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1.
Angew Chem Int Ed Engl ; 61(34): e202206976, 2022 Aug 22.
Artigo em Inglês | MEDLINE | ID: mdl-35785514

RESUMO

Circularly polarized luminescence (CPL) and Raman optical activity (ROA) were observed in a single spectroscopic experiment for a purely organic molecule, an event that had so far been limited to lanthanide-based complexes. The present observation was achieved for [16]cycloparaphenylene lemniscate, a double macrocycle constrained by a rigid 9,9'-bicarbazole subunit, which introduces a chirality source and allows the molecule to be resolved into two configurationally stable enantiomers. Distortion of oligophenylene loops in this lemniscular structure produces a large magnetic transition dipole moment while maintaining the π-conjugation-induced enhancement of the Raman signal, causing the appearance of the CPL/ROA couple. A two-photon mechanism is proposed to explain the population of the lowest-energy excited electronic state prior to the simultaneous emission-scattering event.

2.
Phys Chem Chem Phys ; 23(25): 13996-14003, 2021 Jun 30.
Artigo em Inglês | MEDLINE | ID: mdl-34151326

RESUMO

In this article the Raman and Raman Optical Activity (ROA) spectra of a series of enantiomeric twisted anthracenes are presented. The evolution of their vibrational spectra is understood in the context of the variation of π-electron delocalization as a result of the twisting imparted by the belt structure and in terms of the modulation of the resonance Raman/ROA effects which are photonic properties also tuned by anthracene twisting. The Raman/ROA vibrational spectra are simulated by several theoretical approaches to account for their vibrational and electronic properties including the theoretical evaluation of resonance effects. We furthermore incorporate a vibrational and ROA activity dissection analysis as provided in the Pyvib2 program valid to establish correlations among vibrational modes of different molecules with different electronic structures and equivalent vibrational dynamics. This paper is one of the very first attempts to use ROA spectroscopy in π-conjugated molecules with twisted and helical morphologies that contrast with the well-known cases of ROA studies of chiral helicenes in which the impact of π-electron delocalization in the electronic/photonic/vibrational (Raman/ROA) spectra is negligible.

3.
Angew Chem Int Ed Engl ; 59(23): 9080-9087, 2020 06 02.
Artigo em Inglês | MEDLINE | ID: mdl-32125060

RESUMO

Poly(phenylacetylene)s are a family of helical polymers constituted by conjugated double bonds. Raman spectra of these polymers show a structural fingerprint of the polyene backbone which, in combination with its helical orientation, makes them good candidates to be studied by Raman optical activity (ROA). Four different well-known poly(phenylacetylene)s adopting different scaffolds and ten different helical senses have been prepared. Raman and ROA spectra were recorded and allowed to establish ROA-spectrum/helical-sense relationships: a left/right-handed orientation of the polyene backbone (Mhelix /Phelix ) produces a triplet of positive/negative ROA bands. Raman and ROA spectra of each polymer exhibited the same profile, and the sign of the ROA spectrum was opposite to the lowest-energy electronic circular dichroism (ECD) band, indicating a resonance effect. Resonance ROA appears then as an indicator of the helical sense of poly(phenylacetylene)s, especially for those with an extra Cotton band in the ECD spectrum, where a wrong helical sense is assigned based on ECD, while ROA alerts of this misassignment.

5.
JBJS Case Connect ; 12(1)2022 03 16.
Artigo em Inglês | MEDLINE | ID: mdl-35294409

RESUMO

CASE: The modified direct anterior approach (MDAA) is a recently popular surgical technique for total hip arthroplasty (THA), with well-documented challenges. Characterized as acute hip and back pain, we present the case of a 78-year-old woman who developed an iliopsoas hematoma after an MDAA THA and discuss the management of this incident. CONCLUSIONS: Iliopsoas hematoma after THA poses a unique challenge and should be considered in patients with acute hip and back pain, with loss of strength on the affected limb after an MDAA THA.


Assuntos
Artroplastia de Quadril , Idoso , Artroplastia de Quadril/efeitos adversos , Artroplastia de Quadril/métodos , Feminino , Hematoma/diagnóstico por imagem , Hematoma/etiologia , Hematoma/cirurgia , Quadril/cirurgia , Humanos , Espaço Retroperitoneal/cirurgia , Coxa da Perna/cirurgia
7.
Sex Dev ; 13(5-6): 286-296, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-32396908

RESUMO

The sex of sea turtles is determined by temperature during egg incubation. Thus, climate change affects the sex ratio, exacerbating their vulnerability to extinction. Understanding spatiotemporal effects of temperature on sex determination at the gonadal level may facilitate the design of strategies to mitigate the effects of global warming. Here, we used qRT-PCR and immunofluorescence to analyze the spatiotemporal expression of Dmrt1 and Foxl2 in developing gonads of Lepidochelys olivacea incubated at male-producing temperature (MPT, 26°C) or female-producing temperature (FPT, 33°C). Although both transcription factors are expressed in bipotential gonads up to stage 25, the timing of their sexually dimorphic regulation differs. Whereas the dimorphic expression of Dmrt1 protein initiates at stage 24, Foxl2 protein was expressed specifically in females at stage 25. Interestingly, whereas Dmrt1 colocalizes with Sox9 in cell nuclei of primary medullary cords to form the testis cords, Foxl2 protein is first detected in Sox9-negative cells of primary medullary cords, prior to its substantial expression in the ovarian cortex. Thus, results suggest that the temperature-dependent regulation of sexual pathways is stochastic among the cells of primary medullary cords in undifferentiated bipotential gonads of the olive ridley.

11.
Br J Gen Pract ; 64(627): e627-33, 2014 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-25267048

RESUMO

BACKGROUND: The influence of socioeconomic development is often disregarded in epidemiological studies into the prevalence of cardiovascular risk factors. AIM: To analyse the relationship between major cardiovascular risk factors and socioeconomic indicators. DESIGN AND SETTING: Cross-sectional, population-wide study in primary care practices in the health area of Don Benito-Villanueva de la Serena, Badajoz, Extremadura, Spain. METHOD: A total of 2833 people aged 25-79 years (mean age 51.2 years), representative of the population, participated in the study. The prevalence and odds ratios (ORs) were calculated for diabetes, arterial hypertension, obesity, hypercholesterolaemia, smoking, and sedentary behaviour, according to level of education and employment status. RESULTS: A high prevalence of cardiovascular risk factors related to the level of education and employment status. Females who had not studied at university had a higher risk of obesity (OR = 2.5, 95% confidence interval [CI] = 1.5 to 4.2), smoking (OR 2.5, 95% CI = 1.7 to 3.7), and sedentary behaviour (OR = 2.5, 95% CI = 1.5 to 3.9) than females with a university education. Males who had not studied at university showed an increased risk of smoking (OR = 2.1, 95% CI = 1.4 to 3.1), arterial hypertension (OR = 1.5, 95% CI = 1.0 to 2.4), hypercholesterolaemia (OR = 1.5, 95% CI = 1.0 to 2.2), and obesity (OR = 1.5, 95% CI = 1.0 to 2.3) than males with a university education. The risk of obesity was higher in unemployed females than those in paid employment (OR =1.4, 95% CI = 1.1 to 1.9), but they showed a lower risk of smoking (OR = 0.7, 95% CI = 0.5 to 0.9). CONCLUSION: The study results confirm an inverse association between the level of education and the prevalence of cardiovascular risk factors. Public health studies and interventions are needed to understand this association and develop interventions targeted at the population that is at greatest risk.


Assuntos
Doenças Cardiovasculares/epidemiologia , Hipertensão/epidemiologia , Obesidade/epidemiologia , Fumar/epidemiologia , Adulto , Doenças Cardiovasculares/prevenção & controle , Estudos Transversais , Escolaridade , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Obesidade/complicações , Razão de Chances , Vigilância da População , Prevalência , Fatores de Risco , Fatores Socioeconômicos , Espanha/epidemiologia
14.
Gac Sanit ; 26 Suppl 1: 14-9, 2012 Mar.
Artigo em Espanhol | MEDLINE | ID: mdl-21996448

RESUMO

Primary care reforms started thirty years ago, but not fully developed their potential. Improvements should be suggested to be accompanied by adequate funding, operational capacity and organization and clinical skills adapt to upgrading and trivialized demand, bureaucracy and medicalization. Organizational-suggested reforms have not shown conclusive differences yet. On the other hand, neither pro-content nor pro-coordination reforms have shown any impact on the derived demand, the cost of care attention or the health outcomes. Thanks to the support of the information systems, bureaucracy has been reduced and care continuity may be promoted. In the middle management level, some measures have been suggested to promote accessibility, restore capitation by payment systems, perform and resolve capacity, improve integration of social care and health care resources, actively engage professionals with the health system-objectives of quality and efficiency and, finally, add more clinical, preventive and community collaboration-contents.


Assuntos
Reforma dos Serviços de Saúde/organização & administração , Programas Nacionais de Saúde/organização & administração , Atenção Primária à Saúde/organização & administração , Comportamento Cooperativo , Reforma dos Serviços de Saúde/métodos , Reforma dos Serviços de Saúde/tendências , Política de Saúde , Necessidades e Demandas de Serviços de Saúde , Serviços de Assistência Domiciliar/organização & administração , Humanos , Sistemas de Informação , Informática Médica , Modelos Organizacionais , Programas Nacionais de Saúde/economia , Inovação Organizacional , Atenção Primária à Saúde/economia , Autonomia Profissional , Reembolso de Incentivo , Espanha , Gestão da Qualidade Total
16.
Rev. Fac. Med. UNAM ; 58(6): 18-23, nov.-dic. 2015. graf
Artigo em Espanhol | LILACS | ID: biblio-957065

RESUMO

Resumen La fractura por avulsión de la tuberosidad tibial es una patología poco común. Es una lesión característica de la infancia, con afección directa a la fisis, que amerita un diagnóstico oportuno y un tratamiento óptimo a fin de evitar complicaciones en el crecimiento, la mayoría de ellas graves. La reducción abierta y fijación interna ha probado ser un tratamiento adecuado en la mayoría de este tipo de lesiones; sin embargo, el procedimiento quirúrgico es un riesgo agregado al daño de la lesión per se. Con un adecuado tratamiento y rehabilitación la lesión tiende a una evolución por lo general satisfactoria. Tomando en cuenta la baja incidencia de esta patología, en el siguiente artículo reportamos el caso de un paciente de 13 años con avulsión de tuberosidad tibial tipo III de Watson-Jones, el abordaje diagnóstico-terapéutico y el éxito obtenido a 2 años de seguimiento; asimismo, realizamos una revisión de la literatura.


Abstract Tibial tubercle avulsion is an uncommon disease, usually found during childhood, with direct physis affection, that needs an accurate diagnosis and an optimum treatment in order to avoid growth complications which could have disastrous consequences for the child. Open reduction and internal fixation has been reported as an adequate treatment in most of these injuries; nevertheless, surgery increases the risk upon the injury itself. With an appropriate treatment and rehabilitation this injury tends to have a satisfactory evolution. Considering the low incidence of this pathology, a case report of a 13-year-old boy with a Watson-Jones type III avulsion, a diagnostic-therapeutic approach and the successful evolution for a two-years follow up is described, as well as a literature review.

18.
Acta Ortop Mex ; 23(2): 94-7, 2009.
Artigo em Espanhol | MEDLINE | ID: mdl-19432366

RESUMO

The fractures by plastic deformation in the forearm of children are not common and they are produced by an applied forces to the upper extremity. The produced stress over the bone structure is near to the plastic limit. If the deformity is angulated more than 20 degrees, the correction must be done surgically or by closed means; if it is less than 20 degrees and the patient is younger than five years old, the physiological remodelling should be permitted. It is duty of the orthopaedic surgeon to maintain clinical supervision, taking care of range of motion specially on pronation and supination.


Assuntos
Fraturas do Rádio/diagnóstico por imagem , Fraturas do Rádio/cirurgia , Pré-Escolar , Feminino , Humanos , Radiografia , Rádio (Anatomia)/anormalidades
19.
Aten Primaria ; 40(6): 277-82, 2008 Jun.
Artigo em Espanhol | MEDLINE | ID: mdl-18588797

RESUMO

OBJECTIVES: To developed an evaluation of primary care (PC) from the analysis of the new differences in PC among the autonomous communities nowadays. DESIGN: Cross ecological study. SETTING: Spain. PARTICIPANTS: The 17 autonomous communities. MEASUREMENTS: Indicators of service supplies, diagnostic and therapeutic resolution habilities, access to hospital diagnostic, relationship and access doctor-patient, effectiveness and efficiency, public budget in PC and patient noticed quality. RESULTS: In all the indicators, leftist regional Governments have obtained a better punctuation than conservative ones. The main differences are in relation to the percentage of overcrowded doctor quotas (more than 1500 inhabitants per family doctor, with a 27.4% of difference); in limited access to diagnostic proves from PC services (25.3%); in PC services supplies (17.1%) in infirmary staff per habitant (10.9%), in pharmacological waste increase (10.9%); in the PC expending per capita (10.3%) and in the percentage of people who think that PC has improved. By means of quarter weighting, the differences of punctuation obtained by the regions are from a maximum of 46 (Aragón) to a minimum of 26 (Canary Islands), with an average of 39.94%. CONCLUSIONS: Six years after finishing the health transferences, there are important differences in the development of the PC, and the conservative autonomous communities have the deepest deficient one.


Assuntos
Atenção Primária à Saúde/organização & administração , Governo Local , Política Organizacional , Espanha
20.
Gac Sanit ; 20 Suppl 1: 182-91, 2006 Mar.
Artigo em Espanhol | MEDLINE | ID: mdl-16539981

RESUMO

As patients live longer, and more illnesses become chronic, comorbidity rates increase. This increase shows in attended morbidity registers, and its importance is revealed by the use of services, treatments, the survival rates and the patients life quality. A frequent coexistence of illnesses, such as diabetes and depression, increases the cost of primary care and emergency treatments and the number of hospital admissions; increases the probability of cardiovascular risk and non-adherence to treatment and diet; causes a perception of poor physical and mental health and, on the whole, increases global costs. The annual mortality rate shoots up when anemia and cardiovascular or kidney failure occur. Mental comorbidity has a greater effect on the patients perception of their life quality than physical comorbidity. Comorbidity increases the number of hospital admissions which could have been prevented, as well as the avoidable complications related to them. Suicidal thoughts occur more frequently in patients suffering from chronic obstructive pulmonary disease (COPD) than in those suffering from other chronic organic illnesses. In patients suffering from atrial fibrillation, the risk of acute coronary crisis increases as they age and the comorbidity increases the use of angiotensin-converting enzymes (ICAE), antidepressant drugs and the visits to the psychiatrist.


Assuntos
Comorbidade , Atenção Primária à Saúde , Adolescente , Adulto , Idoso , Idoso de 80 Anos ou mais , Doença Crônica/economia , Doença Crônica/epidemiologia , Doença Crônica/terapia , Comorbidade/tendências , Uso de Medicamentos/tendências , Feminino , Serviços de Saúde/economia , Serviços de Saúde/estatística & dados numéricos , Inquéritos Epidemiológicos , Humanos , Longevidade , Masculino , Pessoa de Meia-Idade , Dinâmica Populacional , Prevalência , Atenção Primária à Saúde/economia , Atenção Primária à Saúde/estatística & dados numéricos , Atenção Primária à Saúde/tendências , Qualidade de Vida , Espanha/epidemiologia , Adulto Jovem
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