Fast and efficient direct formation of size-controlled nanostructures of coordination polymers based on copper(i)-iodine bearing functional pyridine terminal ligands

We report on the direct formation of 1D nanostructures of two coordination polymers based on copper(i)-iodine double chains decorated with ethyl isonicotinate or 2-amino-5-nitropyridine as terminal ligands. The use of different reaction conditions, e.g. energy of the formation process, solvents, and/or concentration of reactants, has allowed the control of the size of the fibres and ribbons directly formed in this process going from micron- to submicron- up to nano-size. We show experiments that direct the formation of materials kinetically versus thermodynamically controlled, adjusting simple experimental parameters. Finally, a morphological study on the Cu(i)-iodine bearing 2-amino-5-nitropyridine nanofibres has confirmed their reversible molecular recognition ability towards acetic acid vapoursWe are grateful for financial support from the Spanish Ministerio de Economía y Competitividad (MAT2013-46502-C2-2P, MAT2016-75883-C2-2-P, BES-2015-071534) and also to the scientific computing center (CCC) of the Autónoma University of Madrid for their tim

Differences in expression profiling and biomarkers between histological colorectal carcinomas subsets from the serrated pathway.

Histological subtypes of colorectal carcinomas (CRCs) arising from the serrated route, such as serrated adenocarcinoma (SAC) and CRC showing histological and molecular features of microsatellite instability (hmMSI-H), share common features (female gender, right-sided location, mucinous histology and altered CpG methylation) but dramatically differ in terms of prognosis, development of immune response and treatment options. Despite this, to date no expression profiling comparison has been carried out for finding out functions and molecules responsible for such differences. METHODS AND RESULTS: Molecular signatures of SAC and hmMSI-H were obtained by transcriptomic array; qPCR and immunohistochemistry (IHC) were used to validate differentially expressed genes. An over-representation of innate immunity functions (granulomonocytic recruitment, chemokine production, TLR signaling, antigen processing and presentation) were obtained from this comparison and ICAM1 was more expressed in hmMSI-H whereas two genes (CRCP and CXCL14) were more expressed in SAC. These array results were subsequently validated by qPCR, and CXCL14 and ICAM1 by IHC. Information retrieved from public databanks confirmed our findings. CONCLUSIONS: Our findings highlight specific functions and genes which provide a better understanding of the role of the immune response in the serrated pathological route and may be of help in identifying actionable molecules. This article is protected by copyright. All rights reserved.pre-print664 K

Micro and nano smart composite films based on copper-iodine coordination polymer as thermochromic biocompatible sensors

Herein is presented the preparation and characterization of a composite material obtained by the combination of nanosheets of a coordination polymer (CP) based on the copper(I)-I double chain with response to temperature and pressure with polylactic acid (PLA) as biodegradable organic matrix. The new films of composite materials are generated using a simple and low-cost method and can be created with long lateral dimensions and thicknesses ranging from a few microns to a few nanometers. Studies show that the new material maintains the optical response versus the temperature, while the elasticity and flexibility of the PLA totally quenches the response to pressure previously observed for the CP. This new material can act as a reversible sensor at low temperatures, thanks to the flexibility of the copper(I)-iodine chain that conforms the CP. The addition of CP to the PLA matrix reduces the elastic modulus and ultimate elongation of the organic matrix, although it does not reduce its tensile strengthThis article has been funded by the Spanish Ministerio de Economía y Competitividad (and the current Ministerio de Ciencia, Innovación y Universidades) (MAT2016-77608-C3-1-P, MAT2016-75883-C2-2-P, MAT2016-75586-C4-4-P, CTQ2016-75816-C2-1P). J.C.-E. acknowledges the financial support by the “FPI-MINECO” Program of MINECO (Grant BES-2015-071534

Micro and nano smart composite films based on copper-iodine coordination polymer as thermochromic biocompatible sensors

Herein is presented the preparation and characterization of a composite material obtained by the combination of nanosheets of a coordination polymer (CP) based on the copper(I)-I double chain with response to temperature and pressure with polylactic acid (PLA) as biodegradable organic matrix. The new films of composite materials are generated using a simple and low-cost method and can be created with long lateral dimensions and thicknesses ranging from a few microns to a few nanometers. Studies show that the new material maintains the optical response versus the temperature, while the elasticity and flexibility of the PLA totally quenches the response to pressure previously observed for the CP. This new material can act as a reversible sensor at low temperatures, thanks to the flexibility of the copper(I)-iodine chain that conforms the CP. The addition of CP to the PLA matrix reduces the elastic modulus and ultimate elongation of the organic matrix, although it does not reduce its tensile strength

Methylome profiling reveals functions and genes which are differentially methylated in serrated compared to conventional colorectal carcinoma.

Background: Serrated adenocarcinoma (SAC) is a recently recognized colorectal cancer (CRC) subtype accounting for 7.5–8.7 % of CRCs. It has been shown that SAC has a worse prognosis and different histological and molecular features compared to conventional carcinoma (CC) but, to date, there is no study analysing its methylome profile. Results: The methylation status of 450,000 CpG sites using the Infinium Human Methylation 450 BeadChip array was investigated in 103 colorectal specimens, including 39 SACs and 34 matched CCs, from Spanish and Finnish patients. Microarray data showed a higher representation of morphogenesis-, neurogenesis-, cytoskeleton- and vesicle transport-related functions and also significant differential methylation of 15 genes, including the iodothyronine deiodinase DIO3 and the forkhead family transcription factor FOXD2 genes which were validated at the CpG, mRNA and protein level using pyrosequencing, methylation-specific PCR, quantitative polymerase chain reaction (qPCR) and immunohistochemistry. A quantification study of the methylation status of CpG sequences in FOXD2 demonstrated a novel region controlling gene expression. Moreover, differences in these markers were also evident when comparing SAC with CRC showing molecular and histological features of high-level microsatellite instability. Conclusions: This methylome study demonstrates distinct epigenetic regulation patterns in SAC which are consistent to previous expression profile studies and that DIO3 and FOXD2 might be molecular targets for a specific histologyoriented treatment of CRC.post-print2306 K

Adaptation of the person centered therapeutic relationship patient version (PCTR‐PT) to a version for physiotherapists (PCTR‐PHYS) and evaluation of its psychometric properties

[EN] Background and Purpose The therapeutic relationship is a central component for developing person-centered care within physiotherapy services. However, it is necessary to understand how this relationship is perceived by both parties involved. The Person Centered Therapeutic Relationship-Patient scale (PCTR-PT) was constructed to identify patients' perceptions. No instruments are currently available to correlate patients' and physiotherapists' perceptions of the therapeutic relationship. This study sought to adapt the PCTR-PT to develop a version for physiotherapists, the Person Centered Therapeutic Relationship Scale for Physiotherapists (PCTR-PHYS) and to determine its psychometric properties. Methods A three-stage study was performed: (1) item generation, (2) pretesting of the questionnaire, (3) analysis of psychometric properties. Factor validity and psychometric properties were analyzed by confirmatory factor analysis (CFA). Convergent validity was calculated. Internal consistency was verified using the Cronbach's alpha coefficient. The intraclass correlation coefficient (ICC) was used to examine temporal stability. Results Thirty-three physiotherapists participated in two rounds of cognitive interviews and 343 participated in the analysis of psychometric properties. The CFA confirmed the four-structure model. Reliability of the tool was confirmed by Cronbach's alpha (α = 0.863) for all four dimensions, as all were above 0.70, ranging from 0.704 (relational bond) and 0.898 (therapeutic communication). Test-retest was performed with 2-week intervals, indicating an appropriate stability for the scale (ICC = 0.908). Discussion The Person Centered Therapeutic Relationship Scale for Physiotherapists is a useful, valid and applicable instrument to evaluate the person-centered therapeutic relationship during physiotherapy interventions. It will enable the comparison of patients' and physiotherapists' perceptions. To provide person-centered care in physiotherapy services, there is a clear need to incorporate specific resources into clinical practice to evaluate the quality of the therapeutic relationship from the perspective of both the persons being treated and the professionals providing care.SIPublicación en abierto financiada por el Consorcio de Bibliotecas Universitarias de Castilla y León (BUCLE), con cargo al Programa Operativo 2014ES16RFOP009 FEDER 2014-2020 DE CASTILLA Y LEÓN, Actuación:20007-CL - Apoyo Consorcio BUCL

Control and Simplicity in the Nanoprocessing of Semiconducting Copper-Iodine Double Chain Coordination Polymers

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/abs/10.1021/acs.inorgchem.8b00364Two coordination polymers (CPs), based on Cu(I)-I double zig-zag chains bearing isonicotinic acid or 3-chloroisonicotinic acid as terminal ligands with molecular recognition capabilities, have been synthesized and fully characterized. Both compounds present extended networks with supramolecular interactions directed by the formation of H-bonds between the complementary carboxylic groups, giving supramolecular sheets. The chloro substituent allows establishing additional Cl···Cl supramolecular interactions that reinforce the stability of the supramolecular sheets. These CPs are semiconductor materials; however, the presence of chlorine produces slight changes in the I-Cu-I chains, generating a worse overlap in the Cu-I orbitals, thus determining a decrease in its electrical conductivity value. These experimental results have also been corroborated by theoretical calculations using the study of the morphology of the density of states and 3D orbital isodensities, which determine that conductivity is mostly produced through the Cu-I skeleton and is less efficient in the case of the chloro derivative compound. A fast and efficient bottom-up approach based on the self-assembly of the initial building blocks and the low solutibility of these CPs has proved very useful for the production of nanostructuresWe thank the Spanish MINECO (projects MAT2016-75883-C2-2-P, CTQ2017-87201-P, and fellowship BES-2015-071534) and the Generalitat Valenciana (PrometeoII/2014/076 project) for financial suppor

Multiphoton imaging of melanoma 3D models with plasmonic nanocapsules

We report the synthesis of plasmonic nanocapsules and the cellular responses they induce in 3D melanoma models for their perspective use as a photothermal therapeutic agent. The wall of the nanocapsules is composed of polyelectrolytes. The inner part is functionalized with discrete gold nanoislands. The cavity of the nanocapsules contains a fluorescent payload to show their ability for loading a cargo. The nanocapsules exhibit simultaneous two-photon luminescent, fluorescent properties and X-ray contrasting ability. The average fluorescence lifetime (τ) of the nanocapsules measured with FLIM (0.3 ns) is maintained regardless of the intracellular environment, thus proving their abilities for bioimaging of models such as 3D spheroids with a complex architecture. Their multimodal imaging properties are exploited for the first time to study tumorspheres cellular responses exposed to the nanocapsules. Specifically, we studied cellular uptake, toxicity, intracellular fate, generation of reactive oxygen species, and effect on the levels of hypoxia by using multi-photon and confocal laser scanning microscopy. Because of the high X-ray attenuation and atomic number of the gold nanostructure, we imaged the nanocapsule-cell interactions without processing the sample. We confirmed maintenance of the nanocapsules’ geometry in the intracellular milieu with no impairment of the cellular ultrastructure. Furthermore, we observed the lack of cellular toxicity and no alteration in oxygen or reactive oxygen species levels. These results in 3D melanoma models contribute to the development of these nanocapsules for their exploitation in future applications as agents for imaging-guided photothermal therapy. Statement of Significance: The novelty of the work is that our plasmonic nanocapsules are multimodal. They are responsive to X-ray and to multiphoton and single-photon excitation. This allowed us to study their interaction with 2D and 3D cellular structures and specifically to obtain information on tumor cell parameters such as hypoxia, reactive oxygen species, and toxicity. These nanocapsules will be further validated as imaging-guided photothermal probe

Study of IDO1 gene expression in histological variants of colorectal carcinoma.

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