Staff directory
Claudio Roscini
Senior Researcher
claudio.roscini(ELIMINAR)@icn2.cat
Nanostructured Functional Materials
- ORCID: 0000-0002-0157-8934
Publications
2024
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Methylxanthines for halogen bonded cocrystals with 1,4-diiodotetrafluorobenzene: green synthesis, structure, photophysics and DFT studies
Benito, Monica; Nunez, Rosario; Sinha, Sohini; Roscini, Claudio; Hidalgo-Rosa, Yoan; Schott, Eduardo; Zarate, Ximena; Molins, Elies Crystengcomm; 2024. 10.1039/d4ce00138a.
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Multidimensional Data Encoding Based on Multicolor Microencapsulated Thermoresponsive Fluorescent Phase Change Materials
Otaegui, Jaume Ramon; Ruiz-Molina, Daniel; Hernando, Jordi; Roscini, Claudio Advanced Functional Materials; 2024. 10.1002/adfm.202402510.
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Rationalizing the carborane versus phenyl-driven luminescence in related dicarboxylic ligands and their antenna effect for their Eu3+ and Tb3+ metal-organic frameworks: a combined experimental and computational study
Li, Zhen; Roscini, Claudio; Nunez, Rosario; Teixidor, Francesc; Vinas, Clara; Ruiz, Eliseo; Planas, Jose Giner Journal Of Materials Chemistry c; 12 (6): 2101 - 2109. 2024. 10.1039/d3tc04018f.
2023
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A Metal-Organic Framework Incorporating Eight Different Size Rare-Earth Metal Elements: Toward Multifunctionality A La Carte
Li, Z; Li, XB; Light, ME; Carrillo, AE; Arauzo, A; Valvidares, M; Roscini, C; Teixidor, F; Vinas, C; Gandara, F; Bartolomé, E; Planas, JG Advanced Functional Materials; 33 (47) 2023. 10.1002/adfm.202307369. IF: 19.000
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Multistimuli-responsive smart windows based on paraffin-polymer composites
Otaegui, JR; Ruiz-Molina, D; Hernando, J; Roscini, C Chemical Engineering Journal; 463: 142390. 2023. 10.1016/j.cej.2023.142390. IF: 15.100
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Water-Stable Upconverting Coordination Polymer Nanoparticles for Transparent Films and Anticounterfeiting Patterns with Air-Stable Upconversion
Zhang, JD; Ruiz-Molina, D; Novio, F; Roscini, C Acs Applied Materials & Interfaces; 15 (6): 8377 - 8386. 2023. 10.1021/acsami.2c16354. IF: 9.500
2022
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Multimodal Fluorescence Switching Materials: One Dye to Have Them All
Otaegui J.R., Carrascull-Marín A., Ruiz-Molina D., Hernando J., Roscini C. Advanced Optical Materials; 2022. 10.1002/adom.202200083.
Off/on, on/off, and on1/on2 fluorescence switching systems find application in a variety of areas, for each of which a particular dye or dye-switch tether must be specifically designed and synthesized. Herein it is demonstrated that such tight requirement can be avoided by using easily prepared mixtures of readily available emitters and phase change materials (PCMs). By proper selection of the PCM and, if needed, additives, thermo- and photothermoresponsive materials showing all classes of emission switching modes can be prepared from a single dye and without chemical modifications. This strategy can be generalized to distinct emitters and, thanks to the facile and versatile printability of dye–PCM mixtures, it can be used for the fabrication of fluorescent patterns showing complex (photo)thermal responses with direct applicability in sensing and anti-counterfeiting. © 2022 The Authors. Advanced Optical Materials published by Wiley-VCH GmbH.
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Tunable Thermofluorochromic Sensors Based on Conjugated Polymers
Bellacanzone C., Otaegui J.R., Hernando J., Ruiz-Molina D., Roscini C. Advanced Optical Materials; 10 (10, 2102423) 2022. 10.1002/adom.202102423. IF: 9.926
Even though thermofluorochromic materials are eternal candidates for their use in multiple applications, they are still limited as they require complex synthetic strategies to accomplish tunable optical properties and/or provide optical changes only over a very wide temperature range. By taking advantage of the high sensitivity of the optical properties of conjugated polymers and oligomers to the external environment, herein phase change material (PCM)-based thermofluorochromic mixtures are created, where the solid-to-liquid transition of the PCM host triggers a sharp fluorescence color change of the dispersed polymers/oligomers. Fluorophore conjugation length, concentration, and PCM nature can be used to vary the spectral properties of the resulting materials along the visible region, covering a large part of the CIE 1931 color space. For the preparation of functional devices, this behavior can be directly transferred to the solid state by soaking or printing cellulose papers with the obtained thermofluorochromic mixtures as well as by structuring them into solid lipid particles that can be dispersed within polymer matrices. The resulting materials show very promising features as thermal sensors and anticounterfeiting labels. © 2022 The Authors. Advanced Optical Materials published by Wiley-VCH GmbH.
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Water-Stable Carborane-Based Eu3+/Tb3+Metal-Organic Frameworks for Tunable Time-Dependent Emission Color and Their Application in Anticounterfeiting Bar-Coding
Li Z., Núñez R., Light M.E., Ruiz E., Teixidor F., Viñas C., Ruiz-Molina D., Roscini C., Planas J.G. Chemistry of Materials; 2022. 10.1021/acs.chemmater.2c00323.
Luminescent lanthanide metal-organic frameworks (Ln-MOFs) have been shown to exhibit relevant optical properties of interest for practical applications, though their implementation still remains a challenge. To be suitable for practical applications, Ln-MOFs must be not only water stable but also printable, easy to prepare, and produced in high yields. Herein, we design and synthesize a series of mCB-EuyTb1-y (y = 0-1) MOFs using a highly hydrophobic ligand mCBL1: 1,7-di(4-carboxyphenyl)-1,7-dicarba-closo-dodecaborane. The new materials are stable in water and at high temperature. Tunable emission from green to red, energy transfer (ET) from Tb3+ to Eu3+, and time-dependent emission of the series of mixed-metal mCB-EuyTb1-y MOFs are reported. An outstanding increase in the quantum yield (QY) of 239% of mCB-Eu (20.5%) in the mixed mCB-Eu0.1Tb0.9 (69.2%) is achieved, along with an increased and tunable lifetime luminescence (from about 0.5 to 10 000 μs), all of these promoted by a highly effective ET process. The observed time-dependent emission (and color), in addition to the high QY, provides a simple method for designing high-security anticounterfeiting materials. We report a convenient method to prepare mixed-metal Eu/Tb coordination polymers (CPs) that are printable from water inks for potential applications, among which anticounterfeiting and bar-coding have been selected as a proof-of-concept. © 2022 The Authors. Published by American Chemical Society.
2021
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Encapsulation and sedimentation of nanomaterials through complex coacervation
González-Monje P., Ayala García A., Ruiz-Molina D., Roscini C. Journal of Colloid and Interface Science; 589: 500 - 510. 2021. 10.1016/j.jcis.2020.12.067. IF: 8.128
Hypothesis: Nanoparticles removal from seawage water is a health and environmental challenge, due to the increasing use of these materials of excellent colloidal stability. Herein we hypothesize to reach this objective through complex coacervation, a straightforward, low-cost process, normally accomplished with non-toxic and biodegradable macromolecules. Highly dense polymer-rich colloidal droplets (the coacervates) obtained from a reversible charge-driven phase separation, entrap suspended nanomaterials, allowing their settling and potential recovery. Experiments: In this work we apply this process to highly stable aqueous colloidal dispersions of different surface charge, size, type and state (solid or liquid). We systematically investigate the effects of the biopolymers excess and the nanomaterials concentration and charge on the encapsulation and sedimentation efficiency and rate. This strategy is also applied to real laboratory water-based wastes. Findings: Long-lasting colloidal suspensions are succesfully destabilized through coacervate formation, which ensures high nanomaterials encapsulation efficiencies (~85%), payloads and highly tranparent supernatants (%T ~90%), within two hours. Lower polymer excess induces faster clearance and less sediments, while preserving effective nanomaterials removal. Preliminary experiments also validate the method for the clearance of real water residuals, making complex coacervation a promising scalable, low-cost and ecofriendly alternative to concentrate, separate or recover suspended micro/nanomaterials from aqueous sludges. © 2020 Elsevier Inc.
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Photoactivable ruthenium-based coordination polymer nanoparticles for light-induced chemotherapy
Zhang J., Ramu V., Zhou X.-Q., Frias C., Ruiz-Molina D., Bonnet S., Roscini C., Novio F. Nanomaterials; 11 (11, 3089) 2021. 10.3390/nano11113089. IF: 5.076
Green light photoactive Ru-based coordination polymer nanoparticles (CPNs), with chemical formula [[Ru(biqbpy)]1.5 (bis)](PF6)3 (biqbpy = 6,6′-bis[N-(isoquinolyl)-1-amino]-2,2′-bipyridine; bis = bis(imidazol-1-yl)-hexane), were obtained through polymerization of the trans-[Ru(biqbpy) (dmso)Cl]Cl complex (Complex 1) and bis bridging ligands. The as-synthesized CPNs (50 ± 12 nm di-ameter) showed high colloidal and chemical stability in physiological solutions. The axial bis(imidazole) ligands coordinated to the ruthenium center were photosubstituted by water upon light irradiation in aqueous medium to generate the aqueous substituted and active ruthenium complexes. The UV-Vis spectral variations observed for the suspension upon irradiation corroborated the photoactivation of the CPNs, while High Performance Liquid Chromatography (HPLC) of irradiated particles in physiological media allowed for the first time precisely quantifying the amount of photoreleased complex from the polymeric material. In vitro studies with A431 and A549 cancer cell lines revealed an 11-fold increased uptake for the nanoparticles compared to the monomeric complex [Ru(biqbpy)(N-methylimidazole)2 ](PF6)2 (Complex 2). After irradiation (520 nm, 39.3 J/cm2), the CPNs yielded up to a two-fold increase in cytotoxicity compared to the same CPNs kept in the dark, indicating a selective effect by light irradiation. Meanwhile, the absence of1 O2 production from both nanostructured and monomeric prodrugs concluded that light-induced cell death is not caused by a photodynamic effect but rather by photoactivated chemotherapy. © 2021 by the authors. Licensee MDPI, Basel, Switzerland.
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Thermoresponsive multicolor-emissive materials based on solid lipid nanoparticles
Otaegui J.R., Ruiz-Molina D., Latterini L., Hernando J., Roscini C. Materials Horizons; 8 (11): 3043 - 3054. 2021. 10.1039/d1mh01050f. IF: 13.266
Despite the recent advances in the field of thermofluorochromism, the fabrication of thermoresponsive multicolor-emissive materials in a simple, low-cost and versatile manner still remains a challenge. Herein we accomplish this goal by expanding the concept of matrix-induced thermofluorochromism, where a sudden two-state variation of dyes' emission is promoted by the solid-liquid transition of a surrounding phase change material (e.g., paraffins). We demonstrate that this behavior can be transferred to the nanoscale by the synthesis of dye-loaded solid lipid nanoparticles, different types of which can then be combined into a single platform to obtain multicolor thermofluorochromism using a single type of emitter. Because of the reduced dimensions of these particles, they can be utilized to prepare transparent nanocomposites and inkjet-printed patterns showing complex thermoresponsive luminescence signals and applications ranging from smart displays to thermal sensing and high-security anti-counterfeiting. © 2021 The Royal Society of Chemistry.
2020
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Highly transparent photochromic films with a tunable and fast solution-like response
Torres-Pierna H., Ruiz-Molina D., Roscini C. Materials Horizons; 7 (10): 2749 - 2759. 2020. 10.1039/d0mh01073a. IF: 12.319
The increasing interest towards photochromic films and their practical applications is driving researchers in the continuous design and synthesis of novel organic photochromic dyes with optimized performances in polymeric matrices. However, whereas their photochromic properties could be readily rationalized in organic liquid solutions, these could not be directly extrapolated to polymers as their performance changes unpredictably upon integration into a solid matrix. This leads to a time-consuming synthetic re-tuning of the dye chemical structure and/or the polymeric medium. To avoid this, herein we report an efficient, straightforward and universal strategy to embed commercial T-type organic photochromic dyes of different nature in a polymeric material without compromising their optimum solution absorption and isomerization kinetics. Our approach is based on trapping emulsified nanodroplets of a hydrophobic solution enclosing the dye into a hydrophilic polymeric matrix. The material is prepared through one single process using commercially available materials, without further modification of the components (the dye and the polymer matrix) nor requiring previous encapsulation steps. The films, which manifest true solution liquid-like and finely tunable photochromic behavior, are also highly transparent, recyclable, and scalable, and show enhanced fatigue resistance, making them highly suitable for different smart glass applications. © 2020 The Royal Society of Chemistry.
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Shape Memory Polyurethane Microcapsules with Active Deformation
Zhang F., Zhao T., Ruiz-Molina D., Liu Y., Roscini C., Leng J., Smoukov S.K. ACS Applied Materials and Interfaces; 2020. 10.1021/acsami.0c14882. IF: 8.758
From smart self-tightening sutures and expandable stents to morphing airplane wings, shape memory structures are increasingly present in our daily life. The lack of methods for synthesizing intricate structures from them on the micron and submicron level, however, is stopping the field from developing. In particular, the methods for the synthesis of shape memory polymers (SMPs) and structures at this scale and the effect of new geometries remain unexplored. Here, we describe the synthesis of shape memory polyurethane (PU) capsules accomplished by interfacial polymerization of emulsified droplets. The emulsified droplets contain the monomers for the hard segments, while the continuous aqueous phase contains the soft segments. A trifunctional chemical cross-linker for shape memory PU synthesis was utilized to eliminate creep and improve the recovery ratios of the final capsules. We observe an anomalous dependence of the recovery ratio with the amount of programmed strain compared to previous SMPs. We develop quantitative characterization methods and theory to show that when dealing with thin-shell objects, alternative parameters to quantify recovery ratios are needed. We show that while achieving 94-99% area recovery ratios, the linear capsule recovery ratios can be as low as 70%. This quantification method allows us to convert from observed linear aspect ratios in capsules to find out unrecovered area strain and stress. The hollow structure of the capsules grants high internal volume for some applications (e.g., drug delivery), which benefit from much higher loading of active ingredients than polymeric particles. The methods we developed for capsule synthesis and programming could be easily scaled up for larger volume applications. Copyright © 2020 American Chemical Society.
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Solid Materials with Near-Infrared-Induced Fluorescence Modulation
Otaegui J.R., Rubirola P., Ruiz-Molina D., Hernando J., Roscini C. Advanced Optical Materials; 8 (21, 2001063) 2020. 10.1002/adom.202001063. IF: 8.286
Solid molecular materials modulating their luminescent properties upon irradiation are typically based on photochromic dyes. Despite these are potentially interesting for applications such as anticounterfeiting, bioimaging, optical data storage, and writable/erasable devices, key features are preventing their use in marketable products: the lack of straightforward strategies to obtain near infrared (NIR) radiation-responding photochromic dyes and the dramatic response modification these molecules suffer in solids. Herein a photochrome-free approach is reported to achieve solid materials whose luminescence modulation is induced by NIR radiation. This strategy is based on the capacity of phase change materials (PCMs) to modify the emission properties of fluorescent dyes upon photothermally induced interconversion between their solid and liquid states. The preparation of several NIR-responsive thermofluorochromic materials of high fatigue resistance and nondestructive readout is illustrated and this approach is extended to different commercially available dyes, taking advantage of distinct fluorescence modulation mechanisms, providing, thus, color tunability. The modulation response is straightforwardly tuned by simply varying the irradiation power density, the gold nanoshell concentration, and/or the PCM type. This tunability allows to accomplish NIR-activated multistate thermofluorochromic materials and fast/slow/irreversible responses in NIR-writings/drawings of good spatial resolution, which can be of interest for barcodings, anticounterfeiting technologies and (re)writable devices. © 2020 Wiley-VCH GmbH
2019
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Color-Tunable White-Light-Emitting Materials Based on Liquid-Filled Capsules and Thermally Responsive Dyes
Vázquez-Mera N.A., Otaegui J.R., Sánchez R.S., Prats G., Guirado G., Ruiz-Molina D., Roscini C., Hernando J. ACS Applied Materials and Interfaces; 11 (19): 17751 - 17758. 2019. 10.1021/acsami.9b02169. IF: 8.456
Color-tunable white-light-emitting materials are currently attracting much attention because of their potential applications in artificial lighting, sensing, and imaging. However, preparation of these systems from organic emitters is often cumbersome due to the interchromophoric interactions occurring upon solvent drying in the final solid materials, which can be hardly predicted and may lead to detrimental effects. To circumvent these obstacles, we have developed a new fabrication methodology that relies on dye encapsulation within liquid-filled capsules, thus enabling direct transfer of the luminescent properties from solution to the solid state and as such, rational design of miniaturized white-light-emitting materials. By introducing a thermally responsive chromophore into the capsules, these materials are further endowed with color tunability, which does not only allow ample modulation of the emitted color but also facilitate external fine control of the system so as to ensure precise realization of white light at the desired temperature and excitation wavelength. © 2019 American Chemical Society.
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Solid Materials with Tunable Reverse Photochromism
Julià-López A., Ruiz-Molina D., Hernando J., Roscini C. ACS Applied Materials and Interfaces; 11 (12): 11884 - 11892. 2019. 10.1021/acsami.8b22335. IF: 8.456
Herein, we report a novel, straightforward, and universal strategy to achieve solid materials with highly tunable reverse photochromism. This was accomplished by means of commercially available spiropyran dyes, which can produce different types of stable merocyanine states (i.e., nonprotonated and protonated forms) displaying distinct reverse photochromic properties (i.e., colors and coloration rates). To finely control the concentration ratio of these species and, as such, tailor the optical performance of the photochromes, we exploited their differential interaction with surrounding media of distinctive nature (i.e., nonvolatile protic and aprotic polar solvents). In this way, solutions displaying different photochromic responses were prepared for individual spiropyrans without requiring chemical derivatization, an approach that can be generalized to other spiro dyes with distinct acid-base properties. To transfer this behavior to the solid state, core-shell capsules of these solutions were prepared, which were then used as ink materials for the fabrication of flexible polymeric films with unprecedented tunability of their photochromic properties that can be employed as rewritable multicolored devices. © 2019 American Chemical Society.
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Thermal Control of Intermolecular Interactions and Tuning of Fluorescent-State Energies
Massaro G., Zampini G., Ruiz-Molina D., Hernando J., Roscini C., Latterini L. Journal of Physical Chemistry C; 123 (8): 4632 - 4637. 2019. 10.1021/acs.jpcc.8b09774. IF: 4.309
The prospect of tuning the energy of emitting states through external stimuli opens the possibility of shifting the energy of emitting units on demand and controlling the bimolecular processes they are involved in. To prove this concept, the fluorescence properties of three differently 9,10-substituted anthracene (ANT) derivatives are investigated in a phase-change material (eicosane). The liquid-to-solid transition of the medium leads to an increase of the local dye concentration, a shortening of the intermolecular distances, and the establishment of excited- and ground-state interactions. As a result, a new contribution to the overall luminescence that derives from the downshifted emission (up to 0.7 eV) from excimer-like species is observed. The addition of a second dye (a Pt-porphyrin) reduces the efficiency of excited- and ground-state complexes between fluorophore units, although it does not prevent the formation of multichromophoric aggregates where interactions between Pt-porphyrin and the emissive state of ANT derivatives are observed. The emission of excimer-like species, formed upon solidification of the medium, can be exploited to further down-shift the fluorescence through energy-transfer processes to a suitable energy acceptor, such as rubrene. © 2019 American Chemical Society.
2018
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Molecular-based upconversion in homo/heterogeneous liquids and in micro/nanostructured solid materials
Latterini L., Massaro G., Penconi M., Gentili P.L., Roscini C., Ortica F. Dalton Transactions; 47 (26): 8557 - 8565. 2018. 10.1039/c8dt00020d. IF: 4.099
Radiation upconversion can be an elegant and efficient strategy to minimize waste in energy harvesting and storage processes. The upconversion based on triplet-triplet annihilation processes of molecular dyes is a very versatile approach, but it requires a systematic photophysical characterization of the systems to optimize the upconversion yields and develop materials for technological applications. This paper represents an overview of the work carried out in our laboratories for the study and characterization of a molecular dye pair, 2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphyrin platinum(ii) (PtOEP) and 1,3,6,8-tetraphenylpyrene (TPPy), suitable as the sensitizer and emitter, respectively, in a triplet-triplet annihilation based upconversion process. The investigation has been carried out in various media with increasing complexity. First, we used the dye pair to characterize the UC-efficiencies in homogeneous solvents of different viscosities and in oil-in-water microemulsions; then we explored the possibility to achieve upconversion in solid materials, like nanostructured silica matrices and liquid filled microcapsules. The possibility to achieve upconversion emission even in confined and rigid media has been confirmed and can inspire further applications of the process. © The Royal Society of Chemistry 2018.
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Off/On Fluorescent Nanoparticles for Tunable High-Temperature Threshold Sensing
Julià López A., Ruiz-Molina D., Landfester K., Bannwarth M.B., Roscini C. Advanced Functional Materials; 28 (28, 1801492) 2018. 10.1002/adfm.201801492. IF: 13.325
Herein, a versatile threshold temperature sensor based on the glass transition temperature-triggered fluorescence activation of a dye/developer duo, encapsulated in polymeric nanoparticles is reported. The emission enhancement, detectable even by unaided eye is completed within a narrow temperature range and activates at adjustable threshold temperatures up to 200 °C. Fluorescence is chosen as sensing probe due to its high detection sensitivity together with an advanced spatial and temporal resolution. The strategy is based on nanoparticles prepared from standard thermoplastic polymers, a fluorescence developer, and the commercially available Rhodamine B base dye, a well-known and widely used fluorescent molecule. By making nanoparticles of different thermoplastic polymers, fast, abrupt, and irreversible disaggregation induced fluorescence enhancement, with tunable threshold temperature depending on the nanoparticles polymer glass transition is achieved. As a proof-of-concept for the versatility of this novel family of NPs, their use for sensing the thermal history of environments and surfaces exposed to the threshold temperature is showed. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Solvent-Tuned Supramolecular Assembly of Fluorescent Catechol/Pyrene Amphiphilic Molecules
Nador F., Wnuk K., Roscini C., Solorzano R., Faraudo J., Ruiz-Molina D., Novio F. Chemistry - A European Journal; 24 (55): 14724 - 14732. 2018. 10.1002/chem.201802249. IF: 5.160
The synthesis and structuration of a novel low-molecular-weight amphiphilic catechol compound is reported. The combination of a hydrophilic tail containing a catechol unit and a pyrene-based hydrophobic head favors solvent-tuned supramolecular assembly. Formation of hollow nanocapsules/vesicles occurs in concentrated solutions of polar protic and nonprotic organic solvents, whereas a fibril-like aggregation process is favored in water, even at low concentrations. The emission properties of the pyrene moiety allow monitoring of the self-assembly process, which could be confirmed by optical and electronic microscopy. In organic solvents and at low concentrations, this compound remains in its nonassembled monomeric form. As the concentration increases, the aggregation containing preassociated pyrene moieties becomes more evident up to a critical micellar concentration, at which vesicle-like structures are formed. In contrast, nanosized twist beltlike fibers are observed in water, even at low concentrations, whereas microplate structures appear at high concentrations. The interactions between molecules in different solvents were studied by using molecular dynamics simulations, which have confirmed different solvent-driven supramolecular interactions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Sonochemical Synthesis of Optically Tuneable Conjugated Polymer Nanoparticles
Bellacanzone C., Roscini C., del Carmen Ruiz Delgado M., Ponce Ortiz R., Ruiz-Molina D. Particle and Particle Systems Characterization; 35 (2, 1700322) 2018. 10.1002/ppsc.201700322. IF: 4.384
The development of novel and simple methodologies for the obtaining of semiconductive polymer nanoparticles with fine-tuned optical properties represents nowadays a challenging research area as it involves a simultaneous chemical modification and nanostructuration of the polymer. Here, starting from poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene], this objective is achieved with the one-pot synthesis of oligomers with tunable conjugation length and their nanostructuration, employing a miniemulsion method. Ultrasound irradiation of heterogeneous mixtures leads to the formation of hypochlorous acid that disrupts the electronic conjugation through polymer chain cleavage. Moreover, control over the degree of the electronic conjugation of the oligomers, and therefore of the optical properties, is achieved simply by varying the polymer concentration of the initial solution. Finally, the presence of surfactants during the sonication allows for the formation of nanoparticles with progressive spectral shift of the main absorption (from λmax = 476 to 306 nm) and emission bands (from λmax = 597 to 481 nm). The integration of conducting polymer nanoparticles into polymeric matrices yields self-standing and flexible fluorescent films. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
2017
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Photochromism of dihydroazulene-based polymeric thin films
Torres-Pierna H., Roscini C., Vlasceanu A., Broman S.L., Jevric M., Cacciarini M., Nielsen M.B. Dyes and Pigments; 145: 359 - 364. 2017. 10.1016/j.dyepig.2017.06.015. IF: 3.473
We report on the preparation of polymeric thin films doped with six dihydroazulene derivatives whose photochromic properties were previously screened in organic solution studies. Spectroscopic investigations into the photochromic behavior of the polymeric matrices have given important insights on the stability and the photophysical properties of the photoswitches impregnated into polymers. © 2017 Elsevier Ltd
2016
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Switchable colloids, thin-films and interphases based on metal complexes with non-innocent ligands: The case of valence tautomerism and their applications
Vázquez-Mera N.A., Novio F., Roscini C., Bellacanzone C., Guardingo M., Hernando J., Ruiz-Molina D. Journal of Materials Chemistry C; 4 (25): 5879 - 5889. 2016. 10.1039/c6tc00038j. IF: 5.066
Successful nanostructuration approaches developed in the last few years have allowed the preparation of robust valence tautomeric (VT) switchable (micro-/nano-) structures of a variety of dimensions and morphologies. These results are expected to definitely foster the implementation of these materials on hybrid molecular electronic devices but also endorse new applications in other different fields such as sensing, drug delivery or water remediation, among others. © The Royal Society of Chemistry 2016.
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Temperature-Controlled Switchable Photochromism in Solid Materials
Julià-López A., Hernando J., Ruiz-Molina D., González-Monje P., Sedó J., Roscini C. Angewandte Chemie - International Edition; 55 (48): 15044 - 15048. 2016. 10.1002/anie.201608408. IF: 11.709
A novel strategy to achieve thermally switchable photochromism in solid materials is reported, which relies on the preparation of polymeric core–shell capsules containing solutions of photochromic dyes in acidic phase-change materials. Upon changing the phase (solid or liquid) of the encapsulated medium, one of the two photochromic states of the system is selectively stabilized on demand, allowing for reversible interconversion between direct and reverse photochromism when thermally scanning through the melting temperature of the phase-change material. This strategy, which does not require the addition of external agents or chemical modification of the dyes, proved to be general for different spiropyran photochromes and to be applicable to the fabrication of a variety of functional materials by simply embedding the capsules obtained into a solid matrix of choice. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Thermally Switchable Molecular Upconversion Emission
Massaro G., Hernando J., Ruiz-Molina D., Roscini C., Latterini L. Chemistry of Materials; 28 (3): 738 - 745. 2016. 10.1021/acs.chemmater.5b03532. IF: 9.407
In this work a novel strategy is introduced to achieve thermally switchable emission from photon upconversion (UC) systems based on organic dyes. When these molecules were dissolved at low concentrations in phase-change media, a reversible, sharp, and nearly complete interconversion from blue upconverted emission to red luminescence was observed around the solid-to-liquid transition of the system. This result was rationalized in terms of dye aggregation, which selectively occurs in the solid state and dramatically enhances the inter-chromophoric energy transfer processes leading to UC. Notably, this behavior is extendable to different media and dyes, which allows an easy tuning of the switching temperature and emission colors. In addition, with proper selection of the phase-change medium, our strategy permits facile preparation of solid molecular materials showing photon UC at room temperature and even at sub-micromolar dye concentrations. © 2016 American Chemical Society.
2015
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Liquid-Filled Valence Tautomeric Microcapsules: A Solid Material with Solution-Like Behavior
Vázquez-Mera N.A., Roscini C., Hernando J., Ruiz-Molina D. Advanced Functional Materials; 25 (26): 4129 - 4134. 2015. 10.1002/adfm.201501166. IF: 11.805
The integration of stimuli-responsive valence tautomeric (VT) molecular systems into solid materials without compromising their functionality is a major bottleneck for the use of these compounds in high-added value applications. In this work, an innovative, simple, and universal approach is described to tackle this challenge based on the confinement of the active species into liquid-filled polymeric capsules. A microstructured solid with optimized solution-like behavior is obtained in this way, whose VT properties can be rationally tuned upon variation of the encapsulated solvent. Incorporation of the resulting capsules into thin films or other matrices of interest allows successful transfer of valence tautomerism from the liquid phase to solid materials, thus paving the way to the fabrication of functional devices based on spin transition compounds. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
2014
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Bio- and Bioinspired Nanomaterials
Ruiz-Molina D., Novio F., Roscini C. Bio- and Bioinspired Nanomaterials; 9783527335817: 1 - 457. 2014. 10.1002/9783527675821.
A comprehensive overview of nanomaterials that are inspired by or targeted at biology, including some of the latest breakthrough research. Throughout, valuable contributions from top-level scientists illustrate how bionanomaterials could lead to novel devices or structures with unique properties. The first and second part cover the most relevant synthetic and bioinspired nanomaterials, including surfaces with extreme wettability properties, functional materials with improved adhesion or structural and functional systems based on the complex and hierarchical organization of natural composites. These lessons from nature are explored in the last section where bioinspired materials are proposed for biomedical applications, showing their potential for future applications in drug delivery, theragnosis, and regenerative medicine. A navigational guide aimed at advanced and specialist readers, while equally relevant for readers in research, academia or private companies focused on high added-value contributions. Young researchers will also find this an indispensable guide in choosing or continuing to work in this stimulating area, which involves a wide range of disciplines, including chemistry, physics, materials science and engineering, biology, and medicine. © 2015 Wiley-VCH Verlag GmbH & Co. KGaA. All rights reserved.
2013
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Liquid-filled capsules as fast responsive photochromic materials
Vázquez-Mera, N.; Roscini, C.; Hernando, J.; Ruiz-Molina, D. Advanced Optical Materials; 1: 631 - 636. 2013. 10.1002/adom.201300121. IF: 0.000