Synergism between organic and inorganic moieties: in the search of new hybrid materials for optics and biomedicine

232 p.In this work different versatile photoactive hybrid materials with interesting features for optics and biomedicine are achieved and exhaustively characterized. Firstly, by means of the occlusion of different fluorescent dyes, by the crystallization inclusion method, into several 1D-channeled magnesium aluminophosphate (MgAPO) hosts (with different sized and shaped pores), optically dense fluorescent hybrid materials which show highly anisotropic response to linearly polarized light are obtained. Depending on the dye embedded within the selected MgAPO framework, interesting applications have been attained, such as one-directional artificial photonic antenna systems covering the whole UV-Visible spectral range, Second Harmonic Generators under NIR radiation, optically switchable hybrid systems and white light emitters. White light emission is also obtained from the luminescence that arises from embedding simultaneously different small aromatic molecules into a Metal Organic Framework (MOF), named [Zn2(bdc)2(dpNDI)]n, which contains a photoactive naphtalemediimide as organic pillar. The incorporation of halide-substituted aromatic molecules into this MOF also promotes phosphorescence at room temperature. Finally, the attachment of a BODIPY chromophore to a cyclometalated Ir(III) metallic centre results in the achievement of efficient photosensitizers for singlet oxygen generation upon visible excitation light. Moreover, these hybrid compounds also show fluorescence emission, thus, they are interesting for bioimaging as well, and as a consequence, extensible to their use in theragnosis

Synergism between organic and inorganic moieties: in the search of new hybrid materials for optics and biomedicine

232 p.In this work different versatile photoactive hybrid materials with interesting features for optics and biomedicine are achieved and exhaustively characterized. Firstly, by means of the occlusion of different fluorescent dyes, by the crystallization inclusion method, into several 1D-channeled magnesium aluminophosphate (MgAPO) hosts (with different sized and shaped pores), optically dense fluorescent hybrid materials which show highly anisotropic response to linearly polarized light are obtained. Depending on the dye embedded within the selected MgAPO framework, interesting applications have been attained, such as one-directional artificial photonic antenna systems covering the whole UV-Visible spectral range, Second Harmonic Generators under NIR radiation, optically switchable hybrid systems and white light emitters. White light emission is also obtained from the luminescence that arises from embedding simultaneously different small aromatic molecules into a Metal Organic Framework (MOF), named [Zn2(bdc)2(dpNDI)]n, which contains a photoactive naphtalemediimide as organic pillar. The incorporation of halide-substituted aromatic molecules into this MOF also promotes phosphorescence at room temperature. Finally, the attachment of a BODIPY chromophore to a cyclometalated Ir(III) metallic centre results in the achievement of efficient photosensitizers for singlet oxygen generation upon visible excitation light. Moreover, these hybrid compounds also show fluorescence emission, thus, they are interesting for bioimaging as well, and as a consequence, extensible to their use in theragnosis

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

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

Koloratzaile fotoaktiboen belaunaldi berria

Nature is a source of inspiration for humankind and helps in technological advance. As a matter of fact, the reproduction of the photosynthesis, where natural chromophores absorb the incoming sunlight, is a long seeking challenge. To mimic such antenna systems new organic dyes are designed. However, single molecules show intrinsic limitations to absorb the whole electromagnetic spectrum, for light traveling, and to withstand prolonged irradiation regimes. To offset such shortcoming, multichromophoric dyes are an appealing alternative. In these complex molecular structures dissimilar dyes are covalently linked to promote energy transfer between them, which is the key pathway. Thus, multichromohores enable a broadband and efficient absorption. Therefore, multichromophoric dyes emerge as the next generation of ap-plied photoactive systems for artificial antennae in optic and photovoltaic devices. Herein, we detail the main structural and photophysical requirements to develop efficient and stable multichromophores. As a proof of concept, we showcase multichromophoric dyes based on rhodamine, perylene red and BODIPY and describe their photonic performance applied as lasers and sensors.; Gizakiok, maiz, naturan inspiratzen gara garapen teknologikoa bultzatzeko. Bada, fotosin-tesia horren adibide argia da. Prozesu natural horretan, eguzki-argia kromoforo naturalen bidez xurgatzen da, eta gaur egun antena-sistema natural hori modu eraginkorrean imitatzeko azterlan ugari egiten ari dira, koloratzaile organiko berrien diseinuan oinarrituta. Hala ere, molekula sinpleak direnez, zenbait muga izaten dituzte; adibidez, zailtasunak dituzte espektro elektromagnetiko osoan argia xurgatzeko, argi-energia garraiatzeko eta erradiazio jarraituaren pean luze irauteko. Hala, hainbat kromoforoz osatutako koloratzaileak, multikromoforo deritzenak, irtenbide aproposa dira. Molekula-egitura horietan, kromoforo edo koloratzaile ezberdinak modu kobalentean konbinatzen dira eta energia-trukea sustatzen da. Hortaz, antena naturalak imitatzeko funtsezkoa den prozesua lortzen da eta argiaren xurgapen zabala eta eraginkorra bermatzen da. Hori dela eta, koloratzaileen kimikan, multikromoforoak etorkizuneko sistema fotoaktibotzat hartzen dira antena artifizialak garatzeko eta gailu optiko eta fotovoltaikoetan aplikatzeko. Argitalpen honetan, beraz, antena eraginkor eta egonkorrak garatzeko ezinbestekoak diren irizpide molekularrak eta fotofisikoak zehazten dira. Adibide gisa, errodaminan, perileno gorrian eta BODIPYan oinarritutako koloratzaile multikromoforikoak aurkezten dira, eta horien portaera fotonikoa deskribatzen da laser eta sentsore bezala erabiltzeko

Red haloBODIPYs as theragnostic agents: The role of the substitution at meso position

Three different molecular designs based on BODIPY dye have been proposed as photosensitizers (PSs) for photodynamic therapy (PDT) by the inclusion of halogen atoms (Iodine) at 2,6-positions and with extended conjugation at 3, 5-positions and varying the substitution at meso position. The synthesis is described and their main photophysical features including singlet oxygen production and triplet states were characterized by absorption and fluorescence spectroscopy (steady-state and time-correlated) and nanosecond transient absorption spectroscopy. The results were compared with the commercial Chlorin e6. The three new red-halogen-BODIPYs showed a great balance between singlet oxygen generation (Phi(Delta)>= 0.40) and fluorescence (Phi(fl)>= 0.22) for potential application on PDT, and particularly in theragnosis. In vitro experiments in HeLa cells were done to study their performance and to elucidate the best potential candidate for PDT.This research was funded by the Basque Government, grant numbers IT912-16, IT-1302-19 and IT1639-22. This work is supported by Min-isterio de Ciencia, Innovacion y Universidades-Agencia Estatal de Investigacion (MCI/AEI) , grant numbers MAT2017-83856-C3-2-P and 3-P, PID2020-114347RB-C32, PID2020-114755 GB-C32 and the Uni-versity of the Basque Country (UPV/EHU) , grant number COLAB19/01. R.P.M. thanks UPV/EHU for postdoctoral felowship (DOCREC 20/55) . Open Access funding is provided by University of Basque Country

One-Directional Antenna Systems: Energy Transfer from Monomers to JAggregates within 1D Nanoporous Aluminophosphates

A cyanine dye (PIC) was occluded into two 1D-nanopoporus Mg-containing aluminophosphates with different pore size (MgAPO-5 and MgAPO-36 with AFI and ATS zeolitic structure types, with cylindrical channels of 7.3 Å diameter and elliptical channels of 6.7 Å × 7.5 Å, respectively) by crystallization inclusion method. Different J-aggregates are photophysically characterized as a consequence of the different pore size of the MgAPO frameworks, with emission bands at 565 nm and at 610 nm in MgAPO-5 and MgAPO-36, respectively. Computational results indicate a more linear geometry of the J-aggregates inside the nanochannels of the MgAPO-36 sample than those in MgAPO-5, which is as a consequence of the more constrained environment in the former. For the same reason, the fluorescence of the PIC monomers at 550 nm is also activated within the MgAPO-36 channels. Owing to the strategic distribution of the fluorescent PIC species in MgAPO-36 crystals (monomers at one edge and J-aggregates with intriguing emission properties at the other edge) an efficient and one-directional antenna system is obtained. The unidirectional energy transfer process from monomers to J-aggregates is demonstrated by remote excitation experiments along tens of microns of distance.Financial support from Gobierno Vasco (IT912-16) and Ministerio de Economía y Competitividad “MINECO” (through Projects MAT2014-51937-C3-3-P, MAT2016-77496-R and MAT-2015-65767-P) is acknowledged. R.S.L. and V.M.M. acknowledge niversidad del PaísVasco (UPV-EHU) for a postdoctoral fellowship and MINECO for a “Ramón y Cajal” Contract RYC-2011-09505), respectively. H.U. gratefully acknowledges the financial support of the European Research Council (#280064), the FWO (G056314N, G0B5514N, G081916N), and JSPS KAKENHI (JP17H03003, JP17H05244, JP17H05458). Centro Técnico de Informática (CSIC) is acknowledged for running the calculations and Accelrys for providing the computational softwar