Determination of zinc in marine/lacustrine sediments by graphite furnace atomic absorption spectrometry using Pd/Mg chemical modifier and slurry sampling

Effectiveness of Pd/Mg chemical modifier for the accurate direct determination of zinc in marine/lacustrine sediments by graphite furnace atomic absorption spectrometry (GF-AAS) using slurry samples was evaluated. A calibration curve prepared by aqueous zinc standard solution with addition of Pd/Mg chemical modifier is used to determine the zinc concentration in the sediment. The accuracy of the proposed method was confirmed using Certified Reference Materials, NMIJ CRM 7303-a (lacustrine sediment) from National Metrology Institute of Japan, National Institute of Advanced Industrial Science and Technology, Japan, and MESS-3 (marine sediment) and PACS-2 (marine sediment) from National Research Council, Canada. The analytical results obtained by employing Pd/Mg modifier are in good agreement with the certified values of all the reference sediment materials. Although for NRC MESS-3 an accurate determination of zinc is achieved even without the chemical modifier, the use of Pd/Mg chemical modifier is recommended as it leads to establishment of a reliable and accurate direct analytical method. One quantitative analysis takes less than 15 minutes after we obtain dried sediment samples, which is several tens of times faster than conventional analytical methods using acid digested sample solutions. The detection limits are 0.13?µg?g^?1 (213.9?nm) and 16?µg?g^?1 (307.6?nm), respectively, in sediment samples, when 40?mg of dried powdered samples are suspended in 20?mL of 0.1?mol?L^?1 nitric acid and a 10?µl portion of the slurry sample is measured. The precision of the proposed method is 8–15% (RSD).     

Copper‐Free Huisgen Cycloaddition for the 14‐3‐3‐Templated Synthesis of Fusicoccin‐Peptide Conjugates

Mid‐sized molecules have emerged as an attractive chemical space and potentially provide a robust basis for the development of synthetic agents to control intracellular protein interactions. However, the limited cell permeability and chemical tractability of such agents remain to be addressed. We envisioned that target‐templated synthesis of such mid‐sized molecules might provide a solution. Here, we exploited a copper‐free Huisgen cycloaddition for template synthesis using a peptide fragment containing a 4,8‐diazacyclononyne (DACN) moiety and an azide‐containing fusicoccin derivative in the presence or absence of recombinant 14‐3‐3ζ protein in vitro. Time‐course changes in the yield of products demonstrated that the reaction was accelerated in the presence of 14‐3‐3 and one of the regioisomers was generated predominantly, supporting the template effect.     

Synthesis of polymers having a phospholipid polar group connected to a poly(oxyethylene) chain and their protein adsorption-resistance properties

New methacrylates having a phospholipid polar group which was connected to various lengths of poly(oxyethylene) chains to form a polymerizable group (MEOnPC) were synthesized. The MEOnPC could polymerize with n-butyl methacrylate (BMA) in ethanol using a conventional radical polymerization technique. The unit mole fraction of MEOnPC in the polymer corresponded to that in the feed monomer solution. The MEOnPC polymers were soluble in ethanol, insoluble in water, but swelled in water and became hydrated. On the surface of a poly(BMA) membrane coated with MEOnPC, the phosphorylcholine groups of the MEOnPC unit present were determined by x-ray photoelectron spectroscopy. As a fundamental evaluation for biomedical materials, adsorption of one of the plasma proteins, fibrinogen, on acrylic beads coated with the MEOnPC polymers was evaluated. The amount of fibrinogen adsorbed on the MEOnPC polymer was smaller than that on the original acrylic beads, poly(BMA) and poly(2-hydroxyethyl methacrylate). The increase in the MEOnPC unit mole fraction in the polymer showed more effective protein adsorption-resistant properties. © 1996 John Wiley & Sons, Inc.     

Preparation and properties of isotactic and syndiotactic poly(methyl methacrylate)s,uniform with respect to molecular weight

Highly isotactic (it-) and highly syndiotactic (st-) poly(methyl methacrylate)s (PMMAs) uniform with respect to molecular weight (stereoregular, uniform PMMAs) were isolated up to the 100mer from it- and st-PMMAs by supercritical fluid chromatography (SFC) and characterized by NMR and mass spectroscopies. Glass transition temperatures (Tg's) of the uniform it- and st-PMMAs were higher than those of the corresponding PMMAs with MWD and with similar molecular weight on average. The Tg values of the uniform it-and st-PMMAs series obeyed the relationship, Tg = Tg∞ - K/M, where M and Tg∞ denote molecular weight and Tg at infinite M, respectively. The reciprocal melting points (1/Tm) of uniform it-PMMA (degree of polymerization, DP = 28–44), obtained from methanol solutions by evaporating the solvent, increased linearly with increasing 1/DP. Extrapolation of the linear relation to 1/DP = 0 gave the Tm of it-PMMA with infinite DP; Tm∞ = 171.1°C. Thermal degradation behavior was studied by thermogravimetry and by SFC analysis of degradation products. In gel-permeation chromatography (GPC) measurements, the it-50mer eluted faster than the st-50mer. Calibration curves for it- and st-PMMAs could be obtained using series of the uniform PMMAs. The instrumental spreading factor determined using it-25mer, it-50mer, st-25mer and st-50mer for our GPC chromatograph was 0.070 ml when the volume of the sample solution was 0.003ml. GPC analysis of a mixture of the it- and st-50mers in tetrahydrofuran indicated formation of a stereocomplex in the solution, and was found quite useful to elucidate the minimum sequence length required for complex formation.     

New phenylethanoid glycosides from Bacopa monniera

Three new phenylethanoid glycosides, viz. monnierasides I-III (1-3) along with the known analogue plantainoside B were isolated from the glycosidic fraction of Bacopa monniera. Their structures were elucidated mainly on the basis of two dimensional (2D) NMR spectral analyses.     

Electron-transfer polymers. XXXIX. Redox polymers based on duroquinonyl glycol

Redox polyurethanes, polyesters, and alternate copolyurethanes and copolycarbonates from two kinds of benzoquinonyl glycol were prepared based on 2-(duroquinonyl)-propan-1,3-diol. The oxidized polymer is stable. When the fully reduced polymer in solution is exposed to air the durohydroquinonyl residues are oxidized to the quinone form while the less substituted hydroquinonyl glycol residues remain stable in the reduced form. There is thus prepared polymer with oxidized and reduced groups alternating along the chain.