Study of temperature transitions in solid poly(oxymethylene) by thermal analysis methods

Poly(oxymethylene)s with different molecular mass and chemical structure were studied using DSC, dynamic mechanical relaxation, thermomechanical analysis, and thermogravimetry.Molecular mobilities of two types were found in the amorphous phase of poly(oxymethylene). Unconstrained chains of poly(oxymethylene) soften at –70°C and then amorphous chains with different restraints from the crystalline phase are successively activated in a wide temperature interval.Dedicated to Professor Bernhard Wunderlich on the occasion of his 65th birthdayThis work has been supported by DuPont Company     

On the origin of dynamic instability of molecular systems

The vibronic origin of dynamic instability of molecular systems considered earlier, is here given a more complete and rigorous treatment. It is shown that the nonvibronic contribution to the curvature of the adiabatic potential arising due to nuclear displacements under fixed electronic density distribution, is always positive, and hence the only reason for dynamic instability is the pseudo Jahn-Teller effect. For some examples of special interest (planar equilateral NH₃, planar square CH₄ and linear H ₃ ⁺ ) the molecular excited states, responsible for the instability of the ground state, are revealed by means of ab initio calculations.     

Mechanism of Cp<Subscript>2</Subscript>ZrCl<Subscript>2</Subscript>-catalyzed olefin hydroalumination by alkylalanes

The composition of intermediates of the Cp₂ZrCl₂-catalyzed hydroalumination of α-olefins by isobutylalanes (HAlBuⁱ ₂, AlBuⁱ ₃, ClAlBuⁱ ₂) was studied by dynamic ¹H and ¹³C NMR pectroscopy. The reaction of Cp₂ZrCl₂ with isobutylalanes affords the complex (Cp₂ZrHCl·HAlBuⁱ ₂)₂ responsible for α-olefin hydroalumination.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 311–322, February, 2005.     

Synthesis, structures, and properties of spiro[6-azaperimidine-2,4′-cyclohexa-2′,5′-dien]-1′-one derivatives

The reaction of 5-amino-4-chloroquinolines with 4-amino-2,6-di-tert-butylphenol yielded derivatives of spiro[6-azaperimidine-2,4′-cyclohexa-2′,5′-dien]-1′-one, which exhibit photo-and thermochromic properties in solutions. The structure of 2′,6′-di-tert-butyl-5,7,9-trimethylspiro[6-aza,-2,3-dihydroperimidine-2,4′-cyclohexa-2′,5′-dien]-1′-one was established by X-ray diffraction study. The ring-chain isomerization of 2′,6′-di-tert-butyl-5,7-dimethyl-and 2′,6′-di-tert-butyl-5,7,8-trimethylspiro[6-aza-2,3-dihydroperimidine-2,4′-cyclohexa-2′,5′-dien]-1′-ones was studied by dynamic NMR spectroscopy. Deceased. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2028–2034, November, 1997.     

Intramolecular Dynamics and Molecular Structure of Europium(III) Chelate Complexes with Crown Ethers as Studied by NMR Spectroscopy

Earlier the intramolecular inversion of the 18-crown-6 molecules was found in the complex ion pairs [Ln(ptfa)₂ (18-crown-6)]⁺ [Ln(ptfa)₄]⁻ (H₂O)₄ where Ln = La(1), Ce (2), Pr (3), Nd (4), and ptfa is 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione. In this work the peculiarities of the molecular structure and dynamics were studied for [Eu(ptfa)₂ (18-crown-6)]⁺ [Eu(ptfa)₄]⁻ (H₂O)₄ (5) by NMR spectroscopy techniques. Through VT-NMR spectra analysis the temperature dependence was obtained for the rate constant. The free energy ΔG^‡(320) of 18-crown-6 ring inversion activation was found to be 65 ± 5 kJ mol⁻¹ for 5 in CDCl₃. This result is comparable with the earlier data [S.P. Babailov and D.A. Mainichev: J. Inclusion Phenom. Macrocyclic Chem. 43, 187–193 (2002)] for complexes 2, 3, 4 in deuterated toluene (ΔG^‡(320)=65 ± 9, 64 ± 9, 64 ± 9 kJ mol⁻¹ respectively). It was found by relaxation NMR spectroscopy that the effective distance between Ln and protons of the crown molecule is 4.5 ± 0.2 Å. The analysis of structural parameters testifies that the crown ether and chelated anions are in the first coordination sphere of a Ln cation. Obtained geometrical parameters show that the complex cations of Eu, Ce and Pr have similar spatial structures.This revised version was published online in July 2005 with a corrected issue number.     

Orthokinetic Aggregation in Two Dimensions of Monodisperse and Bidisperse Colloidal Systems

Orthokinetic aggregation of colloids trapped at the air–liquid interface was studied by direct imaging in a couette cell. This method allowed us to follow the temporal evolution of both the cluster-mass distribution and the cluster structure at a shear rate where Brownian aggregation is suppressed. The interactions between the monodisperse latex particles floating at the air–liquid interface were controlled either by varying the electrolyte concentration or by creating a bidisperse system through the addition of small particles. The results show that the clusters in all of the systems are characterized by a high fractal dimension, indicating that the clusters are rearranged and densified by the shear. Kinetic analysis suggests that aggregation of monodisperse systems mainly proceeds through homogeneous aggregation, i.e., large clusters sticking to other large clusters. The bidisperse system, finally, with a size ratio around 10, favored a more heterogeneous aggregation among small and large clusters throughout the aggregation process; a slightly lower fractal dimension was observed compared to the strongly aggregated monodisperse system.     

Annealing of Polypropylene/Polyethylene Blends Near to the Melting Points in TMDSC

Annealing experiments have been carried out just below the melting temperature of both polyethylene (LLDPE) and polypropylene (PP) and their blends. The total melting enthalpy measured after the annealing cycle was greater by 10-15% with respect to the value having been measured before it. During the annealing period the heat capacity decreases to a lower value within the first 2-3 min. Heat capacities of PP (either in pure form or in the blends) measured during the heating cycle following the annealing cycle have the same value as during the cooling section. The heat capacities of the LLDPE in the heating cycle following the annealing were those of the preceding heating cycle. The total heat flows in the cooling section following the annealing cycle were greater than those in another cooling cycle at the same temperatures indicating that the crystallisation takes place during the cooling rather than during the annealing periods. The presence of LLDPE decreases the crystallisation temperature of PP. The presence of SEBS in the blend results in a greater crystallisation temperature than that of pure PP. The crystallisation temperature of LLDPE increases with increasing levels of PP. This revised version was published online in July 2006 with corrections to the Cover Date.     

Dynamic covalent approach to [2]- and [3]roxtanes by utilizing a reversible thiol-disulfide interchange reaction

A dynamic covalent approach to disulfide-containing [2]- and [3]rotaxanes is described. Symmetrical dumbbell-shaped compounds with two secondary ammonium centers and a central located disulfide bond were synthesized as components of rotaxanes. The rotaxanes were synthesized from the dumbbell-shaped compounds and dibenzo-[24]crown-8 (DB24C8) with catalysis by benzenethiol. The yields of isolated rotaxanes reached about 90 % under optimized conditions. A kinetic study on the reaction forming [2]rotaxane 2 a and [3]rotaxane 3 a suggested a plausible reaction mechanism comprising several steps, including 1) initiation, 2) [2]rotaxane formation, and 3) [3]rotaxane formation. The whole reaction was found to be reversible in the presence of thiols, and thermodynamic control over product distribution was thus possible by varying the temperature, solvent, initial ratio of substrates, and concentration. The steric bulk of the end-capping groups had almost no influence on rotaxane yields, but the structure of the thiol was crucial for reaction rates. Amines and phosphines were also effective as catalysts. The structural characterization of the rotaxanes included an X-ray crystallographic study on [3]rotaxane 3 a.     

Rapid and sensitive determination of ephedrine and pseudoephedrine by micellar electrokinetic chromatography with on-line regenerating covalent coating

A rapid, sensitive and reproducible micellar electrokinetic chromatographic method using hexamethyldisilazane as on-line regenerating covalent coating was developed for the quantification of ephedrine (E) and pseudoephedrine (PE). E and PE were derivatized with 4-chloro-7-nitrobenzo-2-oxa-1,3-diazol for laser-induced fluorescence detection. The on-line regenerating covalent coating formed a combinative double coating with the subsequently produced dynamic SDS coating. The total coating can be easily removed and conveniently regenerated on-line. The simple coating procedure was described. By a series of optimization, a running buffer of 20 mm Na(2)B(4)O(7) + 16 mm SDS was applied for the separation of the derivatives. Linear relationships for E and PE were obtained in the range of 0.044-6.60 microg mL(-1) (correlation coefficients: 0.9975 for E, 0.9981 for PE), and the detection limits for E and PE were 1.71 and 0.67 ng mL(-1), respectively. The separation speed, the reproducibility and the sensitivity were much improved over those of other capillary electrophoresis methods more recently reported. The method was applied to the analysis of the two alkaloids in traditional herbal preparations with recoveries in the range 92.8-104.8%.