Reaction products (adducts) of acrylamide with N termini of hemoglobin (Hb) are regularly observed in persons without known exposure. The average Hb adduct level measured in Swedish adults is preliminarily estimated to correspond to a daily intake approaching 100 microg of acrylamide. Because this uptake rate could be associated with a considerable cancer risk, it was considered important to identify its origin. It was hypothesized that acrylamide was formed at elevated temperatures in cooking, which was indicated in earlier studies of rats fed fried animal feed. This paper reports the analysis of acrylamide formed during heating of different human foodstuffs. Acrylamide levels in foodstuffs were analyzed by an improved gas chromatographic-mass spectrometric (GC-MS) method after bromination of acrylamide and by a new method for measurement of the underivatized acrylamide by liquid chromatography-mass spectrometry (LC-MS), using the MS/MS mode. For both methods the reproducibility, given as coefficient of variation, was approximately 5%, and the recovery close to 100%. For the GC-MS method the achieved detection level of acrylamide was 5 microg/kg and for the LC-MS/MS method, 10 microg/kg. The analytic values obtained with the LC-MS/MS method were 0.99 (0.95-1.04; 95% confidence interval) of the GC-MS values. The LC-MS/MS method is simpler and preferable for most routine analyses. Taken together, the various analytic data should be considered as proof of the identity of acrylamide. Studies with laboratory-heated foods revealed a temperature dependence of acrylamide formation. Moderate levels of acrylamide (5-50 microg/kg) were measured in heated protein-rich foods and higher contents (150-4000 microg/kg) in carbohydrate-rich foods, such as potato, beetroot, and also certain heated commercial potato products and crispbread. Acrylamide could not be detected in unheated control or boiled foods (<5 microg/kg). Consumption habits indicate that the acrylamide levels in the studied heated foods could lead to a daily intake of a few tens of micrograms.
We report a new method to probe the solid-liquid interface through the use of a thin liquid layer on a solid surface. An ambient pressure XPS (AP-XPS) endstation that is capable of detecting high kinetic energy photoelectrons (7 keV) at a pressure up to 110 Torr has been constructed and commissioned. Additionally, we have deployed a “dip & pull” method to create a stable nanometers-thick aqueous electrolyte on platinum working electrode surface. Combining the newly constructed AP-XPS system, “dip & pull” approach, with a “tender” X-ray synchrotron source (2 keV–7 keV), we are able to access the interface between liquid and solid dense phases with photoelectrons and directly probe important phenomena occurring at the narrow solid-liquid interface region in an electrochemical system. Using this approach, we have performed electrochemical oxidation of the Pt electrode at an oxygen evolution reaction (OER) potential. Under this potential, we observe the formation of both Pt2+ and Pt4+ interfacial species on the Pt working electrode in situ. We believe this thin-film approach and the use of “tender” AP-XPS highlighted in this study is an innovative new approach to probe this key solid-liquid interface region of electrochemistry.
The acrylamide content of heated foodstuffs should be considered to be the net result of complex reactions leading to the formation and elimination/degradation of this compound. The present study, involving primarily homogenized potato heated in an oven, was designed to characterize parameters that influence these reactions, including the heating temperature, duration of heating, pH, and concentrations of various components. Higher temperature (200 degrees C) combined with prolonged heating times produced reduced levels of acrylamide, due to elimination/degradation processes. At certain concentrations the presence of asparagine or monosaccharides (in particular, fructose and also glucose and glyceraldehyde) was found to increase the net content of acrylamide. Addition of other free amino acids or a protein-rich food component strongly reduced the acrylamide content, probably by promoting competing reactions and/or covalently binding acrylamide formed. The dependence on pH of the acrylamide content exhibited a maximum around pH 8; in particular, lower pH was shown to enhance elimination and decelerate formation of acrylamide. In contrast, the effects of additions of antioxidants or peroxides on acrylamide content were small or nonexistent.
During the past decade, the application of ambient pressure photoemission spectroscopy (APPES) has been recognized as an important in situ tool to study environmental and materials science, energy related science, and many other fields. Several APPES endstations are currently under planning or development at the USA and international light sources, which will lead to a rapid expansion of this technique. The present work describes the design and performance of a new APPES instrument at the Advanced Light Source beamline 9.3.2 at Lawrence Berkeley National Laboratory. This new instrument, Scienta R4000 HiPP, is a result of collaboration between Advanced Light Source and its industrial partner VG-Scienta. The R4000 HiPP provides superior electron transmission as well as spectromicroscopy modes with 16 microm spatial resolution in one dimension and angle-resolved modes with simulated 0.5 degrees angular resolution at 24 degrees acceptance. Under maximum transmission mode, the electron detection efficiency is more than an order of magnitude better than the previous endstation at beamline 9.3.2. Herein we describe the design and performance of the system, which has been utilized to record spectra above 2 mbar.
Exposure to acrylamide (AA) has been monitored by mass spectrometric detection of the adduct, N-(2-carbamoylethyl)valine (CEV), to the N-termini of hemoglobin (Hb), according to the N-alkyl Edman method. In these studies, a conspicuous background level, about 40 pmol/g of globin, of apparently the same adduct was regularly observed in Hb from persons without known exposure to AA. For testing of the hypothesis that this adduct originates from AA formed in cooking, rats were fed fried animal standard diet for 1 or 2 months. These animals exhibited a strong increase of the level of the studied Hb adduct, compared to control rats fed unfried diet. By gas chromatography/tandem mass spectrometry, the identity with CEV was confirmed by the concordance of the product ion spectrum of the studied adduct with that of a verified standard and by interpretation of the fragment ions. Further support of the chemical structure, at the same time pinpointing AA as the causative reactive factor, was obtained through the demonstration that AA is formed in the heating of the feed and that the level of AA in the fried feed is compatible with the measured levels of the CEV adduct. The raised CEV adduct levels observed in experimental animals are of a magnitude that is similar to the background level in nonsmoking humans. These data render it likely that cooking of food is a major source of the background dose of AA also in humans. An evaluation of cancer tests of AA and available data for its metabolism leads to the estimation that the background dose of AA is associated with a considerable cancer risk.
The interfaces of the nanostructured dye-sensitized solid heterojunction TiO(2)/Ru-dye/CuI have been studied using photoelectron spectroscopy of core and valence levels, x-ray absorption spectroscopy and atomic force microscopy. A nanostructured anatase TiO(2) film sensitized with RuL(2)(NCS)(2) [cis-bis(4,4(')-dicarboxy-2,2(')-bipyridine)-bis(isothio-cyanato)-ruthenium(II)] was prepared in a controlled way using a novel combined in-situ and ex-situ (Ar atmosphere) method. Onto this film CuI was deposited in-situ. The formation of the dye-CuI interface and the changes brought upon the dye-TiO(2) interface could be monitored in a stepwise fashion. A direct interaction between the dye NCS groups and the CuI is evident in the core level photoelectron spectra. Concerning the energy matching of the valence electronic levels, the photoelectron spectra indicate that the dye HOMO overlaps in energy with the Cu 3d-I 5p hydrid states. The CuI grow in the form of particles, which at the initial stages displace the dye molecules causing dye-TiO(2) bond breaking. Consequently, the very efficient charge injection channel provided by the dye-TiO(2) carboxylic bonding is directly affected for a substantial part of the dye molecules. This may be of importance for the functional properties of such a heterojunction.
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