The reaction of 3,5-diamino-4,4?-bis(1H-pyrazole) (3,5-H2L) with copper(II) and nickel(II) acetates under solvothermal conditions led to the four mixed-metal metal-organic frameworks (MIXMOFs) [CuxNi1-x(3,5-L)] (CuxNi1-x, x = 0.05, 0.1, 0.2, 0.5), which were thoroughly characterized in the solid state. The textural analysis unveiled their macroporous nature, with BET specific surface areas falling in the 140-240 m2/g range. Despite the low specific surface areas, their CO2 adsorption capacity at ambient temperature and pressure (highest: Cu0.05Ni0.95 and Cu0.2Ni0.8; 5.6 wt % CO2) and isosteric heat of adsorption (highest: Cu0.2Ni0.8; Qst = 26.2 kJ/mol) are reasonably high. All of the MIXMOFs were tested as heterogeneous catalysts in carbon dioxide electrochemical reduction (CO2RR) in acetonitrile solution at variable potential. The best results were obtained at E = -1.5 V vs Ag/AgCl/KClsat: besides H2 from the hydrogen evolution (HER) side reaction, CO and CH4 were the main reduction products observed under the applied conditions. Cu0.05Ni0.95 showed the best performance with an overall [CO + CH4] conversion of ~200 ppm and a Faradaic efficiency of ~52%. CO2RR product selectivity seems to be correlated to the most abundant metal ion in the catalyst: while the Ni-richest phase Cu0.05Ni0.95 mainly produces CO, Cu0.5Ni0.5 mostly generates CH4. The preferential CO2 adsorption sites determined through GCMC simulations are close to the metal centers. For low copper loading, a prevalent end-on interaction of the type O=C=O···NiII is observed, but the progressive increase of the copper content in the MIXMOF equals the metal-gas distances with simultaneous MII···O=C=O···MII activation by two nearby metal ions and a bridging CO2 coordination mode. The analysis of the spent catalyst revealed partial formation of metal nanoparticles under the applied strongly reducing conditions.

Metal terpyridine complexes have gained substantial interest in many application fields, such as catalysis and supramolecular chemistry. In recent years, the biological activity of terpyridine and its metal complexes has aroused considerable regard. On this basis, we synthesised new terpyridine derivatives of trehalose and glucose to improve the water solubility of terpyridine ligands and target them in cancer cells through glucose transporters. Glucose derivative and its copper(II) and iron(II) complexes showed antiproliferative activity. Interestingly, trehalose residue reduced the cytotoxicity of terpyridine. Moreover, we tested the ability of parent terpyridine ligands and their copper complexes to inhibit proteasome activity as an antineoplastic mechanism.

Electron paramagnetic resonance (EPR) spectroscopy is a nondestructive, noninvasive, highly sensitive and accurate analytical technique applicable to chemical species that possess one or more unpaired electrons. The first part of this chapter summarizes the basic principles, instrumentation and methodology of EPR spectroscopy. In the second part, the main applications of EPR to the study of indigenous and transient organic free radicals present in soil humic substances and their interactions with organic chemicals, together with paramagnetic transition metal ions in soil constituents, are described. The chapter ends with a brief overview of spin derivatization approaches and conclusion and perspectives.

The aim of this research is to study the effect of silica gel and montmorillonite clay (maghnite), often used as adsorbents in chemical applications, on the structure of hybrid poly(vinylidene fluoride) (PVDF) membranes. The membranes were synthesized using the precipitation-phase inversion method. In order to recognize the different structural changes of the PVDF in the samples various characterization techniques were tested, such as the contact angle, the scanning electron micros-copy, the attenuated total reflectance-Fourier-transform infrared spectroscopy, porosity, measure-ment of pore size and measurements of hydraulic permeability. The review of the results allowed us to understand the effects of silica gel and maghnite on the PVDF membranes in terms of crystal phases transition, hydrophobic character, porosity, morphology and pure water permeability. The synthesized membranes were tested for the removal of copper and nickel from aqueous solution.

Face masks are an effective protection tool to prevent bacterial and viral transmission. However, commercial face masks contain filters made of materials that are not capable of inactivating either SARS-CoV-2. In this regard, we report the development of an antiviral coating of polyurethane and Copper nanoparticles on a face mask filter fabricated with a spray technology that is capable of inactivating more than 99% of SARS-CoV-2 particles in 30 min of contact.

The transition away from fossil fuel and ultimately to a carbon-neutral energy sector requires new storage materials for hydrogen and methane as well as new solutions for carbon capture and storage. Among the investigated adsorbents, activated carbons are considered especially promising because they have a high specific surface area, are lightweight, thermally and chemically stable, and easy to produce. Moreover, their porosity can be tuned and they can be produced from inexpensive and environmentally friendly raw materials. This study reports on the development and characterization of activated carbons synthesized starting from amorphous cellulose with and without the inclusion of copper nanoparticles. The aim was to investigate how the presence of different concentrations of metal nanoparticles affects porosity and gas storage properties. Therefore, the research work focused on synthesis and characterization of physical and chemical properties of pristine and metal-doped activated carbons materials and on further investigation to analyze their hydrogen, methane and carbon dioxide adsorption capacity. For an optimized Cu content the microporosity is improved, resulting in a specific surface area increase of 25%, which leads to a H uptake (at 77 K) higher than the theoretical value predicted by the Chahine Rule. For CH, the storage capacity is improved by the addition of Cu but less importantly because the size of the molecule hampers easy access of the smaller pores. For CO a 26% increase in adsorption capacity compared to pure activated carbon was achieved, which translated with an absolute value of over 48 wt% at 298 K and 15 bar of pressure.

Glycerol is the main by-product of biodiesel production; its upgrading to more valuable products is a demanding issue. Hydrogenolysis to 1,2-propanediol is one of the most interesting processes among the possible upgrading routes. In this study, we propose novel copper/zirconia catalysts prepared by advanced preparation methods, including copper deposition via metal-organic framework (MOF) and support preparation via the sol-gel route. The catalysts were characterized by N physisorption, X-ray diffraction, Scanning Electron Microscopy, H-TPR and NH-TPD analyses and tested in a commercial batch reactor. The catalyst prepared by copper deposition via MOF decomposition onto commercial zirconia showed the best catalytic performance, reaching 75% yield. The improved catalytic performance was assigned to a proper combination of redox and acid properties. In particular, a non-negligible fraction of cuprous oxide and of weak acid sites seems fundamental to preferentially activate the selective pathway. In particular, these features avoid the overhydrogenolysis of 1,2-propanediol to 1-propanol and enhance glycerol dehydration to hydroxyacetone and the successive hydrogenation of hydroxyacetone to 1,2-propanediol.

Hyaluronic acid (Hy) is a glycosaminoglycan widely distributed in humans and it is the main component of the extracellular matrix. The wide range of physiological functions includes hydration and turgidity maintenance of tissue, extracellular matrix structure, regulation of innate immunity, and protection and lubrication of joints. The molecular and mechanical properties make this biocompatible polymer very used for several applications, such as tissue engineering, treatment of osteoarthritis and drug targeting [1,2]. The potential applications of Hy has been recently widen by the conjugation with carnosine (Car), a multifuntional dipeptide widely distributed in several animal species. Also this dipeptide exerts a variety of physiological properties, including antioxidant, antiglycating, and antiaggregant abilities [3]. The bioconjugation of carnosine effectively inhibits the rapid dipeptide degradation in serum catalyzed by carnosinase [4], making the new HyCar derivative [5] a promising compound to better treat several diseases and/or prevent their onset. Based on these data, a series of Hy-Car derivatives have been synthesized and patented by us in recent years, by using two different molecular weights (200 and 700 kDa) and different loading percentages of carnosine. All of them have been structurally characterized. The ability of the HyCar derivatives to inhibit the aggregation of the amyloid-? peptide (whose dyshomeostasis is involved in the onset of Alzheimer's disease) and the relative toxicity has been recently reported [6]. Moreover, The antioxidant property of the HyCar derivatives and that of their copper(II) complexes has been tested by using several assays and methodological approaches. References [1] Kogan G, ?oltés L, Stern R, Gemeiner P, Biotechnol. Lett. 2007, 29, 17-25. [2] Yadav AK, Mishra P, Agrawal GP, J. Drug Target. 2008, 16, 91-107. [3] Bellia F, Vecchio G, Cuzzocrea S, Calabrese V, Rizzarelli E, Mol. Aspects Med., 2011, 32, 258-266. [4]Bellia F, Vecchio G, Rizzarelli E, Amino Acids 2012, 43, 153-163. [5]Sciuto S, Greco V, Rizzarelli E, Bellia F, Lanza V, Vaccaro S, Messina L, WO2016016847A1. [6]Greco V, Naletova I, Ahmed IMM, Vaccaro S, Messina L, La Mendola D, Bellia F, Sciuto S, Satriano C, Rizzarelli E, Sci. Rep. 2020, 10, 15998.

Nerve growth factor (NGF) is a protein essential to neurons survival, which interacts with its receptor as a non-covalent dimer. Peptides belonging to NGF N-terminal domain are able to mimic the activity of the whole protein. Such activity is affected by the presence of copper ions. The metal is released in the synaptic cleft where proteins, not yet identified, may bind and transfer to human copper transporter 1 (hCtr1), for copper uptake in neurons. The measurements of the stability constants of copper complexes formed by amyloid beta and hCtr1 peptide fragments suggest that beta-amyloid (A?) can perform this task. In this work, the stability constant values of copper complex species formed with the dimeric form of N-terminal domain, sequence 1-15 of the protein, were determined by means of potentiometric measurements. At physiological pH, NGF peptides bind one equivalent of copper ion with higher affinity of A? and lower than hCtr1 peptide frag-ments. Therefore, in the synaptic cleft, NGF may act as a potential copper chelating molecule, ion-ophore or chaperone for hCtr1 for metal uptake. Copper dyshomeostasis and mild acidic environment may modify the balance between metal, NGF, and A?, with consequences on the metal cellular uptake and therefore be among causes of the Alzheimer's disease onset.

Preferential oxidation of carbon monoxide in hydrogen-rich streams needs a suitable catalyst that selectively oxidizes CO avoiding H2 oxidation. Among the proposed catalysts, copper oxide supported on ceria (CuO/CeO2) received wide interest due to its intrinsic activity and selectivity and low cost with respect to noble metals. In particular, it has been shown that the performances are significantly affected by optimizing the copper-ceria interaction, and then the copper dispersion. In this light, reducing to nanoscale levels has been proven to be the solution. In this chapter, results of the effect of nano and subnano structures of CuO/CeO2 catalysts on the CO-PROX performance are reviewed and critically discussed. At nanosize, Cu dispersion and oxygen mobility are both enhanced. Furthermore, the copper reduction to the metallic Cu (H2 oxidation sites) is limited and CO2 desorption is activated at lower temperatures. The role of dopants and/or supports as graphene and carbon nanotubes in improving the intrinsic activity and the resistance to the inhibiting effect of carbon dioxide and water vapor are also discussed, highlighting the effect of dopants on the modification of the redox properties by increasing bulk and/or surface oxygen vacancies.

We study surface charge transfer doping of exfoliated black phosphorus (bP) flakes by copper using scanning tunneling microscopy (STM) and spectroscopy (STS) at room temperature. The tunneling spectra reveal a gap in correspondence of Cu islands, which is tentatively attributed to Coulomb blockade phenomena. Moreover, using line spectroscopic measurements across small copper islands, we exploit the potential of the local investigation, showing that the n-type doping effect of copper on bP is short-ranged. These experimental results are substantiated by first-principles simulations, which quantify the role of cluster size for an effective n-type doping of bP and show an electronic decoupling of the topmost bP layer from the underlying layers driven by the copper cluster, consistent with the Coulomb blockade interpretation. Our results provide novel understanding--difficult to retrieve by transport measurements--of the doping of bP by copper, which appears promising for the implementation of ultrasharp p-n junctions in bP.

Crystallization of adducts of simple copper(I) and silver(I) salts (MX) with triphenylphosphine from 'N,N,N?,N'-tetramethylethylenediamine', 'tmeda', has yielded adducts of 1:1:1 MX:PPh3:tmeda stoichiometry, all of which have been characterized by room temperature single crystal X-ray structure determinations. In all adducts, the complex is mononuclear [M(PPh3)(N,N?-tmeda)X] with four-coordinate N2PMX metal atom environments (M = Cu, X = Cl, Br, I; M = Ag, X = Cl or NO3). The tricyclohexylphosphine species [Ag(Pcy3)(N,N?-tmeda)(ONO2)], also in a N2PAgX metal environment, has been defined. A number of similar silver(I) adducts are obtained by using 1,2-diaminopropane, 'pn' as solvent. The chloride, bromide and iodide complexes are isomorphous, the complexes being mononuclear, [Ag(PPh3)(pn)X], with four-coordinate N2PAgX environments, the pn ligand chelating. An isomorphous arsenic analogue of the bromide has also been isolated. All complexes have been characterized by IR and NMR (1H and 31P) spectroscopy.

We report the first example of cooperative catalysis by DBU and CuCl2, which allows the carboxylation of homopropargylic amines to high value added 6-methylene-1,3-oxazin-2-ones. This reaction also represents the first efficient method for the catalytic incorporation of CO2 into an acyclic substrate to give oxazinones. DFT calculations are in agreement with a mechanism involving: a) deprotonation of the substrate by DBU; b) CO2 capture with formation of a copper carbamate; c) 6-exo-dig cyclization through intramolecular triple bond insertion; and d) protonolysis, with regeneration of DBU and CuCl2 catalysts. The structure of a representative product has been confirmed by XDR analysis. (C) 2020 Elsevier Inc. All rights reserved.

Copper plays an important role as a regulator in many pathologies involving the angiogenesis process. In cancerogenesis, tumor progression, and angiogenic diseases, copper homeostasis is altered. Although many details in the pathways involved are still unknown, some copper-specific ligands have been successfully used as therapeutic agents. Copper-binding peptides able to modulate angiogenesis represent a possible way to value new drugs. We previously reported that a fragment (VEGF73-101) of vascular endothelial growth factor (VEGF165), a potent angiogenic, induced an apoptotic effect on human umbilical vein endothelial cells. The aim of this study was to investigate the putative copper ionophoric activity of VEGF73-101, as well as establish a relationship between the structure of the peptide fragment and the cytotoxic activity in the presence of copper(II) ions. Here, we studied the stoichiometry and the conformation of the VEGF73-101/Cu(II) complexes and some of its mutated peptides by electrospray ionization mass spectrometry and circular dichroism spectroscopy. Furthermore, we evaluated the effect of all peptides in the absence and presence of copper ions by cell viability and cytofuorimetric assays. The obtained results suggest that VEGF73-101 could be considered an interesting candidate in the development of new molecules with ionophoric properties as agents in antiangiogenic therapeutic approaches.

In this work the warpage of a power modules ceramic substrates due to temperature variation has been numerically calculated. It has been used a not linear finite element model, which account the experimentally characterized material properties, including the copper elastoplasticity. Model results have been compared with dedicated interferometric measurements to validate the model. As application example, it has been calculated the benefit in terms of temperature warpage realized with a different substrate design option.

Soil tends to strongly retain heavy metals (HM) in their colloids and accumulate them. Edaphic contamination by HM compounds not only implies a detriment on the provided ecosystem services but also a risk for the environment and the health of living beings. The most common soil decontamination techniques involve high costs and environmental alterations. In this context, bioremediation methods are most appropriate as they stimulate the processes that naturally occur in soil. Among them, phytoremediation is a sustainable alternative. The vast majority of plant species are able to associate with arbuscular mycorrhizal fungi (AMF). This association plays a key role in the maintenance of functionality and diversity of ecosystems, and it also improves the survival and tolerance of plants to adverse conditions, enhances edaphic structure and increase the volume of explored soil, through the formation of hyphal networks. For this, it is considered that the AMF increase the efficiency of the bioremediation processes by adsorbing or absorbing the HM through the hyphal network or translocating it towards the host plant. The microPIXE technique allows to know the HM accumulation and distribution patterns in plants and microorganisms, being a valuable tool in studying where HM accumulate during the arbuscular mycorrhizal symbiosis. This work aims to use this technique to quantify and to map the location of copper (Cu), a very common toxic element, by using the in vitro culture system of transformed carrot roots associated to the AM fungal strain GC3 (Banco de Glomeromycota in vitro- BGIV). In order to understand the role of AMF in the rhizosphere of plants growing in soils with high content of Cu. In vitro experiments were performed in divided petri plates containing transformed carrot roots colonized by GC3 at one side (root compartment: RC), and sterile soil, artificially contaminated, or not, with 300 ppm of Cu (treatments: Cu+ and Cu-) at the other side, where only hyphae could access (hyphal compartment: HC). After three months, root, mycelia, spores and intraradical vesicules from the RC and HC were sampled at both treatments. Different accumulation patterns were observed between treatments. Cu was only detected in vesicules and roots of Cu+ treatment. P, Zn, Mn and Ca were strongly associated to every AMF structures. These results show an accumulation of HM in the fungal intraradical tissue during the symbiotic association and not in the plant itself

We present density functional theory (DFT) calculations for the heterodiffusion and adsorption for Ag, Au and Cu adatoms on the Pt(110)(1 x 1) (1 x 2) and (1 x 3) surfaces. The adsorption energy shows an important variation as function of the reconstruction order for Pt/Pt and Au/Pt systems, while the adsorption energy varies slightly for Cu/Pt and Ag/Pt. Likewise, the activation energy is examined for different systems and geometries and the highest barrier was found for Pt adatom diffusion. In addition, the estimated diffusion barriers are found to be influenced by reconstruction order for all systems under consideration but with different magnitudes of variation as function of reconstruction order for each system. Indeed, we found that the activation energy varies as function of the reconstruction order but the magnitude of variation is important for Pt/Pt and Cu/Pt systems, whereas the diffusion barrier for Ag/Pt and Au/Pt systems has a slight dependence on the reconstruction order. The analysis of the adatom relaxation with its neighbor atoms as well as the variation of the bond length was provided to more deeply explain the observed trends for each system. The general trend of activation energies for these systems is consistent with available experimental and theoretical data.

In this paper we prove in the exemplary case of the amyloid-beta peptide in complex with Cu(ii) that at the current low temperatures employed in XAS experiments, the time needed for collecting a good quality XAS spectrum is significantly shorter than the time after which structural damage becomes appreciable. Our method takes advantage of the well-known circumstance that the transition of Cu from the oxidized to the reduced form under ionizing radiation can be quantified by monitoring a characteristic peak in the pre-edge region. We show that there exists a sufficiently large time window in which good XAS spectra can be acquired before the structure around the oxidized Cu(ii) ion reorganizes itself into the reduced Cu(i) "resting" structure. We suggest that similar considerations apply to other cases of biological interest, especially when dealing with macromolecules in complex with transition metal ions.

After cellulose, lignin is the most abundant plant-derived polymer in nature. It provides mechanical support to plants, but it has also a defense role against pests and diseases, thanks to antioxidant, bactericidal, and antifungal properties, deriving from its polyphenolic nature. Huge quantities of technical lignins are obtained during several industrial processes and they actually represent a waste of paper pulp and bioethanol industry. Although in the last decades many efforts have been directed to obtain lignin valorization in several fields and for diverse applications, this biobased polymer is still largely underutilized. In particular, very little is known about the possibility to exploit its antioxidant, antifungal, and antibacterial properties in the agronomical field. On the other hand, pest control is often achieved by using copper-based pesticides, but environmental and health issues urge for novel solutions implying reduced copper content. We here describe novel hybrid organic-inorganic materials obtained by combining copper(II) salts with two types of technical lignins. Cu-containing materials (lignin@Cu) have been characterized by different techniques, including X-ray powder diffraction and transmission electron spectroscopy analyses, revealing nanocrystals of brochantite (Cu4SO4(OH)(6)) grown in the lignin matrix. Lignin@Cu was tested for its antifungal and antibacterial profile against a vast panel of pathogens of agronomical interest. Furthermore, preliminary tests on crops in a greenhouse were performed: lignin@Cu had better performances than a commercial pesticide based on copper(II) hydroxide on tomato plants against Rhizoctonia solani, indicating a great potential of these materials as plant protection products.

Dinuclear copper(I) complexes have been prepared starting from bis(diphenylphosphanyl)acetylene (dppa), [Cu(CH3CN)(4)](BF4) and various 1,10-phenanthroline ligands (NN), namely 1,10-phenanthroline (phen), neocuproine (dmp), bathophenanthroline (Bphen), bathocuproine (Bdmp) and 2-phenyl-1,10-phenanthroline (mpp). The resulting [Cu-2(mu-dppa)(2)(NN)(2)](BF4)(2) complexes have been thus obtained in excellent yields (88 to 94 %). X-ray crystal structure analysis of four complexes revealed that the 10-membered dimetallacycle adopts a chair-like conformation in the solid state. Detailed variable temperature NMR investigations have evidenced dynamic coordination/decoordination of the NN ligands as well as ligand exchange reactions. At high temperature (100 degrees C), entropic effects tend to destabilize the dinuclear heteroleptic complexes. As a result, homoleptic mononuclear complexes, i.e. [Cu(NN)(2)](+) and undefined dppa copper(I) complexes, start to appear in solution. In contrast, the heteroleptic coordination scenario is almost exclusively favored at lower temperatures. For most of the dinuclear complexes, the 10-membered dimetallacycle remains flexible and chair-to-chair interconversion occurs faster than the NMR timescale even at -70 degrees C. In the particular case of the mpp derivative, the bulky phenyl substituent prevents the isomerization of the metallacycle and thus contributes to rigidify the structure. This rigidification has a dramatic effect on the emission properties of this particular compound. The emission quantum yield of [Cu-2(mu-dppa)(2)(mpp)(2)](BF4)(2) is effectively one order of magnitude higher when compared to all the other complexes in this series (20 % vs. 0.3-1.7 % in the solid state).