Germline CDH1 variants in hereditary diffuse gastric cancer syndrome with focus on younger women.

PURPOSE: The objective of this study was to determine the male and female frequency of diffuse gastric cancer (DGC), the age at diagnosis, and the country of origin in a selected population with germline CDH1 variants from families with the hereditary diffuse gastric cancer (HDGC) syndrome. METHODS: Relevant literature dating from 1998 to 2021 was systematically searched for data on CDH1 gene. The Wilcoxon rank sum test and the Chi-square test were used to estimate if the difference observed between patients with gastric cancer (GC) and unaffected individuals was significant. RESULTS: We identified 80 families fulfilling the established clinical criteria for HDGC CDH1 genetic screening. There were more women than men with DGC and germline CDH1 variant (65.5%). Stratifying the age at diagnosis, we identified an association between DGC, positive CDH1 screening and young women (≤ 40 years) (p = 0.015). The mean age at diagnosis was 39.6 ys for women and 42.5 ys for men. There was an association between CDH1 carrier status and DGC (p = 0.021). CONCLUSIONS: Young women carrying germline CDH1 variants with DGC are comparatively frequent in the HDGC syndrome, and potentially at higher risk to develop DGC particularly in low-incidence areas for GC.

In Situ Observation of C-C Coupling and Step Poisoning During the Growth of Hydrocarbon Chains on Ni(111).

The synthesis of high-value fuels and plastics starting from small hydrocarbon molecules plays a central role in the current transition towards renewable energy. However, the detailed mechanisms driving the growth of hydrocarbon chains remain to a large extent unknown. Here we investigated the formation of hydrocarbon chains resulting from acetylene polymerization on a Ni(111) model catalyst surface. Exploiting X-ray photoelectron spectroscopy up to near-ambient pressures, the intermediate species and reaction products have been identified. Complementary in situ scanning tunneling microscopy observations shed light onto the C-C coupling mechanism. While the step edges of the metal catalyst are commonly assumed to be the active sites for the C-C coupling, we showed that the polymerization occurs instead on the flat terraces of the metallic surface.

The interplay of mentalization and epistemic trust: a protective mechanism against emotional dysregulation in adolescent internalizing symptoms.

Mentalization is the ability to interpret actions as caused by intentional mental states. Moreover, mentalization facilitates the development of epistemic trust (ET), namely, the ability to evaluate social information as accurate, reliable, and relevant. Recent theoretical literature identifies mentalization as a protective factor, contrasting psychopathology and emotional dysregulation. However, few investigations have explored the concurrent associations between mentalization, ET and emotion dysregulation in the context of internalizing problems in adolescence. In the present study, 482 adolescents from the general population aged between 12 and 19 were assessed with the epistemic trust mistrust credulity questionnaire, the reflective functioning questionnaire- youth, the difficulties in emotion regulation scale, and the youth self-report. We tested the relationship between the variables through serial mediation models. Results showed that mentalization reduces internalizing problems via emotional dysregulation; ET is positively associated with mentalization but not symptomatology. Finally, both epistemic mistrust and epistemic credulity are significantly associated with internalizing symptomatology; those effects are mediated differently by difficulties in emotional regulation. In conclusion, the present study confirms mentalization's role as a protective factor in developmental psychopathology. Nevertheless, exploring the role of the different epistemic stances guarantees a better understanding of psychopathological pathways in adolescence.

Black or red phosphorus yields the same blue phosphorus film.

After the discovery of graphene, many other 2D materials have been predicted theoretically and successfully prepared. In this context, single-sheet black phosphorus - phosphorene - is emerging as a viable contender in the field of (2D) semiconductors. Phosphorene offers high carrier mobility and an anisotropic structure that gives rise to a modulation of physical and chemical properties. This opens the way to many novel and fascinating applications related to field-effect transistors and optoelectronic devices. In previous studies, a single layer of blue phosphorene intermixed with Au atoms was grown using purified black phosphorus as a precursor. Starting from the observation that phosphorus vapor mainly consists of P clusters, in this work we aimed at obtaining blue phosphorus using much less expensive purified red phosphorus as an evaporant. By means of microscopy, spectroscopy and diffraction experiments, we show that black or red phosphorus deposition on Au(111) substrates yields the same blue phosphorus film.

Conservation of Nickel Ion Single-Active Site Character in a Bottom-Up Constructed π-Conjugated Molecular Network.

On-surface chemistry holds the potential for ultimate miniaturization of functional devices. Porphyrins are promising building-blocks in exploring advanced nanoarchitecture concepts. More stable molecular materials of practical interest with improved charge transfer properties can be achieved by covalently interconnecting molecular units. On-surface synthesis allows to construct extended covalent nanostructures at interfaces not conventionally available. Here, we address the synthesis and properties of covalent molecular network composed of interconnected constituents derived from halogenated nickel tetraphenylporphyrin on Au(111). We report that the π-extended two-dimensional material exhibits dispersive electronic features. Concomitantly, the functional Ni cores retain the same single-active site character of their single-molecule counterparts. This opens new pathways when exploiting the high robustness of transition metal cores provided by bottom-up constructed covalent nanomeshes.

Disproportionation of Nitric Oxide at a Surface-Bound Nickel Porphyrinoid.

Uncommon metal oxidation states in porphyrinoid cofactors are responsible for the activity of many enzymes. The F430 and P450nor co-factors, with their reduced NiI - and FeIII -containing tetrapyrrolic cores, are prototypical examples of biological systems involved in methane formation and in the reduction of nitric oxide, respectively. Herein, using a comprehensive range of experimental and theoretical methods, we raise evidence that nickel tetraphenyl porphyrins deposited in vacuo on a copper surface are reactive towards nitric oxide disproportionation at room temperature. The interpretation of the measurements is far from being straightforward due to the high reactivity of the different nitrogen oxides species (eventually present in the residual gas background) and of the possible reaction intermediates. The picture is detailed in order to disentangle the challenging complexity of the system, where even a small fraction of contamination can change the scenario.

Carbide coating on nickel to enhance the stability of supported metal nanoclusters.

The influence on the growth of cobalt (Co)-based nanostructures of a surface carbide (Ni2C) layer formed at the Ni(100) surface is revealed via complementary scanning tunneling microscopy (STM) measurements and first-principles calculations. On clean Ni(100) below 200 °C in the sub-monolayer regime, Co forms randomly distributed two-dimensional (2D) islands, while on Ni2C it grows in the direction perpendicular to the surface as well, thus forming two-atomic-layers high islands. We present a simple yet powerful model that explains the different Co growth modes for the two surfaces. A jagged step decoration, not visible on stepped Ni(100), is present on Ni2C. This contrasting behavior on Ni2C is explained by the sharp differences in the mobility of Co atoms for the two cases. By increasing the temperature, Co dissolution is activated with almost no remaining Co at 250 °C on Ni(100) and Co islands still visible on the Ni2C surface up to 300 °C. The higher thermal stability of Co above the Ni2C surface is rationalized by ab initio calculations, which also suggest the existence of a vacancy-assisted mechanism for Co dissolution in Ni(100). The methodology presented in this paper, combining systematically STM measurements with first-principles calculations and computational modelling, opens the way to controlled engineering of bimetallic surfaces with tailored properties.

Disproportionation of Nitric Oxide at a Surface-Bound Nickel Porphyrinoid.

Uncommon metal oxidation states in porphyrinoid cofactors are responsible for the activity of many enzymes. The F430 and P450nor co-factors, with their reduced NiI- and FeIII-containing tetrapyrrolic cores, are prototypical examples of biological systems involved in methane formation and in the reduction of nitric oxide, respectively. Herein, using a comprehensive range of experimental and theoretical methods, we raise evidence that nickel tetraphenyl porphyrins deposited in vacuo on a copper surface are reactive towards nitric oxide disproportionation at room temperature. The interpretation of the measurements is far from being straightforward due to the high reactivity of the different nitrogen oxides species (eventually present in the residual gas background) and of the possible reaction intermediates. The picture is detailed in order to disentangle the challenging complexity of the system, where even a small fraction of contamination can change the scenario.

Room-Temperature On-Spin-Switching and Tuning in a Porphyrin-Based Multifunctional Interface.

Molecular interfaces formed between metals and molecular compounds offer a great potential as building blocks for future opto-electronics and spintronics devices. Here, a combined theoretical and experimental spectro-microscopy approach is used to show that the charge transfer occurring at the interface between nickel tetraphenyl porphyrins and copper changes both spin and oxidation states of the Ni ion from [Ni(II), S = 0] to [Ni(I), S = 1/2]. The chemically active Ni(I), even in a buried multilayer system, can be functionalized with nitrogen dioxide, allowing a selective tuning of the electronic properties of the Ni center that is switched to a [Ni(II), S = 1] state. While Ni acts as a reversible spin switch, it is found that the electronic structure of the macrocycle backbone, where the frontier orbitals are mainly localized, remains unaffected. These findings pave the way for using the present porphyrin-based system as a platform for the realization of multifunctional devices where the magnetism and the optical/transport properties can be controlled simultaneously by independent stimuli.

Mechanism of CO Intercalation through the Graphene/Ni(111) Interface and Effect of Doping.

Molecules intercalate at the graphene/metal interface even though defect-free graphene is impermeable to any atomic and molecular species in the gas and liquid phase, except hydrogen. The mechanism of molecular intercalation is still a big open question. In this Letter, by means of a combined experimental (STM, XPS, and LEED) and theoretical (DFT) study, we present a proof of how CO molecules succeed in permeating the graphene layer and get into the confined zone between graphene and the Ni(111) surface. The presence of N-dopants in the graphene layer is found to highly facilitate the permeation process, reducing the CO threshold pressure by more than one order of magnitude, through the stabilization of multiatomic vacancy defects that are the open doors to the bidimensional nanospace, with crucial implications for the catalysis under cover and for the graphene-based electrochemistry.

The new FAST module: A portable and transparent add-on module for time-resolved investigations with commercial scanning probe microscopes.

Time resolution is one of the most severe limitations of scanning probe microscopies (SPMs), since the typical image acquisition times are in the order of several seconds or even few minutes. As a consequence, the characterization of dynamical processes occurring at surfaces (e.g. surface diffusion, film growth, self-assembly and chemical reactions) cannot be thoroughly addressed by conventional SPMs. To overcome this limitation, several years ago we developed a first prototype of the FAST module, an add-on instrument capable of driving a commercial scanning tunneling microscope (STM) at and beyond video rate frequencies. Here we report on a fully redesigned version of the FAST module, featuring improved performance and user experience, which can be used both with STMs and atomic force microscopes (AFMs), and offers additional capabilities such as an atom tracking mode. All the new features of the FAST module, including portability between different commercial instruments, are described in detail and practically demonstrated.

Doping of epitaxial graphene by direct incorporation of nickel adatoms.

Direct incorporation of Ni adatoms during graphene growth on Ni(111) is evidenced by scanning tunneling microscopy. The structure and energetics of the observed defects is thoroughly characterized at the atomic level on the basis of density functional theory calculations. Our results show the feasibility of a simple scalable method, which could be potentially used for the realization of macroscopic practical devices, to dope graphene with a transition metal. The method exploits the kinetics of the growth process for the incorporation of Ni adatoms in the graphene network.

On-surface trapping of alkali atoms by crown ethers in ultra high vacuum.

Crown ethers, assembled into a regular 2D array via a chemical guest-host recognition process, have been successfully employed to trap sodium atoms on a surface, under ultra-high vacuum conditions.

Substrate- to Laterally-Driven Self-Assembly Steered by Cu Nanoclusters: The Case of FePcs on an Ultrathin Alumina Film.

We show that, for the formation of a metallorganic monolayer, it is possible to artificially divert from substrate- to laterally-driven self-assembly mechanisms by properly tailoring the corrugation of the potential energy surface of the growth template. By exploiting the capability of an ultrathin alumina film to host metallic nanoparticle seeds, we tune the symmetry of a iron phthalocyanine (FePc) two-dimensional crystal, thus showing that it is possible to switch from trans to lateral dominating interactions in the controlled growth of an organic/inorganic heterostack. Finally, by selecting the size of the metallic clusters, we can also control the FePc-metal interaction strength.

On-surface synthesis of a 2D boroxine framework: a route to a novel 2D material?

The synthesis and preliminary characterization of a boron-based 2D framework are presented. The peculiar electronic and morphological properties of this compound, together with its facile formation process, enable it to be used as a novel smart material for the design of electronic devices.

Real-time imaging of adatom-promoted graphene growth on nickel.

Single adatoms are expected to participate in many processes occurring at solid surfaces, such as the growth of graphene on metals. We demonstrate, both experimentally and theoretically, the catalytic role played by single metal adatoms during the technologically relevant process of graphene growth on nickel (Ni). The catalytic action of individual Ni atoms at the edges of a growing graphene flake was directly captured by scanning tunneling microscopy imaging at the millisecond time scale, while force field molecular dynamics and density functional theory calculations rationalize the experimental observations. Our results unveil the mechanism governing the activity of a single-atom catalyst at work.

Growth of regular nanometric molecular arrays on a functional 2D template based on a chemical guest-host approach.

A regular 2D array of crown molecules, which would spontaneously self-assemble into disordered molecular clusters, is obtained by exploiting a guest-host process, based on the chemical affinity between amino and carboxylic groups on a gold surface. First a carboxylic organic template is formed, which then serves as a host for amino-functionalized crown molecules. The amino-carboxylic interaction thereby drives the formation of a monolayer of guest molecules, regularly distributed at the nanometer scale, preventing their aggregation in unordered clusters observed on a bare gold surface. This method, which can be applied to other guest molecules, represents a novel route to overcome the shape-matching requirements of the standard guest-host architectures. Furthermore, it is intrinsically selective, due to the chemical nature of the anchoring process.

Publisher Correction: Multi-orbital charge transfer at highly oriented organic/metal interfaces.

The original version of this Article contained an error in the spelling of the author Claus Michael Schneider, which was incorrectly given as Claus Michael Schneidery. This has now been corrected in both the PDF and HTML versions of the Article.

Tunability of the CO adsorption energy on a Ni/Cu surface: Site change and coverage effects.

The adsorption energy of carbon monoxide on Ni ad-islands and ultra-thin films grown on the Cu(110) surface can be finely tuned via a complex interplay among diffusion, site change mechanisms, and coverage effects. The observed features of CO desorption can be explained in terms of migration of CO molecules from Cu to Ni islands, competition between bridge and on-top adsorption sites, and repulsive lateral adsorbate-adsorbate interactions. While the CO adsorption energy on clean Cu(110) is of the order of 0.5 eV, Ni-alloying allows for its controlled, continuous tunability in the 0.98-1.15 eV range with Ni coverage. Since CO is a fundamental reactant and intermediate in many heterogeneous catalytic (electro)-conversion reactions, insight into these aspects with atomic level detail provides useful information to potentially drive applicative developments. The tunability range of the CO adsorption energy that we measure is compatible with the already observed tuning of conversion rates by Ni doping of Cu single crystal catalysts for methanol synthesis from a CO2, CO, and H2 stream under ambient pressure conditions.

Imaging on-surface hierarchical assembly of chiral supramolecular networks.

The bottom-up assembly of chiral structures usually relies on a cascade of molecular recognition interactions. A thorough description of these complex stereochemical mechanisms requires the capability of imaging multilevel coordination in real-time. Here we report the first direct observation of hierarchical expression of supramolecular chirality at work, for 10,10'-dibromo-9,9'-bianthryl (DBBA) on Cu(111). Molecular recognition first steers the growth of chiral organometallic chains and then leads to the formation of enantiopure islands. The structure of the networks was determined by noncontact atomic force microscopy (nc-AFM), while high-speed scanning tunnelling microscopy (STM) revealed details of the assembly mechanisms at the ms time-scale. The direct observation of the chirality transfer pathways allowed us to evaluate the enantioselectivity of the interchain coupling.