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In this work a family of multidimensional (2-(1H-tetrazol-5-yl)ethyl) amino acid coordination compounds have been synthesized and thoroughly characterized. For this purpose, glycine, valine, phenylalanine and tyrosine have been selected as starting amino acids and Mn2+, Zn2+ and Cd2+ as metallic nodes. From one side, for Mn2+ based dimer magnetic resonance imaging studies have been conducted, prompted by the number and disposition of the coordinated water molecules and taking into consideration the promising future of manganese-based coordination compounds as bio-compatible substitutes to conventional Gd based contrast agents. From another side, d10 block metal-based complexes allowed exploring photoluminescence properties derived by inâ situ synthesized ligands. Finally, amino acid preserved structural chirality allowed us to examine chiroptical properties, particularly focusing on circularly polarized luminescence.
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Pain is one of the most common reasons for consultation and one of the most difficult tasks to handle for doctors. If it is chronic, the frequency of disorders increases associates that we cannot exclude from the treatment, and further complicates your treatment. The Asociation International Association for the Study of Pain (IAPS)1 defines the pain as "a sensory and emotional experience unpleasant associated with actual or potential tissue damage, or described in terms of such damage". So the pain is not only a nociceptive experience, but also involves emotional and subjective components, considering that It can even occur without a somatic cause justify. Its nature is complex, including factors biological and others such as subjective experience, education and emotion. Therefore pain is a personal, multidimensional problem, unique experience and non-transferable of the person who suffers it. Being a pharmacological and non-pharmacological approach is necessary for its management.
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Manejo da Dor , Dor , Humanos , Dor/tratamento farmacológico , Dor/etiologia , Dor/psicologia , Adaptação PsicológicaRESUMO
A series of substituted derivatives of tetraaza[7]helicenes were synthesized and the influence of the substitution on their photophysical and photoredox-catalytic properties was studied. The combination of their high fluorescence quantum yields of up to 0.65 and their circularly polarized luminescence (CPL) activity results in CPL brightness values (BCPL ) that are among the highest recorded for [7]helicenes so far. A sulfonylation/hetarylation reaction using cyanopyridines as substrates for photoinduced electron transfer (PET) from the excited helicenes was conducted to test for viability in photoredox catalysis. DFT calculations predict the introduction of electron withdrawing substituents to yield more oxidizing catalysts.
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We report on the chemical design of chiral molecular junctions with stress-dependent conductance, whose helicity is maintained during the stretching of a single molecule junction due to the stapling of both ends of the inner helix. In the reported compounds, different conductive pathways are observed, with clearly different conductance values and plateau-length distributions, attributed to different conformations of the helical structures. The large chiro-optical responses and the potential use of these molecules as unimolecular spin filters have been theoretically proved using state-of-the-art Density Functional Theory (DFT) calculations, including a fully ab-initio estimation of the CISS-originating spin polarization which is done, for the first time, for a realistic molecular system.
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COVID-19 , Hemofilia A , Humanos , Hemofilia A/terapia , Hemofilia A/psicologia , COVID-19/epidemiologia , PacientesRESUMO
The present work reports on a detailed discussion about the synthesis, characterization, and luminescence properties of three pairs of enantiopure 3D metal-organic frameworks (MOFs) with general formula {[Ln2(L/D-tart)3(H2O)2]·3H2O}n (3D_Ln-L/D, where Ln = Sm(III), Eu(III) or Gd(III), and L/D-tart = L- or D-tartrate), and ten pairs of enantiopure 2D coordination polymers (CPs) with general formula [Ln(L/D-Htart)2(OH)(H2O)2]n (2D_Ln-L/D, where Ln = Y(III), Sm(III), Eu(III), Gd(III), Tb(III), Dy(III), Ho(III), Er(III), Tm(III) or Yb(III), and L/D-Htart = hydrogen L- or D-tartrate) based on single-crystal X-ray structures. Enantiopure nature of the samples has been further corroborated by Root Mean Square Deviation (RMSD) as well as by circular dichroism (CD) spectra. Solid-state emission spectra of Eu(III), Tb(III), and Dy(III)-based compounds confirm the occurrence of ligand-to-metal charge transfers in view of the characteristic emissions for these lanthanide ions, and emission decay curves were also recorded to estimate the emission lifetimes for the reported compounds. A complete theoretical study was accomplished to better understand the energy transfers occurring in the Eu-based counterparts, which allows for explaining the different performances of 3D-MOFs and 2D-layered compounds. As inferred from the colorimetric diagrams, emission characteristics of Eu-based 2D CPs depend on the temperature, so their luminescent thermometry has been determined on the basis of a ratiometric analysis between the ligand-centered and Eu-centered emission. Finally, a detailed study of the polarized luminescence intensity emitted by the samples is also accomplished to support the occurrence of chiro-optical activity.
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Circularly polarized luminescent (CPL) films with high dissymmetry factors hold great potential for optoelectronic applications. Herein, we propose a strategy for achieving strongly dissymetric CPL in nanocomposite films based on chirality induction and energy transfer to semiconductor nanocrystals. First, focusing on a purely organic system, aggregation-induced emission (AIE) and CPL activity of organic liquid crystals (LCs) forming helical nanofilaments was detected, featuring green emission with high dissymmetry factors glum â¼ 10-2. The handedness of helical filaments, and thus the sign of CPL, was controlled via minute amounts of a small chiral organic dopant. Second, nanocomposite films were fabricated by incorporating InP/ZnS semiconductor quantum dots (QDs) into the LC matrix, which induced the chiral assembly of QDs and endowed them with chiroptical properties. Due to the spectral matching of the components, energy transfer (ET) from LC to QDs was possible enabling a convenient way of tuning CPL wavelengths by varying the LC/QD ratio. As obtained, composite films exhibited absolute glum values up to â¼10-2 and thermally on/off switchable luminescence. Overall, we demonstrate the induction of chiroptical properties by the assembly of nonchiral building QDs on the chiral organic template and energy transfer from organic films to QDs, representing a simple and versatile approach to tune the CPL activity of organic materials.
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Three achiral polycyclic aromatic fluorophoresânamely, 1-pyrenecarboxylic acid, 9-anthracenecarboxylic acid, and perylene-3,9-dicarboxylic acidâwere chosen based on their desired properties before being incorporated into the construction of a K+-carrying gamma-cyclodextrin (γ-CD)-based metal-organic framework (CD-MOF-1) and γ-CD-containing hybrid frameworks (CD-HFs). Among these fluorophores, only the pyrene-carrying one shows significant noncovalent bonding interactions with γ-CD in solution. This fluorophore is encapsulated in a CD-HF with a trigonal superstructure instead of the common cubic CD-MOF-1 found in the case of the other two fluorophores. Single-crystal X-ray diffraction analysis of the trigonal CD-HF reveals a π-stacked chiral positioning of the pyrene-carrying fluorophore inside the (γ-CD)2 tunnels and held uniformly around an enantiomorphous 32 screw axis along the c direction in the solid-state structure. This helix-like structure demonstrates an additional level of chirality over and above the point-chiral stereogenic centers of γ-CD and the axial chirality associated with the self-assembled π-stacked fluorophores. These arrangements result in specifically generated photophysical and chiroptical properties, such as the controlled emergence of circularly polarized luminescence (CPL) emission. In this manner, a complete understanding of the mechanism of chirality transfer from a chiral host (CD-HF) to an encapsulated achiral fluorophore has been achieved, an attribute which is often missing in the development of materials with CPL.
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Ciclodextrinas , Estruturas Metalorgânicas , Corantes Fluorescentes/química , Luminescência , PirenosRESUMO
BACKGROUND: Hemophilia is characterized by the development of joint bleeds that cause long-term joint damage (hemophilic arthropathy). Joint damage leads to disability and affects psychosocial aspects in patients with hemophilia. OBJECTIVE: To compare the clinical situation, perception of disease and quality of life, and coping strategies in adult patients with hemophilia in El Salvador and Spain. METHODS: In this comparative clinical study, 43 patients with hemophilia aged between 18 and 50 years old from Spain and El Salvador participated. After obtaining the patients' consent, they completed the Illness Perception Questionnaire-Revised (IPQ-R), Hemophilia-QoL and Inventory of Coping strategies questionnaires. Joint status was assessed using the Hemophilia Joint Health Score and based on a record of clinical and treatment data. RESULTS: Hemophilia patients from Spain showed an improved perception of quality of life (p <0.05), although there were only differences in the self-criticism variable (p = 0.04) for coping strategies. Joint damage and age correlated (p <0.05) negatively with perception of disease, perceived quality of life and coping strategies in both populations. There were differences (p <0.05) between the two populations based on HIV and HCV coinfections in perception of disease and perceived quality of life. CONCLUSION: Patients with hemophilia in El Salvador exhibit a poorer perception of disease and quality of life. Despite differences in access to treatment from one country to the other, there is no difference in coping with the disease. Older patients are better able to adapt to the disease.
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The first enantioselective addition of alkyl BODIPYs to Morita-Baylis-Hillman (MBH) carbonates is reported. This is the first reported enantioselective methodology using the methylene position of BODIPYs as a nucleophile. The reaction is efficiently catalyzed by cinchona alkaloids, achieving high enantioselectivities and total diastereoselectivity. The use of cinchona alkaloid pseudo enantiomers (chinine/cinchonine) allows us to obtain both pairs of enantiomers in similar yields and enantioselectivities, a common issue in this type of reaction. The photophysical study of these dyes (absorption and fluorescence) has been performed in order to determine their parameters and explore future possible application in bioimaging. In addition, electronic circular dichroism (ECD) studies supported by time-dependent density functional theory (TD-DFT) calculations were also performed.
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INTRODUCTION: The episodic or on-demand administration of clotting factor concentrates in hemophilia patients in the event of hemorrhage is employed to restore hemostasis. Adherence to on-demand treatments needs to be assessed in order to improve patient management, avoiding adverse effects and serious clinical complications. AIM: To validate the Spanish version of the treatment adherence scale in patients with hemophilia, namely, Validated Hemophilia Regimen Treatment Adherence Scale-PRN (VERITAS-PRN). METHODS: Eighty-five patients were recruited in three hemophilia patient associations in Spain. The VERITAS-PRN scale was adapted through a back-translation process from English to Spanish. A native Spanish bilingual translator translated the scale from English to Spanish, and subsequently another native English bilingual translator translated the scale from Spanish to English. The scale was applied twice (two months apart) to assess test-retest reliability. RESULTS: Internal consistency reliability was slightly lower in the VERITAS-PRN in Spanish (0.80) versus the English version (0.85). There were no differences (p > 0.05) between the means of the dimensions or in the total scores between the sample of patients in Spain and the USA. The test-retest reliability coefficient of the scores on the total scale was 0.80 [CI, 0.74-0.86]. The test-retest reliability coefficient was greater than 0.90 in all subscales. CONCLUSION: The Spanish version of VERITAS-PRN has high consistency and empirical validity. This scale is useful for assessing the degree of adherence to treatment in adult patients with hemophilia following episodic infusion treatment.
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The carrier testing, genetic counseling and prenatal diagnosis have become an integrated part of the comprehensive care for hemophilia, but quality of life and management of carriers frequently remain suboptimal. It is paramount to evaluate the physical and psycho-social impact of them as problematic physical, psychological and social situations are not uncommon. There are to instruct them about their hemorrhagic possible symptoms and condition for offering solutions that meet their needs and help them enjoy a satisfactory quality of life in all life stages.
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Hemofilia A , Hemofilia B , Qualidade de Vida , Gerenciamento Clínico , Feminino , Triagem de Portadores Genéticos , Aconselhamento Genético , Hemofilia A/epidemiologia , Hemofilia A/genética , Hemofilia A/psicologia , Hemofilia A/terapia , Hemofilia B/epidemiologia , Hemofilia B/genética , Hemofilia B/psicologia , Hemofilia B/terapia , Humanos , Gravidez , Diagnóstico Pré-NatalRESUMO
In this work we describe the linear and non-linear (chiro)optical properties of an enantiopure bis-perylenediimide (PDI) cyclohexane derivative. This compound exhibits upconversion based on a two-photon absorption (TPA) process with a cross-section value of 70 GM together with emission of circularly polarized luminescence (CPL), showing a glum in the range of 10-3. This simple structure represents one of the scarce examples of purely organic compounds combining both TPA and CPL responses, together with large values of molar absorptivity and fluorescence quantum yield with emission in the 500-600 nm. Self-assembly induced by introduction of a poor solvent allows for a spectacular shift of the emission into the near-infrared (NIR, 650-750 nm) by formation of well-defined rotationally displaced dimers. Therefore, we are here presenting a versatile platform whose optical properties can be simply tuned by self-assembly or by functionalization of the electron-deficient aromatic core of PDIs.
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PURPOSE: To build a multidimensional questionnaire of adherence for a patient with hemophilia that includes not only clinical but also psychosocial aspects. PATIENTS AND METHODS: One hundred and forty-six patients with haemophilia (A and B) were recruited from several Hemophilia Treatment Centers for this study. The recruitment was performed through a personal interview (20-25 mins for each patient). A literature review was carried out (different databases). In the first version (136 items), all items were subjected to an external judgment (experts in hemophilia) and also presented and discussed with a group of patients. It was made a study of content validity and homogeneity index and reliability coefficients of score were calculated with an alpha coefficient. Empirical validation was made with Pearson correlation. RESULTS: The Haemo-Adhaesione scale was composed of 5 dimensions and 10 questions about basic haemophilia concepts. It was shown to be valid and reliable to assess adherence in the Spanish population. Its internal consistency was good in all dimensions. The Rasch model was used to confirm the multidimensional structure of the scale. Significant and negative correlations were observed with the VERITAS-Pro and VERITAS-PRN scale in all dimensions, and in the total score. CONCLUSIONS: The Haemo-Adhaesione scale is a good measure of adherence for PWH. Its multidimensional structure favors the inclusion of the objective and subjective aspects implicit in its definition, as well as its dynamic nature. Patients with greater adherence are those who have more awareness of their disease, and as a result, they are more compliant with prescription and their self-care. It also discriminates between patients who follow one treatment or another.
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: Prophylaxis has helped improve patients' perception of their quality of life, enabling them to lead a more normal life. For these reasons prophylactic treatment is nowadays considered a gold standard in the treatment of severe hemophilia A or B. Despite its benefits in terms of preventing bleeding and preserving patients' health, this intensive treatment is not always adhered to by patients with hemophilia - promotion of adherence should involve a multidisciplinary team which addresses not only the clinical aspects of a condition but also the different psychosocial aspects affecting patients and their (social, family and healthcare) environment.
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Hemofilia A/prevenção & controle , Hemofilia B/prevenção & controle , Hemorragia/prevenção & controle , Gerenciamento Clínico , Hemofilia A/complicações , Hemofilia B/complicações , Hemorragia/etiologia , Humanos , Estilo de Vida , Cooperação do Paciente , Qualidade de VidaRESUMO
INTRODUCTION: Chronic diseases, after diagnosis, involve changes that have to favour coping with the new situation. The resources used will help control, manage and adapt to the disease. The psychological aspects may be influencing how the individual faces the situation. AIM: To assess whether perceptions or beliefs and illness behaviour influence the choice of coping strategies for young and adult patients with haemophilia. METHODS: Multicenter cross-sectional descriptive study. We recruited 63 patients with haemophilia A and B, adolescents, young and adults, and both types of treatment. A clinical and sociodemographic data sheet, the Coping Strategies Inventory (CSI), the Illness Perception Questionnaire-revised (IPQ-R) and the Illness Behaviour Questionnaire (IBQ) were used. RESULTS: Patients with haemophilia use appropriate coping strategies, both cognitive and behavioural. Most of them are on-demand treatment, and despite arthropathy, they perceive good control of haemophilia. However, patients in prophylactic treatment are those employed more maladaptive coping strategies, less perception of control and hypochondriacal behaviour to the disease. The age variable may be relevant but we did not find significant differences. CONCLUSIONS: Coping strategies used by patients with haemophilia are adequate. Although it is noted that the perception of the disease, its controllability or not, affects illness behaviour and consequently how coping with haemophilia. These are based on personal characteristics, cognitive and attitudinal dispositions that the individual consciously use to solve or face adverse situations. The analysis of coping styles of patients could be a tool for professionals to manage properly the disease.
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Adaptação Psicológica , Hemofilia A/psicologia , Adulto , Estudos Transversais , Feminino , Humanos , Masculino , Inquéritos e QuestionáriosRESUMO
Here we describe a new class of CPL switches based on oxophilic interactions between chiral sulfoxide-containing ortho-phenylene ethynylene (o-OPE) foldamers and cationic metals. These systems represent a unique case combining high glum values (up to 0.7 × 10-2) and high quantum yields in both folded ON and unfolded OFF CPL states.
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BACKGROUND: The influence of parents can be an important variable in the development of eating disorders (EDs). However, few studies exist which simultaneously assess parents and their children, especially in different clinical groups. METHODS: Our study examines the differences in ED symptoms as measured on the Eating Disorder Inventory (EDI), in parents and their children as patients with anorexia nervosa (AN), bulimia nervosa (BN), unspecified eating disorder (UED) and a control group (CG). RESULTS: The mothers in the clinical group scored higher in ineffectiveness, interoceptive awareness, maturity fears, social insecurity and impulse regulation than the mothers in the control group. The patients’ fathers scored higher on impulse regulation than those in the control group. In addition, the fathers of patients in the BN group scored higher than the fathers of patients in the UED group in body dissatisfaction. They also scored higher in impulse regulation than the fathers of patients with AN. Ineffectiveness and impulse regulation were the variables in which patients’ scores were most similar to their parents. CONCLUSIONS: These results show the presence of ED psychological variables in both parents, not just mothers. Prevention and intervention activities for eating disorders must be designed to also give an active role to the father.