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Background: The COVID-19 vaccination campaign began in Italy at the end of December 2020, with the primary aim of immunizing healthcare professionals, using the EMA approved mRNA vaccines (Comirnaty® by Pfizer/BioNTech; mRNA-1273 by Moderna) and recombinant adenoviral vaccine (Vaxzevria® by AstraZeneca). The study aimed at evaluating the prevalence and motivations underlying Vaccine Hesitancy, as well as the incidence and type of adverse events associated with COVID-19 vaccination. Methods: Cross-sectional study. Data were collected January 1st to 28th 2021 using a purposely created online self-administered questionnaire from a selected cohort of Italian physicians. Results: Overall, 7,881 questionnaires were analyzed: 6,612 physicians had received one dose, and 1,670 two doses of Comirnaty®; 30 had received one dose of mRNA-1273. Vaccine Hesitancy rate was 3.6%; it correlated with prior SARS-CoV-2 infection, diabetes, Adverse Eventss at previous vaccinations and refusal of 2020 flu vaccine, and was mainly motivated by concerns about vaccine Adverse Events. Typical Adverse Events were pain/itching/paresthesia at the inoculation site, followed by headache, fever, fatigue and myalgia/arthralgia occurring more frequently after the second dose (77.8 vs 66.9%; p<0.001), and in subjects with a prior SARS-CoV-2 infection. Conclusion: Adherence to COVID-19 vaccination is high among physicians. Adverse Events are typically mild and more frequent in people with a prior SARS-CoV-2 infection.
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COVID-19 , Vacunas contra la Influenza , Médicos , COVID-19/prevención & control , Vacunas contra la COVID-19/efectos adversos , Estudios Transversales , Humanos , SARS-CoV-2 , Vacunación/efectos adversos , Vacilación a la VacunaciónRESUMEN
ABSTRACT: Background. Vaccination is one of the most effective tools available to Public Health. Its potential usefulness is threatened by the rise of vaccine hesitancy among the general population, which has grown as much as to prompt the World Health Organization to express its concerns on the matter. The risk posed by vaccine hesitancy is even more concerning in the light of the efforts to curb the ongoing COVID-19 pandemic, which focus mainly on mass vaccination campaigns. This holds especially true when applied to healthcare professionals, among whom vaccine hesitancy can be particularly detrimental. For these reasons, our study focuses on potential determinants of vaccine hesitancy among healthcare professionals. Study design. The study is a cross-sectional study. Methods. Data were collected from January 1st to February 16th, by means of a self-administered online questionnaire in a cohort of Italian healthcare professionals. Results. Overall, 10,898 questionnaires were collected. Among the respondents, 1.1% expressed vaccine hesitancy. Hesitancy was less frequent in professionals involved in Primary Care and in the Clinical Scien-ces/Public Health group. Among clinicians, paediatricians, oncologists, and geriatrists showed especially accepting attitudes towards vaccination. Lower hesitancy rates were also registered among the respondents who already had received influenza vaccination and who never had any adverse effects following vaccination. Higher hesitancy rates were observed among individuals who had family members aged >65 years and with a history of severe adverse reactions to vaccination. Conclusion. Vaccine hesitancy rates were extremely low among participants in our study. Some medical specialties shown were particularly accepting towards vaccination. The potential predictors and protective factors pointed out by our analysis might allow more refined targets.
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COVID-19 , Anciano , COVID-19/prevención & control , Vacunas contra la COVID-19 , Estudios Transversales , Humanos , Pandemias/prevención & control , SARS-CoV-2 , Confianza , Vacunación , Vacilación a la VacunaciónRESUMEN
Fluorescence bioimaging is a powerful, versatile, method for investigating, both in vivo and in vitro, the complex structures and functions of living organisms in real time and space, also using super-resolution techniques. Being poorly invasive, fluorescence bioimaging is suitable for long-term observation of biological processes. Long-term detection is partially prevented by photobleaching of organic fluorescent probes. Semiconductor quantum dots, in contrast, are ultrastable, fluorescent contrast agents detectable even at the single nanoparticle level. Emission color of quantum dots is size dependent and nanoprobes emitting in the near infrared (NIR) region are ideal for low back-ground in vivo imaging. Biocompatibility of nanoparticles, containing toxic elements, is debated. Recent safety concerns enforced the search for alternative ultrastable luminescent nanoprobes. Most recent results demonstrated that optimized silicon quantum dots (Si QDs) and fluorescent nanodiamonds (FNDs) show almost no photobleaching in a physiological environment. Moreover in vitro and in vivo toxicity studies demonstrated their unique biocompatibility. Si QDs and FNDs are hence ideal diagnostic tools and promising non-toxic vectors for the delivery of therapeutic cargos. Most relevant examples of applications of Si QDs and FNDs to long-term bioimaging are discussed in this review comparing the toxicity and the stability of different nanoprobes.
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Colorantes Fluorescentes , Nanodiamantes , Imagen Óptica/métodos , Puntos Cuánticos , Silicio , Animales , Línea Celular Tumoral , Humanos , RatonesRESUMEN
The ability to find synergic solutions is the core of scientific research and scientific advancement. This is particularly true for medicine, where multimodal imaging and theranostic tools represent the frontier research. Nanotechnology, which by its very nature is multidisciplinary, has opened up the way to the engineering of new organized materials endowed with improved performances. In particular, merging nanoparticles and luminescent signalling can lead to the creation of unique tools for the design of inexpensive, hand-held diagnostic and theranostic kits. In this wide scenario, dye-doped silica nanoparticles constitute very effective nanoplatforms to obtain efficient luminescent, stable, biocompatible and targeted agents for biomedical applications. In this review we discuss the state of the art in the field of luminescent silica-based nanoparticles for medical imaging, starting with an overview of the most common synthetic approaches to these materials. Trying to rationalize the presentation of this extremely multifaceted and complex subject, we have gathered significant examples of systems applied in cancer research, also discussing those that take a multifunctional approach, including theranostic structures. Nanoprobes designed for applications that do not include cancer are a minor part, but interesting achievements have been published and we present a selection of these in the subsequent section. To conclude, we propose a debate on the advantages of creating chemosensors based on luminescent silica nanoparticles. This is far from easy but is a particularly valuable goal in the medical field and therefore subject to extensive research worldwide.
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Colorantes Fluorescentes/química , Nanomedicina , Nanopartículas/química , Dióxido de Silicio/química , Antineoplásicos/química , Antineoplásicos/toxicidad , Apoptosis/efectos de los fármacos , Portadores de Fármacos , Humanos , Inmunoensayo , Neoplasias/diagnósticoRESUMEN
Night-work, loading to subversion of physiological circadian rhythms and habits, may cause a lowering of work performance, an increase in the risk of accidental events and, more generally, a perception of less satisfactory living condition. In our experience we have interviewed 359 workers (night-workers and not). We found, in line with the Literature, that night-workers receive a less satisfactory quality of sleep, often associated with daytime sleepiness. The prevalence of disorders of various organs and systems is higher in these subjects, as well as the consumption of caffeine and nicotine. Regarding road and work-accidents, a similar trend is not so clearly confirmed in our series; in this context we have, nevertheless, to take account of some potential bias. Our experience confirmed that night-work may produce animpact on the individual overall well-being and, consequently, on the companies' productivity. To reduce this impact and the related costs, it is necessary to plan interventions on both workers and work organization.
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Ritmo Circadiano , Exposición Profesional , Salud Laboral , Tolerancia al Trabajo Programado , Adulto , Anciano , Femenino , Humanos , Italia , Masculino , Persona de Mediana Edad , Adulto JovenRESUMEN
Cardiovascular and metabolic risk factors prevalence is studied with an increasing interest, involving also working-age people, Several studies had evidenced that shift-work is a key factor in the etiology of cardiovascular illnesses. Railway workers--especially those who are involved in the monitoring of rail traffic--are often shift-workers. Their shift-schedule is based on a rotation of--in this order--afternoon, morning and night. Regarding the important role played by this kind of workers for the public safety, the evaluation of their cardiovascular risk is of utmost importance. In this study we evaluated the prevalence of cardiovascular risk factors in railway shift-workers to define prevention strategies.
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Enfermedades Cardiovasculares/epidemiología , Enfermedades Metabólicas/epidemiología , Enfermedades Profesionales/epidemiología , Vías Férreas , Tolerancia al Trabajo Programado , Adulto , Femenino , Humanos , Masculino , Persona de Mediana Edad , Factores de Riesgo , Encuestas y CuestionariosRESUMEN
During last years life expectation and working-life are increased and, consequently, the evaluation of workers whit chronic age-related diseases is more frequent than in the previous decades. We analyzed 9616 (2337 females and 7279 males) medical reports collected during health surveillance. Workers with arterial hypertension were 1770 (254 females and 1516 males) with an average age of 49.02 years +/- 9.52, and an average BMI of 27.9 +/- 4.43 Kg/m_. Workers who reported a complete fitness-to-work certification were 88.6%, ones with a fitness-to-work certification whit limitations were 11.2%, and only 0.2% were unfit to work. Our data confirm the importance of company strategies oriented to health promotion on the workplaces considering the progressive ageing of the workforces.
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Hipertensión/epidemiología , Salud Laboral , Adulto , Anciano , Anciano de 80 o más Años , Femenino , Humanos , Masculino , Persona de Mediana Edad , Medición de Riesgo , Adulto JovenRESUMEN
The object of this study is to determine the cytokine release from PBMCs exposed to Pd model nanoparticles emitted from catalytic converters. PBMCs of 8 healthy non-atopic women were incubated in the presence of Pd nanoparticles (5-10 nm) or salt (potassium hexa-chloropalladate) 10-5 and 10-6 M. Release of cytokines in supernatant of PBMCs was then determined. In cultures without LPS, IL-10 and IL-17 release from PBMCs was inhibited by Pd salt, while Pd nanoparticles inhibited TNF-alpha and IL-17 release. In LPS-stimulated cultures, release of IFN-gamma, TNF-alpha, IL-10 and IL-17 was inhibited by Pd salt, whereas IFN-gamma release was enhanced and TNF-alpha and IL-17 release was inhibited by Pd nanoparticles. In conclusion, Pd salt inhibits cytokine release, whereas Pd nanoparticles exert modulatory effects enhancing the release of IFN-gamma, a Th1 cytokine typical of delayed allergic reactions. This result is interesting considering the increase of allergic contact dermatitis to Pd in people exposed to Pd nanoparticles in urban environments.
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Citocinas/sangre , Leucocitos Mononucleares/fisiología , Paladio/farmacología , Adulto , Citocinas/metabolismo , Femenino , Humanos , Interferón gamma/sangre , Interferón gamma/metabolismo , Interleucina-10/sangre , Interleucina-10/metabolismo , Interleucina-17/sangre , Interleucina-17/metabolismo , Interleucina-5/sangre , Interleucina-5/metabolismo , Leucocitos Mononucleares/efectos de los fármacos , Leucocitos Mononucleares/metabolismo , Persona de Mediana Edad , Selección de Paciente , Valores de Referencia , Factor de Necrosis Tumoral alfa/sangre , Factor de Necrosis Tumoral alfa/metabolismoRESUMEN
Italian law on occupational exposure to noise identify 87 dBA as ceiling exposure level and 80 dBA as action level; the respect of ceiling level can be achieved by using devices, as ear plugs, whose efficacy must be verified. We studied 8119 audiometric of workers exposed to noise between 80 and 87 dBA. The hearing level of those who use ear plugs is significantly better than who don't use. Different devices show different efficacy, but for all, in the exposure setting studied, the level of protection that is provided is enough safe for othological protection. The workers must be informed about the efficacy of the protection and sensibilized to the use of the ear plugs within the periodical clinical surveillance.
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Ruido en el Ambiente de Trabajo/efectos adversos , Ruido en el Ambiente de Trabajo/legislación & jurisprudencia , Exposición Profesional/legislación & jurisprudencia , Exposición Profesional/prevención & control , Adolescente , Adulto , Anciano , Humanos , Italia , Persona de Mediana Edad , Medición de RiesgoRESUMEN
In the last eleven years in the Careggi Hospital 4941 occupational accident has been registered, and 2951 workers were involved (28.9% of the total of the workers present in the period). The highest frequency of accident has been registered within the cooking staff, about one half of whom had an accident, and 7.2% more than 0.6 accident for person-year; the more serious consequences were registered for traffic accident, more than half happened coming to the workplace before the beginning of the work. Only 154 workers registered more than 0.6 accidents for person-year.
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Accidentes de Trabajo/estadística & datos numéricos , Personal de Salud , Adulto , Anciano , Hospitales de Enseñanza , Humanos , Italia , Persona de Mediana EdadRESUMEN
We want to evaluate the incidence of allergic problems in a population of catering students at the beginning and after 3 and 5 years of their course. We enrolled in the study 601 students of a professional catering school: 412 in the first year and 189 in the fifth years. We used two questionnaires to investigate respiratory problems and dermatological ones. All the subjects were also patch tested with 10 aptens. The incidence of reported symptoms of allergy was higher in fifth year than in first one. We can observe a rising in positive reaction between the two group of students to Balsam Perù, Nickel, Fragrance mix and Garlic. In particular we found an higher incidence of positive patch reaction in female population. On the contrary the rising in positive reaction to Garlic is higher in male. About two third of the subjects positive to garlic present a sensitization to diallyl disulphide. The rising of positive patch test reactions to Garlic and Balsam Perù should be caused by the contact with cooking spices. The higher incidence of allergic pathology between students during fifth year of school and students at first year is probably due to scholastic practical activity.
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Culinaria , Ajo , Hipersensibilidad/epidemiología , Enfermedades Profesionales/epidemiología , Estudiantes , Adolescente , Adulto , Femenino , Humanos , Hipersensibilidad/etiología , Masculino , Enfermedades Profesionales/etiologíaRESUMEN
Bottom-up self-assembly of simple molecular compounds is a prime pathway to complex materials with interesting structures and functions. Coupled reaction systems are known to spontaneously produce highly ordered patterns, so far observed in soft matter. Here we show that similar phenomena can occur during silica-carbonate crystallization, the emerging order being preserved. The resulting materials, called silica biomorphs, exhibit non-crystallographic curved morphologies and hierarchical textures, much reminiscent of structural principles found in natural biominerals. We have used a fluorescent chemosensor to probe local conditions during the growth of such self-organized nanostructures. We demonstrate that the pH oscillates in the local microenvironment near the growth front due to chemical coupling, which becomes manifest in the final mineralized architectures as intrinsic banding patterns with the same periodicity. A better understanding of dynamic autocatalytic crystallization processes in such simple model systems is key to the rational development of advanced materials and to unravel the mechanisms of biomineralization.
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Carbonatos/química , Cristalización/métodos , Nanoestructuras/química , Dióxido de Silicio/química , Materiales Biomiméticos/química , Precipitación Química , Colorantes Fluorescentes , Concentración de Iones de Hidrógeno , Microscopía Fluorescente , Minerales , Técnicas de Sonda Molecular , Nanoestructuras/ultraestructuraRESUMEN
C60@lysozyme showed significant visible light-induced singlet oxygen generation in water, indicating the potential of this hybrid as an agent for photodynamic therapy. The reactive oxygen species (ROS) concentration generated by C60@lysozyme during irradiation depends on the light source, the irradiation time and the concentration of the hybrid. C60@lysozyme significantly reduced the HeLa cell viability in response to visible light irradiation. The generation of H2O2, due to the photoactivity of C60@lysozyme, causes cell death via easy permeation of hydrogen peroxide through the cell membrane and activation of endogenous ROS production.
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Most methods used for the characterization of graphene produced by liquid phase exfoliation require the deposition of the liquid sample on a substrate and subsequent drying. Because of this or other post-synthetic treatments, the reliability of the data in describing the actual features of the graphene particles in the pristine solution becomes questionable. Hence there is a need for new methods that permit the study of graphene directly in solution. Fluorescence imaging is at present the most convenient and sensitive method to visualize nanosized objects in solution. Here we report the development of a new method for visualizing and tracking exfoliated graphene directly in solution using a conventional set-up for fluorescence microscopy. We functionalized a fluorescent surfactant typically used for exfoliating graphite in aqueous phase (Pluronic P123) with two different fluorophores, in order to make graphene detectable by fluorescence microscopy. The photophysical interactions between the fluorescent surfactant and graphene were investigated at the bulk level. Finally, fluorescence microscopy allowed us to track the carbon particles produced and to identify two different populations of particles with sizes of 265 ± 25 and 1100 ± 200 nm respectively. The correlation of these results with TEM and DLS data is discussed.
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The electrochemical and photophysical properties of a variety of neutral pi-associated [2]catenanes have been explored by using cyclic voltammetry, absorption and luminescence spectrophotometry and the measurement of exited-state lifetimes. Several trends that could be correlated with interactions between the mechanically linked components of the structures were revealed from comparative study of catenane precursors, model compounds and the [2]catenanes themselves. Throughout, emphasis is placed on pair-wise comparisons between systems which differ in a single structural feature. Substitution in a catenane of a pyromellitic diimide unit by a naphthalene diimide yields more readily reduced derivatives, whose absorption spectra reveal charge transfer within the catenane to be a lower energy process of reduced intensity. Conversion of the butadiyne links within the diimide macrocycle of the catenanes to saturated chains results in an increase in both the energy and intensity of their charge-transfer bands; electrochemically these derivatives are all harder to reduce than the parent systems. Replacement of one of the electron-donating components of the catenanes with a less effective aromatic donor bearing a carboxy group also decreases the energy and intensity of the charge-transfer feature and is accompanied by a slightly more ready reduction. A sequence of reduction and translational events is proposed to explain the intriguing electrochemical behaviour of a catenane that contains one pyromellitic and one naphthalene diimide. For some systems the photophysical and electrochemical techniques, whilst exploring distinct physical phenomena, are shown to be in good agreement by comparison of shifts of electrochemical reduction waves with those of charge-transfer absorption features.
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Respiratory diseases are frequent in tunnel construction workers. A group of 144 subjects randomly selected from the population of 2516 workers engaged in the construction of the railway tunnel under the Appennine Mountains, from Bologna to Firenze was investigated. A group of 69 males comparable for age, living area and habits was studied as a control group. Assessment of air pollutants (NO, NO2, SO2, total dust, silica %) was carried out by means of fixed monitoring stations as well as personal monitors. All the subjects included in the study were examined with a standardised protocol which included physical examination, lung function tests (before and after shift work) and a questionnaire to college respiratory symptoms. Low concentrations of environmental pollutants were evidenced. Significantly lower values of FEV1 and PEF were determined in the worker group pared to controls. A significant decrease in respiratory parameters was shown after shift work. Variables capable of influencing the decrease in parameters include smoking habits, work activity, presence of cough and expectoration, period of the year (spirometries resulted worse in the winter time). Significantly lower values of FEV1 and PEF were evidenced in the workers compared to controls. In spite of the present low work environmental exposure conditions, some physiologic parameters appear altered in tunnel construction workers. This may depend on a variety of noxious agents present in the working environment.
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Polvo , Enfermedades Profesionales/fisiopatología , Hipersensibilidad Respiratoria/fisiopatología , Emisiones de Vehículos/efectos adversos , Adulto , Monitoreo del Ambiente , Monitoreo Epidemiológico , Humanos , Italia/epidemiología , Masculino , Enfermedades Profesionales/epidemiología , Hipersensibilidad Respiratoria/epidemiología , Factores de RiesgoRESUMEN
Fluorescence imaging techniques are becoming essential for preclinical investigations, necessitating the development of suitable tools for in vivo measurements. Nanotechnology entered this field to help overcome many of the current technical limitations, and luminescent nanoparticles (NPs) are one of the most promising materials proposed for future diagnostic implementation. NPs also constitute a versatile platform that can allow facile multi-functionalization to perform multimodal imaging or theranostics (simultaneous diagnosis and therapy). In this contribution we have mainly focused on dye doped silica or silica-based NPs conjugated with targeting moieties to enable imaging of specific cancer cells. We also cite and briefly discuss a few non-targeted systems for completeness. We summarize common synthetic approaches to these materials, and then survey the most recent imaging applications of silica-based nanoparticles in cancer. The field of theranostics is particularly important and stimulating, so, even though it is not the central topic of this paper, we have included some significant examples. We conclude with a short section on NP-based systems already in clinical trials and examples of specific applications in childhood tumors. This review aims to describe and discuss, through focused examples, the great potential of these materials in the medical field, with the aim to encourage further research to implement applications, which today are still rare.
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Colorantes Fluorescentes/química , Nanopartículas , Neoplasias/diagnóstico , Dióxido de Silicio/química , Óxido Ferrosoférrico/química , Humanos , Imagen por Resonancia Magnética , Micelas , Nanopartículas/química , Neoplasias/patología , Polietilenglicoles/química , Espectrometría RamanRESUMEN
Bone tumours and tumour-like lesions of the hip in children are rare. Signs and symptoms of these tumours are generally nonspecific. Delay of diagnosis is not uncommon. A high index of suspicion in young patients presenting with persistent pain and without history of trauma, that is unresolved with conservative therapy should prompt further investigation, including radiographs or computed tomography scan of the pelvis. In the experience of the Istituto Rizzoli, in patients less than 14 years (mean 9 years, ranged from 6 months to 14 years), 752 tumours and tumours-like lesions occurred in the pelvis or proximal femur, involving the hip. Tumour-like lesions accounted for 322 cases (simple bone cyst in 255, eosinophilic granuloma in 43, aneurismal bone cyst in 34), benign tumours for 340 cases (osteoid osteoma in 229, fibrous dysplasia in 63, exostosis in 48) and malignant tumours for 80 cases (Ewing's sarcoma in 53 and osteosarcoma in 27). The epidemiology, pathology, clinical presentation, and radiograph findings are discussed for each of these tumours.Treatment of these tumours differs from observation or minimally invasive treatment for most pseudotumoural lesions, intralesional excision or termoablation for benign bone tumours and wide resection for malignant bone tumours. In this latter group, chemotherapy is required and often administered pre- and postoperatively.
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Neoplasias Femorales/patología , Cadera , Osteoma Osteoide/patología , Sarcoma de Ewing/patología , Adolescente , Quistes Óseos Aneurismáticos/epidemiología , Quistes Óseos Aneurismáticos/patología , Quistes Óseos Aneurismáticos/terapia , Niño , Preescolar , Bases de Datos Factuales , Granuloma Eosinófilo/epidemiología , Granuloma Eosinófilo/patología , Granuloma Eosinófilo/terapia , Exostosis/epidemiología , Exostosis/patología , Exostosis/terapia , Femenino , Neoplasias Femorales/epidemiología , Neoplasias Femorales/terapia , Displasia Fibrosa Monostótica/epidemiología , Displasia Fibrosa Monostótica/patología , Displasia Fibrosa Monostótica/terapia , Humanos , Lactante , Italia/epidemiología , Masculino , Osteoma Osteoide/epidemiología , Osteoma Osteoide/terapia , Dolor , Sarcoma de Ewing/epidemiología , Sarcoma de Ewing/terapiaRESUMEN
OBJECTIVE: Myocardial scintigraphy and/or conventional angiography (CA) are often performed before cardiac surgery in an attempt to identify unsuspected coronary artery disease which might result in significant cardiac morbidity and mortality. Multidetector CT coronary angiography (MDCTCA) has a recognised high negative predictive value and may provide a non-invasive alternative in this subset of patients. The aim of this study was to evaluate the clinical value of MDCTCA as a preoperative screening test in candidates for non-coronary cardiac surgery. METHODS: 132 patients underwent MDCTCA (Somatom Sensation 16 Cardiac, Siemens) in the assessment of the cardiac risk profile before surgery. Coronary arteries were screened for > or = 50% stenosis. Patients without significant stenosis (Group 1) underwent surgery without any adjunctive screening tests while all patients with coronary lesions > or = 50% at MDCTCA (Group 2) underwent CA. RESULTS: 16 patients (12.1%) were excluded due to poor image quality. 72 patients without significant coronary stenosis at MDCTCA were submitted to surgery. 30 out of 36 patients with significant (> or = 50%) coronary stenosis at MDCTCA and CA underwent adjunctive bypass surgery or coronary angioplasty. In 8 patients, MDCTCA overestimated the severity of the coronary lesions (> 50% MDCTCA, < 50% CA). No severe cardiovascular perioperative events such as myocardial ischaemia, myocardial infarction or cardiac failure occurred in any patient in Group 1. CONCLUSIONS: MDCTCA seems to be effective as a preoperative screening test prior to non-coronary cardiac surgery. In this era of cost containment and optimal care of patients, MDCTCA is able to provide coronary vessel and ventricular function evaluation and may become the method of choice for the assessment of a cardiovascular risk profile prior to major surgery.
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Angiografía Coronaria/métodos , Enfermedad Coronaria/diagnóstico por imagen , Cuidados Preoperatorios/métodos , Tomografía Computarizada por Rayos X/métodos , Biomarcadores/sangre , Femenino , Hospitalización , Humanos , Procesamiento de Imagen Asistido por Computador/métodos , Masculino , Persona de Mediana Edad , Medición de Riesgo , Factores de RiesgoRESUMEN
The synthesis, redox behavior, and photophysical properties of a series of Ru(II) bipyridyl complexes having diimine ligands with phosphonate and phosphonic acid substituents are presented. The phosphonate-containing ligands examined include diethyl 4-(2,2'-bipyrid-4-yl)benzylphosphonate (bpbzp), diethyl 4-(2,2'-bipyrid-4-yl)-phenylphosphonate (bppp), and 4,4'-(diethyl phosphonato)-2,2'-bipyridine (bpdp), and the [(bpy)2Ru(L)](PF6)2 complexes of both the diethyl phosphonate and the phosphonic acid were prepared. The Ru(III/II) potentials are more positive for the phosphonate complexes than for the phosphonic acids, and the first reduction is localized on the phosphonate-containing ligand for the bppp and bpdp complexes. The first reduction of the phosphonic acid complexes is at more negative potentials and cannot be distinguished from bpy reduction. For the bppp and bpdp complexes luminescence arises from a Ru(d pi)-->bpy-phosphonate (pi*) MLCT state; the phosphonic acid complexes luminescence at higher energies from a MLCT state not clearly isolated on one ligand. Iron(III) and copper(II) complex with and very efficiently quench the luminescence of all the phosphonic acid complexes in nonaqueous solvents. The quenching mechanism is discussed on the basis of luminescence decay and picosecond transient absorption measurements.