UV-curable inks, coatings, and adhesives are being increasingly used in food packaging systems. When exposed to UV energy, UV-photoinitiators (PI's) present in the formulations produce free radicals which catalyze polymerization of monomers and pre-polymers into resins. In addition to photopolymerization, other free radical reactions occur in these systems resulting in the formation of chemically varied photolytic decomposition products, many of which are low molecular weight chemical species with high migration potential. This research conducted model experiments in which 24 commonly used PI's were exposed to UV-energy at the typical upper limit of commercial UV-printing press conditions. UV-irradiated PI's were analyzed by gas chromatography-mass spectrometry (GC-MS) and electrospray-mass spectrometry (ESI-MS) in order to identify photolytic decomposition products. Subsequently, migration studies of 258 UV-cure food packaging samples were conducted using GC-MS; PI's and photolytic decomposition products were found in nearly all samples analyzed. One hundred-thirteen photolytic decomposition products were identified. Eighteen intact PI's and 21 photolytic decomposition products were observed as migrants from the 258 samples analyzed, and these were evaluated for frequency of occurrence and migratory concentration range. The most commonly observed PI's were 2-hydroxy-2-methylpropiophenone and benzophenone. The most commonly observed photolytic decomposition products were 2,4,6-trimethylbenzaldehyde and 1-phenyl-2-butanone. This compilation of PI photolytic decomposition data and associated migration data will aid industry in identifying and tracing non-intentionally added substances (NIAS) in food packaging materials.
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http://dx.doi.org/10.3390/molecules24193592 | DOI Listing |
J Am Chem Soc
July 2024
Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, 200433 Shanghai, China.
Carbonyl nitrenes are versatile intermediates that have been extensively characterized; however, their phosphorus analogues remain largely unknown. Herein, we report the observation of a rare example of carbonyl phosphinidene NHC(O)P, which was generated through the photolytic (193 nm) dehydrogenation of phosphinecarboxamide (NHC(O)PH) in a solid N-matrix at 12 K. The characterization of NHC(O)P in the triplet ground state with matrix-isolation IR and ultraviolet-visible (UV-vis) spectroscopy is supported by comprehensive isotope labeling experiments (D and N) and quantum chemical calculations.
View Article and Find Full Text PDFThis work reports the synthesis and characterization of a novel pentameric tin chloro cluster, (vinylSn)SnClO(OH)(-BuCO) (1), and explores its application as an efficient negative-tone photoresist in a 1 : 2 weight ratio blend with [(-BuSn)O(OH)](BF) (2). Through e-beam lithography, a small high-resolution pattern (HP = 20 nm) is achieved for the blend photoresist (3) at a dose of 2080 μC cm. Additionally, EUV lithography demonstrates the development of a high-resolution pattern (HP = 16 nm) at an EUV dose of 70 mJ cm.
View Article and Find Full Text PDFPhys Chem Chem Phys
March 2024
Laboratory of Molecular Spectroscopy, Institute of Chemistry, ELTE Eötvös Loránd University, PO Box 32, Budapest H-1518, Hungary.
Exploration of the photolytic dynamics of sulfurous compounds is essential, eventually contributing not only to our comprehension of their fundamental organic chemistry but also shedding light on astrophysical implications. This study aims to investigate two astrochemically relevant sulfur-containing molecules, namely, thiourea (TU) and its -methylated counterpart, -methyl thiourea (NMTU), in cryogenic matrices. These molecules were deposited both in solid Ar and in a quantum host, specifically in solid -H matrices, with the latter exhibiting unique properties.
View Article and Find Full Text PDFEnviron Sci Technol
March 2024
Department of Chemistry, University of California, Irvine, California 92697-2025, United States.
The mechanism and kinetics of reactive oxygen species (ROS) formation when atmospheric secondary organic aerosol (SOA) is exposed to solar radiation are poorly understood. In this study, we combined an in situ UV-vis irradiation system with electron paramagnetic resonance (EPR) spectroscopy to characterize the photolytic formation of ROS in aqueous extracts of SOA formed by the oxidation of isoprene, α-pinene, α-terpineol, and toluene. We observed substantial formation of free radicals, including OH, superoxide (HO), and organic radicals (R/RO) upon irradiation.
View Article and Find Full Text PDFNanoscale Adv
December 2023
Department of Chemistry, National Tsing Hua University Hsinchu 30013 Taiwan
This work reports the success in accessing high-resolution negative-tone EUV photoresists without radical chain growth in the aggregation mechanism. The synthesis of a highly hydroxylated HfO(OH)(RCO) cluster 3 (R = -butyl or -Bu) is described; its EUV performance enables high resolution patterns HP = 18 nm under only 30 mJ cm. This photoresist also achieves high resolution patterns for e-beam lithography.
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