Cholesteric Liquid Crystal Polyesteramides: Non-Viral Vectors

Polyesteramides PNOBDME (C34H38N2O6)n, Poly[oxy(1,2-dodecane)-oxy-carbonyl-1,4-phenylene-amine-carbonyl-1,4-phenylene-carbonyl-amine-1,4-phenylene-carbonyl], and PNOBEE (C26H22N2O6)n, Poly[oxy(1,2-butylene)-oxy-carbonyl-1,4-phenylene-amine-carbonyl-1,4-phenylene-carbonyl-amine-1,4-phenylene-carbonyl], have been designed and synthesized as cholesteric liquid crystals (LCs)—through a condensation reaction between 4- 4′-(terephthaloyl-diaminedibenzoic chloride) (NOBC) and racemic glycol, DL-1,2-dodecanediol or DL-1,2-butanediol, respectively—as chemical modifications of multifunctional cholesteric LC polyesters, involving new properties but holding the precursor helical macromolecular structures. The new compounds have been characterized by 1H and 13C-NMR, COSY and HSQC, exhibiting two 1H-independent sets of signals observed for each enantiomer, attributed to two diastereomeric conformers, gg and gt, of the torsion containing the asymmetric carbon atom in the spacer. They have also been characterized by x-ray diffraction with synchrotron radiation source. Thermal behaviour of the new compounds is studied by thermogravimetric (TG) and differential scanning calorimetry (DSC) analysis. The substitution of the ester groups in the mesogen by amide groups causes an increase of thermal stability with respect to the precursors. Optical rotatory dispersion (ORD) is evaluated. Morphology of powdered PNOBDME exhibits spherical clusters of about 5 μm in diameter homogeneously dispersed. Molecular models show helical polymeric chains with stereoregular head-tail, isotactic structure, explained as due to the higher reactivity of the primary hydroxyl with respect to the secondary one in the glycol through the polycondensation reaction. Besides being biocompatible, these synthetic polyesteramides have proved to act as non-viral vectors in gene therapy and be able to transfect DNA to the nucleus cell. Similar new cationic cholesteric liquid crystal polyesters have also been synthesized in our laboratory

NON-VIRAL VECTORS FOR GENE THERAPY BASED ON CHOLESTERIC LIQUID-CRYSTAL POLYMERS. STRUCTURE ANALYSIS BY SAXS.

Cholesteric Liquid Crystal Polymers (ChLCP), synthetized in our laboratory through a stereoselective polycondensation reaction1 as multifunctional optically active materials, have been extensively characterized 2 by NMR, Raman spectroscopy, steady-state fluorescence, molecular modeling, and SAXS/WAXS. These ChLCP behave both as thermotropic and lyotropic, confering interesting macromolecular properties indicative of potential application on the biomedical and engineering field. They have shown to be biocompatible against macrophages and fibroblasts cellular lines, and able to interact with biomacromolecules such as lipids (both neutral and cationi) and nucleic acids, the structures of the complexes being identified by synchrotron radiation source 3, 4, 5. Cationic liposomial/surfactant systems based on our CLCP were developed which entrapped DNA plasmids, acting as non viral cationic vectors for gene therapy, which successfully transfected in several tumor cell lines 6, 7. Cationic functionalized ChLCP have been synthesized, dispersed in TAE (0,04M TRIS; 0,001M EDTA) and complexed directly with commercial DNA of increasing complexity: [Poly-A]; [Poly-C]; [Poly-G]; [PolydT]; [PolyC-PolyG]; [PolyAC-PolydT]; commercial calf thymus DNA and plasmid. Three different proportions ChLCP:DNA were prepared: (1:2), (1:1), and (2:1) respectively by mixing and digesting for 12h in a swinging shaker. Neutron scattering experiments, had shown sufficient contrast (scattering length density difference) between new cholesteric PTOBEE-Ammonium (1.5 to 1.9 x 1010 /cm2) and polynucleotide [PolyC-PolyG] (3.32 x 1010 /cm2) for contrast variation SANS experiments. This experiment was successfully performed at NIST 8. The structure of the cationic complexes has been studied by SAXS at the BM16 beamline at ESRF, at room temperature. A monochromatized beam at = 0,9795 Å was used. Two-dimensional data recorded by an image-plate detector was placed at 5975 cm from the sample. The program Fit2D was employed to evaluate the beam centre position and to generate a mask file. Binary data are normalized by the detector response and pixels are radially averaged into 1D. Silver behenate (d= 58.3 Å) was used to calibrate the angular axis. Structural analysis of the cationic complexes is proposed.Peer reviewe

Structure of non-viral vectors based on cholesteric liquid-crystal polymers by SAXS

Cationic polymers, at physiological pH, are used to condense anionic nucleic acids, as healing agent, into nano-sized particle-like complexes called “polyplexes”, through self-assembly driven by electrostatic interactions. By compressing DNA molecules to a relatively small size, cellular internalization is facilitated and, thus, transfection efficacy is improved.New non-viral vector formulations are proposed for gene therapy.Cationic liquid-crystal polymers, synthetized as cholesteric and biocompatible, are directly complexed with polynucleotides of increasing complexity (both single and double stranded)or with two kinds of deoxyribonucleic acid (Plasmid PBR322 and calf-thymus DNA). Structural information of thepolyplexes is studied by SAXS at the BM16 beamline at ESRF.The radii of gyration (Rg) of the Cholesteric Liquid-Crystal Polymer aggregates and polyplexes suspended in TAE, have been calculated from the slope of the corresponding Guinier plots Ln (I) vs q2 (slope = Rg2/3). Information about the shape is estimated by plotting I(q) vs q*Rg.Fractal nature is also analyzed from Porod plots[Ln I(q)-B] vs Ln (q).The interaction between the new cationic cholesteric liquid-crystal polymers and oligonucleotides and DNA is confirmed in all the studied cases.Peer reviewe

De la esencia de la arquitectura a lo esencial del espacio. Forma y concepto en la arquitectura de Mies van de Rohe

Esta investigación parte del supuesto de que toda arquitectura coherente tiene siempre un sustrato conceptual que mueve al arquitecto a proyectar y a construir. El mundo de las formas arquitectónicas es lugar de múltiples debates donde se encuentran inquietudes, pensamientos, voluntades, intenciones que se materializan en una forma concreta de hacer y entender la arquitectura. Establecer las relaciones entre el mundo de los conceptos y las formas arquitectónicas del movimiento moderno, en este caso de Mies van der Rohe, permite profundizar en las claves de la arquitectura moderna de la mano de uno de los arquitectos que imprimió carácter al lenguaje del vidrio y del acero. La re-construcción con motivo del centenario de su nacimiento (1886), de algunas de sus obras más significativas, como el pabellón de Barcelona (1987), o la restauración de otras como el bloque de apartamentos de la colonia Weisenhoff (1986), la casa Tugendhat (1986), o la Farnsworth, suponen el triunfo de la idea sobre la materia. Una idea de arquitectura que es capaz de re-generar, re-construir y re-habilitar aquellos modelos que fueron su exponente y que aún hoy sorprenden por la claridad de sus planteamientos. Si se compara la obra construida con los escasos escritos que publicó Mies, crece el interés por estudiar a un arquitecto cuyas máximas se graban en la conciencia como sentencias éticas o pautas de comportamiento: Menos es más, Dios está en el detalle, Construcción frente a arquitectura... El espacio universal La belleza es la verdad ¿Cómo se traduce el camino que él se traza de búsqueda incesante de la verdad, de la esencia de la arquitectura, al espacio arquitectónico? El estudio se centra en el análisis de dos obras de Mies van der Rohe: la casa Tugendhat y la casa Farnsworth. Son obras muy significadas en la trayectoria profesional de Mies van der RoheSantatecla Fayos, J. (2005). De la esencia de la arquitectura a lo esencial del espacio. Forma y concepto en la arquitectura de Mies van de Rohe [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/2628Palanci

Estudio y análisis de las herramientas para el cálculo de cobertura radioeléctrica Linkplanner, RadioGis y Xirio online

Se va a analizar y comparar distinto informático basado en la simulación detallada sobre enlaces radioeléctricos. Dichas simulaciones estarán destinadas a cubrir las necesidades de servicio pertinentes. Así los programas serán capaces de trabajar en distintos tipos de coberturas y transmisiones radioeléctricas dando todo tipo de servicios como puede ser banda ancha inalámbrica, navegación aérea o servicio móvil entre muchos otros. Nos centraremos en la tecnología Wimax en banda libre (5,8GHz) y se tendrán en cuenta tanto la elevación del terreno como si se atraviesa mar o atenuaciones atmosféricas como por ejemplo lluvia. También se podrá elegir el tipo de recomendación específica para cada tipo de cálculo en cuestión. Para todo ello usaremos las demo o versiones gratuitas de las aplicaciones informáticas Linkplanner, Radio Gis y Xirio online. Se realizarán idénticas simulaciones para cada programa en las cuales se estudiarán los distintos resultados ofrecidos de cada aplicación, y se compararán los resultados obtenidos ofreciendo un estudio de todas sus posibilidades y limitaciones técnicas. También se estudiarán los materiales a utilizar en el Linkplanner, pues este programa contiene los productos de Motorola, materiales de fabricación de uso actual, obteniendo unos resultados muy reales. A destacar que estas aplicaciones pueden hacer uso si la aplicación lo requiere de trabajar vía Internet, basándose en el Google Maps, Google Earth o mapas topográficos de España entre otros.Mezquita Fayos, J. (2013). Estudio y análisis de las herramientas para el cálculo de cobertura radioeléctrica Linkplanner, RadioGis y Xirio online. Universitat Politècnica de València. http://hdl.handle.net/10251/32413Archivo delegad

Diseño de antenas compactas para aplicaciones de Energy Harvesting

Mi proyecto final de grado ha consistido en estudiar la teoría, diseñar, construir y medir una Rectenna para aplicaciones de Energy Harvesting. Para ello previamente hemos estudiado la teoría del diseño de las antenas y rectificadores, para diseñarlos adaptándolos a nuestras necesidades y simularlos con su correspondiente software informático para ver que la parte teórica y los resultados obtenidos de la simulación cumplen con nuestro objetivo marcado. Finalmente implementaremos conjuntamente estos circuitos (antena y rectificador) para obtener los prototipos que construiremos. Estos prototipos serán construidos y montados con los materiales adecuados y finalmente probados y medidos con los correspondientes aparatos de medida. Por último compararemos los resultados obtenidos de la simulación con los resultados obtenidos de las medidas reales de nuestro prototipo realizando un estudio detallado.My final Degree project has focused on studying the theory, the design, the implementation and the measurement of a Rectenna. Firstly, we have studied the theory of planar antenna design and rectifiers, in order to design them adapted to our needs and then we have simulated them with the corresponding software to meet our objectives. Finally we have jointly implemented these circuits (antenna and rectifier) in the prototypes we built. These prototypes have been fabricated with the appropriate materials and finally tested and measured with the corresponding devices. Finally we have compared the results of the simulations with the measurements of our prototype, to validate the resultsMezquita Fayos, J. (2015). Diseño de antenas compactas para aplicaciones de Energy Harvesting. Universitat Politècnica de València. http://hdl.handle.net/10251/50917TFG

Natural coagulants: analysis of potential use for drinking water treatment in developed and developing countries

[EN] Drinking water must be colorless, odorless and tasteless, and free of substances or micro-organisms that can cause disease. The process to obtain drinking water is purification, understood as the treatment to make water suitable for human consumption. Water purification is traditionally composed of a sequence of standard treatments including coagulation-flocculation, sedimentation, filtration, and disinfection. Some compounds named coagulants are used for coagulation-flocculation, which is the stage in which the suspended matter is removed and the water is clarified. Coagulants are usually synthetic, therefore represent a high cost and are difficult to gets in some areas, especially in developing countries. In addition, their use is being revised and restricted in different international standards, in order to control or prohibit its use because of the possible hazard effects that the remains of these products in treated water can cause to people. In contrast to synthetic coagulants, there are several natural compounds with coagulation properties which have some advantages such as easy availability and safety. At present, scientific community is paying more attention to natural coagulants as legal restrictions to synthetic ones are becoming more severe. This paper is a review of natural coagulants as an alternative to chemical coagulants, in which their potential application in the treatment of drinking water is analysed.García-Fayos, B.; Arnal Arnal, JM.; Sancho, M. (2018). Natural coagulants: analysis of potential use for drinking water treatment in developed and developing countries. Desalination and Water Treatment. 103:307-314. https://doi.org/10.5004/dwt.2018.22005S30731410

Tracking of learning level on design and safety skills in two core subjects of the chemical engineering degree at UPV

[EN] Chemical engineers develop their profession in areas in which design of processes and safety of installations, equipment and procedures designed are especially relevant due to the impact and consequences that a failure of these items represent. Therefore, curriculum of chemical engineers chemical engineering should include these disciplines as a valuable skill. In the Universitat Politècnica of València (UPV), design and safety competence training is worked in the curriculum of chemical engineering degree through several subjects. "Experimentation in Chemical Engineering III" (EIq3) from 3rd course, semester B and "Industrial Processes of Chemical Engineering" (PIIQ) from 4th course semester A, are core courses specially focussed on the development of several activities to work these skills. In EIq3 students design a production process to obtain oil from almond for cosmetic purposes. This design project includes: lab work to study and understand the stages of the production process and its performance, drawing of block and flow diagram of the process by using Autocad and recommendation of basic safety measures in the installation. In the following semester, students of PIIQ study different production processes and design a process to obtain olive oil. This design includes drawing of block and flow diagram of the full process, selection and justification of safety measures needed and its implementation in the installation through its drawing in the flow diagram. Safety is also strengthened through an activity of safety presentation about an item related to the installation that students should prepare and defense. This work collects and analyses the evolution of the learning level and its deepness into safety and design skills through the analysis of the results obtained along the several control points stablished in EIq3 and PIIQ courses. These control points are: deliverables of academic works at the beginning of EIq3, assessment of design project and written exam at the end of EIq3 and academic results at the end of PIIQ of several academic years. Progressive work along these two consecutive courses in safety and design skills have allowed to obtain a deeper degree of learning in these disciplines and better results in a medium term compared with the previous academic years in which these activities and methodology were not performed in both subjects.García-Fayos, B.; Sancho, M.; Arnal Arnal, JM. (2019). Tracking of learning level on design and safety skills in two core subjects of the chemical engineering degree at UPV. IATED. 6484-6491. https://doi.org/10.21125/inted.2019.1571S6484649

Development of a rubric for the evaluation of "design and project" competence in an experimental subject of chemical engineering degree

[EN] "Experimentation in Chemical Engineering III" is the last experimental core course of the Chemical Engineering Degree at the Universitat Politècnica València (UPV). It is a practical course of 4.5 ECTS which is taught in the 2nd semester of the 3rd year, in which students perform experimental sessions related to the subject "Separation Processes¿ taught in the previous semester. The subject has to work the competence "Design and Project", both in its specific and transversal approach. In order to develop suitably such competence, in 2016 it was requested an ¿Innovation and Education Improvement Project¿ (PIME), through the Institute of Education Sciences of the UPV, with the aim of integrate the Project Oriented Learning (POL) as the main methodology. The Project was implemented during the academic year 2017-2018 and the main objective was to perform experimental sessions to obtain data that would be used in the design project. Transition to POL methodology implied the design and development of new activities [1] and a change in the way that the evaluation was performed. The design project was the main learning product obtained and it is used to assess the development of the ¿Design and project¿ competence in the students. The tool used to evaluate the design project is a rubric. Rubric includes the evaluation criteria and their different levels of achievement and scoring, and allows a more homogeneous assessment by all the lecturers that evaluate the project. This paper describes the development process of the rubric and presents the final version which is currently used in the subject after two years of implementation that includes several changes made. This work will also describe the way that score of each item contributes to the final grade of the project and of the competence. The rubric presented can be applied to other subjects in which similar design projects would be performed, after adapting it to the particular context of each subject.Sancho, M.; García-Fayos, B.; Arnal Arnal, JM. (2019). Development of a rubric for the evaluation of "design and project" competence in an experimental subject of chemical engineering degree. IATED. 6395-6403. https://doi.org/10.21125/inted.2019.1552S6395640

David Haid and the Mannheim Theater of Mies van der Rohe

[EN] This article investigates the role played by David N. Haid - a graduate student at IIT and assistant in Mies van der Rohe s office - developed in the National Theater project, which was submitted to the competition announced by the city of Mannheim in 1952 and decided in the spring of 1953. The archival work and the method of comparative analysis reveal two important aspects. Firstly, that Mies van der Rohe s project for the competition on invitation is contemporary with the final master s project, entitled An Arts Center, which Haid defended in June 1953, a master thesis supervised by Mies, as stated in his preface. Secondly, the resemblance between Haid s proposal for a multi-purpose Arts Center and Mies s Mannheim Theater is very evident, with the two projects being identical in almost every aspect: metrics, proportion, structure, and even the construction of the two models and the staging of their photographs. The temporal and architectural coincidence of the two works reveals the decisive role that David Haid played in this singular project, hitherto only attributed to Mies van der Rohe.[ES] Este artículo investiga el papel que David N. Haid estudiante de posgrado del IIT y ayudante en la oficina de Mies van der Rohe desempeñó en el proyecto del Teatro Nacional, presentado al concurso convocado por la ciudad de Mannheim en 1952 y resuelto en la primavera de 1953. El trabajo de archivo y el método de análisis comparativo ponen de manifiesto dos aspectos importantes. En primer lugar, que el proyecto realizado por Mies van der Rohe para el concurso bajo invitación es coetáneo con el proyecto final de máster, titulado An Arts Center y defendido por Haid en junio de 1953; una tesina que fue supervisada por Mies, tal y como consta en su prefacio. En segundo lugar, que el parecido entre la propuesta de Haid para un centro de arte polivalente y el Teatro de Mannheim de Mies es muy evidente, siendo ambos proyectos idénticos en casi todos los aspectos: métrica, proporción, estructura, e incluso la construcción de sendas maquetas y puesta en escena de sus fotografías. La coincidencia temporal y arquitectónica de ambos trabajos revela el rol tan determinante que David Haid tuvo en este singular proyecto, hasta la fecha únicamente atribuido a Mies van der Rohe.Santatecla Fayos, J.; García-Requejo, Z.; Lizondo Sevilla, L. (2022). David Haid y el Teatro de Mannheim de Mies van der Rohe. VLC arquitectura. Research Journal. 9(2):99-121. https://doi.org/10.4995/vlc.2022.15747991219