Photoactive Nanomaterials Inspired by Nature: LTL Zeolite Doped with Laser Dyes as Artificial Light Harvesting Systems

The herein reported work describes the development of hierarchically-organized fluorescent nanomaterials inspired by plant antenna systems. These hybrid materials are based on nanostructured zeolitic materials (LTL zeolite) doped with laser dyes, which implies a synergism between organic and inorganic moieties. The non-interconnected channeled structure and pore dimensions (7.1 angstrom) of the inorganic host are ideal to order and align the allocated fluorophores inside, inferring also high thermal and chemical stability. These artificial antennae harvest a broad range of chromatic radiation and convert it into predominant red-edge or alternatively white-light emission, just choosing the right dye combination and concentration ratio to modulate the efficiency of the ongoing energy transfer hops. A further degree of organization can be achieved by functionalizing the channel entrances of LTL zeolite with specific tailor-made (stopcock) molecules via a covalent linkage. These molecules plug the channels to avoid the leakage of the guest molecules absorbed inside, as well as connect the inner space of the zeolite with the outside thanks to energy transfer processes, making the coupling of the material with external devices easier.This work was supported by the Basque Government (IT912-16) and Spanish MICINN (MAT2014-51937-C3-3-P) projects. Leire Gartzia also thanks the Basque Goberment for a Post-doctoral grant. Yi Xiao from Dalian University (China) is kindly acknowledged for the supply and synthesis of the stopcock molecule

Water Adsorption on the β-Dicalcium Silicate Surface from DFT Simulations

beta-dicalcium silicate (beta-Ca2SiO4 or beta-C2S in cement chemistry notation) is one of the most important minerals in cement. An improvement of its hydration rate would be the key point for developing environmentally-friendly cements with lower energy consumption and CO2 emissions. However, there is a lack of fundamental understanding on the water/beta-C2S surface interactions. In this work, we aim to evaluate the water adsorption on three beta-C2S surfaces at the atomic scale using density functional theory (DFT) calculations. Our results indicate that thermodynamically favorable water adsorption takes place in several surface sites with a broad range of adsorption energies (-0.78 to -1.48 eV) depending on the particular mineral surface and adsorption site. To clarify the key factor governing the adsorption of the electronic properties of water at the surface were analyzed. The partial density of states (DOS), charge analysis, and electron density difference analyses suggest a dual interaction of water with a beta-C2S (100) surface including a nucleophilic interaction of the water oxygen lone pair with surface calcium atoms and an electrophilic interaction (hydrogen bond) of one water hydrogen with surface oxygen atoms. Despite the elucidation of the adsorption mechanism, no correlation was found between the electronic structure and the adsorption energies.National Natural Science Foundation of China (No. 51602148), the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD), the Program for Innovative Research Team in the University of Ministry of Education of China (No. IRT_15R35), the financial support from the Departamento de Educacion, Politica Linguistica y Cultura del Gobierno Vasco (IT912-16) and the ELKARTEK project

8-PropargylaminoBODIPY: unprecedented blue-emitting pyrromethene dye. Synthesis, photophysics and laser properties

Highly emitting 8-propargylaminoBODIPY (8-PAB) 2 was prepared in 94% yield. Unlike any other BODIPY structure hitherto described in the literature, 2 displays efficient emission in the blue region of the visible spectrum with a fluorescence quantum yield up to 0.94 and high laser efficiency (35%) at 483 nm.Grants GTO-2007-C02-69094 (CONCyTEG) (Mexico), MAT2007-65778-C02-01 and -02 of the Spanish MICINN are gratefully acknowledged. V. Martin thanks CSIC for her JAE-postdoctoral contract.Peer reviewe

Bichromatic laser emission from dipyrromethene dyes incorporated into solid polymeric media

9 pages, 9 figures.Bichromatic laser emission from dipyrromethene-based solid-state dye lasers is reported. The dependence of this dual emission on different factors and its origin and causes are discussed in the light of different models proposed in the literature. Our experimental results indicate that the long-wavelength emission can be explained in terms of reabsorption/reemission effects and inhomogeneous broadening of the S0-S1 transition. The short-wavelength emission corresponds to the usual S0-S1 transition and dominates at low dye concentration.This work was supported by Project Nos. MAT2004-04643-C03-01 and MAT2004-04643-C03-02 of the Spanish CICYT. One of the authors (M.Á.) thanks Ministerio de Ciencia y Tecnología (MCT) for a predoctoral grant. Another author (M.L.) thanks Comunidad Autónoma de Madrid for a postdoctoral grant and MCT for a Juan de la Cierva contract.Peer reviewe

Ready Access to Molecular Rotors Based on Boron Dipyrromethene Dyes-Coumarin Dyads Featuring Broadband Absorption

Herein we report on a straightforward access method for boron dipyrromethene dyes (BODIPYs)-coumarin hybrids linked through their respective 8- and 6- positions, with wide functionalization of the coumarin fragment, using salicylaldehyde as a versatile building block. The computationally-assisted photophysical study unveils broadband absorption upon proper functionalization of the coumarin, as well as the key role of the conformational freedom of the coumarin appended at the meso position of the BODIPY. Such free motion almost suppresses the fluorescence signal, but enables us to apply these dyads as molecular rotors to monitor the surrounding microviscosity.This research was funded by Spanish Ministerio de Economia y Competitividad (project MAT2017-83856-C3-3-P), Gobierno Vasco (project IT912-16), CONACyT (grants 253623, 123732) and Dirección de Apoyo a la Investigación (DAIP-UG CIIC318/2019)

Linde Type L Zeolite: A Privileged Porous Support to Develop Photoactive and Catalytic Nanomaterials

Among the wide assortment of zeolites based on aluminosilicates, Linde Type L (LTL) zeolite outstands as a support host owing to its porous framework and high adsorption surfaces. Thus, the incorporation of suitable guest molecules (fluorophores or metals) allows the development of photoactive and catalytic nanomaterials. In this chapter, we describe the design of materials based on LTL zeolite to achieve artificial antennae, inspired in the natural photosynthesis, and ecofriendly materials for the catalytic reforming of biogas. First, we describe the microwave-assisted synthesis of LTL zeolite with tunable size and morphology. Afterward, we test the energy transfer probability between the guest fluorophores into the LTL zeolite pores as the key process enabling the antenna behavior of this hybrid material with broadband absorption and tunable emission or predominant red fluorescence. Finally, we also test the behavior of LTL zeolite as a support material for the catalytic reforming of biogas. To this aim, suitable metals were impregnated onto LTL zeolite featuring different shapes and alkaline metal exchange. Activity tests indicated that disk- and cylinder-shaped hosts were the most active ones, especially when bimetallic (Rh-Ni) catalysts were prepared. However, the alkaline metal exchange was ineffective to increase the hydrogen yield

Functionalized Fluorescent Silica Nanoparticles for Bioimaging of Cancer Cells

Functionalized fluorescent silica nanoparticles were designed and synthesized to selectively target cancer cells for bioimaging analysis. The synthesis method and characterization of functionalized fluorescent silica nanoparticles (50–60 nm), as well as internalization and subcellular localization in HeLa cells is reported here. The dye, rhodamine 101 (R101) was physically embedded during the sol–gel synthesis. The dye loading was optimized by varying the synthesis conditions (temperature and dye concentration added to the gel) and by the use of different organotriethoxysilanes as a second silica precursor. Additionally, R101, was also covalently bound to the functionalized external surface of the silica nanoparticles. The quantum yields of the dye-doped silica nanoparticles range from 0.25 to 0.50 and demonstrated an enhanced brightness of 230–260 fold respect to the free dye in solution. The shell of the nanoparticles was further decorated with PEG of 2000 Da and folic acid (FA) to ensure good stability in water and to enhance selectivity to cancer cells, respectively. In vitro assays with HeLa cells showed that fluorescent nanoparticles were internalized by cells accumulating exclusively into lysosomes. Quantitative analysis showed a significantly higher accumulation of FA functionalized fluorescent silica nanoparticles compared to nanoparticles without FA, proving that the former may represent good candidates for targeting cancer cells.This research was funded by the Basque Government, grant numbers IT912-16 and IT-1302-19; Ministry of Economy and Competitiveness (MINECO), grant numbers MAT2017-83856-C3-3-P and CTM2016-81130-R; and the University of the Basque Country (UPV/EHU), grant number COLAB19/01

Photophysical and laser emission studies of 8-polyphenylene-substituted BODIPY dyes in liquid solution and in solid polymeric matrices

In our search for efficient and photostable laser dyes, four new dyes with the basic structure of the commercial BODIPY laser dye PM567, with either an 8-diphenylene or an 8-p-triphenylene group, both substituted at the terminal polyphenylene position with an acetoxymethyl (dyes P2Ar1Ac and P3Ar1Ac, respectively) or a methacryloyloxymethyl group (dyes P2Ar1MA and P3Ar1MA, respectively), have been synthesized. The photophysical and lasing properties of the dyes have been studied both dissolved in liquid solvents (acetoxymethyl dyes) and incorporated into solid polymeric matrices, in the latter case as solutions (acetoxymethyl dyes) or as copolymers with methyl methacrylate (methacryloyloxymethyl dyes). In liquid solution, the photophysics of P2Ar1Ac and P3Ar1Ac is scarcely affected by the number (two or three) of p-phenylene units. Quantum mechanical calculations reveal that the p-phenylene units in these dyes are twisted ca. 37◦ each other, an that the first 8-p-phenylene group stands nearly perpendicular to the aromatic BODIPY plane, resulting in electronic decoupling of the two chromophores. P2Ar1Ac exhibits a somewhat lower photodegradation quantum yield under UV and visible irradiation, if compared with P3Ar1Ac or with PM567, likely because of its also lower rate constant for the reaction with in situ-generated singlet molecular oxygen. Both acetoxymethyl dyes emit laser radiation in solution in all the solvents tried, under transversal pumping at 532 nm. In ethyl acetate, with a dye concentration of 0.80 × 10−3 M, laser efficiencies as high as 80% have been observed. When the 8-polyphenylene dyes were incorporated into solid poly(methyl methacrylate) (PMMA) matrices, as solutions or as copolymers, the fluorescence emission increased with respect to that of the parent PM567 dye dissolved in the same matrix, and lasing efficiencies in the range 18–31% were obtained, with good photostability. The dye P2Ar1Ac dissolved in PMMA was found to exhibit the best overall laser behavior, with a good balance between efficiency and photostability.This work was supported by Project MAT2004-04643-C03-01 of the Spanish CICYT. M. Liras thanks Comunidad Aut´onoma de Madrid for a predoctoral scholarship and Ministerio de Educaci´on y Ciencia for a Juan de la Cierva contract.M. A´ lvarez thanks Ministerio de Educaci´on y Ciencia for a predoctoral scholarship. The 8-polyphenylene-substituted boron-dipyrromethene dyes described in this paper and their utilization in liquid and solidstate dye lasers are covered by Spanish PatentNo. P200701763 filed on 25 June 2007.Peer reviewe

Tailoring the Photophysical Signatures of BODIPY Dyes: Toward Fluorescence Standards across the Visible Spectral Region

The modern synthetic routes in organic chemistry, as well as the recent advances in high-resolution spectroscopic and microscopic techniques, have awakened a renewable interest in the development of organic fluorophores. In this regard, boron-dipyrrin (BODIPY) dyes are ranked at the top position as luminophores to be applied in photonics or biophotonics. This chromophore outstands not only by its excellent and tunable photophysical signatures, but also by the chemical versatility of its core, which is readily available to a myriad of functionalization routes. In this chapter, we show that, after a rational design, bright and photostable BODIPYs can be achieved along the whole visible spectral region, being suitable as molecular probes or active media of lasers. Alternatively, the selective functionalization of the dipyrrin core, mainly at meso position, can induce new photophysical phenomena (such as charge transfer) paving the way to the development of fluorescent sensors, where the fluorescent response is sensitive to a specific environmental property