170,691 research outputs found
Plasticity of plant development in apricot as determined by genome and surrounding light. Iacona C, Cirilli M, Silvestri C, Pistelli L., Muleo R
No full textsee pd
Using genome plasticity to generate in Vitro Rootstocks Tolerant Waterlogging in Vivo. Muleo R, Iacona C, Pistelli L., Cirilli M, Silvestri C
No full textsee pd
Crystal structure of (S)-3-(1-methylethyl)-5-[(1-naphthalenyloxy)methyl]-2-oxazolidinone, C17H19NO3
No full textThe title compd. is monoclinic, space group P21, a 8.269(9), b 6.215(9), c 14.816(8) Å, β 91.85(6)°, Z = 2, R = 0.044, Rw = 0.119 for 1213 reflections for I > 2σ. At. coordinates are given. ts structure has been solved by direct methods and refined to R=4.88% for all observed reflections.
Its overall structure is composed by a naphthyloxy and oxazolidin rings linked by a rotatable methylenic group. These rings are disposed in an almost orthogonal way because their least squared planes give a dihedral angle of 87.39(0.11)\%
The chiral selector N-(2’-S-hydroxypropyl)-N,N’-bis(3,5-dichlorobenzoyl)-1R,2R-diamino-cyclohexane
No full textThe title compound, C23H24Cl4N2O3, is a chiral selector used as a stationary phase in the chromatographic separation of enantiomers. Its structure was solved by direct methods and its absolute configuration was confirmed
The Italian journal of geosciences is increasing its appeal among geoscientists
No full textThis is an Editorial of the new Editorial Board of the Italian Journal of Geosciences, composed by Marco Balini (Milan), Hugo Bucher (Zürich), Simonetta Cirilli (Perugia), Laura Crispini (Genoa), Maurizio Mazzucchelli (Modena), and Giulio Ottonello (Genoa), which underlines the progress in the appeal of the journal among Geoscientists
Panoramic overview of unconventional approaches to detect chiral information
No full textThe concept of inherent chirality has gained considerable attention due to the possible synthesis of π-conjugated monomers that can be employed for preparing chiral electrode surfaces after electrooligomerization [1]. These materials have been used in enantiorecognition measurements involving chiral analytes, resulting in high selectivity based on diastereomeric interactions between the deposited enantiopure antipode and the probes dissolved in solution. In this context the high enantioselectivity of such chiral surfaces was used in combination with the mechanical and electrical properties of polypyrrole (Ppy) films to develop three new straightforward read-outs for the absolute on-off recognition of enantiomers of a chiral probe in solution; i) electromechanical deformation (a) [2], ii) electrochemically induced light emission (b) [3] and iii) self-induced enantioselective trajectories (c) [4]. These new approaches allow to convert chiral information present at the molecular level into macroscopic actuation, light emission or controlled trajectories. Furthermore, such systems allow correlating the output signal with the concentration of the enantiomers present in solution, even in the case of mixtures containing different ratios of the molecular antipodes.
[1] Arnaboldi, S.; Benincori, T.; Cirilli, R.; Kutner, W.; Magni, M.; Mussini, P. R.; Noworyta, K.; Sannicolo,̀ F. Chem. Sci. 2015, 6, 1706− 1711.
[2] Arnaboldi, S.; Gupta, B.; Benincori, T.; Bonetti, G.; Cirilli, R.; Kuhn, A. Anal. Chem. 2020, 92, 10042−10047.
[3] Salinas, G.; Arnaboldi, S.; Bonetti, G.; Cirilli, R.; Benincori, T.; Kuhn, A. Chirality 2021, 33, 875-882.
[4] Arnaboldi, S.; Salinas, G.; Karajic, A.; Garrigue, P.; Benincori, T.; Cirilli, R.; Bichon, S.; Gounel, S.; Mano, N.; Kuhn, A. Nat. Chem. 2021, 13, 1241-1247.
Keywords: (inherent)chirality; bipolar electrochemistry, chiral actuator, chiral swimmers, light emitting diodes
This work has been funded by the European Research Council (ERC) under the HORIZON-ERC-2021 program (grant agreement no 101040798, ERC Starting Grant CHEIR)
Spin selectivity properties displayed by chiral electrode surfaces under an external magnetic field
No full textThe combination of spintronics with magneto- electrochemistry, particularly involving truly chiral molecular spin selectors, was promoted by the discovery of the Chiral Induced Spin Selectivity (CISS) effect by Ron Naaman and coworkers, observing spin polarization in photo-ejected electrons transmitted through a thin layer of enantiopure material adsorbed on gold, acting as an electron spin filter [1].
In this frame we present an innovative set-up which includes i) a non-ferromagnetic electrode (ITO) modified with a thin electroactive chiral film (the spin filter), ii) achiral redox couples dissolved in aqueous or organic solutions and iii) an external permanent magnet which was placed near the chiral film, considering as spin filters four different types of chiral selectors (with different stereogenic elements, i.e. helix, stereogenic axis and chiral pendant). [2,3,4]
A spectacular unforeseen effect was observed by means of cyclovoltammetry (CV), in fact CV peaks recorded in the presence of achiral redox couples reveal an impressive potential shift by flipping the magnet orientation (north vs south). This effect was also specular by changing the spin injector configuration.
The importance of these studies includes possible applications in the field of spintronics, electronics, chemical sensoristic and so on and provides a striking evidence of the spin selectivity properties of chiral thin films.
References:
[1] O. B Dor, S. Yochelis, S. P. Mathew, R. Naaman, Y. Paltiel, Nat. Commun. 4 (2013), 3256.
[2] T. Benincori, S. Arnaboldi, M. Magni, S. Grecchi, R. Cirilli, C. Fontanesi, P. R. Mussini, Chem. Sci., DOI: 10.1039/C8SC04126A (2019).
[3] S. Arnaboldi, S. Cauteruccio, S. Grecchi, T. Benincori, M. Marcaccio, A. Orbelli Biroli, G. Longhi, E. Licandro P. R. Mussini, Chem. Sci., 10 (2019) 1539-1548.
[4] S. Arnaboldi, T. Benincori, A. Penoni, L. Vaghi, R. Cirilli, S. Abbate, G. Longhi, G. Mazzeo, S. Grecchi, M. Panigati, P. R. Mussini, Chem. Sci., DOI: 10.1039/C8SC04862B (2019)
Spin Filter Properties of Chiral Thin Film Highlighted by an External Magnetic Field
No full textThe study of the mutual influence between chirality, electron spin and magnetism is a well-documented field of research, in fact implications span from pure fundamental research, to chemical applications of both analytical and synthetic character, to multidisciplinary purposes.1,2 In this context the interrelated disciplines of magnetoelectrochemistry, spintronics and Spin Dependent Electrochemistry (SDE) play a crucial role. In particular, the combination of spintronics with magneto- electrochemistry, involving truly chiral molecular spin selectors, was promoted by the discovery of the Chiral Induced Spin Selectivity (CISS) effect by Ron Naaman and coworkers, observing spin polarization in photo-ejected electrons transmitted through a thin layer of enantiopure material adsorbed on gold, acting as an electron spin filter3.
Our proposed strategy is a variation of the SDE protocol, in fact the innovative set-up involves i) a non-ferromagnetic electrode (ITO as working electrode) covered by thin electroactive chiral films as electron source, ii) achiral redox couples dissolved in aqueous or organic solutions and iii) an external permanent magnet which was placed perpendicular to the electrode surface, considering as spin filters four different types of chiral selectors (with different stereogenic elements, i.e. helix, stereogenic axis and chiral pendant). 4,5,6
A spectacular unforeseen effect was observed performing cyclic voltammetry (CV) experiments under applied magnetic field, in fact the CV peaks of achiral, chemically reversible redox couples undergo impressive potential shifts by flipping the magnet orientation (north vs south), with specular results changing the film configuration.
The importance of these studies includes possible applications in the field of spintronics, electronics, chemical sensoristic and so on and provides a striking evidence of the spin selectivity properties of chiral thin films.
References:
1 G. A. Printz, Science, 1998, 282, 1660-1663.
2 P. L. Popa, N. T. Kemp, H. Majjad, G. Dalmas, V. Faramarzi, C. Andreas, R. Hertel, B. Doudin, Proc. Natl. Acad. Sci., 2014, 111, 10433-10437
3 O. B Dor, S. Yochelis, S. P. Mathew, R. Naaman, Y. Paltiel, Nat. Commun., 2013, 4, 3256-3262.
4 T. Benincori, S. Arnaboldi, M. Magni, S. Grecchi, R. Cirilli, C. Fontanesi, P. R. Mussini, Chem. Sci., 2019, 10, 2750-2757.
5 S. Arnaboldi, S. Cauteruccio, S. Grecchi, T. Benincori, M. Marcaccio, A. Orbelli Biroli, G. Longhi, E. Licandro P. R. Mussini, Chem. Sci., 2019, 10, 1539-1548.
6 . Arnaboldi, T. Benincori, A. Penoni, L. Vaghi, R. Cirilli, S. Abbate, G. Longhi, G. Mazzeo, S. Grecchi, M. Panigati, P. R. Mussini, Chem. Sci., 2019, 10, 2708-2717
Electrochemistry of, and electrochemistry in, chiral and inherently chiral ionic liquid media
No full textIonic liquids ILs are attractive media for electrochemistry and electroanalysis, since, in addition to other useful properties, they provide both solvent and supporting electrolyte; moreover, they feature an extremely well defined structure at the interphase with a charged electrode, resembling somehow a bulk liquid crystal, extending for many layers, also standing in the presence of water traces, and possibly tunable by in-situ present additives. [1-3] For this reason chiral ionic liquids (CILs), of which a rich palette is already available, are surprisingly still nearly unexplored by electrochemists, in spite of appearing quite attractive, since they could transmit chiral information more effectively than chiral organic solvents or chiral supporting electrolytes. [1]
In this context, we have recently started a detailed investigation of (a) bio-based chiral ionic liquids and (b) inherently chiral ionic liquids (ICILs), investigating both their physico-chemical and electrochemical features and their performance as media for chiral electroanalysis experiments. Our bio-based CILs featu- re cations with a building block of natural origin, including one or more localized stereocentres, from which their chirality arises (as in most so far available CILs) [4]. Instead, in our ICILs chirality is intrinsic of the whole biheteroaromatic cation, which features a stereogenic axis related to a torsion between two equal heteroaromatic moieties, with a related energy barrier too high to be overcome at room temperature, so that the ICIL can be obtained in two stable enantiopure antipodes. In inherently chiral molecules and materials both chirality and functional properties originate from the same structural element, which can coincide with the main molecular backbone; thus their chirality manifestations can be very powerful, as recently evidenced by some of us in electroanalytical, chiroptical and magneto-electrochemistry experiments with electrodes modified by inherently chiral oligomer thin films.
Actually, while interesting but (at least so far) small are the chirality effects observed working in our bio- based CILs with localized stereocentres [4], large peak potential differences have been observed for the enantiomers of very different chiral probes in CV experiments in an enantiopure bulk ICIL. Very conve- niently, impressive enantiodiscrimination is observed even using ICILs (or other related inherently chiral molecular salts, solid at room T, but of easier synthesis) as low-concentration chiral additives in common achiral ionic liquids (ILs) [5,6]. Furthermore, similar impressive performances have also been observed dissolving in an achiral IL a thiahelicene-based additive, an inherently chiral oligothiophene, but un- charged and based on a different stereogenic element, i.e. a helical scaffold. Among possible explanations we are considering the possibility of a chiral reorganization effect by the inherently chiral additives in the locally highly ordered IL structure at the interphase with the charged electrode, similarly to the well- known transitions from nematic to cholesteric order induced by chiral additives in bulk liquid crystals.
The support of Fondazione Cariplo/Regione Lombardia "Avviso congiunto per l’incremento del- l’attrattività del sistema di ricerca lombardo e della competitività dei ricercatori candidati su strumenti ERC - edizione 2016” (Project 2016-0923) is gratefully acknowledged.
[1] S. Arnaboldi, M. Magni, P.R. Mussini, Curr. Opin. Electrochem. 8 (2018) 60-72.
[2] K. Ma, R. Jarosova, G.M. Swain, G.J. Blanchard, Langmuir 32 (2016) 9507-9512.
[3] A.Lahiri Cui, T. Carstens, N. Borisenko, G. Pulletikurthi, C. Kuhl, F. Endres, J. Phys. Chem. C 120 (2016) 9341-9349.
[4] M. Longhi, S. Arnaboldi, E. Husanu, S. Grecchi, I.F. Buzzi, R. Cirilli, S. Rizzo, C. Chiappe, P.R. Mussini, L. Guazzelli, Electrochim. Acta 298 (2019) 194-209.
[5] S. Rizzo, S. Arnaboldi, V. Mihali, R. Cirilli, A. Forni, A. Gennaro, A.A. Isse, M. Pierini, P.R. Mussini, F. Sannicolò, Angew. Chem. Int. Ed. 56 (2017) 2079-2082.
[6] S. Rizzo, S. Arnaboldi, R. Cirilli, A. Gennaro, A.A. Isse, F. Sannicolò, P.R. Mussini, Electrochem. Comm. 89 (2018) 57-61
Cancer incidence in people with residential exposure to a municipal waste incinerator: an ecological study in Modena (Italy), 1991-2005
No full textWe conducted a retrospective ecological study to assess cancer incidence during the period 1991-2005 in proximity of a municipal waste incinerator (MWI) in Modena (Italy). We identified three bands of increasing distance from the MWI, up to a radius of 5 km and used the residence as surrogate marker of the exposure. Residential history for Modena's population was reconstructed and residents were associated to the most appropriate census unit. Age-standardized incidence ratios (ASR) and standardized incidence ratios (SIR) were estimated for all cancers and selected sites. Variations in cancer incidence were investigated using space and space-time scan statistic. Deprivation index was taken into account as potential confounding factor. During the 15-year study period, 16,443 new cases of cancer were diagnosed among residents in Modena. The space-time clustering test identified three significant clusters but their shapes were not associable to the MWI exposition. The purely spatial analysis not showed statistically significant clusters. The SIR computed for all cancers and selected sites did not show any excess of risk in the area closest to the plant. Higher SIR for leukaemia was found in the second band from MWI (2-3.5 km) for females (SIR, age and DI adjusted: 1.35, 95%CI: 1.01-1.79) and for both sexes (SIR, age and DI adjusted: 1.28, 95%CI: 1.03-1.57), but not a spatial trend was observed, thus excluding a possible link with MWI. In conclusion, bearing in mind the intrinsic limits of the study, the results suggest that there is no detectable increase of cancer risk for people living in proximity to the Modena MWI
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