Structural and theoretical study of copper(ii)-5-fluoro uracil acetate coordination compounds: Single-crystal to single-crystal transformation as possible humidity sensor

This paper describes the synthesis and characterization of seven different copper(II) coordination compounds, as well as the formation of a protonated ligand involving all compounds from the same reaction. Their synthesis required hydrothermal conditions, causing the partial in situ transformation of 5-fluoro uracil-1-acetic acid (5-FUA) into an oxalate ion (ox), as well as the protonation of the 4,4′-bipyridine (bipy) ligand through a catalytic process resulting from the presence of Cu(II) within the reaction. These initial conditions allowed obtaining the new coordination compounds [Cu2(5-FUA)2(ox)(bipy)]n·2n H2O (CP2), [Cu(5-FUA)2(H2O)(bipy)]n·2n H2O (CP3), as well as the ionic pair [(H2bipy)+2 2NO3−] (1). The mother liquor evolved rapidly at room temperature and atmospheric pressure, due to the change in concentration of the initial reagents and the presence of the new chemical species generated in the reaction process, yielding CPs [Cu(5-FUA)2(bipy)]n·3.5n H2O, [Cu3(ox)3(bipy)4]n and [Cu(ox)(bipy)]n. The molecular compound [Cu(5-FUA)2(H2O)4]·4H2O (more thermodynamically stable) ended up in the mother liquor after filtration at longer reaction times at 25 °C and 1 atm., cohabiting in the medium with the other crystalline solids in different proportions. In addition, the evaporation of H2O caused the single-crystal to single-crystal transformation (SCSC) of [Cu(5-FUA)2(H2O)(bipy)]n·2n H2O (CP3) into [Cu(5-FUA)2(bipy)]n·2n H2O (CP4). A theoretical study was performed to analyze the thermodynamic stability of the phases. The observed SCSC transformation also involved a perceptible color change, highlighting this compound as a possible water sensorPID2019-108028GB-C22, TED2021-131132B-C2

Rational design of copper(II)-uracil nanoprocessed coordination polymers to improve their cytotoxic activity in biological media

This work is focused on the rational structural design of two isostructural Cu(II) nano-coordination polymers (NCPs) with uracil-1-acetic acid (UAcOH) (CP1n) and 5-fluorouracil-1-acetic acid (CP2n). Suitable single crystals for ꭕ-ray diffraction studies of CP1 and CP2 were prepared under hydrothermal conditions, enabling their structural determination as 1D-CP ladder-like polymeric structures. The control of the synthetic parameters allows their processability into water colloids based on nanoplates (CP1n and CP2n). These NCPs are stable in water at physiological pHs for long periods. However, interestingly, CP1n is chemically altered in culture media. These transformations provoke the partial release of its building blocks and the formation of new species, such as [Cu(UAcO)2(H2O)4]·2H2O (Cu(II)-complex), and species corresponding to the partial reduction of the Cu(II) centers. The cytotoxic studies of CP1n versus human pancreatic adenocarcinoma and human uveal melanoma cells show that CP1n produces a decrease in the cell viability, while their UAcOH and Cu(II)-complex are not cytotoxic under similar conditions. The copper reduction species detected in the hydrolysis of CP1n are closely related to the formation of the reactive oxygen species (ROS) detected in the cytotoxic studies. These results prompted us to prepare CP2n that was designed to improve the cytotoxicity by the substitution of UAcO by 5-FUAcO, taking into account the anticancer activity of the 5-fluorouracil moiety. The new CP2n has a similar behavior to CP1n both in water and in biological media. However, its subtle structural differences are vital in improving its cytotoxic activity. Indeed, the release during the hydrolysis of species containing the 5-fluorouracil moiety provokes a remarkable increase in cellular toxicity and a significant increase in ROS species formationThe authors thank the financial support from the Spanish Ministerio de Economía y Competitividad (PID2019- 108028GB-C22, PID2019-108028GB-C21, MAT2016-77608- C3-1-P, MAT2016-75883-C2-1-P, MAT2016-75883-C2-2-P, MAT2016-75586-C4-4-P, and CTQ2017-87201-PAEI/ FEDER, UE) and the Generalidad Valenciana (Prometeo/ 2019/076

Multifunctional coordination polymers based on copper with modified nucleobases, easily modulated in size and conductivity

This Accepted Manuscript will be available for reuse under a CC BY-NC-ND licence after 24 months of embargo periodAll supplementary files included with this article are available online at: https://doi.org/10.1016/j.jinorgbio.2019.110805The research data (crystallographic data) associated with this article are available online at Cambridge Crystallographic Data Center: - CCDC 1934513: Experimental Crystal Structure Determination, 2019, DOI: 10.5517/ccdc.csd.cc22y0nq - CCDC 1934514: Experimental Crystal Structure Determination, 2019, DOI: 10.5517/ccdc.csd.cc22y0pr - CCDC 1934515: Experimental Crystal Structure Determination, 2019, DOI: 10.5517/ccdc.csd.cc22y0qsIn this work, three mono- and bidimensional coordination polymers (CPs) based on Cu(II) and Cu(I) ([Cu2(TAcO)2(C2O4)(4,4′-bpy)]·4H2O (CP1), [Cu2(UAcO)2(C2O4)(4,4′-bpy)]·2H2O (CP2) and [Cu2(TAcO)2(4,4′-bpy)] (CP3)), decorated with thymine and uracil-1-acetate (TAcO and UAcO), 4,4′-bipyridine (4,4′-bpy) and oxalate are synthetized. The supramolecular structures of the CPs are based on the formation of non-canonical hydrogen bonds established between the free moieties of nucleobases. Interestingly, the presence of Cu(II) centers provide for compound CP1, magnetism and semiconducting properties. Additionally, CP1 has been doped with iodine, increasing its electrical conductivity up to two orders of magnitude. Moreover, the size of the materials can be modulated from millimeters to the nanoscale, depending on the crystallization conditions and/or using ultrasoundThis work has been funded by Universidad del País Vasco/Euskal Herriko Unibertsitatea (GIU17/50 and PP617/37), Gobierno Vasco (PIBA18-59) and Ministerio de Economía y Competitividad (MAT2016-75883-C2-1-P, CTQ2017-87201-P, MAT2016-75883-C2-2-P

Direct Formation of Sub-Micron and Nanoparticles of a Bioinspired Coordination Polymer Based on Copper with Adenine

We report on the use of different reaction conditions, e.g., temperature, time, and/or concentration of reactants, to gain control over the particle formation of a bioinspired coordination polymer based on copper(II) and adenine, allowing homogeneous particle production from micro- to submicro-, and up to nano-size. Additionally, studies on this reaction carried out in the presence of different surfactants gives rise to the control of the particle size due to the modulation of the electrostatic interactions. Stability of the water suspensions obtained within the time and pH has been evaluated. We have also studied that there is no significant effect of the size reduction in the magnetic properties of the Cu(II)-adenine coordination polymer

3D Printing of a Thermo- and Solvatochromic Composite Material Based on a Cu(II)–Thymine Coordination Polymer with Moisture Sensing Capabilities

This is the peer reviewed version of the following article: Advanced Functional Materials 29.15 (2019): 1808424, which has been published in final form at https://doi.org/10.1002/adfm.201808424. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived VersionsThis work presents the fabrication of 3D-printed composite objects based on copper(II) 1D coordination polymer (CP1) decorated with thymine along its chains with potential utility as an environmental humidity sensor and as a water sensor in organic solvents. This new composite object has a remarkable sensitivity, ranging from 0.3% to 4% of water in organic solvents. The sensing capacity is related to the structural transformation due to the loss of water molecules that CP1 undergoes with temperature or by solvent molecules' competition, which induces significant change in color simultaneously. The CP1 and 3D printed materials are stable in air over 1 year and also at biological pHs (5–7), therefore suggesting potential applications as robust colorimetric sensors. These results open the door to generate a family of new 3D printed materials based on the integration of multifunctional coordination polymers with organic polymersN.M. and V.G.V. contributed equally to this work. The authors thank financial support from the Spanish Ministerio de Economía y Competitividad (MAT2016‐77608‐C3‐1‐P, MAT2016‐75883‐C2‐2‐P) and the National Research Foundation, Prime Minister's Office, Singapore, under its Campus for Research Excellence and Technological Enterprise (CREATE) programme. O.H. acknowledges the support for Ph.D. students from The Hebrew University of Jerusalem. J.I.M. acknowledges the financial support by the “Ramón y Cajal” Program of MINECO (Grant RYC‐2015‐17730) and the EU via the ERC‐Synergy Program (Grant ERC‐2013‐SYG‐610256 NANOCOSMOS). A.E.P.‐P. acknowledges a TALENTO grant (2017‐T1/IND5148) from Comunidad de Madrid. The authors acknowledge DESY (Hamburg, Germany), a member of the Helmholtz Association HGF, for the provision of experimental facilities. Parts of this research were carried out at beamline P02.1 PETRA III under the proposal I‐20170717 EC. V.G.V. thanks to the Ministry of Education, Youth and Sports, the Madrid Community and the European Social Fund. The authors thank Deseada Diaz Barrero, from Autonoma University of Madrid, Applied Physics Department, for the study of diffuse reflectance of the compound presented her