Miscibility, crystallization kinetics, and morphology of poly(beta-hydroxybutyrate) and poly(methyl acrylate) blends

The miscibility, spherulite growth kinetics, and morphology of binary blends of poly(beta-hydroxybutyrate) (PHB) and poly(methyl acrylate) (PMA) were studied with differential scanning calorimetry, optical microscopy, and small-angle X-ray scattering (SAXS). As the PMA content increases in the blends, the glass-transition temperature and cold-crystallization temperature increase, but the melting point decreases. The interaction parameter between PHB and PMA, obtained from an analysis of the equilibrium-melting-point depression, is -0.074. The presence of an amorphous PMA component results in a reduction in the rate of spherulite growth of PRE. The radial growth rates of spherulites were analyzed with the Lauritzen-Hoffman model. The spherulites of PHB were volume-filled, indicating the inclusion of PMA within the spherulites. The long period obtained from SAXS increases with increased PMA content, implying that the amorphous PMA is entrapped in the interlamellar region of PHB during the crystallization process of PHB. All the results presented show that PHB and PMA are miscible in the melt. (C) 2000 John Wiley & Sons, Inc.

Spectroscopy of several beta-diketone compounds and their tautomers

Six beta-diketone compounds, 1,3-bis(4-nitrophenyl)-1,3-propanedione (1), 1-(4-nitrophenyl)-3-(3-nitrophenyl)-1,3-propanedione(2), 1,3-bis(3-nitrophenyl)-1,3-propanedione(3) 1,3-bis(4-amimophenyl)-1,3-propanedione(4), 1-(4-amimophenyl)-3-( 3-amimophenyl)-1,3-propanedione(5) and 1,3-bis (3-amimophenyl)-1,3-propanedione(6) were synthesized, Their structures were characterized by IR, UV-Vis, fluorescence and NMR spectroscopy, The percentage of keto tautomer, enol-keto equilibrium constant and enol tautomer ratio of them were also determined, The percentage of keto tautomer is increased in the order from compound 1 to 3 and decreased in the order from compound 4 to 6, which show the effect of substituent on the tautomer. The results of enol tautomer ratio of compounds 2 and 5 indicated that b-form of enol is slightly more favorable than its a-form.

Electric field-induced conformational transition of bovine serum albumin from alpha-helix to beta-sheet

The irreversible conformational transition of bovine serum albumin (BSA) from alpha-helix to beta-sheet, induced by electric field near the electrode surface, was monitored by circular dichroism (CD) with a long optical path thin layer cell (LOPTLC).

Hydrothermal synthesis and crystal structure of [{Cu(2,2 '-bpy)(2)}(2)Mo8O26]: a beta-octamolybdate cluster covalently bonded to two {Cu(2,2 '-bpy)(2)}(2+) coordination complexes via bridging oxo groups

An organic-inorganic hybrid solid, (Cu(2,2'-bpy)(2))(2)Mo8O26, has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. Dark green crystals crystallize in the orthorhombic system, space group Pna21, a = 24.164(5), b = 18.281(4), c = 11.877(2) Angstrom, alpha = 90 degrees, beta = 90 degrees, gamma = 90 degrees, V= 5247(2) Angstrom (3), Z = 4, lambda (MoK alpha) = 0.71073 Angstrom (R(F) = 0.0331 for 5353 reflections). Data were collected on a Siemens P4 four-circle diffractometer at 293 K in the range 1.69 degrees < theta < 25.04 degrees using the omega -scan technique. The structure was solved by the direct method and refined by full-matrix least squares on F-2 using SHELXL-93. The structure of this compound consists of discrete (Cu(2,2'-bpy)(2))(2)Mo8O26 clusters, constructed from beta -octamolybdate subunits ((Mo8O26)(4-)) covalently bonded to two (Cu(2,2'-bpy)(2))(2+) coordination complexes via bridging oxo groups that connect two adjacent molybdenum sites. (C) 2001 Academic Press.

A comparative study on the electroluminescence properties of some terbium beta-diketonate complexes

By comparing the phosphorescence spectra of Gd(acac)(3) (acac=acetylacetone), Gd(TFacac)3 (TFacac=1,1,1-trifluoroacetylacetone), the effects of fluorine replacement of hydrogen on the triplet state energy of the ligands were revealed. Fluorine can lower the triplet state energy of Hacac and make it more suitable for energy transfer towards the D-5(4) state of terbium. Organic electroluminescent devices (OELDs) with the corresponding trivalent terbium complexes as emissive layers were fabricated. Triple-layer-type devices with a structure of glass substrate/ITO (indium tin oxide)/PVK [poly(N-vinylcarbazole)]/PVK : Tb complex: PBD [2-(4-biphenyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole]/PBD/Al exhibit bright green luminescence upon applying a dc voltage. The luminance of a device with Tb(TFacac)(3)phen (1,10-phenanthroline) and Tb( TFacac) 3 as emissive layer is higher than that of the corresponding devices with Tb(acac)(3)(phen) and Tb(acac)(3) as emissive layers. The EL device with Tb(TFacac)(3)(phen) as emitter exhibits characteristic emission of Tb3+ ions with a maximum luminance of 58 cd m(-2) at 25 V.

Mechanical properties of poly(beta-hydroxybutyrate)/poly(ethylene oxide) blends

Tensile properties of poly (P-hydroxybutyrate)/poly (ethylene oxide) (PHB/PEO) blends were reported in this paper. It was found that the blends of PHB with different molecular-weight PEO exhibited different mechanical properties. The mechanical properties of the blends of PHB and PEO3 (M-w=0.3x10(6)) were very poor. However, the blends of PHB and PEO5 (M-w=5x10(6)) showed compatible in mechanical properties. Excellent synergism was observed not only in tensile stress and tensile elongation but also in modulus. Moreover, the ductility of the blends could be improved further under proper heat-treatment.

Study on the properties of poly(beta-hydroxybutyrate) grafted with maleic anhydride

The thermal stability, crystallization behavior and biodegradability of poly(beta -hydroxybutyrate) (PHB) grafted with maleic anhydride (MA) were studied by DSC,TGA, optical microscopy and WAXD. The results showed that thermal stability of maleated PHB was obviously improved, comparing with that of pure PHB. The temperature of decomposition was enhanced about 20 degreesC After grafting MA, the crystallization behavior of PHB changed evidently. The rate of spherulite growth decreased, the crystallization temperature from the melt state reduced, and the cold crystallization temperature from the glass state increased. With the increase in graft degree, the banding texture of spherulite became more distinct and orderly. Moreover, the introduction of MA groups promoted the biodegradation of PHB.

Miscibility and crystallization behavior of poly(beta-hydroxybutyrate)/poly(ethylene oxide) blends

The miscibility and crystallization behavior of poly(beta-hydroxybutyrate) (PHB)/poly(ethylene oxide) (PEO) blends were studied by differential scanning calorimetry(DSC) and polarizing microscopy (POM). It is found that the miscibility is related to the composition of the blends. When the PEO content is over 20 percent, the miscible blends turn into partially miscible and the phase separation can be observed with POM. The addition of the PEO influences not only the morphology of PHB crystals and the radial growth rate of spherulites, but also the cold crystallization temperature.

Synthesis, structure characterization of the complexes of beta-alkoxycarbonylethyltin trichlorides with Schiff base ligands

Thirty - two title complexes (ROCOCHRCH2SnCl3)-C-1 . (2 - HOC6H4CH = NC6H4 - X) (R = Me, Et, n - Bu; R-1 = H, Me; X = H,4' - Cl, 3' - Pr, 3' - OH, 3', 4' - Cl-2, 4' - OMe) were synthesized and characterized by elemental analysis,UV - vis, IR, H-1 NMR. The crystal structure of n - BuOCOCH2CH2SnCl3 . (2 - HOC6H4CH - NC6H4OMe - 4') were determined by the X - ray diffraction analysis, The crystal belongs to monoclinic system, with a = 1.4661 (3)nm, b = 0.9307 (2)nm, c = 1.7888 (4)nm, beta = 94.04 (3)degrees, V = 2.4348nm(3), D-c = 1.581mg/m(3), Z = 4, F(000) = 1160, mu = 1.405mm(-1), R = 0.0354, R-w = 0,0486, space group: P2(1)/c. The complexes exist as a discrete monomer. The tin atom has a distorted octahedral geometry due to intramolecular coordination of the carbonyl oxygen and the phenolic oxygen of the Schiff base ligands, The coordination number of tin atom is 6.

Mass spectrometry study combined with theoretical calculation on the unimolecular fragmentation of tetrahydroimidazole-substituted methylene beta-diketones

Studies of low-energy collision-induced dissociation and isotopic labeling on ionized tetrahydroimidazole-substituted methylene P-diketones by tandem mass spectrometry showed that their unimolecular fragmentations may involve the reactions of intermediate ion/neutral complexes and multistep rearrangements. The corresponding mechanisms were proved by semiemipirical calculations of PM3 and AM1 methods.

Nonisothermal crystallization and melting behavior of poly(beta-hydroxybutyrate)-poly(vinyl-acetate) blends

Nonisothermal crystallization and melting behavior of poly(P-hydroxybutyrate) (PHB)-poly(vinyl acetate) (PVAc) blends from the melt were investigated by differential scanning calorimetry using various cooling rates. The results show that crystallization of PHB from the melt in the PHB-PVAc blends depends greatly upon cooling rates and blend compositions. For a given composition, the crystallization process begins at higher temperatures when slower scanning rates are used. At a given cooling rate, the presence of PVAc reduces the overall PHB crystallization rate. The Avrami analysis modified by Jeziorny and a new method were used to describe the nonisothermal crystallization process of PHB-PVAc blends very well. The double-melting phenomenon is found to be caused by crystallization during heating in DSC. (C) 1999 John Wiley & Sons, Inc.

Isothermal crystallization kinetics and melting behavior of poly(beta-hydroxybutyrate)/poly(vinyl acetate) blends

The overall isothermal crystallization kinetics and melting behavior of poly(beta-hydroxybutyrate) (PHB)/poly(vinyl acetate) (PVAc) blends were studied by using differential scanning calorimetry(DSC). The Avrami analysis indicates that the addition of PVAc into PHB results in the decrease in the overall crystallization rate of the PHB phase, but does not affect PHB's nucleation mechanism and geometry of crystal growth. The activation energy of the overall process of crystallization increases with the increasing PVAc content in the blends. The phenomenon of multiple melting endotherms is observed, which is caused by melting and recrystallization during the DSC heating run. (C) 1998 Elsevier Science Ltd. All rights reserved.

Structure and non-linear optical properties of beta-barium borate

The non-linear optical (NLO) properties of crystalline beta-BaB2O4 (beta-barium borate, BBO) have been investigated from the chemical bond viewpoint. The contributions of each type of chemical bond to the total NLO coefficient have been quantitatively determined. The calculations indicate that the true space group of BBO is R3 rather than R3c.

Miscibility and crystallization of poly(beta-hydroxybutyrate)/poly(vinyl acetate-co-vinyl alcohol) blends

Poly(vinyl acetate-co-vinyl alcohol) copolymers (P(VAc-co-VA)) were synthesized by hydrolysis-alcoholysis of PVAc. The miscibility, crystallization, and morphology of poly(P-hydroxybutyrate) (PHB) and P(VAc-co-VA) blends were studied by differential scanning calorimetry, optical microscopy (OM), and SAXS. It is found that the P(VAc-co-VA)s with vinyl alcohol content of 9, 15, and 22 mol % will form a miscible phase with the amorphous part of PHB in the solution-cast samples. The melting-quenched samples of PHB/P(VAc-co-VA) blends with different vinyl alcohol content show different phase behavior. PHB and P(VAc-co-VA9) with low vinyl alcohol content (9% mel) will form a miscible blend in the melt state. PHB and P(VAc-co-VA15) with 15 mol % vinyl alcohol will not form miscible blends while PHB/P(VAc-co-VA15) blend with 20/80 composition will form a partially miscible blend in the melt state. PHB and P(VAc-co-VA22) with 22 mol % vinyl alcohol are not miscible in the whole composition range. The single glass transition temperature of the blends within the whole composition range suggests that PHB and P(VAc-co-VA9) are totally miscible in the melt. The crystallization kinetics was studied from the whole crystallization and spherulite growth for the miscible blends. The equilibrium melting point of PHB in the PHB/P(VAc-co-VA9) blends, which was obtained from DSC results using the Hoffman-Weeks equation, decreases with the increase in P(VAc-co-VA9) content. The negative value of the interaction parameter determined from the equilibrium melting point depression supports the miscibility between the components. The kinetics of spherulitic crystallization of PHB in the blends was analyzed according to nucleation theory in the temperature range studied in this work. The best fit of the data to the kinetic theory is obtained by employing WLF parameters and the equilibrium melting points obtained by DSC. The addition of P(VAc-co-VA) did not affect the crystalline structure of PHB, as shown by the WAXD results. The long periods of blends obtained from SAXS increase with the increase in P(VAc-co-VA) content. It indicates that the amorphous P(VAc-co-VA) was rejected to interlamellar phase corporating with the amorphous part of PHB.

Miscibility and specific interactions in poly(beta-hydroxybutyrate-co-beta-hydroxyvalerate) and poly(P-vinylphenol) blends

The blends of poly(beta-hydroxybutyrate-co-beta-hydroxyvalerate) (P(HB-co-HV)/poly(p-vinylphenol)(PVPh) were investigated by differential scanning calorimetry (DSC), Fourier transform IR (FT-IR) spectroscopy and high-resolution solid-state C-13 NMR techniques. Single glass transition temperatures existing in the whole composition range indicates that these blends are miscible. The presence of hydrogen bonding between the hydroxyl of PVPh and carbonyl of P(HB-co-HV), shown by FT-IR spectra, is the origin of the miscibility. Furthermore, results obtained by high-resolution solid-state C-13 NMR give more information about the structure of the blends. (C) 1998 Elsevier Science Ltd. All rights reserved.