Microwave synthesis and photophysical characterization of hybrid materials based on the encapsulation of dyes into unidirectional aluminophosphates

35 p.In this work, hemicyanine dyes LDS 722 and LDS 730 are encapsulated into the 1D nanochannels of MgAPO-11 and MgAPO-5 aluminophosphates via crystallisation inclusion method. The synthesis of the hybrid material has been optimized through a systematic variation of the crystallization conditions and gel composition in order to obtain the purest phase possible suitable for optical applications. The tight tting between the molecular sizes of the guest dyes and the pore dimensions of the hosts has favoured a rigid planar conformation of the dyes. Consequently, the occlusion has led to a great enhancement of the uorescence with respect to the dye in solution together with an alignment along the channels

Exploiting the photophysical features of DMAN template in ITQ-51 zeotype in the search for FRET energy transfer

The combination between photoactive molecules and inorganic structures is of great interest for the development of advanced materials in the field of optics. Particularly, zeotypes with extra-large pore size are attractive because they allow the encapsulation of bulky dyes. The microporous aluminophoshate Mg-ITQ-51 (IFO-type structure) represents an ideal candidate because of the synergic combination of two crucial features: the IFO framework itself, which is composed of non-interconnected one-dimensional extra-large elliptical channels with a diameter up to 11 Å able to host bulky guest species, and the particular organic structure-directing agent used for the synthesis (1,8-bis(dimethylamino)naphthalene, DMAN), which efficiently fills the IFO pores, and is itself a photoactive molecule with interesting fluorescence properties in the blue range of the visible spectrum, thus providing a densely-incorporated donor species for FRET processes. Besides, occlusion of DMAN dye in the framework triggers a notable improvement of its fluorescence properties by confinement effect. To extend the action of the material and to mimic processes such as photosynthesis in which FRET is essential, two robust laser dyes with bulky size, rhodamine 123 and Nile Blue, have been encapsulated for the first time in a zeolitic framework, together with DMAN, in a straightforward one-pot synthesis. Thus, photoactive systems with emission in the entire visible range have been achieved due to a partial FRET between organic chromophores protected in a rigid aluminophosphate matrix.This research was supported by MCIN/AEI/10.13039/501100011033 (projects PID2020-114347RB-C32 and PID2019-107968RB-I00), and Gobierno Vasco – Eusko Jaurlaritza (project IT1639-22). Centro Técnico de Informática-CSIC is acknowledged for running the calculations and BIOVIA for providing the computational software. The authors thank for technical and human support provided by SGIker (UPV/EHU/ ERDF, EU)

Balizko molekula fotoaktibo multifuntzionala biomedikuntzarako

Light-emitting organic molecules are appealing for diagnosis in biomedicine. Fluorescence is a valuable tool to visualize ongoing biochemical processes and biomolecules in the human body with great sensibility and easily. Thus, photoactive dyes are applied as fluorescent tags, probes and sensors to monitor biochemical processes, organelles and biomolecules, respectively, by means of fluorescence microscopy. Moreover, no-fluorescent dyes but able to generate singlet oxygen can be applied as photosensitizers for photodynamic therapy in the treatment of cancer. In each of the aforementioned areas dealing with biophotonics, different chromophores are required owing to the opposite photophysical signatures demanded. Herein, we propose BODIPY called chromophore as a molecular scaffold for diagnosis and therapy. The chemical versatility and tunable photophysics of this chromophoric core enables tailoring by the appropriate substitution pattern. Therefore, our aim is to highlight the importance of molecular design to develop fluorophores as well as photosensitizers based solely in BODIPY.; Argia igortzeko gai diren molekula organikoek arreta handia jaso dute azkenaldian biomedikuntzaren esparruan, batez ere diagnosian erabiltzeko helburuarekin. Izan ere, fluoreszentzia, baliabide ezin hobea da gorputzean gertatzen diren hainbat prozesu biokimiko monitorizatzeko eta biomolekulak sentikortasun handiz detektatzeko. Hori dela eta, fotoaktiboak diren kromoforoak markatzaile, zunda edo sentsore fluoreszente gisa erabiltzen dira mikroskopia fluoreszenteari esker; hots, prozesu biokimikoak jarraitzeko, organuluak ikusteko edota biomolekulak detektatzeko. Fluoreszentziarik ez duten kromoforoak, ordea, oxigeno singletea sortzeko gaitasuna ere izan dezakete eta fotosentikortzaile izaerarekin erabil daitezke terapia fotodinamikoan, minbiziaren aurkako tratamenduan. Argi dago, biofotonikako arlo baterako zein besterako eskakizun fotofisikoak guztiz bestelakoak direla eta kromoforo ezberdinak diseinatzea ezinbestekoa dela. Horregatik, lan honetan, BODIPY izeneko kromoforo-familia oinarrizko molekula-egituratzat hartzen da, diagnosian zein terapian aplikatu ahal izateko. Kromoforo mota horren abantaila nagusia da bere egitura eta propietateak erraz molda daitezkeela. Horrela, egituraren gainean ordezkapen sinple batzuk eginda hainbat eskakizun modu errazean ase daitezke. Hortaz, gure helburu nagusia da BODIPYan oinarritutako fluoroforoak zein fotosentikortzaileak garatzea eta diseinu molekularraren garrantzia azpimarratzea

Tuning the Photonic Behavior of Symmetrical bis-BODIPY Architectures: The Key Role of the Spacer Moiety

Herein we describe the synthesis, computationally assisted spectroscopy, and lasing properties of a new library of symmetric bridged bis-BODIPYs that differ in the nature of the spacer. Access to a series of BODIPY dimers is straightforward through synthetic modifications of the pending ortho-hydroxymethyl group of readily available C-8 (meso) ortho-hydroxymethyl phenyl BODIPYs. In this way, we have carried out the first systematic study of the photonic behavior of symmetric bridged bis-BODIPYs, which is effectively modulated by the length and/or stereoelectronic properties of the spacer unit. The designed bis-BODIPYs display bright fluorescence and laser emission in non-polar media. The fluorescence response is governed by the induction of a non-emissive intramolecular charge transfer (ICT) process, which is significantly enhanced in polar media. The effectiveness of the fluorescence quenching and also the prevailing charge transfer mechanism (from the spacer itself or between the BODIPY units) rely directly on the electron-releasing ability of the spacer. Moreover, the linker moiety can also promote intramolecular excitonic interactions, leading to excimer-like emission characterized by new spectral bands and the lengthening of lifetimes. The substantial influence of the bridging moiety on the emission behavior of these BODIPY dyads and their solvent-sensitivity highlight the intricate molecular dynamics upon excitation in multichromophoric systems. In this regard, the present work represents a breakthrough in the complex relationship between the molecular structure of the chromophores and their photophysical signatures, thus providing key guidelines for rationalizing the design of tailored bis-BODIPYs with potential advanced applications.We gratefully acknowledge the Spanish Ministerio de Economia y Competitividad (MINECO) (MAT2017-83856-C3-1-P and 3-P; CTQ2015-66702-R), Ministerio de Economia y Competitividad (MINECO), and Fondo Europeo de Desarrollo Regional (FEDER) (CTQ2015-66702-R, MINECO/FEDER, UE), Ministerio de Ciencia, Innovacion y Universidades (MCIU), Agencia Estatal de Investigacion (AEI), Fondo Europeo de Desarrollo Regional (FEDER) (RTI2018-094862-B-I00, MCIU/AEI/FEDER, UE), and Gobierno Vasco (project IT91216) for financial support. AO-S and RS-L thank UPV/EHU and Gobierno Vasco for a predoctoral fellowship and a postdoctoral contract, respectively

Koloratzailez dopatutako Material Zeotipiko Fotoaktibo Berriak: optikarako balizko aplikazio bila

346 p. (eng.) 246 p. (eusk.)En esta tesis se desarrollan y estudian materiales híbridos zeotípicos fotoactivos para la obtención de sistemas multifuncionales en estado sólido con interesantes propiedades ópticas aptas para aplicaciones en el campo de la fotónica. Para ello, se atrapan colorantes orgánicos en nanocavidades restringidas de estructuras inorgánicas de aluminofosfato dopadas con metales (con Si o Mg, obteniendo estructuras tipo SAPO y MgAPO, respectivamente) para promover procesos fotofísicos nuevos y/o mejorados en los materiales por efecto sinérgico, en comparación con los fluoróforos aislados.En este trabajo se preparan un gran número de materiales de colorante-AlPO, combinando varias estructuras con diferentes formas y tamaños de poros/canales en el rango de dimensiones moleculares, con una amplia gama de colorantes orgánicos, principalmente de las familias de estirilos y aromáticos fusionados de tres anillos. La inclusión de fluoróforos en las cavidades de los AlPOs realizada "in situ" por el método de inclusión por cristalización permite el desarrollo directo de materiales híbridos fluorescentes con funcionalidades ópticas destacadas y específicas en un solo paso y en cortos periodos de tiempo, describiendo así una síntesis rentable y eficiente para sistemas avanzados.Por un lado, como resultado de la sinergia entre moléculas fotoactivas push-pull con anfitriones de aluminofosfato canalizados en 1D (AFI, ATS y AEL) y una estructura de tipo jaula-3D (CHA), se obtienen sistemas sólidos ópticamente densos con capacidad de fluorescencia mejorada y respuesta altamente anisotrópica a la luz linealmente polarizada. A través de esta estrategia las aplicaciones logradas son diversas, desde emisores NIR hasta generadores de segundo armónico y láseres en estado sólido a nivel de partícula.Por otro lado, la oclusión simultánea de diferentes especies fotoactivas en los aluminofosfatos (IFO y AEL) promueve la probabilidad de procesos de FRET en cascada entre moléculas orgánicas ocluidas en el espacio restringido de los canales zeotípicos. La coencapsulación de especies adecuadas y racionalmente seleccionadas (pares FRET) proporciones idóneas conduce a nuevos sistemas de antenas artificiales, con propiedades como la emisión sintonizable y la emisión de luz blanca.A lo largo de este trabajo, las síntesis de los materiales híbridos dopados con colorantes se optimizan (variando la composición del gel, la temperatura y el tiempo y método de calentamiento) y la morfología y cristalización de todas las fases presentadas se comprueban mediante técnicas de SEM y difracción de rayos-X en polvo. Las propiedades fotofísicas de los materiales híbridos y de los colorantes fotoactivos se analizan en profundidad mediante técnicas de estado estacionario y resueltas en el tiempo (espectroscopias de absorción y emisión), así como mediante microscopía de fluorescencia, que permite el análisis a nivel de partícula. Además, se demuestra la aplicabilidad final de los materiales mediante técnicas sofisticadas como la detección de señales de generación de segundos armónicos y la respuesta de acción del microláse

A Concise Route to Water-Soluble 2,6-Disubstituted BODIPY-Carbohydrate Fluorophores by Direct Ferrier-Type C-Glycosylation

8 pags., 5 figs., 1 tab.Novel, linker-free, BODIPY-carbohydrate derivatives containing sugar residues at positions C2 and C6 are efficiently obtained by, hitherto unreported, Ferrier-type C-glycosylation of 8- aryl-1,3,5,7-tetramethyl BODIPYs with commercially available tri-Oacetyl-D-glucal followed by saponification. This transformation, which involves the electrophilic aromatic substitution (SEAr) of the dipyrrin framework with an allylic oxocarbenium ion, provides easy access to BODIPY-carbohydrate hybrids with excellent photophysical properties and a weaker tendency to aggregate in concentrated water solutionsThe authors gratefully acknowledge the Spanish Ministerio de Ciencia e Innovación for financial support (Projects RTI2018- 094862-B-100, MAT2017-83856-C3-1-P and -3-P, and PiD2020-114755GB-C31 and -C33) and the Gobierno Vasco (Project IT912-16) for financial support.Peer reviewe

A Revisit of the Underlying Fundamentals in the Laser Emission from BODIPYs

This chapter aims to provide a comprehensive assessment of the laser performance of commercially available laser dyes based on the boron-dipyrromethene (BODIPY) chromophore in a liquid state, as well as to remark the main underlying photophysical signatures triggering such photonic behavior. First, we describe their light absorption and fluorescence properties in solution. This spectroscopic study is supplemented with quantum mechanics calculations and electrochemical measurements. Afterward, the dyes are tested as active media of tunable lasers under transversal pumping. The recorded laser efficiencies and photostabilities are correlated with the registered photophysical properties identifying the main structural guidelines and photonic parameters, which rule the laser bands’ position, intensity, and stability. As a result, we provide a comparative dataset of the laser performance, not available hitherto. Besides, the unraveling of the complex molecular structure-photophysics-laser relationship should help in the rational design of new tunable dye lasers with an improved photonic response along the entire visible region and reaching eventually the near infrared

Article White Light Emission by Simultaneous One Pot Encapsulation of Dyes into One-Dimensional Channelled Aluminophosphate

[EN] By simultaneous occlusion of rationally chosen dyes, emitting in the blue, green and red region of the electromagnetic spectrum, into the one-dimensional channels of a magnesium-aluminophosphate with AEL-zeolitic type structure, MgAPO-11, a solid-state system with e cient white light emission under UV excitation, was achieved. The dyes herein selected—acridine (AC), pyronin Y (PY), and hemicyanine LDS722—ensure overall a good match between their molecular sizes and the MgAPO-11 channel dimensions. The occlusion was carried out via the crystallization inclusion method, in a suitable proportion of the three dyes to render e cient white fluorescence systems by means of fine-tuned FRET (fluorescence resonance energy transfer) energy transfer processes. The FRET processes are thoroughly examined by the analysis of fluorescence decay traces using the femtosecond fluorescence up-conversion technique.This research was funded by Gobierno Vasco (IT912-16), Ministerio de Economía y Competitividad (MINECO), the Spanish Agencia Estatal de Investigación, and the EU’s Fondo Europeo de Desarrollo Regional under projects MAT2017-83856-C3-3-P and MAT2016-77496-R, and C1/C2 KU Leuven, FuEPoNa (3E190382).Peer reviewe

Extended BODIPYs as Red–NIR Laser Radiation Sources with Emission from 610 nm to 750 nm

Herein, we report the synthetic access to a set of π-extended BODIPYs featuring a penta-arylated (phenyl and/or thiophene) dipyrrin framework. We take advantage of the full chemoselective control of 8-methylthio-2,3,5,6-tetrabromoBODIPY when we conduct the Liebeskind–Srogl cross-coupling (LSCC) to functionalize exclusively the meso-position, followed by the tetra-Suzuki reaction to arylate the halogenated sites. All these laser dyes display absorption and emission bands in the red edge of the visible spectrum reaching the near-infrared with thiophene functionalization. The emission efficiency, both fluorescence and laser, of the polyphenylBODIPYs can be enhanced upon decoration of the peripheral phenyls with electron donor/acceptor groups at para positions. Alternatively, the polythiopheneBODIPYs show an astonishing laser performance despite the charge transfer character of the emitting state. Therefore, these BODIPYs are suitable as a palette of stable and bright laser sources covering the spectral region from 610 nm to 750 nm

Acetoxymethyl-BODIPY Dyes: A Universal Platform for the Fluorescence Labeling of Nucleophiles

Current methods for the preparation of functional small-molecule fluorophores generally require labor-intensive, multi-step synthetic routes for all the major chromophore groups. In spite of recent significant contributions from numerous laboratories, the paucity of rapid, straightforward and wide-scope synthetic strategies in this field is limiting the development of advanced probes for bioimaging, sensing and therapeutic applications. We describe herein a general and robust methodology for the one-step fluorescent labeling of a wide variety of molecules having C-, N-, P-, O-, S-, or halide-nucleophilic centers, using stable and readily available acetoxymethyl-BODIPYs as reagents in the presence of an acid catalyst. This modular methodology allows a very facile preparation of mono- and di-functional probes incorporating a broad assortment of biomolecules, enzyme cofactors, natural products, and other chromophores, as well as chemical functionalities for a wide range of applications including bioorthogonal conjugation, polymerization, and supramolecular chemistry, among others. The photophysical properties and preliminary applications of the new probes in live-cell imaging were also studied. The described strategy could enable the high-throughput engineering of novel BODIPY dyes with diverse functionalities for basic and applied research with potential for innovative technological applications.We gratefully acknowledge financial support from Instituto de Salud Carlos III/FEDER “A way to make Europe/”Investing in your future" (project 20/01754), and MCIN/AEI/10.13039/501100011033 (projects PID2020-114347RB-C31 and PID2020-114347RB-C32), and Gobierno Vasco-Eusko Jaurlaritza (project IT1639-22). A.B.-M. and L.C. thank MICIN for a FPI (BES-2015-073571) and a FPU (FPU2017-01317) predoctoral contract, respectively. R.P.M thanks MIU and NGEU for a postdoctoral contract (MARSA21/71). A.O.S. thanks UPV-EHU for a predoctoral fellowship.Peer reviewe