Strategies for the development of a voltammetric sensor for the determination of hydrogen peroxide at high concentrations

Different strategies are presented for the development of a voltammetric sensor for in-line measurement and monitoring of H₂O₂ in high concentrations (up to 30 g/l) as used in textile bleaching systems. When using macroelectrodes, signal saturation is observed even at medium concentrations. Some improvement can be achieved by hydrodynamic electrodes like ring-disk electrodes. Satisfactory results up to the desired level in practical solutions (possessing only limited conductivity) are obtained with Pt-microelectrodes.     

Temperature dependence of magnetization in nanocrystalline FeCoZr alloy

The temperature dependence of magnetization of a nanocrystalline Fe₆₀Co₃₀Zr₁₀ alloy annealed at various temperatures to varying crystal sizes was investigated down to 5 K in the field range up to 5 T. The fitting procedure gave T^3/2 as the leading term irrespective of the crystal size. We suggest that the increase of the coefficient by this term for smaller crystals may be connected to an increased relative volume of their surface.     

Competitive influence of atactic polystyrene and supercritical carbon dioxide on the conformation of syndiotactic polystyrene

The crystallization behavior of miscible syndiotactic polystyrene (sPS) and atactic polystyrene (aPS) blends with different sPS/aPS weight ratios was investigated in supercritical CO₂ by using Fourier‐transform infrared spectroscopy, differential scanning calorimetry, and wide‐angle X‐ray diffraction. Supercritical CO₂ and aPS exhibited different effects on the conformational change of sPS and competed with each other. Increasing the content of amorphous aPS in the blends made its effect on the conformational change of sPS gradually surpass that of supercritical CO₂. Supercritical CO₂ favored the formation of the helical conformation of sPS in lower temperature range and the all trans planar conformation in higher temperature range, instead of forming the latter one only in higher temperature range in ambient atmosphere. However, increasing aPS content in the blends pushed the range for forming the helical conformation to lower temperature and made the all trans planar conformation dominant in aPS/sPS 25/75 blend after treating in supercritical CO₂ above 60 °C. The all trans planar zigzag conformation was more favorable than the helical conformation after mixing aPS in sPS in supercritical CO₂. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1755–1764, 2007     

Synthesis and characterization of liquid crystalline side‐chain block copolymers containing luminescent 4,4′‐bis(biphenyl)fluorene pendants

A series of new liquid crystalline homopolymers, copolymers, and block copolymers were polymerized from styrene‐macroinitiator ( SMi ) and methacrylates with pendent 4,4′‐bis(biphenyl)fluorene ( M1 ) and biphenyl‐4‐ylfluorene ( M2 ) groups through atom transfer radical polymerization (ATRP). The number‐average molecular weights (Mn) of polymers P1 ‐ P4 were 10,007, 14,852, 6,275, and 10,463 g mol^?1 with polydispersity indices values of 1.21, 1.15, 1.31, and 1.22, respectively. All polymers exhibit the nematic phase. The thermal, mesogenic, and photoluminescent properties of all polymers were investigated. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4564–4572, 2007     

Interfacial dynamics‐based modelling of turbulent cavitating flows,Part‐2: Time‐dependent computations

The interfacial dynamics‐based cavitation model, developed in Part‐1, is further employed for unsteady flow computations. The pressure‐based operator‐splitting algorithm (PISO) is extended to handle the time‐dependent cavitating flows with particular focus on the coupling of the cavitation and turbulence models, and the large density ratio associated with cavitation. Furthermore, the compressibility effect is important for unsteady cavitating flows because in a water–vapour mixture, depending on the composition, the speed of sound inside the cavity can vary by an order of magnitude. The implications of the issue of the speed of the sound are assessed with alternative modelling approaches. Depending on the geometric confinement of the nozzle, compressibility model and cavitation numbers, either auto‐oscillation or quasi‐steady behaviour is observed. The adverse pressure gradient in the closure region is stronger at the maximum cavity size. One can also observe that the mass transfer process contributes to the cavitation dynamics. Compared to the steady flow computations, the velocity and vapour volume fraction distributions within the cavity are noticeably improved with time‐dependent computations. Copyright © 2004 John Wiley & Sons, Ltd.     

Crystallographic report: Crystal structure of a one‐dimensional zinc(II) coordination polymer containing 4,4′‐biphenyldicarboxylate hemihydrate

A one‐dimensional zinc(II) coordination polymer has been constructed from zinc(II), 4,4′‐biphenyldicarboxylate and pyridine in which each zinc(II) atom is coordinated by two pyridine ligands and two monodentate 4,4′‐biphenyldicarboxylate ligands that define a distorted tetrahedral geometry. Copyright © 2003 John Wiley & Sons, Ltd.     

Medicinal Organometallic Chemistry: Designing Metal Arene Complexes as Anticancer Agents

The field of medicinal inorganic chemistry is rapidly advancing. In particular organometallic complexes have much potential as therapeutic and diagnostic agents. The carbon‐bound and other ligands allow the thermodynamic and kinetic reactivity of the metal ion to be controlled and also provide a scaffold for functionalization. The establishment of structure–activity relationships and elucidation of the speciation of complexes under conditions relevant to drug testing and formulation are crucial for the further development of promising medicinal applications of organometallic complexes. Specific examples involving the design of ruthenium and osmium arene complexes as anticancer agents are discussed.     

Genetically Encoded Bioluminescent Indicator for ERK2 Dimer in Living Cells

In this study, a genetically encoded bioluminescent indicator for ERK2 dimer was developed with the split Renilla luciferase complementation method, in which the formation of ERK2 dimer induces a spontaneous emission of bioluminescence in living cells. In response to extracellular stimuli, such as epidermal growth factor (EGF) or 17β‐estradiol (E2), extracellular signal‐regulated kinase 2 (ERK2) is phosphorylated by its upstream kinase MEK, and also phosphorylates its substrates in various regions of the cell, including the nucleus. Phosphorylated ERK2 is led to form its dimer, thereby transporting itself into the nucleus. We demonstrated with the indicator that stimulation with EGF or E2 induces the formation of ERK2 dimer in living MCF‐7 cells. The dynamics of this dimer formation was examined and discussed.     

Weak Attractive Ligand–Polymer and Related Interactions in Catalysis and Reactivity: Impact,Applications, and Modeling

The notion of weak attractive ligand–polymer interactions is introduced, and its potential application, importance, and conceptual links with “cooperative” ligand–substrate interactions are discussed. Synthetic models of weak attractive ligand–polymer interactions are described, in which intramolecular weak C? H???F? C interactions (the existence of which remains contentious) have been detected by NMR spectroscopy and neutron and X‐ray diffraction experiments. These C? H???F? C interactions carry important implications for the design of catalysts for olefin polymerization, because they provide support for the practical feasibility of ortho‐F???H_β ligand–polymer contacts proposed for living Group 4 fluorinated phenoxyimine catalysts. The notion of weak attractive noncovalent interactions between an “active” ligand and the growing polymer chain is a novel concept in polyolefin catalysis.