Acrylamide formation in food: a mechanistic perspective

Earliest reports on the origin of acrylamide in food have confirmed asparagine as the main amino acid responsible for its formation. Available evidence suggests that sugars and other carbonyl compounds play a specific role in the decarboxylation process of asparagine, a necessary step in the generation of acrylamide. It has been proposed that Schiff base intermediate formed between asparagine and the sugar provides a low energy alternative to the decarboxylation from the intact Amadori product through generation and decomposition of oxazolidin-5-one intermediate, leading to the formation of a relatively stable azomethine ylide. Literature data indicate the propensity of such protonated ylides to undergo irreversible 1,2-prototropic shift and produce, in this case, decarboxylated Schiff bases which can easily rearrange into corresponding Amadori products. Decarboxylated Amadori products can either undergo the well known beta-elimination process initiated by the sugar moiety to produce 3-aminopropanamide and 1-deoxyglucosone or undergo 1,2-elimination initiated by the amino acid moiety to directly generate acrylamide. On the other hand, the Schiff intermediate can either hydrolyze and release 3-aminopropanamide or similarly undergo amino acid initiated 1,2-elimination to directly form acrylamide. Other thermolytic pathways to acrylamide--considered marginal at this stage--via the Strecker aldehyde, acrolein, and acrylic acid, are also addressed. Despite significant progress in the understanding of the mechanistic aspects of acrylamide formation, concrete evidence for the role of the different proposed intermediates in foods is still lacking.     

Effect of pH on the reactivity ratios in the copolymerization of acrylic acid and acrylamide

The content of acrylic acid and acrylamide in their copolymers can be controlled by changing pH. The reactivity ratio of acrylic acid decreases with increasing pH, while the reactivity ratio of acrylamide increases with increasing pH. At low pH values, acrylamide is present in its protonated form which causes its reactivity to be low whereas at high pH values the reactivity of acrylic acid is decreased owing to its dissociation. When the monomer and radical approach each other, the acrylate anion becomes the least reactive species because of its symmetrical charge distribution, like charge repulsion and barium ion screening effect. HMO calculations were performed for models of all monomers and polymer radicals involved in copolymerizations. The experimental results concerning the reactivity of acrylic acid and acrylamide in copolymerization and the observed reactivity ratios were discussed on the basis of HMO calculations and resonance and Coulomb electrostatic effects. The observed reactivity ratios were correlated with the calculated differences in resonance energies computed for the models of transition states involved in copolymerizations.     

聚（丙烯酸—丙烯酰胺）—碱金属盐复合物的合成与表征

作为功能材料的一个新品种,高分子固体电解质有极其广泛的应用前景[1]。近年来人们致力于对体系的改性研究[2-5],以提高电解质的室温离子电导率和获得适合的力学性能。本研究用水溶液聚合工艺,以过硫酸盐为引发剂,以丙烯酸为主单体、丙烯酰胺为第二单体,加入适当的增塑剂...     

Anisotropic hydrogel thickness gradient films derivatized to yield three-dimensional composite materials

We report the preparation of in-plane density gradients of amino-terminated molecules and gold particles through derivatization of laterally varying thickness gradients of poly(acrylic acid) (PAA) or poly(acrylamide) (PAAm) films. PAA and PAAm gradients were formed by Zn(II)-catalyzed electropolymerization of acrylic acid (AA) or acrylamide (AAm) in the presence of an in-plane electrochemical potential gradient applied to Au or indium-tin-oxide (ITO) working electrodes. PAA thickness gradients were converted into density gradients of fluorocarbons or biocompatible groups by derivatizing with NH(2)CH(2)(CF(2))(6)CF(3) or an Arg-Gly-Asp (RGD)-containing peptide, respectively. X-ray photoelectron spectroscopy (XPS) and XPS imaging were used to characterize the modified PAA gradients. Transition regions as narrow as 104 mum were achieved for fluorocarbon gradients. PAAm gradients were treated with gold particles to form a density gradient of gold particles. Surface plasmon resonance imaging and scanning electron microscopy (SEM) as well as UV-visible absorption measurements were used to characterize the gold particle density gradients. It is likely that the gold particles were attached both on the surface and inside the PAAm film.     

Rotational barriers in monomeric CH2=CX-COOH and CH2=CX-CONH2 (X is H or CH3) and vibrational analysis of methacrylic acid and methacrylamide

The internal rotations in acrylic and methacrylic acids CH2=CX-COOH and their amides CH2=CX-CONH2 (X is H or CH3) were investigated by DFT-B3LYP calculations with 6-311+G** basis set. The potential energy curves were consistent with two minima that correspond to planar cis and trans conformation in the case of the acids (or cis and near-trans forms in the case of the amides). Acrylic acid and acrylamide were predicted to have the cis form as the low and predominant conformation of the molecules. In the case of the methacrylic acid and methacrylamide, the conformational relative stability was predicted to reverse as going from the acrylic to the metha compounds. The trans conformer in methacrylic acid or the near-trans in methacrylamide were predicted to be thermodynamically low energy structures of the molecules. The CCCO rotational barrier was calculated to vary from 4 to 6kcal/mol in the four molecules. The OCOH and OCNH torsional barriers were calculated to be about 13 and 22kcal/mol in the acids and the amides, respectively. The vibrational frequencies of methacrylic acid and methacrylamide were computed at the DFT-B3LYP/6-311+G** level and reliable vibrational assignments were made on the basis of normal coordinate analyses and comparison with experimental data of both molecules in their low energy conformations.     

Fluorescence and viscometry study of complexation of poly(acrylic acid) with poly(acrylamide) and hydrolysed poly(acrylamide)

Interpolymer complexation of poly(acrylic acid) with poly(acrylamide) and hydrolysed poly(acrylamide) was studied by fluorescence spectroscopy and viscometry in dilute aqueous solutions. Changes in chain conformation and flexibility due to the interpolymer association are reflected in the intramolecular excimer fluorescence of pyrene groups covalently attached to the polymer chain. Both poly(acrylamide) and hydrolysed poly(acrylamide) form stable complexes with poly(acrylic acid) at low pH. The molecular weight of poly(acrylic acid) and solution properties such as pH and ionic strength were found to influence the stability and the structure of the complexes. In addition, the polymer solutions mixing time showed an effect on the mean stoichiometry of the complex. The intrinsic viscosity of the solutions of mixed polymers at low pH suggested a compact polymer structure for the complex.     

应用FRAP技术评价蛋白在聚丙烯酰胺-丙烯酸凝胶中的扩散行为

药物分子从药物载体中的释放行为与载体的结构有密切关系.本实验中采用丙烯酰胺和丙烯酸等材料,运用水相沉淀的方法,制备了4种不同单体配比的聚丙烯酰胺-丙烯酸(P(Am-co-Ac))共聚物水凝胶.运用红外分析方法对P(Am-co-Ac)组成进行表征.使用荧光漂白恢复法(FRAP,fluorescence recovery after photobleaching)观察荧光素FITC标记的牛血清白蛋白(BSA)在聚丙烯酰胺-丙烯酸中的扩散行为,并以激光共聚焦显微镜进行实时成像.实验表明,FITC-BSA在不同单体配比的共聚物中的扩散系数是不同的.通过调节聚合物中单体的配比能够达到控制蛋白释放速率的作用,从而为调控蛋白和多肽类药物的缓控释放提供了可能性.     

Effect of the composition of polyacrylimide-forming copolymers on their processing

Thermomechanical studies of thermosetting copolymers of acrylonitrile with methacrylic acid and acrylamide with acrylic acid that form similar polyacrylimide foam plastics during curing have been performed. The dependence of the glass-transition temperatures of the copolymers on the degrees of intramolecular imidization has been calculated and confirmed experimentally. Procedures to control the curing rate have been proposed. The influence of plasticizing additives on the glass-transition temperatures, imidization, and foaming of foam-forming compositions has been studied. Plasticized powdered foam-forming compositions with delayed imidization have been developed, and temperature conditions for their processing have been determined.     

Preparation of PAA/AM/MMT Hybrid by Intercalation Polymerization

Over the last few years, Montmorillonite (MMT) was widely used as a special inorganic material for preparing Polymer/MMT nanocompsites. MMT is a clay imineral consisting of stacked silicate sheets whose thickness is about 10A. Through intercalation a large number of polymer-clay nanocomposites have been prepared such as Nylon-clay hybrid [1], PS-clay hybrid [2], Poly (methyl methacrylate) (PMMA)-clay hybrid [3], etc. In this article, the synthesis and properties of Poly (acrylic acid/acrylamide)/MMT hybrid (PAAAM/MMT) were studied. X-ray diffraction and Transmission electron microscopy were used to characterize the hybrid material. DSC has been used to study its property. Results showed that the intercalating reagents have entered the space of MMT's layers and enlarged them. At the same time, the MMT dispersed homogeneously in acrylic acid and acrylamide monomers that allow MMT to disperse in PAAAM matrix in the monolayer form.     

A Nonhydrolyzable-Water Soluble Crosslinker: Tetrallylpiperazinium Dichloride and its Copolymers with Acrylic Acid and Acrylamide

Abstract

A versatile crosslinking agent, tetraallyl piperazinium dichloride (TAP) has been prepared and demonstrated to be useful in copolymerization with water soluble monomers such as acrylic acid and acrylamide. Although the crosslinker itself does not readily homopolymerize in water, it forms transparent rigid hydrogels within a reasonable period of time when copolymerized with acrylic acid. Being nonhydrolysable, the crosslinker presented is superior to other common water soluble crosslinking agents such as methylene or ethylene bis(acrylamides). Since this crosslinker has a low toxicity, it may be used for bioapplications such as gel electrophoresis etc.     

Determination of acrylamide monomer in polyacrylamide degradation studies by high-performance liquid chromatography

A high-performance liquid chromatography method using C18 and ion-exchange columns in series is developed for the determination of acrylamide and acrylic acid monomers in polymeric samples. The C18 column acts as a guard column, trapping surfactants and impurities and retaining the nonionic species. The ion-exchange column then separates the monomers according to their respective ionic strengths. This method has been proven in the laboratory to work successfully for all types of acrylamide/acrylic acid polymers and matrices. Detection limits for both monomers can be achieved in the parts-per-billion range. The method is used to study the possible degradation of polyacrylamide to acrylamide monomer in the presence of glyphosate (a herbicide) and sunlight. Polyacrylamide is used as a spray drift reduction aid in combination with glyphosate. In normal applications, the polymer and herbicide are in contact with each other in the presence of sunlight. The results show that the polymer does not degrade to acrylamide in the presence of glyphosate or sunlight or any combination of the two. It is also observed that glyphosate influences the solubility of polyacrylamide, and care must be used when combining the two.     

Isolation and Characterization of Acrylamidase from <Emphasis Type="Italic">Arthrobacter</Emphasis> sp. DBV1 and Its Ability to Biodegrade Acrylamide

Although acrylamide finds diverse industrial applications, its presence in the environment is hazardous due to its carcinogenic, neurotoxic, and teratogenic properties. In spite of the general toxicity of acrylamide in the monomer form, some microorganisms are able to use it as a source of energy by catabolizing it to ammonia and acrylic acid by means of acrylamidase (EC 3.5.1.4). The present work reports on a novel soil isolate as an acrylamide-degrading bacteria. Based on biochemical characterization and 16S ribosomal RNA (rRNA) gene sequence, the bacterial strain was identified as Gram-positive Arthrobacter sp. DBV1. The optimum growth conditions were found to be temperature (30 °C) and pH 6.0 to 7.0. Evaluation of the effect of concentration of acrylamide (10–50 mM) incorporated into minimal medium showed maximum growth of Arthrobacter sp. DBV1 at 30 mM acrylamide. The biodegradation of acrylamide was confirmed by HPLC analysis. Acrylamidase was isolated and characterized for temperature and pH optima, substrate specificity by using different amides, and the effect of different activators/inhibitors such as metal ions and amino acids. These finding suggests that the strain could be attractive for biodegradation of acrylamide from the environment and also possibly from foods containing preformed acrylamide.     

Copolymerization of acrylic acid amides with alkenyl halides

The binary radical copolymerization of acrylic acid amides (acrylamide and N-cyclohexen-1-ylacrylamide) with alkenyl halides (vinyl chloride, vinyl bromide, and allyl chloride) has been studied. The constants of relative activity of the monomers used are calculated. For the systems under investigation, the occurrence of dehydrochlorination of a polymer chain and protonation of a carbonyl group occur is confirmed. Allyl chloride shows the most pronounced tendency toward dehydrochlorination, while in the case of vinyl chloride, this tendency is the least distinct. The polymer-analogous transformations result in copolymers containing polyene fragments and units of ammonium or oxonium amide salts.     

Probing the effects of external species on poly(acrylate acid) chain dynamics by using cationic AIE-active fluorophore

We report here our results on the investigation of the chain dynamics of poly(acrylic acid) in aqueous solution. The concentration of poly(acrylic acid) was approximately 3.8×10~(-4) mol/L, two orders of magnitude higher than that reported in the literature. The p H value of the solution was 3.9, and the hydrogen bonds between the intrinsic and ionized carboxylic acid groups formed dynamic networks, which captured aggregation-induced emission-active molecules(a tetra-quaternary ammonium modified tetraphenylethene derivative) inside the polymer coils and induced fluorescence emission. The hydrogen bonds can be classified as intra- or intermolecular; both can be probed based on the emission change of the tetra-quaternary ammonium modified tetraphenylethene probes. The effects of different external stimuli on the polymer chain dynamics were investigated using different metal cations(including Na~+, Li~+, Zn~(2+), Ni~(2+), Ca~(2+), and Co~(2+)), different cation concentrations(1×10~(-6) to 4×10~(-4) mol/L), different poly(acrylic acid) molecular weights(5, 240, and 450 k Da), and different copolymers. The experimental results indicate that the long poly(acrylic acid) chains(high molecular weight) tend to form dense globular coils and exclude the probe molecules outside, which are robust and unsusceptible to water-soluble metal cations. However, the shorter poly(acrylic acid) chains tend to form intermolecular hydrogen bonds, which are helpful in capturing more probe molecules inside the networks, thus inducing stronger emission. Because of the dual functions of forming hydrogen bonds with carboxylic groups and acting as an acceptor of protons from the carboxylic acid group to form cationic species, copolymerization with acrylate amide [poly(acrylic acid)-co-poly(acrylamide)] can greatly affect the chain dynamics of poly(acrylic acid) segments, which is reflected by the drastically decreased emission intensity from the fluorescent probes.     

Synthesis of water-soluble fullerene-containing vinyl polymers by low-temperature radiation-induced living polymerization

Water-soluble polymers of acrylamide and acrylic acid that contain fullerene (more than 90% C₆₀) have been prepared by the low-temperature radiation-induced living polymerization. In the absorption spectra of these polymers, a monotonically decaying absorption typical of the covalently bound fullerene or its associates is observed in the range 240–700 nm. The radiation initiation of the process allows preparation of high-purity polymers useful for designing medicinal preparations.     

PAAM高吸水树脂反相悬浮聚合

采用反相悬浮聚合法,通过部分中和丙烯酸与丙烯酰胺共聚制备了聚(丙烯酸-丙烯酰胺)(PAAM)高吸水树脂,讨论了聚合过程主要影响因素对其吸液性能的影响,并对其进行了FTIR、TGA测试,得到最佳的合成工艺配方:单体质量浓度为30%,中和度N为75%,丙烯酸与丙烯酰胺的摩尔比为7∶3,交联剂、引发剂和分散剂质量浓度分别为0.065%、0.7%和0.5%(相对于单体总质量),单体溶液的滴加速度为2～3mL/min,聚合温度和时间分别为70℃和1.5h。此时在蒸馏水、0.9%NaCl溶液%(wt)中最大吸水倍率分别为Qw=1300g/g、Qs=93g/g(Qw为蒸馏水中吸水倍率,Qs为0.9%NaCl溶液中的吸水倍率,下同),树脂在320℃之前都是比较稳定的,可以适应较高的使用温度。     

氧化淀粉基高吸水性树脂的制备及表征

以过硫酸铵为引发剂,N,N’-亚甲基双丙烯酰胺为交联剂,制备氧化淀粉―丙烯酸―丙烯酰胺高吸水性树脂,并采用红外光谱、X射线衍射等手段对产品的结构进行表征。通过单因素实验优化其制备工艺,最佳工艺条件为:氧化淀粉基体用量为50%,丙烯酸/丙烯酰胺质量比为4∶1,丙烯酸中和度为70%,引发剂过硫酸铵用量为0.5%,交联剂N,N’-亚甲基双丙烯酸胺用量为0.15%,反应温度为80℃,反应时间为3 h。此条件下,氧化淀粉基高吸水性树脂的吸水率达到972.4 g/g。     

Studies on Permeation of Bovine Serum Albumin (BSA) Through Photo-Modified Functionalized Asymmetric Membrane

UV-initiated photo-modification by hydrophilic functional moieties (viz. acrylic acid, acrylamide) is performed on the photo-responsive Polyether sulfone (PES) membrane. Characterization of the modified membranes has been done by porometry, Fourier Transform-IR (FTIR), contact angle, thermogravimetry, X-ray diffraction and gel permeation chromatography. The grafting of acrylamide is higher compared to acrylic acid, as is evidenced from weight increase, as well as porometry studies. The separation abilities of Bovine Serum Albumin (BSA) have been experimented through all the membranes and results show that modified membranes possess a better separation ability compared to virgin polyether sulfone. The separation order follows the trend: PES-g-(AM) > PES-g-(AA) > PES. pH dependence conformational changes of BSA macromolecule influence the separation. The increase in pH results in the decreasing trend in separation. The water flux recovery ratio (FRR) for the virgin PES membrane is minimum compared to other two grafted membranes.     

丙烯酸与丙烯酰胺共聚制备高吸水性树脂

采用溶液聚合法,以N,N’-亚甲基双丙烯酰胺（NMBA）为交联剂,过硫酸钾（KPS）为引发剂合成了高吸水性树脂聚（丙烯酸-丙烯酰胺）（P（AA—AM））,研究了单体配比、丙烯酸中和度、引发剂及交联剂用量、反应温度对树脂在去离子水和0．9％盐水中吸水率的影响．最佳条件下制备的树脂在去离子水中吸水率为750g·g^-1,在0．9％盐水中吸水率为85g·g^-1．     

Effect of synthesis conditions on molecular characteristics of acrylamide copolymers with acrylic acid,carriers of cationic biologically active substances

Methods of molecular hydrodynamics and optics were used to study properties of aqueous solutions of acrylamide copolymers with acrylic acid. Dependences of the molecular characteristics of the copolymers on their synthesis conditions were determined and conditions were found in which the process of radical copolymerization of acrylamide with acrylic acid yields water-soluble carboxyl-containing acrylamide copolymers with molecular masses not exceeding 4×10⁴ Da.