Synthesis of well‐defined syndiotactic poly(methyl methacrylate) with low‐temperature atom transfer radical polymerization in fluoroalcohol

The copper‐mediated atom transfer radical polymerization of methyl methacrylate (MMA) in 1,1,1,3,3,3‐hexafluoro‐2‐propanol (HFIP) was studied to simultaneously control the molecular weight and tacticity. The polymerization using tris[2‐(dimethylamino)ethyl]amine (Me₆TREN) as a ligand was performed even at ?78°C with a number‐average molecular weight (M_n) of 13,400 and a polydispersity (weight‐average molecular weight/number‐average molecular weight) of 1.31, although the measured M_n's were much higher than the theoretical ones. The addition of copper(II) bromide (CuBr₂) apparently affected the early stage of the polymerization; that is, the polymerization could proceed in a controlled manner under the condition of [MMA]₀/[methyl α‐bromoisobutyrate]₀/[CuBr]₀/[CuBr₂]₀/[Me₆TREN]₀ = 200/1/1/0.2/1.2 at ?20°C with an MMA/HFIP ratio of 1/4 (v/v). For the field desorption mass spectrum of Cu^IBr/Me₆TREN in HFIP, there were [Cu(Me₆TREN)Br]⁺ and [Cu(Me₆TREN)OCH(CF₃)₂]⁺, indicating that HFIP should coordinate to the Cu^I/Me₆TREN complex. The syndiotacticity of the obtained poly(methyl methacrylate)s increased with the decreasing polymerization temperature; the racemo content was 84% for ?78°C, 77% for ?30°C, 75% for ?20°C, and 63% for 30°C. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1436–1446, 2006     

Tristimulus colorimetry using a digital still camera and its application to determination of iron and residual chlorine in water samples.

Tristimulus colorimetry using a digital still camera (DSC) as a colorimeter has been developed. A photograph of a sample and standard solutions was taken simultaneously with the DSC, and it was transferred to a PC. On the PC, the colors of the sample and of the standard solutions were analyzed and L* (brightness), a* (red-green component), and b* (yellow-blue component) values were determined with laboratory-made software. A dedicated light-box containing white-color LEDs as light source was made of white acrylic to make constant exposure at each photograph. Various settings of the DSC, such as exposure mode, white balance, and so on, that affect analytical figures, were studied with determination of iron with 1,10-phenanthroline. This method was successfully applied to the determinations of iron in a river water sample and of residual chlorine in tap water samples with N,N-diethylphenylenediamine (DPD).     

Determination of hexabromocyclododecane diastereoisomers and tetrabromobisphenol A in water and sediment by liquid chromatography/mass spectrometry.

A method to determine alpha-, beta- and gamma-hexabromocyclododecane (HBCD) and tetrabromobisphenol A (TBBPA) in water and sediments was presented using solid phase extraction (SPE) and/or solvent extraction. Recoveries from sediments were approximately 100% for all the chemicals, while recoveries of alpha-, beta- and gamma-HBCDs from water were dependent on the extraction method. In the case of dichloromethane (CH2Cl2) extraction, recoveries of alpha-, beta- and gamma-HBCD from landfill leachates were 77%, 88% and 92%, respectively. Technical difficulties in HBCD measurement are discussed in terms of the physico-chemical properties of HBCD isomers. The method was applied to landfill samples and marine sediment.     

Characteristics of a protein error in determination of serum protein in the presence of inorganic salt.

There is a possibility that the color development of the dye-binding method based on a protein error of a pH indicator is affected by the coexisting inorganic salt. Thus, the author theoretically and experimentally investigated the effect of the inorganic salt on the protein error. In a theoretical analysis, the anion of an inorganic salt, like the dissociated dye and buffer anions, was assumed to react with the protein, forming a colorless anion-protein complex. The calculated results were compared with those obtained by experiments using three pH indicators and various kinds of inorganic salts. The calculated results obtained are as follows: (1) The color development decreases with increasing the concentration of the inorganic salt and the equilibrium constant of the reaction between the inorganic salt and protein; (2) The rate of the absorbance decrease is larger for a lower concentration of the inorganic salt than for a higher one; (3) The larger is the equilibrium constant, the larger is the absorbance decrease. The absorbance decrease was caused by the anion, and was increased by increasing the anion concentration. The magnitude of the effect of the anion was iodide > bromide > chloride, which was associated with their ionic radius. The difference in the effect of the anion was thought to indicate that the equilibrium constant, in other words, the bonding strength of the anion to protein is iodide > bromide > chloride.     

High-performance liquid chromatographic method for determining trichothecene mycotoxins by post-column fluorescence derivatization

The method described here is based on a separation of deoxynivalenol, nivalenol and fusarenon-X on a C18 column using aqueous acetonitrile, and successive post-column fluorescence derivatization involving an alkaline decomposition to form formaldehyde and modified Hantzsch reaction with methyl acetoacetate and ammonium acetate (lambda ex = 370 nm and lambda em = 460 nm). By this method, 5-10 ng of the standard trichothecenes could be determined. By employing a clean-up procedure with a florisil column and a Sep-Pak CN cartridge, 61.4-96.9% recoveries were obtained for deoxynivalenol and nivalenol added to corn, wheat and barley at concentration levels of 0.05-1 ppm.     

Relativistic time delays in the Dirac approach to nucleon-nucleus scattering

In connection with a characteristic feature of the effective optical potential in the Dirac approach two types of time delays are considered in the relativistic eikonal approximation. One is obtained from the scattering amplitude and the other given by the wave packet motion in the interaction region. These time delays turn out to differ in sign at intermediate energies, in contrast to the agreement between corresponding nonrelativistic time delays.     

Inhibitory effects of non-steroidal anti-inflammatory drugs on superoxide generation.

Effects of non-steroidal anti-inflammatory drugs (NSAID: amfenac sodium, diclofenac sodium, indomethacin and ketoprofen) on the generation of superoxide anion (O2-) by isolated rat polymorphonuclear leukocytes (PMN) were studied spectrophotometrically using cytochrome c. The effects of these drugs were also studied on O2- production by the xanthine-xanthine oxidase and reduced nicotinamide adenine dinucleotide phosphate (NADPH)-NADPH oxidase systems. Amfenac sodium, at 0.1 mM, inhibited significantly O2- generation in rat PMN induced by opsonized zymosan. At 0.5 mM, diclofenac sodium and indomethacin inhibited the O2- generation in rat PMN. All of the above drugs slightly inhibited O2- production by the xanthine-xanthine oxidase system. On the other hand, O2- production by the NADPH-NADPH oxidase system was significantly inhibited by the addition of amfenac sodium, ketoprofen or indomethacin. These results suggest that non-steroidal anti-inflammatory drugs do not work as an O2- scavenger and block O2- production by the NADPH-NADPH oxidase system of rat PMN. It is concluded that amfenac sodium and the other drugs are able to inhibit granulocyte O2- production by blocking the activation of NADPH-oxidase.     

A facile synthesis of (−)-prostaglandin E1 via a three-component coupling process

A very short synthesis of chiral prostaglandin E₁ methyl ester is described.     

Tris(1‐ethyl‐3‐methyl­imidazolium) hexa­chloro­lanthanate

In the title complex, (C₆H₁₁N₂)₃[LaCl₆], centrosymmetric octahedral hexa­chloro­lanthanate anions are located at the corners and face‐centers of the monoclinic unit cell. The ring H atoms of the cations interact with the Cl atoms of the anions via hydrogen bonding, and bifurcation of the hydrogen bonding is observed. Cation–cation interactions via hydrogen bonding between the ring H atoms and π‐electrons of aromatic rings are also observed as in other imidazolium salts.