Extraordinary transport behavior of gases in isothermally annealed poly(4‐methyl‐1‐pentene) membranes

Poly(4‐methyl‐1‐pentene) (PMP) membranes were modified through isothermal annealing to investigate the change of their crystalline structure and rigid and mobile amorphous fractions (RAF and MAF), assuming a three‐phase model, affected the gas transport behavior. The crystalline structure was characterized by wide‐angle X‐ray diffraction (WAXD) and small‐angle X‐ray scattering (SAXS) techniques, and the free volume properties were analyzed by positron annihilation lifetime spectroscopy. Compared with the pristine membrane, the annealed membranes show higher crystallinity; the crystals undergo partial structural change from form III to form I. The lamellar crystal thickness, rigid amorphous fraction thickness, and long period in the lamellar stacks increase with crystallinity. The annealed PMP membranes exhibit higher permeability due to the increase in larger size free volumes in MAF and higher selectivity due to the increase in smaller size free volumes in RAF, respectively. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2368–2376     

Layered confinement of protein in synthetic fluorinated mica via stepwise polyamine exchange

We have developed a process to incorporate the model protein, bovine serum albumin (BSA), into the layered spacing of swelled mica. By a stepwise intercalation, the sodium form of synthetic fluorinated mica (Mica) was first exchanged with the poly(oxyalkylene)-diamine salts (POA-amine) through an ionic exchange reaction and then the BSA embedment. The first step of the Mica space expansion from the pristine 12 A to 18-93 A was affected by hydrophobic POP-amines (POP2000 of 2000 g/mol and POP4000 of 4000 g/mol M(w)) and the hydrophilic POE2000 that intercalated Na+-Mica to afford different basal spacing (39, 93, and 18 A, respectively). The POA modification was necessary for the BSA intercalation and resulted in an uncompressed form of protein conformation in the layered confinement (XRD d spacing = 60-71 A). For comparison, direct intercalation rendered only low d spacing (30 A), in which BSA was embedded in a compressed conformation. The BSA-mica complexes were characterized by X-ray, TGA, and solution analyses. The stepwise process provides a new method for embedding large protein molecules into the clay layered structure generating protein/layered silicate complexes.     

A scanning tunneling microscopy study of distyrylbenzene on Ag/Ge(111)-(sqr rt of 3 x sqr rt of 3)R30 degrees

The adsorption and self-organized monolayers of trans,trans-distyrylbenzene (tt-DSB) and cis,cis-distyrylbenzene (cc-DSB) on Ag/Ge(111)-(sqr rt of 3 x sqr rt of 3)R30 degrees (Ag/Ge(111)-sqr rt of 3) were studied by low-temperature scanning tunneling microscopy (STM) in ultrahigh vacuum. tt-DSB and cc-DSB overlayers were prepared by vapor deposition at a substrate temperature of 200 K and imaged after the samples were cooled to 100 K. High-resolution images allow identification of the internal structure of individual tt-DSB molecules with three phenyl rings and their molecular arrangements on the Ag/Ge(111)-sqr rt of 3 surface. It is found that the intermolecular distance between two terminal phenyl rings in tt-DSB is about twice the lattice constant of Ag/Ge(111)-sqr rt of 3. Such a lattice match makes Ag/Ge(111)-sqr rt of 3 an ideal substrate for tt-DSB self-organization and the formation of a (3 x 1) overlayer unit cell. The structural model and the molecule registry corresponding to STM images for the adlayers of tt-DSB on Ag/Ge(111)-sqr rt of 3 are proposed and discussed. For cc-DSB adsorption on Ag/Ge(111)-sqr rt of 3, uniform molecular overlayers with two discernible molecular images corresponding to two major types of cc-DSB conformers were observed. The coexistence of multiple conformers and the mismatch of molecular dimension of cc-DSB with the substrate unit cell length limit the growth of large cc-DSB domains.     

Determinations of geniposide using LC/MS/MS methods via forming ammonium and acetate adducts

In this paper, we report method development work to determine geniposide using LC/MS/MS via the formation of positive and negative ion adducts. Geniposide, which has been recognized to have choleretic effects, is the major iridoid glycoside component of Gardenia herbs. To enhance the sensitivity of LC/MS detection of geniposide, a small amount of volatile additives such as ammonium acetate and acetic acid are added into mobile phase solvents to form positive and negative adducts, which can then ionize via electrospray processes. The formation of positive adducts is due to the complexation between geniposide and ammonium ions ([M + NH₄]⁺). The formation of anionic adducts [M + CH₃COO]⁻ is believed to occur via hydrogen bonds bridging acetate ions and glucose groups on the geniposide molecule. Mobile phase solvents containing acetonitrile and aqueous solution (0.2 mM ammonium acetate or 0.1% acetic acid) at the ratio 15: 85 are employed to elute geniposide using C8 reverse phase liquid chromatography columns with electrospray tandem mass spectrometry determinations. Using geniposide standards, the methods are validated at the concentration ranges of 5 to 1000 ng/mL and 20 to 5000 ng/mL using ammonium and acetate adducts respectively. The correlation coefficients of the standard curves are 0.9999 using both ammonium and acetate adducts. The detection limits of using ammonium and acetate adducts are 1 and 5 ng/mL respectively. The measurement accuracy and precision of using ammonium adducts are within 12% and 3% respectively, whereas the accuracy and precision are within 6 and 11% respectively using acetate adducts. When the validated calibration curves of the ammonium adduct of geniposide are used to determine spiked control samples in rat blood dialysates, the determination errors of accuracy and precision are within 12% and 10% respectively.     

High-performance liquid chromatographic determination of 18 alpha-glycyrrhetinic acid and 18 beta-glycyrrhetinic acid in rat plasma: application to pharmacokinetic study.

A high-performance liquid chromatographic method for the separation and determination of 18 alpha-glycyrrhetinic acid and 18 beta-glycyrrhetinic acid has been developed. Indomethacin was used as an internal standard. The drugs were separated on a reversed-phase column and detected by UV detection at a wavelength of 254 nm. Methanol-water-perchloric acid-ammonia (80:20:0.4:0.4, v/v) was used as the mobile phase at pH of 7.0-7.5. The detection limit of both compounds was 0.1 microgram/ml in rat plasma. The method was applied to pharmacokinetic studies of glycyrrhetinic acids in rats. The results suggest that the pharmacokinetics appeared to be non-linear in nature.     

A graph-theoretic approach to modeling metabolic pathways

Summary The metabolic pathways of medazepam, oxazepam, and diazepam were modeled using graph-theoretic transforms which are incorporable into computer-assisted metabolic analysis programs. The information, represented in the form of a graph-theoretic transform kit, which was obtained from these pathways was then used to predict the metabolites of other benzodiazepine compounds. The transform kits gave statistically significant predictions with respect to a statistical method for evaluating the performance of the transform kits.     

Conformation of receptor-associated PGI2: An investigation by molecular modeling

Summary To elucidate the conformation of receptor-associated prostacyclin (PGI₂), we first performed structure-activity correlation analysis of over 200 PGI₂ analogues and derived from this analysis several crucial features pertaining to structural requirements for PGI₂ activity [Ah-lim Tsai and Kenneth K. Wu, Eicosanoids, 2 (1989) 131–143]. These structural features proved to be useful guidelines for selecting model molecules for further investigations by molecular mechanics. By properly selecting four analogues with either rigid or uniquely oriented -side chain structure for geometric fitting, we succeeded in maximally minimizing the degree of freedom of the carboxylate terminus of PGI₂. We were able to define the spatial relationship among the four critical functional groups, i.e., C1-COOH, C6a-O, C11-OH and C15-OH. More information is needed, however, to define the geometry of the -side chain, particularly for the moiety beyond C15. Nevertheless, results from structure-activity correlation analysis and molecular modeling provide useful information regarding the conformation of receptor-associated PGI₂, which assumes an elongated conformation instead of the traditional hairpin structure.     

Characterization of glucoamylase immobilized on celite

Immobilization of glucoamylase (EC 3.2.1.3) on Celite R649 bio-catalyst carrier for hydrolysis of maltose and maltodextrin has been investigated in both packed bed and recirculated batch reactors. The kinetics parameters on the hydrolysis of maltose were estimated from the packed bed reactor. It is found that this immobilized enzyme is as efficient as the soluble enzyme in catalyzing hydrolysis of maltose. However, it is less efficient than the soluble enzyme in hydrolyzing 30% (w/v) maltodextrin, giving a maximum dextrose equivalent (DE) value of 96.0% instead of 98.2%.     

Surfactant effect on enhancing (S)-naproxen prodrug production from racemic naproxen by lipase

In the enantioselective esterification of racemic naproxen with 4(2-hydroxyethyl) morpholine by Lipase MY in organic solvents, a productivity improvement of the desired (S)-naproxen ester from 0.42 to 0.72 mM at the reaction time of 130 h was observed, when the surfactantbis (2-ethylhexyl) sodium sulfosuccinate (AOT) was added in the reaction mixture. The presence of a small amount of exogenously added water dramatically activated the enzyme in AOT/cyclohexane-reversed micelles. Desorption of the surfactant molecule from the enzyme mass and solubilization of the enzyme into reversed micelles were used to elucidate an existing maximum of the initial rate of (S)-naproxen synthesis with the water content. Moreover, the effects of alcohol and surfactant concentration on the enzyme activity are reported.