Synthesis, structure and properties of novel Cu(II)-based metal-organic frameworks

Porous crystalline materials are known to be useful for a number of applications, including sensing, 1 drug delivery, 2 solid state catalysis3 and controlled absorption and release of liquids, gases and small molecules in solution. 4,5 Within this general definition, a class of materials that has seen its importance grow exponentially in the past two decades has been that of the Metal-Organic Frameworks, or MOFs. These materials have shown a lot of potential, especially in devices aimed at sequestering greenhouse gases (such as CO2 and CH4) from the atmosphere, 6 as well as in fuel tanks for hydrogen-powered cars. 7 The characteristics that allow MOFs to be used for such purposes are their high internal surface area to volume ratio, their relatively high thermal stability and the possibility to fine-tune their structure to optimize a given MOF for a given application. 8 Another feature of some MOFs, especially those built with semiflexible organic linkers9 between metallic nodes, is that they can change their conformation and therefore their pore size and internal surface area, in response to an external stimulus. 2,10 This behavior is especially interesting for systems which can be engineered to absorb and then release small molecules in a controlled manner. 11,12 This last property is one that I set out to exploit in my thesis work, starting from Cu(II) molecular complexes previously synthesized in the University of Cape Town (UCT) laboratories and varying experimental conditions in order to get MOFs of similar systems. Thus, this work will mainly describe the several novel crystal structures I obtained during my research. Each chapter will also discuss the basic spectroscopic and thermal properties of the material explored therein. Of these crystals, two are novel Cu(II)-based coordination polymers, which were named 1-MBUCT and 2-MBUCT, with seldom-seen coordination characteristics and other interesting features, including solvent-filled cavities within their crystal structure, which makes them promising candidates to be fully considered MOFs. After exploring the synthesis and structure of the materials, this work will mainly focus on determining whether the cavities inside 1-MBUCT and 2-MBUCT are accessible to other guests, without disrupting the overall morphology of the material. This was done through solvent exchange experiments, which were inconclusive but nonetheless suggested that these materials did indeed retain their shape, while allowing guest molecules inside their pores, thus being worthy of being described as MOFs. 6 All other structures are byproducts obtained during various attempts to optimize the synthesis of these MOFs, and are often examples of unusual compound classes in their own right. The first of these compounds is a Cu-based [12]crown-6 cyclical compound in which two monomethyl sulfide anions for every copper ion act as bridging ligands within the ring-like structure of the molecule, while the second is a discrete molecular complex formed by two 2,6- pyridinedicarboxylic acid molecules chelating a Cu(II) ion. The main point of interest of the last byproduct, instead, is not its structure, but rather the fact that all the carboxylic acid groups of the 3,5-pyridinedicarboxylic acid molecules included in the complex were subject to an esterification reaction. Such a reaction was unexpected, as the components of this system did not correspond to those found in any reported esterification reaction performed on 3,5-pyridinedicarboxylic acid

Elsa Morante e il cinema: "L’isola di Arturo" di Damiano Damiani

Although its intensity and duration, the relation between Elsa Morante and the cinema is less studied by the critics, perhaps because of the scarceness of information. But the discovery of many new documents in these years permitted to know the plots written (but not realized9 by the Author from 1933 till 1952 (there are three different plots: Il diavolo, Miss Italia and Verranno a te sull’aure). It is also possible to have a clear idea of the collaboration with some directors like: Alberto Lattuada, Luchino Visconti, Franco Zeffirelli, Pier Paolo Pasolini. A close analysis of the cinematographic version of the novel L’Isola di Arturo, directed by Damiano Damiani in 1962, permits to determine that the dissatisfaction which Morante expressed in many circumstances derives from a lack of dialogue between her and the director damiano Damiani.Pure se intenso e continuato nel tempo, il rapporto tra Elsa Morante e il cinema è sempre rimasto un argomento poco sondato dalla critica, forse anche per la scarsità di informazioni al riguardo. Negli ultimi anni, tuttavia, molti nuovi documenti sono stati reperiti, e tali scoperte hanno reso possibile conoscere i soggetti cinematografici da lei scritti (ma mai realizzati) tra il 1939 e il 1952 (sono tre: Il diavolo, Miss Italia e Verranno a te sull’aure...), nonché farsi un’idea concreta delle sue varie collaborazioni con registi come Alberto Lattuada, Luchino Visconti, Franco Zeffirelli, Pier Paolo Pasolini. Differentemente, un’analisi attenta della trasposizione cinematografica de L’isola di Arturo, diretta da Damiano Damiani nel 1962, mostra come l’esibita insoddisfazione della scrittrice, espressa in più occasioni, nasca per l’appunto da un’assenza di dialogo tra i due artisti

Le Cronache cinematografiche di Elsa Morante (1950-1951)

Between March 1950 and November 1951, Elsa Morante conducted a film review program, broadcast by Radio RAI. The original recordings have never been found; but the recent discovery of the preparatory papers allows us to learn about Morante’s preferences and ideas on cinema. At the time, the program was short-lived, due to the intervention of an arbitrary censorship by the executives of RAI

Elsa Morante e il cinema: il trattamento di "Miss Italia"

Dopo il ritrovamento del dattiloscritto originale da parte dell'autore, il contributo presenta per la prima volta e analizza il trattamento cinematografico "Miss Italia", scritto da Elsa Morante nel 1949, ma mai trasposto in film

Correction to: Effects of immune suppression for transplantation on inflammatory colorectal cancer progression (Oncogenesis, (2018), 7, 6, (46), 10.1038/s41389-018-0055-5)

At the time of publication, the html version of this paper contained an error; the authors Imerio Angriman and Lucrezia Furian were not tagged as equally contributing authors. This has now been fixed in the html version of the paper, the PDF was correct at the time of publication. Erratum for Effects of immune suppression for transplantation on inflammatory colorectal cancer progression. [Oncogenesis. 2018

The polo-like kinase 1 (PLK1) inhibitor NMS-P937 is effective in a new model of disseminated primary CD56+ acute monoblastic leukaemia

CD56 is expressed in 15–20% of acute myeloid leukaemias (AML) and is associated with extramedullary diffusion, multidrug resistance and poor prognosis. We describe the establishment and characterisation of a novel disseminated model of AML (AML-NS8), generated by injection into mice of leukaemic blasts freshly isolated from a patient with an aggressive CD56+ monoblastic AML (M5a). The model reproduced typical manifestations of this leukaemia, including presence of extramedullary masses and central nervous system involvement, and the original phenotype, karyotype and genotype of leukaemic cells were retained in vivo. Recently Polo-Like Kinase 1 (PLK1) has emerged as a new candidate drug target in AML. We therefore tested our PLK1 inhibitor NMS-P937 in this model either in the engraftment or in the established disease settings. Both schedules showed good efficacy compared to standard therapies, with a significant increase in median survival time (MST) expecially in the established disease setting (MST = 28, 36, 62 days for vehicle, cytarabine and NMS-P937, respectively). Importantly, we could also demonstrate that NMS-P937 induced specific biomarker modulation in extramedullary tissues. This new in vivo model of CD56+ AML that recapitulates the human tumour lends support for the therapeutic use of PLK1 inhibitors in AML

From synthesis to device fabrication: elucidating the structural and electronic properties of C7-BTBT-C7

We report the polymorph investigation, crystallographic study and fabrication of organic field-effect transistors (OFETs) in solution-processed thin films of a prototypical organic semiconductor, i.e., 2,7-diheptylbenzo[b]benzo[4,5]thieno[2,3-d]thiophene (C7-BTBT-C7). We found that this molecule self-assembles solely into one type of stable crystal form, regardless of the experimental conditions employed when using conventional and non-conventional methods of crystallization. The integration of blends of C7-BTBT-C7 with polystyrene as active materials in OFETs fabricated using a solution shearing technique led to a field-effect mobility of 1.42 ± 0.45 cm2 V−1 s−1 in the saturation regime when a coating speed of 10 mm s−1 was employed. The intrinsic structural properties control the overlap of the frontier orbitals, thereby affecting the device performance. The interplay between the crystal packing, thin film morphology and uniformity and its impact on the device performance are reported.We acknowledge the Paul Scherrer Institut, Villigen, Switzerland, for the provision of synchrotron radiation beam time at the beamline MS-X04SA of the SLS (ID proposal 20201790). P. P., L. F., N. M., N. T., J. C., P. S., M. M. T., Y. G., E. M., and L. M., contributors of the paper, are the members of the UHMob project. This work has received funding from the European Union's Horizon 2020 research and innovation program under the Marie Sklodowska-Curie grant no. 811284. G. S. is a FNRS Research Associate (Belgian National Fund for Scientific Research). G. S. acknowledges financial support from the Francqui Foundation (Francqui Start-Up Grant). G. S. thanks the FNRS for financial support through the research project COHERENCE2 (no. F.4536.23). M. M. T. and L. F. also acknowledge MCIN through the project GENESIS PID2019 and the “Severo Ochoa” Programme for Centers of Excellence in R&D (FUNFUTURE CEX2019-000917-S), and the Generalitat de Catalunya (2017-SGR-918).With funding from the Spanish government through the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000917-S).Peer reviewe

Transiently delocalized states enhance hole mobility in organic molecular semiconductors

Evidence shows that charge carriers in organic semiconductors self-localize because of dynamic disorder. Nevertheless, some organic semiconductors feature reduced mobility at increasing temperature, a hallmark for delocalized band transport. Here we present the temperature-dependent mobility in two record-mobility organic semiconductors: dinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]-thiophene (DNTT) and its alkylated derivative, C8-DNTT-C8. By combining terahertz photoconductivity measurements with atomistic non-adiabatic molecular dynamics simulations, we show that while both crystals display a power-law decrease of the mobility (μ) with temperature (T) following μ ∝ T −n, the exponent n differs substantially. Modelling reveals that the differences between the two chemically similar semiconductors can be traced to the delocalization of the different states that are thermally accessible by charge carriers, which in turn depends on their specific electronic band structure. The emerging picture is that of holes surfing on a dynamic manifold of vibrationally dressed extended states with a temperature-dependent mobility that provides a sensitive fingerprint for the underlying density of states

Dinaphthotetrathienoacenes : synthesis, characterization, and applications in organic field-effect transistors

The charge transport properties of organic semiconductors are limited by dynamic disorder that tends to localize charges in organic crystals. It is the main hurdle to overcome in order to significantly increase charge carrier mobility. We propose an innovative design that combines a chemical structure based on sulfur-rich thienoacene with a solid-state herringbone packing and present the synthesis, physicochemical characterization and charge transport properties of two new thienoacenes bearing a central tetrathienyl core fused with two external naphthyl rings: DN4T and isoDN4T. Both compounds crystallize with a herringbone pattern structure and present transfer integrals ranging from 33 to 99 meV (for the former) within the herringbone plane of charge transport. Molecular dynamics simulations point towards an efficient resilience of the transfer integrals to the intermolecular sliding motion commonly responsible for strong variations of the electronic coupling in the crystal. Best device performances were reached with DN4T with hole mobility up to μ = 2.1 cm² V-1 s-1 in polycrystalline OFETs, showing the effectiveness of the electronic coupling enabled by the new aromatic core. These promising results pave the way to the design of high-performing materials based on this new thienoacene, notably through the introduction of alkyl side-chains

Sex-related differences in oncologic outcomes, operative complications and health-related quality of life after curative-intent oesophageal cancer treatment: multicentre retrospective analysis

Background: Oesophageal cancer, in particular adenocarcinoma, has a strong male predominance. However, the impact of patient sex on operative and oncologic outcomes and recovery of health-related quality of life is poorly documented, and was the focus of this large multicentre cohort study. Methods: All consecutive patients who underwent oncological oesophagectomy from 2009 to 2015 in the 20 European iNvestigation of SUrveillance after Resection for Esophageal cancer study group centres were assessed. Clinicopathologic variables, therapeutic approach, postoperative complications, survival and health-related quality of life data were compared between male and female patients. Multivariable analyses adjusted for age, sex, tumour histology, treatment protocol and major complications. Specific subgroup analyses comparing adenocarcinoma versus squamous cell cancer for all key outcomes were performed. Results: Overall, 3974 patients were analysed, 3083 (77.6%) male and 891 (22.4%) female; adenocarcinoma was predominant in both groups, while squamous cell cancer was observed more commonly in female patients (39.8% versus 15.1%, P < 0.001). Multivariable analysis demonstrated improved outcomes in female patients for overall survival (HRmales 1.24, 95% c.i. 1.07 to 1.44) and disease-free survival (HRmales 1.22, 95% c.i. 1.05 to 1.43), which was caused by the adenocarcinoma subgroup, whereas this difference was not confirmed in squamous cell cancer. Male patients presented higher health-related quality of life functional scores but also a higher risk of financial problems, while female patients had lower overall summary scores and more persistent gastrointestinal symptoms. Conclusion: This study reveals uniquely that female sex is associated with more favourable long-term survival after curative treatment for oesophageal cancer, especially adenocarcinoma, although long-term overall and gastrointestinal health-related quality of life are poorer in women