A route to benzodithiophene systems by exploiting a ligand-free Suzuki-Miyaura coupling reaction in deep eutectic solvents

Benzo[1,2-b:4,3-b\u2019]dithiophene (BDT) and its derivatives belong to an interesting class of thiophene-based aromatic \uf070-conjugated compounds that are widely studied as functional organic materials inserted, for instance, as units in mono and polydisperse oligomers [1], or as \uf070-spacers in push-pull organic chromophores for photovoltaic applications [2]. Moreover, BDTs are key intermediates for the synthesis of inherent chiral tetrathia[7]helicenes, which are an attractive class of heterohelicenes with unique physicochemical and chiroptical properties due to their helix-like structure [3]. Thus, BDT is a key starting molecule which can allow access to more complex and interesting systems through a selective and judicious functionalization of the \uf061 and \uf062-positions of the terminal thiophene rings. Building on our recent studies on the synthesis and functionalization of BDTs [4], we questioned whether a novel class of 2,7-diarylsubstituted BDTs 1 (Figure 1) could be synthesized via a palladium-catalysed Suzuki-Miyaura reaction between heteroaryl halides 2 and organoboron derivatives 3 in Deep Eutectic Solvents (DESs), which have proven to be effective as sustainable and environmentally responsible reaction media in several transition-metal-catalyzed reactions [5].In this communication, we report our preliminary results on the preparation of diarylsubstituted BDTs 1, and discuss the substrate scope of the proposed protocol. Some of the compounds so far obtained display interesting photophysical properties, which are currently under investigation

The 9p21 Rs 1333040 polymorphism is associated with coronary microvascular obstruction in ST-segment elevation myocardial infarction treated by primary angioplasty

Background: Microvascular obstruction (MVO) after primary percutaneous coronary intervention (pPCI) leads to higher incidence of both early and late complications. A number of single nucleotide polymorphisms in 9p21 chromosome have been shown to affect angiogenesis in response to ischaemia. In particular, Rs1333040 with its three genotypic vriants C/C, T/C and T/T might influence the occurrence of MVO after pPCI. Methods: We enrolled ST-elevation myocardial infarction (STEMI) patients undergoing pPCI. The Rs1333040 polymorphism was evaluated by polymerase chain reaction-restriction fragment length polymorphism using restriction endonucleases (Bsml). Two expert operators unaware of the patients' identity performed the angiographic analysis; collaterals were assessed applying Rentrop's classification. Angiographic MVO was defined as a post-pPCI Thrombolysis In Myocardial Infarction (TIMI)<3 or TIMI 3 with myocardial blush grade 0 or 1, whereas electrocardiographic MVO was defined as ST segment resolution Results: Among our 133 STEMI patients (mean age 63 +/- 11 years, men 72%), 35 (26%) and 53 (40%) respectively experienced angiographic or electrocardiographic MVO. Angiographic and electrocardiographic MVO were different among the three variants (p= 0.03 and p=0.02 respectively). In particular, T/T genotype was associated with a higher incidence of both angiographic and electrocardiographic MVO compared with C/C genotype (p=0.04 and p=0.03 respectively). Moreover, Rentrop score <2 detection rate differed among the three genotypes (p=0.03). In particular T/T genotype was associated with a higher incidence of a Rentrop score <2 as compared with C/C genotype (p= 0.02). Conclusion: Rs1333040 polymorphism genetic variants portend different MVO incidence. In particular, T/T genotype is related to angiographic and electrocardiographic MVO and to worse collaterals towards the culprit artery

A comparative study of electrochemical, spectroscopic and structural properties of phenyl, thienyl and furyl substituted ethylenes

a detailed electrochemical and photophysical comparative study of three parallel series of phenyl, thienyl and furyl substituted ethylenes has been carried out, implemented by the computational calculation of selected terms. Relationships have been highlighted between molecular structure (number and type of aromatic rings) and important functional properties (in particular, electronic features and oligomerization ability). Interestingly, some of the studied heteroaryl-ethylenes show emission in the solid state displaying an aggregation-induced emission behavior

A Comprehensive Statistical Description of Radio-through-Gamma-Ray Spectral Energy Distributions of All Known Blazars

We combined multi-wavelength data for blazars from the Roma-BZCAT catalog and analyzed hundreds of X-ray spectra. We present the fluxes and spectral energy distributions (SEDs), in 12 frequency bands from radio to γ-rays, for a final sample of 2214 blazars. Using a model-independent statistical approach, we looked for systematic trends in the SEDs; the most significant trends involved the radio luminosities and X-ray spectral indices of the blazars. We used a principal component analysis (PCA) to determine the basis vectors of the blazar SEDs and, in order to maximize the size of the sample, imputed missing fluxes using the K-nearest neighbors method. Using more than an order of magnitude more data than was available when Fossati et al. first reported trends of SED shape with blazar luminosity, we confirmed the anti-correlation between radio luminosity and synchrotron peak frequency, although with greater scatter than was seen in the smaller sample. The same trend can be seen between bolometric luminosity and synchrotron peak frequency. Finally, we used all of the available blazar data to determine an empirical SED description that depends only on the radio luminosity at 1.4 GHz and the redshift. We verified that this statistically significant relation was not a result of the luminosity-luminosity correlations that are natural in flux-limited samples (I.e., where the correlation is actually caused by the redshift rather than the luminosity)

Enantioselective voltammetry on achiral electrodes

An attractive target in electroanalysis is the availability of chiral media affording enantioselection in terms of significant peak potential difference between the antipodes of chiral probes in voltammetry experiments on achiral electrodes. Previous literature attempts pointed to enantioselectivity increasing with the structural order of the chiral medium; on the other hand, outstanding enantioselection performance has been recently observed working on electrode surfaces consisting in "inherently chiral" oligomer films [1-2]. Combining both strategies, we have recently developed two inherently chiral ionic liquids, ICILs, consisting of dialkylated bicollidinium salts, with an atropoisomeric bipyridinium cation featuring at least one octyl chain and bistrifilimide counteranions. They showed high enantioselectivity when tested even as low concentration additives in commercial achiral ionic liquid media [3] and also as chiral bulk media. Importantly, similar ability was also shown by other terms of the same family, having shorter alkyl chains and/or different counteranions, solid at room temperature but of easier synthesis. As a first tentative explanation we are considering the high supramolecular order of even simple ionic liquids at the interphase with a charged surface. A chiral additive could result in chiral reorganization of this peculiar interphase, as in the case of nematic-to-cholesteric transitions induced by chiral dopants in liquid crystals. This allowed us to include in our chiral voltammetry experiments a quite larger number of inherently chiral selectors based on different stereogenic elements, i.e., the bicollidine and bibenzimidazole atropoisomeric scaffolds and the tetrathielicene helicoidal scaffold. They all proved successful. The support of Fondazione Cariplo/Regione Lombardia "Avviso congiunto per l\u2019incremento dell\u2019attrattivit\ue0 del sistema di ricerca lombardo e della competitivit\ue0 dei ricercatori candidati su strumenti ERC - edizione 2016\u201d (Project 2016-0923) is gratefully acknowledged. [1] F. Sannicol\uf2, S. Arnaboldi, T. Benincori, V. Bonometti, R. Cirilli, L. Dunsch, W. Kutner, G. Longhi, P. R. Mussini, M. Panigati, M. Pierini, S. Rizzo, Angew. Chem. Int. Ed. 53 (2014) 2623 [2] S. Arnaboldi, P. Mussini, M. Magni, F. Sannicol\uf2, T. Benincori, R. Cirilli, K. Noworyta, W. Kutner, Chem. Sci. 6 (2015) 1706 [3] S. Rizzo, S. Arnaboldi, V. Mihali, R. Cirilli, A. Forni, A. Gennaro, A. A. Isse, M. Pierini, P. R. Mussini, F. Sannicol\uf2, Angew. Chem. Int. Ed 56 (2017) 207

Strategies for High Enantioselectivity in Electroanalysis: Implementing Inherently Chiral Selectors as Electrode Surfaces or at Electrode|Ionic Liquid Interfaces

Strategies for High Enantioselectivity in Electroanalysis: Implementing Inherently Chiral Selectors as Electrode Surfaces or at Electrode|Ionic Liquid Interfaces Patrizia R. Mussini,*1 Serena Arnaboldi1, Mirko Magni1, Sara Grecchi1, Tiziana Benincori2, Simona Rizzo3, Emanuela Licandro1, Silvia Cauteruccio1, Francesco Sannicol\uf21 1Universit\ue0 degli Studi di Milano, Dip. di Chimica, Via Golgi 19, 20133 Milano, Italy, 2 Universit\ue0 degli Studi dell'Insubria, Dip. di Scienza e Alta Tecnologia, Como, Italy 3 Istituto di Scienze e Tecnologie Molecolari, CNR, Milano, Italy E-mail: [email protected] Chiral electroanalysis could be regarded as the highest recognition degree in electrochemical sensing, implying the ability to discriminate between specular images of a given electroactive molecule in terms of significant peak potential difference. A groundbreaking strategy was recently proposed, based on the use of "inherently chiral" molecular selectors, i.e. with chirality and key functional properties originating from the same structural element. Large differences in peak potentials have been observed for the enantiomers of different chiral probes: (a) working on inherently chiral electrode surfaces consisting of thin electroactive oligomer films1 (often including macrocycle terms) electrodeposited from enantiopure inherently chiral monomers with atropisomeric or helical scaffolds; (b) working on achiral electrodes, implementing inherent chirality in their interphase with an ionic liquid medium2 exploiting the latter's peculiarly high order. Inherently chiral ionic liquids ICILs were developed as double salts of an atropisomeric 3,3\u2032-bipyridine scaffold with long alkyl chains and a suitable anion, Even more convenient, the new ICILs as well as other family terms solid at room temperature but of easier synthesis, or other inherently chiral salts, can be efficiently applied as low-concentration chiral additives in commercial achiral ionic liquids: large peak potential differences, regularly increasing with additive concentration, have been observed for the enantiomers of different probes on achiral electrodes. Work is in progress to strengthen and rationalize the first proofs of concepts by developing, characterizing and testing a wider variety of inherently chiral selectors with different chiral probes, particularly of pharmaceutical interest, with more optimized and detailed protocols, and with the support of other techniques, particularly aiming to the recognition mechanism elucidation.. The inherent chirality research is currently supported by Regione Lombardia and Fondazione Cariplo (Avviso congiunto per l\u2019incremento dell\u2019attrattivit\ue0 del sistema di ricerca lombardo e della competitivit\ue0 dei ricercatori candidati su strumenti ERC-edizione 2016, Project 2016-0923). 1 Angew. Chem., 2014, 53, 2623. Chem. Eur J. 2014, 20, 15298; Chem. Sci. 2015, 6, 1706; Anal. Bional. Chem. 2016, 408, 7243; Chem. Eur J. 2016, 22, 10839 2 Angew. Chem. 2017, 56, 2079; Electrochem. Comm. 2018, 89, 57

Enantioselective voltammetry in chiral ionic liquid media

Enantioselective voltammetry in chiral ionic liquid media P. R. Mussini1*, S. Arnaboldi1, M. Longhi1, I.F. Buzzi1, S. Grecchi1, F. Sannicol\uf21, Simona Rizzo2, Voichita Michali1, E. Licandro1, S. Cauteruccio1, T. Bellini3, G. Zanchetta3, A. Gennaro,4 A.A. Isse4, C. Chiappe5, L. Guazzelli5 1 Universit\ue0 degli Studi di Milano, Dip. di Chimica, Via Golgi 19, 20133 Milano, Italy 2 Istituto di Scienze e Tecnologie Molecolari, CNR, via Golgi 19, 20133 Milano, Italy 3 Universit\ue0 degli Studi di Milano, Dip. di Biotecnologie Mediche e Medicina Traslazionale, Via Fratelli Cervi 93, 20090 Segrate (MI), Italy 4 Universit\ue0 degli Studi di Padova, Dip.di Scienze Chimiche, Via Marzolo 1, 35131 Padova, Italy 5 Universit\ue0 degli Studi di Pisa, Dip. di Farmacia, via Bonanno 33, 56126 Pisa, Italy. *[email protected] Chiral media enabling enantiorecognition of chiral probes on achiral electrodes (in terms of significantly different peak potentials for the two probe enantiomers) represent an attractive target in voltammetry. Concerning possible ad hoc strategies, (a) on one hand, transmission of the chiral information should be more and more efficient with increasing structural order at the chiral medium| charged electrode interphase, and it has been recently shown that ionic liquid|electrode interphases are extremely well organized for many layers [1]; (b) on the other hand, outstanding enantioselection performances have been recently observed on electrode surfaces consisting in "inherently chiral" oligomer films, in which chirality originates from the whole main molecular backbone (also determining the material electroactivity), on account of a tailored torsion with high racemization barrier [2-6]. Combining both approaches, we recently developed two "inherently chiral" ionic liquids, consisting of dialkylated bicollidinium salts, with an atropisomeric bipyridinium cation featuring at least one octyl chain and bistrifilimidate counteranions.[7] They show high enantioselectivity in terms of wide potential differences for the enantiomers of a chiral probe when tested even as low concentration additives in commercial achiral ionic liquids. Importantly, similar ability (increasing with additive concentration) was also shown by other selectors of the same family, having shorter alkyl chains and/or different counteranions, and thus solid at room temperature but easier to synthesize [7]. Using such chiral selectors as additives in an achiral ionic liquid rather than as bulk media is even more attractive, since only a small quantity of the enantiopure selector is needed and a low melting point is no more required, but only sufficient solubility in the achiral ionic liquid. For instance, this allowed us to successfully exploit as additives for chiral voltammetry in ionic liquids other inherently chiral selectors based on different stereogenic elements, i.e., a bibenzimidazole atropisomeric scaffold [8,9] and a helicene one. The study provides further evidence of the general validity of the "inherent chirality" strategy, since large potential differences are observed on achiral electrodes for the enantiomers of chiral probes even of very different structure and electroactivity (like in our parallel research on inherently chiral electrodes), and possibly even in experiments with more than one chiral probe. Work is also in progress to better elucidate the process, including evaluation of the twisting power of our selectors as well as comparison with a family of ionic liquids and additives having cations derived from the natural pool, in which chirality originates from one or more stereocentres. References [1] Langmuir 2016, 32, 9507-9512. [2] Angew. Chem. Int. Ed. 2014, 53, 2623 [3] Chem. Eur. J. 2014, 20, 15298. [4] Chem. Sci. 2015, 6,1706. [5] Chem. Eur. J. 2016 , 22,10839. [6] Anal. Bioanal. Chem. 2016, 408, 7243. [7] Angew. Chem. Int. Ed. 2017, 56, 2079. [8] Electrochim. Acta 2015, 179, 250-262. [9] Electrochem. Comm. 2018, accepted. Acknowledgment. The support of Fondazione Cariplo/Regione Lombardia "Avviso congiunto per l\u2019incremento dell\u2019attrattivit\ue0 del sistema di ricerca lombardo e della competitivit\ue0 dei ricercatori candidati su strumenti ERC - edizione 2016\u201d (Project 2016-0923) to our chiral electrochemistry and electroanalysis research is gratefully acknowledged

Internet of Things for Sustainability: Perspectives in Privacy, Cybersecurity, and Future Trends

In the sustainability IoT, the cybersecurity risks to things, sensors, and monitoring systems are distinct from the conventional networking systems in many aspects. The interaction of sustainability IoT with the physical world phenomena (e.g., weather, climate, water, and oceans) is mostly not found in the modern information technology systems. Accordingly, actuation, the ability of these devices to make changes in real world based on sensing and monitoring, requires special consideration in terms of privacy and security. Moreover, the energy efficiency, safety, power, performance requirements of these device distinguish them from conventional computers systems. In this chapter, the cybersecurity approaches towards sustainability IoT are discussed in detail. The sustainability IoT risk categorization, risk mitigation goals, and implementation aspects are analyzed. The openness paradox and data dichotomy between privacy and sharing is analyzed. Accordingly, the IoT technology and security standard developments activities are highlighted. The perspectives on opportunities and challenges in IoT for sustainability are given. Finally, the chapter concludes with a discussion of sustainability IoT cybersecurity case studies

Alignment of Microarray Data

The aim in microarray data analysis is to discover patterns of gene expression and to identify similar genes. Simply comparing new gene sequences to known DNA sequences often does not reveal the function of a new gene; thus, more sophisticated techniques are in order. Nowadays, data mining techniques, and in particular the clustering process, play an important role in bioinformatics. To analyze vast amounts of data can be difficult; thus, a way to cluster similar data is needed. This chapter is devoted to illustrate the general data mining approach used in microarray data analysis, combining clustering, alignment and similarity, and to highlight a novel similarity measure capable of capturing hidden correlations between data