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1.
J Am Chem Soc ; 146(9): 6326-6335, 2024 Mar 06.
Artículo en Inglés | MEDLINE | ID: mdl-38408316

RESUMEN

Herein, we report the synthesis of carbene-stabilized 1,3-diaza-2,4-diphosphabutenes CAACMePNPNCAACMe 4CAAC (CAACMe = 1-[2,6-bis(isopropyl)phenyl]-3,3,5,5-tetramethyl-2-pyrrolidinylidene) and IPrPNPNIPr 4NHC (IPr = 1,3-Bis(2,6-diisopropylphenyl)-imidazol-2-ylidene). The bonding in both systems is defined by a delocalized polar covalent π-system, with 4NHC exhibiting increased conjugation relative to 4CAAC. The nature of the stabilizing carbene also influences the redox properties of the compound, with 4CAAC undergoing potassium-mediated reduction to the closed-shell P-P bonded dimer K252, which upon treatment with Kryptofix-2,2,2 converts to the transient radical anion [Kcrypt][5], the formal one-electron reduction product of 4CAAC. In contrast, 4NHC undergoes reversible one-electron oxidation to the stable radical cation [6NHC][SbF6]. Computational and spectroscopic analyses of both radical species are suggestive of unevenly delocalized spin, with the bulk of the spin density residing on phosphorus in both cases.

2.
J Am Chem Soc ; 145(13): 7107-7112, 2023 Apr 05.
Artículo en Inglés | MEDLINE | ID: mdl-36961302

RESUMEN

We report the synthesis of the monomeric phosphaborene Ar*P═B(TMP) (2) (Ar* = 2,6-bis(triisopropylphenyl)-3,5-diisopropylphenyl) containing 2-coordinate phosphorus and boron centers. Compound 2 has a PB bond length of 1.741(3) Å, the shortest reported to date. Computational examination of the bonding in 2 reveals, in addition to the σ bond, the presence of a single classical π bond and a large Wiberg bond index of 1.9707, consistent with double bond, and not triple bond, character. The chemistry of 2 is marked by its low reactivity, which is rationalized by examination of the frontier molecular orbitals and steric considerations.

3.
J Am Chem Soc ; 145(16): 9223-9232, 2023 Apr 26.
Artículo en Inglés | MEDLINE | ID: mdl-37067405

RESUMEN

Herein, we report the synthesis of an acyclic carbene-stabilized diphospha(aminyl) PNP radical CAACMePNPCAACMe 4 (CAACMe = 1-[2,6-bis(isopropyl)phenyl]-3,3,5,5-tetramethyl-2-pyrrolidinylidene) by a facile one-pot, seven-electron reduction of hexachlorophosphazene chloride [Cl3PNPCl3][Cl]. The PNP radical 4 features a conjugated framework with spin density primarily localized on the central nitrogen atom as well as the flanking carbenes. Unlike other tripnictogen radicals, 4 undergoes facile one-electron oxidation and reduction to yield nonclassical nitrenium and amide species [5]+ and [6]-, respectively. The cation [5]+ exhibits conformational flexibility in the solution state between the expected W-shaped geometry [5b]+ and a previously unobserved linear heteroallene-type structure [5a]+, which was characterized in the solid state. The equilibrium was explored both computationally and experimentally, showing that [5a]+ is favored over [5b]+ both enthalpically (ΔH = -2.9 × 103 ± 80 J mol-1) and entropically (ΔS = 4.2 ± 0.25 J mol-1 K-1). The formal amide [6]- displays remarkable flexibility in its coordination chemistry due to the presence of multiple Lewis basic centers, as evidenced by the structure of its potassium complex K262, which exhibits µ, κ-P, κ-P, and η3-PNP coordination modes. Protonation of [6]- leads to the formation of an amine 7, which features a trigonal planar geometry around nitrogen.

4.
Bioinformatics ; 38(7): 1930-1937, 2022 03 28.
Artículo en Inglés | MEDLINE | ID: mdl-35043937

RESUMEN

MOTIVATION: Analysis of volatile organic compounds (VOCs) in exhaled breath by proton transfer reaction time-of-flight mass spectrometry (PTR-TOF-MS) is of increasing interest for real-time, non-invasive diagnosis, phenotyping and therapeutic drug monitoring in the clinics. However, there is currently a lack of methods and software tools for the processing of PTR-TOF-MS data from cohorts and suited for biomarker discovery studies. RESULTS: We developed a comprehensive suite of algorithms that process raw data from patient acquisitions and generate the table of feature intensities. Notably, we included an innovative two-dimensional peak deconvolution model based on penalized splines signal regression for accurate estimation of the temporal profile and feature quantification, as well as a method to specifically select the VOCs from exhaled breath. The workflow was implemented as the ptairMS software, which contains a graphical interface to facilitate cohort management and data analysis. The approach was validated on both simulated and experimental datasets, and we showed that the sensitivity and specificity of the VOC detection reached 99% and 98.4%, respectively, and that the error of quantification was below 8.1% for concentrations down to 19 ppb. AVAILABILITY AND IMPLEMENTATION: The ptairMS software is publicly available as an R package on Bioconductor (doi: 10.18129/B9.bioc.ptairMS), as well as its companion experiment package ptairData (doi: 10.18129/B9.bioc.ptairData). SUPPLEMENTARY INFORMATION: Supplementary data are available at Bioinformatics online.


Asunto(s)
Percepción del Tiempo , Compuestos Orgánicos Volátiles , Humanos , Protones , Pruebas Respiratorias/métodos , Tiempo de Reacción , Espectrometría de Masas/métodos , Compuestos Orgánicos Volátiles/análisis , Biomarcadores/análisis
5.
Chemistry ; 29(2): e202202897, 2023 Jan 09.
Artículo en Inglés | MEDLINE | ID: mdl-36196020

RESUMEN

Stoichiometric reaction of phosphine-borane adducts RR'PH⋅BH3 (R=Ph, R'=H, Ph, Et, and R=R'=t Bu) with the strong acid HNTf2 (Tf=SO2 CF3 ) leads to H2 elimination and the formation of the triflimido derivatives, RR'PH⋅BH2 (NTf2 ). Subsequent deprotonation by using bases, such as diisopropylethylamine or the carbene IPr (IPr=N,N'-bis(2,6-diisopropylphenyl)imidazol-2-ylidene), led to the formation of P-mono- or -disubstituted polyphosphinoboranes [RR'P-BH2 ]n . Evidence for the intermediacy of transient phosphinoborane monomers, RR'PBH2 , was provided by trapping reactions.

6.
BMC Geriatr ; 23(1): 431, 2023 07 12.
Artículo en Inglés | MEDLINE | ID: mdl-37438723

RESUMEN

BACKGROUND: Group model building (GMB), is a qualitative focus group like study design from the field of system dynamics, that leads a group of topic experts (often key stakeholders of a problem), through a set of scripted activities to create a conceptual model of their shared view on this problems' key contributing factors and their interactions. By offering a specific step wise approach to the complexity of a problem, GMB has provided better understanding and overview of complex problems across different scientific domains, in addition to traditional research methods. As the development of geriatric syndromes and organization of geriatric care are often complex issues that are difficult to research, understand and resolve, GMB might be a useful methodology to better address these issues. This study aimed to describe the methodology of online GMB using a geriatric case study. METHODS: Four online GMB sessions were designed by two clinician researchers. A GMB methodology expert was consulted for optimal design. Scriptapedia scripts formed the core of the sessions. These scripts were adapted to the online format. Experts were recruited purposefully and included seven local health care professionals, one patient representative and one healthcare insurance data analyst. The outcome was a conceptual model of older adults' emergency department visits, which was discussed in a separate article. RESULTS: During implementation of these four sessions, the sessions were adjusted and two extra (non-scripted) sessions were added because defining unambiguous contributing factors to the geriatric case was challenging for the experts. Paraphrasing, categorizing, iterative plenary reflection, and reserving extra time were used to help experts overcome this challenge. All sessions were held in April and May 2021. CONCLUSION: This study shows that GMB can help unravel complex problems in geriatrics, both pathophysiological as organizational, by creating step wise overview of their key contributing factors and interactions. Furthermore, it shows that GMB can be used by clinicians, researchers and health policy makers to better understand complex geriatric problems. Moreover, this paper can help to overcome specific implementational challenges in the geriatric field.


Asunto(s)
Servicio de Urgencia en Hospital , Geriatría , Humanos , Anciano , Grupos Focales , Instituciones de Salud , Personal de Salud
7.
J Am Chem Soc ; 144(50): 23179-23190, 2022 12 21.
Artículo en Inglés | MEDLINE | ID: mdl-36484741

RESUMEN

The reactions of the N-heterocyclic carbenes (NHCs) IDipp and ItBu and the cyclic(alkyl)amino carbene (CAAC) CAACMe with polyaminoborane [MeNH-BH2]n were investigated. Stoichiometric quantities of each carbene were found to cause rapid and complete depolymerization, with the major B-N-containing product identified as the NHC-aminoborane adduct, IDipp-BH2NMeH (1), cyclic borazane [MeNH-BH2]3, or borazine [MeNBH]3 with IDipp, ItBu, and CAACMe, respectively. With substoichiometric quantities of IDipp and ItBu (down to 10 and 2.5 mol %, respectively), complete loss of high molar mass material was also detected, indicating that the depolymerization is catalytic. The main products of the reaction with substoichiometric IDipp were IDipp-BH2NMeH (1) and [MeNH-BH2]3 and with substoichiometric ItBu, [MeNH-BH2]3, and [MeNBH]3 with product ratios dependent on the quantity of NHC used. Under analogous conditions with CAACMe, high molar mass material persisted alongside the formation of [MeNBH]3. Further reactivity studies with cyclic borazane [MeNH-BH2]3 and MeNH2·BH3 provided insights into depolymerization pathways. IDipp showed no reactivity toward [MeNH-BH2]3, whereas with 3 equiv of ItBu and CAACMe, the dehydrogenation product [MeNBH]3, was formed. With MeNH2·BH3, 2 equiv of carbene were used as the first acts to accept dihydrogen; the major products with IDipp, ItBu, and CAACMe were IDipp-BH2NMeH (1), [MeNBH]3, and (CAACMeH)HB═NMeH (2), respectively. The double E-H (E = B, N) bond activation product (CAACMeH)HB═NMe(HCAACMe) (3) was isolated from the reaction between 3 equiv of CAACMe and MeNH2·BH3. A unified mechanism for donor-mediated depolymerization of [MeHN-BH2]n is proposed.


Asunto(s)
Hidrógeno , Metano , Temperatura , Catálisis
8.
Malar J ; 21(1): 23, 2022 Jan 24.
Artículo en Inglés | MEDLINE | ID: mdl-35073934

RESUMEN

BACKGROUND: Surveillance programmes often use malaria rapid diagnostic tests (RDTs) to determine the proportion of the population carrying parasites in their peripheral blood to assess the malaria transmission intensity. Despite an increasing number of reports on false-negative and false-positive RDT results, there is a lack of systematic quality control activities for RDTs deployed in malaria surveillance programmes. METHODS: The diagnostic performance of field-deployed RDTs used for malaria surveys was assessed by retrospective molecular analysis of the blood retained on the tests. RESULTS: Of the 2865 RDTs that were collected in 2018 on Bioko Island and analysed in this study, 4.7% had a false-negative result. These false-negative RDTs were associated with low parasite density infections. In 16.6% of analysed samples, masked pfhrp2 and pfhrp3 gene deletions were identified, in which at least one Plasmodium falciparum strain carried a gene deletion. Among all positive RDTs analysed, 28.4% were tested negative by qPCR and therefore considered to be false-positive. Analysing the questionnaire data collected from the participants, this high proportion of false-positive RDTs could be explained by P. falciparum histidine rich protein 2 (PfHRP2) antigen persistence after recent malaria treatment. CONCLUSION: Malaria surveillance depending solely on RDTs needs well-integrated quality control procedures to assess the extent and impact of reduced sensitivity and specificity of RDTs on malaria control programmes.


Asunto(s)
Antígenos de Protozoos/análisis , Coinfección/diagnóstico , Pruebas Diagnósticas de Rutina/estadística & datos numéricos , Malaria/diagnóstico , Vigilancia de la Población , Proteínas Protozoarias/análisis , Coinfección/epidemiología , Guinea Ecuatorial/epidemiología , Reacciones Falso Positivas , Incidencia , Malaria/epidemiología , Malaria Falciparum/diagnóstico , Malaria Falciparum/epidemiología , Ácidos Nucleicos/análisis , Plasmodium falciparum/aislamiento & purificación , Plasmodium malariae/aislamiento & purificación , Plasmodium ovale/aislamiento & purificación , Estudios Retrospectivos
9.
Transfus Med ; 32(5): 366-374, 2022 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-35668008

RESUMEN

BACKGROUND AND OBJECTIVES: Current genotyping techniques allow typing of all relevant red cell, human leukocyte and platelet antigens in a single analysis. Even genetic markers related to donor health can be added. Implementation of this technology will affect various stakeholders within the transfusion chain. This study aims to systematically map the anticipated advantages and disadvantages of a national rollout of blood group genotyping of donors, which will affect the availability of rare donors and the implementation of an extensively typed blood transfusion policy. MATERIALS AND METHODS: Two focus-group sessions were held with a wide representation of stakeholders, including representatives of donor and patient organisations. A dedicated software tool was used to collect the reflections of participants on genotyping for blood group antigens and extensive matching. Additionally, stakeholders and experts discussed various prepared propositions. All information collected was categorised. RESULTS: From 162 statements collected, 59 statements (36%) were labelled as 'hopes' and 77 (48%) as 'fears'. Twenty-six (16%) statements remained unlabelled. The statements were divided in 18 categories under seven main themes: patient health, genotyping, privacy issues and ethical aspects, donor management, inventory management and logistics, hospital and transfusion laboratory and general aspects. The discussion on the propositions was analysed and summarised. CONCLUSION: Stakeholders believe that a genotyped donor pool can result in a reduction of alloimmunization and higher availability of typed blood products. There are concerns regarding logistics, costs, consent for extended typing, data sharing, privacy issues and donor management. These concerns need to be carefully addressed before further implementation.


Asunto(s)
Antígenos de Grupos Sanguíneos , Donantes de Sangre , Antígenos de Grupos Sanguíneos/genética , Tipificación y Pruebas Cruzadas Sanguíneas , Grupos Focales , Marcadores Genéticos , Genotipo , Humanos
10.
N Z Vet J ; 70(2): 109-118, 2022 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-34213388

RESUMEN

CASE HISTORIES: Medical records of a veterinary hospital in Belgium were reviewed for dogs (n = 5) that presented between 2016 and 2019 with laryngeal paralysis secondary to bite wounds to the cervical region received while fighting with other dogs. The time elapsed between the trauma and presentation was from a few hours up to 5 days. CLINICAL FINDINGS AND TREATMENT: Bilateral laryngeal paralysis was identified in three dogs and unilateral laryngeal paralysis in two dogs via endoscopic assessment of laryngeal function. The primary concomitant lesions included tracheal injury in 3/5 dogs and oesophageal injury in 1/5 dogs. One dog with bilateral laryngeal paralysis was treated medically as no signs of dyspnoea were present. Surgical management was elected in 4/5 dogs based on evaluation of their clinical status and lesions revealed by endoscopic examination of upper gastrointestinal and respiratory tracts. Dogs underwent surgical procedures that were determined to be appropriate for treatment of the lesions identified on clinical examination, diagnostic imaging, and endoscopy. The cervical region was explored through a ventral midline approach in 2/4 cases, to close tracheal perforations. Temporary tracheostomy was performed in 2/4 cases. Procedures to correct brachycephalic airway obstructive syndrome were performed in 2/4 cases. Cricoarytenoid lateralisation was performed in 2/4 dogs. Dogs were hospitalised for 2-10 days and received antimicrobial therapy before surgery and for 2-3 weeks after surgery. Physical examination and respiratory function were normal in 3/5 dogs 4-6 months after discharge. Information regarding outcomes for two cases was obtained from the owners by telephone assessment 1-6 months after surgery. The owner of each dog reported the respiratory function to be excellent. DIAGNOSIS: Uni- or bilateral, transient or permanent laryngeal paralysis with concomitant oesophageal, tracheal, or laryngeal lesions following cervical dog bite injuries diagnosed by endoscopic examination of upper gastrointestinal and respiratory tracts. CLINICAL RELEVANCE: This case series describes the diagnosis and management of dogs with laryngeal paralysis secondary to cervical dog bite injuries. To the authors' knowledge, this is the first published report documenting bilateral laryngeal paralysis secondary to cervical dog bite injuries. Clinicians should be aware of this pathology and the importance of investigating laryngeal function in dogs presenting with cervical bites, particularly those with inspiratory dyspnoea. Upper airway and digestive endoscopy are recommended for complete assessment of cervical traumatic injuries.


Asunto(s)
Mordeduras y Picaduras , Laringe , Parálisis de los Pliegues Vocales , Animales , Mordeduras y Picaduras/veterinaria , Perros , Laringe/lesiones , Laringe/cirugía , Tráquea , Parálisis de los Pliegues Vocales/etiología , Parálisis de los Pliegues Vocales/veterinaria
11.
Transfusion ; 61(8): 2356-2367, 2021 08.
Artículo en Inglés | MEDLINE | ID: mdl-34058022

RESUMEN

BACKGROUND: As Western blood transfusion practices are changing, there is interest and need in anticipating the future demand of blood products and how a blood establishment can actively prepare for various long-term developments. This article provides an overview of how a scenario approach was used to prioritize key categories of drivers for the future demand of red blood cells and the organizational implications thereof for Sanquin, the Dutch national blood establishment. STUDY DESIGN AND METHODS: Based on previously identified drivers from interviews and a literature review (Step 1), we conducted scenario sessions and a survey to rank a list of drivers ("themes") with its related opportunities and threats (Step 2), to identify mitigating measures per theme through focus groups (Step 3). RESULTS: In Step 2, 10 themes were found that were classified in terms of importance and uncertainty. These were plotted on a two-dimensional graph with an ellipse to indicate the interquartile ranges per theme. Experts rated the top three most important themes to be the blood supply organization, precision medicine, and red blood cell replacements. In Step 3, focus groups identified specific mitigating measures per theme. These measures had parallel ideas, such as the need for an innovative mentality, internal and external communication and collaboration, and building Sanquin's reputation and trust with the public. CONCLUSION: Having identified the most important themes with suggestions for mitigating measures, Sanquin can take steps to become adaptive and proactive. Other blood establishments may also use a scenario approach to create contextualized long-term strategies.


Asunto(s)
Bancos de Sangre , Donantes de Sangre , Transfusión de Eritrocitos , Eritrocitos/citología , Humanos , Países Bajos , Medicina de Precisión
12.
Rev Med Liege ; 76(12): 884-889, 2021 12.
Artículo en Francés | MEDLINE | ID: mdl-34881833

RESUMEN

The continuous and multidisciplinary care of children with type 1 diabetes contributes improving their quality of life. Nevertheless, psychological follow-up issues among parents of a diabetic child are less developed in studies. At present, there is a need to develop research on psychological parental adjustment in order to identify risk and protective factors for understanding the parental experience and improving the initiatives to prevent the parental distress. Our results argue for a crucial role of intolerance of uncertainty in parental concerns. This study supports the continuous psychological follow-up of parents in close collaboration with medical teams.


La prise en charge continue et pluridisciplinaire des enfants atteints de diabète de type 1 contribue à l'amélioration de leur qualité de vie. Cependant, les enjeux du suivi psychologique des parents d'un enfant diabétique sont moins développés dans les travaux de la littérature. À l'heure actuelle, il est nécessaire de réaliser des recherches portant sur l'ajustement psychologique parental afin d'identifier les facteurs de risque et de protection dans la compréhension du vécu des parents dans le but d'améliorer les initiatives de prévention de la détresse parentale. Nos résultats plaident pour un rôle non négligeable du facteur d'intolérance à l'incertitude au maintien des inquiétudes parentales. Cette étude confirme l'intérêt d'un suivi psychologique continu des parents en étroite collaboration avec les équipes médicales.


Asunto(s)
Diabetes Mellitus Tipo 1 , Adaptación Psicológica , Niño , Ajuste Emocional , Humanos , Padres , Estudios Prospectivos , Calidad de Vida , Estrés Psicológico
13.
Bioinformatics ; 35(19): 3752-3760, 2019 10 01.
Artículo en Inglés | MEDLINE | ID: mdl-30851093

RESUMEN

MOTIVATION: Developing a robust and performant data analysis workflow that integrates all necessary components whilst still being able to scale over multiple compute nodes is a challenging task. We introduce a generic method based on the microservice architecture, where software tools are encapsulated as Docker containers that can be connected into scientific workflows and executed using the Kubernetes container orchestrator. RESULTS: We developed a Virtual Research Environment (VRE) which facilitates rapid integration of new tools and developing scalable and interoperable workflows for performing metabolomics data analysis. The environment can be launched on-demand on cloud resources and desktop computers. IT-expertise requirements on the user side are kept to a minimum, and workflows can be re-used effortlessly by any novice user. We validate our method in the field of metabolomics on two mass spectrometry, one nuclear magnetic resonance spectroscopy and one fluxomics study. We showed that the method scales dynamically with increasing availability of computational resources. We demonstrated that the method facilitates interoperability using integration of the major software suites resulting in a turn-key workflow encompassing all steps for mass-spectrometry-based metabolomics including preprocessing, statistics and identification. Microservices is a generic methodology that can serve any scientific discipline and opens up for new types of large-scale integrative science. AVAILABILITY AND IMPLEMENTATION: The PhenoMeNal consortium maintains a web portal (https://portal.phenomenal-h2020.eu) providing a GUI for launching the Virtual Research Environment. The GitHub repository https://github.com/phnmnl/ hosts the source code of all projects. SUPPLEMENTARY INFORMATION: Supplementary data are available at Bioinformatics online.


Asunto(s)
Análisis de Datos , Metabolómica , Biología Computacional , Programas Informáticos , Flujo de Trabajo
14.
J Am Chem Soc ; 141(51): 20009-20015, 2019 12 26.
Artículo en Inglés | MEDLINE | ID: mdl-31756293

RESUMEN

We report well-defined Ti(III) metallocene complexes Cp*2TiMe (1Me) and Cp*2TiH (1H) (Cp* = η5-C5Me5) as the first isolable early transition metal precatalysts for the dehydropolymerization of amine-boranes RNH2·BH3. These earth-abundant metal catalysts combine high activity with broad substrate scope. In contrast to late transition metal catalysts, 1Me displays reactivity toward a variety of primary amine-boranes, including those containing reactive moieties such as olefinic groups. The ability to functionalize the side chain of the resultant polyaminoborane [RNH-BH2]n provides a promising method for controlling properties. Mechanistic investigation of the dehydrogenation of secondary amine-borane Me2NH·BH3 supports a bond-metathesis/ß-hydride elimination, redox-neutral mechanism with a Ti(III)-H resting state.

15.
Chemistry ; 25(17): 4305-4308, 2019 Mar 21.
Artículo en Inglés | MEDLINE | ID: mdl-30723967

RESUMEN

Isolable cationic PtII and PtIV alkylidenes, proposed intermediates in catalytic organic transformations, are reported. The bonding in these species was probed by experimental, structural, spectroscopic, electrochemical and computational methods, providing direct evidence for π-bonding, the often-theorized relativistic stabilization of these species, and the influence of oxidation state.

16.
Bioinformatics ; 33(23): 3767-3775, 2017 Dec 01.
Artículo en Inglés | MEDLINE | ID: mdl-29036359

RESUMEN

MOTIVATION: Flow Injection Analysis coupled to High-Resolution Mass Spectrometry (FIA-HRMS) is a promising approach for high-throughput metabolomics. FIA-HRMS data, however, cannot be preprocessed with current software tools which rely on liquid chromatography separation, or handle low resolution data only. RESULTS: We thus developed the proFIA package, which implements a suite of innovative algorithms to preprocess FIA-HRMS raw files, and generates the table of peak intensities. The workflow consists of 3 steps: (i) noise estimation, peak detection and quantification, (ii) peak grouping across samples and (iii) missing value imputation. In addition, we have implemented a new indicator to quantify the potential alteration of the feature peak shape due to matrix effect. The preprocessing is fast (less than 15 s per file), and the value of the main parameters (ppm and dmz) can be easily inferred from the mass resolution of the instrument. Application to two metabolomics datasets (including spiked serum samples) showed high precision (96%) and recall (98%) compared with manual integration. These results demonstrate that proFIA achieves very efficient and robust detection and quantification of FIA-HRMS data, and opens new opportunities for high-throughput phenotyping. AVAILABILITY AND IMPLEMENTATION: The proFIA software (as well as the plasFIA dataset) is available as an R package on the Bioconductor repository (http://bioconductor.org/packages/proFIA), and as a Galaxy module on the Main Toolshed (https://toolshed.g2.bx.psu.edu), and on the Workflow4Metabolomics online infrastructure (http://workflow4metabolomics.org). CONTACT: alexis.delabriere@cea.fr or etienne.thevenot@cea.fr. SUPPLEMENTARY INFORMATION: Supplementary data are available at Bioinformatics online.


Asunto(s)
Análisis de Inyección de Flujo/métodos , Espectrometría de Masas/métodos , Programas Informáticos , Metabolómica/métodos , Flujo de Trabajo
17.
Inorg Chem ; 57(1): 495-506, 2018 Jan 02.
Artículo en Inglés | MEDLINE | ID: mdl-29260872

RESUMEN

Three PCsp3P pincer ligands differing in the aryl group linking the phosphine arms with the anchoring carbon donor were used to support square planar Ni(II) bromide complexes 1-3Br. Exchange of the coordinating bromide anion for the more weakly coordinating triflate (OTf) or hexafluoroantimonate (SbF6) anions was accomplished by treatment with AgX or TlX salts to give compounds 1-3X; compounds 1OTf, 1SbF6, 2Br, 2OTf, 3Br, and 3SbF6 were all characterized by X-ray crystallography. The reactions of these Ni(II) compounds with the amine-N-oxide oxygen atom transfer agents ONMe3 and ONMePh2 were explored. For ONMe3, reactions with 2 equiv gave products in which one arm of the pincer ligand was oxidized to a P═O unit, with the other amine-N-oxide ligated to the Ni(II) center, forming products 5-6X; compounds 4OTf, 5OTf, and 6SbF6 were characterized crystallographically. Transient amine-N-oxide adducts prior to ligand oxidation were observed in some reactions. For the more effective O atom donor ONMePh2, reactions were very rapid and a second oxidation of the remaining phosphine arm was observed, producing a Ni(II) species with an OCO pincer ligand (7SbF6). All compounds were fully characterized. Experiments aimed at trapping transient Ni(IV) oxo intermediates (with cyclohexadiene, KH, and various Lewis acids) indicated that such species were not involved in the reaction. This was supported by density functional theory (DFT) computations at the B3PW91 level, which indicated that direct O atom insertion into the Ni-P bonds without the intermediacy of a Ni oxo species was the low-energy pathway.

18.
J Microsc ; 265(1): 73-80, 2017 01.
Artículo en Inglés | MEDLINE | ID: mdl-27649067

RESUMEN

In this paper, we propose an algorithm to obtain a three-dimensional reconstruction of a single nanoparticle based on the method of atom counting. The location of atoms in three dimensions has been successfully performed using simulations of high-angle-annular-dark-field images from only three zone-axis projections, [110], [310] and [211], for a face-centred cubic particle. These three orientations are typically accessible by low-tilt holders often used in high-performance scanning transmission electron microscopes.

19.
Rev Med Liege ; 72(11): 488-493, 2017 Nov.
Artículo en Francés | MEDLINE | ID: mdl-29171947

RESUMEN

The aim of the study was to assess the degree of similarity between the distress expressed by parents of a child cancer survivor and the distress perceived by the oncologist. Overall, 61 parents of a child cancer survivor (between 4 and 6 years of cancer remission) were recruited in Belgian hospitals (Province of Liège). Parents filled out questionnaires about the intolerance of uncertainty (IUS), positive beliefs about worry (WW-II), parental worries about the evolution of their child's health (QIPS-R15), problem orientation (NPOQ), cognitive avoidance (CAQ), ruminations (Mini-CERTS), and anxiety/depression (HADS). Eight oncologists who having taken care of the child filled out the «OncoMed¼ questionnaire that examines their perception of the parental distress (e.g. anxiety, worries). Parents suffered from anxiety,worries about their child's health and showed a low level of tolerance of uncertainty. Overall, oncologists demonstrated a low perceived distress compared to the level of parental distress. The study highlights the need to detect early parents who are intolerant of uncertainty in order to offer them an efficient psychological follow-up. This study underlines finally the necessity to develop medical perception tools about the distress in order to strengthen the medical communication and the follow-up of these families.


L'objectif de l'étude est de mesurer le degré de concordance entre la détresse exprimée par les parents d'un enfant en rémission de cancer et la détresse perçue par l'oncologue. Au total, 61 parents d'un enfant en rémission de cancer (de 4 années à 6 années de rémission) sont recrutés dans les hôpitaux belges (Province de Liège). Les parents remplissent des questionnaires relatifs à l'intolérance à l'incertitude (QII), aux croyances positives à l'égard de l'inquiétude (PSI-II), aux inquiétudes relatives à l'évolution de la santé de l'enfant (QIPS-R15), à l'orientation de l'attitude face à un problème (QAP), à l'évitement cognitif (QEC), aux ruminations (Mini-CERTS) et à l'anxiété/dépression (HADS). Huit oncologues ayant pris en charge l'enfant répondent au questionnaire «OncoMed¼ évaluant leur perception de la détresse du parent (e.g. anxiété, inquiétudes). Les parents souffrent d'anxiété, d'inquiétudes relatives à la santé de leur enfant et ont une faible tolérance à l'incertitude. Les oncologues perçoivent en moyenne, une détresse moins élevée que celle rapportée par les parents. L'étude souligne l'importance de détecter, dès la prise en charge de l'enfant, le facteur d'intolérance à l'incertitude chez le parent afin de lui proposer un suivi psychologique adéquat. Cette étude souligne enfin la nécessité de développer des outils de perception médicale de la détresse afin de renforcer la communication médicale et le suivi de ces familles.


Asunto(s)
Neoplasias/psicología , Oncólogos/psicología , Padres/psicología , Percepción , Estrés Psicológico , Adolescente , Adulto , Ansiedad/epidemiología , Ansiedad/etiología , Actitud del Personal de Salud , Bélgica/epidemiología , Supervivientes de Cáncer/psicología , Niño , Preescolar , Femenino , Humanos , Masculino , Persona de Mediana Edad , Oncólogos/estadística & datos numéricos , Relaciones Padres-Hijo , Estrés Psicológico/epidemiología , Estrés Psicológico/etiología , Encuestas y Cuestionarios
20.
Rev Med Liege ; 72(3): 139-145, 2017 Mar.
Artículo en Francés | MEDLINE | ID: mdl-28387491

RESUMEN

Studies in pediatric oncology describe a relative good quality of life in child cancer survivor. However, few studies were interested in the parents of a child cancer survivor. 61 parents are recruited in the Belgian hospitals. Three groups of parents are constituted : the parents whose child is in 4 years of survivorship (group 1), in 5 years of survivorship (group 2) and in 6 years of survivorship (group 3). Clinical scales and a Stroop emotion task are administered. Parents (of the 3 groups) present a low tolerance of uncertainty, have excessive worries about the evolution of the health of their child, and suffer from anxious symptoms. The Stroop emotion tasks reveals a cognitive bias of the attention in favour of threatening stimuli. The study highlights the importance to detect parents who are intolerant of uncertainty at the cancer diagnosis stage and their continuous psychological follow-up once the treatments are ended.


Les études en oncologie pédiatrique décrivent une relativement bonne qualité de vie chez les enfants survivants de cancer. À ce jour, peu d'études se sont intéressées aux parents d'un enfant survivant de cancer. Soixante-et-un parents sont recrutés dans les hôpitaux belges. Trois groupes de parents sont constitués : les parents dont l'enfant est à 4 ans de rémission (groupe 1), à 5 ans de rémission (groupe 2) et à 6 ans de rémission (groupe 3). Des échelles cliniques et une tâche de Stroop émotion sont administrées. Les parents (des 3 groupes) présentent une faible tolérance à l'incertitude, ont des inquiétudes excessives quant à l'évolution de la santé de leur enfant et souffrent de symptômes anxieux. Le Stroop émotion révèle un biais cognitif de l'attention en faveur des stimuli de nature menaçante. L'étude met en exergue l'importance de détecter les parents intolérants à l'incertitude lors du diagnostic d'annonce du cancer et leur suivi psychologique continu une fois les traitements terminés.


Asunto(s)
Sesgo , Supervivientes de Cáncer , Padres/psicología , Incertidumbre , Adolescente , Adulto , Ansiedad/psicología , Bélgica , Niño , Humanos , Acontecimientos que Cambian la Vida , Persona de Mediana Edad , Encuestas y Cuestionarios
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