Two Photochromic Complexes Assembled by a Nonphotochromic Ligand: Photogenerated Radical Enhanced Room-Temperature Phosphorescence.

Stimulating tunable room-temperature phosphorescence (RTP) is still a challenge in photochromic systems, which is vital for multifunctional coordination materials. Herein, we synthesized two new photochromic chain complexes through self-assembly of the nonphotochromic 1,3,5-tris(4-pyridyl)benzene ligand, diphosphonate, and Ln(III) ions (1 for Ln(III) = Dy and 2 for Ln(III) = Gd). Both compounds showed fast photoresponses with the color turning from yellow to dark gray with a reversible decoloration by heating or storage in the dark. The electron transfer photochromic behavior with the generated stable radicals was further confirmed by the room-temperature UV-vis and electron paramagnetic resonance spectra. Furthermore, via tuning the generation and disappearance of stable radicals, reversible room-temperature fluorescence and phosphorescence for both compounds were switched by light irradiation and a thermal treatment, with an enhanced intensity for RTP and a decrease in fluorescence during the duration of Xe-lamp light irradiation. This work provides a new strategy that photogenerated radicals could promote and enhance RTP properties in functional materials.

Bisphenol F Disrupts Thyroid Hormone Signaling and Postembryonic Development in Xenopus laevis.

The safety of bisphenol A (BPA) alternatives has attracted much attention due to their wide use. In this study, we investigated the effects of bisphenol F (BPF), an alternative to BPA, on thyroid hormone (TH) signaling and postembryonic development in vertebrates using T3-induced and spontaneous Xenopus metamorphosis as models. We found that in the T3-induced metamorphosis assay, higher concentrations of BPF (100-10000 nM) antagonized T3-induced TH-response gene transcription and morphological changes including intestinal remodeling in a concentration-dependent manner, whereas 10 nM BPF exerted stimulatory effects on T3-induced integral metamorphosis when inhibited T3-induced TH-response gene transcription, demonstrating TH signaling disrupting effects of BPF. In the spontaneous metamorphosis assay, correspondingly, BPF inhibited development at metamorphic climax (with high endogenous TH levels), but promoted pre- and pro-metamorphic development (with low endogenous TH levels), displaying a developmental stage-dependent manner. Importantly, we observed agonistic actions of BPF on Notch signaling in intestines, showing that BPF disrupts vertebrate development possibly via multi pathways besides TH signaling. Thus, we infer the biphasic concentration-response relationship between BPF exposure and T3-induced metamorphosis could result from the interactions of TH signaling with other signaling pathways such as Notch signaling. Our study highlights the adverse influences of BPF on vertebrate development.

Tetrabromobisphenol A disrupts vertebrate development via thyroid hormone signaling pathway in a developmental stage-dependent manner.

Data concerning effects of tetrabromobisphenol A (TBBPA) on thyroid hormone (TH)-dependent vertebrate development have been limited, although TBBPA has been demonstrated in vitro to disrupt the TH signaling pathway at the transcriptional level. In this study, we investigated the effects of TBBPA on T3-induced and spontaneous Xenopus laevis metamorphosis, which share many similarities with TH-dependent development in higher vertebrates. In a 6-day T3-induced metamorphosis assay using premetamorphic tadpoles, 10-1000 nM TBBPA exhibited inhibitory effects on T3-induced expression of TH-response genes and morphological changes in a concentration-dependent manner, with a weak stimulatory action on tadpole development and TH-response gene expression in the absence of T3 induction. In a spontaneous metamorphosis assay, we further found that TBBPA promoted tadpole development from stage 51 to 56 (pre- and prometamorphic stages) but inhibited metamorphic development from stage 57 to 66 (metamorphic climax). These results strongly show that TBBPA, even at low concentrations, disrupts TH-dependent development in a developmental stage-dependent manner, i.e., TBBPA exhibits an antagonistic activity at the developmental stages when animals have high endogenous TH levels, whereas it acts as an agonist at the developmental stages when animals have low endogenous TH levels. Our study highlights the adverse influences of TBBPA on TH-dependent development in vertebrates.

Synergism of Light-Induced [4 + 4] Cycloaddition and Electron Transfer Toward Switchable Photoluminescence and Single-Molecule Magnet Behavior in a Dy4 Cubane.

Molecular materials possessing switchable magneto-optical properties are of great interest due to their potential applications in spintronics and molecular devices. However, switching their photoluminescence (PL) and single-molecule magnet (SMM) behavior via light-induced structural changes still constitutes a formidable challenge. Here, a series of cubane structures were synthesized via self-assembly of 9-anthracene carboxylic acid (HAC) and rare-earth ions. All complexes exhibited obvious photochromic phenomena and complete PL quenching upon Xe lamp irradiation, which were realized via the synergistic effect of photogenerated radicals and [4 + 4] photocycloaddition of the AC components. The quenched PL showed the largest fluorescence intensity change (99.72%) in electron-transfer photochromic materials. A reversible decoloration process was realized via mechanical grinding, which is unexpectedly in the electron-transfer photochromic materials. Importantly, an SMM behavior of the Dy analog was observed after room-temperature irradiation due to the photocycloaddition of AC ligands and the photogenerated stable radicals changed the electrostatic ligand field and magnetic coupling. Moreover, based on the remarkably photochromic and photoluminescent properties of these compounds, 2 demos were applied to support their application in information anti-counterfeiting and inkless printing. This work, for the first time utilizing the simultaneous modulation of photocycloaddition and photogenerated radicals in one system, realizes complete PL quenching and light-induced SMM behavior, providing a dynamical switch for the construction of multifunctional polymorphic materials with optical response and optical storage devices.

Effects of perfluorooctanesulfonate and perfluorobutanesulfonate on the growth and sexual development of Xenopus laevis.

Perfluorobutanesulfonate (PFBS), as a substitute for perfluorooctanesulfonate (PFOS), is widespread in the environment and biotic samples as well as PFOS. To investigate effects of PFOS and PFBS on the growth and sexual development of amphibians, we exposed Xenopus laevis tadpoles at a series of concentrations of PFOS and PFBS (0.1; 1; 100; 1,000 µg/l) as well as 17-beta-estradiol (E2, 100 ng/l) and 5 alpha-androstan-17-beta-ol-3-one (DHT, 100 ng/l) from stage 46/47 to 2 months postmetamorphosis. We found that neither PFOS nor PFBS had a significant effect on the survival and growth. However, they caused hepatohistological impairment at higher concentrations (100; 1,000 µg/l). Unlike E2, PFOS at all concentrations did not alter the sex ratio and induce intersex, but caused degeneration of spermatogonia in testes except for the lowest concentration. PFBS had no effect on the sex ratio and gonadal histology. PFOS and PFBS promoted expression of estrogen receptor (ER) and androgen receptor (AR), but not affected aromatase expression in the brain. The increase in expression of ER and AR suggests an increase in the responsiveness to the corresponding sex hormone and potential effects on sexual development. Our results show that PFBS as well as PFOS have adverse effects on hepato-histology and sexual development on X. laevis. Also, PFOS- and PFBS-induced increase in ER and AR expression highlights the need to further study effects of PFOS and PFBS on subsequently gonadal development, sexual dimorphism, and secondary sex characteristics in X. laevis. It is debatable that PFBS is widely used as a substitute of PFOS.

Light actuated stable radicals of the 9-anthracene carboxylic acid for designing new photochromic complexes.

The photogeneration of stable radicals is important but still challenging in the field of optical switching, displays, and other devices. Herein, crystalline 9-anthracene carboxylic acid (9-AC) and a mononuclear complex constructed from this ligand were for the first time discovered to show radical-induced photochromism and photomagnetism after Xe lamp light irradiation. This study finds a simple radical-actuated photochromic molecule for constructing a novel system of photochromic materials.

Reductions of bacterial antibiotic resistance through five biological treatment processes treated municipal wastewater.

Wastewater treatment plants are hot spots for antibiotic-resistant bacteria (ARB) and antibiotic resistance genes (ARGs). However, limited studies have been conducted to compare the reductions of ARB and ARGs by various biological treatment processes. The study explored the reductions of heterotrophic bacteria resistant to six groups of antibiotics (vancomycin, gentamicin, erythromycin, cephalexin, tetracycline, and sulfadiazine) and corresponding resistance genes (vanA, aacC1, ereA, ampC, tetA, and sulI) by five bench-scale biological reactors. Results demonstrated that membrane bioreactor (MBR) and sequencing batch reactor (SBR) significantly reduced ARB abundances in the ranges of 2.80∼3.54 log and 2.70∼3.13 log, respectively, followed by activated sludge (AS). Biological filter (BF) and anaerobic (upflow anaerobic sludge blanket, UASB) techniques led to relatively low reductions. In contrast, ARGs were not equally reduced as ARB. AS and SBR also showed significant potentials on ARGs reduction, whilst MBR and UASB could not reduce ARGs effectively. Redundancy analysis implied that the purification of wastewater quality parameters (COD, NH4 (+)-N, and turbidity) performed a positive correlation to ARB and ARGs reductions.

Low concentrations of 17ß-trenbolone induce female-to-male reversal and mortality in the frog Pelophylax nigromaculatus.

Trenbolone, as a growth promoter in animal agriculture, has become an environmental androgen in surface water. Here, we aimed to reveal the effects of 17ß-trenbolone on survival, growth, and gonadal differentiation in the frog Pelophylax nigromaculatus, which is widespread in East Asia and undergoing population decline. P. nigromaculatus tadpoles were exposed to 17ß-trenbolone (0.1, 1, 10 µg/L) from Gosner stage 24/25 to complete metamorphosis. We found that 17ß-trenbolone resulted in significantly high mortality in a concentration-dependent manner, with a decrease in body weight in the high concentration group compared with the solvent control. Based on gross gonadal morphology, no females were observed, instead of about 15% ambiguous sexes and 85% males, in all 17ß-trenbolone treatment groups. Like normal testes, the gonads with sex-ambiguous morphology exhibited testicular histology, showing that the sex-ambiguous gonads were incomplete ovary-to-testis reversals (IOTTRs) with certain ovarian morphological features. In the IOTTRs, the transcriptional levels of ovary-biased genes decreased drastically relative to normal ovaries, and even declined to the levels in normal testes. These observations confirmed that all test concentrations of 17ß-trenbolone resulted in 100% sex reversal, although some sex-reversed testes retained some ovarian characteristics at the morphological level. To our knowledge, this is the first report strongly demonstrating that trenbolone can cause female-to-male reversal in amphibians. Given that the lowest concentration tested is environmentally relevant, our study highlights the risks of trenbolone and other environmental androgens for P. nigromaculatus and other amphibians, in particular the species with high sensitivity of gonadal differentiation to androgenic chemicals.

Environmental (anti-)androgenic chemicals affect germinal vesicle breakdown (GVBD) of Xenopus laevis oocytes in vitro.

Progesterone-induced germinal vesicle breakdown (GVBD) of Xenopus oocytes in vitro was used to study endocrine disrupting activity of chemicals in previous studies. In this study, we investigated for the first time effects of environmental androgens on oocyte maturation and effects of anti-androgens on androgen-induced oocyte maturation, using Xenopus GVBD in vitro. Trenbolone and nandrolone, two environmental androgens, were found to induce Xenopus GVBD at low concentrations. The potential of trenbolone to induce GVBD was approximately 100-fold lower than that of testosterone, while nandrolone had a several-fold lower potential than testosterone. Our findings have aroused new concerns for effects of environmental androgens on amphibian oocyte maturation at environmentally relevant concentrations, and suggested that Xenopus GVBD can be used to test androgenic activity of suspicious environmental androgens. Androgen receptor (AR) antagonist flutamide at 10 µM only exhibited a weakly inhibitory effect on androgen-induced GVBD, while another known AR antagonist vinclozolin had no effect even at high concentrations. The results show that Xenopus GVBD is not sensitive to AR-mediated environmental anti-androgens. In contrast to flutamide and vinclozolin, methoxychlor (a weaker AR antagonist) inhibited dramatically androgen-induced GVBD, suggesting that androgen-induced Xenopus GVBD can be used to study non-AR-mediated effects of chemicals on oocyte maturation.