Isothermal crystallization kinetics of poly(3‐hydroxybutyrate)/layered double hydroxide nanocomposites

Poly(3‐hydroxybutyrate) (PHB)/layered double hydroxides (LDHs) nanocomposites were prepared by mixing PHB and poly(ethylene glycol) phosphonates (PEOPAs)‐modified LDH (PMLDH) in chloroform solution. Both X‐ray diffraction data and TEM micrographs of PHB/PMLDH nanocomposites indicate that the PMLDHs are randomly dispersed and exfoliated into the PHB matrix. In this study, the effect of PMLDH on the isothermal crystallization behavior of PHB was investigated using a differential scanning calorimeter (DSC) and polarized optical microscopy. Isothermal crystallization results of PHB/PMLDH nanocomposites show that the addition of 2 wt % PMLDH into PHB induced more heterogeneous nucleation in the crystallization significantly increasing the crystallization rate and reducing their activation energy. By adding more PMLDH into the PHB probably causes more steric hindrance of the diffusion of PHB, reducing the transportation ability of polymer chains during crystallization, thus increasing the activation energy. The correlation among crystallization kinetics, melting behavior and crystalline structure of PHB/PMLDH nanocomposites can also be discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3337–3347, 2006     

Interfacial effects on stress distribution in model composites

Raman mechanical spectroscopy was used to examine interfacial effects on the stress distribution in model polydiacetylene fiber/epoxy composites. Epoxy release agents were coated on fiber surfaces to modify the interfacial adhesion properties. The modified fiber surfaces were then characterized by scanning electron microscopy and x-ray photoelectron spectroscopy as well as optical microscopy. No difference in the maximum stress value or stress distribution was observed for the two types of fibers, coated or uncoated, used in composites. This suggests that adhesion properties at the composite interface do not affect tensile stress transfer efficiency nor, therefore, the composite tensile modulus along the fiber axis direction in uniaxial composites. Experimental data were also compared with theoretical calculations assuming perfect bonding between fiber and matrix, and idealized frictional force transfer mechanism at the fiber–matrix interface.     

Enhancement of the imprinting effect in cholesterol-imprinted microporous silica

A sol-gel method has been used to fabricate a cholesterol MIP for application in polar solutions. In this study, (cholesteryl propylcarbamate)triethoxysilane and tetraethyl orthosilicate were used as the hydrophobic monomer and crosslinker, respectively. The MIP had a larger pore volume when formation of the polymer was catalyzed at a higher pH than when it was formed at lower pH values, with the pore diameters being 3.5 nm and 2 nm, respectively for materials formed at high and low pH values. Both of these pore volumes were greater than those found for the respective control polymers formed without template. However, only the polymers formed at low pH values showed an imprinting effect. Compared with other methods explored, the sol-gel procedure gave only a small amount of non-specific binding for both the MIP and NIP when synthesized at low pH values. The largest imprinting-induced promotion of binding (IPB) value of the MIP (13 650%) was obtained with [HCl] = 0.01 M in the sol-gel solution. The MIP showed high selectivity towards cholesterol in comparison with other steroid hormones, and also to a lesser extent recognized vitamin D3 in methanol solution containing 5 vol.% water.     

Synthesis and light emitting properties of polyacetylenes having pendent fluorene groups

Five novel fluorene‐containing polymers, poly[(9,9‐dimethylfluoren‐2‐yl)acetylene] ( PFA1 ), poly[(1‐pentyl‐2‐(9,9‐dimethylfluoren‐2‐yl)acetylene) ( PFA2 ), poly[1‐decyl‐2‐(9,9‐dimethylfluoren‐2‐yl)acetylene] ( PFA3 ), poly[1‐phenyl‐2‐(9,9‐dimethylfluoren‐2‐yl)acetylene] ( PFA4 ), and poly[1‐(3,4‐difluorophenyl)‐2‐(9,9‐dimethylfluoren‐2‐yl)acetylene] ( PFA5 ) were synthesized by the polymerization of the corresponding fluorene‐substituted acetylenic monomers ( M1–M5), using WCl₆, MoCl_5, and TaCl₅ as catalysts and n‐Bu₄Sn as a cocatalyst. The synthesized polymers were thermally stable and readily soluble in common organic solvents. The degradation temperatures for a 5% weight loss of the polymers were ∼352–503 °C under nitrogen. PFA1–PFA5 show emission peaks from 402 to 590 nm. Besides, their electroluminescent properties were studied in heterostructure light‐emitting diodes (LEDs), using PFA2–PFA5 as an emitting layer. The PFA5 device revealed an orange‐red emission peak at 602 nm with a maximum luminescence of 923 cd/m² at 8 V. A device with the ITO/PEDOT/ a mixture of PFA2 (98 wt %) and PFA5 (2 wt %)/Ca/Al showed near white emission. Its maximum luminance and current efficiency are 450 cd/m² at 15 V and 1.3 cd/A, respectively. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 519–531, 2006     

Highly substituted poly(2,3‐diphenyl‐1,4‐phenylenevinylene) derivatives having bulky phenyl and fluorenyl pendant groups: Synthesis,characterization, and electro‐optical properties

Two series of poly(2,3‐diphenyl‐1,4‐phenylenevinylene) (DP‐PPV) derivatives containing multiple bulky substituents were synthesized. In the first series, two different groups were incorporated on C‐5,6 positions of the phenylene moiety to increase steric hindrance and to obtain blue‐shifted emissions. In the second series, bulky fluorenyl groups with two hexyl chains on the C‐9 position were introduced on two phenyl pendants to increase the solubility as well as steric hindrance to prevent close packing of the main chain. Polymers with high molecular weights and fine‐tuned electro‐optical properties were obtained by controlling the feed ratio of different monomers during polymerization. The maximum photoluminescent emissions of the thin films are located between 384 and 541 nm. Cyclic voltammetric analysis reveals that the band gaps of these light‐emitting materials are in the range from 2.4 to 3.3 eV. A double‐layer EL device with the configuration of ITO/PEDOT/P4/Ca/Al emitted pure green light with CIE′1931 at (0.24, 0.5). Using copolymer P6 as the emissive layer, the maximum luminescence and current efficiency were both improved when compared with the homopolymer P4. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6738–6749, 2006     

Characterization of N-terminal processing of group VIA phospholipase A<Subscript>2</Subscript> and of potential cleavage sites of amyloid precursor protein constructs by automated identification of signature peptides in LC/MS/MS analyses of proteolytic digests

Dysregulation of proteolytic processing of the amyloid precursor protein (APP) contributes to the pathogenesis of Alzheimer's Disease, and the Group VIA phospholipase A(2) (iPLA(2)beta) is the dominant PLA(2) enzyme in the central nervous system and is subject to regulatory proteolytic processing. We have identified novel N-terminal variants of iPLA(2)beta and previously unrecognized proteolysis sites in APP constructs with a C-terminal 6-myc tag by automated identification of signature peptides in LC/MS/MS analyses of proteolytic digests. We have developed a Signature-Discovery (SD) program to characterize protein isoforms by identifying signature peptides that arise from proteolytic processing in vivo. This program analyzes MS/MS data from LC analyses of proteolytic digests of protein mixtures that can include incompletely resolved components in biological samples. This reduces requirements for purification and thereby minimizes artifactual modifications during sample processing. A new algorithm to generate the theoretical signature peptide set and to calculate similarity scores between predicted and observed mass spectra has been tested and optimized with model proteins. The program has been applied to the identification of variants of proteins of biological interest, including APP cleavage products and iPLA(2)beta, and such applications demonstrate the utility of this approach.     

Fragmentation processes of methylbutyl trifluoroacetates studied by tandem quadrupole mass spectrometry and isotope labeling

The fragmentation patterns of 3-methyl-2-butyl trifluoroacetate and 2-methyl-2-butyl trifluoroacetate were investigated by GC/MS/MS, with electron impact and collision-induced dissociation, on regular and isotope-labeled (deuterium and ¹⁸O) esters. The atoms found in various fragments could be traced back to specific positions in the parent molecules. In this way, molecular rearrangements potentially occurring during the formation of esters by trifluoroacetolysis of 3-methyl-2-butyl p-toluenesulfonate or trifluoroacetic acid addition to various 2-methylbutenes could be shown. Rearrangements also occurred during the fragmentation, particularly during the expulsion of the small fragments CO, C₂H₄ and F₂CO. For the decompositions of oxygen-containing ions these rearrangements were highly specific. By contrast, alkyl cations lead to fragments that are fully scrambled (statistical label distribution). Alkene radical cations ([C_nH_2n]^{+ ˙}) fragment to daughter ions that are extensively, but less than statistically scrambled. Hydrogen scrambling may also occur in fluoroalkyl cation fragments.