Mechanochemical preparation of donor/acceptor adducts based on coronene and silver(i) pyrazolate metallacycles

The preparation of materials having optical properties is a fertile area of research because of their application in OLEDs, sensors, and semiconducting materials science field. Moreover, considering environmental concerns, there is an increasing need in the scientific community to enhance the preparative methods using eco-friendly approaches. In this work, the mechanochemical liquid assisted grinding (LAG) method is applied for the syntheses of hybrid organometallic/organic materials made of pi-acidic silver(i) or copper(i) metallacycles, with bridging ligands such as 3,5-bis(trifluoromethyl)pyrazolate or 3,5-dinitro-pyrazolate, and coronene, a highly symmetric polycyclic aromatic molecule (PAH). The LAG method was monitored by FT-IR spectroscopy and SEM; the former was applied to study the slight structural modification upon interactions, and the latter was used to depict the changes in the solid surface morphology upon CH2Cl2-assisted grinding. On the other hand, the dissolution of the materials reversibly yields the starting compounds. The stacked materials were characterized by elemental and TGA analyses, and photoluminescence (PL), and IR spectroscopies. The PL study highlights the room temperature quenching of the coronene emissions at 505 nm, indicating the occurrence of dispersive electrostatic interactions. Interestingly, the solid-state UV-Vis study allowed the calculations of direct (2.27 eV) and indirect (2.78 eV) band gaps for the D/A adduct {[3,5-(CF3)2pz]Ag}3@coronene, 1, with values featuring the materials in the semiconductor band gap range, useful for application in OFETs or OPVs

Coinage Metal Compounds With 4-Methoxy-Diphenylphosphane Benzoate Ligand Inhibit Female Cancer Cell Growth

In the continuous effort to find new metal-based compounds as alternatives to platinum related anticancer drugs, 11th group metal phosphane compounds have been thoroughly considered. Tris-arylphosphane metal derivatives have been extensively considered heteroleptic metal compounds exhibiting remarkable cytotoxic activities. Functional groups in the aryl moieties modulate the activity reinforcing or eliminating it. Previous works have highlighted that the presence of hydrophilic groups in the phosphane ligands, such as COOH or OH, hampers the anticancer activity of gold azolate/PPh3 compounds. To increase the polarity of the triarylphosphane ligand without affecting the activity, we considered the preparation of esters starting from the 4-diphenylphosphanebenzoic acid. The resulting phosphanes are poorer donators than the PPh3, leading to poly-phosphane M(I) compounds, and they exhibit intense emissive properties. A homologous series of L3MX-type compounds (where M = Au and X = Cl, M = Cu and X = BF4, and M = Ag and X = PF6) were obtained with the 4-methoxy-diphenylphosphane benzoate. The homologous metal compounds have been characterized by analytical and spectroscopic methods and, remarkably, their formation was associated with high frequencies of 31P NMR chemical shift variations (5–35 ppm in CDCl3). The new complexes and the ligand were evaluated on sensitive and cisplatin-resistant human tumor cell lines. The ligand is ineffective on cells while the complexes exert a notable antiproliferative effect. The homologous series of the L3MX complexes were able to significantly reduce the cell viability of human triple-negative breast cancer cells (MDAMB- 231), representing the most aggressive subtype of breast cancer, and of ovarian carcinoma (A2780). Among these coinage metal compounds, L3AgPF6 results the most interesting, showing the lowest GI50 values in all cell lines. Interestingly, this silver complex is more cytotoxic than cisplatin, taken as a reference drug. The investigation of the mechanism of action of L3AgPF6 in A2780 cells highlighted the induction of the apoptotic pathway, the depolarization of the mitochondrial inner membrane, and a significant accumulation in cells

An Image-Based Computational Fluid Dynamics Study of Mitral Regurgitation in Presence of Prolapse

Purpose: In this work we performed an imaged-based computational study of the systolic fluid dynamics in presence of mitral valve regurgitation (MVR). In particular, we compared healthy and different regurgitant scenarios with the aim of quantifying different hemodynamic quantities. Methods: We performed computational fluid dynamic (CFD) simulations in the left ventricle, left atrium and aortic root, with a resistive immersed method, a turbulence model, and with imposed systolic wall motion reconstructed from Cine-MRI images, which allowed us to segment also the mitral valve. For the regurgitant scenarios we considered an increase of the heart rate and a dilation of the left ventricle. Results: Our results highlighted that MVR gave rise to regurgitant jets through the mitral orifice impinging against the atrial walls and scratching against the mitral valve leading to high values of wall shear stresses (WSSs) with respect to the healthy case. Conclusion: CFD with prescribed wall motion and immersed mitral valve revealed to be an effective tool to quantitatively describe hemodynamics in case of MVR and to compare different regurgitant scenarios. Our findings highlighted in particular the presence of transition to turbulence in the atrium and allowed us to quantify some important cardiac indices such as cardiac output and WSS

Hydrologic control on natural land subsidence in the shallow coastal aquifer of the Ravenna coast, Italy

Abstract. Multiple processes contributing to natural land subsidence in a shallow coastal aquifer near Ravenna (Italy) were identified by analysing the relationships among different data set time series (water table level, rainfall, land reclamation drainage, sea level, etc.) and establishing the correlations with vertical ground motion observed at a high-resolution settlement gauge. Our study highlights the presence of three deformation components related to different processes controlling land subsidence: elastic, delayed-elastic, and irreversible (plastic) components. The elastic and delayed-elastic components are closely related to water table fluctuations that change the effective stress in two portions of the coastal aquifer at a daily (in the sandy unconfined portion) and seasonal time scales (in the layered clay-rich semi-confined prodelta portion), respectively. The irreversible component represents the trend in the land subsidence time series and is due to primary consolidation (pore pressure dissipation) of the fine-grained prodelta levels above where the settlement gauge is located. The amplitudes of the elastic component can be up to 0.2–0.3 mm whereas the amplitude of the delayed-elastic component reaches 0.89 mm. The primary consolidation rate of deformation is 0.9 mm yr−1 and constrains the likely age of prodelta sediments deposition to 1300–2800 years before present. The delayed-elastic subsidence rate has similar magnitude to that due to primary consolidation and is connected to poroelastic effects in the prodelta sequence following seasonal variations in water table. Our findings are important for planning land subsidence management and monitoring strategies especially where the surface aquifer structure is heterogeneous due to different depositional settings. The natural land subsidence rate in the Holocene sediments of the shallow coastal aquifer of Ravenna (North eastern Italy) that we measured in this study accounts for 10 %–20 % of the total current land subsidence rate observed in this portion of Ravenna coastal area (10–20 mm yr−1)

Multi-Targeted Anticancer Activity of Imidazolate Phosphane Gold(I) Compounds by Inhibition of DHFR and TrxR in Breast Cancer Cells

A class of phosphane gold(I) compounds, made of azoles and phosphane ligands, was evaluated for a screening on the regards of Breast Cancer cell panels (BC). The compounds possess N-Au-P or Cl-Au-P bonds around the central metal, and they differ for the presence of aprotic or protic polar groups in the azoles and/or the phosphane moieties to tune their hydrophilicity. Among the six candidates, only the compounds having the P-Au-N environment and not displaying neither the hydroxyl nor carboxyl groups in the ligands were found active. The compounds were screened by MTT tests in SKBR3, A17, and MDA-MB231 cancer cells, and two compounds (namely the 4,5-dicyano-imidazolate-1yl-gold(I)-(triphenylphosphane, 5, and 4,5-dichloro-imidazolate-1yl-gold(I)-triphenylphosphane, 6) were found very cytotoxic, with the most active with an IC50 value of 3.46 μM in MDA-MB231 cells. By performing enzymatic assays in the treated cells lysates, the residual enzymatic activity of dihydrofolate reductase (DHFR) has been measured after cell treatment for 4 or 12 h in comparison with control cells. Upon 12 h of treatment, the activity of DHFR was significantly reduced in both SKBR3 and A17 cells by compounds 5 and 6, but not in human MDA-MB231 cells; interestingly, it was found remarkably high after 4 h of treatment, revealing a time dependence for the DHFR enzymatic assays. The DHFR inhibition data have been compared to those for the thioredoxin reductase (TrxR), the most recognized molecular target for gold compounds. For this latter, similar residual activities (i.e., 37 and 49% for the match of SKBR3 cells and compound 5 or 6, respectively) were found. Binding studies on the regards of ct-DNA (calf-thymus-DNA) and of plasma transporters proteins, such as BSA (bovine serum albumin) and ATF (apo transferrin), were performed. As expected for gold compounds, the data support strong binding to proteins (Ksv values range: 1.51 ÷ 2.46 × 104 M−1) and a weaker interaction with ct-DNA's minor groove (Ksv values range: 1.55 ÷ 6.12 × 103 M−1)

Turbulent blood dynamics in the left heart in the presence of mitral regurgitation: a computational study based on multi-series cine-MRI

In this work, we performed a computational image-based study of blood dynamics in the whole left heart, both in a healthy subject and in a patient with mitral valve regurgitation. We elaborated multi-series cine-MRI with the aim of reconstructing the geometry and the corresponding motion of left ventricle, left atrium, mitral and aortic valves, and aortic root of the subjects. This allowed us to prescribe such motion to computational blood dynamics simulations where, for the frst time, the whole left heart motion of the subject is considered, allowing us to obtain reliable subject-specifc information. The fnal aim is to investigate and compare between the subjects the occurrence of turbulence and the risk of hemolysis and of thrombi formation. In particular, we modeled blood with the Navier–Stokes equations in the arbitrary Lagrangian–Eulerian framework, with a large eddy simulation model to describe the transition to turbulence and a resistive method to manage the valve dynamics, and we used a fnite element discretization implemented in an in-house code for the numerical solution

Synchrotron characterization of hexagonal and cubic lipidic phases loaded with azolate/phosphane gold(I) compounds: a new approach to the uploading of gold(I)-based drugs

none9Gold(I) phosphane compounds have recently attracted a renewed interest as potential new protagonists in cancer therapy. A class of phosphane gold(I) complexes containing azolate ligands has been successfully tested against several cancer cell lines and, in particular, against basal-like breast (BLB) cancer, a form characterized by strongly severe diagnosis and short life lapse after classic chemotherapy. Even though the anticancer activity of gold(I) phosphane compounds is thoroughly ascertained, no study has been devoted to the possibility of their delivery in nanovectors. Herein, nonlamellar lyotropic liquid crystalline lipid nanosystems, a promising class of smart materials, have been used to encapsulate gold(I) azolate/phosphane complexes. In particular, ((triphenylphosphine)-gold(I)-(4,5-dichloroimidazolyl-1H-1yl)) (C-I) and ((triphenylphosphine)-gold(I)-(4,5-dicyanoimidazolyl-1H-1yl)) (C-II) have been encapsulated in three different lipid matrices: monoolein (GMO), phytantriol (PHYT) and dioleoyl-phosphatidylethanolamine (DOPE). An integrated experimental approach involving X-ray diffraction and UV resonant Raman (UVRR) spectroscopy, based on synchrotron light and attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, has been employed to establish the effects of drug encapsulation on the structure and phase behavior of the host mesophases. The results indicate that gold(I) complexes C-I and C-II are successfully encapsulated in the three lipid matrices as evidenced by the drug-induced phase transitions or by the changes in the mesophase lattice parameters observed in X-ray diffraction experiments and by the spectral changes occurring in UV resonant Raman spectra upon loading the lipid matrices with C-I and C-II.openPaola Astolfi, Michela Pisani, Elisabetta Giorgini, Barbara Rossi, Alessandro Damin, Francesco Vita, Oriano Francescangeli, Lorenzo Luciani, Rossana GalassiAstolfi, Paola; Pisani, Michela; Giorgini, Elisabetta; Rossi, Barbara; Damin, Alessandro; Vita, Francesco; Francescangeli, Oriano; Luciani, Lorenzo; Galassi, Rossan

Daidzein plus isolase associated with zinc improves clinical symptoms and quality of life in patients with LUTS due to benign prostatic hyperplasia: Results from a phase I-II study

Objective: In the last years there is a growing interest in nutraceutical substances that seems able to improve clinical symptoms in patients with lower urinary tract symptoms (LUTS) due to benign prostatic hyperplasia (BPH). In this paper, we evaluated both efficacy and safety of a combination of daidzein with isolase and zinc in patients with LUTS due to BPH. Materials and methods: In a phase I-II study clinical trial we enrolled patients with clinical and instrumental diagnosis of LUTS associated to BPH that received a six-month treatment with a combination of daidzein with isolase and zinc (1 tablet/day). Clinical, laboratory and instrumental analyses were carried out at the time of admission (T0) and 6 months after the ending of the treatment (T1). The Italian version of International Prostatic Symptom Score (IPSS), International Index of Erectile Function (IIEF-5) and Quality of Well-Being (QoL) questionnaires were used. The development of adverse drug reactions (ADRs) and drug interactions (DDIs) were recorded using the Naranjo scale and drug interaction probability scale. Student's t test and Anova test were used for statistical analysis, and the threshold of statistical significance was set at P < 0.05. Results: We enrolled 71 patients, 62 (87.3%) completed the follow-up and we documented a significant differences between T0 and T1 in terms of IPSS [21.5 ± 1.2 vs 16.2 ± 1.5; (-4.8); p < 0.001], Cmax [9.7 ± 3.7 vs 15.3 ± 2.5; (+5.6); p < 0.001] and QoL [0.56 ± 0.15 vs 0.84 ± 0.19; (+0.28); p < 0.001]. In contrast, no significant difference were recorded in terms of IIEF-5 [p = 0.50] and PSA [p = 0.67]. Finally, we did not record any significant ADRs or DDIs during the study. Conclusions: In this study, we documented that a combination of daidzein with isolase and zinc, reduces the clinical symptoms of LUTS and improves the quality of life in patients with BPH, without the development of ADRs or DDIs

Technique for supine percutaneous nephrolithotomy

Percutaneous nephrolithotomy is the gold standard for large kidney stones. Supine approach has proved to be safe and effective. Herein we present an educational video about our stepwise technique of supine PCNL in a safe way

Libertatis dulcedo. Omaggio di allievi e amici a Giovannella Cresci Marrone

Nel 2021 Giovannella Cresci Marrone, Professore Ordinario di Storia Romana presso l’Università Ca’ Foscari Venezia, è andata in pensione. Il volume ripercorre i suoi diversi interessi, attraverso la prospettiva di colleghi che con lei hanno condiviso esperienze particolarmente importanti dal punto di vista professionale e personale. All’indagine dei nuclei tematici che hanno caratterizzato la sua attività di ricerca segue una riflessione sugli aspetti maggiormente innovativi della sua didattica e del suo impegno istituzionale. Il volume si configura come un riconoscimento del fondamentale ruolo che Giovannella ha rivestito per i suoi numerosi allievi, i suoi moltissimi studenti e per tutti coloro che hanno in diversi modi potuto trarre profitto dal suo magistero.This book is a collection of essays in honour of Giovannella Cresci Marrone, Professor of Roman History at Ca’ Foscari University of Venice, on the occasion of her retirement on 1 October 2021. The volume explores Giovannella’s interests through the eyes of a group of colleagues, who, over the years and since the very beginning of her academic career, have shared with her significant experiences in a professional and personal capacity. The essays cover the main domains of Giovannella’s scientific research: epigraphy and regional history, ancient writing cultures, historiography and political history, from the Greek classical period to the uses of the past in the twentieth century. Specific attention is given to the multiple patterns through which different areas of Italy were incorporated into the Roman world and to the scrutiny of several key figures of ancient history, such as Themistocles, Alexander the Great, Caesar, and Augustus, as well as their receptions. They also consider Giovannella’s innovative teaching methodologies and her commitment to the institutions at which she worked. The book is conceived as a tribute to the crucial role that Giovannella has played for her many pupils, for her countless students, and for all those who have had the privilege of benefiting in different ways from her mentorship