Molecular imprinting polymers for the separation of toluic acid isomers

Molecular imprinting polymers (MIPs) were prepared with styrene, 4‐vinyl pyridine, and divinylbenzene for the separation of toluic acid isomers. The uptake and selectivity were investigated, with respect to how they were governed by the swelling degree of a soft MIP that contained a small amount of crosslinker. The optimum swelling range led to high uptake and the easy removal of the template without sacrificing the selectivity, which was controlled by the shape and size of the imprinting cavity under the same functional monomer, to the guest molecule. The original imprinting cavities were reversibly maintained within the range of 200% swelling and shrinking of MIPs throughout the template extraction. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 650–654, 2005     

Infrared studies on the isomers of kamlolenic acid

Summary Thecis-trans and positional configuration of α-and β-kamlolenic acids have been investigated. Infrared data of the two isomers, their acetyl derivatives and maleic anhydride adducts, and the permanganate oxidation products of the addition compounds, together with the selective epoxidation of the exocyclic double bond of the maleinated derivatives, have been used to confirm the structure of the three conjugated double bonds in α-kamlolenic acid ascis-9-trans 11-trans 13. and β-kamlolenic acid astrans 9-trans 11-trans 13.     

Electropolymerization kinetics of a binary mixture of pyrrole and o‐aminobenzoic acid and characterization of the obtained polymer films

Poly (pyrrol‐co‐o‐aminobenzoic acid) has been synthesized electrochemically from an aqueous acid medium. The initial rate of electrocopolymerization reaction on platinum electrode is small and the rate law is: Rate = K₂ [D]^1.02[HCl] ^1.44[M]^2.00. The apparent activation energy (E_a) is found to be 90.11 kJ mol^?1. The polymer films obtained have been characterized by cyclic voltammetry, X‐ray diffraction, elemental analysis, thermogravimetric analysis, scanning electron microscopy, ¹H NMR, and IR‐spectroscopy. The mechanism of the electrochemical polymerization reaction has been discussed. The monomer reactivity ratios (r₁ and r₂) were calculated. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Separation of hydroxybenzoic acid isomers using the molecular imprinting technique

Molecular imprinting polymers (MIPs) for salicylic acid (SA), 3‐hydroxybenzoic acid (3HBA), and 4‐hydroxybenzoic acid (4HBA) were synthesized using styrene and 4‐vinylpyridine (4‐VPy) as functional monomer and divinylbenzene (DVB) as crosslinker. The adsorption characteristics of hydroxybenzoic acid (HBA) isomers on each MIP were investigated. The materials used for the polymerization of each 3HBA and 4HBA‐MIPs were adsorbed relatively well. This verifies that the MIPs that can adsorb template selectively were synthesized. However, SA‐MIP had no molecular imprinting effect. SA has intramolecular hydrogen bond and it is difficult to adsorb on recognition site of SA‐MIP, because its structure differs from that of recognition site of SA‐MIP. It indicates that SA‐MIP had no recognition effect. 1,2,3,4‐Tetrahydro‐1‐naphthol (THN)‐MIP was synthesized, which is similar to SA with intramolecular hydrogen bond. SA was separated selectively using THN‐MIP. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Electropolymerization of pyrrole and characterization of the obtained polymer films

Electrochemical oxidative polymerization of pyrrole on platinum electrode in acid medium was carried out. Different reaction parameters were investigated such as current density, acid concentration, monomer concentration, and temperature with duration of time. The orders of the electropolymerization reaction were found to be 1.3, 1.26, and 1.2 with respect to current density, acid concentration, and monomer concentration, respectively. The apparent activation energy was found to be 38.3 kJ mol^?1. The obtained polymer films were characterized by ¹H‐NMR, elemental analysis, thermogravimetric analysis, and cyclic voltammetry. The mechanism of the electrochemical polymerization reaction was also discussed. The surface morphology of the obtained polymer film was characterized by X‐ray diffraction and scanning electron microscopy. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1783–1792, 2003     

Enzymatic enrichment of conjugated linoleic acid isomers and incorporation into triglycerides

A method was developed for the enrichment of either the cis9,trans11 or the trans10,cis12 isomer of conjugated linoleic acid (CLA) from a synthetic CLA mixture consisting predominantly of these isomers in equal amounts. Lipases were screened for their ability to selectively esterify one isomer at a significantly greater rate than the other isomer. An immobilized lipase from Rhizomucor miehei was nonselective, but a lipase from Geotrichum candidum esterified the cis9,trans11 isomer more rapidly than the trans10,cis12 isomer. This selectivity was exploited at the kilogram scale to prepare an ester fraction with a content of 91% cis9,trans11 CLA and an unreacted free fatty acid fraction consisting of 82% trans10,cis12 CLA, based on total CLA content. The components of the reaction mixture were separated by molecular distillation. Each enriched fraction was then incorporated into palm oil triglycerides by interesterification with the non-selective lipase from R. miehei. Two triglyceride fats resulted, which were enriched in either cis9,trans11 CLA (26.5% cis9,trans11 and 1.7% trans10,cis12) or trans10,cis12 CLA (3.5% cis9,trans11 and 22.9% trans10,cis12).     

Positional and geometrical isomers of linoleic acid in partially hydrogenated oils

The geometrical and positional isomers of linoleic acid of a partially hydrogenated canola oil-based spread were isolated and identified. Through partial hydrazine reduction and mass spectral studies,cis-9,trans-13 octadecadienoic acid was identified as the major isomer. Other quantitatively important isomers characterized werecis-9,trans-12;trans-9,cis-12 andcis-9,cis-15. These four were also the major isomers in margarine based on common vegetable oils. A number of minor isomers were detected and some structures identified weretrans-9,trans-12;trans-8,cis-12;trans-8,cis-13;cis-8,cis-13;trans-9,cis-15;trans-10,cis-15 andcis-9,cis-13. The proportions of the various isomers are given for some margarines in the Canadian retail market. The amounts oftrans-9,trans-12 isomer in Canadian margarines were generally below 0.5% of the total fatty acids.     

去甲肾上腺素聚合物的电化学沉积及性质研究

采用循环伏安法研究了金电极上去甲肾上腺素(NA)电氧化形成聚合膜的过程,结合电化学和红外光谱研究提出该聚合膜可能是聚吲哚膜的类似物,且该聚合膜具有较好的阳离子选择透过性。     

Analysis of conjugated linoleic acid isomers and content in french cheeses

Conjugated linoleic acid (CLA) occurs in food as a result of microbial enzymatic reactions, free radical-type oxidation, and heat treatment. CLA is found in animal products, such as meat and dairy products, especially in cheeses. The CLA composition of 12 different French cheeses was determined by a combination of different analytical methods: reversed-phase high-performance liquid chromatography (RP-HPLC), gas chromatography-mass spectrometry (GC-MS), GC-Fourier transform infrared (GC-FTIR), and silver nitrate thin-layer chromatography (AgNO₃-TLC). New isomers (Δ8,10- and Δ11,13-octadecadienoic acids with all possible cis and trans configurations) that co-eluted with previously identified isomers (Δ9c,11t-; Δ9t,11c-; Δ10c,12t-; Δ10t,12c-; Δ11c,13c-; Δ9c,11c-; Δ10c,12c-; Δ9t,11t-; Δ10t12t-octadecadienoic acids) were detected. Δ9c,11t-Octadecadienoic acid was the major CLA isomer in these cheeses. All isomers were present in each product, whatever the production process. However, CLA content in the cheeses varied from 5.3 to 15.80 mg/g of cheese fat, which depended primarily on the origin of the milk (season, geography) and somewhat on the production process.     

Trans- and cis-octadecenoic acid isomers in the hump and milk lipids from Camelus dromedarius

The distribution profiles of individual trans- as well as cis-18∶1 isomers from the fat prepared from the hump adipose tissue and the milk from Camelus dromedarius (the single-humped Arabian species) are described. Gas-liquid chromatography on two capillary columns with different polarities and lengths were used for this purpose in combination with argentation thin-layer chromatography. A comparison of the profiles established is made with that of true ruminant fats. In the fats from the dromedarius as well as from true ruminants, the trans-18∶1 isomers have their ethylenic bonds in all positions between Δ4 and Δ16. The prominent trans isomer is the 11–18∶1 (vaccenic) acid in all species, and the complete distribution profiles are quite similar. Concerning the cis isomers, the prominent isomer is oleic acid, followed by cis-vaccenic acid, as in true ruminant fats. Other cis isomers encompass the Δ6–8 and the Δ12 to Δ15 isomers. Camelidae (suborder Tylopoda) and Bovidae (suborder Ruminantia) have evolved independently since the Eocene, that is for approximately 50 million years. Despite this considerable period, and the profound differences in anatomy, morphology, physiology, ecological and dietary habits between the extant species of these suborders, the rumen microflora has continued to synthesize the same trans- and cis-octadecenoic acid isomers, in comparable proportions, at least as deduced from their composition profiles. We conclude that the trans-18∶1 acid profile is not intrinsically species-dependent, but it can be affected by the nature and the proportions of dietary unsaturated fatty acids that themselves depend on the feed, and that may be species-specific.     

Polymorphism in single-acid triglycerides of positional and geometric isomers of octadecenoic acid

The polymorphism of 25 glycerol trioctadecenoates with double bonds ranging from Δ4-Δ17 was investigated by differential scanning calorimetry. Triglycerides withcis bonds in odd positions Δ7-Δ13 exhibited three intermediate melting (β′-) forms, but those withcis bonds in even positions, exceptcis Δ4, lacked β′-forms. Among thetrans compounds, only Δ11, 13, and 14 showed β′-forms. Thecis andtrans Δ5 triglycerides were unusual, because they readily assumed low melting (α-) forms that were not easily converted to high melting (β-) forms. β-Form mp of compounds in each series (cis ortrans) alternated depending upon double bond position; an even position correlated with high mp. Heats of fusion (ΔH_f) for β-forms, likewise, fluctuated with double bond position but nonuniformly;trans Δ6 had the highest ΔH_f (43 cal/g),cis Δ12 the lowest (21 cal/g).     

Fish oil tetracosenoic acid isomers and GLC analyses of polyunsaturated fatty acids

The total tetracosenoic acid (24∶1) levels in nine marine oils examined ranged from 0.4 to 1.1% of the total fatty acids. Gas-liquid chromatography (GLC) analysis of whole fish oil fatty acid methyl esters usually shows a single 24∶1 peak, as the dominant (60–90%) isomer is 24∶1ω9, and the minor peaks are not seen. Isolation and oxidative fission demonstrate that the lesser isomers present in these oils (in the first peak to elute) include 24∶1ω15, 24∶1ω13 and 24∶1ω11, which are not resolvable from each other on open-tubular GLC; 24∶1ω9 is followed by a peak for 24∶1ω7. The complex first 24∶1 isomer peak of fish oil fatty acids tends to coincide with or just follows the 22∶6ω3 peak in GLC analyses carried out on Carbowax-20M type open-tubular (capillary) columns. Presented in part at the Annual Meeting of the American Oil Chemists' Society, Baltimore, MD, April 1990.     

Silver-ion high-performance liquid chromatographic separation and identification of conjugated linoleic acid isomers

This is the first report of the application of silverion impregnated high-performance liquid chromatography (Ag⁺-HPLC) to the separation of complex mixtures of conjugated linolenic acid (CLA) isomers present in commercial CLA sources and foods and in biological specimens. This method showed a clear separation of CLA isomers into three groups related to their trans,trans, cis,trans or trans,cis, and cis,cis configuration of the conjugated double-bound system. In addition, this method separated within each geometrical isomeric group. Following Ag⁺-HPLC isolation, gas chromatography (GC)-electron impact mass spectrometry, and GC-direct deposition-Fourier transformed infrared spectroscopy were used to confirm the identity of two major positional isomers in the cis/trans region, i.e., Δ8,10- and Δ11,13-octadecadienoic acid, which had not been chromatographically resolved previously, Furthermore, the potential of this method was demonstrated by showing different Ag⁺-HPLC profiles exhibiting patterns of isomeric distributions for biological specimens from animals fed a diet containing a commerical CLA preparation, as well as for a commerical cheese product.     

Aqueous dispersions of reduced graphene oxide and multi wall carbon nanotubes for enhanced glucose oxidase bioelectrode performance

Aqueous dispersions of reduced graphene oxide (rGO) and multi walled carbon nanotubes (MWCNT) were fabricated through a modified chemical reduction method. The significant advantage of the method developed here is the omission of any stabilising compound or organic solvent to obtain stable rGO–MWCNT dispersions. Significantly biological entities, in this case the enzyme glucose oxidase (GOx), can be successfully incorporated into the dispersion. These dispersions were characterised using XPS, SEM, zeta potential and particle size measurements which showed that the dispersion stability is not sacrificed with the addition of GOx, and significantly, the electrical properties of the rGO and MWCNTs are maintained. In this study, rGO acts as an effective dispersing agent for MWCNTs and does not affect the solubility or electroactivity of the GOx. Bioelectrodes fabricated from these rGO–MWCNT–GOx dispersions were characterised electrochemically to test their feasibility in facilitating direct electron transfer (DET) from the redox centre of the enzyme to the electrode. The DET results showed that the specific catalytic current generated at an optimised rGO–MWCNT–GOx electrode was 72 μA/μg GOx, which is 144 times more efficient than other literature values for similar systems. The remarkable specific catalytic current can be attributed to the use of purified enzyme, the efficiency of charge transfer within the rGO–MWCNT composite and the ability of the electrode to facilitate direct electron transfer.     

Retention behavior of trans isomers of eicosapentaenoic and docosahexaenoic acid methyl esters on a polyethylene glycol stationary phase

A polyethylene glycol (PEG) stationary phase was evaluated for the separation of mono‐trans isomers of eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) methyl esters. The resolution patterns were compared to patterns achieved with previously applied conditions on a cyanopropyl phase. There were no overlaps between all‐cis EPA/DHA and their mono‐trans isomers on the PEG phase. Because of overlap between 22:0 and 22:1 isomers, the PEG column is not a good choice for analyses of EPA trans isomers in crude fish oils. However, if the saturated and monounsaturated fatty acids are not present in significant amounts, PEG can be a better choice than cyanopropyl columns.     

Modulation of arachidonic acid distribution by conjugated linoleic acid isomers and linoleic acid in MCF-7 and SW480 cancer cells

The relationship between growth and alterations in arachidonic acid (AA) metabolism in human breast (MCF-7) and colon (SW480) cancer cells was studied. Four different fatty acid preparations were evaluated: a mixture of conjugated linoleic acid (CLA) isomers (c9,t11, t10,c12, c11,t13, and minor amounts of other isomers), the pure c9,t11-CLA isomer, the pure t10,c12-CLA isomer, and linoleic acid (LA) (all at a lipid concentration of 16 microg/mL). 14C-AA uptake into the monoglyceride fraction of MCF-7 cells was significantly increased following 24 h incubation with the CLA mixture (P < 0.05) and c9,t11-CLA (P < 0.02). In contrast to the MCF-7 cells, 14C-AA uptake into the triglyceride fraction of the SW480 cells was increased while uptake into the phospholipids was reduced following treatment with the CLA mixture (P < 0.02) and c9,t11-CLA (P < 0.05). Distribution of 14C-AA among phospholipid classes was altered by CLA treatments in both cell lines. The c9,t11-CLA isomer decreased (P < 0.05) uptake of 14C-AA into phosphatidylcholine while increasing (P < 0.05) uptake into phosphatidylethanolamine in both cell lines. Both the CLA mixture and the t10,c12-CLA isomer increased (P < 0.01) uptake of 14C-AA into phosphatidylserine in the SW480 cells but had no effect on this phospholipid in the MCF-7 cells. Release of 14C-AA derivatives was not altered by CLA treatments but was increased (P < 0.05) by LA in the SW480 cell line. The CLA mixture of isomers and c9,t11-CLA isomer inhibited 14C-AA conversion to 14C-prostaglandin E2 (PGE2) by 20-30% (P < 0.05) while increasing 14C-PGF2alpha by 17-44% relative to controls in both cell lines. LA significantly (P < 0.05) increased 14C-PGD2 by 13-19% in both cell lines and increased 14C-PGE2 by 20% in the SW480 cell line only. LA significantly (P < 0.05) increased 5-hydroperoxyeicosatetraenoate by 27% in the MCF-7 cell line. Lipid peroxidation, as determined by increased levels of 8-epi-prostaglandin F2alpha (8-epi-PGF2alpha), was observed following treatment with c9,t11-CLA isomer in both cell lines (P < 0.02) and with t10,c12-CLA isomer in the MCF-7 cell line only (P < 0.05). These data indicate that the growth-promoting effects of LA in the SW480 cell line may be associated with enhanced conversion of AA to PGE2 but that the growth-suppressing effects of CLA isomers in both cell lines may be due to changes in AA distribution among cellular lipids and an altered prostaglandin profile.     

Quantum‐chemical treatment of the linoleic acid molecule and two of its conjugated isomers

The structural, vibrational and electronic properties of the linoleic acid molecule and two of its conjugated isomers were investigated theoretically by performing the molecular mechanics (MM+ force field), the semi‐empirical self‐consistent‐field molecular‐orbital (PM3), and the density functional theory (B3LYP) calculations. The geometries of the considered molecules were optimized; the vibrational dynamics and the electronic properties were calculated in their ground states in the gas phase. It was found that the excess charge accumulated on hydrogen atoms bonded to double‐bonded carbon atoms is relatively small, which may cause these hydrogen atoms to be easily abstracted.     

Improved synthesis and characterization of saturated branched‐chain fatty acid isomers

The development of viable technologies for producing green products from renewable fats and oils is highly desirable since such materials can serve as replacements for non‐renewable and poorly biodegradable petroleum‐based products. Mixtures of saturated branched‐chain fatty acid isomers (sbc‐FAs), commonly referred to as isostearic acid, are important intermediates for the production of biodegradable lubricants, cosmetics, emollients, and hydraulic fluids. Present methods for producing sbc‐FAs, however, often give low yields of sbc‐FAs or sbc‐FA preparations with a high content of dimer acid fatty acid co‐products. This study reports an improved route to synthesizing sbc‐FAs from monounsaturated fatty acids using a modified H‐Ferrierite zeolite catalyst in conjunction with small amounts of triphenylphosphine additive. The yields of sbc‐FAs (up to 80 wt%) and co‐products (up to15 wt%) were determined using a modification of a previously reported GC method. A more detailed analysis of the distribution of sbc‐FA isomers in the products was made by the combined use of GC × GC‐TOF‐MS. Additionally, it was found that the H‐Ferrierite zeolite catalyst was recyclable and reusable up to 10 times without significant loss of activity and selectivity for sbc‐FAs.