Facile synthesis of reduced graphene oxide-gold nanohybrid for potential use in industrial waste-water treatment

Here, we report a facile approach, by the photochemical reduction technique, for in situ synthesis of Au-reduced graphene oxide (Au-RGO) nanohybrids, which demonstrate excellent adsorption capacities and recyclability for a broad range of dyes. High-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) data confirm the successful synthesis of Au-RGO nanohybrids. The effect of several experimental parameters (temperature and pH) variation can effectively control the dye adsorption capability. Furthermore, kinetic adsorption data reveal that the adsorption process follows a pseudo second-order model. The negative value of Gibbs free energy (Delta G(0)) confirms spontaneity while the positive enthalpy (Delta H-0) indicates the endothermic nature of the adsorption process. Picosecond resolved fluorescence technique unravels the excited state dynamical processes of dye molecules adsorbed on the Au-RGO surface. Time resolved fluorescence quenching of Rh123 after adsorption on Au-RGO nanohybrids indicates efficient energy transfer from Rh123 to Au nanoparticles. A prototype device has been fabricated using Au-RGO nanohybrids on a syringe filter (pore size: 0.220 mu m) and the experimental data indicate efficient removal of dyes from waste water with high recyclability. The application of this nanohybrid may lead to the development of an efficient reusable adsorbent in portable water purification. GRAPHICS

All-Polymer Microcavities for the Fluorescence Radiative Rate 2 Modification of a Diketopyrrolopyrrole Derivative

Controlling the radiative rate of emitters with 6 macromolecular photonic structures promises flexible devices with 7 enhanced performances that are easy to scale up. For instance, radiative rate enhancement empowers low-threshold lasers, while rate suppression affects recombination in photovoltaic and photochemical processes. However, claims of the Purcell effect with polymer structures are controversial, as the low dielectric contrast typical of suitable polymers is commonly not enough to provide the necessary confinement. Here we show all-polymer planar microcavities with photonic band gaps tuned to the photoluminescence of a diketopyrrolopyrrole derivative, which allows a change in the fluorescence lifetime. Radiative and nonradiative rates were disentangled systematically by measuring the external quantum efficiencies and comparing the planar microcavities with a series of references designed to exclude any extrinsic effects. For the first time, this analysis shows unambiguously the dye radiative emission rate variations obtained with macromolecular dielectric mirrors. When different0 waveguides, chemical environments, and effective refractive index effects in the structure were accounted for, the change in the radiative lifetime was assigned to the Purcell effect. This was possible through the exploitation of photonic structures made of polyvinylcarbazole as a high-index material and the perfluorinated Aquivion as a low-index one, which produced the largest dielectric contrast ever obtained in planar polymer cavities. This characteristic induces the high confinement of the radiation electric field within the cavity layer, causing a record intensity enhancement and the steering the radiative rate. Current limits and requirements to achieve the full control of radiative rates with polymer planar microcavities are also addressed

Molecular Mechanisms of Light Harvesting in the Minor Antenna {CP}29 in Near-Native Membrane Lipidic Environment

CP29, a chlorophyll a/b-xanthophyll binding protein, bridges energy transfer between the major LHCII antenna complexes and photosystem II reaction centers. It hosts one of the two identified quenching sites, making it crucial for regulated photoprotection mechanisms. Until now, the photophysics of CP29 has been studied on the purified protein in detergent solutions since spectrally overlapping signals affect in vivo measurements. However, the protein in detergent assumes non-native conformations compared to its physiological state in the thylakoid membrane. Here, we report a detailed photophysical study on CP29 inserted in discoidal lipid bilayers, known as nanodiscs, which mimic the native membrane environment. Using picosecond time-resolved fluorescence and femtosecond transient absorption (TA), we observed shortening of the Chl fluorescence lifetime with a decrease of the carotenoid triplet formation yield for CP29 in nanodiscs as compared to the protein in detergent. Global analysis of TA data suggests a (1)Chl* quenching mechanism dependent on excitation energy transfer to a carotenoid dark state, likely the proposed S*, which is believed to be formed due to a carotenoid conformational change affecting the S-1 state. We suggest that the accessibility of the S* state in different local environments plays a key role in determining the quenching of Chl excited states. In vivo, non-photochemical quenching is activated by de-epoxidation of violaxanthin into zeaxanthin. CP29-zeaxanthin in nanodiscs further shortens the Chl lifetime, which underlines the critical role of zeaxanthin in modulating photoprotection activity.Published under an exclusive license by AIP Publishing

Dual Amplified Spontaneous Emission and Lasing from Nanographene Films

Chemically synthesized zigzag-edged nanographenes (NG) have recently demonstrated great success as the active laser units in solution-processed organic distributed feedback (DFB) lasers. Here, we report the first observation of dual amplified spontaneous emission (ASE) from a large-size NG derivative (with 12 benzenoid rings) dispersed in a polystyrene film. ASE is observed simultaneously at the 685 and 739 nm wavelengths, which correspond to different transitions of the photoluminescence spectrum. Ultrafast pump-probe spectroscopy has been used to ascertain the underlying photophysical processes taking place in the films. DFB lasers, based on these materials and top-layer nanostructured polymeric resonators (i.e., one or two-dimensional surface relief gratings), have been fabricated and characterized. Lasers emitting close to either one of the two possible ASE wavelengths, or simultaneously at both of them, have been prepared by proper selection of the resonator parameters.The Alicante team was funded by Spanish Government (MINECO) and European Community (FEDER), grant number MAT2015-66586-R. The researcher R.M-M was funded by a MINECO FPI fellowship (No. BES-2016-077681). The Singapore team was funded by the NRF Investigatorship programme (NRF-NRFI05-2019-0005). The Milan team has received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (grant agreement No. 816313). G.M.P. acknowledges funding from Fondazione Cariplo, grant No. 2018-0979. C.D. and S.S. acknowledge funding from ERC Starting Grant SOLENALGAE (No. 679814)

Structural coloration by inkjet-printing of optical microcavities and metasurfaces

Structural color generation by plasmonic and other means has attracted significant interest as a solution to avoid inks based on dyes. Prominent advantages include better robustness compared with organic dyes while also providing high chromaticity and brightness in ultrathin films. However, lack of cheap and scalable fabrication techniques has so far limited structural coloration to only a few applications and functional devices. Here, we demonstrate reflective (plasmonic) structural coloration at high resolution by inkjet printing on non-patterned surfaces. The method is flexible, scalable to large areas, and avoids complicated or costly fabrication steps. Optical microcavities on flexible plastic substrates were made starting with an inkjet-printed silver film as a bottom mirror. Inkjet-printed organic dielectric micropixels then served as the spacer layer, resulting in optical microcavities with reflective structural colors after coating with a thin semi-transparent metallic top layer. Optimization of ink formulation allowed for uniform pixels with minimum coffee stain effects as well as control of spacer thickness (around 50-150 nm) and color by varying the solid content of the ink. We investigate the possibility to obtain red, green and blue (RGB) pixels and demonstrate the improvement of particularly the blue coloration using wavelength-dependent plasmon absorption of gold nanoislands as a top mirror. Inkjet printing of optical microcavities and plasmonic cavities may find use in various applications, such as reflective displays in color.Funding Agencies|Swedish Foundation for Strategic Research; AForsk Foundation; Wenner-Gren Foundations; Swedish Research Council; Royal Swedish Academy of Sciences; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009 00971]</p

Three-in-one approach towards efficient organic dye-sensitized solar cells: aggregation suppression, panchromatic absorption and resonance energy transfer

In the present study, protoporphyrin IX (PPIX) and squarine (SQ2) have been used in a co-sensitized dye-sensitized solar cell (DSSC) to apply their high absorption coefficients in the visible and NIR region of the solar spectrum and to probe the possibility of Förster resonance energy transfer (FRET) between the two dyes. FRET from the donor PPIX to acceptor SQ2 was observed from detailed investigation of the excited-state photophysics of the dye mixture, using time-resolved fluorescence decay measurements. The electron transfer time scales from the dyes to TiO2 have also been characterized for each dye. The current–voltage (I–V) characteristics and the wavelength-dependent photocurrent measurements of the co-sensitized DSSCs reveal that FRET between the two dyes increase the photocurrent as well as the efficiency of the device. From the absorption spectra of the co-sensitized photoanodes, PPIX was observed to be efficiently acting as a co-adsorbent and to reduce the dye aggregation problem of SQ2. It has further been proven by a comparison of the device performance with a chenodeoxycholic acid (CDCA) added to a SQ2-sensitized DSSC. Apart from increasing the absorption window, the FRET-induced enhanced photocurrent and the anti-aggregating behavior of PPIX towards SQ2 are crucial points that improve the performance of the co-sensitized DSSC

Noniridescent Biomimetic Photonic Microdomes by Inkjet Printing

Certain bird species have evolved spectacular colors that arise from organized nanostructures of melanin. Its high refractive index (similar to 1.8) and broadband absorptive properties enable vivid structural colors that are nonsusceptible to photo-bleaching. Mimicking natural melanin structural coloration could enable several important applications, in particular, for non-iridescent systems with colors that are independent of incidence angle. Here, we address this by forming melanin photonic crystal microdomes by inkjet printing. Owing to their curved nature, the microdomes exhibit noniridescent vivid structural coloration, tunable throughout the visible range via the size of the nanoparticles. Large-area arrays (&amp;gt;1 cm(2)) of high-quality photonic microdomes could be printed on both rigid and flexible substrates. Combined with scalable fabrication and the nontoxicity of melanin, the presented photonic microdomes with noniridescent structural coloration may find use in a variety of applications, including sensing, displays, and anticounterfeit holograms.Funding Agencies|Wenner-Gren Foundation; Swedish Research CouncilSwedish Research Council; Knut and Alice Wallenberg foundationKnut &amp; Alice Wallenberg Foundation; Swedish Foundation for Strategic researchSwedish Foundation for Strategic Research; Linkoping University; Wallenberg Wood Science Center the Wallenberg Wood Science Centre; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009 00971]</p

Photosystem II monomeric antenna CP26 plays a key role in nonphotochemical quenching in Chlamydomonas

Targeted mutagenesis and complementation in Chlamydomonas reveal the functions of CP26, a monomeric antenna of photosystem II, demonstrating its key role in regulating photoprotection.Thermal dissipation of excess excitation energy, called nonphotochemical quenching (NPQ), is 1 of the main photoprotective mechanisms in oxygenic photosynthetic organisms. Here, we investigated the function of the monomeric photosystem II (PSII) antenna protein CP26 in photoprotection and light harvesting in Chlamydomonas reinhardtii, a model organism for green algae. We used CRISPR/Cas9 genome editing and complementation to generate cp26 knockout mutants (named k6#) that did not negatively affect CP29 accumulation, which differed from previous cp26 mutants, allowing us to compare mutants specifically deprived of CP26, CP29, or both. The absence of CP26 partially affected PSII activity, causing reduced growth at low or medium light but not at high irradiances. However, the main phenotype observed in k6# mutants was a more than 70% reduction of NPQ compared to the wild type (Wt). This phenotype was fully rescued by genetic complementation and complemented strains accumulating different levels of CP26, demonstrating that &amp; SIM;50% of CP26 content, compared to the Wt, was sufficient to restore the NPQ capacity. Our findings demonstrate a pivotal role for CP26 in NPQ induction, while CP29 is crucial for PSII activity. The genetic engineering of these 2 proteins could be a promising strategy to regulate the photosynthetic efficiency of microalgae under different light regimes