Physiological and Transcriptional Effects of Mixtures of Environmental Estrogens, Androgens, Progestins, and Glucocorticoids in Zebrafish.

Fishes are exposed to mixtures of different classes of steroids, but ecotoxicological implications are not sufficiently known. Here, we systematically analyze effects of different combinations of steroid mixtures in zebrafish embryos to assess their joint activities on physiology and transcriptional alterations of steroid-specific target genes at 96 and 120 h post fertilization. In binary mixtures of clobetasol propionate (CLO) with estradiol (E2) or androstenedione (A4), each steroid exhibited its own expression profile. This was also the case in mixtures of 5-, 8-, and 13-different classes of steroids in exposure concentrations of 10-10,000 ng/L. The transcriptional expression of most genes in different mixtures was steroid-specific except for genes encoding aromatase (cyp19b), sulfotransferase (sult2st3), and cyp2k22 that were induced by androgens, progestins, and glucocorticoids. Marked alterations occurred for sult2st3 in binary mixtures of CLO + E2 and CLO + A4. Glucocorticoids increased the heart rate and muscle contractions. In mixtures containing estrogens, induction of the cyp19b transcript occurred at 10 ng/L and protc from the anticoagulation system at 100 ng/L. Our study demonstrates that steroids can act independently in mixtures; the sum of individual steroid profiles is expressed. However, some genes, including cyp19b, sult2st3, and cyp2k22, are regulated by several steroids. This joint effect on different pathways may be of concern for fish development.

Synthesis and characterization of bicontinuous cubic poly(3,4-ethylene dioxythiophene) gyroid (PEDOT GYR) gels.

We describe the synthesis and characterization of bicontinuous cubic poly(3,4-ethylenedioxythiophene) (PEDOT) conducting polymer gels prepared within lyotropic cubic poly(oxyethylene)10 nonylphenol ether (NP-10) templates with Ia3[combining macron]d (gyroid, GYR) symmetry. The chemical polymerization of EDOT monomer in the hydrophobic channels of the NP-10 GYR phase was initiated by AgNO3, a mild oxidant that is activated when exposed to ultraviolet (UV) radiation. The morphology and physical properties of the resulting PEDOT gels were examined as a function of temperature and frequency using optical and electron microscopy, small-angle X-ray scattering (SAXS), dynamic mechanical spectroscopy, and electrochemical impedance spectroscopy (EIS). Microscopy and SAXS results showed that the PEDOT gels remained ordered and stable after the UV-initiated chemical polymerization, confirming the successful templated-synthesis of PEDOT in bicontinuous GYR nanostructures. In comparison to unpolymerized 3,4-ethylenedioxythiophene (EDOT) gel phases, the PEDOT structures had a higher storage modulus, presumably due to the formation of semi-rigid PEDOT-rich nanochannels. Additionally, the storage modulus (G') for PEDOT gels decreased only modestly with increasing temperature, from ∼1.2 × 10(5) Pa (10 °C) to ∼7 × 10(4) Pa (40 °C), whereas G' for the NP-10 and EDOT gels decreased dramatically, from ∼5.0 × 10(4) Pa (10 °C) to ∼1.5 × 10(2) Pa (40 °C). EIS revealed that the impedance of the PEDOT gels was smaller than the impedance of EDOT gels at both high frequencies (PEDOT ∼10(2) Ω and EDOT 2-3 × 10(4) Ω at 10(5) Hz) and low frequencies (PEDOT 10(3)-10(5) Ω and EDOT ∼5 × 10(5) Ω at 10(-1) Hz). These results indicated that PEDOT gels were highly ordered, mechanically stable and electrically conductive, and thus should be of interest for applications for which such properties are important, including low impedance and compliant coatings for biomedical electrodes.

Interfacial manipulations: controlling nanoscale assembly in bulk, thin film, and solution block copolymer systems.

Nanostructured soft materials from self-assembled block copolymers (BCP)s and polymer blends can enable the reliable, high-throughput, and cost-effective generation of nanoscale structural motifs for many emerging technologies. Our research group has studied the phase behavior of BCPs in bulk, thin film, and solution environments with a particular focus on using interfacial manipulations to control self-assembly and to access a vast array of nanoscale morphologies and orientations. These interfacial manipulations can be synthetic alterations that are directly incorporated into the BCP chain to modify polymer-polymer interactions, post-polymerization and non-synthetic modifications that affect block interactions, or changes to the polymer specimen's external surroundings to control self-assembly in a confining environment. Herein, we describe methods that we have employed to manipulate BCP self-assembly for various application targets, and we discuss the key effects of such manipulations on the resulting nanoscale morphologies.

Double-Gyroid Network Morphology in Tapered Diblock Copolymers.

We report the formation of a double-gyroid network morphology in normal-tapered poly(isoprene-b-isoprene/styrene-b-styrene) [P(I-IS-S)] and inverse-tapered poly(isoprene-b- styrene/isoprene-b-styrene) [P(I-SI-S)] diblock copolymers. Our tapered diblock copolymers with overall poly(styrene) volume fractions of 0.65 (normal-tapered) and 0.67 (inverse-tapered), and tapered regions comprising 30 volume percent of the total polymer, were shown to self-assemble into the double-gyroid network morphology through a combination of small angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). The block copolymers were synthesized by anionic polymerization, where the tapered region between the pure poly(isoprene) and poly(styrene) blocks was generated using a semi-batch feed with programmed syringe pumps. The overall composition of these tapered copolymers lies within the expected network-forming region for conventional poly(isoprene-b-styrene) [P(I-S)] diblock copolymers. Dynamic mechanical analysis (DMA) clearly demonstrated that the order-disorder transition temperatures (T(ODT)'s) of the network-forming tapered block copolymers were depressed when compared to the T(ODT) of their non-tapered counterpart, with the P(I-SI-S) showing the greater drop in T(ODT). These results indicate that it is possible to manipulate the copolymer composition profile between blocks in a diblock copolymer, allowing significant control over the T(ODT), while maintaining the ability to form complex network structures.