4,4'-Bis(diethylamino)benzophenone

Migration of photoinitiators from cardboard into dry food: evaluation of Tenax(R) as a food simulant.[Pubmed:27146794]

Food Addit Contam Part A Chem Anal Control Expo Risk Assess. 2016 May;33(5):913-20.

Photoinitiators are widely used to cure ink on packaging materials used in food applications such as cardboards for the packaging of dry foods. Conventional migration testing for long-term storage at ambient temperature with Tenax((R)) was applied to paperboard for the following photoinitiators: benzophenone (BP), 4,4'-bis(diethylamino)benzophenone (DEAB), 2-chloro-9H-thioxanthen-9-one (CTX), 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX), 4-(dimethylamino)benzophenone (DMBP), 2-ethylanthraquinone (EA), 2-ethylhexyl-4-dimethylaminobenzoate (EDB), ethyl-4-dimethylaminobenzoate (EDMAB), 4-hydroxybenzophenone (4-HBP), 2-hydroxy-4-methoxybenzophenone (HMBP), 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone (HMMP), 2-isopropyl-9H-thioxanthen-9-one (ITX), 4-methylbenzophenone (MBP) and Michler's ketone (MK). Test conditions (10 days at 60 degrees C) were according to Regulation (EU) No. 10/2011 and showed different migration patterns for the different photoinitiators. The results were compared with the migration in cereals after a storage of 6 months at room temperature. The simulation with Tenax at 60 degrees C overestimated actual migration in cereals up to a maximum of 92%. In addition, the effect of a lower contact temperature and the impact of the Tenax pore size were investigated. Analogous simulation performed with rice instead of Tenax resulted in insufficiently low migration rates, showing Tenax is a much stronger adsorbent than rice and cereals.

Aggregation induced emission enhancement of 4,4'-bis(diethylamino)benzophenone with an exceptionally large blue shift and its potential use as glucose sensor.[Pubmed:25525803]

Phys Chem Chem Phys. 2015 Feb 7;17(5):3343-54.

Optical emission from a luminogen in solid state is generally red shifted with respect to its solution phase emission. However, in our present study, we report exceptionally large blue shifted enhanced emission from aggregated hydrosol of 4,4'-bis(diethylamino)benzophenone (BZP) compared to its solution phase emission in any good solvent. This exceptional blue emission from aggregated structure of BZP arises from its locally excited states with the concomitant suppression of twisted intramolecular charge transfer (TICT) motion. This is known as aggregation induced locally excited (AILE) state emission. A broad red shifted emission is also observed in case of larger aggregated structure of BZP and it originates from the excited intramolecular charge transfer (ICT) state of planar BZP. Morphology of the aggregated BZP is also studied by scanning electron microscopy and optical microscopy. This AILE emission of the luminogen is used for sensing glucose in aqueous solution at very low concentration. The quenching of AILE in presence of glucose has been explained due to hydrogen bonded complexation between glucose and BZP molecule present at the surface of the aggregated structure and is responsible for crystal softening, i.e. loosening of crystal packing.

Evaluation of the migration of 15 photo-initiators from cardboard packaging into Tenax((R)) using ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS).[Pubmed:24447245]

Food Addit Contam Part A Chem Anal Control Expo Risk Assess. 2014 Apr;31(4):767-75.

Photo-initiators are widely used to cure ink on packaging materials used in food applications such as plastic films or cartonboards. In migration studies, food simulants are very often used to simulate food, like Tenax((R)), which is the simulant for dry foodstuffs. In this paper a fast and reliable confirmation method for the determination of the following photo-initiators in Tenax((R)) is described: benzophenone (BP), 4,4'-bis(diethylamino)benzophenone (DEAB), 2-chloro-9H-thioxanthen-9-one (CTX), 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX), 2,4-diethyl-9H-thioxanthen-9-one (DETX), 2,2-dimethoxy-2-phenyl acetophenone (DMPA), 4-(dimethylamino)benzophenone (DMBP), 2-ethylanthraquinone (EA), ethyl-4-dimethylaminobenzoate (EDMAB), 1-hydroxylcyclohexyl phenyl ketone (HCPK), 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone (HMMP), 2-isopropyl-9H-thioxanthen-9-one (ITX), 4-methylbenzophenone (MBP), Michler's ketone (MK), and 4-phenylbenzophenone (PBZ). After the migration study was completed, the simulant Tenax((R)) was extracted using acetonitrile, followed by analysis on ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). Quantification was carried out using benzophenone-d10 (BP-d10) as internal standard. The presented method is validated in terms of matrix effect, specificity, linearity, recovery, precision and sensitivity, showing the method can detect all photo-initiators at very low concentrations (LOD < 0.125 microg g(-1) for all substances). Finally, the procedure was applied to real samples, proving the capabilities of the presented method.

Survey on the occurrence of photo-initiators and amine synergists in cartonboard packaging on the German market and their migration into the packaged foodstuffs.[Pubmed:24107105]

Food Addit Contam Part A Chem Anal Control Expo Risk Assess. 2013;30(11):1993-2016.

In a surveillance study from 2008 to 2011, in total 310 food products, predominately packed in cartonboard, were collected from the German market. First, the packaging materials were analysed for their content of six photo-initiators and five amine synergists by high-performance liquid chromatography with diode array detection (HPLC-DAD). If high amounts of these substances were detected, subsequently the foodstuffs were analysed by means of HPLC-MS or tandem MS, respectively. Benzophenone (BP) was detected in 49% of the packaging materials and was thus the most often determined compound, followed by 4-methylbenzophenone (MBP, 8%), 1-hydroxy-cyclohexylphenylketone (HCHPK, 7%) and methyl-o-benzoylbenzoate (MOBB, 5%). In total, 99 foodstuffs were analysed and in 20 cases one or more photo-initiators and/or amine synergists were detected in quantities above the legally acceptable limits in food. This resulted in several notifications in the European Rapid Alert System for Food and Feed (RASFF); the best known is MBP in breakfast cereals. Contamination of the foodstuff by the photo-initiators and/or amine synergists also occurred when it was in indirect contact with the printed packaging material and no adequate barrier material was used to prevent migration. The data also clearly demonstrate that polyethylene films are not suitable to inhibit migration. Storage of samples until the best before date showed that HCHPK, BP and MBP migrate very easily via the gas phase. In contrast, 4-phenylbenzophenone and 4,4'-bis(diethylamino)benzophenone migrated only very slowly or, respectively, not in quantifiable amounts into the foodstuffs. Differences in transfer rates for HCHPK, BP and MBP from several packagings into food and Tenax((R)), respectively, lead to the assumption that both the food matrix as well as the extent of cross-linking of the printing ink during curing may have an influence on the level of migration.

Metathesis reactions of a manganese borylene complex with polar heteroatom-carbon double bonds: a pathway to previously inaccessible carbene complexes.[Pubmed:23692498]

J Am Chem Soc. 2013 Jun 12;135(23):8726-34.

A comprehensive study has been carried out to investigate the metathesis reactivity of the terminal alkylborylene complex [(eta(5)-C5H5)(OC)2Mn horizontal lineB(tBu)] (1). Its reactions with 3,3',5,5'-tetrakis(trifluoromethyl)benzophenone, 4,4'-dimethylbenzophenone, 2-adamantanone, 4,4'-bis(diethylamino)benzophenone, and 1,2-diphenylcyclopropen-3-one afforded the metathesis products [(eta(5)-C5H5)(OC)2Mn horizontal lineCR2] (R = C6H3-3,5-(CF3)23a, C6H4-4-Me 3b, C6H4-4-NEt23d; CR2 = adamantylidene 3c, cyclo-C3Ph23e). The cycloaddition intermediates were detected by NMR spectroscopy from reactions involving ketones with more electron-withdrawing substituents. The reaction of 1 with dicyclohexylcarbodiimide (DCC) only proceeds to form the cycloaddition product [(eta(5)-C5H5)(OC)2Mn{kappa(2)-C,B-C( horizontal lineNCy)N(Cy)B(tBu)}] (4), which upon warming, rearranges to afford complex [(eta(5)-C5H5)(OC)2Mn{CN(Cy)B(tBu)CN(Cy)}] (5). The reaction of 1 with triphenylphosphine sulfide SPPh3 also yields the metathesis product [(eta(5)-C5H5)(OC)2Mn(PPh3)] via an intermediate which is likely to be a eta(2)-thioboryl complex [(eta(5)-C5H5)(OC)2Mn{(eta(2)-SB(tBu)}] (6). Similar reactions have been studied using an iron borylene complex [(Me3P)(OC)3Fe horizontal lineB(Dur)] (Dur = 2,3,5,6-tetramethylphenyl, 9). Extensive computational studies have been also carried out to gain mechanistic insights in these reactions, which provided reaction pathways that fit well with the experimental data.

Three-dimensional biodegradable structures fabricated by two-photon polymerization.[Pubmed:19437724]

Langmuir. 2009 Mar 3;25(5):3219-23.

Two-photon polymerization has been employed to fabricate three-dimensional structures using the biodegradable triblock copolymer poly(epsilon-caprolactone-co-trimethylenecarbonate)-b-poly(ethylene glycol)-b-poly(epsilon-caprolactone-co-trimethylenecarbonate) with 4,4'-bis(diethylamino)benzophenone as the photoinitiator. The fabricated structures were of good quality and had four micron resolution. Initial cytotoxicity tests show that the material does not affect cell proliferation. These studies demonstrate the potential of two-photon polymerization as a technology for the fabrication of biodegradable scaffolds for tissue engineering.

Conformations of substituted benzophenones.[Pubmed:18369292]

Acta Crystallogr B. 2008 Apr;64(Pt 2):206-16.

The inclination of the two aryl rings (ring twists) in a series of benzophenone molecules has been examined. For each structure the dihedral angle (between the planes of the two sets of six aromatic C atoms) relates to both the steric considerations of the single molecule and the packing forces related to the crystal structure. Six new benzophenone structures are incorporated into the study including 2,2'-dihydroxy-4,4'-dimethoxybenzophenone (I), C(15)H(14)O(5), that appears to have the smallest reported twist angle, 37.85 (5) degrees , of any substituted benzophenone reported to date. Three further benzophenones, 4,4'-bis(diethylamino)benzophenone (II), C(21)H(28)N(2)O, 3,4-dihydroxybenzophenone (III), C(13)H(10)O(3), and 3-hydroxybenzophenone (IV), C(13)H(10)O(2), have similar ring twists [49.83 (5), 49.84 (5) and 51.61 (5) degrees , respectively] that are comparable with the value of 54 degrees found for the orthorhombic form of unsubstituted benzophenone. 4-Chloro-4'-hydroxybenzophenone (V), C(13)H(9)ClO(2), has a ring twist of 64.66 (8) degrees that is close to the value of 65 degrees found in the metastable monoclinic form of unsubstituted benzophenone and 2-amino-2',5-dichlorobenzophenone (VI), C(13)H(9)Cl(2)NO(2), has a large ring twist of 83.72 (6) degrees . Comparisons with a further 98 substituted benzophenone molecules from the Cambridge Structural Database (CSD) have been made.

[Migration of bisphenol A and benzophenones from paper and paperboard products used in contact with food].[Pubmed:16862986]

Shokuhin Eiseigaku Zasshi. 2006 Jun;47(3):99-104.

Migration of bisphenol A (BPA) and benzophenones, i.e., benzophenone (BZ), 4-(dimethylamino)benzophenone (DMAB), Michler's ketone (MK) and 4,4'-bis(diethylamino)benzophenone (DEAB), from 21 paper and paperboard products (15 recycled paperboard boxes and 6 virgin paper products) used in contact with food was examined. Migration levels of compounds from recycled paperboard were compared under various food-simulating conditions. BPA showed the highest migration into 20% ethanol and benzophenones into 95% ethanol. No compounds migrated from virgin paper products, but compounds did migrate into food simulants from recycled paperboard food boxes. BPA migrated into 20% ethanol from all recycled paperboard food boxes between 1.0 and 18.7 ng/mL. Into 95% ethanol, migration of BZ was observed in 8 samples (1.0-18.9 ng/mL), DMAB in 12 samples (1.2-3.7 ng/mL), MK in 13 samples (1.9-9.0 ng/mL), and DEAB in 13 samples (1.0-10.6 ng/mL). The highest migration level was 27.2 ng/mL and most of the migration levels were below 10 ng/mL. These values are sufficiently low compared with the TDI and NOAEL levels. Moreover, the amount of food in daily meals that comes into contact with paperboard products is relatively small. Consequently, it was concluded that there was no safety concern regarding the tested compounds in recycled paperboard food boxes.

Barium hydroxide lime turns yellow after desiccation.[Pubmed:16115986]

Anesth Analg. 2005 Sep;101(3):748-52, table of contents.

Ethyl violet is added to carbon dioxide absorbents and normally serves as an indicator of absorbent exhaustion. During the course of several prior studies of anesthetic breakdown, we noted (but did not publish) that barium hydroxide lime (BL), but not soda lime, turns yellow upon desiccation. We hypothesize that ethyl violet undergoes chemical reaction to produce a yellow colorant in desiccated BL. We qualitatively studied the time course of yellow color development during desiccation of these absorbents with dry oxygen. The yellow colorant was extracted from desiccated absorbent with diethyl ether, separated with chromatography, and analyzed with proton nuclear magnetic resonance and combined gas chromatography and mass spectrometry. The yellow color develops after BL has reached nearly complete desiccation. We successfully identified that ethyl violet decomposes into the yellow colorant 4,4'-bis(diethylamino)benzophenone upon desiccation of BL. The color is not intense, is not useful for identifying low levels of absorbent desiccation, and may be difficult to see through tinted canisters. It may be possible for BL to be sufficiently desiccated to allow chemical breakdown of anesthetics, but not yet show yellow coloration. However, if yellow coloration exists, one should assume that it has become desiccated.

Chemical analysis and genotoxicological safety assessment of paper and paperboard used for food packaging.[Pubmed:15207384]

Food Chem Toxicol. 2004 Aug;42(8):1323-37.

This study presents the research on the chemical analysis and genotoxicity of 28 virgin/recycled paper products in food-contact use. In the chemical analysis, paper products were extracted by reflux with ethanol, and analyzed by gas chromatography/mass spectrometry. 4,4'-bis(dimethylamino)benzophenone (Michler's ketone: MK), 4,4'-bis(diethylamino)benzophenone (DEAB), 4-(dimethylamino)benzophenone (DMAB) and bisphenol A (BPA) were found characteristically in recycled products. Seventy-five percent of the recycled paper products contained MK (1.7-12 microg/g), 67% contained DEAB (0.64-10 micro g/g), 33% contained DMAB (0.68-0.9 microg/g) and 67% contained BPA (0.19-26 microg/g). Although, BPA was also detected in virgin paper products, the detection levels in the recycled products were ten or more times higher than those in the virgin products. The genotoxicity of paper and paperboard extracts and compounds found in them were investigated by Rec-assay and comet assay. Of the 28 products tested by Rec-assay using Bacillus subtilis, 13 possessed DNA-damaging activity. More recycled than virgin products (75% against 25%) exhibited such activity, which, of the compounds, was observed in BPA, 1,2-benzisothiazoline-3-one (BIT), 2-(thiocyanomethylthio)benzothiazole, 2,4,5,6-tetrachloro-isophthalonitrile, 2,4,6-trichlorophenol (TCP), and pentachlorophenol. The critical toxicant in one virgin paper product was concluded to be BIT. Eight samples with DNA-damaging activity were also tested by comet assay using HL-60 cells; six induced comet cells significantly (five times or higher than the control) without a decrease of viable cells. TCP, BZ, DEAB, and BIT also caused a slight increase in comet cells. In conclusion, we showed that most recycled paper products contain chemicals such as MK, DEAB, DMAB, and BPA, and possess genotoxicity. However, the levels of the chemicals in the recycled products could not explain their genotoxic effects.