A New MBH Adduct as an Efficient Ligand in the Synthesis of Metallodrugs: Characterization,Geometrical Optimization,XRD, Biological Activities,and Molecular Docking Studies

This article reports the synthesis, characterization, geometrical optimization, and biological studies of new MBH-based organometallic compounds of medicinal significance. The ligand (MNHA) was prepared via the Morita–Baylis–Hillman (MBH) synthetic route, from aromatic aldehyde containing multiple functional groups. Metal complexes were prepared in an alkaline medium and under other suitable reaction conditions. Spectral and elemental analyses were used to identify the structural and molecular formulas of each compound. Optimized geometry was determined through density functional theory (DFT) B3LYP and 6-311++ G (d,p) basis set for the MBH adduct, whereas structures of novel complexes were optimized with the semi-empirical PM6 method. Powder XRD analysis furnished the crystal class of complexes, with Co³⁺, Cr³⁺, and Mn²⁺ being cubic, while Ni²⁺ was hexagonal, and Cu²⁺ was orthorhombic. Moreover, the ligand, along with Ni²⁺ and Co³⁺ complexes, showed profound antibacterial action against S. aureus, E. coli, B. pumilis, and S. typhi. Additionally, all of the complexes were shown to persist in the positive antioxidant potential of the ligand. Contrarily, not a single metal complex conserved the antifungal potentials of the ligand.     

Entanglement Robustness via Spatial Deformation of Identical Particle Wave Functions

We address the problem of entanglement protection against surrounding noise by a procedure suitably exploiting spatial indistinguishability of identical subsystems. To this purpose, we take two initially separated and entangled identical qubits interacting with two independent noisy environments. Three typical models of environments are considered: amplitude damping channel, phase damping channel and depolarizing channel. After the interaction, we deform the wave functions of the two qubits to make them spatially overlap before performing spatially localized operations and classical communication (sLOCC) and eventually computing the entanglement of the resulting state. This way, we show that spatial indistinguishability of identical qubits can be utilized within the sLOCC operational framework to partially recover the quantum correlations spoiled by the environment. A general behavior emerges: the higher the spatial indistinguishability achieved via deformation, the larger the amount of recovered entanglement.     

Sustainable Approaches to the Synthesis of Metallophthalocyanines in Solution

This work aims to investigate more sustainable reaction conditions for the synthesis of metallophthalocyanines. Anisole, glycerol and their mixtures have been investigated as reaction media for the tetramerization of phthalonitriles. Acetates of three divalent first-transition metal cations, Co(II), Cu(II) and Zn(II), were used and several bases were tested, depending on the chosen substrates and reaction conditions, with a view to making the whole process more sustainable while ensuring its scalability. Unsubstituted phthalocyanines were synthesized to analyze the behavior of the different metal ions in terms of reactivity in the new reaction media, resulting in a general Cu > Co > Zn trend, while the nonpolar tetra-tert-butyl substitution was investigated to evaluate the synthesis of soluble derivatives in the new conditions. Furthermore, the potassium hydroxide (KOH)-aided statistical synthesis of the unsymmetrical 9(10), 16(17), 23(24)-tri-tert-butyl-2-iodophthalocyaninato zinc(II), starting from 4-tert-butylphthalonitrile and 4-iodophthalonitrile in a glycerol/anisole mixture, proceeded with a satisfactory 26% yield. Our results provide insights into the investigation of new reaction environments and the understanding of their strengths and weaknesses, with a view to further increasing the sustainability of the synthesis of metallomacrocycles with high added value while lowering their production cost.     

Modification of Amorphous Mesoporous Zirconia Nanoparticles with Bisphosphonic Acids: A Straightforward Approach for Tailoring the Surface Properties of the Nanoparticles

The use of readily prepared bisphosphonic acids obtained in few steps through a thio-Michael addition of commercially available thiols on tetraethyl vinylidenebisphosphonate enables the straightforward surface modification of amorphous mesoporous zirconia nanoparticles. Simple stirring of the zirconia nanoparticles in a buffered aqueous solution of the proper bisphosphonic acid leads to the surface functionalization of the nanoparticles with different kinds of functional groups, charge and hydrophobic properties. Formation of both chemisorbed and physisorbed layers of the bisphosphonic acid take place, observing after extensive washing a grafting density of 1.1 molecules/nm² with negligible release in neutral or acidic pH conditions, demonstrating stronger loading compared to monophosphonate derivatives. The modified nanoparticles were characterized by IR, XPS, ζ-potential analysis to investigate the loading of the bisphosphonic acid, FE-SEM to investigate the size and morphologies of the nanoparticles and ³¹P and ¹H MAS NMR to investigate the coordination motif of the phosphonate units on the surface. All these analytical techniques demonstrated the strong affinity of the bisphosphonic moiety for the Zr(IV) metal centers. The functionalization with bisphosphonic acids represents a straightforward covalent approach for tailoring the superficial properties of zirconia nanoparticles, much straightforward compared the classic use of trisalkoxysilane or trichlorosilane reagents typically employed for the functionalization of silica and metal oxide nanoparticles. Extension of the use of bisphosphonates to other metal oxide nanoparticles is advisable.     

Synthesis of amphiphilic block copolymers via ring opening polymerization and reversible addition-fragmentation chain transfer polymerization

Amphiphilic block copolymers were synthesized via a dual initiator chain transfer agent (inifer) that successfully initiated the ring opening polymerization (ROP) of l -lactide (LLA) and subsequently mediated the reversible addition-fragmentation chain transfer (RAFT) polymerization of poly(ethylene glycol) ethyl ether methacrylate (PEGEEMA). The formation of each polymer block was confirmed using ¹H nuclear magnetic resonance spectroscopy, as well as gel permeation chromatography, and comprehensive kinetics studies provide valuable insights into the factors influencing the synthesis of well-defined block copolymers. The effect of monomer concentration, reaction time, and molar ratios of inifer to catalyst on the ROP of LLA are discussed, as well as the ability to produce poly(lactide) blocks of different molecular weights. The synthesis of hydrophilic PPEGEEMA blocks was also monitored via kinetics to provide a better understanding of the role the chain transfer agent plays in facilitating the complex and sterically demanding RAFT polymerization of PEGEEMA.     

Non-maturing deposits modelling in a Ornstein-Uhlenbeck framework

This paper builds a multivariate Lévy-driven Ornstein-Uhlenbeck process for the management of non-maturing deposits, that are a major source of funding for banks. The contribution of the paper is both theoretical and operational. On the theoretical side, the novelty of this model is to include three independent sources of randomness in a Lévy framework: market interest rates, deposit rates and deposit volumes. The choice of a Lévy background driving process allows us to model rare but severe events. On the operational side, we propose a procedure to include severe volume outflows with positive probability in future scenarios simulation, explaining its implementation with an illustrative example using Italian banking sector data.     

Liquid mulch based on poly(vinyl alcohol). PVA-soil interaction

This study is meant to provide a contribution in recent developments of biodegradable polymeric materials applied in agricultural practices with particular reference to the mulching segment. Special attention has been devoted to material based on renewable resources or utilization of waste products from agro-industrial activities, thus suggesting cost-effective and environmentally sound solutions to specific social needs. In the present contribution PVA solubility at room temperature has been improved by premixing with chemical additives and proteic materials. Waste materials from ethanol production by corn fermentation and from wood industries have been used as, respectively starch-based and lignocellulosic additives. The prepared formulations were applied on the soil by conventional spraying agricultural equipment. Time of permanence of the film formed on the soil was monitored as well as the effect on corn growth and yield production. Finally, in order to investigate the final fate of the PVA applied on the soil, a test was performed in lysimeters, with half of the lysimeters cropped with maize plants. PVA amount applied for the mulching test was in order of 5-10 g PVA/1 m²; under those conditions it resulted completely absorbed and no presence of PVA was recorded in the leached solutions.     

Characteristics and degradation of hybrid composite films prepared from PVA,starch and lignocellulosics

A research cooperation between USDA and the University of Pisa led to the development of several composite blends of poly(vinyl alcohol) (PVA) and lignocellulosic fibers. The cast films were prepared by blending orange fibers (OR-fibers) and PVA with and without cornstarch to yield flexible and cohesive films. To improve properties, films were also prepared by crosslinking PVA, starch and OR-fibers with hexamethoxymethylmelamine (HMMM). Films were evaluated for their thermal stability, water permeability and biodegradation. Thermal gravimetric analyses indicated the potential usefulness of such blends in several thermoplastic applications. Films were permeable to water, and retained the moisture content in the soil while retaining their integrity. Films generally biodegraded within 30 days in compost, achieving between 50-80% mineralization. Both neat PVA and blends that had been crosslinked showed comparatively slow degradation. A possible stimulating effect of lingocellulosic fillers on the biodegradation of PVA in blends has been observed.     

ChemInform Abstract: H2O Nucleation Around Au+

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