Kisspeptin stimulates sheep ovarian follicular development in vitro through homologous receptors.

The present study was conducted to elucidate (1) the influence of kisspeptin (KP) on the in vitro development of preantral follicles (PFs) and (2) evolution of KP receptor gene (KISS1R) expression during ovarian follicular development in sheep. Kisspeptin was supplemented (0-100 µg/ml) in the culture medium of PFs for 6 days. The cumulus-oocyte complexes (COCs) from cultured PFs were subsequently matured to metaphase II (MII) for an additional 24 h. The proportions of PFs exhibiting growth, antrum formation, average increase in diameter, and maturation of oocytes to MII stage were the indicators of follicular development in vitro. The expression of the kisspeptin receptor gene at each development stages of in vivo developed (preantral, early antral, antral, large antral and COCs from Graafian follicles) and in vitro cultured PFs supplemented with KP was assessed using a real-time polymerase chain reaction. The best development in all the parameters under study was elicited with 10 µg/ml of KP. Supplementation of KP (10 µg/ml) in a medium containing other growth factors (insulin-like growth factor-I) and hormones (growth hormone, thyroxine, follicle-stimulating hormone) resulted in better PF development. The KISS1R gene was expressed in follicular cells and oocytes at all the development stages of both in vivo developed and in vitro cultured follicles. Higher KISS1R gene expression was supported by culture medium containing KP along with other hormones and growth factors. Accordingly, it is suggested that one of the mechanisms through which KP and other growth factors and hormones influence the ovarian follicular development in mammals is through the upregulation of expression of the KP receptor gene.

Acid-Modulated Synthesis of Novel π-Conjugated Microporous Polymers for Efficient Metal-Free Photocatalytic Hydrogen Evolution.

Simple synthetic modifications that tune the molecular structures, thereby the properties of the molecules, are of topical interest. Herein, we report the synthesis of two novel cationic rosaniline-based conjugated microporous polymers (CMPs) from identical monomers via simple acid modulation (Acetic acid and BF3 ⋅ Et2 O). The condensation reaction of rosaniline with 2,4,6-triformylphloroglucinol in acetic acid renders ß-ketoenamine-linked CMP (CMP-A) while changing the acid to BF3 ⋅ Et2 O, the linkages transform to enol and undergoes BF2 -complexation, leading to boranil CMP (CMP-B). BF2 -functionalities in boranil CMP significantly modified the optical and functional properties compared to ß-ketoenamine-linked CMP. The cationic-delocalization along with the extended π-delocalization supported by chromophoric BF2 -groups allow CMP-B to exhibit broad absorption spanning the visible to Near-Infrared region (NIR). The absorption red-edge of CMP-B appears around 1277 nm (optical band gap ∼1.58 eV) while CMP-A displays at 981 nm (optical band gap ∼1.83 eV). Most interestingly, as a photocatalyst, CMP-B catalyzes hydrogen evolution with a superior rate of 252 µmol g-1 over CMP-A (100 µmol g-1 ). It is about 2.5 times higher performance. The transient photocurrent measurements, electrochemical impedance data, and in-depth mott-Schottky analysis demonstrate that the BF2 -group in CMP-B generates photoinduced charge carriers and their migration towards the active sites for photocatalysis. These polymers show significant photocatalytic H2 generation without any supportive metal co-catalyst. The BF2 complexed building blocks are a unique class of metal-free photocatalysts for hydrogen evolution through green and cost-effective approach.

Low-cost electrochemical detection of l-tyrosine using an rGO-Cu modified pencil graphite electrode and its surface orientation on a Ag electrode using an ex situ spectroelectrochemical method.

A low cost reduced graphene oxide-copper hybrid nano thin-film modified Pencil Graphite Electrode has been employed to detect the l-tyrosine enantiomer. The free-standing rGO-Cu hybrid nano-thin film was prepared by a simple one-step liquid-liquid interface method. Electrochemical Cyclic Voltammetry, Differential Pulse Voltammetry, pH-dependent and scan rate dependent studies on bare PGE, Cu, rGO, and rGO-Cu for l-tyrosine have been explained in detail. The rGO-Cu modified PGE based biosensor exhibits good detection of l-tyrosine. The linear range detection limit was estimated to be 1 × 10-7 M. The calculated sensitivity is 0.4 µA ppm-1 mm2. This electroactive biosensor is easily fabricated and controlled and is cost-effective. The surface orientation of l-tyrosine on the Ag electrode at a particular potential and its comparison with vibrational DFT calculations have been studied for the first time.

Single sea urchin-MoO3 nanostructure for surface enhanced Raman spectroscopy of dyes.

Enhancing the surface-enhanced Raman scattering (SERS) activity of semiconductor metal oxide nanostructures by controlling the morphology and oxygen vacancies towards trace detection of organics is of significant interest. In this study, MoO3 with a novel sea urchin morphology is synthesized employing chemical bath deposition and consists of hundreds of ∼15 µm long spikes originating from the core forming 20-40 micron globular structures. The spikes taper to form 20 nm sharp tips. SERS of rhodamine 6G (R6G) over MoO3 sea urchins has been investigated and compared to that of 1D h-MoO3 nanorod arrays. The SERS activity is morphology dependent and the sea urchin-like morphology exhibits higher SERS activity with an enhancement factor (EF) of the order 105 and a detection limit of 100 nM, while for h-MoO3 nanorods, the corresponding values are 103 and 1 µM, respectively. X-ray photoelectron spectroscopy reveals a high concentration of Mo+5 states in sea urchins indicating lattice oxygen vacancies. The observed EF is quite high for a metal oxide substrate and is attributed to the enhanced charge transfer between analyte molecules and the substrate promoted by the oxygen vacancies along with surface defects and hydroxyl groups on MoO3 sea urchins providing more active sites for the adsorption of probe molecules. The role of oxygen vacancies is confirmed by the lower EF value exhibited by the stoichiometric 1D h-MoO3. Raman mapping of a single sea urchin is achieved with good R6G intensity and indicates that the tips of spiky features are involved in SERS enhancement. The reusability of substrates is shown for repeated cycles of R6G adsorption by UV irradiation exploiting the photocatalytic activity of MoO3 nanostructures.

Improved surface-enhanced Raman and catalytic activities of reduced graphene oxide-osmium hybrid nano thin films.

Reduced graphene oxide-osmium (rGO-Os) hybrid nano dendtrites have been prepared by simple liquid/liquid interface method for the first time. The method involves the introduction of phase-transfered metal organic precursor in toluene phase and GO dispersion in the aqueous phase along with hydrazine hydrate as the reducing agent. Dendritic networks of Os nanoparticles and their aggregates decorating rGO layers are obtained. The substrate shows improved catalytic and surface-enhanced activities comparable with previous reports. The catalytic activity was tested for the reduction of p-nitroaniline into p-phenyldiamine with an excess amount of NaBH4. The catalytic activity factors of these hybrid films are 2.3 s-1 g-1 (Os film) and 4.4 s-1 g-1 (rGO-Os hybrid film), which are comparable with other noble metal nanoparticles such as Au, Ag, but lower than Pd-based catalysts. Surface-enhanced Raman spectroscopy (SERS) measurements have been done on rhodamine 6G (R6G) and methylene blue dyes. The enhancement factor for the R6G adsorbed on rGO-Os thin film is 1.0 × 105 and for Os thin film is 7 × 103. There is a 14-fold enhancement observed for Os hybrids with rGO. The enhanced catalytic and SERS activities of rGO-Os hybrid thin film prepared by simple liquid/liquid interface method open up new challenges in electrocatalytic application and SERS-based detection of biomolecules.

Films of Reduced Graphene Oxide with Metal Oxide Nanoparticles Formed at a Liquid/Liquid Interface as Reusable Surface Enhanced Raman Scattering Substrates for Dyes.

Free standing, thin films of reduced graphene oxide (rGO) with ZnO, CuO and SnO(2) nanostructures are prepared at a water/toluene interface utilizing simple interfacial reaction and self-assembly. rGO-ZnO, rGO-CuO and rGO-SnO(2) films exhibit unique morphologies such as hexagonal cylinders, elongated splinters, and balls, respectively, wrapped by rGO layers. The hybrid films exhibit surface enhanced Raman scattering (SERS) of rhodamine 6G dye with enhancement factors one order higher than bare metal oxide caused by a synergic effect of charge transfer between the dye, metal oxide and rGO. Doping with Ag+ ions improves SERS enhancement in rGO-Ag­ZnO hybrid films, exploiting the electromagnetic effect of metal surface plasmons. Detection sensitivity up to 10 µM dye with an enhancement factor of 104 is shown. The enhanced photodegradation rate by the hybrid films is utilized for UV induced regeneration of the used SERS substrate and is demonstrated for successive use of different analytes.

Hybrid materials of ZnO nanostructures with reduced graphene oxide and gold nanoparticles: enhanced photodegradation rates in relation to their composition and morphology.

Binary and ternary hybrid systems of ZnO possessing nanoparticle and nanorod morphologies on reduced graphene oxide (rGO) and rGO with Au nanoparticles are explored as photocatalysts and a comparative study of their photodegradation performance is presented. Various preparation methods such as solution phase and hydrothermal routes have been employed to produce rGO-ZnO hybrids and rGO-Au-ZnO hybrids to impart different morphologies and defect states in ZnO. All the hybrids exhibit faster photodegradation kinetics and the rGO-Au-ZnO system exhibits the highest rate, five times faster than bare ZnO, followed by the binary systems, rGO-ZnO nanoparticles and nanorods. Various factors such as structure, morphology, charge transfer and adsorption are considered to explain the observed kinetics. Excited state electron transfer from ZnO to both rGO and Au levels facilitates faster dye degradation for rGO-Au-ZnO and is reflected as highly quenched band edge and defect state photoluminescence. Intimate physical interfaces formed between rGO, Au and ZnO in the hybrid material during in situ reactions favour charge transfer across the components. The charge transfer contribution even dominates the adsorption factor and the rGO-Au-ZnO system with a slightly lower adsorption capacity than the rGO-ZnO system exhibits a higher degradation rate. A power law dependence of the photodegradation rate on light intensity is also expressed.