Thiophene-based helicenes : eclectic scaffolds in organometallic chemistry

Helicenes are ortho-annulated polycyclic aromatic compounds, endowed with an inherently chiral \u3c0-conjugated system that are intensively studied in different areas of science.1 Among helicenes, thiophene-based helicenes are emerging as an intriguing and promising class of screw-shaped structures, thanks to the presence of the thiophene rings, which confer peculiar chemical, structural, and electronic features.2 For several years, we have been interested in the synthesis and functionalization of tetrathia[7]helicenes (7-TH, Figure 1), which are configurationally stable heterohelicenes, potentially very interesting for applications in optoelectronics,3 catalysis,4 and biology.5 In particular, transition metal-based 7-TH systems are an extremely appealing class of complexes, in which the coordination of metals with the \u3c0-helical ligand, bearing proper coordinating groups, provides unusual chiral architectures. Indeed, the selective functionalization of 2 and 13 positions of the 7-TH scaffold allows the introduction of a variety of substituents, including those with efficient coordinating ability (e.g. cyano, phosphane, phosphine oxide). In this communication we report our recent studies on the synthesis and characterization of 7-TH-based organometallic complexes, and their potential applications in optoelectronics and catalysis

Synthesis and characterization of a tetrathia[7]helicenebased rhenium(I) complex

Tetrathia[7]helicenes (7-TH), formed by thiophene and benzene rings ortho-fused in an alternating fashion, are emerging as one of the most popular class of chiral helical-shaped molecules, thanks to their peculiar electronic and chiroptical properties suitable for manifold applications in different areas of science.1 In particular, transition metal-based 7-TH systems are an extremely appealing class of complexes, in which the coordination of metals with the \uf070-helical ligand, bearing appropriate coordinating functionalities, provides original chiral architectures. Indeed, the effective functionalization of the \uf061-position(s) of the terminal thiophene ring(s) of the 7-TH scaffold allows the introduction of a variety of substituents, including those with efficient coordinating ability (e.g. cyano2, phosphane3, phosphine oxide4). For example, Rh(I)5 and Au(I)6 complexes based on 7-TH phosphanes have been successfully used in the homogenous transition metal catalysis. In our ongoing studies on 7-TH-based organometallic complexes, we have focused on a novel field of investigation concerning the development of rhenium-based polynuclear complexes containing 7-TH phosphine oxide ligands. In this communication, we describe the synthesis and the characterization of a novel dinuclear rhenium(I) complex (Figure 1), along with the elucidation of its tridimensional structure by single crystal X-ray diffraction studies

Adaptive Patch Selection to Improve Vision Transformers through Reinforcement Learning

In recent years, Transformers have revolutionized the management of Natural Language Processing tasks, and Vision Transformers (ViTs) promise to do the same for Computer Vision ones. However, the adoption of ViTs is hampered by their computational cost. Indeed, given an image divided into patches, it is necessary to compute for each layer the attention of each patch with respect to all the others. Researchers have proposed many solutions to reduce the computational cost of attention layers by adopting techniques such as quantization, knowledge distillation and manipulation of input images. In this paper, we aim to contribute to the solution of this problem. In particular, we propose a new framework, called AgentViT, which uses Reinforcement Learning to train an agent that selects the most important patches to improve the learning of a ViT. The goal of AgentViT is to reduce the number of patches processed by a ViT, and thus its computational load, while still maintaining competitive performance. We tested AgentViT on CIFAR10, FashionMNIST, and Imagenette+ (which is a subset of ImageNet) in the image classification task and obtained promising performance when compared to baseline ViTs and other related approaches available in the literatur

A fine-grained approach for visual interpretability of convolutional neural networks

In this paper, we propose Multilayer network-based Visual Interpreter (MuVI), a framework for visual interpretability of Convolutional Neural Networks (CNNs) based on their mapping into multilayer networks. The peculiarity of MuVI is that it constructs a pixel-level heatmap of the salient parts of an image processed by a CNN, where the importance of each pixel depends on all layers of the CNN and not only on the final ones, as in the existing approaches in the literature. MuVI first maps the CNN into a multilayer network. It then uses this representation to identify the parts of the CNN that most influence the prediction results by extracting those paths within the multilayer network whose nodes correspond to the most active areas of the feature maps. The weight of the paths is given by the sum of the weights of the arcs corresponding to the activations across all feature maps of the CNN; this characteristic allows MuVI to consider all layers of the CNN, not just the last ones. Finally, MuVI constructs the visual interpretability heatmap by selecting the paths with the highest weights. The experimental tests performed show that MuVI is able to achieve very satisfactory results in terms of AUC insertion (0.25), AUC deletion (0.11), % Increase in Confidence (12.32), Average Drop % (51.22), Pointing Game Accuracy (0.28) and Computation time (26.226s). These results, taking all these measures together, are better than those obtained by the classical approaches already proposed in the literature, such as SmoothGrad, Grad-CAM, Grad-CAM++, and RISE. They are also comparable to state-of-the-art approaches in the literature, such as Score-CAM and HSIC

Cemented versus cementless megaprosthesis in proximal femur metastatic disease: A systematic review

the proximal femur is the long bone most commonly affected by metastatic disease. there are many treatment options, such as hip megaprostheses. a topic still widely debated in literature is non-the use of cemented or uncemented megaprostheses in this kind of patients. the purpose of this review is to examine both these surgical options to understand which of them should be preferred in metastatic patients. twelve articles were finally included in the review. eight authors used cemented mega-prostheses, two cementless megaprostheses and two authors used both techniques. better functional outcomes and lower infection rates were found in cementless mega-prostheses. more studies have to be performed to choose the better technique and improve patients’ quality of life

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

Calibration of non‐catching precipitation measurement instruments: A review

open14Non-catching type gauges are the emerging class of in situ precipitation measurement instruments. For these instruments, rigorous testing and calibration are more challenging than for traditional gauges. Hydrometeors characteristics like particle size, shape, fall velocity and density must be reproduced in a controlled environment to provide the reference precipitation, instead of the equivalent water flow used for catching-type gauges. They are generally calibrated by the manufacturers using internal procedures developed for the specific technology employed. No agreed methodology exists, and the adopted procedures are rarely traceable to internationally recognized standards. The EURAMET project 18NRM03 ‘INCIPIT’ on ‘Calibration and accuracy of non-catching instruments to measure liquid/solid atmospheric precipitation’, funded by the European Metrology Programme for Innovation and Research (EMPIR), was initiated in 2019 to investigate calibration and accuracy issues of non-catching measuring instruments used for liquid/solid atmospheric precipitation measurement. A survey of the existing models of non-catching type instruments was initially performed and this paper provides an overview and a description of their working principles and the adopted calibration procedures. Both literature works and technical manuals disclosed by manufacturers are summarized and discussed, while current limitations and metrological requirements are identified.openLanza, L. G.; Merlone, A.; Cauteruccio, A.; Chinchella, E.; Stagnaro, M.; Dobre, M.; Garcia Izquierdo, M. C.; Nielsen, J.; Kjeldsen, H.; Roulet, Y. A.; Coppa, G.; Musacchio, C.; Bordianu, C.; Parrondo, M.Lanza, L. G.; Merlone, A.; Cauteruccio, A.; Chinchella, E.; Stagnaro, M.; Dobre, M.; Garcia Izquierdo, M. C.; Nielsen, J.; Kjeldsen, H.; Roulet, Y. A.; Coppa, G.; Musacchio, C.; Bordianu, C.; Parrondo, M

Dirhenium Coordination Complex Endowed with an Intrinsically Chiral Helical-Shaped Diphosphine Oxide

A one-pot, multicomponent strategy was used to synthesize the first example of the dirhenium carbonyl coordination complex 2, in which the two metal atoms are connected through a chiral helical-shaped diphosphine oxide. Thanks to the flexibility of the helix of helicene 1, complex 2 was isolated in quite a good yield as a stable compound. It was characterized by analytical and spectroscopic techniques as well as by single-crystal X-ray analysis, which confirmed the chemical structure and the peculiar architecture of 2. In addition, computational studies were in agreement with the transitions observed in the experimental UV\u2013vis spectrum, revealing the presence of two bands with maxima at about 520 (metal-to-ligand charge transfer) and 400 nm (IL

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