Correction: Neutral inverse-sandwich rare-earth metal complexes of the benzene tetraanion.

[This corrects the article DOI: 10.1039/D4SC02491E.].

Nail salon dust reveals alarmingly high photoinitiator levels: Assessing occupational risks.

Photoinitiators (PIs) are chemical additives that generate active substances, such as free radicals to initiate photopolymerization. Traditionally, polymerization has been considered a green technique that seldomly generates contaminants. However, many researches have confirmed toxicity effects of PIs, such as carcinogenicity, cytotoxicity, endocrine disrupting effects. Surprisingly, we found high levels of PIs in indoor dust. Our analysis revealed comparable levels of PIs in dust from printing shops (geometric mean, GM: 1.33 ×103 ng/g) and control environments (GM: 874 ng/g), underscoring the widespread presence of PIs across various settings. Alarmingly, in dust samples from nail salons, PIs were detected at total concentrations ranging from 610 to 1.04 × 107 ng/g (GM: 1.87 ×105 ng/g), significantly exceeding those in the control environments (GM: 1.43 ×103 ng/g). Nail salon workers' occupational exposure to PIs through dust ingestion was estimated at 4.86 ng/kg body weight/day. Additionally, an in vitro simulated digestion test suggested that between 10 % and 42 % of PIs present in ingested dust could become bioaccessible to humans. This is the first study to report on PIs in the specific environments of nail salons and printing shops. This study highlights the urgent need for public awareness regarding the potential health risks posed by PIs to occupational workers, marking an important step towards our understanding of environmental pollution caused by PIs.

Neutral inverse-sandwich rare-earth metal complexes of the benzene tetraanion.

Rare-earth metal complexes of the parent benzene tetraanion and neutral inverse-sandwich rare-earth metal arene complexes have remained elusive. Here, we report the first neutral inverse-sandwich rare-earth metal complexes of the parent benzene tetraanion supported by a monoanionic ß-diketiminate (BDI) ligand. Reduction of the trivalent rare-earth metal diiodide precursors (BDI)MI2(THF) (BDI = HC(C(Me)N[C6H3-(3-pentyl)2-2,6])2; M = Y, 1-Y; M = Sm, 1-Sm) in benzene or para-xylene by potassium graphite yielded the neutral inverse-sandwich rare-earth metal arene complexes [(BDI)M(THF) n ]2(µ-η6,η6-arene) (M = Y, Sm; arene = benzene, 2-M; arene = para-xylene, 3-M). Single crystal X-ray diffraction, spectroscopic and magnetic characterization studies, together with density functional theory (DFT) calculations confirm that these neutral rare-earth metal arene complexes possess an [M3+-(arene)4--M3+] electronic structure with strong metal-arene δ interactions. The arene exchange reactivity shows that 2-Sm has higher stability than 3-Sm. Furthermore, 2-Sm can behave as a four-electron reductant to reduce unsaturated organic substrates. Particularly, while the reaction of 2-Sm with 1,3,5,7-cyclooctatetraene (COT) yielded (BDI)Sm(η8-COT) (4-Sm), 2-Sm reacted with 1,4-diphenylbutadiyne to afford (BDI)Sm(η4-C4Ph2) (5-Sm), the first rare-earth metallacyclopentatriene complex.

Reduction of Thorium Tris(amido)arene Complexes: Reversible Double and Single C-C Couplings.

The reduction chemistry of thorium complexes is less explored compared to that of their uranium counterparts. Here, we report the synthesis, characterization, and reduction chemistry of two thorium(IV) complexes, (AdTPBN3)ThCl (1) and (DtbpTPBN3)ThCl(THF) (4) [RTPBN3 = 1,3,5-[2-(RN)C6H4]3C6H3; R = 1-adamantyl (Ad) or 3,5-di-tert-butylphenyl (Dtbp); THF = tetrahydrofuran], supported by tripodal tris(amido)arene ligands with different N-substituents. Reduction of 1 with excessive potassium in n-pentane yielded a double C-C coupling product, [(AdTPBN3)ThK(Et2O)2]2 (3), featuring a unique tetraanionic tricyclic core. On the other hand, reduction of 4 with 1 equiv of KC8 in hexanes/1,2-dimethoxyethane (DME) afforded a single C-C coupling product, [(DtbpTPBN3)Th(DME)]2 (5), with a dianionic bis(cyclohexadienyl) core. The solid- and solution-state structures of dinuclear thorium(IV) complexes 3 and 5 were established by X-ray crystallography and NMR spectroscopy. In addition, reactivity studies show that 3 and 5 can behave as thorium(II) and thorium(III) synthons to reduce organic halides. For instance, 3 and 5 are able to reduce 4 and 2 equiv of benzyl chloride, respectively, to regenerate 1 and 4 with concomitant formation of dibenzyl. Reversible C-C couplings under redox conditions provide an alternative approach to exploiting the potential of thorium arene complexes in redox chemistry.

The hidden diet: Synthetic antioxidants in packaged food and their impact on human exposure and health.

Synthetic antioxidants (AOs) are commonly used in everyday items and industrial products to inhibit oxidative deterioration. However, the presence of AOs in food packaging and packaged foods has not been thoroughly documented. Moreover, studies on human exposure to AOs through skin contact with packaging or ingesting packaged foods are limited. In this study, we analyzed twenty-three AOs-including synthetic phenolic antioxidants (SPAs) and organophosphite antioxidants (OPAs)-along with six transformation products in various food samples and their packaging materials. We found AOs in food products at concentrations ranging from 1.30 × 103 to 1.77 × 105 ng/g, which exceeded the levels in both outer packaging (6.05 × 102-3.07 × 104 ng/g) and inner packaging (2.27 × 102-1.09 × 105 ng/g). The most common AOs detected in foodstuffs were tris(2,4-di-tert-butylphenyl) phosphate (AO168O), butylated hydroxytoluene (BHT), and octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (AO1076), together constituting 95.7 % of the total AOs found. Our preliminary exposure assessment revealed that dietary exposure-estimated at a median of 2.55 × 104 ng/kg body weight/day for children and 1.24 × 104 ng/kg body weight/day for adults-is a more significant exposure route than dermal contact with packaging. Notably, four AOs were identified in food for the first time, with BHT making up 76.8 % and 67.6 % of the total BHT intake for children and adults, respectively. These findings suggest that food consumption is a significant source of BHT exposure. The estimated daily intakes of AOs via consumption of foodstuffs were compared with the recommended acceptable daily intake to assess the risks. This systematic investigation into AOs contributes to understanding potential exposure and health risks associated with AOs in packaged foods. It emphasizes the need for further evaluation of human exposure to these substances.

Occurrence, Fate, Human Exposure, and Toxicity of Commercial Photoinitiators.

Photoinitiators (PIs) are a family of anthropogenic chemicals used in polymerization systems that generate active substances to initiate polymerization reactions under certain radiations. Although polymerization is considered a green method, its wide application in various commercial products, such as UV-curable inks, paints, and varnishes, has led to ubiquitous environmental issues caused by PIs. In this study, we present an overview of the current knowledge on the environmental occurrence, human exposure, and toxicity of PIs and provide suggestions for future research based on numerous available studies. The residual concentrations of PIs in commercial products, such as food packaging materials, are at microgram per gram levels. The migration of PIs from food packaging materials to foodstuffs has been confirmed by more than 100 reports of food contamination caused by PIs. Furthermore, more than 20 PIs have been detected in water, sediment, sewage sludge, and indoor dust collected from Asia, the United States, and Europe. Human internal exposure was also confirmed by the detection of PIs in serum. In addition, PIs were present in human breast milk, indicating that breastfeeding is an exposure pathway for infants. Among the most available studies, benzophenone is the dominant congener detected in the environment and humans. Toxicity studies of PIs reveal multiple toxic end points, such as carcinogenicity and endocrine-disrupting effects. Future investigations should focus on synergistic/antagonistic toxicity effects caused by PIs coexposure and metabolism/transformation pathways of newly identified PIs. Furthermore, future research should aim to develop "greener" PIs with high efficiency, low migration, and low toxicity.

Studying paraben-induced estrogen receptor- and steroid hormone-related endocrine disruption effects via multi-level approaches.

Increasing concerns have been raised on the health risks of parabens in the regard of their widespread applications and potential endocrine disrupting activities. In this study, four typical parabens, including methyl paraben (MeP), ethyl paraben (EtP), propyl paraben (PrP), and butyl paraben (BuP) were systematically investigated for their estrogen receptor- and steroid hormone-related endocrine disruptions using multi-level approaches. Paraben exposure promoted the proliferation of MCF-7 cells, increased the luciferase activity in MVLN cells, and induced the vitellogenin (vtg) expression in zebrafish larvae, showing the typical estrogenic effects. The in vitro protein assays further revealed that PrP and BuP could bind with two isoforms of estrogen receptors (ERs). The estrogenic activities of parabens were predicted to be positively correlated with their chemical structure complexity by using molecular docking analysis. Furthermore, the synthesis and secretion of estradiol (E2) and testosterone (T) were significantly disturbed in H295R cells and zebrafish larvae, which could be regulated by paraben-induced transcriptional disturbance in both in vitro steroidogenesis and in vivo hypothalamic-pituitary-gonadal (HPG) axis. Parabens could disturb the endocrine system by activating the ERs and disrupting the steroid hormone synthesis and secretion, suggesting their potential deleterious risks to the environment and human health.

Constructing an MCF-7 breast cancer cell-based transient transfection assay for screening RARα (Ant)agonistic activities of emerging phenolic compounds.

The screening of compounds with endocrine disrupting effects has been attracting increasing attention due to the continuous release of emerging chemicals into the environment. Testing the (ant)agonistic activities of these chemicals on the retinoic acid receptor α (RARα), a vital nuclear receptor, is necessary to explain their perturbation in the endocrine system in vivo. In the present study, MCF-7 breast carcinoma cells were transiently transfected with a RARα expression vector (pEF1α-RARα-RFP) and a reporter vector containing a retinoic acid reaction element (pRARE-TA-Luc). Under optimized conditions, the performance of the newly constructed system was evaluated for its feasibility in screening the (ant)agonistic effects of emerging phenolic compounds on RARα. The results showed that this transient transfection cell model responded well to stimulation with (ant)agonists of RARα, and the EC50 and IC50 values were 0.87 nM and 2.67 µM for AM580 and Ro41-5253, respectively. Its application in testing several emerging phenolic compounds revealed that triclosan (TCS) and tetrabromobisphenol A (TBBPA) exerted notable RARα antagonistic activities. This newly developed bioassay based on MCF-7 is promising in identifying the agonistic or antagonistic activities of xenobiotics on RARα and has good potential for studying RARα signaling-involved toxicological effects of emerging chemicals of concern.

Diagnostic value of MRI-DWI signal intensity value combined with serum PGI, PGII and CA199 in early gastric cancer.

To explore the diagnostic value of MRI-DWI signal intensity value combined with serum PGI. PGII and CA199 in early gastric cancer. Sixty cases of gastric cancer patients admitted to our hospital from December 2019 to December 2020 were selected as the gastric cancer group and 80 cases of healthy volunteers who underwent physical examination in our hospital during the same period were selected as the healthy group. All the 60 patients underwent MRI-DWI examination, and the pathological diagnosis results were regarded as the gold standard. MRI-DWI images, MRI-DWI signal intensity values of patients with different degrees of gastric cancer differentiation. Serum PGI, PGII and CA199 levels of subjects in the two groups were compared. AUC was used to evaluate the diagnostic value of MRI-DWI signal intensity value combined with serum PGI, PG II and CA199 for early gastric cancer. In the healthy group, T1W1 showed relatively uniform low signal intensity. While T2WI showed no significant increase in signal intensity. In the gastric cancer group. There was diffuse gastric wall thickening, local thickening or mass formation; T1WI and WATS showed slightly lower signal intensity in the lesion area. T2WI, FLAIR and B-TFE showed slightly uneven or moderately increased signal intensity. DWI showed limited diffusion, and the signal intensity increased uniformly or more uniformly, and the range of increase was clear. The signal intensity of MRI-DWI was 89.12 ± 8.14 in patients with low differentiation, 82.17 ± 6.35 in patients with moderate differentiation, and 74.52 ± 4.53 in patients with high differentiation. There were significant differences in the signal intensity of MRI-DWI among the three groups, and the difference was statistically significant (F=12.214, P <0.05). Serum PGI levels of subjects in the gastric cancer group were significantly lower than those in the healthy group, and the levels of PGII and CA199 were significantly higher than that in the healthy group, with statistical significance (P <0.05). The AUC, sensitivity and specificity of MRI-DWI signal intensity value and serum PGI, PGII and CA199 combined indexes in the diagnosis of gastric cancer were significantly higher than those of the independent indexes, with statistical significance (P <0.05). Conclusion: MRI-DWI signal strength value, serum PGI, PGII and CA199 levels are closely related to the occurrence and development of early gastric cancer. The combined detection and diagnosis efficiency is higher, which is helpful to improve the detection rate of early gastric cancer and is worthy of extensive clinical application.