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Acta Palaeomedica - International Journal of Palaeomedicine
In this issue we celebrate traditional osteological methods in papers addressing deviant burials and post-mortem mutilation as well as evidence of autoptic practices, respectively from Tuscany and Spain, a comprehensive analysis of malaria in Ancient Egypt, and congenital spine anomalies in prehistoric Sicily. This set of papers is corroborated by additional contributions from Australia and Germany presenting bioarchaeological findings in South Australia and the importance of plaster casts in German collections.
Editor-in-Chief
Francesco M. Galassi
Managing Editor
Elena Varott
Rationalization of monomer/cyclotrimer chemistry of coinage metals azolate compounds leading to unexpected biological properties
Rationalization of monomer/cyclotrimer chemistry of coinage metals azolate compounds leading to unexpected biological properties
Rossana Galassi
School of Science and Technology, Chemistry Division, Camerino University, Via Sant’ Agostino, 1 62032 Italy. E-mail: [email protected]
Crystal structures of cyclic trinuclear complexes of the d10 monovalent coinage metals are fascinating for their elegant self-assembly, their supramolecular stackings based on non-classic chemical bonding, and for their remarkably - rich optoelectronic properties. The significance of this class of complexes embraces cross-sectional chemistry areas, including metalloaromaticity, metallophilic bondings, supramolecular assemblies, M-M bonded excimers and exciplexes, and host/guest chemistry. Moreover, this class of complexes are surprising for their fascinating luminescence properties and their acid/base behavior.[1] Their synthesis proceeds by combining azolate salts with coinage metal precursors, where the departure of a leaving group i. e. PPh3, Me2S or the treatment with the M2O affords to cyclic rearrangements. However, it is possible to modulate the syntheses and the properties of the final products by changing the susbstituents in the azolate. By introducing withdrawing groups such as CF3, NO2, Cl, CN, mononuclear derivatives can be obtained showing solubility properties in aqueous media: these latter azolate gold(I) phosphane derivatives were found to be good candidate for biological studies. Azolate gold(I) phosphane compounds resulted to be cytotoxic on the regards of many panel of cancer cells, in addition to cis-platin resistant cells.[2] Moreover, they inhibit pivotal enzymes, such as the seleno dependent ThioredoxinaReductase (TrxR),[2]and an enzyme involved in DNA synthesis such as DeHydroFolateReductase [3] On these new azolate gold(I) phosphane compounds different cell viability assays (MTT assays) were performed on a human in vitro model of HER2-overexpressing breast cancer: SKBR-3 cells. After this preliminary screening, the most promising and effective compounds were selected to extend the study on A17 cell line, a murine preclinical model of Basal Like Breast Cancer (BLBC).[4] In this seminar, the chemistry, the characterization and the biological studies with the aforementioned azolate compounds will be presented.
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[1] R. Galassi et al. Comm. Inorg. Chem., 2015 submitted.
[2] R. Galassi et al., Dalton Trans., 2012, (41), pp 5307-5318.
[3] R. Galassi et al., Dalton Trans., 2015, (44), pp 3043-3056.
[4] M. Galiè et al., Carcinogenesis , 2005, (11), pp 1868-
Fonti per i materiali e le tecniche del disegno genovese a lapis, in (a cura di) M. C. Galassi e M. Priarone, L’underdrawing del disegno genovese. Dentro la genesi dell’opera grafica attraverso l’esame nell’infrarosso, Genova University Press, 2014, pp. 13-16
Acta Palaeomedica. International Journal of Palaeomedicine
The first issue of this journal aims to offer its new readership with a very interesting set of topics, ranging from the Black Death to family interrelations of Egyptian pharaohs, from the discovery of skeletons dated to the 4th century BC in Syracuse to the study of cranial trepanation in mummies in Cuba, and much more, including some book reviews.
[Editor-in-Chief: Francesco M. Galassi; Managing Editor: Varotto Elena
Coinage metals trinuclear metallocycles: old and new aspects of this class of compounds
Coinage metals trinuclear metallocycles: old and new aspects of this class of compounds
Galassi R. a, Oumarou C. S. a, Omary A. M. b, Nesterov V. b, Burini A.a
aSchool of Science and Technology, Chemistry Division, University of Camerino, Via S. Agostino 1, 62032 Camerino; e-mail: [email protected]
b Department of Chemistry, University of North Texas, Denton, 1155 Union Circle, TX 76203, USA; e-mail: [email protected]
Azoles such as imidazoles and pyrazoles are optimal bridging ligands to obtain C,N or N,N trinuclear coinage metals metallocycles. Since past decade till now, few worldwide research groups including us have focused their attention to their synthesis and characterization.[1] Moreover, the photophysical properties[2] the extended network of metallophilic bondings in the supramolecular structure and the pi-acid/pi-base chemistry[3] of these compounds directed the research to theoretical studies bringing to a better interpretation of the experimental behaviors.[4] Here we report the synthesis of new coinage metals metallocycles and their spectroscopic characterizations highlighting points of continuity with the previous analogs and new features for new perspective research lines. As in example, the 1-vinylimidazole resembles the acid-base chemistry of the 1-benzylimidazole gold(I) metallocycle, while substitution in position 4,5 of 1-benzylimidazole with electron-withdrawing group, do not allow the formation of metallocycles with the same synthethic route and mononuclear gold(I) derivatives have been obtained. The nature of the heterocycle and of the substituents, in addition to their position in the azolate ligand defines and tunes the properties of the final products.
References:
1) Galassi, R.; Burini, A.; Omary-Rawanashed, M., Omary, M. A., Comm. Inorg. Chem. 2014, in submission.
2) Rawashdeh-Omary, M. A.; Omary, M. A.; Fackler Jr, J. P, Galassi R., Pietroni, B. R.; Burini, A. J. Am. Chem. Soc 2001, 123; 9689-9691.
3) Burini, A.;. Fackler Jr, J. P; Galassi R., Grant, T. A.. Omary, M. A; Rawashdeh-Omary, M. A.; Pietroni, B. R.; Staples R. J. J. Am. Chem. Soc., 2000; 11264-11265.
4) Galassi, R.; Ricci, S.; Burini, A.; Macchioni, A; Marmottini, F.; Tekarli, S. M.; Nesterov, N.V.; Omary, M. A. Inorg. Chem. 2013, 52, 14124-14137
Supramolecular Chemistry and photophysical Properties of a New Gold (I) Cyclic Trinuclear Complex, [Au(μ-C2,N3-1-vinylimidazole)]3
Supramolecular Chemistry and photophysical Properties of a New Gold (I) Cyclic Trinuclear Complex, [Au(μ-C2,N3-1-vinylimidazole)]3
R. Galassia, A. Burinia, C. S. Oumaroua, V. N. Nesterov b, M. A. Omary b.
a Dipartimento di Scienze Chimica, Università di Camerino, Via Sant Agostino, 1, 62032 Camerino, Italia
b Department of Chemistry, University of North Texas, Denton, TX 76203, USA
email: [email protected]
In the past years several cyclic trinuclear complexes (CTC’s) have been synthetized and characterized on the basis of the capacity of d10 transition metal ions to give bicoordinated linear compounds. This intriguing class of compounds display pi-acid/ pi-base properties that can be finely tuned by: the nature of the metal, the substituents on the ligand or the ligand itself. [1] These complexes are attractive building blocks to obtain supramolecular compounds showing interesting photopysical properties [2] or heterobimetallic cyclic trinuclear complexes with potential use in mixed-metal catalysis [3]. Here we report the synthesis of a novel gold (I) CTC, [Au(μ-C2,N3-1-vinylimidazole)]3, and the study of some photophysical properties of its supramolecular derivatives obtained by the intercalation of metal ions in between the metallocycles.
[1] S.M. Terkali, T.R. Cundari, M.A. Omary, J. Am. Chem. Soc. 2008, 130, 1669
[2] a) A. Burini, R. Bravi, J. P. Fackler Jr, Galassi R., T. A. Grant, M. A. Omary, B. R. Pietroni, R. J. Staples . Inorg. Chem. 2000, 39; 3158.b) Burini A, Fackler J. P, JR, Galassi R., Grant T. A, Omary M. A, Rawashdeh-Omary M. A, Pietroni B. R, Staples R.J. J. Am. Chem. Soc. 2000, 122; 11264.
[3] A. Mohamed, R. Galassi, F. Papa, A. Burini, J.P. Fackler , Jr. Inorg. Chem. 2006, 45, 7770-7776
[5] R. Galassi, S. Ricci, A. Burini, A. Macchioni, L. Rocchiagiani, F. Marmottini, S.M. Terkali, V.N. Nesterov, M.A. Omary, Inorg. Chem. 2013, 52, 14124-1413
INTELLIMAN. WP5 T5-3-1. Attention-Based Cloth Manipulation from Model-free Topological Representation
This dataset contains data related to a novel attention-based neural architecture capable of solving a smoothing task for deformable objects, such as clothes and fabric, by means of a single robotic arm. In particular, the dataset contains the data used for the training on a model-free learning-based policy for cloth smoothing task and the script used to collect the resulting data. The data were produced in the framework of Horizon Europe INTELLIMAN project and are presented in the publication:
K. Galassi, B. Wu, J. Perez, G. Palli and J. -M. Renders, "Attention-Based Cloth Manipulation from Model-free Topological Representation", 2024 IEEE International Conference on Robotics and Automation (ICRA), Yokohama, Japan, 2024, pp. 18207-18213, doi: 10.1109/ICRA57147.2024.10610241
Solventless VOC chemisorption by silver metallocycles
Solventless VOC chemisorption by silver metallocycles
Oumarou C. S.a, Tekarli S.,b Nesterov V.,b Omary M. A.,b Burini A.,a Galassi R.,a
aSchool of Science and Technology, Chemistry Division, University of Camerino, Via S. Agostino 1, 62032 Camerino; e-mail: [email protected]
b Department of Chemistry, University of North Texas, Denton, TX 76203, USA
Prior work has focused on detection/sensing aspects of VOCs,[1] this work proposes a method for their simultaneous filtration and removal through their strong chemisorption to a silver(I) metallocyclic trimer.[2] A solid cyclotrimer can quantitatively remove entire molar integers of VOCs (1-3 equivalents of VOCs per mole of the nitrated trimer) from the vapor phase in a solventless “green” chemical process, which is unprecedented for this class of cyclic d10 complexes.
Figure 1. Illustration of quadrupole-dipole interactions involving the [Ag(μ-Pz-2CF3)]3 or [Ag(3,5-(NO2)2pz)]3 trimers and acetonitrile using M06/CEP-31G(d). MEP surfaces are plotted in two manners, either mapped on electron density surfaces (rainbow plots with the color scale shown; isodensity = 0.0004) or positive (blue) and negative (red) regions in space (range = ± 2.2 a. u.; isodensity = 0.02)
[1] Yaghi et al., PNAS 2008, 105, 11623
[2] R. Galassi, S. Ricci, A. Burini, A. Macchioni, L. Rocchigiani, F. Marmottini, S. Tekarli, V. Nesterov, M. A. Omary, J. Am. Chem. Soc., 2013, submitted
The history of prion disease
Appeared within 'In Context' sectionAbstract not availableFrancesco M Galassi, Maciej Henneberg, Frank J Rühl
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