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Here, we demonstrate for the first time the ability of a porous π-conjugated semiconducting polymer film to enable facile electrolyte penetration through vertically stacked redox-active polymer layers, thereby enabling electrochromic switching between p-type and/or n-type polymers. The polymers P1 and P2, with structures diketopyrrolopyrrole (DPP)-πbridge-3,4,-ethylenedioxythiophene (EDOT)-πbridge [πbridge = 2,5-thienyl for P1 and πbridge = 2,5-thiazolyl for P2] are selected as the p-type polymers and N2200 (a known naphthalenediimide-dithiophene semiconductor) as the n-type polymer. Single-layer porous and dense (control) polymer films are fabricated and extensively characterized using optical microscopy, atomic force microscopy, scanning electron microscopy, and grazing incidence wide-angle X-ray scattering. The semiconducting films are then incorporated into single and multilayer electrochromic devices (ECDs). It is found that when a p-type (P2) porous top layer is used in a multilayer ECD, it enables electrolyte penetration to the bottom layer, enabling oxidative electrochromic switching of the P1 bottom layer at low potentials (+0.4 V versus +1.2 V with dense P2). Importantly, when using a porous P1 as the top layer with an n-type N2200 bottom layer, dynamic oxidative-reductive electrochromic switching is also realized. These results offer a proof of concept for development of new types of multilayer electrochromic devices where precise control of the semiconductor film morphology and polymer electronic structure is essential.
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A series of donor-π-acceptor-π-donor (D-π-A-π-D) compounds based on naphthalendiimide (NDI) and perylenediimide (PDI) central cores combined with triphenylamine and phenylcarbazole donor groups have been synthesized, characterized and tested in top-contact/bottom gate organic field-effect transistors (OFETs). The results showed high electron mobilities, up to 0.3â cm2 V-1 s-1 , in the case of NDI derivatives and moderate values of around 10-3 â cm2 V-1 s-1 for PDI-based semiconductors. Quantum chemical calculations were performed in order to support the experimental data. The results suggest that adequate molecular characteristics and larger crystalline domains in NDI vs. PDI semiconducting films may be the reasons behind the enhanced electrical properties of NDI derivatives. Furthermore, when the lateral donor substituents are triphenylamine groups, the mobilities were slightly higher in comparison to phenylcarbazole donor groups due to an improved electron-donating character. Other characterization techniques, such as AFM, X-ray diffraction or spectroelectrochemistry, among others, have been performed to analyze supramolecular order, charge carriers' nature and stability, parameters closely related to charge transport characteristics.
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RESUMEN En el marco del Tercer Congreso Internacional de Salud Nutricional en la Primera Infancia: Más allá de los Determinantes Biológicos, compartimos la experiencia del Instituto Nacional de Perinatología sobre relactancia como una intervención eficaz para mejorar las tasas de lactancia materna exclusiva. En este documento se plasman algunas reflexiones sobre el proceso de relactancia sustentadas en la evidencia disponible hasta el momento. Se plantean elementos para tener en cuenta durante las intervenciones bajo la perspectiva psicosocial, cultural y económica como factores que frecuentemente constituyen obstáculos para el éxito de la lactancia materna.
ABSTRACT Within the framework of the Third International Congress on Nutritional Health in Early Childhood: Beyond Biological Determinants, we are sharing the experience of the National Institute of Perinatology on relactation as an effective intervention to improve exclusive breastfeeding rates. In this document, we present some reflections on the relactation process based on the available evidence to date. We propose elements to be considered during interventions from a psychosocial, cultural, and economic perspective, as these factors often pose obstacles to the success of breastfeeding.
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The development of n-type organic semiconductors critically relies on the design and synthesis of highly electron-deficient building blocks with good solubility and small steric hindrance. We report here a strongly electron-deficient dithienylpyrazinediimide (TPDI) and its n-type semiconducting polymers. The pyrazine substitution leads to the resulting polymers with much lower-lying lowest unoccupied molecular orbital (LUMO) levels and improved backbone planarity compared to the reported dithienylbenzodiimide (TBDI)- and fluorinated dithienylbenzodiimide (TFBDI)-based polymer analogues, thus yielding n-type transport character with an electron mobility up to 0.44 cm2 V-1 s-1 in organic thin-film transistors. These results demonstrate that dithienylpyrazinediimide is a highly promising electron-deficient building block for constructing high-performance n-type polymers and the incorporation of pyrazine into imide-functionalized (hetero)arenes is an effective strategy to develop n-type polymers with deep-lying frontier molecular orbital (FMO) levels for organic optoelectronic devices.
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El virus de papiloma humano de alto riesgo oncogénico (VPH-AR) es causa necesaria pero no suficiente para la ocurrencia de cáncer de cuello uterino (CCU). Mujeres portadoras del virus de inmunodeficiencia humana (VIH) presentan mayor riesgo de desarrollar lesiones precursoras del cáncer de cuello de útero, por ello, el objetivo del presente trabajo prospectivo de corte transversal fue determinar la frecuencia de VPH-AR y otras infecciones de transmisión sexual-ITS (condilomas, sífilis, virus del herpes simple, gonorrea, citomegalovirus, hepatitis B) en 218 mujeres con y sin VIH que acudieron al Programa Nacional de Lucha contra el SIDA (PRONASIDA) desde julio 2017 hasta marzo 2021. Se encontró que 16/54 (29,6%) mujeres VIH-positivas presentaron infección por VPH-AR en comparación a 41/164 (25%) mujeres VIH-negativas (p>0,05). En relación a la edad, mujeres VIH positivas presentaron una frecuencia comparable de infección por VPH-AR (30 años 30,2%), a diferencia de mujeres VIH negativas donde hubo una disminución significativa de la infección por VPH-AR luego de los 30 años (30 años 18,8%, p= 0,028). Esto podría explicarse por la inmunosupresión observada en mujeres VIH positivas que podría favorecer infecciones persistentes, sugiriendo que deben ser controladas más cercanamente. Además, se observó mayor frecuencia de otras ITS en mujeres VIH positivas (29,6% vs 15,8%, p=0,026), lo cual sugiere que aparte del monitoreo más cercano, es fundamental fortalecer la educación sobre factores de riesgo para la ITS sobre todo VPH y VIH, así como la realización de prevención primaria por vacunación contra el VPH.
High-risk human papillomavirus (HPV-HR) is a necessary but not sufficient cause for cervical cancer (CC). Women carriers of human immunodeficiency virus (HIV) present an increased risk for the development of cervical cancer precursor lesions, therefore, the objective of the present prospective cross-sectional study was to determine the frequency of HPV-HR and other sexually transmitted infections-STIs (condylomas, syphilis, herpes simplex virus, gonorrhoea, cytomegalovirus, hepatitis B) in 218 women with and without HIV who attended the Ministry of Health from July 2017 to March 2021. It was found that 16/54 (29.6%) HIV-positive women had HPV infection compared to 41/164 (25%) HIV-negative women (p>0.05). In relation to age, HIV-positive women had a comparable frequency of HPV infection (30 years 30.2%), unlike HIV-negative women whom above 30 years of age presented a significant decrease in HPV-AR infection (30 years 18.8%, p:0.028). This could be explained by the immunosuppression observed in HIV-positive women which could favour persistent infections, suggesting that they should be controlled more closely. In addition, other STIs were observed to be more frequent in HIV-positive women (29.6% vs 15.8%, p:0.026), which suggests that apart from closer monitoring, it is essential to strengthen education on risk factors for STIs, especially HPV and HIV, as well as the implementation of primary prevention by vaccination against HPV.
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In this work, as an equivocal proof of the potential of microwave irradiation in organic synthesis, a complex pyrazine-decorated benzotriazole derivative that is challenging to prepare under conventional conditions has been obtained upon microwave irradiation, thus efficiently improving the process and yields, dramatically decreasing the reaction times and resulting in an environmentally friendly synthetic procedure. In addition, this useful derivative could be applied in organic electronics, specifically in organic field-effect transistors (OFETs), exhibiting the highest electron mobilities reported to date for benzotriazole discrete molecules, of around 10-2 cm2V-1s-1.
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Microondas , Semiconductores , Electrones , Transistores Electrónicos , TriazolesRESUMEN
Four difluorenoheteroles having a central quinoidal core with the heteroring varying as furan, thiophene, its dioxide derivative and pyrrole have shown to be medium character diradicals. Solid-state structures, optical, photophysical, magnetic, and electrochemical properties have been discussed in terms of diradical character, variation of aromatic character and captodative effects (electron affinity). Organic field-effect transistors (OFETs) have been prepared, showing balanced hole and electron mobilities of the order of 10-3 â cm2 V-1 s-1 or ambipolar charge transport which is first inferred from their redox amphoterism. Quantum chemical calculations show that the electrical behavior is originated from the medium diradical character which produces similar reorganization energies for hole and electron transports. The vision of a diradical as simultaneously bearing pseudo-hole and pseudo-electron defects might justify the reduced values of reorganization energies for both regimes. Structure-function relationships between diradical and ambipolar electrical behavior are revealed.
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Three crystalline N-trimethyltriindoles endowed with different functionalities at 3, 8 and 13 positions (either unsubstituted or with three methoxy or three acetyl groups attached) are investigated, and clear correlations between the electronic nature of the substituents and their solid-state organization, electronic properties and semiconductor behavior are established. The three compounds give rise to similar columnar hexagonal crystalline structures; however, the insertion of electron-donor methoxy groups results in slightly shorter stacking distances when compared with the unsubstituted derivative, whereas the insertion of electron-withdrawing acetyl groups lowers the crystallinity of the system. Functionalization significantly affects hole mobilities with the triacetyl derivative showing the lowest mobility within the series in agreement with the lower degree of order. However, attaching three methoxy groups also results in lower hole mobility values in the OFETs (0.022 vs. 0.0014 cm2 V-1 s-1) in spite of the shorter stacking distances. This counterintuitive behavior has been explained with the help of DFT calculations performed to rationalize the interplay between the intramolecular and intermolecular properties, which point to lower transfer integrals in the trimethoxy derivative due to the HOMO wave function extension over the peripheral methoxy groups. The results of this study provide useful insights into how peripheral substituents influence the fundamental charge transport parameters of chemically modified triindole platforms of fundamental importance to design new derivatives with improved semiconducting performance.
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The university accreditation system in Chile appears to be influenced by tensions between interest groups from well-established institutions and newer (private) institutions. These institutions depend to a certain extent on accreditation decisions to obtain indirect public funding. However, the system relies on faculty nominated by conglomerates formed by these same institutions to decide on accreditation. This arrangement creates a potential conflict of interest that can jeopardize the accreditation's legitimacy. We explore this potential bias through an empirical study examining voting behaviour by commissioners of the Chilean National Commission of Accreditation from March 2013 to October 2016. We assess whether commissioners appeared as favouring institutions within their appointing conglomerates. To our knowledge, this is the first study in the region designed to examine the presence of bias in higher education accreditation. Findings indicate commissioners, on average, tended to favour institutions in their appointing conglomerates. We discuss the findings in the broader context of a forthcoming reform of the accreditation system.
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Usher syndrome, the most prevalent cause of combined hereditary vision and hearing impairment, is clinically and genetically heterogeneous. Moreover, several conditions with phenotypes overlapping Usher syndrome have been described. This makes the molecular diagnosis of hereditary deaf-blindness challenging. Here, we performed exome sequencing and analysis on 7 Mexican and 52 Iranian probands with combined retinal degeneration and hearing impairment (without intellectual disability). Clinical assessment involved ophthalmological examination and hearing loss questionnaire. Usher syndrome, most frequently due to biallelic variants in MYO7A (USH1B in 16 probands), USH2A (17 probands), and ADGRV1 (USH2C in 7 probands), was diagnosed in 44 of 59 (75%) unrelated probands. Almost half of the identified variants were novel. Nine of 59 (15%) probands displayed other genetic entities with dual sensory impairment, including Alström syndrome (3 patients), cone-rod dystrophy and hearing loss 1 (2 probands), and Heimler syndrome (1 patient). Unexpected findings included one proband each with Scheie syndrome, coenzyme Q10 deficiency, and pseudoxanthoma elasticum. In four probands, including three Usher cases, dual sensory impairment was either modified/aggravated or caused by variants in distinct genes associated with retinal degeneration and/or hearing loss. The overall diagnostic yield of whole exome analysis in our deaf-blind cohort was 92%. Two (3%) probands were partially solved and only 3 (5%) remained without any molecular diagnosis. In many cases, the molecular diagnosis is important to guide genetic counseling, to support prognostic outcomes and decisions with currently available and evolving treatment modalities.
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Degeneración Retiniana , Síndromes de Usher , Humanos , Irán , Mutación , Linaje , Fenotipo , Degeneración Retiniana/genética , Síndromes de Usher/diagnóstico , Síndromes de Usher/genéticaRESUMEN
The present paper is aimed at demonstrating the capabilities of digital image analysis (DIA) to support conservation of painted artwork. Laser-induced fluorescence (LIF) imaging has been usually used in the diagnosis of wall paintings. In this case, LIF is applied to the case study of a painted wooden canopy, and most successful data processing techniques are presented in the discussion of results. The Jesús del Gran Poder canopy, completed by Francisco Ruiz Gijón in 1692, is an oil panel painting on wood. Eight panels of the canopy have been study by LIF. This technique is capable of remotely acquiring hyperspectral images operating in fluorescence mode following ultraviolet laser excitation. LIF spectra combined with principal component analysis, spectral angle mapper, and DIA provide a chemical mapping of the treated wooden surface of the panels. Besides, LIF spectrum is as a fingerprint of the panels that allows stablishing differences between them. LIF imaging analysis has proven to be a very useful tool for mapping retouching work, tracking previous restorations, and detecting chemicals on the wood in order to monitor restorations.
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Mitochondria modify their function and morphology to satisfy the bioenergetic demand of the cells. Cancer cells take advantage of these features to sustain their metabolic, proliferative, metastatic, and survival necessities. Understanding the morphological changes to mitochondria in the different grades of triple-negative breast cancer (TNBC) could help to design new treatments. Consequently, this research explored mitochondrial morphology and the gene expression of some proteins related to mitochondrial dynamics, as well as proteins associated with oxidative and non-oxidative metabolism in metastatic and non-metastatic TNBC. We found that mitochondrial morphology and metabolism are different in metastatic and non-metastatic TNBC. In metastatic TNBC, there is overexpression of genes related to mitochondrial dynamics, fatty-acid metabolism, and glycolysis. These features are accompanied by a fused mitochondrial morphology. By comparison, in non-metastatic TNBC, there is a stress-associated mitochondrial morphology with hyperfragmented mitochondria, accompanied by the upregulated expression of genes associated with the biogenesis of mitochondria; both of which are characteristics related to the higher production of reactive oxygen species observed in this cell line. These differences between metastatic and non-metastatic TNBC should provide a better understanding of metastasis and contribute to the development of improved specific and personalized therapies for TNBC.
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Glucólisis , Lipogénesis , Mitocondrias/patología , Dinámicas Mitocondriales , Proteínas Mitocondriales/genética , Especies Reactivas de Oxígeno/metabolismo , Neoplasias de la Mama Triple Negativas/secundario , Metabolismo Energético , Transición Epitelial-Mesenquimal , Humanos , Mitocondrias/metabolismo , Oxidación-Reducción , Transcriptoma , Neoplasias de la Mama Triple Negativas/genética , Neoplasias de la Mama Triple Negativas/metabolismo , Células Tumorales CultivadasRESUMEN
A distannylated electron-deficient bithiophene imide (BTI-Tin) monomer was synthesized and polymerized with imide-functionalized co-units to afford homopolymer PBTI and copolymer P(BTI-BTI2), both featuring an acceptor-acceptor backbone with high molecular weight. Both polymers exhibited excellent unipolar n-type character in transistors with electron mobility up to 2.60â cm2 V-1 s-1 . When applied as acceptor materials in all-polymer solar cells, PBTI and P(BTI-BTI2) achieved high power-conversion efficiency (PCE) of 6.67 % and 8.61 %, respectively. The PCE (6.67 %) of polymer PBTI, synthesized from the distannylated monomer, is much higher than that (0.14 %) of the same polymer PBTI*, synthesized from typical dibrominated monomer. The 8.61 % PCE of copolymer P(BTI-BTI2) is also higher than those (<1 %) of homopolymers synthesized from dibrominated monomers. The results demonstrate the success of BTI-Tin for accessing n-type polymers with greatly improved device performance.
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Unpaired electrons of organic radicals can offer high electrical conductivity without doping, but they typically suffer from low stability. Herein, we report two organic diradicaloids based on quinoidal oligothiophene derivative (QOT), that is, BTICN and QTICN, with high stability and conductivity by employing imide-bridged fused molecular frameworks. The attachment of a strong electron-withdrawing imide group to the tetracyano-capped QOT backbones enables extremely deeply aligned LUMO levels (from -4.58 to -4.69 eV), cross-conjugated diradical characters, and remarkable ambient stabilities of the diradicaloids with half-lives > 60 days, which are among the highest for QOT diradicals and also the widely explored polyaromatic hydrocarbon (PAH)-based diradicals. Specifically, QTICN based on a tetrathiophene imide exhibits a cross-conjugation assisted self-doping in the film state as revealed by XPS and Raman studies. This property in combination with its ordered packing yields a high electrical conductivity of 0.34 S cm-1 for the QTICN films with substantial ambient stability, which is also among the highest values in organic radical-based undoped conductive materials reported to date. When used as an n-type thermoelectric material, QTICN shows a promising power factor of 1.52 uW m-1 K-2. Our results not only provide new insights into the electron conduction mechanism of the self-doped QOT diradicaloids but also demonstrate the great potential of fused quinoidal oligothiophene imides in developing stable diradicals and high-performance doping-free n-type conductive materials.
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Polyhydroxyalkanoates (PHAs) have emerged as a promising biodegradable and biocompatible material for scaffold manufacturing in the tissue engineering field and food packaging. Surface modification is usually required to improve cell biocompatibility and/or reduce bacteria proliferation. Picosecond laser ablation was applied for surface micro structuring of short- and medium-chain length-PHAs and its blend. The response of each material as a function of laser energy and wavelength was analyzed. Picosecond pulsed laser modified the surface topography without affecting the material properties. UV wavelength irradiation showed halved ablation thresholds compared to VIS wavelength, revealing a greater photochemical nature of the ablation process at UV wavelength. Nevertheless, the ablation rate and, therefore, ablation efficiency did not show a clear dependence on beam wavelength. The different mechanical behavior of the considered PHAs did not lead to different ablation thresholds on each polymer at a constant wavelength, suggesting the interplay of the material mechanical parameters to equalize ablation thresholds. Blended-PHA showed a significant reduction in the ablation threshold under VIS irradiation respect to the neat PHAs. Picosecond ablation was proved to be a convenient technique for micro structuring of PHAs to generate surface microfeatures appropriate to influence cell behavior and improve the biocompatibility of scaffolds in tissue engineering.
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Monomers 4,7-dibromo-2H-benzo[d]1,2,3-triazole (m1) and 4,7-(bis(4-bromophenyl)ethynyl)-2H-benzo[d]1,2,3-triazole (m2) have been synthesized in good yields using different procedures. Monomers m1 and m2 have been employed for building new copolymers of fluorene derivatives by a Suzuki reaction under microwave irradiation using the same conditions. In each case different chain lengths have been achieved, while m1 gives rise to polymers for m2 oligomers have been obtained (with a number of monomer units lower than 7). Special interest has been paid to their photophysical properties due to excited state properties of these D-A units alternates, which have been investigated by density functional theory (DFT) calculations using two methods: (i) An oligomer approach and (ii) by periodic boundary conditions (PBC). It is highly remarkable the tunability of the photophysical properties as a function of the different monomer functionalization derived from 2H-benzo[d]1,2,3-triazole units. In fact, a strong modulation of the absorption and emission properties have been found by functionalizing the nitrogen N-2 of the benzotriazole units or by elongation of the π-conjugated core with the introduction of alkynylphenyl groups. Furthermore, the charge transport properties of these newly synthesized macromolecules have been approached by their implementation in organic field-effect transistors (OFETs) in order to assess their potential as active materials in organic optoelectronics.
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A series of four oligomers of cyclopentadithiophene-vinylenes end capped with pyridine groups was prepared and their optical and electronic properties studied. Treatment with trifluoroacetic acid (TFA) leads to the bisprotonation of the nitrogens of the pyridine, which has an important impact on the optical properties. Excess treatment with TFA provokes the oxidation of the conjugated core, generating radical cations and dications. The ease of the TFA treatment in solution was extended to protonation in the solid-state where further characterization of the neutral and TFA-treated samples was carried out in electrically active substrates in organic field-effect transistors. Finally, the new molecules were found to be excellent conductors in single-molecule junctions thanks to strong electron delocalization and resonance orbital mediated transport. These studies show the opening of a spectrum of possibilities by suitable terminal substitution of π-cores.
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Porous scaffolds made of elastomeric materials are of great interest for soft tissue engineering. Poly(L-lactide-co-ε-caprolactone) (PLCL) is a bio-resorbable elastomeric copolymer with tailorable properties, which make this material an appropriate candidate to be used as scaffold for vascular, tendon, and nerve healing applications. Here, extrusion was applied to produce porous scaffolds of PLCL, using NaCl particles as a leachable agent. The effects of the particle proportion and size on leaching performance, dimensional stability, mechanical properties, and ageing of the scaffolds were analyzed. The efficiency of the particle leaching and scaffold swelling when wet were observed to be dependent on the porogenerator proportion, while the secant moduli and ultimate tensile strengths were dependent on the pore size. Porosity, swelling, and mechanical properties of the extruded scaffolds were tailorable, varying with the proportion and size of porogenerator particles and showed similar values to human soft tissues like nerves and veins (E = 7-15 MPa, σu = 7 MPa). Up to 300-mm length micro-porous PLCL tube with 400-µm thickness wall was extruded, proving extrusion as a high-throughput manufacturing process to produce tubular elastomeric bio-resorbable porous scaffolds of unrestricted length with tunable mechanical properties.
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Introducción. Según el Instituto Nacional de Estadística e Informática (INEI), en el año 2017 existían en nuestro país tres millones de personas con discapacidad. De ellos, el 5% posee una importante limitación funcional, por lo que requieren de un cuidador; quien puede ver afectada su actividad física y emocional, e incluso enfermar. Objetivo. Establecer la relación entre el nivel de funcionalidad de la persona con discapacidad y la carga de trabajo del cuidador. Métodos. Se incluyeron a 50 cuidadores y 50 personas con discapacidad, en quienes se aplicó el Test de Zarit y Zarit, para medir y clasificar la sobrecarga de trabajo del cuidador en tres categorías: ausencia de sobrecarga, sobrecarga ligera y sobrecarga intensa; y la Escala Functional Independence Measure (FIM), para evaluar el nivel de funcionalidad en la persona con discapacidad, en tres categorías: dependencia completa, dependencia relativa e independencia funcional. Resultados. La mayoría de cuidadores de las personas con discapacidad refirieron tener intensa carga de trabajo, que es mayor al cuidar a personas con dependencia completa y menor al atender a personas con independencia funcional. Sin embargo, no se encontró una asociación estadísticamente significativa. Conclusión. Es frecuente que los cuidadores con sobrecarga intensa estén a cargo de pacientes con dependencia completa o relativa, en personas registradas en el Servicio de Atención Integral para Personas con Discapacidad (SAIPD) del Instituto Nacional de Bienestar Familiar (INABIF), durante el año 2018. Futuros estudios con metodologías cuantitativa y cualitativa podrían corroborar una posible relación entre estas variables.
Introduction. According to the National Institute of Statistics and Informatics (INEI), in 2017 there were three million people with disabilities in our country. Of these, 5% have a significant functional limitation, so they have to require a caregiver; who can see affected his physical and emotional activity, and eventually, they get sick. Objective. To establish the relationship between the burden of the caregiver and level of functionality of the person with disabilities. Methods. 50 caregivers and 50 people with disabilities were included. The Functional Independence Measure (FIM) is an accepted instrument for measuring disability, in three categories: complete dependence, relative dependence and independence. The Zarit and Zarit Test measures the burden of caregiver; classifying it into three categories: absence of burden, light burden and intense burden. Results. The majority of caregivers of people with disabilities reported having an intense burden, this being greater when caring for a person with complete dependence and lower when caring for a person with functional independence. However, no statistically significant association was found. Conclusion. It is common for caregivers with intense burden to be in charge of patients with complete or relative dependence, in people registered in the Comprehensive Care Service for People with Disabilities (SAIPD) of the Instituto Nacional de Bienestar Familiar (INABIF), during the year 2018. Future studies, with a better methodology, could corroborate a possible relationship between these variables.