Pharmacological treatments and medication-related problems in nursing homes in Catalonia: a multidisciplinary approach.

Background: Aging correlates with increased frailty, multi-morbidity, and chronic diseases. Furthermore, treating the aged often entails polypharmacy to achieve optimal disease management, augmenting medication-related problems (MRPs). Few guidelines and tools address the problem of polypharmacy and MRPs, mainly within the institutionalized elderly population. Routine pharmacological review is needed among institutionalized patients. This pharmacological review may improve with a multidisciplinary approach of a collaboration of multiple health professionals. This study aimed to describe institutionalized patients, systematically review their medication plans, and then give recommendations and identify MRPs. Methods: A cross-sectional study was performed using data obtained from patients living in five nursing homes in the northern area of Barcelona, Spain. The inclusion criteria comprised institutionalized patients with public health coverage provided by the Health Department of Catalonia. A detailed description of the clinical characteristics, chronic diseases, pharmacological treatments, recommendations, incomplete data, and MRPs, such as potential drug-drug interactions, therapeutic duplications, contraindications, and drugs deemed inappropriate or of doubtful efficacy, was made. The clinical pharmacologist was the medical doctor specialist who acted as the coordinator of the multidisciplinary team and actively reviewed all the prescribed medications to make recommendations and detect MRPs. Results: A total of 483 patients were included. Patients had a mean age of 86.3 (SD 8.8) years, and 72.0% were female individuals. All patients had at least three health-related problems, with a mean of 17.4 (SD 5.6). All patients, except one, had a minimum of one prescription, with a mean of 8.22 drugs prescribed (SD 3.5) per patient. Recommendations were made for 82.4% of the patients. Of these recommendations, verification of adequate use was made for 69.3% and withdrawal of a drug for 49.5%. Conclusion: This study demonstrates a high prevalence of health-related problems and several prescribed drugs in nursing homes in Catalonia. Many recommendations were made, confirming the increased proportion of polypharmacy, MRPs, and the need for standardized interventions. A multidisciplinary team approach, including general practitioners, geriatric assessments, a clinical pharmacist, and a clinical pharmacologist, should address this problem.

The Need for the Closer Monitoring of Novel Drugs in MS: A Siponimod Retrospective Cohort Study (Realhes Study).

BACKGROUND: Severe cases of lymphopenia have been reported during siponimod clinical trials, which may negatively impact its benefit/risk profile. OBJECTIVE: We aimed to evaluate the incidence of lymphopenia following the initiation of siponimod treatment in clinical practice. The secondary objectives included the analysis of factors predisposing to and the clinical relevance of lymphopenia events. METHODS: In this multicenter retrospective cohort study, information collected from the medical records of 129 patients with MS from 15 tertiary hospitals in Spain who initiated treatment with Siponimod were followed-up for at least 3 months, including at least one lymphocyte count evaluation per patient. RESULTS: Of the 129 patients, 121 (93.6%) reported lymphopenia events, including 110 (85.3%) with grade ≤ 3 and 11 (8.5%) with grade 4 lymphopenia, higher than those reported in the pivotal clinical trial (73.3% and 3.3% for grade ≤ 3 and grade 4 lymphopenia, respectively). The study included an unexpectedly high proportion of male subjects (72.9%), which might have led to an underestimation of the actual magnitude of the risk. CONCLUSIONS: In this study, the incidence and severity of lymphopenia after starting siponimod treatment were higher than those reported in previous clinical trials. Therefore, our results reinforce the need for the closer monitoring of novel MS drugs in clinical practice, as well as larger and longer follow-up studies to properly characterize this risk.

Fe(II) complexes of pyridine-substituted thiosemicarbazone ligands as catalysts for oxidations with hydrogen peroxide.

The reaction of three [FeII(TSC)2] complexes, where TSC is a pyridine-substituted thiosemicarbazone of the HDpT or HBpT families, with H2O2 in acetonitrile solution does not result in the accumulation of the corresponding [FeIII(TSC)2]+ complexes. Instead, a mixture of diamagnetic low-spin FeII species is generated. According to the MS spectra, those species result from the sequential addition of up to five oxygen atoms to the complex. This capability for the addition of oxygen atoms suggested that oxygen atom transfer to external substrates may be possible, and these TSC complexes were tested in the oxidation of thioanisole and styrene with H2O2. As hypothesized, the complexes are active in both the oxidation of thioanisole to its sulfoxide and styrene to benzaldehyde, with time scales indicating the participation of the species containing added oxygen atoms. Interestingly, the free thiosemicarbazone ligands and the [Zn(Dp44mT)2] complex also catalyse the selective sulfoxidation of thioanisole, but they are ineffective in catalysing styrene oxidation to benzaldehyde. These findings open up new directions for the development of thiosemicarbazone-based metal catalysts for oxidation processes.

Successful Root Canal Treatment of an Atypical Mandibular Canine with a Boomerang-shaped Root and Canal System with a Large Periapical lesion-A Case Report with 9-year Follow-up.

AIM: This report describes an atypical mandibular canine with a single boomerang-shaped root and root canal system with a large periapical lesion managed by root canal treatment. METHODS: The chief complaint of a 16-year-old male was acute pain and an abnormal sensation in the right mandibular canine (tooth #27). The clinical examination revealed that tooth #27 had an unusual coronal morphology. The buccal aspect of the tooth resembled that of a normal canine but was significantly broader than expected. On the lingual aspect of the crown; however, there was an unusual cusp-like structure with ridges that was slightly less prominent than the buccal incisal tip. The intraoral periapical radiographs revealed a complex root with an obvious cow horn-shaped canal mesially and distally, but with the suggestion of a root structure joining the mesial and distal extensions. A large periapical lesion was present. Computed tomography revealed the presence of a single root and canal system shaped like a boomerang. Root canal treatment was performed and the patient was followed-up for 9 years. RESULTS: Following root canal treatment, the patient had no symptoms, no mobility, no periodontal pockets, or root resorption. At 9 years, the cone beam computed tomography images confirmed that satisfactory healing of the periapical tissues had occurred. CONCLUSION: The mandibular right canine had a unique boomerang-shaped root and canal system. Effective shaping and cleaning of the complex canal shape plus thermoplastic root filling aided the successful healing of the periapical lesion.

ToxR activates the Vibrio cholerae virulence genes by tethering DNA to the membrane through versatile binding to multiple sites.

ToxR, a Vibrio cholerae transmembrane one-component signal transduction factor, lies within a regulatory cascade that results in the expression of ToxT, toxin coregulated pilus, and cholera toxin. While ToxR has been extensively studied for its ability to activate or repress various genes in V. cholerae, here we present the crystal structures of the ToxR cytoplasmic domain bound to DNA at the toxT and ompU promoters. The structures confirm some predicted interactions, yet reveal other unexpected promoter interactions with implications for other potential regulatory roles for ToxR. We show that ToxR is a versatile virulence regulator that recognizes diverse and extensive, eukaryotic-like regulatory DNA sequences, that relies more on DNA structural elements than specific sequences for binding. Using this topological DNA recognition mechanism, ToxR can bind both in tandem and in a twofold inverted-repeat-driven manner. Its regulatory action is based on coordinated multiple binding to promoter regions near the transcription start site, which can remove the repressing H-NS proteins and prepares the DNA for optimal interaction with the RNA polymerase.

Validation of the Spanish electronic version of the BREAST-Q questionnaire.

BACKGROUND: Patient-reported outcome measures (PROMs) have gained considerable interest in health care moving beyond traditional outcome measures of morbidity and mortality. In breast cancer surgery, women's' perceptions of appearance, function and quality of life have become increasingly important. The BREAST-Q questionnaire is a validated PROM for use in cosmetic and reconstructive breast surgery in clinical practice. The objective of this study was to validate the Spanish electronic version of the BREAST-Q questionnaire, to verify the measurement equivalence of digital and paper versions and to identify the possible disadvantages and advantages of implementing this new tool. METHODS: The study population included 113 patients undergoing breast cancer survey at a single hospital in Barcelona (Spain) who were able to complete both the electronic and paper versions of the preoperative module of the BREAST-Q questionnaire. RESULTS: The intraclass correlation coefficient (ICC) in the four domains of the questionnaire between the two versions of the questionnaire was >0.9, with a weighted kappa of >0.74 at item level. The reliability of the internal consistency was also excellent, with Cronbach's alpha coefficient of >0.70 in all domains. Age was a limiting factor for the delivery of the electronic version of BREAST-Q, with 69 years of age as the cut-off point to obtain reliable results. CONCLUSIONS: The interchangeability of the electronic and paper versions of the BREAST-Q questionnaire facilitates implementation of this instrument in routine surgical oncological practice.

Iron complexes of bridging azo ligands in aqueous solution: changes in the thermal switching mechanism on coordination and oxidation state of metal centres.

Three azobenzenes CN(C6H4)-NN-(C5H4N) (py-iso), CN(C6H4)-NN-(C6H4)CN (cyano-iso) and CN(C6H4)-NN-(C6H4)NC (iso-iso) with good coordinating groups (pyridine, phenylcyano or phenylisocyano) at the ends of the diazenyl unit have been synthesized and fully characterised. These compounds have been used as ligands in the synthesis of water-soluble metallic species by coordination to {FeII(CN)53-} units, either in one or two of the anchoring groups of the derivatives. Both the azo derivatives and their complexes are photochemically active with respect to their trans-to-cis isomerisation process. Their cis-to-trans reverse thermal reaction has been thoroughly studied as a function of the donor groups, solvent, temperature and pressure, in order to gain insight into the rotation or inversion mechanisms involved in the process. A comparison of the isomerisation mechanism between the iron complexes and the corresponding free ligands revealed an interesting fine tuning of the process on coordination of the {FeII(CN)53-} moieties, which may even produce, in some cases, non-photoswitchable species containing typically photoactive units.

Patient-centered care in Coronary Heart Disease: what do you want to measure? A systematic review of reviews on patient-reported outcome measures.

BACKGROUND: The number of published articles on Patient-Reported Outcomes Measures (PROMs) in Coronary Heart Disease (CHD), a leading cause of disability-adjusted life years lost worldwide, has been growing in the last decades. The aim of this study was to identify all the disease-specific PROMs developed for or used in CHD and summarize their characteristics (regardless of the construct), to facilitate the selection of the most adequate one for each purpose. METHODS: A systematic review of reviews was conducted in MEDLINE, Scopus, and the Cochrane Database of Systematic Reviews. PROQOLID and BiblioPRO libraries were also checked. PROMs were classified by construct and information was extracted from different sources regarding their main characteristics such as aim, number of items, specific dimensions, original language, and metric properties that have been assessed. RESULTS: After title and abstract screening of 1224 articles, 114 publications were included for full text review. Finally, we identified 56 PROMs: 12 symptoms scales, 3 measuring functional status, 21 measuring Health-Related Quality of Life (HRQL), and 20 focused on other constructs. Three of the symptoms scales were specifically designed for a study (no metric properties evaluated), and only five have been included in a published study in the last decade. Regarding functional status, reliability and validity have been assessed for Duke Activity Index and Seattle Angina Questionnaire, which present multiple language versions. For HRQL, most of the PROMs included physical, emotional, and social domains. Responsiveness has only been evaluated for 10 out the 21 HRQL PROMs identified. Other constructs included psychological aspects, self-efficacy, attitudes, perceptions, threats and expectations about the treatment, knowledge, adjustment, or limitation for work, social support, or self-care. CONCLUSIONS: There is a wide variety of instruments to assess the patients' perspective in CHD, covering several constructs. This is the first systematic review of specific PROMs for CHD including all constructs. It has practical significance, as it summarizes relevant information that may help clinicians, researchers, and other healthcare stakeholders to choose the most adequate instrument for promoting shared decision making in a trend towards value-based healthcare.

Epignatus: manejo quirúrgico y multidisciplinar. Un caso clínico / Epignathus: surgical and multidisciplinary management. A case report

El epignatus es una forma poco frecuente de teratoma que puede localizarse en cualquier punto de la cavidad oral o faringe. Son tumores con una elevada mortalidad debido a la obstrucción severa de vía aérea que producen, por lo que el diagnóstico prenatal es importante para establecer un plan terapéutico. El procedimiento ex-utero intrapartum treatment, o EXIT, es el método gold standard que permite asegurar la vía aérea de estos pacientes. La resección del tumor debe ser precoz y completa, ya que posee valor pronóstico. Existen numerosas patologías y secuelas derivadas del epignatus, la mayoría de ellas debido al efecto de masa que produce durante el desarrollo. Algunas de ellas incluyen fisura palatina, micrognatia o discrepancia anteroposterior mandibulomaxilar con mordida abierta anterior. Describimos este caso con el fin de remarcar la importancia del tratamiento quirúrgico del epignatus y mostrar el complejo manejo multidisciplinar que se realizó para esta patología tan infrecuente. Además de ello, se proponen maneras de mejorar dicha cirugía, como la implementación de modelos estereolitográficos o la reconstrucción virtual tridimensional (3D). (AU)

Epignathus are a rare presentation of congenital teratomas. As they arise from the oral cavity and pharynx they often cause severe airway obstruction leading to high mortality rates. Therefore, prenatal diagnosis is essential to establish a treatment plan. The “ex-utero intrapartum treatment” or EXIT is the gold standard procedure to ensure the upper airway flow. If feasible, early complete resection should be performed as it plays a key role in the prognosis. Several malformations are related to epignathus, most of them due to the mass effect of the epignathus growth during fetal development. Some of them include cleft palate, micrognathia or anterior-posterior maxillomandibular discrepancy with open bite. We report this case to highlight the importance of an optimal surgical treatment for epignathus, and to describe an example of the complex multidisciplinary management needed for this rare entity. Furthermore, we also propose some techniques that could be implemented to improve the surgical outcomes, like stereolithographic models or virtual three-dimensional reconstruction (3D). (AU)

Structure and inhibition of SARS-CoV-1 and SARS-CoV-2 main proteases by oral antiviral compound AG7404.

Severe acute respiratory syndrome coronaviruses 1 and 2 (SARS-CoV-1 and SARS-CoV-2) pose a threat to global public health. The 3C-like main protease (Mpro), which presents structural similarity with the active site domain of enterovirus 3C protease, is one of the best-characterized drug targets of these viruses. Here we studied the antiviral activity of the orally bioavailable enterovirus protease inhibitor AG7404 against SARS-CoV-1 and SARS-CoV-2 from a structural, biochemical, and cellular perspective, comparing it with the related molecule rupintrivir (AG7800). Crystallographic structures of AG7404 in complex with SARS-CoV-1 Mpro and SARS-CoV-2 Mpro and of rupintrivir in complex with SARS-CoV-2 Mpro were solved, revealing that all protein residues interacting with the inhibitors are conserved between the two proteins. A detailed analysis of protein-inhibitor interactions indicates that AG7404 has a better fit to the active site of the target protease than rupintrivir. This observation was further confirmed by biochemical FRET assays showing IC50 values of 47 µM and 101 µM for AG7404 and rupintrivir, respectively, in the case of SARS-CoV-2 Mpro. Equivalent IC50 values for SARS-CoV-1 also revealed greater inhibitory capacity of AG7404, with a value of 29 µM vs. 66 µM for rupintrivir. Finally, the antiviral activity of the two inhibitors against SARS-CoV-2 was confirmed in a human cell culture model of SARS-CoV-2 infection, although rupintrivir showed a higher potency and selectivity index in this assay.

Follow-up care of 12 months of patients with bladder cancer in Spain: A multicenter prospective cohort study.

The therapeutic approach of bladder cancer strongly determines its prognosis. We describe the treatments and outcomes for a Spanish cohort of patients with bladder cancer for the first 12 months after diagnosis and identify the factors that influenced the decision to undergo the treatment received. We conducted a multicenter, prospective, cohort study including primary bladder cancer patients during the first 12 months after diagnosis. The clinical outcomes were performance status (ECOG), adverse events and any cause of mortality. We stratified the analysis by factors that might influence the treatments received. We conducted univariate and multivariable logistic regression models to assess which patient and tumor characteristics were associated with receiving adjuvant treatment in the subgroup of noninvasive bladder cancer patients. In total, 314 patients were included (85% men; 53.8% >70 years) in 7 tertiary Spanish hospitals; 82.2% had a noninvasive urothelial bladder cancer (NMIBC). Patients received mostly surgery plus adjuvant therapy (67.7%). BCG (32.8% patients) was the most frequently administered adjuvant therapy, followed by intravesical chemotherapy (17.8% patients) and radiotherapy (10.8%). The variability of administered treatments among hospitals was low. Patients with NMIBC were more likely to receive adjuvant therapy if they had a higher educational level, some comorbidities and a high-grade tumor. The number of fully active patients (ECOG 0) significantly decreased during the first year of follow-up from 58% to 36 % (OR: 2.41, 95%CI 1.82-3.20); at 12-month follow-up 10.8% patients had died from any cause. In conclusion, most of the patients had a NMIBC. Surgery alone or plus adjuvant therapy were the commonest curative options of bladder cancer. BCG therapy was the adjuvant therapy most frequently administered. Higher educational level, presence of comorbidities and a high-grade tumor were associated with adjuvant therapy. Patient performance status was worsening over time. Almost 1 of 10 patients died during the first year of follow-up.

Homo- and heterometallic chiral dynamic architectures from allyl-palladium(II) building blocks.

New chiral tetranuclear square-like homo- and heterometallamacrocycles containing allyl-palladium and either {Pd(P-P)*} or {Pt(P-P)*} optically pure moieties (P-P* = (2S,3S)-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphanyl)butane ((S,S)-DIOP) and (2S,4S)-2,4-bis(diphenylphosphanyl)pentane ((S,S)-BDPP)) have been obtained by the self-assembly of [Pd(η3-2-Me-C3H4)(4-PPh2py)2]+ and [M(P-P)*(H2O)2]2+ building blocks in a 1 : 1 molar ratio. The supramolecular assemblies thus prepared [{Pd(η3-2-Me-C3H4)}2(4-PPh2py)4{M(P-P)*}2](CF3SO3)6 (M = Pd, Pt) have been fully characterised by multinuclear NMR spectroscopy and MS spectrometry. The structures display remarkable differences on their dynamic behaviour in solution that depend on the lability and thermodynamic strength of M-py bonds. The structural characteristics of the new metallamacrocyles obtained have also been unambiguously established by XRD analysis. The architectures have been assayed as catalytic precursors in the asymmetric allylic alkylation reaction.

Assessing rheoencephalography dynamics through analysis of the interactions among brain and cardiac networks during general anesthesia.

Cerebral blood flow (CBF) reflects the rate of delivery of arterial blood to the brain. Since no nutrients, oxygen or water can be stored in the cranial cavity due to space and pressure restrictions, a continuous perfusion of the brain is critical for survival. Anesthetic procedures are known to affect cerebral hemodynamics, but CBF is only monitored in critical patients due, among others, to the lack of a continuous and affordable bedside monitor for this purpose. A potential solution through bioelectrical impedance technology, also known as rheoencephalography (REG), is proposed, that could fill the existing gap for a low-cost and effective CBF monitoring tool. The underlying hypothesis is that REG signals carry information on CBF that might be recovered by means of the application of advanced signal processing techniques, allowing to track CBF alterations during anesthetic procedures. The analysis of REG signals was based on geometric features extracted from the time domain in the first place, since this is the standard processing strategy for this type of physiological data. Geometric features were tested to distinguish between different anesthetic depths, and they proved to be capable of tracking cerebral hemodynamic changes during anesthesia. Furthermore, an approach based on Poincaré plot features was proposed, where the reconstructed attractors form REG signals showed significant differences between different anesthetic states. This was a key finding, providing an alternative to standard processing of REG signals and supporting the hypothesis that REG signals do carry CBF information. Furthermore, the analysis of cerebral hemodynamics during anesthetic procedures was performed by means of studying causal relationships between global hemodynamics, cerebral hemodynamics and electroencephalogram (EEG) based-parameters. Interactions were detected during anesthetic drug infusion and patient positioning (Trendelenburg positioning and passive leg raise), providing evidence of the causal coupling between hemodynamics and brain activity. The provided alternative of REG signal processing confirmed the hypothesis that REG signals carry information on CBF. The simplicity of the technology, together with its low cost and easily interpretable outcomes, should provide a new opportunity for REG to reach standard clinical practice. Moreover, causal relationships among the hemodynamic physiological signals and brain activity were assessed, suggesting that the inclusion of REG information in depth of anesthesia monitors could be of valuable use to prevent unwanted CBF alterations during anesthetic procedures.

Molecular Approach to Alkali-Metal Encapsulation by a Prussian Blue Analogue FeII/CoIII Cube in Aqueous Solution: A Kineticomechanistic Exchange Study.

The preparation of a series of alkali-metal inclusion complexes of the molecular cube [{CoIII(Me3-tacn)}4{FeII(CN)6}4]4- (Me3-tacn = 1,4,7-trimethyl-1,4,7-triazacyclononane), a mixed-valent Prussian Blue analogue bearing bridging cyanido ligands, has been achieved by following a redox-triggered self-assembly process. The molecular cubes are extremely robust and soluble in aqueous media ranging from 5 M [H+] to 2 M [OH-]. All the complexes have been characterized by the standard mass spectometry, UV-vis, inductively coupled plasma, multinuclear NMR spectroscopy, and electrochemistry. Furthermore, X-ray diffraction analysis of the sodium and lithium salts has also been achieved, and the inclusion of moieties of the form {M-OH2}+ (M = Li, Na) is confirmed. These inclusion complexes in aqueous solution are rather inert to cation exchange and are characterized by a significant decrease in acidity of the confined water molecule due to hydrogen bonding inside the cubic cage. Exchange of the encapsulated cationic {M-OH2}+ or M+ units by other alkali metals has also been studied from a kineticomechanistic perspective at different concentrations, temperatures, ionic strengths, and pressures. In all cases, the thermal and pressure activation parameters obtained agree with a process that is dominated by differences in hydration of the cations entering and exiting the cage, although the size of the portal enabling the exchange also plays a determinant role, thus not allowing the large Cs+ cation to enter. All the exchange substitutions studied follow a thermodynamic sequence that relates with the size and polarizing capability of the different alkali cations; even so, the process can be reversed, allowing the entry of {Li-OH2}+ units upon adsorption of the cube on an anion exchange resin and subsequent washing with a Li+ solution.

Adaptation and psychometric validation of Diabetes Health Profile (DHP-18) in patients with type 2 diabetes in Quito, Ecuador: a cross-sectional study.

INTRODUCTION: The Diabetes Health Profile (DHP-18), structured in three dimensions (psychological distress (PD), barriers to activity (BA) and disinhibited eating (DE)), assesses the psychological and behavioural burden of living with type 2 diabetes. The objectives were to adapt the DHP-18 linguistically and culturally for use with patients with type 2 DM in Ecuador, and to evaluate its psychometric properties. METHODS: Participants were recruited using purposive sampling through patient clubs at primary health centres in Quito, Ecuador. The DHP-18 validation consisted in the linguistic validation made by two Ecuadorian doctors and eight patient interviews. And in the psychometric validation, where participants provided clinical and sociodemographic data and responded to the SF-12v2 health survey and the linguistically and culturally adapted version of the DHP-18. The original measurement model was evaluated with confirmatory factor analysis (CFA). Reliability was assessed through internal consistency using Cronbach's alpha and test-retest reproducibility by administering DHP-18 in a random subgroup of the participants two weeks after (n = 75) using intraclass correlation coefficient (ICC). Convergent validity was assessed by establishing previous hypotheses of the expected correlations with the SF12v2 using Spearman's coefficient. RESULTS: Firstly, the DHP-18 was linguistically and culturally adapted. Secondly, in the psychometric validation, we included 146 participants, 58.2% female, the mean age was 56.8 and 31% had diabetes complications. The CFA indicated a good fit to the original three factor model (χ2 (132) = 162.738, p < 0.001; CFI = 0.990; TLI = 0.989; SRMR = 0.086 and RMSEA = 0.040. The BA dimension showed the lowest standardized factorial loads (λ) (ranging from 0.21 to 0.77), while λ ranged from 0.57 to 0.89 and from 0.46 to 0.73, for the PD and DE dimensions respectively. Cronbach's alphas were 0.81, 0.63 and 0.74 and ICCs 0.70, 0.57 and 0.62 for PD, BA and DE, respectively. Regarding convergent validity, we observed weaker correlations than expected between DHP-18 dimensions and SF-12v2 dimensions (r > -0.40 in two of three hypotheses). CONCLUSIONS: The original three factor model showed good fit to the data. Although reliability parameters were adequate for PD and DE dimensions, the BA presented lower internal consistency and future analysis should verify the applicability and cultural equivalence of some of the items of this dimension to Ecuador.

Base-assisted synthesis of 4-pyridinate gold(I) metallaligands: a study of their use in self-assembly reactions.

The synthesis of di- and tritopic gold(i) metallaligands of the type [(Au4-py)2(µ2-diphosphane)] (diphosphane = bis(diphenylphosphanyl)isopropane or dppip (1), 1,2-bis(diphenylphosphanyl)ethane or dppe (2), 1,3-bis(diphenylphosphanyl)propane or dppp (3) and 1,4-bis(diphenylphosphanyl)butane or dppb (4)) and [(Au4-py)3(µ3-triphosphane)] (triphosphane = 1,1,1-tris(diphenylphosphanylmethyl)ethane or triphos (5) and 1,3,5-tris(diphenylphosphanyl)benzene or triphosph (6)) from [(AuCl)2(µ2-diphosphane)] or [(AuCl)3(µ3-triphosphane)] and 4-pyridylboronic acid in the presence of Cs2CO3 has been conducted. Interestingly, when [(AuCl)2(µ2-dppm)] (dppm = bis(diphenylphosphanyl)methane) was used as a starting material, the cyclic tetranuclear gold(i) compound [(Au4-py)2(CH)2{µ2-Au(PPh2)2}2] (I) was obtained instead. All the products have been characterized by IR and multinuclear NMR spectroscopy, mass spectrometry and elemental analysis and in the case of 1, 3, 5 and I by X-ray crystallography, which showed the presence of aurophilic interactions in all of them. The obtained metallaligands have been used as building blocks in self-assembly reactions with cis-blocked palladium or platinum acceptor moieties producing [2 + 2] metallamacrocycles or trigonal bipyramidal (TBP) [2 + 3] metallacages in good yields. The photophysical properties of both the metallaligands and the corresponding assemblies have been investigated.

Five-year quality of life in patients with high-risk localized prostate cancer treated with external beam radiotherapy alone versus external beam radiotherapy with high-dose-rate brachytherapy boost: a prospective multicenter study.

PURPOSE: Brachytherapy (BT) and external beam radiation therapy (EBRT) are effective treatments for high-risk prostate cancer (PCa). However, the impact of these treatments on health-related quality of life (HRQL) remains unclear. In this study, we compared EBRT alone with EBRT plus a boost with high-dose rate (HDR)-BT to determine the impact on HRQL in patients with high-risk PCa. MATERIAL AND METHODS: Prospective, multicenter study comparing patients with high-risk PCa treated with EBRT alone or EBRT + HDR-BT from 2004 to 2006. HRQL was assessed at baseline (pre-treatment) and periodically over the 5-year follow-up, using the SF-36 (v.2), EPIC, and FACT-G and FACT-P questionnaires. RESULTS: A total of 129 patients were included in the study, of these, 41 received EBRT alone and 88 EBRT + HDR-BT. All patients received hormonotherapy. Baseline clinical characteristics were similar, except for a slightly higher mean number of comorbidities in the EBRT group. During follow-up, the only significant between-group difference was a greater worsening on EPIC hormonal domain in the EBRT alone group (p = 0.028). There were no significant differences in time and interaction of treatment in SF-36, and FACT-G and FACT-P questionnaires or EPIC urinary incontinence, urinary irritative-obstructive, and bowel and sexual domains over the 5-year follow-up. Oncological outcomes were similar in both groups. CONCLUSIONS: After five years of follow-up, EBRT alone or combined with HDR-BT boost had a similar impact on HRQL in patients with high-risk localized PCa. However, patients in the EBRT alone group experienced greater worsening of hormonal domain according to EPIC questionnaire.

Gold(i)-doped films: new routes for efficient room temperature phosphorescent materials.

The synthesis of four novel gold(i)-phosphane complexes coordinated to 9-phenanthrene chromophore has been carried out through the reaction of 9-phenanthreneboronic acid and the corresponding AuClPR3 (PR3 = PPh3 for triphenylphosphane (1a); 1,4-bis(diphenylphosphanyl)butane or dppb (2b); bis(diphenylphosphanyl)acetylene or dppa (2c); (AuCl)2(diphos) (diphos = bis(diphenylphosphanyl)methane or dppm (3)) sources. The X-ray crystal structures of compounds 1a and 2b show the existence of MOF-like intermolecular assemblies that contain empty inner cavities in the absence of aurophilic contacts. In contrast, the formation of a tetranuclear complex with intramolecular aurophilic interactions was evidenced for 3. Photophysical characterization indicates dual emission in all gold(i) complexes when oxygen is removed from the sample, while only fluorescence emission is recorded for the uncoordinated ligand. The introduction of the compounds within PMMA and Zeonex was assayed, and luminescent films containing gold(i) complexes where phosphorescence is the sole pathway for emission are obtained, instead of the dual emission (with significant fluorescence contribution) recorded in solution.