UPLC-ELSD Determination of 1-Octacosanol in Raw Material and Health Products

Determination of the levels of 1-octacosanol is important in food stuff for the study of its pharmacological activities and health benefits. In this study, a novel, simple and fast internal standard method for the non-derivatization ultra-performance liquid chromatographic determination of 1-octacosanol in raw materials and health products was developed and validated based on evaporative light scattering detection. The linearity (r ² > 0.998), recovery (99.1–100.2%, RSD <2.7%), intra- and inter-day precision (RSD <3.8%), limit of detection (1.0 mg/L), limit of quantification (2.2 mg/L) of the 1-octacosanol were determined. The method was successfully applied to nine real 1-octacosanol products. The results of analyses had close agreement with the labeled claims of 1-octacosanol content in these products. Compared with the classical gas chromatography method, the developed method was simpler, faster and more environmentally friendly due to avoiding any derivatization step. This protocol represents a rapid and feasible method for quality control of 1-octacosanol products.

     

LC Coupled with TOFMS for Metabonomics Study of Mini-pigs with Atherosclerosis

In this study, serum metabolic profiles of mini-pigs with atherosclerosis (AS) were analyzed by LC–TOFMS. Partial least-squares to latent structure-discriminant analysis and orthogonal projection to latent structure-discriminant analysis were used for group differentiation and selection of potential biomarkers. The mini-pig disease models were constructed by feeding a high-fat diet and inducing coronary injury, in accordance with the mechanism of AS pathogenesis. To characterize the development of AS, serum samples were collected and analyzed at two time points (two and ten weeks). Separate distinct clustering of results from normal and model mini-pigs could be observed for both the two and ten-week samples. With the development of AS, the metabolism of the model mini-pigs was more substantially disturbed. Major metabolites contributing to the discrimination were fatty acids, lysophosphatidylcholines, and bile acids. These potential biomarkers are related with inflammation, oxidative stress, and abnormal lipid and energy metabolism.

     

The Structure of Hydrated Poly (D, L - Lactic Acid) Studied With X-Ray Diffraction and Molecular Simulation Methods

The effect of hydration on the molecular structure of amorphous poly (D, L-lactic acid) (PDLLA) with 50:50 L-to-D ratio has been studied by combining experiments with molecular simulations. X-ray diffraction measurements revealed significant changes upon hydration in the structure functions of the copolymer. Large changes in the structure functions at ~ 10 days of incubation coincided with the large increase in the water uptake from ~1 to ~40% and the formation of voids in the film. Computer modeling based on the recently developed TIGER2/TIGER3 mixed sampling scheme was used to interpret these changes by efficiently equilibrating both dry and hydrated models of PDLLA. Realistic models of bulk amorphous PDLLA structure were generated as demonstrated by close agreement between the calculated and the experimental structure functions. These molecular simulations were used to identify the interactions between water and the polymer at the atomic level including the change of positional order between atoms in the polymer due to hydration. Changes in the partial O-O structure functions, about 95% of which were due to water-polymer interactions, were apparent in the radial distribution functions. These changes, and somewhat smaller changes in the C-C and C-O partial structure functions, clearly demonstrated the ability of the model to capture the hydrogen bonding interactions between water and the polymer, with the probability of water forming hydrogen bonds with the carbonyl oxygen of the ester group being about four times higher than with its ether oxygen.     

Broadband excitation pulses for high‐field solid‐state nuclear magnetic resonance spectroscopy

In nuclear magnetic resonance spectroscopy, experimental limits due to the radiofrequency transmitter and/or coil means that conventional radiofrequency pulses (“hard pulses”) are sometimes not sufficiently powerful to excite magnetization uniformly over a desired range of frequencies. Effects due to nonuniform excitation are most frequently encountered at high magnetic fields for nuclei with a large range of chemical shifts. Using optimal control theory, we have designed broadband excitation pulses that are suitable for solid‐state samples under magic‐angle‐spinning conditions. These pulses are easy to implement, robust to spinning frequency variations, and radiofrequency inhomogeneities, and only four times as long as a corresponding hard pulse. The utility of these pulses for uniformly exciting ¹³C nuclei is demonstrated on a 900 MHz (21.1 T) spectrometer. Copyright © 2012 John Wiley & Sons, Ltd.     

Transformation of macromonomers into ring‐opening polymerization macroinitiators: A detailed initiation efficiency study

In the present study, n‐butyl acrylate macromonomer (BAMM) (M_n = 1900 g mol^?1; PDI = 1.96) has been synthesized via a high‐temperature polymerization process. Subsequently, the olefinic termini of the BAMM have been transformed into a diol via a dihydroxylation process using KMnO₄ as an oxidizing agent. The OH‐terminated macroinitiator pBA(OH)₂ has subsequently been employed for the ring‐opening polymerization (ROP) of ε‐caprolactone via various catalytic systems, that is, organo‐(1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene), metal (tin(II) 2‐ethylhexanoate), and enzymatic catalysis (Novozym® 435). The obtained pBA‐b‐pCL block copolymers and the initiation efficiency of the BAMM macroinitiator have been investigated via size exclusion chromatography (SEC), electrospray ionization–mass spectrometry (ESI‐MS) hyphenated with SEC and liquid chromatography at the critical conditions of both poly(ε‐caprolactone) (pCL) and pBA. The in vitro enzyme catalysis (eROP) approach proved to be the most efficient catalysis system due to minor transesterification side reactions during the polymerization process. However, side reactions such as transesterifications occur in each catalytic system and—while they cannot be suppressed—they can be minimized. The species generated during the eROP process include the desired block copolymer pBA‐b‐pCL as main species as well as pCL homopolymer and residual macroinitiator pBA(OH)₂. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Polymer electrolyte membranes based on polystyrenes with phosphonic acid via long alkyl side chains

A series of polystyrenes with phosphonic acid ( 5 ) via long alkyl side chains (4, 6, and 8 methylene units) were prepared by the radical polymerization of the corresponding diethyl ω‐(4‐vinylphenoxy)alkylphosphonates, followed by the hydrolysis with trimethylsilyl bromide. The resulting phosphonated polystyrene membranes had a high oxidative stability against Fenton's reagent at room temperature. The membranes prepared from 5 exhibited a very low water uptake, similar to that of Nafion 117 over the wide range of 30 to 80% relative humidity (RH). The proton conductivities of these membranes are lower than that of Nafion 117 in the range of 30 to 90% RH, but comparable or higher than those of the reported phosphonated polymers with higher IEC values, such as the phosphonated poly(N‐phenylacrylamide) (PDPAA, IEC: 6.72 mequiv/g) and fluorinated polymers with pendant phosphonic acids (M47, IEC: 8.5 mequiv/g), at low RH conditions despite the much lower IEC values (3.0–3.8 mequiv/g) of these membranes. These results suggest that the flexible pendant side chains of 5 would contribute to the formation of hydrogen‐bonding networks by considering the very low water uptake of these polymers. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Biodegradable aromatic copolyesters made from bicyclic acetalized galactaric acid

Random poly(hexamethylene terephthalate‐co‐galactarate)s and poly(dodecamethylene terephthalate‐co‐galactarate)s copolyesters covering the whole range of compositions were obtained with weight‐average molecular weights of ～30,000–50,000 g mol^?1 by melt polycondensation. They were thermally stable above 300 °C, and displayed T_g in the +20 to ?20 °C range with values steadily decreasing with the content in galactarate units. All the copolyesters were semicrystalline with T_m between 50 and 150 °C and those made from dodecanediol were able to crystallize from the melt at a crystallization rate depending on composition. Copolyesters containing up to 50% of galactaric units retained the crystal structure of their respective polyterephthalate homopolyesters, whereas they adopted the structure of the respective polygalactarates when the content in Galx units reached 70%. Stress‐strain essays revealed decay in the mechanical parameters as the aromatic units were replaced by Galx. Incubation in aqueous buffer revealed that hydrolysis of the polyesters were largely enhanced by copolymerization and evidenced the capacity of the Galx unit for making aromatic polyesters susceptible to biodegradation. A detailed NMR analysis complemented by SEM observations indicated that hydrolysis took place by preferred splitting of galactarate ester bonds with releasing of alkanediol and Galx‐diacid. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012