Stereocomplexation and mechanical properties of polylactide-<Emphasis Type="Italic">b</Emphasis>-poly(propylene glycol)-<Emphasis Type="Italic">b</Emphasis>-polylactide blend films: Effects of polylactide block length and blend ratio

In the present work, poly(propylene glycol) (PPG) was block copolymerized to form polylactide-poly(propylene glycol)-polylactide (PL-PPG-PL) triblock copolymers for preparing flexible stereocomplex PL (scPL) blend films. The scPL blend films were prepared by solution blending of poly(L-lactide)-PPG-poly(L-lactide) (PLL-PPG-PLL) and poly(D-lactide)- PPG-poly(D-lactide) (PDL-PPG-PDL) triblock copolymers before film casting. The influences of PL end-block lengths (2 × 10⁴ and 4 × 10⁴ g/mol) and blend ratios (75/25, 50/50 and 25/75 W/W) on the stereocomplexation and mechanical properties of the blend films were evaluated. From DSC and WAXD results, the 50/50 blend films had complete stereocomplexation. Phase separation between the scPL and PPG phases was not observed from their SEM images. The tensile stress and elongation at break increased with the sterecomplex crystallinities and PL end-block lengths. The PPG middle-blocks enhanced elongation at break of the scPL films. The results showed that the PL-PPG-PL triblock structures did not affect stereocomplexation of the PLL/PDL block blending. In conclusion, the phase compatibility and flexibility of the scPL films were improved by PPG block copolymerization.     

Protein Fractionation of Cowpea (Vigna unguiculata (L.) Walp) Leaf, Flower and Seed by Capillary Electrophoresis and Its Potential for Variety Identification

The proteins of different faction of cowpea [Vigna unguiculata (L.) Walp] were fractionated by capillary electrophoresis (CE). The extracting solvent system was one of the most critical factors in the optimization exercise. To improve reproducibility, seed samples needed to be defatted with chloroform/methanol (V:V=2:1) as preferred prior to protein extraction. Proteins were extracted from seeds, leaves and flowers with 50% aqueous 1‐propanol and separated on a 50 (m×20 cm fused silica capillary column using a UV detector at 200 nm. Separation was conducted at constant voltage (10 kV, 40°C), using iminodiacetic acid (pH 2.5) containing 0.05% hydroxypropylmethylcellulose (HPMC) and 20% acetonitile. The results showed that proteins extracted from all fraction of cowpea were successfully separated by CE in less than 20 min. Seed extracts provided the greatest number of eluted protein peaks, followed by flower and leaf, respectively. The seed‐protein extracts provided unique CE patterns for different varieties; hence the seed was the tissue chosen as being most suitable for variety identification. As a result, an optimized procedure was developed to provide rapid identification of cowpea varieties, based on capillary electrophoregram patterns.     

Stereocomplexation and Mechanical Properties of Polylactide-b-poly(propylene glycol)-b-polylactide Blend Films: Effects of Polylactide Block Length and Blend Ratio

In the present work, poly(propylene glycol)(PPG) was block copolymerized to form polylactide-poly(propylene glycol)-polylactide(PL-PPG-PL) triblock copolymers for preparing flexible stereocomplex PL(sc PL) blend films. The sc PL blend films were prepared by solution blending of poly(L-lactide)-PPG-poly(L-lactide)(PLL-PPG-PLL) and poly(D-lactide)-PPG-poly(D-lactide)(PDL-PPG-PDL) triblock copolymers before film casting. The influences of PL end-block lengths(2×10~4 and 4×10~4 g/mol) and blend ratios(75/25, 50/50 and 25/75 W/W) on the stereocomplexation and mechanical properties of the blend films were evaluated. From DSC and WAXD results, the 50/50 blend films had complete stereocomplexation. Phase separation between the sc PL and PPG phases was not observed from their SEM images. The tensile stress and elongation at break increased with the sterecomplex crystallinities and PL end-block lengths. The PPG middle-blocks enhanced elongation at break of the sc PL films. The results showed that the PL-PPG-PL triblock structures did not affect stereocomplexation of the PLL/PDL block blending. In conclusion, the phase compatibility and flexibility of the sc PL films were improved by PPG block copolymerization.     

Sensitive and simplified analysis of natural and synthetic steroids in water and solids using on-line solid-phase extraction and microwave-assisted solvent extraction coupled to liquid chromatography tandem mass spectrometry atmospheric pressure photoionization

Analytical methods for the determination of several natural and synthetic steroids in water and solid samples were developed using liquid chromatography tandem mass spectrometry. Atmospheric pressure photoionization (APPI) in positive mode was used as the source which appeared to reduce background and interferences as compared to electrospray ionization. Toluene was identified as the most appropriate dopant and its concentration optimized to enhance ionization efficiency. Method detection limits were in the low-nanogram-per-liter range for water samples using on-line solid-phase extraction and near 0.2 ng/g using microwave-assisted solvent extraction for solid samples. This on-line method, using APPI as a source and toluene as a dopant, is beneficial as it saves time due to on-line extraction and reduces interference and matrix effects using gas-phase photoionization. Groundwater, wastewater, runoff, and soil samples were collected and analyzed using the method indicating that traces of several androgens, estrogens, and other steroid-like compounds do occur in samples impacted by animal waste.

Crystal Structure of Curcumenol: Evidence of Asymmetric O–H...O (bridged) Hydrogen-Bonded Closed Dimer

Curcumenol, C₁₅H₂₂O₂, was isolated from Globba malaccensis Ridl. The compound was crystallized from ethylacetate/hexane solution in the monoclinic system, space group C2, with cell dimensions a = 16.8467(4) , b = 7.6799(2) , c = 11.8613(10) , = 115.9970(10)°. The molecules form a distorted centrosymmetric dimer linked by hydrogen bonds between the hydroxyl O2 atom and the bridged O1 ether atom (O2...O1(–x+2, y, –z+1), 2.8297(15) ; (O2–H2O–O1), 169(2)°). This is an interesting example of an O–H...O (bridged ether) asymmetric hydrogen-bonded dimer.     

Organo-Montmorillonite as a Controlled Release Reservoir for Triclosan in Silicone Elastomer: A Flow Micro-Calorimetry and Leaching Study

Summary: Organically modified montmorillonite (o-MMT) in a room temperature addition cured silicone elastomer (PDMS) has been found to control the release of 2,4,2′-trichloro-2′-hydroxy diphenylether (triclosan (TCS)) from the composite. The effect of o-MMT gallery polarity on controlled release was investigated via different intercalants and the interaction of triclosan with the o-MMT was investigated using flow micro-calorimetry (FMC). The latter was found not to be a universal predictor of controlled release activity of the composite as combined TCS and PDMS interactions with MMT/o-MMT leading to intercalation (observed using WAXS) and controlled release activity must also be considered. Southern Clay Products Cloisite® 15A (C15A) gave the most sustained release of TCS whilst also featuring a uniform gallery spacing in the composite. A pore structure based on self-assembled C15A intercalant alkyl tails is tentatively proposed.     

Electron capture detector response and dissociative electron attachment cross sections in chloroalkanes and chloroalkenes

Electron capture detectors (ECDs) are widely used in gas chromatography to detect electronegative compounds. In this work, we examine the connections between the ECD response and the cross sections for dissociative electron attachment (DEA) determined from low energy electron beam studies in the chloroalkane family, stressing in particular the role of temporary anion state energies. We show that attachment rate coefficients computed from these cross sections are well correlated with ECD response, and that the latter decreases exponentially with increasing energies of the lowest anion states. ECD measurements are also carried out in monochloroalkanes substituted with unsaturated ethenyl and phenyl moieties, and the response is shown to depend strongly on the mixing between the unsaturated pi* and the C-Cl sigma* temporary anions as exhibited by the vertical attachment energies (VAEs) of these states. The results show good correlations between the chloroalkene and phenyl chloride ECD responses and the VAEs for the mixed states.