The metal-driven self-assembly strategy is well-established for the construction of discrete architectures featuring a cavity. The resulting molecular rings and cages are potentially useful as hosts ...for complementary guests. Recent years have seen growing interest in the introduction of given functionalities, including redox properties which, among others, allow modulating the ionic charge of the cavity. Depending on which subunit is electroactive, various situations can be encountered, with a global redox activity which is ligand- and/or metal-centered and which involves or not electronic interactions between the constituting units. In this feature article, we propose to survey those different situations by exploring some recent examples of the growing family of redox-active self-assembled rings and cages.
The growing family of redox-active rings and cages prepared using the coordination-driven self-assembly strategy is reviewed.
The height of increasing trees Broutin, N.; Devroye, L.; McLeish, E. ...
Random structures & algorithms,
07/2008, Letnik:
32, Številka:
4
Journal Article
The aim of the review is to give an updated vision of synthetic aspects in the field of the TTF chemistry with, as a guideline, the central role of electrophilic alkynes in the synthesis of ...1,3-dithiole and TTF systems. Of particular interest will be dimethyl acetylenedicarboxylate (DMAD) and acetylenedicarbaldehyde (ADCA) or its monodiethylacetal (ADCA-MA), which can be regarded as prototypical electrophilic alkynes. Their dienophilic and dipolarophilic properties, combined with their electrophilicity, have been widely exploited in the development of highly functional TTFs. This review also presents the more recent interest in organic materials, particularly in the use of electrophilic alkynes as starting building blocks for the synthesis of highly extended sulfur-rich and highly functionalized TTF derivatives.
An electron-rich redox-active M 2 L 4 cage is depicted. The cage is constructed through coordination driven self-assembly of a 9-(1,3-dithiol-2-ylidene)fluorene bis-pyridyl ligand in the presence of ...the Pd(BF 4 ) 2 (CH 3 CN) 4 complex. The corresponding discrete structure has been fully characterized in the solution as well in the solid state (crystal structure), showing notably that each of the four ligands surrounding the cavity can be reversibly oxidized upon a one electron process.
An electroactive and luminescent foldamer based on an oligopyridine biscarboxamide skeleton was synthesized and characterised. Its conformation in the solid state proved to be strongly affected by ...the peripheral pyrene units. The latter also endow the target derivative with recognition abilities toward electron-withdrawing molecules, which allow tuning of the spectroscopic properties of the foldamer.
E. Piaton, L. Villeneuve, C. Maurice, C. Paulin, M. Cottier, B. Fontanière, M. Salle, D. Seigneurin, S. Vancina, E. Decullier, F. N. Gilly and E. Cotte
Intraperitoneal free cancer cells in ...non‐gynaecological adenocarcinomas: a reproducibility study
Objective: In recent years, therapeutic approaches including cytoreductive surgery followed by intraperitoneal chemotherapy have proven effective in peritoneal carcinomatosis of colorectal origin. If cytology is to be used to include patients in aggressive treatment regimens, it is necessary to evaluate its performance, particularly in terms of specificity. The aim of this study was to assess interobserver agreement for the detection of intraperitoneal free cancer cells (IFCCs) in patients with non‐gynaecological adenocarcinomas.
Methods: Over a 5‐year period, 1223 patients were recruited in 19 French surgery departments. Peritoneal samples were examined in 14 dispersed pathology laboratories. Giemsa‐stained slides were sent to a control reader blind to the previous diagnosis. Discordant cases, concordant positive results and a random selection of negative concordant cases were reviewed by a panel of seven cytopathologists. The ‘final diagnosis’ was that of the consensus meetings but took into account locally‐processed slides.
Results: Gathering dubious cases with negative results, a 95.6% concordance was achieved between local readers and the control reader. IFCCs were ascertained by the panel in 85 cases (7.0%). Eight of 873 colorectal cancers cases viewed locally were falsely positive (0.9%). Radiotherapy and neoadjuvant therapy had no impact on the false‐positive rate as assessed by final validation by the panel (P > 0.05). Samples initially considered as dubious were reclassified as negative by the panel in 24 of 25 cases (96.0%).
Conclusions: The panel consensus allowed reclassification of most dubious/equivocal peritoneal cytology cases, whereas clearcut distinction between benign and malignant cases was correctly achieved in almost all cases.
BACKGROUND: We conducted a feasibility and acceptability study of video-observed therapy (VOT) among patients with multidrug-resistant TB (MDR-TB) and other types of drug-resistant TB (DR-TB) in the ...Philippines.METHODS: Patients aged ≥13 years were approached to
use VOT. A smartphone with VOT mobile application to video-record medication intake was provided. Healthcare workers (HCWs) monitored adherence by watching videos via a web-based dashboard. Good adherence was defined as intake of >90% of expected doses. Feasibility and acceptability were
assessed using a semi-structured questionnaire on a Likert scale.RESULTS: Of 308 patients, 110 (36%) patients chose VOT; 67 completed treatment using VOT and 43 stopped VOT prior to treatment outcome; 74/110 (67%) had good adherence. The treatment success rate was 88% and the loss
to follow-up rate was 8.1%. Among HCWs, 90% (9/10) had a positive perception of VOT. All HCWs agreed that VOT data accurately reflect medication intake of the patients; 88/89 (99%) mentioned benefits of VOT, notably convenience, sense of comfort, privacy and security.CONCLUSIONS:
VOT is feasible and acceptable for both patients and HCWs. This study could provide guidance to the country programme to launch VOT for treatment of patients with MDR-TB and other DR-TB.
Nombre de recherches en psychologie sociale soulignent la présence et le poids des biais évaluatifs chez les enseignant-e-s, comme les stéréotypes des garçons plus scientifiques. En parallèle les ...textes officiels (BO 2006) pointent la nécessité d’une formation à l’égalité et la mixité. Cette recherche part des résistances formulées par les étudiant-e-s en master des métiers de l’enseignement face aux notions de biais perceptifs. 77 étudiant-e-s de master 2 préparant au professorat des 1er et 2nd degrés ont commenté une évaluation de CM2 (garçon ou fille), satisfaisante sauf en mathématiques. Les résultats confirment les stéréotypes « genrés » en mathématiques, ainsi qu’une variation de discours selon le statut professionnel des étudiant-e-s, soulevant l’importance d’inclure dans la formation une sensibilisation aux problématiques de genre.
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