Isolation and evaluation of erythroid progenitors in the livers of larval, froglet, and adult Xenopus tropicalis.

Xenopus liver maintains erythropoietic activity from the larval to the adult stage. During metamorphosis, thyroid hormone mediates apoptosis of larval-type erythroid progenitors and proliferation of adult-type erythroid progenitors, and a globin switch occurs during this time. In addition, the whole-body mass and the liver also change; however, whether there is a change in the absolute number of erythroid progenitors is unclear. To isolate and evaluate erythroid progenitors in the Xenopus liver, we developed monoclonal ER9 antibodies against the erythropoietin receptor (EPOR) of Xenopus. ER9 recognized erythrocytes, but not white blood cells or thrombocytes. The specificity of ER9 for EPOR manifested as its inhibitory effect on the proliferation of a Xenopus EPOR-expressing cell line. Furthermore, ER9 recognition was consistent with epor gene expression. ER9 staining with Acridine orange (AO) allowed erythrocyte fractionation through fluorescence-activated cell sorting. The ER9+ and AO-red (AOr)high fractions were highly enriched in erythroid progenitors and primarily localized to the liver. The method developed using ER9 and AO was also applied to larvae and froglets with different progenitor populations from adult frogs. The liver to body weight and the number of ER9+ AOrhigh cells per unit body weight were significantly higher in adults than in larvae and froglets, and the number of ER9+ AOrhigh cells per unit liver weight was the highest in froglets. Collectively, our results show increased erythropoiesis in the froglet liver and demonstrate growth-dependent changes in erythropoiesis patterns in specific organs of Xenopus.

Efficient Visible-Light-Driven CO2 Reduction by a Cobalt Molecular Catalyst Covalently Linked to Mesoporous Carbon Nitride.

Achieving visible-light-driven carbon dioxide reduction with high selectivity control and durability while using only earth abundant elements requires new strategies. Hybrid catalytic material was prepared upon covalent grafting a Co-quaterpyridine molecular complex to semiconductive mesoporous graphitic carbon nitride (mpg-C3N4) through an amide linkage. The molecular material was characterized by various spectroscopic techniques, including XPS, IR, and impedance spectroscopy. It proved to be a selective catalyst for CO production in acetonitrile using a solar simulator with a high 98% selectivity, while being remarkably robust since no degradation was observed after 4 days of irradiation (ca. 500 catalytic cycles). This unique combination of a selective molecular catalyst with a simple and robust semiconductive material opens new pathways for CO2 catalytic light-driven reduction.

Graphitic carbon nitride prepared from urea as a photocatalyst for visible-light carbon dioxide reduction with the aid of a mononuclear ruthenium(II) complex.

Graphitic carbon nitride (g-C3N4) was synthesized by heating urea at different temperatures (773-923 K) in air, and was examined as a photocatalyst for CO2 reduction. With increasing synthesis temperature, the conversion of urea into g-C3N4 was facilitated, as confirmed by X-ray diffraction, FTIR spectroscopy and elemental analysis. The as-synthesized g-C3N4 samples, further modified with Ag nanoparticles, were capable of reducing CO2 into formate under visible light (λ > 400 nm) in the presence of triethanolamine as an electron donor, with the aid of a molecular Ru(II) cocatalyst (RuP). The CO2 reduction activity was improved by increasing the synthesis temperature of g-C3N4, with the maximum activity obtained at 873-923 K. This trend was also consistent with that observed in photocatalytic H2 evolution using Pt-loaded g-C3N4. The photocatalytic activities of RuP/g-C3N4 for CO2 reduction and H2 evolution were thus shown to be strongly associated with the generation of the crystallized g-C3N4 phase.

A Carbon Nitride/Fe Quaterpyridine Catalytic System for Photostimulated CO2-to-CO Conversion with Visible Light.

Efficient and selective photostimulated CO2-to-CO reduction by a photocatalytic system consisting of an iron-complex catalyst and a mesoporous graphitic carbon nitride (mpg-C3N4) redox photosensitizer is reported for the first time. Irradiation in the visible region (λ ≥ 400 nm) of an CH3CN/triethanolamine (4:1, v/v) solution containing [Fe(qpy)(H2O)2]2+ (qpy = 2,2':6',2'':6'',2''-quaterpyridine) and mpg-C3N4 resulted in CO evolution with 97% selectivity, a turnover number of 155, and an apparent quantum yield of ca. 4.2%. This hybrid catalytic system, comprising only earth abundant elements, opens new perspectives for solar fuels production using CO2 as a renewable feedstock.

A Stable, Narrow-Gap Oxyfluoride Photocatalyst for Visible-Light Hydrogen Evolution and Carbon Dioxide Reduction.

Mixed anion compounds such as oxynitrides and oxychalcogenides are recognized as potential candidates of visible-light-driven photocatalysts since, as compared with oxygen 2p orbitals, p orbitals of less electronegative anion (e.g., N3-, S2-) can form a valence band that has more negative potential. In this regard, oxyfluorides appear unsuitable because of the higher electronegativity of fluorine. Here we show an exceptional case, an anion-ordered pyrochlore oxyfluoride Pb2Ti2O5.4F1.2 that has a small band gap (ca. 2.4 eV). With suitable modification of Pb2Ti2O5.4F1.2 by promoters such as platinum nanoparticles and a binuclear ruthenium(II) complex, Pb2Ti2O5.4F1.2 worked as a stable photocatalyst for visible-light-driven H2 evolution and CO2 reduction. Density functional theory calculations have revealed that the unprecedented visible-light-response of Pb2Ti2O5.4F1.2 arises from strong interaction between Pb-6s and O-2p orbitals, which is enabled by a short Pb-O bond in the pyrochlore lattice due to the fluorine substitution.

Undoped Layered Perovskite Oxynitride Li2 LaTa2 O6 N for Photocatalytic CO2 Reduction with Visible Light.

Oxynitrides are promising visible-light-responsive photocatalysts, but their structures are almost confined with three-dimensional (3D) structures such as perovskites. A phase-pure Li2 LaTa2 O6 N with a layered perovskite structure was successfully prepared by thermal ammonolysis of a lithium-rich oxide precursor. Li2 LaTa2 O6 N exhibited high crystallinity and visible-light absorption up to 500 nm. As opposed to well-known 3D oxynitride perovskites, Li2 LaTa2 O6 N supported by a binuclear RuII complex was capable of stably and selectively converting CO2 into formate under visible light (λ>400 nm). Transient absorption spectroscopy indicated that, as compared to 3D oxynitrides, Li2 LaTa2 O6 N possesses a lower density of mid-gap states that work as recombination centers of photogenerated electron/hole pairs, but a higher density of reactive electrons, which is responsible for the higher photocatalytic performance of this layered oxynitride.

Interfacial Manipulation by Rutile TiO2 Nanoparticles to Boost CO2 Reduction into CO on a Metal-Complex/Semiconductor Hybrid Photocatalyst.

Metal-complex/semiconductor hybrids have attracted attention as photocatalysts for visible-light CO2 reduction, and electron transfer from the metal complex to the semiconductor is critically important to improve the performance. Here rutile TiO2 nanoparticles having 5-10 nm in size were employed as modifiers to improve interfacial charge transfer between semiconducting carbon nitride nanosheets (NS-C3N4) and a supramolecular Ru(II)-Re(I) binuclear complex (RuRe). The RuRe/TiO2/NS-C3N4 hybrid was capable of photocatalyzing CO2 reduction into CO with high selectivity under visible light (λ > 400 nm), outperforming an analogue without TiO2 by a factor of 4, in terms of both CO formation rate and turnover number (TON). The enhanced photocatalytic activity was attributed primarily to prolonged lifetime of free and/or shallowly trapped electrons generated in TiO2/NS-C3N4 under visible-light irradiation, as revealed by transient absorption spectroscopy. Experimental results also indicated that the TiO2 modifier served as a good adsorption site for RuRe, which resulted in the suppression of undesirable desorption of the complex, thereby contributing to the improved photocatalytic performance. This study presents the first successful example of interfacial manipulation in a metal-complex/semiconductor hybrid photocatalyst for improved visible-light CO2 reduction to produce CO.

Robust Binding between Carbon Nitride Nanosheets and a Binuclear Ruthenium(II) Complex Enabling Durable, Selective CO2 Reduction under Visible Light in Aqueous Solution.

Carbon nitride nanosheets (NS-C3 N4 ) were found to undergo robust binding with a binuclear ruthenium(II) complex (RuRu') even in basic aqueous solution. A hybrid material consisting of NS-C3 N4 (further modified with nanoparticulate Ag) and RuRu' promoted the photocatalytic reduction of CO2 to formate in aqueous media, in conjunction with high selectivity (approximately 98 %) and a good turnover number (>2000 with respect to the loaded Ru complex). These represent the highest values yet reported for a powder-based photocatalytic system during CO2 reduction under visible light in an aqueous environment. We also assessed the desorption of RuRu' from the Ag/C3 N4 surface, a factor that can contribute to a loss of activity. It was determined that desorption is not induced by salt additives, pH changes, or photoirradiation, which partly explains the high photocatalytic performance of this material.

Development of hybrid photocatalysts constructed with a metal complex and graphitic carbon nitride for visible-light-driven CO2 reduction.

Photocatalytic CO2 reduction with visible light has long been studied as a potential means to address the problems of global warming and the depletion of fossil fuels. Hybrid systems that consist of a metal complex and a particulate semiconductor are expected to be promising because of the excellent electrochemical (and/or photocatalytic) ability of metal complexes for CO2 reduction and the high efficiency of semiconductors for water oxidation. However, a satisfactory system has not been developed to date. Our group has been developing such hybrid materials for visible-light-driven CO2 reduction. This Perspective highlights our recent progress in the development of metal-complex/semiconductor hybrid materials for photocatalytic CO2 reduction with a focus on graphitic carbon nitride as the semiconductor component.

Nature-Inspired, Highly Durable CO2 Reduction System Consisting of a Binuclear Ruthenium(II) Complex and an Organic Semiconductor Using Visible Light.

A metal-free organic semiconductor of mesoporous graphitic carbon nitride (C3N4) coupled with a Ru(II) binuclear complex (RuRu') containing photosensitizer and catalytic units selectively reduced CO2 into HCOOH under visible light (λ > 400 nm) in the presence of a suitable electron donor with high durability, even in aqueous solution. Modification of C3N4 with Ag nanoparticles resulted in a RuRu'/Ag/C3N4 photocatalyst that exhibited a very high turnover number (>33000 with respect to the amount of RuRu'), while maintaining high selectivity for HCOOH production (87-99%). This turnover number was 30 times greater than that reported previously using C3N4 modified with a mononuclear Ru(II) complex, and by far the highest among the metal-complex/semiconductor hybrid systems reported to date. The results of photocatalytic reactions, emission decay measurements, and time-resolved infrared spectroscopy indicated that Ag nanoparticles on C3N4 collected electrons having lifetimes of several milliseconds from the conduction band of C3N4, which were transferred to the excited state of RuRu', thereby promoting photocatalytic CO2 reduction driven by two-step photoexcitation of C3N4 and RuRu'. This study also revealed that the RuRu'/Ag/C3N4 hybrid photocatalyst worked efficiently in water containing a proper electron donor, despite the intrinsic hydrophobic nature of C3N4 and low solubility of CO2 in an aqueous environment.

Unique Solvent Effects on Visible-Light CO2 Reduction over Ruthenium(II)-Complex/Carbon Nitride Hybrid Photocatalysts.

Photocatalytic CO2 reduction using hybrids of carbon nitride (C3N4) and a Ru(II) complex under visible light was studied with respect to reaction solvent. Three different Ru(II) complexes, trans(Cl)-[Ru(X2bpy) (CO)2Cl2] (X2bpy = 2,2'-bipyridine with substituents X in the 4-positions, X = COOH, PO3H2, or CH2PO3H2), were employed as promoters and will be abbreviated as RuC (X = COOH), RuP (X = PO3H2), and RuCP (X = CH2PO3H2). When C3N4 modified with a larger amount of RuCP (>7.8 µmol g(-1)) was employed as a photocatalyst in a solvent having a relatively high donor number (e.g., N,N-dimethylacetamide (DMA), N,N-dimethylformamide (DMF), and dimethyl sulfoxide (DMSO)) with the aid of triethanolamine (TEOA) as an electron donor, the hybrid photocatalyst exhibited high performance for CO2 reduction, producing CO and HCOOH with relatively high CO selectivity (40-70%). On the other hand, HCOOH was the major product when RuC/C3N4 or RuP/C3N4 was employed regardless of the loading amount of the Ru(II) complex and the reaction solvent. Results of photocatalytic reactions and UV-visible diffuse reflectance spectroscopy indicated that polymeric Ru species, which were formed in situ from RuCP on C3N4 under irradiation in a solvent having a high donor number, were active catalysts for CO formation. Nonsacrificial CO2 reduction using RuP/C3N4 was accomplished in a DMA solution containing methanol as an electron donor, which means that visible light energy was stored as chemical energy in the form of CO and formaldehyde (ΔG° = +67.6 kJ mol(-1)). This study demonstrated the first successful example of an energy conversion scheme using carbon nitride through photocatalytic CO2 reduction.

Visible-light-driven CO2 reduction with carbon nitride: enhancing the activity of ruthenium catalysts.

A heterogeneous photocatalyst system that consists of a ruthenium complex and carbon nitride (C3N4), which act as the catalytic and light-harvesting units, respectively, was developed for the reduction of CO2 into formic acid. Promoting the injection of electrons from C3N4 into the ruthenium unit as well as strengthening the electronic interactions between the two units enhanced its activity. The use of a suitable solvent further improved the performance, resulting in a turnover number of greater than 1000 and an apparent quantum yield of 5.7% at 400 nm. These are the best values that have been reported for heterogeneous photocatalysts for CO2 reduction under visible-light irradiation to date.