Random Copolymers of 1,5-Dioxepan-2-one

ABSTRACT

Copolymers of 1,5-dioxepan-2-one (DXO) and e-caprolactone (?-CL), δ-valerolactone (δ-VL) or L-lactide (LLA) have been synthesized and characterized. High molecular weight copolymers were obtained using stannous-2-ethyl hexanoate as catalyst in bulk. Reactivity ratios for the copolymerization of DXO and δ-VL were determined at 110°C as r_VL=0.5 and r_DXO=2.3. At high conversion, depolymerization of δ-VL occurred, resulting in lower molecular weight and variations in the copolymer composition.

Physical properties, such as crystallinity and melting temperature of the DXO-copolymers proved to be strongly dependent on the choice of comonomer and on the molar composition of the copolymers. DXO appears to be incorporated into the poly-?-caprolactone (PCL) crystals and to some extent into the poly-δ-valerolactone (PVL) crystals, resulting in a more gradual decrease in crystallinity with increasing amount of DXO.     

Aromatic polyesters containing cardo perhydrocumyl cyclohexylidene groups: Synthesis,characterization and gas permeation study

Three bisphenols containing cardo perhydrocumyl cyclohexylidene group, namely; 1,1-bis(4-hydroxyphenyl)-4-perhydrocumylcyclohexane, 1,1-bis(4-hydroxy-3-methylphenyl)-4-perhydrocumylcyclohexane and 1,1-bis(4-hydroxy-3,5-dimethylphenyl)-4-perhydrocumylcyclohexane were synthesized starting from p-cumyl phenol. Each of these bisphenols was polycondensed with both terephthaloyl chloride and isophthaloyl chloride by phase transfer-catalyzed interfacial polymerization to obtain a series of new aromatic polyesters. Inherent viscosities and number average molecular weights of polyesters were in the range 0.51-0.64 dL/g and 17390-41430?g/mol, respectively which indicated the formation of reasonably high molecular weight polymers. The detailed NMR studies revealed that axial and equatorial identity of the phenyl rings of bisphenols was retained in polyesters resulting in constitutional isomerism. Polyesters containing perhydrocumyl cyclohexylidene groups showed excellent solubility in organic solvents viz, chloroform, dichloromethane, 1,1,2,2-tetrachloroethane and tetrahydrofuran. The self-standing films of polyesters could be cast from their chloroform solution. The 10% weight loss temperatures and glass transition temperatures of polyesters were in the range 453–485?°C and 201–267?°C, respectively demonstrating their excellent thermal characteristics. The gas permeability study of polyesters was carried out for He, H₂ and N₂ by variable-volume method. An improvement in permeability and decrease in selectivity was observed due to symmetric methyl substituents while reverse trend was observed in case of polyesters with asymmetric methyl substituents.     

Secondary ion yields produced by keV atomic and polyatomic ion impacts on a self-assembled monolayer surface

A suite of keV polyatomic or 'cluster' projectiles was used to bombard unoxidized and oxidized self-assembled monolayer surfaces. Negative secondary ion yields, collected at the limit of single ion impacts, were measured and compared for both molecular and fragment ions. In contrast to targets that are orders of magnitude thicker than the penetration range of the primary ions, secondary ion yields from polyatomic projectile impacts on self-assembled monolayers show little to no enhancement when compared with monatomic projectiles at the same velocity. This unusual trend is most likely due to the structural arrangement and bonding characteristics of the monolayer molecules with the Au(111). Copyright 1999 John Wiley & Sons, Ltd.     

Fusion around the barrier for 7Li+12C

Fusion cross-sections for the ⁷Li + ¹²C reaction have been measured at energies above the Coulomb barrier by the direct detection of evaporation residues. The heavy evaporation residues with energies below 3 MeV could not be separated out from the α-particles in the spectrum and hence their contribution was estimated using statistical model calculations. The present work indicates that suppression of fusion cross-sections due to the breakup of ⁷Li may not be significant for ⁷Li + ¹²C reaction at energies around the barrier.     

Optische Aktivität und Magnetrotation als Beiträge zur chemischen Bindung und zur Elektronenkonfiguration der 1. Periode des Systems der Elemente (1). Teil II

Zusammenfassung Es wird über die Synthesen der L,L-, D,D- und D,L-Formen des 1,4-Cyclo-Phe-digly-phe-digly, des D,D-1,3-Cyclo-D-Phe-gly-D-phe-trigly sowie der Dimethyl- und Dibenzylester der 1,4-L,L-Cyclo-glu-digly-glu-digly berichtet und die Reversibilit?t der zum Drehungsbetrage Null für den sichtbaren Bereich der optischen Aktivit?t beim übergang derα-trans-trans-Formen in die ebenen polarisierten elektronenisomerenβ-Formen besprochen, eine Beobachtung, die bisher an allen 1,4 symmetrisch substituierten L-L, und D,D-Formen gemacht wurde (vgl. insbesondere die diesbezüglichen Tyrosin-Typen). Das Drehungsverhalten wird mit dem übergang der tetraedrischen Asymmetriezentren inga-1,4-Stellung in die durch entgegengesetzte Spinanordnungen ausgezeichneten Proton-stabilisierten ebenen Biradikale an Cα ₁ und Cα ₄, begründet. — Die Beobachtungen an Cyclopeptiden in Verbindung mit früheren Befunden über dieα- undβ-Elektronenleitung lieferten Beitr?ge zur Elektronenanordnung im Diamant- und Graphitgitter, letztere haben als Prototypen aliphatischer bzw. aromatischer Verbindungen zu neuen Vorstellungen über die Verknüpfung der Elektronenkonfiguration mit der Raumstruktur, über Radikale und Onium-Verbindungen, über die C-C(Einfach)- und C=C(Doppel)-Bindung geführt. — Das Studium von SH/SS-Redox-systemen unter Beteiligung eines³⁵-markierten cyclischen Hexapeptiddisulfids lieferte einen wichtigenBeitrag zur Frage des Peptidkettenauf- und umbaus, wie auch von Cyclopeptiden z. B. vom Typ des Cyclo-L-his-digly-L-tyr-digly; durch Polarisation erzeugte metastabile, angeregte Zust?nde konnten nachgewiesen werden. – Schlie?lich werden die Halbleitereffekte von Polypeptiden, Fermentmodellen etc. besprochen und dieβ-überg?nge unter und oberhalb der Energieschwelle mit den Vorg?ngen in Gittern verknüpft. — Schlie?lich wird über dieα- undgb-Formen von Polarkomplexverbindungen sowie über polare Heterocyclen mit Dreipunktstruktur berichtet. Mit 10 Abbildungen in 34 Einzeldarstellungen Herrn Prof. Dr. F. Micheel zum 60. Geburtstag gewidmet.     

Electrochemical performance of magnetic nanoparticle-decorated reduced graphene oxide (MRGO) in various aqueous electrolyte solutions

Journal of Solid State Electrochemistry - The objective of this work is twofold: (1) to improve the electrochemical performance of reduced graphene oxide (RGO) by decorating RGO sheets with...     

Real meromorphic functions and linear differential polynomials

We determine all real meromorphic functions f in the plane such that f has finitely many zeros, the poles of f have bounded multiplicities, and f and F have finitely many non-real zeros, where F is a linear differential polynomial given by F = f (k) +Σk-1j=0ajf(j) , in which k≥2 and the coefficients aj are real numbers with a0≠0.     

Optische Aktivität und Magnetrotation als Beiträge zur chemischen Bindung und zur Elektronenkonfiguration der 1. Periode des Systems der Elemente (1). Teil I

Ohne ZusammenfassungHerrn Prof. Dr. Micheel Zum 60. Geburtstag gewidmet.     

Sorption of inorganic nanoparticles in woven cellulose fabrics

Titanium dioxide was deposited from aqueous suspension onto cellulosic surfaces.Titania was sourced from Degussa (P25TM,70:30 anatase:rutile).Dry uptake of particles was shown to be rapid and dominant with one-third of the deposition occurring in less than 30 s and over one-half in the first minute.Isotherms were recorded to compare the rate of titanium deposition on dry and pre-wetted cotton.In the dry case uptake reached a maximum in 30 min whereas in the pre-wetted case the uptake was seen to continue beyond 180 min.A broad trend of higher deposition occurring at lower pH was seen,corresponding to the region where surface charges were opposite and thus attractive.Dry pickup was less significant at high pH.The response to varying ionic strength was complex and was attributed to the combined effect of charge screening,particle aggregation and consequent particle entrapment or occlusion.Titania deposition into the interstices of woven cotton sheets resulted in the formation of inorganic,nanoparticulate skeletons which could be isolated by controlled combustion of the cellulose and thus cotton was suggested to have potential for the templated synthesis of high surface area semiconductor materials.