ethers via decarboxylative sp(C)–sp(C) coupling

An efficient Fe(acac)₃-catalyzed decarboxylative C(sp²)–C(sp³) coupling reaction via oxidation of C–H bond adjacent to an oxygen atom has been developed successfully, in which cyclic ethers are selectively transformed into the corresponding alkenylation products with good chemical yields and excellent stereoselectivities. The mechanism was studied and the reaction was supposed to proceed through a radical oxidative coupling process.     

Study of entangled network formation in concentrated solutions of polymer by ~(13)C NMR

Information about the exact location of topological and cohesional entanglements at molecular level has been obtained by 13C NMR relaxation analysis. The results show that about 20% of the carbon atoms in the main chain are entangled in the 25% (by weight) solution, which is independent of the content of the 1,2-segment in polybutadiene and of the kind of solvent. However, the entanglement of the carbon atone on the end group of the side chain is very weak, they behave as slipping freely at the junctions.     

A comparison of different types of gold–carbon composite electrode for detection of arsenic(III)

A study has been conducted using abrasively modified basal and edge-plane graphite, carbon-paste, and carbon–epoxy electrodes to create gold–carbon composite electrodes. Using either nano or micro-sized gold particles their suitability for use in detecting arsenic(III) is assessed. It was found that gold arrays prepared from micron-sized particles gave the best performance for arsenic detection. In particular micron arrays produced in carbon-paste electrodes with an easily renewable surface work well for detection of arsenic, producing a detection limit of 5(±2)×10^–9 mol L^–1, with a high sensitivity of 10(±0.1) A mol^–1 L.     

The effect of cobalt addition on sintering and microstructural behaviour of silver–tungsten (Ag–W) composite

The present investigation has been revealed that homogeneous silver-tungsten (Ag–W) composite powders doped with cobalt as sinter aid can be produced by the two-stage reduction of co-precipitated tungstate. The sintering of the powders has been studied using dilatometry and the results showed that the critical level for activated sintering is of the order of 0.3 mass percent cobalt with respect to the tungsten content of the compact powder. This critical level is equivalent to approximately six to seven atomic layer coverage of the tungsten particles by cobalt. The levels of cobalt addition above the critical amount leads to the formation of cobalt tungsten (CoW₃) intermetallic compound precipitates, which become trapped within the silver phase in the sintered composite material. Microstructural evaluation of sintered specimens has been carried out using optical and electron microscopy. Transmission electron microscopy results revealed the neck formation between adjacent tungsten particles along with the presence of silver around the tungsten particles. Energy dispersive X-ray (EDX) analysis also confirmed that amounts of cobalt was 0.3 mass percent, in the region containing the silver at the tungsten particle interface which agreed with the level of activated sintering.     

Poly(vinylferrocenium) perchlorate–polyaniline composite film-coated electrode for amperometric determination of hydroquinone

Poly(vinylferrocenium) perchlorate–polyaniline (PVF⁺–PANI) composite film was synthesized electrochemically on Pt electrode in a methylene chloride solution containing a mixture of poly(vinylferrocene) (PVF) polymer and aniline monomer. PVF⁺ polymer in the composite film was used as an electron transfer mediator. The composite coating showed significant electrochemical activity towards hydroquinone (HQ) at pH 4, with high sensitivity and a wide linearity range. The interaction of HQ with PVF⁺ and PANI homopolymer films was investigated electrochemically and spectroscopically. HQ molecules are accumulated on the electrode surface due to trapping by both polymers in the composite film and then oxidized catalytically by PANI. The most significant contribution of PVF⁺ polymer is that it facilitates electron transfer in the composite film. The linear response range was found to be between 1.60 × 10⁻⁴ mM and 115 mM (R ² = 0.999) at 0.45 V vs saturated calomel electrode. The limit of detection (LOD) was 4.94 × 10⁻⁵ mM.     

Attapulgite with poly(methylene blue) composite film–Electrocatalytic determination of ascorbic acid

A conductive composite film consisted of natural nanostructure attapulgite (AT) with poly(methylene blue) (PMB) was constructed on glassy carbon (GC) electrode. The electrode exhibited an effective electrocatalytic activity towards the oxidation of ascorbic acid (AA) and well-defined oxidation peaks were observed in 0.1 M phosphate buffer solutions (PBS, pH 7.0) via cyclic voltammetry. Linear calibration plot was obtained over the range of 1.0 × 10⁻⁵ to 5.0 × 10⁻² M for ascorbic acid with the detection limit value of 1.0 × 10⁻⁶ M. The main interfering factor in biological samples was experimentally excluded. In addition, UV–Vis spectra were applied to reveal the formation of the nanocomposite film of PMB-AT.     

Catalytic diastereoselective and enantioconvergent C(sp~3)–C(sp~3) cross-coupling of racemic partners

正Carbon-carbon bond formation is the core of organic synthesis.Transition metal-catalyzed cross-coupling reaction between organohalides and organometallic reagents is one of the most important and straightforward methods for construction of C-C bonds.The catalytic cross coupling between two sp~2-carbon centers,e.g.,aryl-aryl cross-     

Triethanolamine zinc phosphite, (C6H13NO3)Zn2(HPO3): a templated network or a network of clusters?

(C6H13NO3)Zn2(HPO3) (I) displays an extended hybrid organic/inorganic structure in which the triethanolamine organic species acts as an anionic tetradentate ligand, rather than a typical protonated cationic template. Crystal data for I: Mr = 357.89, monoclinic, P2(1)/c (no. 14), a = 8.4216(4) angstroms, b = 9.9262(5) angstroms, c = 12.8494(6) angstroms, beta = 91.824(1) degrees, V = 1073.6(1) angstroms3, Z = 4.     

Ag(I)-catalyzed C–H borylation of terminal alkynes

An efficient Ag(I)-catalyzed borylation method of terminal alkynes is reported. The obtained borylated alkynes are shown to engage in C–Br, C–CN, C–N, and C–C bond formation with various reaction partners. Meanwhile the Ag(I) catalyst could be regenerated in the presence of PPh₃ and BF₃.     

Transport of C1–C3 hydrocarbons in poly(phenylene oxides) membranes

Transport of CH₄, C₂H₄ and C₂H₆ in poly(phenylene oxides) membranes at low pressures has been studied. The relation between the free volume and permeability of the polymers was analyzed in terms of the `dual-sorption' model. The accessible free volume of the polymers was estimated assuming the density of a sorbed fluid is equal to the density of the corresponding liquid. Transient separation of the three-component mixture CH₄/C₂H₄/C₂H₆ was studied.     

Polyurethane–poly(vinylidene fluoride) (PU–PVDF) thin film composite membranes for gas separation

Aqueous polyurethane dispersions (PUDs) with poly(dimethylsiloxane) (PDMS), or mixed poly(dimethylsiloxane)/poly(ethylene glycol) (PDMS/PEG) as the soft segment were synthesized, and made into thin films for characterization with differential scanning calorimetry (DSC), thermogarvimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), size exclusion chromatography (SEC) and transmission electron microscopy (TEM). Seven thin film composite (TFC) membranes prepared on PUDs and PVDF substrates were evaluated by the separation of air as well as hydrocarbon–nitrogen mixtures. A promising membrane was then selected for further investigation of the morphological structure and permselectivities, using pure gases and binary mixtures of ethylene, ethane, propylene and propane with nitrogen at ambient temperature. It was found that PDMS/PEG-based PU membrane was typically solubility-selective for condensable hydrocarbons, and nitrogen permeance was marginally enhanced in hydrocarbon–nitrogen mixtures. It appears that the copolymer membrane with both urethane and PEG segments can effectively tolerate the swelling caused by the condensable gases. As a result, the selectivities of propylene and propane to nitrogen were substantially improved, e.g., in a mixture containing 28% propylene and 72% nitrogen, the selectivity of propylene to nitrogen reached 29.2 with a propylene permeance of 34.4 gas permeation unit (GPU).     

Enantiospecific Synthesis of (–)-Cuspareine and (–)-Galipinine

An enantiospecific route to the synthesis of tetrahydroquinoline alkaloids (–)-cuspareine and (–)-galipinine is reported. Coupling of an iodide derivative of D-serine with aromatic dithianes and Pd-catalyzed intramolecular C–N coupling are the key steps in the synthesis.     

Transition-Metal-Free C(sp2)–C(sp2) Cross-Coupling of Diazo Quinones with Catechol Boronic Esters

A transition-metal-free C(sp²)−C(sp²) bond formation reaction by the cross-coupling of diazo quinones with catechol boronic esters was developed. With this protocol, a variety of biaryls and alkenyl phenols were obtained in good to high yields under mild conditions. The reaction tolerates various functionalities and is applicable to the derivatization of pharmaceuticals and natural products. The synthetic utility of the method was demonstrated by the short synthesis of multi-substituted triphenylenes and three bioactive natural products, honokiol, moracin M, and stemofuran A. Mechanistic studies and density functional theory (DFT) calculations revealed that the reaction involves attack of the boronic ester by a singlet quinone carbene followed by a 1,2-rearrangement through a stepwise mechanism.     

Thermodynamics of binary mixtures of aliphatic linear alkanes (C6–C12) at 298.15 K

This article reports experimental values of speeds of sound, densities and refractive indices on mixing of the binary mixtures n-hexane + (n-heptane, n-octane, n-nonane, n-decane, n-undecane, or n-dodecane) at 298.15?K and atmospheric pressure, over the whole concentration range. The corresponding excess and derived properties were computed from the experimental data. The results were fitted by means of the Redlich–Kister equation, such parameters being gathered. Different estimation methods (equations of state, mixing rules, Collision Factor and Free Length Theory) were applied, qualitative agreement between the experimental and theoretical values both in magnitude and sign being obtained.