Exciplex Emission and Förster Resonance Energy Transfer in Polycyclic Aromatic Hydrocarbon-Based Bischromophoric Cyclophanes and Homo[2]catenanes.

Energy transfer and exciplex emission are not only crucial photophysical processes in many living organisms but also important for the development of smart photonic materials. We report, herein, the rationally designed synthesis and characterization of two highly charged bischromophoric homo[2]catenanes and one cyclophane incorporating a combination of polycyclic aromatic hydrocarbons, i.e., anthracene, pyrene, and perylene, which are intrinsically capable of supporting energy transfer and exciplex formation. The possible coconformations of the homo[2]catenanes, on account of their dynamic behavior, have been probed by Density Functional Theory calculations. The unique photophysical properties of these exotic molecules have been explored by steady-state and time-resolved absorption and fluorescence spectroscopies. The tetracationic pyrene-perylene cyclophane system exhibits emission emanating from a highly efficient Förster resonance energy transfer (FRET) mechanism which occurs in 48 ps, while the octacationic homo[2]catenane displays a weak exciplex photoluminescence following extremely fast (<0.3 ps) exciplex formation. The in-depth fundamental understanding of these photophysical processes involved in the fluorescence of bischromophoric cyclophanes and homo[2]catenanes paves the way for their use in future bioapplications and photonic devices.

Factors influencing professionalism during dental training at the University of Chile: perception of students and patients.

BACKGROUND: The University should be considered a favourable space and agent for the training and transmission of values and attitudes related to professionalism, such as responsibility, teamwork and ethical commitment. In addition, dentistry is a profession with a deep social sense that seeks to solve the oral health problems of the population to improve the quality of life. In this context, our aim was to explore the perception of students and patients about the contribution of the curriculum to the development of professionalism and to identify the factors that strengthen and weaken this perception. METHODS: A qualitative approach was carried out through focus groups and semi-structured interviews with students from the 4th, 5th and 6th year of training and patients treated at the Dental Clinic of our Faculty. RESULTS: In the opinion of patients and students, the factors that debilitate the training in professionalism are associated with weakened professional values/behaviours in the training, the lack of teacher training of the professors and factors of educational environment. On the contrary, factors strengthening the professionalism are mainly related to hallmark values/ professional behaviours trained in the institution and to the good evaluation by patients. The respondents also perceive the implementation of a new curriculum as a positive factor for the training in professionalism. CONCLUSION: The patients and students interviewed believe that the main strength for the training in professionalism in the institution is the development of adaptability for the future professionals to any social context, especially to a vulnerable one, the ability to solve the problems they face and the responsibility towards the patients and their treatment.

Light-Fueled Transformations of a Dynamic Cage-Based Molecular System.

In a chemical equilibrium, the formation of high-energy species-in a closed system-is inefficient due to microscopic reversibility. Here, we demonstrate how this restriction can be circumvented by coupling a dynamic equilibrium to a light-induced E/Z isomerization of an azobenzene imine cage. The stable E-cage resists intermolecular imine exchange reactions that would "open" it. Upon switching, the strained Z-cage isomers undergo imine exchange spontaneously, thus opening the cage. Subsequent isomerization of the Z-open compounds yields a high-energy, kinetically trapped E-open species, which cannot be efficiently obtained from the initial E-cage, thus shifting an imine equilibrium energetically uphill in a closed system. Upon heating, the nucleophile is displaced back into solution and an opening/closing cycle is completed by regenerating the stable all-E-cage. Using this principle, a light-induced cage-to-cage transformation is performed by the addition of a ditopic aldehyde.

Thermally Controlled Exciplex Fluorescence in a Dynamic Homo[2]catenane.

Motion-induced change in emission (MICE) is a phenomenon that can be employed to develop various types of probes, including temperature and viscosity sensors. Although MICE, arising from the conformational motion in particular compounds, has been studied extensively, this phenomenon has not been investigated in depth in mechanically interlocked molecules (MIMs) undergoing coconformational changes. Herein, we report the investigation of a thermoresponsive dynamic homo[2]catenane incorporating pyrene units and displaying relative circumrotational motions of its cyclophanes as evidenced by variable-temperature 1H NMR spectroscopy and supported by its visualization through molecular dynamics simulations and quantum mechanics calculations. The relative coconformational motions induce a significant change in the fluorescence emission of the homo[2]catenane upon changes in temperature compared with its component cyclophanes. This variation in the exciplex emission of the homo[2]catenane is reversible as demonstrated by four complete cooling and heating cycles. This research opens up possibilities of using the coconformational changes in MIMs-based chromophores for probing fluctuations in temperature which could lead to applications in biomedicine or materials science.

[Instruments to assess functional capacity and the presence of frailty in older people]. / Instrumentos para medir la capacidad funcional intrínseca y la fragilidad de personas mayores en la Atención Primaria en Chile.

BACKGROUND: The evaluation of functional capacity and the presence of frailty is an essential prognostic indicator in older people. AIM: To explore the instruments used to characterize the intrinsic functional capacity (CFI) and frailty in elderly people cared at Primary Health Care Centers (PHC) in Chile. MATERIAL AND METHODS: A narrative review of national and international scientific literature was carried out, including observational studies published in Pubmed (since 2015) and Scielo (since 2010) about tools to assess CFI or frailty. Studies in English or Spanish carried out in Chilean beneficiaries of PHC aged 60 years and over, were included. RESULTS: After the first search, 110 articles were selected in Pubmed and 86 in Scielo. According to the relevance of the title and abstract, 36 articles were preliminarily screened, of which 25 were selected for full reading, 12 of which were finally included in this review. In Chile, the main instrument used to assess CFI is the Functional Examination of the Elderly (EFAM). There are few national studies to assess frailty and the instruments used are mainly based on the Fried criteria and the FTI (Frailty Tilburg Indicator). The reviewed studies suggest improving the coverage and reconsidering the predictive capacity of the measurements used for the assessment of CFI and frailty in older people, suggesting the incorporation of handgrip strength as a predictor of frailty. CONCLUSIONS: The main instruments to assess CFI and frailty in older people cared in PHC in Chile are the EFAM, and the Fried and FTI criteria, respectively.

Aggregation-Induced Emission and Circularly Polarized Luminescence Duality in Tetracationic Binaphthyl-Based Cyclophanes.

Here, we report an approach to the synthesis of highly charged enantiopure cyclophanes by the insertion of axially chiral enantiomeric binaphthyl fluorophores into the constitutions of pyridinium-based macrocycles. Remarkably, these fluorescent tetracationic cyclophanes exhibit a significant AIE compared to their neutral optically active binaphthyl precursors. A combination of theoretical calculations and time-resolved spectroscopy reveal that the AIE originates from limited torsional vibrations associated with the axes of chirality present in the chiral enantiomeric binaphthyl units and the fine-tuning of their electronic landscape when incorporated within the cyclophane structure. Furthermore, these highly charged enantiopure cyclophanes display CPL responses both in solution and in the aggregated state. This unique duality of AIE and CPL in these tetracationic cyclophanes is destined to be of major importance in future development of photonic devices and bio-applications.

Molecular Pumps and Motors.

Pumps and motors are essential components of the world as we know it. From the complex proteins that sustain our cells, to the mechanical marvels that power industries, much we take for granted is only possible because of pumps and motors. Although molecular pumps and motors have supported life for eons, it is only recently that chemists have made progress toward designing and building artificial forms of the microscopic machinery present in nature. The advent of artificial molecular machines has granted scientists an unprecedented level of control over the relative motion of components of molecules through the development of kinetically controlled, away-from-thermodynamic equilibrium chemistry. We outline the history of pumps and motors, focusing specifically on the innovations that enable the design and synthesis of the artificial molecular machines central to this Perspective. A key insight connecting biomolecular and artificial molecular machines is that the physical motions by which these machines carry out their function are unambiguously in mechanical equilibrium at every instant. The operation of molecular motors and pumps can be described by trajectory thermodynamics, a theory based on the work of Onsager, which is grounded on the firm foundation of the principle of microscopic reversibility. Free energy derived from thermodynamically non-equilibrium reactions kinetically favors some reaction pathways over others. By designing molecules with kinetic asymmetry, one can engineer potential landscapes to harness external energy to drive the formation and maintenance of geometries of component parts of molecules away-from-equilibrium, that would be impossible to achieve by standard synthetic approaches.

Values related to professionalism in dental education at the University of Chile: Student and faculty perceptions.

OBJECTIVE: It is recognised that professionalism should play a central role in dental education. However, its implementation into the curricula of dental schools is still limited. Our objective was to identify the main values related to professionalism based on the perceptions of students and faculty members from the Faculty of Dentistry, University of Chile. METHODS: A Dental Values Survey was validated and culturally adapted in order to guarantee the greatest possible internal validity. The adapted survey was administered to students and faculty members (416 and 225, respectively). The final survey contained 64 items rated on a Likert scale of 1-5. Each item was categorised according to five dimensions: Altruism, Consciousness, Personal Satisfaction, Quality of Life and Professional Status. The values were compared between faculty and students and among students at different courses. A values scale was constructed by selecting the five items with the highest average score for each dimension. RESULTS: Survey respondents composed 34.32% of the universe, of which 50.46% were faculty and 49.54% were students. Values associated with Altruism, Consciousness and Professional Status, were the highest rated by students and faculty. Values associated with Personal Satisfaction and Quality of Life received the lowest scores for both groups. CONCLUSIONS: To provide the best possible attention to patients (Consciousness), and that patients have access to affordable dental care (Altruism), are the values at the top of our scale. On the other hand, to maintain financial stability and to be well paid (Quality of Life) were the less considered.

Oral health care activities performed by caregivers for institutionalized elderly in Barcelona-Spain.

OBJECTIVES: To describe the frequency of brushing teeth and cleaning of dentures, performed by caregivers, for institutionalized elderly people. METHODS: A cross-sectional study in a sample of 196 caregivers of 31 health centers in Barcelona. The dependent variables were frequency of dental brushing and frequency of cleaning of dentures of the elderly by caregivers. The independent variables were characteristics of caregivers and institutions. We performed bivariate and multivariate descriptive analyses. Robust Poisson regression models were fitted to determine factors associated with the dependent variables and to assess the strength of the association. RESULTS: 83% of caregivers were women, 79% worked on more than one shift, 42% worked only out of necessity, 92% were trained to care for elderly persons, 67% were trained in oral hygiene care for the elderly, and 73% recognized the existence of institutional protocols on oral health among residents. The variables explaining the lower frequency of brushing teeth by caregivers for the elderly, adjusted for the workload, were: no training in the care of elderly persons (PRa 1.7 CI95%: 1.6-1.8), not fully agreeing with the importance of oral health care of the elderly (PRa 2.5 CI95%: 1.5-4.1) and not knowing of the existence of oral health protocols (PRa 1.8 CI95% 1.2-2.6). The variables that explain the lower frequency of cleaning dentures, adjusted for the workload, were lack of training in elderly care (PRa 1.7 CI95%: 1.3-1.9) and not knowing of the existence of protocols (PRa 3.7 CI95%: 1.6-8.7). CONCLUSION: The majority of caregivers perform activities of oral health care for the elderly at least once per day. The frequency of this care depends mainly on whether caregivers are trained to perform these activities, the importance given to oral health, the workload of caregivers and the existence of institutional protocols on oral health of institutionalized elderly persons.

Oral health policies and decision-making process in Brazil, Colombia and Chile.

Public health policies are crucial for the well-being of the general population; however, the health systems of developed countries still do not include oral health in its system. Thus, it is necessary to understand the process of decision-making in oral health policies to create opportunities for countries to achieve an overall positive health outcome, including oral health. This study aimed to identify the factors influencing the inclusion of oral health on the political agenda in Brazil, Colombia, and Chile. The study sample involved decision-makers at political, technical, and academic levels. The extracted data were analyzed using the software Maxqda® and Kingdon´s theoretical model; defining interactive variables that produce a "window of opportunity" to define the agenda and the insertion of theme in formulating public policies. The decision-making process regarding oral health is influenced by many factors like the need to improve the overall oral health of the population, identified through national epidemiological studies, and the importance of individuals in positions involving political decision-making, who advocate for oral health. Strategies were developed in partnership with the academy that focused on the health rights of the population provided by law; territorial and national programs were also developed. The inclusion and creation of oral health policies depend on actors who advocate for thematic and scientific evidence to support decision-making. A close relationship between academia and stakeholders and knowledge translation is important for the development of public policies that can be effective for health systems.

Latin America and the Caribbean Code Against Cancer 1st edition: Formative research on the comprehension and persuasiveness of the recommendations by the general population.

BACKGROUND: Cancer prevention is the most efficient and cost-effective strategy in cancer control. One prevention strategy is giving credible, clear, and evidence-based recommendations to the individual; however, it is key that these messages are accepted and understood properly by the public. This study aimed to pilot the draft recommendations developed as part of the Latin America and the Caribbean (LAC) Code Against Cancer 1st edition, in terms of comprehension and persuasion of each message. METHODS: A mixed method two-wave study, in which two versions of the messages were presented to the general population in five LAC countries. We used an ad-hoc questionnaire and interviews that followed the cognitive-pretesting methodology. RESULTS: Findings suggest that the messages were generally well understood, especially in Spanish speaking countries, and that the messages were generally more understandable than persuasive. We adapted and revised the recommendations based on the findings of the first Wave and held a second iteration in the Spanish speaking countries. We observed a better understanding of most messages in Wave 2. CONCLUSION: The LAC Code Against Cancer is a valuable tool of well understood messages for the public, with concrete actions everyone can take to prevent cancer. Further research should assess particularities of the region for further efficient dissemination of these important health messages, identify key messages for certain population groups and future interventions that strengthen health literacy in rural and less educated populations to increase behavior change.

Knowledge, attitudes, behavioral and organizational factors of health professions students for a competent smoking cessation practice: An instrument adaptation and psychometric validation study in Spanish and English samples.

BACKGROUND: To improve smoking cessation, training of health professions students is essential. However, no specific instrument is available to assess factors that may affect students' learning about smoking cessation practice. AIM: To adapt and validate the Knowledge, Attitudes, Behaviors and Organization questionnaire in the population of undergraduate health professions students. DESIGN: Methodological research. METHODS: The researchers conducted this study with 511 Spanish and 186 English health professions students from four different universities. We used a four-step approach: 1) adaptation of the items to the target population and validation of the content by a panel of experts; 2) a pilot study to test face validity; 3) linguistic adaptation of the Spanish version to English; and 4) the psychometric assessment based on construct validity, criterion validity and internal consistency. RESULTS: Exploratory factor analysis revealed four subscales for the Spanish version, namely 'Individual knowledge and skills', 'Individual attitudes and beliefs', 'Organizational support' and 'Organizational resources', which accounted for 85.1% of the variance. Confirmatory factor analysis in the holdout Spanish and English samples revealed adequate goodness-of-fit values, supporting the factor structure. Hypotheses testing demonstrated significant differences by capacitation in smoking cessation interventions and degree courses, providing further evidence regarding construct validity. All the subscales correlated positively with the criterion variables (5 A's smoking cessation model), except for the 'Organizational resources' subscale, which was not significantly correlated with the 5 A's. The overall Cronbach's alpha was.83 for the Spanish version and.88 for the English one. CONCLUSIONS: Our results provide empirical support for the use of the Knowledge, Attitudes, Behaviors and Organization questionnaire for Students as a reliable and valid instrument to assess knowledge, attitudes, behaviors and organization perceptions in health professions students, which is essential for competent smoking cessation practice. Interestingly, 'Organizational resources' subscale presented the lowest correlations among factors and did not correlate with any component of the 5 A's, suggesting the need of enhancing students' responsibility and involvement during their internships, as well as the interest of some organizations.

N-[2-(3,4-Di-meth-oxy-phen-yl)-2-(phenyl-sulfan-yl)eth-yl]-2-(2-fluoro-phen-yl)acetamide.

The title compound, C24H24FNO3S, is an inter-mediate in the synthesis of fluorine containing iso-quinoline alkaloids, which crystallizes in the triclinic space group P with one mol-ecule in the asymmetric unit. The structure presents a racemic mixture of enanti-omers. The C-S-C-C torsion angle between the benzene ring system and the sulfonyl benzene ring is -178.5 (1)°. In the crystal, N-H⋯O hydrogen bonds between neighbouring mol-ecules form chains of mol-ecules along the a-axis direction.

¿Qué Nos Queda Por Recorrer Para Proveer Salud Oral De Calidad A Las Personas Adultas En Chile?

Existen factores de riesgo comunes entre las enfermedades de la cavidad oral y las enfermedades crónicas no transmisibles, y se conoce sobre su vinculación con la salud general y la calidad de vida. En Chile, la atención odontológica en el sistema público está destinada principalmente a la población infantojuvenil, y solo algunos de los programas odontológicos incluyen componentes con atención para adultos. La mayor parte de la población adulta atendida accede mediante los Programas de Reforzamiento de la Atención Primaria de Salud (PRAPS), cuya sostenibilidad en el tiempo no es posible de determinar, por lo que es relevante poner el foco en aquella población con mayor daño acumulado y que al día de hoy no tiene acceso garantizado a la atención odontológica.

There are common risk factors between diseases of the oral cavity and chronic non-communicable diseases, and it is known that they are related to general health and quality of life. In Chile, dental care in the public system is mainly aimed at the child and adolescent population, and only some of the dental programs include care for adults. Most of the adult population attended has access through the Primary Health Care Reinforcement Program (PHCRP), whose sustainability over time is not possible to determine. So, it is important to focus on the population with the greatest cumulative damage and without guaranteed access to dental care today.

Oral health policies and decision-making process in Brazil, Colombia and Chile

Abstract Public health policies are crucial for the well-being of the general population; however, the health systems of developed countries still do not include oral health in its system. Thus, it is necessary to understand the process of decision-making in oral health policies to create opportunities for countries to achieve an overall positive health outcome, including oral health. This study aimed to identify the factors influencing the inclusion of oral health on the political agenda in Brazil, Colombia, and Chile. The study sample involved decision-makers at political, technical, and academic levels. The extracted data were analyzed using the software Maxqda® and Kingdon´s theoretical model; defining interactive variables that produce a "window of opportunity" to define the agenda and the insertion of theme in formulating public policies. The decision-making process regarding oral health is influenced by many factors like the need to improve the overall oral health of the population, identified through national epidemiological studies, and the importance of individuals in positions involving political decision-making, who advocate for oral health. Strategies were developed in partnership with the academy that focused on the health rights of the population provided by law; territorial and national programs were also developed. The inclusion and creation of oral health policies depend on actors who advocate for thematic and scientific evidence to support decision-making. A close relationship between academia and stakeholders and knowledge translation is important for the development of public policies that can be effective for health systems.

Instrumentos para medir la capacidad funcional intrínseca y la fragilidad de personas mayores en la Atención Primaria en Chile / Instruments to assess functional capacity and the presence of frailty in older people

BACKGROUND: The evaluation of functional capacity and the presence of frailty is an essential prognostic indicator in older people. Aim: To explore the instruments used to characterize the intrinsic functional capacity (CFI) and frailty in elderly people cared at Primary Health Care Centers (PHC) in Chile. MATERIAL AND METHODS: A narrative review of national and international scientific literature was carried out, including observational studies published in Pubmed (since 2015) and Scielo (since 2010) about tools to assess CFI or frailty. Studies in English or Spanish carried out in Chilean beneficiaries of PHC aged 60 years and over, were included. Results: After the first search, 110 articles were selected in Pubmed and 86 in Scielo. According to the relevance of the title and abstract, 36 articles were preliminarily screened, of which 25 were selected for full reading, 12 of which were finally included in this review. In Chile, the main instrument used to assess CFI is the Functional Examination of the Elderly (EFAM). There are few national studies to assess frailty and the instruments used are mainly based on the Fried criteria and the FTI (Frailty Tilburg Indicator). The reviewed studies suggest improving the coverage and reconsidering the predictive capacity of the measurements used for the assessment of CFI and frailty in older people, suggesting the incorporation of handgrip strength as a predictor of frailty. CONCLUSIONS: The main instruments to assess CFI and frailty in older people cared in PHC in Chile are the EFAM, and the Fried and FTI criteria, respectively.

Manifestaciones orales y recuento de linfocitos T CD4+ en pacientes adultos con infección por VIH atendidos en el Hospital San Juan de Dios. Santiago, Chile

Resumen Introducción: Las lesiones orales clasificadas como fuertemente asociadas a infección por VIH se presentan en casos de inmunosupresión profunda (recuento de linfocitos T CD4+ ≤ a 200 céls/mm3 de sangre). Objetivo: Asociar la presencia de lesiones orales fuertemente asociadas a infección por VIH con el recuento sérico de linfocitos T (LT) CD4+ al momento del diagnóstico. Métodos: Se realizó un estudio transversal en PVVIH atendidas en el Hospital San Juan de Dios entre 2013 y 2019. Las lesiones orales se diagnosticaron por el criterio de EC-Clearinghouse - OHARA, y la inmunosupresión fue determinada según el recuento de LT CD4+. Resultados: De los 240 pacientes reclutados, 35 pacientes presentaron lesiones fuertemente asociadas a infección por VIH y 26 de ellos presentaron inmunosupresión profunda. La probabilidad de ocurrencia de una lesión fuertemente asociada a infección por VIH fue 12,3 veces mayor en pacientes con inmunosupresión profunda. Conclusión: Existe una asociación estadísticamente significativa entre un estado de inmunosupresión profunda y la presencia de manifestaciones orales fuertemente asociadas a infección por VIH/SIDA, lo cual posee relevancia clínica pues se presenta como una herramienta clínica de diagnóstico inicial, progresión de la enfermedad y monitorización de la terapia antiretroviral.

Abstract Background: Oral lesions classified as strongly associated with HIV infection occur in cases of severe immunosuppression (CD4+ T lymphocyte count ≤ 200 cells/mm3 of blood). Aim: To associate the presence of oral lesions strongly associated with HIV infection with CD4+ T lymphocytes count at the time of diagnosis. Methods: A cross-sectional study was carried out in PLHIV treated at the San Juan de Dios Hospital between 2013 and 2019. Oral lesions were diagnosed by the EC-Clearinghouse - OHARA criteria and immunosuppression was determined according to the CD4+ T lymphocyte count. Results: Of the 240 recruited patients, 35 had lesions strongly associated with HIV infection and 26 of them had severe immunosuppression. The probability of occurrence of a lesion strongly associated with HIV infection is 12.3 times higher in patients with severe immunosuppression. Conclusion: There is a statistically significant association between a severe immunosuppression and the presence of oral manifestations strongly associated with HIV/ AIDS infection, which has clinical relevance since it is presented as a clinical tool for initial diagnosis, disease progression and monitoring of antiretroviral therapy.

Changes in socioeconomic inequalities in the use of dental care following major healthcare reform in Chile, 2004-2009.

The study examines changes in the distribution and socioeconomic inequalities of dental care utilization among adults after the major healthcare reform in Chile, 2004-2009. We evaluated the proportion of people who visited the dentist at least once in the previous two years, and the mean number of visits. These outcome variables were stratified by sex, age (20-39, 40-59, 60-63; ≥64 years), educational level (primary, secondary, higher), type of health insurance (public, private, uninsured), and socioeconomic status (quintiles of an asset-index). We also used the concentration index (CIndex) to assess the extent of socioeconomic inequalities in the use of dental care, stratified by age and sex as a proxy for dental care needs. The use of dental care significantly increased between 2004 and 2009, especially in those with public health insurance, with lower educational level and lower socioeconomic status. The CIndex for the total population significantly decreased both for the proportion who used dental care, and also the mean number of visits. Findings suggest that the use of dental care increased and socioeconomic-related inequalities in the utilization of dental care declined after a Major Health Reform, which included universal coverage for some dental cares in Chile. However, efforts to ameliorate these inequalities require an approach that moves beyond a sole focus on rectifying health coverage.