Design, synthesis and preliminary analytical evaluation of water soluble reagents for peroxyoxalate chemiluminescence

Describes the investigation into a number of facets of the peroxyoxalate chemiluminescence reaction, and the application of this chemistry to the detection of certain analytes under purely aqueous conditions.

Cellular localization of water soluble, allergenic proteins in rye-grass (Lolium perenne) pollen using monoclonal and specific IgE antibodies with immunogold probes

A postembedding method has been developed for localizing water soluble allergens in rye-grass pollen. This uses dry fixation in glutaraldehyde vapour, followed by 2,2-dimethoxypropane, prior to a 100% ethanol series leading into embedment in LR Gold. This has allowed the attachment of specific monoclonal antibodies to the allergen, which are themselves probed with specific immunogold labels to the antibodies. Wall and cytoplasmic sites have been identified, representing an improvement of fixation and localization of allergens over previous studies employing polyclonal, broad spectrum antibodies.

Rye-grass allergens are labelled in mature pollen grains in the exine (tectum, nexine and central chamber), and in the electron opaque areas of the cytoplasm, especially mitochondria. The allergens are absent from the intine, polysaccharide (P) particles, amyloplasts, Golgi bodies and endoplasmic reticulum. IgE antibodies derived from humans allergic to rye-grass pollen, bind to similar sites in the cytoplasm but only to the outer surface of the pollen grain wall. This method now provides a valuable tool for further developmental studies on the pollen grains, in order to establish the site/s of synthesis of the allergens.

Boron carbon nitride nanostructures from salt melts : tunable water-soluble phosphors

A simple, high yield, chemical process is developed to fabricate layered h-BN nanosheets and BCNO nanoparticles with a diameter of ca. 5 nm at 700 °C. The use of the eutectic LiCl/KCl salt melt medium enhances the kinetics of the reaction between sodium borohydride and urea or guanidine as well as the dispersion of the nanoparticles in water. The carbon content can be tuned from 0 to 50 mol % by adjusting the reactant ratio, thus providing precise control of the light emission of the particles in the range 440–528 nm while reaching a quantum yield of 26%. Because of their green synthesis, low toxicity, small size, and stability against aggregation in water, the as-obtained photoluminescent BCNO nanoparticles show promise for diagnostics and optoelectronics.

Chemiluminescence detection with water-soluble iridium(III) complexes containing a sulfonate-functionalised ancillary ligand

The chemiluminescence from four cyclometalated iridium(III) complexes containing an ancillary bathophenanthroline-disulfonate ligand exhibited a wide range of emission colours (green to red), and in some cases intensities that are far greater than the commonly employed benchmark reagent, [Ru(bpy)3](2+). A similar complex incorporating a sulfonated triazolylpyridine-based ligand enabled the emission to be shifted into the blue region of the spectrum, but the responses with this complex were relatively poor. DFT calculations of electronic structure and emission spectra support the experimental findings.

Water-soluble acrylamide sulfonate copolymer for inhibiting shale hydration

Here we report a water-soluble acrylamide sulfonate copolymer for inhibiting shale hydrate formation. The copolymer, denoted as PANAA, was synthesized via copolymerization of acrylamide (AM), N,N-diallylbenzylamine (NAPA), acrylic acid (AA), and 2-(acrylamide)-2-methylpropane-1-sulfonic acid (AMPS). The performance of this new water-soluble copolymer for inhibiting shale hydration was investigated for the first time. The retention ratio of apparent viscosity of 2 wt % PANAA solution can reach 61.6% at 130 C and further up to 72.2% with 12 000 mg/L NaCl brine. The X-ray diffraction studies show that the addition of copolymer PANAA (5000 mg/L), in combination with a low loading of KCl (3 wt %), remarkably reduces the interlayer spacing of sodium montmorillonite (Na-MMT) in water from 19.04 to 15.65 Å. It has also found that these copolymer solutions, blending with KCl, can improve the retention of indentation hardness from 22% to 74% and increase the antiswelling ratio up to 84%. All results have demonstrated that the PANAA copolymer not only has excellent temperature-resistance and salt-tolerance but also exhibits a significant effect on inhibiting the hydration of clays and shale. © 2014 American Chemical Society.

Water-soluble complexes of an acrylamide copolymer and ionic liquids for inhibiting shale hydration

Here, we report water-soluble complexes of an acrylamide copolymer and ionic liquids for inhibiting shale hydration. The copolymer, denoted as PAAT, was synthesised via copolymerisation of acrylamide (AM), acrylic acid (AA) and N,N-diallyl-4-methylbenzenesulfonamide (TCDAP), and the ionic liquids used were 3-methyl imidazoliumcation-based tetrafluoroborates. X-ray diffraction showed that compared with commonly used KCl, the water-soluble complex of PAAT with 2 wt% ionic liquid 1-methyl-3-H-imidazolium tetrafluoroborate (HmimBF4) could remarkably reduce the d-spacing of sodium montmorillonite in water from 19.24 to 13.16 Å and effectively inhibit clay swelling. It was also found that the PAAT-HmimBF4 complex with 2 wt% HmimBF4 could retain 75% of the shale indentation hardness and increase the anti-swelling ratio to 85%. 13C NMR revealed that there existed interactions between PAAT and HmimBF4. Moreover, the thermal stability of the PAAT-HmimBF4 complex is superior to PAAT, suggesting that this water-soluble complex can be used to inhibit clay and shale hydration in high-temperature oil and gas wells.

Water-soluble complexes of hydrophobically modified polymer and surface active imidazolium-based ionic liquids for enhancing oil recovery

The current study introduces the water-soluble complexes containing hydrophobically associating copolymer and a series of surface activity imidazolium-based ionic liquids (CnmimBr, n=6, 8, 10, 12, 14 and 16). The polymer, denoted as PAAD, was prepared with acrylamide (AM), acrylic acid (AA) and N,N-diallyl-2-dodecylbenzenesulfonamide (DBDAP). And the hydrophobic associative behavior of PAAD was studied by a combination of the pyrene fluorescence probe and viscosimetry. Incorporation of CnmimBr (n=10, 12, 14 and 16) in PAAD leaded to the white thick gel, while the pellucid solutions were obtained in complexes of PAAD and CnmimBr (n=6 and 8); addition of C6mimBr around critical micelle concentration resulted in a large decrease in viscosity of solution. Therefore, we particularly investigated the performance of PAAD/C8mimBr complex. The interfacial tension of PAAD/C8mimBr complex solution and crude oil under different conditions was examined. Moreover, PAAD/C8mimBr complex exhibited superior temperature resistance and shear reversible performance for enhancing oil recovery (EOR) by rheological test. The promising EOR of 21.65% can be obtained by PAAD/C8mimBr complex showing high potential to utilize this kind of new complex in EOR processes.

A water-soluble antimicrobial acrylamide copolymer containing sulfitobetaine for enhanced oil recovery

Herein, we report a novel acrylamide copolymer with antimicrobial property as an enhanced oil recovery chemical. The copolymer was synthesized from acrylamide (AM), acrylic acid (AA) and 2-((2-(acryloyloxy)ethyl)dimethylammonio)ethyl sulfite (ADMES) using oxidation-reduction initiation system. Subsequently, the copolymer AM/AA/ADMES was evaluated and characterized on several aspects such as IR, ¹H NMR, intrinsic viscosity, and dissolubility. The AM/AA/ADMES solution exerted remarkable thickening ability, salt tolerance ability and viscoelasticity. In addition, the rheological properties, temperature resistance ability and long-term stability of AM/AA/ADMES were investigated systematically in the presence of sulfate-reducing bacteria and relatively low viscosity loss could be obtained compared to partially hydrolyzed polyacrylamide. On the basis of core flooding experiments, AM/AA/ADMES was found to be a valuable prospect with 10.5 resistance factor, 4.6 residual resistance factor and up to 11.0% enhanced oil recovery.

Blue electrogenerated chemiluminescence from water-soluble iridium complexes containing sulfonated phenylpyridine or tetraethylene glycol derivatized triazolylpyridine ligands

Incorporating phenylpyridine- and triazolylpyridine-based ligands decorated with methylsulfonate or tetraethylene glycol (TEG) groups, a series of iridium(III) complexes has been created for green and blue electrogenerated chemiluminescence under analytically useful aqueous conditions, with tri-n-propylamine as a coreactant. The relative electrochemiluminescence (ECL) intensities of the complexes were dependent on the sensitivity of the photodetector over the wavelength range and the pulse time of the applied electrochemical potential. In terms of the integrated area of corrected ECL spectra, with a pulse time of 0.5 s, the intensities of the Ir(III) complexes were between 18 and 102 % that of [Ru(bpy)3 ](2+) (bpy=2,2'-bipyridine). However, when the intensities were measured with a typical bialkali photomultiplier tube, the signal of the most effective blue emitter, [Ir(df-ppy)2 (pt-TEG)](+) (df-ppy=2-(2,4-difluorophenyl)pyridine anion, pt-TEG=1-(2-(2-(2-(2-hydroxyethoxy)ethoxy)ethoxy)ethyl)-4-(2-pyridyl)-1,2,3-triazole), was over 1200 % that of the orange-red emitter [Ru(bpy)3 ](2+) . A combined experimental and theoretical investigation of the electrochemical and spectroscopic properties of the Ir(III) complexes indicated that the greater intensity from [Ir(df-ppy)2 (pt-TEG)](+) relative to those of the other Ir(III) complexes resulted from a combination of many factors, rather than being significantly favored in one area.

A novel water-soluble hydrophobically associating polyacrylamide based on oleic imidazoline and sulfonate for enhanced oil recovery

3-(2-(2-Heptadec-8-enyl-4,5-dihydro-imidazol-1-yl)ethylcarbamoyl)acrylic acid (NIMA), 3-(diallyl-amino)-2-hydroxypropyl sulfonate (NDS), acrylamide (AM) and acrylic acid (AA) were successfully utilized to prepare novel acrylamide-based copolymers (named AM/AA/NIMA and AM/AA/NDS/NIMA) which were functionalized by a combination of imidazoline derivative and/or sulfonate via redox free-radical polymerization. The two copolymers were characterized by infrared (IR) spectroscopy, 1H nuclear magnetic resonance (1H NMR), viscosimetry, pyrene fluorescence probe, thermogravimetry (TG) and differential thermogravimetry (DTG). As expected, the polymers exhibited excellent thickening property, shear stability (viscosity retention rate 5.02% and 7.65% at 1000 s-1) and salt-tolerance (10:000 mg L-1 NaCl: viscosity retention rate up to 17.1% and 10.2%) in comparison with similar concentration partially hydrolyzed polyacrylamide (HPAM). The temperature resistance of the AM/AA/NDS/NIMA solution was also remarkably improved and the viscosity retention rate reached 54.8% under 110 °C. According to the core flooding tests, oil recovery could be enhanced by up to 15.46% by 2000 mg L-1 of the AM/AA/NDS/NIMA brine solution at 80 °C.

Analytically useful blue chemiluminescence from a water-soluble iridium(iii) complex containing a tetraethylene glycol functionalised triazolylpyridine ligand

We examine [Ir(df-ppy)2(pt-TEG)](+) as the first highly water soluble, blue-luminescent iridium(iii) complex for chemiluminescence detection. Marked differences in selectivity were observed between the new complex and the conventional [Ru(bpy)3](2+) reagent, which will enable this mode of detection to be extended to new areas of application.

Silk fibroin as a water-soluble bio-resist and its thermal properties

Thermal diffusivity of silk fibroin films, α = (1.6 ± 0.24) × 10-7 m2 s-1, was measured by a direct contact method. It was shown to be reduced down to ∼1 × 10-7 m2 s-1 in the crystallized phase, consistent with the multi-domain composition of β-sheet assemblies. Crystalline silk with β-sheets was made by dipping into alcohol and was used as a positive electron beam lithography (EBL) resist. It is shown by direct IR imaging of the 1619 cm-1 amide-I CO spectral signature and 3290 cm-1 amide-A N-H stretching band that an e-beam is responsible for unzipping β-sheets, which subsequently results in exposed areas returning to a water soluble state. This makes it possible to develop a water-based biocompatible silk resist and use it in lithography applications. The general principles of protein crystallization, traceable to spectral changes in IR amide bands of silk, can be used as a guide for the creation of new protein EBL resists and to quantify the electron dose required for solubility. Foam formation and laser treatments of silk can provide new approaches in surface functionalization and fabrication of 3D bio-scaffolds.

Formation of dynamic duolayer systems at the air/water interface by using non-ionic hydrophilic polymers

The inclusion of a water-soluble polymer, poly(vinyl pyrrolidone) (PVP), into a surface active film composition before application to the water surface leads to the formation of a dynamic duolayer; a novel surface film system. This duolayer shows improved surface viscosity over the monolayer compound alone, while the addition of polymer maintains other film properties such as evaporation control and equilibrium spreading pressure. Brewster Angle Microscopy shows that the duolayer film undergoes a different formation mechanism upon film compression, and the resultant surface pressure/area isotherm is different at lower surface pressures indicating the PVP is present on the water surface at these pressures and squeezed out to the water subphase at higher pressures. The addition of water-soluble polymers to form a dynamic duolayer provides a unique way to produce defect-free and tightly packed films while polymer is associated with the film. This finding provides new knowledge for the design of surface films with improved properties with potential applications in many areas.

Dynamic performance of duolayers at the air/water interface. 1. Experimental analysis

Understanding, and improving, the behavior of thin surface films under exposure to externally applied forces is important for applications such as mimicking biological membranes, water evaporation mitigation, and recovery of oil spills. This paper demonstrates that the incorporation of a water-soluble polymer into the surface film composition, i.e., formation of a three-duolayer system, shows improved performance under an applied dynamic stress, with an evaporation saving of 84% observed after 16 h, compared to 74% for the insoluble three-monolayer alone. Canal viscometry and spreading rate experiments, performed using the same conditions, demonstrated an increased surface viscosity and faster spreading rate for the three-duolayer system, likely contributing to the observed improvement in dynamic performance. Brewster angle microscopy and dye-tagged polymers were used to visualize the system and demonstrated that the duolayer and monolayer system both form a homogeneous film of uniform, single-molecule thickness, with the excess material compacting into small floating reservoirs on the surface. It was also observed that both components have to be applied to the water surface together in order to achieve improved performance under dynamic conditions. These findings have important implications for the use of surface films in various applications where resistance to external disturbance is required.