Stability,Formation and Dissociation Kinetics of the Pentacoordinate Ni2+ and CO2+ Complexes with 1,5-Diazacyclooctane-N,N′-diacetic Acid

The stability constants of the Ni²⁺ and Co²⁺ complexes with 1,5-diazacyclooctane-N,N′-diacetic acid (H₂DACODA) have been determined potentiometrically in 0.5M KNO₃ at 25°. Only M(DACODA) and M(DACODA)OH^? were observed. In addition the formation and dissociation kinetics of the pentacoordinate complexes M(DACODA) has been studied in aqueous solution using a stopped-flow technique. Formation follows the rate law v_f = k_f [M²⁺] [HDACODA^?]/[H⁺], which can be interpreted as a bimolecular process either between M²⁺ and DACODA^2? (k) or between MOH⁺ and HDACODA^? (k). The second order rate constants k are much higher than those expected from water exchange and can only be explained by a strong internal conjugate base effect. In the limiting case, however, this is equivalent to the second possible explanation, which assumes MOH⁺ and HDACODA^? as reactive species. The dissociation rate is given by v_d = (k^ML + k [H⁺]) · [M(DACODA)].     

Spin state dependent peroxidase activity of heme bound amyloid β peptides relevant to Alzheimer's disease

The colocalization of heme rich deposits in the senile plaque of Aβ in the cerebral cortex of the Alzheimer''s disease (AD) brain along with altered heme homeostasis and heme deficiency symptoms in AD patients has invoked the association of heme in AD pathology. Heme bound Aβ complexes, depending on the concentration of the complex or peptide to heme ratio, exhibit an equilibrium between a high-spin mono-His bound peroxidase-type active site and a low-spin bis-His bound cytochrome b type active site. The high-spin heme–Aβ complex shows higher peroxidase activity than free heme, where compound I is the reactive oxidant. It is also capable of oxidizing neurotransmitters like serotonin in the presence of peroxide, owing to the formation of compound I. The low-spin bis-His heme–Aβ complex on the other hand shows enhanced peroxidase activity relative to high-spin heme–Aβ. It reacts with H₂O₂ to produce two stable intermediates, compound 0 and compound I, which are characterized by absorption, EPR and resonance Raman spectroscopy. The stability of compound I of low-spin heme–Aβ is accountable for its enhanced peroxidase activity and oxidation of the neurotransmitter serotonin. The effect of the second sphere Tyr10 residue of Aβ on the formation and stability of the intermediates of low-spin heme–Aβ has also been investigated. The higher stability of compound I for low-spin heme–Aβ is likely due to H-bonding interactions involving Tyr10 in the distal pocket.

Low-spin heme-Aβ forms stable compound 0 and compound I in the presence of H₂O₂ where compound I is responsible for its substantial peroxidase activity. This compound I also oxidizes neurotransmitters which is a typical hallmark of Alzheimer''s disease.     

Efficient synthesis of [1,2,3]triazolo[5,1-c][1,4]benzoxazines through palladium-copper catalysis

A wide variety of [1,2,3]triazolo[5,1-c][1,4]benzoxazines were synthesized through palladium-copper catalyzed reactions of 1-azido-2-(prop-2-ynyloxy)benzene with aryl/vinyl iodides. A plausible reaction mechanism has also been proposed.     

Twin liquid crystals and segmented thermotropic polyesters containing azobenzene—effect of spacer length on LC properties

We report systematic studies on a homologous series of twin liquid crystalline (LC) molecules based on phenyl and naphthyl azobenzene ( PnP and NpnNp ) as well as segmented copolyesters based on them. The twin series had the structure azobenzene–oligooxyethylene–azobenzene, where the ethyleneoxy length was varied from 2 to 6 units. The LC properties of the twin series depended on the chemical structure of the azochromophore and also the length of the central oligooxyethylene segment. The PnP series exhibited smectic LC properties for n > three oligooxyethylene units. Conversely, NpnNp series exhibited spherulitic phases only for the shortest member – Np2Np . One non‐LC short spacer twin ( P2P ) and one LC long spacer twin ( P6P ) were incorporated as part of a main chain polyester composed of fully aliphatic segments of sebacate and di or tetraethylene glycol (DEG/TEG) units by melt polycondensation. Non‐LC P2P formed LC polymers even at low (5 mol %) incorporation in DEG‐based copolymers, whereas the LC‐ P6P could do so only at 30 mol % incorporation. The LC properties of the twin molecules as well as copolymers were studied using differential scanning calorimetry, polarized light microscopy (PLM) along with variable temperature wide angle X‐ray diffraction. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Modeling of reinitiation ability of polymer brushes grown by surface‐initiated photoiniferter‐mediated photopolymerization

A kinetic model developed to investigate surface‐initiated photoiniferter‐mediated photopolymerization (SI‐PMP) and parameterized using experimental thickness data from SI‐PMP of methyl methacrylate is used to examine chain extension by reinitiation. Specifically, the effects of light intensity, concentration of an added deactivator, tetraethylthiuram disulfide (TED), and initial photoiniferter (PI) concentration on the reinitiation ability of surface‐tethered PMMA layers is examined in detail. The simulations show that while increases in [TED] and decreases in light intensity affect overall rates of PMMA layer growth in a similar fashion, their effect on reinitiation ability of PMMA layers is significantly different: reinitiation ability increases with increasing [TED] but it is not improved by decreases in light intensity. Simulations also suggest that polymer layers synthesized in the presence of TED have a greater tendency to form surface‐tethered block copolymers upon reinitiation compared with polymer layers synthesized without TED and at lower light intensity. While both [PI] and [TED] affect the reinitiation ability, the effect of [TED] on reinitiation ability is identical at a given [TED]/[PI] ratio for all PI and TED concentrations tested. These findings obtained from the rate‐based model are instrumental in delineating strategies for creating tethered block copolymer layers or mixed brushes by SI‐PMP. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1586–1593, 2010     

Theoretical study of small clusters of manganese-doped gallium oxide: Mn(GaO)n and Mn2(GaO)n with n?=?1?7

Structures, electronic and magnetic properties of Mn and Mn₂ doped stoichiometric (GaO) _n clusters with n = 1−7 are studied in the framework of density functional theory. Doping of a Mn atom is found to be energetically favorable in (GaO) _n clusters and the equilibrium configurations are found to be determined by the metal–oxygen interactions. Mn prefers to maximize the number of Mn–O bonds by selecting a Ga site in the cluster which increases its coordination with oxygen. Addition of a Mn atom in Mn(GaO) _n clusters results into the ground state to be either ferromagnetic or antiferromagnetic depending on the Mn coordination number and the Mn–Mn bond-length in the given Mn₂(GaO) _n cluster.     

Synthesis of (−)-hygrine, (−)-norhygrine, (−)-pseudohygroline and (−)-hygroline via Nef reaction

Synthesis of tropane alkaloids (−)-hygrine, (−)-norhygrine and sedum alkaloids (−)-pseudohygroline and (−)-hygroline is described from l-proline via Henry and Nef reactions.