Publications
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A copper(II) zig-zag metal–organic coordination polymer: synthesis, crystal structure, topology study, hirshfeld surface analysis and survey different conditions on morphology of a novel nano structure [Cu(L)(SCN)(H2O)2]n.2H2O
Souri B., Hayati P., Rezvani A.R., Mendoza-Meroño R., Janczak J. Inorganic and Nano-Metal Chemistry; 50 (2): 80 - 93. 2020. 10.1080/24701556.2019.1662040. IF: 0.839
One copper(II) coordination polymer compound [Cu(L)(SCN)(H2O)2]n.2H2O (1) where L stand for 2-pyridinecarboxylic acid, was synthesized following two different experimental methods, branch tube and sonochemical irradiation nano methods. Independently of the methodology used, the same crystalline phase is obtained for each compound. Single crystal X-ray analyses on compound 1 showed that Cu2+ ions are 6-coordinated. Additionally, H-bonds incorporate the zig-zag chains in 1 into 2D (along (1,1,0) direction) frameworks. Topological analysis shows that the compound 1 is 2C1 net. Hirshfeld surface analysis of compound 1 was studied. Also, theoretical and experimental morphology were studied. The thermal stability of compound 1 was studied by thermal gravimetric. Finally, the role of reaction time and temperature on growth and final morphology of the structures obtained by sonochemical irradiation are investigated. The results indicated that particle size was reduced with increasing sonication power, temperature, sonication time and decreasing concentration of reactant. © 2019, © 2019 Taylor & Francis Group, LLC.
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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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Luminescent silicon-based nanocarrier for drug delivery in colorectal cancer cells
Marcelo G.A., Montpeyo D., Novio F., Ruiz-Molina D., Lorenzo J., Oliveira E. Dyes and Pigments; 181 (108393) 2020. 10.1016/j.dyepig.2020.108393. IF: 4.613
Nanocarriers sensitive to exogenous or endogenous stimuli emerged as an attractive alternative to target drug delivery, with inorganic silica mesoporous nanoparticles (MNs) playing a core role in the development of a new generation of non-toxic and tuneable nanocarriers. A sensitive nanovector (NANO1) comprising luminescent silicon quantum dots (SiQDs) and functionalized with MNs was synthesised and loaded with doxorubicin (DOX). NANO1 nanoparticles have a size of 74 ± 10 nm and DOX loading percentages of ca. 43%. As a control sample, a similar nanocarrier (NANO2), without SiQDs, was also synthesised and loaded with DOX. Release profile studies, in PBS, revealed the strong NANO1@DOX pH-dependant behaviour, with a pH 5.0 favouring the release of DOX to percentages of ca. 70%. Cytotoxicity assessments of both free and DOX-loaded nanocarriers were evaluated in human cell lines of colon, revealing both free drug and drug-loaded nanoparticles to be concentration-dependent. © 2020 Elsevier Ltd
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Pathway selection as a tool for crystal defect engineering: A case study with a functional coordination polymer
Abrishamkar A., Suárez–García S., Sevim S., Sorrenti A., Pons R., Liu S.-X., Decurtins S., Aromí G., Aguilà D., Pané S., deMello A.J., Rotaru A., Ruiz–Molina D., Puigmartí-Luis J. Applied Materials Today; 20 (100632) 2020. 10.1016/j.apmt.2020.100632. IF: 8.352
New synthetic routes capable of achieving defect engineering of functional crystals through well-controlled pathway selection will spark new breakthroughs and advances towards unprecedented and unique functional materials and devices. In nature, the interplay of chemical reactions with the diffusion of reagents in space and time is already used to favor such pathway selection and trigger the formation of materials with bespoke properties and functions, even when the material composition is preserved. Following this approach, herein we show that a controlled interplay of a coordination reaction with mass transport (i.e. the diffusion of reagents) is essential to favor the generation of charge imbalance defects (i.e. protonation defects) in a final crystal structure (thermodynamic product). We show that this synthetic pathway is achieved with the isolation of a kinetic product (i.e. a metastable state), which can be only accomplished when a controlled interplay of the reaction with mass transport is satisfied. Accounting for the relevance of controlling, tuning and understanding structure-properties correlations, we have studied the spin transition evolution of a well-defined spin-crossover complex as a model system. © 2020 Elsevier Ltd
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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
