From cradle to grave: Deciphering sex-specific disruptions of the nervous and reproductive systems through interactions of 4-methylbenzylidene camphor and nanoplastics in adult zebrafish.

4-methylbenzylidene camphor (4-MBC) and micro/nanoplastics (MNPs) are common in personal care and cosmetic products (PCCPs) and consumer goods; however, they have become pervasive environmental contaminants. MNPs serve as carriers of 4-MBC in both PCCPs and the environment. Our previous study demonstrated that 4-MBC induces estrogenic effects in zebrafish larvae. However, knowledge gaps remain regarding the sex- and tissue-specific accumulation and potential toxicities of chronic coexposure to 4-MBC and MNPs. Herein, adult zebrafish were exposed to environmentally realistic concentrations of 4-MBC (0, 0.4832, and 4832 µg/L), with or without polystyrene nanoplastics (PS-NPs; 50 nm, 1.0 mg/L) for 21 days. Sex-specific accumulation was observed, with higher concentrations in female brains, while males exhibited comparable accumulation in the liver, testes, and brain. Coexposure to PS-NPs intensified the 4-MBC burden in all tested tissues. Dual-omics analysis (transcriptomics and proteomics) revealed dysfunctions in neuronal differentiation, death, and reproduction. 4-MBC-co-PS-NP exposure disrupted the brain histopathology more severely than exposure to 4-MBC alone, inducing sex-specific neurotoxicity and reproductive disruptions. Female zebrafish exhibited autism spectrum disorder-like behavior and disruption of vitellogenesis and oocyte maturation, while male zebrafish showed Parkinson's-like behavior and spermatogenesis disruption. Our findings highlight that PS-NPs enhance tissue accumulation of 4-MBC, leading to sex-specific impairments in the nervous and reproductive systems of zebrafish.

Chemical characterization, absolute configuration and optical purity of (1S)-(+)- and (1R)-(-)-10-camphorsulfonic acid.

Comprehensive chemical characterization for two isomers of camphorsulfonic acid (CSA), occasionally used in the manufacture of active pharmaceutical ingredients (APIs), was performed by nuclear magnetic resonance (NMR) spectroscopy, high-resolution mass spectroscopy in negative electrospray ionization mode and gas chromatography/mass spectrometry (GC/MS) in electron ionization mode. Electronic circular dichroism (ECD) spectra together with quantum chemical calculations using time-dependent density functional theory (TD-DFT) were used to assign the stereochemistry for CSA for the first time and these assignments were then confirmed by single-crystal X-ray diffraction. As crystals were grown under the same conditions of high supersaturation using a mixed solvent without water removal, the crystal structures of the two enantiomers contained one ordered molecule of water in the asymmetric unit. The crystals of the (+)-enantiomer have a 1S,4R configuration and the H atom of the sulfonic acid group combines with the water molecule to form a hydronium ion, namely, hydronium (1S,4R)-(7,7-dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl)methanesulfonate, H3O+·C10H15O4S-. The crystals of the (-)-enantiomer have a 1R,4S configuration. The determination of the optical purity of CSA using NMR spectroscopy with a chiral solvating agent, (1R,2R)-1,2-diphenylethane-1,2-diamine, and GC/MS with a chiral column has been well explored. The results showed that the examined samples of these two isomers of CSA proved to be enantiomerically pure. In particular, for (1R)-(-)-10-camphorsulfonic acid, this is, to our knowledge, the first description on its spectral characterization in a scientific context.

Can TPO as Photoinitiator Replace "Golden Mean" Camphorquinone and Tertiary Amines in Dental Composites? Testing Experimental Composites Containing Different Concentration of Diphenyl(2,4,6-trimethylbenzoyl)phosphine Oxide.

The aim of this research was to compare the biomechanical properties of experimental composites containing a classic photoinitiating system (camphorquinone and 2-(dimethylami-no)ethyl methacrylate) or diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO) as a photoinitiator. The produced light-cured composites consisted of an organic matrix-Bis-GMA (60 wt.%), TEGDMA (40 wt.%) and silanized silica filler (45 wt.%). Composites contained 0.27; 0.5; 0.75 or 1 wt.% TPO. Vickers hardness, microhardness (in the nanoindentation test), diametral tensile strength, resistance to three-point bending and the CIE L* a* b* colorimetric analysis was performed with each composite produced. The highest average Vickers hardness values were obtained for the composite containing 1 wt.% TPO (43.18 ± 1.7HV). The diametral tensile strength remains on regardless of the type and amount of photoinitiator statistically the same level, except for the composite containing 0.5 wt.% TPO for which DTS = 22.70 ± 4.7 MPa and is the lowest recorded value. The highest average diametral tensile strength was obtained for the composite containing 0.75 wt.% TPO (29.73 ± 4.8 MPa). The highest modulus of elasticity characterized the composite containing 0.75 wt.% TPO (5383.33 ± 1067.1 MPa). Composite containing 0.75 wt.% TPO has optimal results in terms of Vickers hardness, diametral tensile strength, flexural strength and modulus of elasticity. Moreover, these results are better than the parameters characterizing the composite containing the CQ/DMAEMA system. In terms of an aesthetic composite containing 0.75 wt.%. TPO is less yellow in color than the composite containing CQ/DMAEMA. This conclusion was objectively confirmed by test CIE L* a* b*.

UV-filters in marine environments: a review of research trends, meta-analysis, and ecotoxicological impacts of 4-methylbenzylidene-camphor and benzophenone-3 on marine invertebrate communities.

The potential adverse effects of UV-filter pollution in marine environments have been the focus of research in recent years. This systematic review aims to determine the extent of this emerging problem, both quantitatively and qualitatively, combining temporal and science mapping analyses to explore the development of the field of UV-filters in the marine environment (from 1990 to 2021), and to outline new research frontiers. The temporal trend analysis revealed an exponential growth of published studies over the last decade (70% since 2016), confirming the emerging role of this topic in environmental science. The meta-analysis determined that 4-methylbenzylidene-camphor (4-MBC) and benzophenone-3 (BP-3) are top-priority environmental pollutants due to their increasing usage and, in turn, a frequent occurrence in marine ecosystems. This meta-analysis determined the focus on these two contaminants for this review. A critical discussion of the applications, regulatory aspects, and environmental occurrences of these selected compounds was provided. The present study also focused on the most recent (2015-2021) field and laboratory studies investigating the ecotoxicological impacts of 4-MBC and BP-3 on marine invertebrates. This review highlights the need for more research efforts to fill the knowledge gaps on the realistic effects these compounds may have when considered individually, in combination, or as subsequent exposures. Overall, this review aims to establish guidelines for further studies to understand the effect of UV-filters on marine ecosystems and marine invertebrate communities.

Optimization of application schedule of camphecene, a novel anti-influenza compound, based on its pharmacokinetic characteristics.

Due to high variability and rapid life cycle, influenza virus is able to develop drug resistance against direct-acting antivirals. Development of novel virus-in113039hibiting drugs is therefore important goal. Previously, we identified camphor derivative, camphecene, as an effective anti-influenza compound. In the present study, we optimize the regimen of its application to avoid high sub-toxic concentrations. The protective activity of camphecene was assessed on the model of lethal pneumonia of mice caused by influenza viruses. Camphecene was administered either once a day or four times a day, alone or in combination with Tamiflu. Mortality and viral titer in the lungs were studied. Pharmacokinetics of camphecene was studied in rabbits. We have demonstrated that camphecene, being used every 6 h at a dose of 7.5 mg/kg/day, results in antiviral effect that was statistically equal to the effect of 100 mg/kg/day once a day, that is, the same effect was achieved by 13 times lower daily dose of the drug. This effect was manifested in decrease of mortality and decrease of virus' titer in the lungs. The studies of pharmacokinetics of camphecene have demonstrated that it does not accumulate in blood plasma and that its m ultiple applications with dosage interval of 65 min are safe. In addition, the results of the study demonstrate also that camphecene possesses additive effect with Tamiflu, allowing to decrease the dose of the latter. The results suggest that due to safety and efficacy, camphecene can be further developed as potential anti-influenza remedy.

Can molecular dynamics explain decreased pathogenicity in mutant camphecene-resistant influenza virus?

ABSTARCTThe development of new anti-influenza drugs remains an active area, and efforts in this direction will likely continue far into the future. In this paper, we present the results of a theoretical study explaining the mechanisms behind the antiviral activity of camphor derivatives. These include camphecene and a number of its analogues. The compounds tested can inhibit hemagglutinin (HA) by binding to it at two possible sites. Moreover, the binding site located at the site of proteolysis is the most important. Serial passaging of influenza in the presence of camphecene leads to the formation of mutation-associated resistance. Specifically, camphecene causes a significant mutation in HA (V615L). This substitution likely reduces the affinity of the compound for the binding site due to steric restriction of the positioning of camphecene in the binding cavity. Molecular dynamics (MD) simulation results show that the mutant HA is a more stable structure in terms of thermodynamics. In other words, launching conformational rearrangements preceding the transition from pre- to post-fusion requires more energy than in wild type HA. This may well explain the lower virulence seen with the camphecene-resistant strain.

Developmental toxicity assessment of 4-MBC in Danio rerio embryo-larval stages.

Enormous production of cosmetic products and its indiscriminate use tends to discharge into the aquatic environment and might threaten non-target organisms inhabiting aquatic ecosystems. In the present study, developmental toxicity of 4-methylbenzylidene camphor (4-MBC), a widely used organic UV filter in personal care products has been evaluated using zebrafish embryo-larval stages. Waterborne exposure induced developmental toxicity and deduced 2.71 mg/L as 96 h LC50 whereas embryos exposed to sub-lethal concentrations (50 and 500 µg/L) caused a significant delay in hatching rate, heart rate, reduced larval length, and restricted hatchlings motility besides the axial curvature. Chronic exposure to 10 dpf resulted in significant decrease in SOD activity at 500 µg/L with no changes in CAT level besides a significant increase in GST enzyme at 5 µg/L concentration in 5 dpf sampled larvae. However, all the three enzymes were significantly elevated in 10 dpf larvae indicating differential oxidative stress during the stages of development. Similar trend is noticed for acetylcholine esterase enzyme activity. A concentration dependent increase in malondialdehyde content was noted in larvae sampled at 5 and 10 dpf. In addition, multixenobiotic resistance (MXR) activity inhibition, and elevated oxidative tissue damage were noticed at 5 dpf with no significant changes in 10 dpf larvae. Furthermore, immunoblot analysis confirms 4-MBC induced apoptosis in zebrafish larvae with promoted cleaved Caspase-3, Bax and inhibited Bcl-2 proteins expression. Subsequently, docking studies revealed the binding potential of 4-MBC to zebrafish Abcb4 and CYP450 8A1 proteins with the binding energy of -8.1 and -8.5 kcal/mol representing target proteins interaction and toxicity potentiation. Our results showed that 4-MBC exposure triggers oxidative stress at sub-lethal concentrations leading to apoptosis, deformities and locomotion perturbations in developing zebrafish.This is first of its kind in systematically demonstrating developmental toxicity of 4-MBC and the information shall be used for aquatic toxicity risk assessment.

Mutagenicity evaluation to UV filters of benzophenone-6, benzophenone-8, and 4-methylbenzylidene camphor by Ames test.

Benzophenone (BPs) and 4-Methylbenzylidene Camphor are used as ultraviolet (UV) filters to protect the skin and hair in personal care products. The discharging of the three chemicals may endanger the receiving water ecosystem. In the present study, the mutagenicity of BP-6, BP-8, and 4-Methylbenzylidene Camphor was tested using the Salmonella typhimurium reverse mutation test (Ames test) in the system with and without rat liver microsomal preparations (S9). Four S.typhimurium strains, TA97, TA98, TA100, and TA102 were employed in the Ames tests. The mutagenicity was detected from all three chemicals. The addition of S9 increased the mutation ratios of three chemicals to four strains, except BP-6 to TA100 strain and 4-MBC to TA97 and TA98 strain. In the mixed experiment, all positive effects were detected in the absence of S9. However, the results all became negative in the presence of S9. For the mixture of BP-6 and 4-MBC, positive results were detected on four tester strains except for the TA100 strain. For the mixture of BP-6, BP-8, and 4-MBC, positive results were detected on four strains. The mixture test results showed antagonism in mutagenicity for the mixture of BP-6 and 4-MBC to TA98 and TA100 strains and the mixture of BP-6, BP-8, and 4-MBC to TA100 and TA102 strains.

Stability study of the antiviral agent camphecene in dried blood spots at different temperatures.

In this study, an optimized procedure of sample preparation for quantitative determination of the antiviral agent camphecene in dried rat blood spots was developed. It has been shown that when using methanol containing 0.1% HCOOH as an extractant, the recovery of the substance increases in comparison with the previously developed method. In addition to this, there is no need to dilute the obtained solutions with water for the analysis of the sample by high-performance liquid chromatography (HPLC) on a column with a reversed-phase sorbent. By using the developed method, the stability of samples of dried rat blood spots containing camphecene in different concentrations at different temperatures was studied. It was found that while the samples were stored at room temperature, apparently, desorption of the substance occurs leading to a loss of more than 15% of its initial amount after 5-10 days. Lowering the temperature increases the stability of samples and their storage at -70°C is possible for 4 weeks.

Zuccagnia punctata Cav. Essential Oil into Poly(ε-caprolactone) Matrices as a Sustainable and Environmentally Friendly Strategy Biorepellent against Triatoma infestans (Klug) (Hemiptera, Reduviidae).

The main strategies against Triatoma infestans (primary vector responsible for the Chagas disease transmission) are the elimination or reduction of its abundance in homes through the application of insecticides or repellents with residual power, and environmental management through the improvement of housing. The use of plant-derived compounds as a source of therapeutic agents (i.e., essential oils from aromatic plants and their components) is a valuable alternative to conventional insecticides and repellents. Essential oil-based insect repellents are environmentally friendly and provide reliable personal protection against the bites of mosquitoes and other blood-sucking insects. This study investigates, for the first time to our knowledge, the potential repellent activity of Zuccagnia punctata essential oil (ZEO) and poly(ε-caprolactone) matrices loaded with ZEO (ZEOP) prepared by solvent casting. The analysis of its essential oil from aerial parts by GC-FID and GC-MS, MS allowed the identification of 25 constituents representing 99.5% of the composition. The main components of the oil were identified as (-)-5,6-dehydrocamphor (62.4%), alpha-pinene (9.1%), thuja-2, 4 (10)-diene (4.6%) and dihydroeugenol (4.5%). ZEOP matrices were homogeneous and opaque, with thickness of 800 ± 140 µm and encapsulation efficiency values above 98%. ZEO and ZEOP at the lowest dose (0.5% wt./wt., 96 h) showed a repellency of 33 and 73% respectively, while at the highest dose (1% wt./wt., 96 h) exhibited a repellent activity of 40 and 66 %, respectively. On the other hand, until 72 h, ZEO showed a strong repellent activity against T. infestans (88% repellency average; Class V) to both concentrations, compared with positive control N-N diethyl-3-methylbenzamide (DEET). The essential oils from the Andean flora have shown an excellent repellent activity, highlighting the repellent activity of Zuccagnia punctata. The effectiveness of ZEO was extended by its incorporation in polymeric systems and could have a potential home or peridomiciliary use, which might help prevent, or at least reduce, Chagas' disease transmission.

Acute toxicity and ecological risk assessment of 4,4'-dihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone and 4-MBC in ultraviolet (UV)-filters.

Ultraviolet (UV) filters are used in cosmetics, personal care products and packaging materials to provide sun protection for human skin and other substances. Little is known about these substances, but they continue to be released into the environment. The acute toxicity of 4,4'-dihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone and 4-MBC to Chlorella vulgaris and Daphnia magna were analyzed in this study. The 96 h-EC50 values of 4,4'-dihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone and 4-MBC on C. vulgaris were 183.60, 3.50 and 0.16874 mg/L, respectively. The 48 h-LC50 of 4,4'-dihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone and 4-MBC on D. magna were 12.50, 3.74 and 0.54445 mg/L, respectively. The toxicity of a mixture of 4,4'-dihydroxybenzophenone and 4-MBC showed addictive effect on C. vulgaris, while the toxicity of mixtures of 4,4'-dihydroxybenzophenone and 2,4,4'-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone and 4-MBC as well as 4,4'-dihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone and 4-MBC all showed antagonistic effect on C. vulgaris. The induced no-effect concentrations of 4,4'-dihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone and 4-MBC by the assessment factor (AF) method were 0.0125, 0.00350 and 0.000169 mg/L, respectively.

(+)-Camphor and (-)-borneol derivatives as potential anti-orthopoxvirus agents.

Although the World Health Organisation had announced that smallpox was eradicated over 40 years ago, the disease and other related pathogenic poxviruses such as monkeypox remain potential bioterrorist weapons and could also re-emerge as natural infections. We have previously reported (+)-camphor and (-)-borneol derivatives with an antiviral activity against the vaccinia virus. This virus is similar to the variola virus (VARV), the causative agent of smallpox, but can be studied at BSL-2 facilities. In the present study, we evaluated the antiviral activity of the most potent compounds against VARV, cowpox virus, and ectromelia virus (ECTV). Among the compounds tested, 4-bromo-N'-((1R,4R)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ylidene)benzohydrazide 18 is the most effective compound against various orthopoxviruses, including VARV, with an EC50 value of 13.9 µM and a selectivity index of 206. Also, (+)-camphor thiosemicarbazone 9 was found to be active against VARV and ECTV.

Kinetics and mechanism of 4-methylbenzylidene camphor degradation by UV-activated persulfate oxidation.

4-Methylbenzylidene camphor (4-MBC), a widely used ultraviolet (UV) filter detected in various aquatic environments, has been shown to evoke estrogenic activity. In this study, the use of UV light-activated persulfate for 4-MBC degradation is evaluated for the first time. Our results showed that the combination of UV and persulfate (UV/persulfate) can significantly remove 4-MBC, with a pseudo-first-order rate constant (kobs) of 0.1349 min-1 under the conditions of [4-MBC]0 = 0.4 µM, [persulfate]0 = 12.6 µM, and initial pH = 7. The kobs and persulfate dose exhibited a linear proportional relationship in the persulfate dose range of 4.2-42 µM. The kobs remained similar at pH 5 and pH 7 but significantly decreased at pH 9. A radical scavenging test indicated that SO4-• was the dominant species in 4-MBC degradation; the second-order rate constant of SO4-• with 4-MBC was calculated to be (2.82 ± 0.05) × 109 M-1 s-1. During the UV/persulfate reaction, 4-MBC was continuously degraded, while SO4-• was gradually converted to SO42-. 4-MBC degradation involved the hydroxylation and demethylation pathways, resulting in the generation of transformation byproducts P1 (m/z 271) and P2 (m/z 243), respectively. The Microtox® acute toxicity test (Vibrio fischeri) showed increasing toxicity during the UV/persulfate degradation of 4-MBC. The 4-MBC degradation rate was markedly lower in outdoor swimming pool water than in deionized water. Graphical abstract.

Camphorquinone alters the expression of extracellular proteases in a 3D co-culture model of the oral mucosa.

OBJECTIVE: Objective of our investigation was to determine the influence of CQ on the expression of antioxidant proteins and extracellular proteases in a 3D co-culture model (3DCCM) of the oral mucosa and to analyze the distribution and stability of CQ within 3D-CCMs. METHODS: 3D-CCMs consist of confluent keratinocytes (OKF6/TERT2) on cell culture inserts on top of human gingival fibroblasts (HGFs) in collagen. The treatment was carried out by adding CQ to the cell culture inserts at two time points with declining concentrations. Mass spectrometry was used to analyze the CQ concentration above and underneath the OKF6/TERT2-layer. The expression of antioxidant genes was analyzed by qRT-PCR and western blot. The regulation of extracellular proteases from different families was analyzed by qRT-PCR and Proteome Profiler arrays. RESULTS: GC/MS analysis showed that CQ was evenly distributed within the model. Heme oxygenase-1, NAD(P)H quinone dehydrogenase 1 (NQO1), and superoxide dismutase 1 were induced on the mRNA and protein level in OKF6/TERT2 cells. In HGFs, only the transcription of NQO1 was induced. The transcription of extracellular proteases was increased mainly in OKF6/TERT2 cells 72 h after the initial treatment. The quantity of ten out of 25 analyzed extracellular proteases in the cell culture supernatant above and six underneath the keratinocyte-layer were modulated by CQ. SIGNIFICANCE: Despite its high reactivity, CQ is able to penetrate a dense keratinocyte-layer, presumably across plasma membranes. CQ initially induced the cellular defense machinery against oxidative stress and altered the expression of extracellular proteases. We assume a relationship between both processes.

Metabolites of 4-methylbenzylidene camphor (4-MBC), butylated hydroxytoluene (BHT), and tris(2-ethylhexyl) trimellitate (TOTM) in urine of children and adolescents in Germany - human biomonitoring results of the German Environmental Survey GerES V (2014-2017).

The UV filter 4-methylbenzylidene camphor (4-MBC), used in cosmetics, the antioxidant butylated hydroxytoluene (BHT), used inter alia as a food additive and in cosmetics, and the plasticizer tris(2-ethylhexyl) trimellitate (TOTM), used mainly in medical devices as substitute for di-(2-ethylhexyl) phthalate (DEHP), are suspected to have endocrine disrupting effects. Human biomonitoring methods that allow for assessing the internal exposure of the general population to these substances were recently developed in a German cooperation to enhance the use of human biomonitoring. First-morning void urine samples from 3- to 17-year-old children and adolescents living in Germany were analysed for metabolites of 4-MBC (N = 447), BHT (N = 2091), and TOTM (N = 431) in the population-representative German Environmental Survey on Children and Adolescents 2014-2017 (GerES V). 4-MBC metabolites were found in quantifiable amounts only in single cases and exposure levels remained well below health-based guidance values. In contrast, ubiquitous exposure to BHT became evident with a geometric mean (GM) urinary concentration of the metabolite BHT acid of 2.346 µg/L (1.989 µg/gcreatinine) and a maximum concentration of 248 µg/L (269 µg/gcrea). The highest GM concentration was found in young children aged 3-5 years, yet no specific sources of exposure could be identified. Also, TOTM metabolites were found in quantifiable amounts only in very few samples. None of these findings could be related to previous hospital treatment or exposure via house dust. The presented results will be the basis to derive reference values for exposure of children and adolescents in Germany to BHT and will facilitate to identify changing exposure levels in the general population.

D-10-camphorsulfonic acid: Safety evaluation.

The safety of D-10-camphorsulfonic acid (CSA) was evaluated by genotoxicity testing and in a subchronic 90-day study in rats. Ames test and in vitro micronucleus test results, either in the absence or the presence of metabolic activation, were negative. Administration of CSA to Wistar rats in the drinking water (0.05, 0.20, or 1.00 mg/mL), for 90 days caused neither test-item-related mortality nor adverse clinical signs. The only macroscopic change seen at necropsy was enlarged testes in the high-dose animals. The 0.20 mg/mL (25 mg/kg bw/day) dose level was considered to be the no observed adverse effect level (NOAEL). A total intake calculation for consumers was performed, based on the intended maximal amount of 0.5 ppm CSA in feed, published transfer factors, and conservative tissue consumption data, resulting in 0.29 µg/kg bw/day. Therefore, the NOAEL is approximately 80,000 × the maximum estimated human exposure, a margin that is more than adequate to ensure consumer safety.

Self-Assembly of Supramolecular Architectures by the Effect of Amino Acid Residues of Quaternary Ammonium Pillar[5]arenes.

Novel water-soluble multifunctional pillar[5]arenes containing amide-ammonium-amino acid moiety were synthesized. The compounds demonstrated a superior ability to bind (1S)-(+)-10-camphorsulfonic acid (S-CSA) and methyl orange dye depending on the nature of the substituent, resulting in the formation one-to-one complexes with both guests. The formation of host-guest complexes was confirmed by ultraviolet (UV), circular dichroism (CD) and 1H NMR spectroscopy. This work demonstrates the first case of using S-CSA as a chiral template for the non-covalent self-assembly of architectures based on pillar[5]arenes. It was shown that pillar[5]arenes with glycine or L-alanine fragments formed aggregates with average hydrodynamic diameters (d) of 165 and 238 nm, respectively. It was established that the addition of S-CSA to the L-alanine-containing derivative led to the formation of micron-sized aggregates with d of 713 nm. This study may advance the design novel stereoselective catalysts and transmembrane amino acid channels.

Bis(4-methyl phenyl)iodonium as an alternative component to diphenyliodonium in camphorquinone-based ternary initiating systems.

OBJECTIVE: To evaluate the influence of different co-initiators (diphenyliodonium hexafluorophosphate - DPI - and bis(4-methyl phenyl)iodonium hexafluorophosphate - BPI) on chemical and mechanical properties of resins. METHODS: Nine experimental resins (50% Bis-GMA and 50% TEGDMA, w/w) with 60 wt% filler particles were formulated. The initiating system used was camphorquinone (CQ-1 mol%) and ethyl dimethylaminobenzoate (EDAB-2 mol%). Experimental groups were established according to DPI and BPI quantities (0.25, 0.5, 0.75, and 1 mol%). The control group was a resin containing only CQ-EDAB. Light transmission through the resin during polymerisation was analysed with a UV-vis spectrophotometer. Real-time polymerisation of the systems was evaluated using an FTIR spectrometer. Real-time polymerisation shrinkage strain was evaluated, and the flexural strength and modulus of materials were obtained by 3-point bending. Experimental groups were statistically analysed by Analysis of Variance and Tukey's test (α = 0.05). Dunnett's test was applied to compare experimental groups with control. RESULTS: Light transmission rapidly increased initially for resins containing DPI or BPI. After 30 s cure, the irradiance on the lower surface of resin specimens was similar for all groups. After 10 s of light irradiation, groups containing DPI and BPI had higher conversion than the control. However, conversion after 120 s post-irradiation was similar for all groups. The rate of polymerisation, shrinkage strain, and the maximum strain rate were higher for groups containing DPI/BPI. The use of iodonium salts increased the flexural strength and flexural moduli of resins. SIGNIFICANCE: DPI and BPI increased resin reactivity similarly. Increased rate of polymerization influenced light transmission through the resin in the first seconds of polymerisation and increased resin shrinkage and rate of shrinkage, as well as flexural strength and moduli.

A New Phosphine for Efficient Free Radical Polymerization under Air.

A new phosphine is proposed as efficient coinitiator for camphorquinone (CQ)-based photoinitiating systems for the free radical polymerization of (meth)acrylates. Remarkably, this new co-initiator can exhibit two functionalities: a phosphine moiety to overcome oxygen inhibition and an iodonium salt moiety as counter cation to initiate the polymerization process. Excellent polymerization performances in the presence of CQ for the free radical polymerization of methacrylates under blue light are observed, and amine-free systems can be easily developed from the proposed structure. The photopolymerization of composites is also investigated in the presence of the new phosphine (without iodonium counter cation) and very interesting depth of cure can be obtained from the new developed photoinitiating system after only 20 s of irradiation with a blue light-emitting diode.

Phototoxic risk assessment of dermally-applied chemicals with structural variety based on photoreactivity and skin deposition.

Combined use of photochemical and pharmacokinetic (PK) data for phototoxic risk assessment was previously proposed, and the system provided reliable phototoxic risk predictions of chemicals in same chemical series. This study aimed to verify the feasibility of the screening system for phototoxic risk assessment on dermally-applied chemicals with wide structural diversity, as a first attempt. Photochemical properties of test chemicals, 2-acetonaphthalene, 4'-methylbenzylidene camphor, 6-methylcoumarin, methyl N-methylanthranilate, and sulisobenzone, were evaluated in terms of UV absorption and reactive oxygen species (ROS) generation, and PK profiles of the test chemicals in rat skin were characterized after dermal co-application. All test chemicals showed strong UVA/B absorption with molar extinction coefficients of over 3000 M-1⋅cm-1, and irradiated 2-acetonaphthalene, 6-methylcoumarin, and methyl N-methylanthranilate exhibited significant ROS generation. Dermally-applied 2-acetonaphthalene and 4'-methylbenzylidene camphor indicated high and long-lasting skin deposition compared with the other test chemicals. Based on the photochemical and PK data, 2-acetonaphthalene was predicted to have potent phototoxic risk. The predicted phototoxic risk of the test chemicals by integration of obtained data was mostly consistent with their in vivo phototoxicity observed in rat skin. The screening strategy employing photochemical and PK data would have high prediction capacity and wide applicability for photosafety evaluation of chemicals.