Stereocomplex formation between enantiomeric poly(α‐methyl‐α‐ethyl‐β‐propiolactones): Effect of molecular weight

Optically pure S(?) and R(+)‐poly(α‐methyl‐α‐ethyl‐β‐propiolactones) (PMEPLs) of controlled low molecular weights were synthesized by anionic polymerization of the corresponding optically active monomers, and characterized using gel permeation chromatography, Maldi‐TOF mass spectrometry, and NMR spectroscopy. Blends of PMEPLs of opposite configurations and different molecular weights were investigated. All blends lead to the formation of a stereocomplex and its crystallization prevails over a wide range of mixing ratios. The stereocomplex melts 30–40 °C above that of the corresponding pure polymers, depending on the molecular weight; pairs of polymers having similar molecular weights exhibit the highest melting temperatures and enthalpies of fusion. Finally, when the stereocomplex is dispersed in a PMEPL matrix, it acts as a very effective nucleation agent for the crystallization of the polymer in excess. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2380–2389, 2007     

Smooth solutions for the motion of a ball in an incompressible perfect fluid

In this paper we investigate the motion of a rigid ball surrounded by an incompressible perfect fluid occupying RN. We prove the existence, uniqueness, and persistence of the regularity for the solutions of this fluid-structure interaction problem.     

Synthesis and Opiate Activity in vitro of Five New p-Nitrophenylalanine4-Enkephalin-like Peptides

Converging data obtained in biochemical and pharmacological bioassays for opiate activity are presented for five new enkephalin-like peptides. The main structural features of the analogues, the synthesis of which is described in detail, were the presence of D -alanine or D -serine in position 2, p-nitrophenylalanine in position 4 and of a free C-terminal carboxylic function. Confirming our previous observations [1], the substitution of phenylalanine by p-nitrophenylalanine enhanced the overall opiate activity but decreased the selectivity towards m?/δ-receptor sites. Tyrosyl-D -alanyl-glycyl-p-nitrophenylalanyl-adamantylalanine was particularly potent in all assays while tyrosyl-D -seryl-glycyl-p-nitrophenylalanyl-leucyl-threonine was very selective in the bioassays on isolated tissues and moderately selective in the binding assay. These results will have to be taken into account in future photoaffinity labelling and quantitative structure-activity relationships (QSAR) studies.     

Reagent-injection flow analysis: application to the determination of nanomolar levels of hydrogen peroxide in seawater

A reagent-injection flow technique, which allows automatic control of the volume of reagent to be injected, is described. The sensitivity of the measurements can be adjusted over a wide range by changing the injection volume. This technique also eliminates problems in photometric determinations arising from refractive index effects and from light scattering by suspended particles in the sample. Consequently, absorbances as small as 0.00004 can be measured. The capabilities of this reagent-injection flow technique were tested by using it to determine hydrogen peroxide in seawater at nanomolar levels with photometric detection. The concentration of hydrogen peroxide was determined as the colored condensation product of N-ethyl-N-(sulfopropyl)aniline and 4-aminoantipyrene; the detection limit was 12 nM.     

Model studies of colloidal silica precipitation using biosilica extracts from<Emphasis Type="Italic"> Equisetum telmateia</Emphasis>

Structural materials containing silicon are produced in single celled organisms through to higher plants and animals. Hydrated amorphous silica is a colloidal mineral of infinite functionality that is formed into structures with microscopic and macroscopic form. Proteins and proteoglycans are suggested to play a critical role in the catalysis of silica polycondensation and in structure direction during the formation of these magnificent structures. This article extends knowledge on the effect of protein containing biosilica extracts from Equisetum telmateia on the kinetics of silica formation and structure regulation. Utilising potassium silicon catecholate as the source of soluble silicon, bioextracts obtained from plant silica by dissolution of the siliceous phase with aqueous HF following extensive acid digestion of the plant cell wall were found to modify the kinetic rate constants for the formation of small silicic acid oligomers under circumneutral pH conditions and to modify the solubility of silicic acid in solution. Addition of the bioextracts at ca. 1 wt% to the reaction medium reduced the sizes and range of sizes of the fundamental silica particles formed and led to the formation of crystalline polymorphs of silica under conditions of ca. neutral pH, room temperature and in the absence of multiply charged cations, conditions assumed to be relevant to the biological mineralization environment. The ability of biological organisms to regulate the formation of silica structures with prevention of crystallinity is discussed as are the implications of this study in terms of the generation of new materials with specific form and function for industrial application.     

The redox series [M(bpy)2(q)]n+, M = Ru or Os, Q = 3,5-di-tert-butyl-n-phenyl-1,2-benzoquinonemonoimine. Isolation and a complete X and W band EPR study of the semiquinone states (n = 1)

The complexes [M(bpy)(2)(Q)](PF(6)) (bpy = 2,2'-bipyridyl; M = Ru, Os; Q = 3,5-di-tert-butyl-N-phenyl-1,2-benzoquinonemonoimine) were isolated and studied by X and W band EPR in a dichloromethane solution at ambient temperatures and at 4 K. For M = Ru, the (14)N hyperfine splitting confirms the Ru(II)/semiquinone formulation, although at a > 1 mT, the (99,101)Ru satellite coupling is unusually high. W band EPR allowed us to determine the relatively small g anisotropy Delta g = g(1) - g(3) = 0.0665 for the ruthenium complex. The osmium analogue exhibits a much higher difference Delta g = 0.370, which is attributed not only to the larger spin-orbit coupling constant of Os versus that of Ru but also to a higher extent of metal contribution to the singly occupied molecular orbital. The difference Delta E between the oxidation and reduction potentials of the radical complexes is larger for the ruthenium compound (Delta E = 0.87 V) than for the osmium analogue (Delta E = 0.72), confirming the difference in metal/ligand interaction. The electrochemically generated states [M(bpy)(2)(Q)](n+), n = 0, 1, 2, and 3, were also characterized using UV-vis-near-infrared spectroelectrochemistry.     

New linear high-valent tetranuclear manganese-oxo cluster relevant to the oxygen-evolving complex of photosystem II with oxo, hydroxo, and aqua coordinated to a single Mn(IV)

An unprecedented atom connectivity, MnIV(mu-O)MnIV(mu-O)2MnIV(mu-O)MnIV, is found in the complex [MnIV4O4(EtO-terpy)4(OH)2(OH2)2](ClO4)(6).8H2O (EtO-terpy=4'-ethoxyl-2,2':6',2' '-terpyridine), which has been characterized by X-ray crystallography, X-ray powder diffraction, EPR spectroscopy, and magnetic studies. This complex is the first example of a compound where a MnIV ion is coordinated by all three types of water-derived ligands: oxo, hydroxo, and aqua. Bond distances and angles for this complex are consistent with a MnIV4 oxidation state assignment. The di-mu-oxo- and mono-mu-oxo-bridged Mn-Mn distances are 2.80 and 3.51 A, respectively. The variable-temperature magnetic susceptibility data for this complex, in the range of 10-300 K, are consistent with an S=0 ground state and were fit using the spin Hamiltonian HHDvV=-J1S2S1-J2S1S1A-J1S1AS2A (S1=S1A=S2=S2A=3/2) with J1=-432 cm-1 and J2=-164 cm-1 (where J1 and J2 are exchange constants through the mono-mu-oxo and the di-mu-oxo bridges, respectively). The first excited spin state of this tetramer is a spin triplet state at 279 cm-1 above the diamagnetic ground state. The next spin states are the S=1 and S=2 levels at about 700 and 820 cm-1 above the S=0 ground state, respectively. These large energy gaps are consistent with the absence of an EPR signal for this complex, even at high temperature.     

Isolation and structural characterization of anionic and neutral compounds resulting from the oxidative addition of HI or CH3I to [IrI2(CO)2](-)

The active iridium species in the methanol carbonylation reaction has been crystallized as the [PPN][IrI(2)(CO)(2)] complex and the X-ray structure solved, showing a cis-geometry and a square planar environment. Hydriodic acid reacts very quickly with this compound to provide [PPN][IrHI(3)(CO)(2)], the X-ray crystal structure of which has been determined. The two CO ligands remain in mutual cis-position in a pseudooctahedral environment. The same cis-arrangement has been observed from the X-ray structure for [PPN][IrI(3)(CH(3))(CO)(2)] resulting from the slower oxidative addition of CH(3)I to [PPN][IrI(2)(CO)(2)]. By iodide abstraction with InI(3), the anionic methyl complex gave rise to the dimeric neutral complex [Ir(2)(mu-I)(2)I(2)(CH(3))(2)(CO)(4)]. An X-ray structure showed that the methyl ligands are in the equatorial positions of the two octahedrons sharing an edge, formed by the two bridging iodide ligands. All these four complexes have been fully characterized by mass spectrometry, (1)H and (13)C NMR, and infrared both in solution and in the solid state. When necessary, the (13)CO- or (13)CH(3)-enriched complexes have been prepared and analyzed.     

Separation of cyanogen bromide peptides of collagen by means of high-performance liquid chromatography

Cyanogen bromide peptides of bovine collagen Types I, II and III were analyzed using high-performance liquid chromatography (HPLC). Elution patterns of each collagen type were unique and reproducible.Elution patters of the CNBr peptides of the a1 and a2 chains of Type I collagen were also unique and together accounted for the major components of Type I collagen.Analysis of the eluted peptides from HPLC of each collagen type by sodium dodecyl sulphate-polyacrylamide gel electrophoresis showed specific patterns for each collagen. Thus, unique and reproducible HPLC chromatograms were obtained, providing a new analytical method that is simple, sensitive and rapid.