The Role of Radical Bridges in Polynuclear Single-Molecule Magnets

Employing radical bridges between anisotropic metal ions has been a viable route to achieve high-performance single-molecule magnets (SMMs). While the bridges have been mainly considered for their ability to promote exchange interactions, the crystal-field effect arising from them has not been taken into account explicitly. This lack of consideration may distort the understanding and limit the development of the entire family. To shed light on this aspect, herein we report a theoretical investigation of a series of N -radical-bridged diterbium complexes. It is found that while promoting strong exchange coupling between the terbium ions, the N -radical induces a crystal field that interferes destructively with that of the outer ligands, and thus reduces the overall SMM behavior. Based on the theoretical results, we conclude that the SMM behavior in this series could be further maximized if the crystal field of the outer ligands is designed to be collinear with that of the radical bridge. This conclusion can be generalized to all exchange-coupled SMMs.     

Simultaneous determination of serotonin and 5-hydroxyindole-3-acetic acid in human urine by automated precolumn derivatization and semi-microbore column liquid chromatography with fluorescence detection.

An improved high-performance liquid-chromatographic (HPLC) assay for the simultaneous determination of serotonin (5-HT) and 5-hydroxyindole-3-acetic acid (5-HIAA) in human urine is reported. Following the automated precolumn derivatization of urinary 5-HT and 5-HIAA with benzylamine, the derivatives are separated by isocratic elution on a reversed-phase C18 semi-microbore column, and are fluorometrically detected at an excitation wavelength of 345 nm and an emission wavelength of 480 nm. The detection limits of 5-HT and 5-HIAA are 7 and 5 nmol/l in urine (0.7 and 0.5 fmol/20-microl injection). The proposed automatic method permits a highly selective and sensitive determination of 5-HT and 5-HIAA in human urine without any sample purification.     

Developing a hybrid emulsion polymerization system to synthesize Fe3O4/polystyrene latexes with narrow size distribution and high magnetite content

A hybrid emulsion polymerization was formulated for synthesizing Fe₃O₄/polystyrene composite latex. This system, containing binary droplets that are magnetic (Mag)‐droplets with a diameter of 100–200 nm and styrene (St)‐droplets with a diameter of 3–4 μm, was obtained by mixing Mag‐miniemulsion and St‐macroemulsion. With extremely low surfactants concentration (?critical micelle concentration, CMC), the nucleated loci are selectively controlled in the Mag‐droplets, as the result of smaller droplet size and larger surface ratio. Both water‐soluble potassium persulfate (KPS) and oil‐soluble 2,2′‐azobis(2‐isobutyronitrile) was adopted to initiate the polymerization. In the presence of KPS, magnetic polystyrene latices with particles size of 60–200 nm, narrow size distribution, and high magnetite content (86 wt % measured by TGA) were attained successfully. The synthesized magnetic Fe₃O_4/polystyrene latices assembled into well‐ordered hexagonal structure in the surface of a carbon supported copper grid. The influence of various parameters on various aspects of the as‐synthesized Fe₃O₄/polystyrene was investigated in detail: type of initiator on composite morphology, feed ratio of Mag‐miniemulsion and St‐macroemulsion on magnetite content, and hydrophobic agent or amount of surfactant on size and size distribution. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5285–5295, 2007     

A numerical study of an unsteady laminar flow in a doubly constricted 3D vessel

Unsteady flow dynamics in doubly constricted 3D vessels have been investigated under pulsatile flow conditions for a full cycle of period T. The coupled non‐linear partial differential equations governing the mass and momentum of a viscous incompressible fluid has been numerically analyzed by a time accurate Finite Volume Scheme in an implicit Euler time marching setting. Roe's flux difference splitting of non‐linear terms and the pseudo‐compressibility technique employed in the current numerical scheme makes it robust both in space and time. Computational experiments are carried out to assess the influence of Reynolds' number and the spacing between two mild constrictions on the pressure drop across the constrictions. The study reveals that the pressure drop across a series of mild constrictions can get physiologically critical and is also found to be sensitive both to the spacing between the constrictions and the oscillatory nature of the inflow profile. The flow separation zone on the downstream constriction is seen to detach from the diverging wall of the constriction leading to vortex shedding with 3D features earlier than that on the wall in the spacing between the two constrictions. Copyright © 2002 John Wiley & Sons, Ltd.     

A Simple Chaotic Circuit with Impulsive Switch Depending on Time and State

This paper presents a simple chaotic circuit consisting of two capacitors, one linear two-port VCCS and one time-state-controlled impulsive switch. The impulsive switch causes rich chaotic and periodic behavior. The circuit dynamics can be simplified into a one-dimensional return map that is piecewise linear and piecewise monotone. Using the return map, we clarify parameter conditions for existence of chaotic and periodic attractors and coexistence state of attractors.     

Determination of midodrine in human plasma by high-performance liquid chromatography with fluorescence detection.

A simple and sensitive fluorometric high-performance liquid chromatographic method was developed for the determination of midodrine in human plasma. After liquid-liquid extraction from plasma, the drug and 2-phenylglycinol (internal standard) were convened into the corresponding fluorescent derivatives by reaction with 3,4-dihydro-6,7-dimethoxy-4-methyl-3-oxoquinoxaline-2-carbonyl chloride, a fluorescence derivatization reagent for amines. The derivatives were separated within 30 min on a reversed-phase column using isocratic elution with acetonitrile-methanol-water (10:30:60, v/v) and were detected spectrofluorometrically at 485 nm with excitation at 400 nm. The detection limit for midodrine was 0.3 pmol (76 pg) per mL plasma at a signal-to-noise ratio of 3.     

Analysis of tetracycline antibiotics using HPLC with pulsed amperometric detection.

The analysis of tetracycline, oxytetracyline, chlortetracycline and doxycycline by high-performance liquid chromatography with pulsed amperometric detection using an anodized boron-doped diamond thin film (BDD) electrode is originally reported. The analyses were carried out using the mobile phase, phosphate buffer (0.01 M, pH 2.5)-acetonitrile (80:20; v/v), on a C18 column (250 x 4.6 mm i.d., 5 microm) at a flow rate of 1.0 mL/min. The optimal PAD waveform parameters at the anodized BDD were 1.5 V (versus Ag/AgCl) detection potential (E(det)) for 290 ms (200 ms delay time and 90 ms integration time), 2.0 V (versus Ag/AgCl) oxidation potential (E(oxd)) for 200 ms oxidation time (t(oxd)) and 0.4 V (versus Ag/AgCI) reduction potential (E(red)) for 200 ms reduction time (t(red)). The proposed method showed the simultaneous determination of tetracycline, oxytetracyline, chlortetracycline and doxycycline with a linear range of 0.1 - 100 microg/mL, detection limits of 0.05 - 0.1 microg/mL and recoveries of 70.8 - 96.0%. The application of this method to real samples was demonstrated and validated using a shrimp sample.     

Effect of the pore surface modification of an inorganic substrate on the plasma‐grafting behavior of pore‐filling‐type organic/inorganic composite membranes

We have investigated the effect of the surface state and surface treatment of the pores of an inorganic substrate on the plasma‐grafting behavior of pore‐filling‐type organic/inorganic composite membranes. Shirasu porous glass (SPG) was used as the inorganic substrate, and methyl acrylate was used as the grafting monomer. The grafting rate increased as the density of silanol on the SPG substrate increased. This result suggests that radicals are generated mainly at the silanol groups on the pore surface by plasma irradiation. The SPG substrates were treated with silane coupling agents used to control the mass of organic material bonded to the pore surface. The thickness of the grafted layer became thinner as the mass of organic material bonded to the pore surface of SPG increased. This decrease in the thickness of the grafted layer could be explained by the decrease in the penetration depth of vacuum ultraviolet rays contained in plasma having a wavelength of less than 160 nm that generated radicals in the pores of the substrate. The thickness of the grafted layer inside the SPG substrates could be controlled through the control of the mass of organic material bonded to the pore surface of the SPG substrate. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 846–856, 2006     

Simultaneous imaging of the structure and fluorescence of a supramolecular nanostructure formed by the coupling of π‐conjugated polymer chains in the intermolecular interaction

We fabricated a micrometer‐long supramolecular chain in which π‐conjugated polyrotaxane was coupled. A new experimental setup was designed and constructed, and the simultaneous direct imaging of the structure and fluorescent function was achieved. Furthermore, we identified the formation of a polymer intertwined network and observed novel fluorescence due to a long‐range interaction via this intertwined network over a distance of 5 μm or more without quenching over 15 min in the near field. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 801–809, 2006     

Spectrophotometric determination of anthracycline anticancer agents with aluminum(III) and chromazurol S in a nonionic surfactant micellar medium.

A simple and highly sensitive spectrophotometric method for the determination of anthracycline anticancer agents, such as Daunorubicin hydrochloride (DAU), was established by using aluminum(III) and Chromazurol S (CAS) in a nonionic surfactant micellar medium. In the case of determination of DAU, the apparent molar absorptivity was 1.3 x 10(5) dm3 mol(-1) cm(-1) at 615 nm. Beer's law was obeyed in the concentration range of 0.028 - 2.82 microg ml(-1) for DAU. Owing to no need for solvent extraction, this method could be applied to assays of DAU and related drugs in pharmaceutical preparations.