Total- and semi-bare noble metal nanoparticles@silica core@shell catalysts for hydrogen generation by formic acid decomposition

Catalysts are involved in a number of established and emerging chemical processes as well as in environmental remediation and energy conversion. Nanoparticles (NPs) can offer several advantages over some conventional catalysts, such as higher efficiency and selectivity. Nowadays, versatile and scalable nanocatalysts that combine activity and stability are still lacking. Here, we report a comprehensive investigation on the production and characterization of hybrid nano-architectures bringing a partial or total bare surface together with their catalytic efficiency evaluation on, as a proof-of-concept, the formic acid decomposition reaction. In this regard, formic acid (FA) is a convenient and safe hydrogen carrier with appealing features for mobile applications, fuel cells technologies, petrochemical processes and energetic applications. Thus, the design of robust catalysts for FA dehydrogenation is strongly demanded. Due to this, we produced and evaluated nano-architectures with various equilibrium between the size-increase of the active part and the barer catalytic surface. Overall, this work paves the way for the development of new approaches for green energy storage and safe delivery

Optical devices provide unprecedented insights into the laser cleaning of calcium oxalate layers

Abstract Calcium oxalates are insoluble colorless or whitish salts constituting noble patina, on both natural and artificial stone artworks' surfaces, the presence of which is extremely valued. The oxalates are not considered detrimental to the substrate, however, being often accompanied by other substances such as gypsum, silicates, and pigmented particles. They may form very adherent, relatively thick and colored layers creating disfiguring effects and hindering legibility of the pictorial surface. For this reason it may be appropriate to diminish their thickness, but patina's partial preservation is particularly required calling for extremely gradual and controllable cleaning approach. Thinning of calcium oxalate patina from a detached 16th century fresco (from Sansepolcro) was performed through the use of laser (Nd:YAG and Er:YAG) systems and chemical means (Carbogel loaded 5 wt.% of tetrasodium EDTA). Optical coherence tomography (OCT), providing a non-invasive stratigraphic cross-section of the examined surface, allowed to distinguish the oxalate from the underlying original layers and therefore to have an overview about its distribution, to numerically evaluate patina's thickness range and to provide the information on the amount of the material both removed and left on the artwork's surface. Laser scanning conoscopic microprofilometry allowed for a high-density sampling of the artwork's surface providing a three-dimensional model of the surface pattern. The obtained 3D models were used to estimate the amount of material removed and to compare them with those provided by OCT. The successful exploitation of the proposed exceptional cleaning monitoring methodology may be seen as an innovative and valid support for the restorers in the conservation of mural painting or other surfaces covered by oxalate layers and may pilot more targeted, cautious and respectful cleaning intervention

Initial experience of dedicated breast PET imaging of ER+ breast cancers using [F-18]fluoroestradiol.

Dedicated breast positron emission tomography (dbPET) is an emerging technology with high sensitivity and spatial resolution that enables detection of sub-centimeter lesions and depiction of intratumoral heterogeneity. In this study, we report our initial experience with dbPET using [F-18]fluoroestradiol (FES) in assessing ER+ primary breast cancers. Six patients with >90% ER+ and HER2- breast cancers were imaged with dbPET and breast MRI. Two patients had ILC, three had IDC, and one had an unknown primary tumor. One ILC patient was treated with letrozole, and another patient with IDC was treated with neoadjuvant chemotherapy without endocrine treatment. In this small cohort, we observed FES uptake in ER+ primary breast tumors with specificity to ER demonstrated in a case with tamoxifen blockade. FES uptake in ILC had a diffused pattern compared to the distinct circumscribed pattern in IDC. In evaluating treatment response, the reduction of SUVmax was observed with residual disease in an ILC patient treated with letrozole, and an IDC patient treated with chemotherapy. Future study is critical to understand the change in FES SUVmax after endocrine therapy and to consider other tracer uptake metrics with SUVmax to describe ER-rich breast cancer. Limitations include variations of FES uptake in different ER+ breast cancer diseases and exclusion of posterior tissues and axillary regions. However, FES-dbPET has a high potential for clinical utility, especially in measuring response to neoadjuvant endocrine treatment. Further development to improve the field of view and studies with a larger cohort of ER+ breast cancer patients are warranted

Modulating the water oxidation catalytic activity of iridium complexes by functionalizing the Cp*-ancillary ligand: hints on the nature of the active species

The catalytic activity toward NaIO4driven water oxidation of a series of [RCp*IrCl(μ-Cl)]2dimeric precursors, containing tetramethylcyclopentadienyl ligands with a variable R substituent (H,1; Me,2; Et,3;nPr,4; CH2CH2NH3+,5; Ph,6; 4-C6H4F,7; 4-C6H4OH,8; Bn,9), has been evaluated at 298 K and pH = 7 (with phosphate buffer). For each dimer, the effect of changing the catalyst (1-10 μM) and NaIO4(5-40 mM) concentration has been studied. All precursors exhibit a high activity with TOF values ranging from 101 min−1to 393 min−1and TON values being always those expected assuming a 100% yield. The catalytic activity was strongly affected by the nature of the R substituent. The highest TOF values were observed when R was electron-donating and small. The results of multiple consecutive injection experiments suggest that a fragment of the initial C5Me4R, still bearing the R-substituent, remains attached at iridium in the active species, despite the oxidativein situdegradation of the same ligand. The decrease of TOF in the second and third catalytic runs was completely ascribed to a drop of the redox potential caused by the conversion of IO4−into IO3−, according to the Nernst equation. This hypothesis was verified by performing catalytic experiments in which the initial redox potential (ΔE) was deliberately varied by using water solutions of IO4−/IO3−mixtures at different relative concentrations. Consistently, TOFversusΔEplots show that, for a given catalyst, the same TOF is obtained at a certain redox potential, irrespective of the initial reaction conditions used. All seems to indicate that after a short activation period, during which the transformation of the precursors occurs, individual active species for each dimer form and remain the same also after multiple additions of the sacrificial oxidant. It can be speculated that such active species are small iridium clusters bearing R-functionalized likelyO,O-bidentate ligands

Conjugating Biotin to Ruthenium(II) Arene Units via Phosphine Ligand Functionalization

Two-step functionalization of 4-diphenylphosphino benzoic acid with biotin afforded 2-(biotinyloxy)ethyl 4-(diphenylphosphanyl)benzoate (LP), that was subsequently used to synthesize the Ru(II) arene complexes [RuCl2(η6-p-cymene)(LP)] (1), [Ru(C2O4)(η6-p-cymene)(LP)] (2) and [Ru(curc)(η6-p-cymene)(LP)]NO3 ([3]NO3), the latter incorporating curcumin (curcH) as an additional bioactive fragment. [Ru(curc)(η6-p-cymene)(PPh3)]NO3 ([4]NO3) was also prepared as a reference compound. Compounds 2 and [3]NO3 exhibited excellent stability in water/DMSO solution while being slowly activated in the cell culture medium over 72 hours. Together with LP, they were therefore assessed for their antiproliferative activity towards a panel of cancer cell lines, with different levels of biotin transporter expression. The apparent affinity of the compounds towards avidin varies, and their antiproliferative activity does not correlate with biotin transporter expression, although it is systematically enhanced when biotin-free cell culture medium is used

Ruthenium(II) Tris-Pyrazolylmethane Complexes in Transfer Hydrogenation Reactions

While ruthenium(II) arene complexes have been widely investigated for their potential in catalytic transfer hydrogenation, studies on homologous compounds replacing the arene ligand with the six-electron donor tris(1-pyrazolyl)methane (tpm) are almost absent in the literature. The reactions of [RuCl(κ3-tpm)(PPh3)2]Cl, 1, with a series of nitrogen ligands (L) proceeded with selective PPh3 mono-substitution, affording the novel complexes [RuCl(κ3-tpm)(PPh3)(L)]Cl (L=NCMe, 2; NCPh, 3; imidazole, 4) in almost quantitative yields. Products 2–4 were fully characterized by IR and multinuclear NMR spectroscopy, moreover the molecular structure of 4 was ascertained by single crystal X-ray diffraction. Compounds 2–4 were evaluated as catalytic precursors in the transfer hydrogenation of a series of ketones with isopropanol as the hydrogen source, and 2 exhibited the highest activity. Extensive NMR experiments and DFT calculations allowed to elucidate the mechanism of the transfer hydrogenation process, suggesting the crucial role played by the tpm ligand, reversibly switching from tri- to bidentate coordination during the catalytic cycle

Testing geological proxies for deep‐time tidal model simulations

Tides are a key driver of a range of Earth system processes, and we now have the capacity to simulate tidal dynamics on a range of temporal and spatial scales. Deep‐time tidal model simulations have been used to provide insight into past ocean circulation patterns, evolution of life and the developments of the Earth‐Moon system's orbital configuration. However, these tidal model simulations are relatively poorly constrained and validated because of a lack of readily available proxies. The feasibility of using two types of proxy is explored here; (1) sedimentary deposits which can directly estimate palaeotidal ranges, and (2) black shale, to constrain three palaeotidal model simulations for different time slices. Specifically, three palaeotidal range proxies were used for the early Devonian (400 Ma), three palaeotidal range proxies and five black shales for the lower Jurassic (185 Ma), and eight black shales for the early Cretaceous (95 Ma). Both tidal proxies confirm the tidal model results in most locations. The model results for 400 Ma and 185 Ma matched 2/3 of the palaeotidal range proxies for each of these periods. The locations of black shale were compared with tidal front locations predicted by the model outputs based on the Simpson–Hunter parameter and the model results from 95 to 185 Ma agree with the black shale proxies in 10/13 of the locations. In the cases where there is a disagreement, the model resolution is probably too low to fully resolve the details of the coastal topography, or—in one case—the palaeobathymetry is incorrect. Consequently, it is argued that it is worth expanding this type of work, and that such data can be used to validate both models and reconstructions

Spatial correlations in hexagons generated via a Kerr nonlinearity

We consider the hexagonal pattern forming in the cross-section of an optical beam produced by a Kerr cavity, and we study the quantum correlations characterizing this structure. By using arguments related to the symmetry broken by the pattern formation, we identify a complete scenario of six-mode entanglement. Five independent phase quadratures combinations, connecting the hexagonal modes, are shown to exhibit sub-shot-noise fluctuations. By means of a non-linear quantum calculation technique, quantum correlations among the mode photon numbers are demonstrated and calculated.Comment: ReVTeX file, 20 pages, 7 eps figure

Pattern formation in 2-frequency forced parametric waves

We present an experimental investigation of superlattice patterns generated on the surface of a fluid via parametric forcing with 2 commensurate frequencies. The spatio-temporal behavior of 4 qualitatively different types of superlattice patterns is described in detail. These states are generated via a number of different 3--wave resonant interactions. They occur either as symmetry--breaking bifurcations of hexagonal patterns composed of a single unstable mode or via nonlinear interactions between the two primary unstable modes generated by the two forcing frequencies. A coherent picture of these states together with the phase space in which they appear is presented. In addition, we describe a number of new superlattice states generated by 4--wave interactions that arise when symmetry constraints rule out 3--wave resonances.Comment: The paper contains 34 pages and 53 figures and provides an extensive review of both the theoretical and experimental work peformed in this syste

Versatile Coordination of Cyclopentadienyl-Arene Ligands and Its Role in Titanium-Catalyzed Ethylene Trimerization

Cationic titanium(IV) complexes with ansa-(η5-cyclopentadienyl,η6-arene) ligands were synthesized and characterized by X-ray crystallography. The strength of the metal-arene interaction in these systems was studied by variable-temperature NMR spectroscopy. Complexes with a C1 bridge between the cyclopentadienyl and arene moieties feature hemilabile coordination behavior of the ligand and consequently are active ethylene trimerization catalysts. Reaction of the titanium(IV) dimethyl cations with CO results in conversion to the analogous cationic titanium(II) dicarbonyl species. Metal-to-ligand backdonation in these formally low-valent complexes gives rise to a strongly bonded, partially reduced arene moiety. In contrast to the η6-arene coordination mode observed for titanium, the more electron-rich vanadium(V) cations [cyclopentadienyl-arene]V(NiPr2)(NC6H4-4-Me)+ feature η1-arene binding, as determined by a crystallographic study. The three different metal-arene coordination modes that we experimentally observed model intermediates in the cycle for titanium-catalyzed ethylene trimerization. The nature of the metal-arene interaction in these systems was studied by DFT calculations.