Oxygen intercalation in PVD graphene grown on copper substrates: A decoupling approach.

We investigate the intercalation process of oxygen in-between a PVD-grown graphene layer and different copper substrates as a methodology for reducing the substrate-layer interaction. This growth method leads to an extended defect-free graphene layer that strongly couples with the substrate. We have found, by means of X-ray photoelectron spectroscopy, that after oxygen exposure at different temperatures, ranging from 280 °C to 550 °C, oxygen intercalates at the interface of graphene grown on Cu foil at an optimal temperature of 500 °C. The low energy electron diffraction technique confirms the adsorption of an atomic oxygen adlayer on top of the Cu surface and below graphene after oxygen exposure at elevated temperature, but no oxidation of the substrate is induced. The emergence of the 2D Raman peak, quenched by the large interaction with the substrate, reveals that the intercalation process induces a structural undoing. As suggested by atomic force microscopy, the oxygen intercalation does not change significantly the surface morphology. Moreover, theoretical simulations provide further insights into the electronic and structural undoing process. This protocol opens the door to an efficient methodology to weaken the graphene-substrate interaction for a more efficient transfer to arbitrary surfaces.

Multistimuli Response Micro- and Nanolayers of a Coordination Polymer Based on Cu2 I2 Chains Linked by 2-Aminopyrazine.

A nonporous laminar coordination polymer of formula [Cu2 I2 (2-aminopyrazine)]n is prepared by direct reaction between CuI and 2-aminopyrazine, two industrially available building blocks. The fine tuning of the reaction conditions allows obtaining [Cu2 I2 (2-aminopyrazine)]n in micrometric and nanometric sizes with same structure and composition. Interestingly, both materials show similar reversible thermo- and pressure-luminescent response as well as reversible electrical response to volatile organic solvents such as acetic acid. X-ray diffraction studies under different conditions, temperatures and pressures, in combination with theoretical calculations allow rationalizing the physical properties of this compound and its changes under physical stimuli. Thus, the emission dramatically increases when lowering the temperature, while an enhancement of the pressure produces a decrease in the emission intensity. These observations emerge as a direct consequence of the high structural flexibility of the Cu2 I2 chains which undergo a contraction in CuCu distances as far as temperature decreases or pressure increases. However, the strong structural changes observed under high pressure lead to an unexpected effect that produces a less effective CuCu orbital overlapping that justifies the decrease in the intensity emission. This work shows the high potential of materials based on Cu2 I2 chains for new applications.

Spectroscopic characterization of the on-surface induced (cyclo)dehydrogenation of a N-heteroaromatic compound on noble metal surfaces.

New nanoarchitectures can be built from polycyclic aromatic hydrocarbons (PAHs) by exploiting the capability of some metal surfaces for inducing cyclodehydrogenation reactions. This bottom-up approach allows the formation of nanostructures with a different dimensionality from the same precursor as a consequence of the diffusion and coupling of the PAHs adsorbed on the surface. In this work we present a thorough study, by means of a combination of X-ray photoemission spectroscopy, near-edge X-ray absorption fine structure and scanning tunneling microscopy with first principle calculations of the structural and chemical transformations undergone by pyridyl-substituted dibenzo[5]helicene on three coinage surfaces, namely Cu(110), Cu(111) and Au(111). Upon annealing, on-surface chemical reactions are promoted affecting the adsorbate/substrate and the molecule/molecule interactions. This thermally induced process favours the transformation from diffusing isolated molecules to polymeric nanographene chains and finally to N-doped graphene.

High-quality PVD graphene growth by fullerene decomposition on Cu foils.

We present a new protocol to grow large-area, high-quality single-layer graphene on Cu foils at relatively low temperatures. We use C60 molecules evaporated in ultra high vacuum conditions as carbon source. This clean environment results in a strong reduction of oxygen-containing groups as depicted by X-ray photoelectron spectroscopy (XPS). Unzipping of C60 is thermally promoted by annealing the substrate at 800ºC during evaporation. The graphene layer extends over areas larger than the Cu crystallite size, although it is changing its orientation with respect to the surface in the wrinkles and grain boundaries, producing a modulated ring in the low energy electron diffraction (LEED) pattern. This protocol is a self-limiting process leading exclusively to one single graphene layer. Raman spectroscopy confirms the high quality of the grown graphene. This layer exhibits an unperturbed Dirac-cone with a clear n-doping of 0.77 eV, which is caused by the interaction between graphene and substrate. Density functional theory (DFT) calculations show that this interaction can be induced by a coupling between graphene and substrate at specific points of the structure leading to a local sp3 configuration, which also contribute to the D-band in the Raman spectra.

Wide allelic heterogeneity with predominance of large IDS gene complex rearrangements in a sample of Mexican patients with Hunter syndrome.

Hunter syndrome or mucopolysaccharidosis type II (MPSII) is caused by pathogenic variants in the IDS gene. This is the first study that examines the mutational spectrum in 25 unrelated Mexican MPSII families. The responsible genotype was identified in 96% of the families (24/25) with 10 novel pathogenic variants: c.133G>C, c.1003C>T, c.1025A>C, c.463_464delinsCCGTATAGCTGG, c.754_767del, c.1132_1133del, c.1463del, c.508-1G>C, c.1006+1G>T and c.(-217_103del). Extensive IDS gene deletions were identified in four patients; using DNA microarray analysis two patients showed the loss of the entire AFF2 gene, and epilepsy developed in only one of them. Wide allelic heterogeneity was noted, with large gene alterations (e.g. IDS/IDSP1 gene inversions, partial to extensive IDS deletions, and one chimeric IDS-IDSP1 allele) that occurred at higher frequencies than previously reported (36% vs 18.9-29%). The frequency of carrier mothers (80%) is consistent with previous descriptions (>70%). Carrier assignment allowed molecular prenatal diagnoses. Notably, somatic and germline mosaicism was identified in one family, and two patients presented thrombocytopenic purpura and pancytopenia after idursulfase enzyme replacement treatment. Our findings suggest a wide allelic heterogeneity in Mexican MPSII patients; DNA microarray analysis contributes to further delineation of the resulting phenotype for IDS and neighboring loci deletions.

The CaPTHUS score as predictor of multiglandular primary hyperparathyroidism in a European population.

PURPOSE: Focused parathyroidectomy has been proven to be a safe technique for the treatment of single-gland primary hyperparathyroidism (PHPT). The CaPTHUS scoring model has been reported to be an accurate preoperative diagnostic tool for distinguishing single-gland (SGD) from multiglandular disease (MGD), including preoperative serum calcium and PTH values plus ultrasound and Sestamibi scanning. The purpose of the present study was to validate the CaPTHUS model for the population in southern Europe, since the North American and the European populations show different clinicopathological profiles in PHPT. METHODS: This is a retrospective review of a prospectively maintained database of patients diagnosed with PHPT who underwent surgical treatment in a single referral center. Differences between SGD and MGD groups were analyzed using chi-square and Fisher's exact tests for categorical variables and Student's t test for continuous variables. Overall diagnostic accuracy of the scoring model was assessed by the area under the receiver operating characteristic (ROC) curve (AUC). A p < 0.05 level was accepted as significant. RESULTS: From January 2001 to November 2014, 241 patients were included in the study, of whom 92.1 % had SGD and 71.8 % had a CaPTHUS score ≥3. SGD was distinguished from MGD (p < 0.001) using the dichotomous scoring model based on an AUC value of 0.762. Scores ≥3 had a sensitivity of 76.5 % and a positive predictive value of 96 % for SGD. CONCLUSIONS: Despite good test performance, a CaPTHUS score ≥3 does not discard MGD definitely. Intraoperative adjuncts are still needed to further reduce the risk of missing MGD during selective parathyroidectomy.

Ultrafast Atomic Diffusion Inducing a Reversible (2sqrt[3]×2sqrt[3])R30°â†”(sqrt[3]×sqrt[3])R30° Transition on Sn/Si(111)∶B.

Dynamical phase transitions are a challenge to identify experimentally and describe theoretically. Here, we study a new reconstruction of Sn on silicon and observe a reversible transition where the surface unit cell divides its area by a factor of 4 at 250 °C. This phase transition is explained by the 24-fold degeneracy of the ground state and a novel diffusive mechanism, where four Sn atoms arranged in a snakelike cluster wiggle at the surface exploring collectively the different quantum mechanical ground states.

Ortho and para hydrogen dimers on G/SiC(0001): combined STM and DFT study.

The hydrogen (H) dimer structures formed upon room-temperature H adsorption on single layer graphene (SLG) grown on SiC(0001) are addressed using a combined theoretical-experimental approach. Our study includes density functional theory (DFT) calculations for the full (6√3 × 6√3)R30° unit cell of the SLG/SiC(0001) substrate and atomically resolved scanning tunneling microscopy images determining simultaneously the graphene lattice and the internal structure of the H adsorbates. We show that H atoms normally group in chemisorbed coupled structures of different sizes and orientations. We make an atomic scale determination of the most stable experimental geometries, the small dimers and ellipsoid-shaped features, and we assign them to hydrogen adsorbed in para dimers and ortho dimers configuration, respectively, through comparison with the theory.

Halo and Pseudohalo Cu(I)-Pyridinato Double Chains with Tunable Physical Properties.

The properties recently reported on the Cu(I)-iodide pyrimidine nonporous 1D-coordination polymer [CuI(ANP)]n (ANP = 2-amino-5-nitropyridine) showing reversible physically and chemically driven electrical response have prompted us to carry a comparative study with the series of [CuX(ANP)]n (X = Cl (1), X = Br (2), X = CN (4), and X = SCN (5)) in order to understand the potential influence of the halide and pseudohalide bridging ligands on the physical properties and their electrical response to vapors of these materials. The structural characterization of the series shows a common feature, the presence of -X-Cu(ANP)-X- (X = Cl, Br, I, SCN) double chain structure. Complex [Cu(ANP)(CN)]n (4) presents a helical single chain. Additionally, the chains show supramolecular interlinked interactions via hydrogen bonding giving rise to the formation of extended networks. Their luminescent and electrical properties have been studied. The results obtained have been correlated with structural changes. Furthermore, the experimental and theoretical results have been compared using the density functional theory (DFT). The electrical response of the materials has been evaluated in the presence of vapors of diethyl ether, dimethyl methylphosphonate (DMMP), CH2Cl2, HAcO, MeOH, and EtOH, to build up simple prototype devices for gas detectors. Selectivity toward gases consisting of molecules with H-bonding donor or acceptor groups is clearly observed. This selective molecular recognition is likely due to the 2-amino-5-nitropyridine terminal ligand.

Adsorption and Coupling of 4-aminophenol on Pt(111) surfaces.

We have deposited 4-aminophenol on Pt(111) surfaces in ultra-high vacuum and studied the strength of its adsorption through a combination of STM, LEED, XPS and ab initio calculations. Although an ordered (2√3×2√3)R30° phase appears, we have observed that molecule-substrate interaction dominates the adsorption geometry and properties of the system. At RT the high catalytic activity of Pt induces aminophenol to lose the H atom from the hydroxyl group, and a proportion of the molecules lose the complete hydroxyl group. After annealing above 420K, all deposited aminophenol molecules have lost the OH moiety and some hydrogen atoms from the amino groups. At this temperature, short single-molecule oligomer chains can be observed. These chains are the product of a new reaction that proceeds via the coupling of radical species that is favoured by surface diffusion.

Tailoring structural and electronic properties of RuO2 nanotubes: a many-body approach and electronic transport.

The electrical conduction properties of ruthenium oxide nanocables are of high interest. These cables can be built as thin shells of RuO2 surrounding an inner solid nanowire of a dielectric insulating silica material. With this motivation we have investigated the structural, electronic and transport properties of RuO2 nanotubes using the density functional formalism, and applying many-body corrections to the electronic band structure. The structures obtained for the thinnest nanotubes are of the rutile type. The structures of nanotubes with larger diameters deviate from the rutile structure and have in common the formation of dimerized Ru-Ru rows along the axial direction. The cohesive energy shows an oscillating behavior as a function of the tube diameter. With the exception of the thinnest nanotubes, there is a correlation such that the electronic band structures of tubes with high cohesive energies show small gaps at the Fermi energy, whereas the less stable nanotubes exhibit metallic behavior, with bands crossing the Fermi surface. The electronic conductance of nanotubes of finite length connected to gold electrodes has been calculated using a Green-function formalism, and correlations have been established between the electronic band structure and the conductance at zero bias.

Could 18F-FDG-PET/CT avoid unnecessary thyroidectomies in patients with cytological diagnosis of follicular neoplasm?

PURPOSE: Preoperative diagnosis of thyroid nodules with "follicular neoplasm" (FN) based on fine-needle aspiration cytology (FNAC) forces thyroidectomy to exclude malignancy. This study explores if (18)F-fluorodeoxyglucose positron emission tomography/computed tomography ((18)F-FDG-PET/CT) provides information enough to prevent unnecessary thyroidectomies in this clinical setting. METHODS: This is a prospective study involving 46 consecutive patients scheduled for thyroidectomy due to follicular neoplasm diagnosis in FNAC (36 follicular, 10 Hürthle cell neoplasms, Bethesda classification) since January 2009 until April 2012. All patients underwent preoperative (18)F-FDG-PET/CT. Abnormal (18)F-FDG thyroid uptake was assessed visually and by measuring the maximum standard uptake value (SUV max). Results were compared with definitive pathology reports. RESULTS: Thirteen out of 46 patients (28.3 %) were finally diagnosed with thyroid cancer. Focal uptake correlated with a greater risk of malignancy (p = 0.009). (18)F-FDG-PET/CT focal uptake showed sensitivity, specificity, positive and negative predictive values and overall accuracy of 92.3, 48.5, 41.4, 94.1 and 60.9 %, respectively. The optimal threshold SUV max to discriminate malignancy was 4.2 with an area under receiver-operating characteristic curve of 0.76 (95 % confidence interval, 0.60-0.90). Use of (18)F-FDG-PET/CT could reduce by 13-25 % the number of thyroidectomies performed for definitive benign nodules. However, it has demonstrated worse predictive ability in the subgroup of patients with diffuse uptake, oncocytic pattern in FNAC and lesions smaller than 2. CONCLUSIONS: (18)F-FDG-PET/CT can play a role in the management of thyroid nodules larger than 2 cm cytologically reported as follicular neoplasm without oncocytic differentiation, allowing the avoidance of a significant number of thyroidectomies for definitive benign lesions.

Development of a full-thickness acellular dermal graft from human skin: Case report of first patient rotator cuff patch augmentation repair.

The processing and initial testing of a new human tissue preparation is described. Full-thickness Acellular Dermal Matrix (ftADM) is the extracellular matrix (ECM) obtained by decellularization of full-thickness human skin from cadaveric donors. The safety, stability and usability of the graft are discussed with respect to the results of the residual cellular content, maintenance of ECM components, and biomechanical properties. Quantitative and qualitative analysis of the ECM demonstrated the absence of cell debris, while the native structure of human dermis was maintained. Biomechanical testing showed stiffness values comparable to other commercial products used for tendon reinforcement, suggesting that our ftADM could be successfully used not only in soft tissue regeneration surgeries, but also in tendon reinforcement. First case of ftADM in rotator cuff augmentation is described. Technical management of the patch during surgery and clinical outcomes are discussed.

Improvement of scanning tunneling microscopy resolution with H-sensitized tips.

Recent scanning tunneling hydrogen microscopy (STHM) experiments on PTCDA (perylene-3,4,9,10-tetracarboxylic-3,4,9,10-dianhydride)/Au(111) have shown unprecedented intramolecular and intermolecular spatial resolution. The origin of this resolution is studied using an accurate STHM theoretical simulation technique that includes a detailed description of the electronic structure of both the tip and sample. Our results show that H2 molecules are dissociated on the Au tip; the adsorbed H atoms change the density of states at the Fermi level (E(F)) of the tip, increasing its p-orbital character and reducing the s-orbital contribution. Also, due to the interaction with the H-decorated tip, E(F) is shifted to the middle of the PTCDA lowest unoccupied molecular orbital peak, increasing dramatically the density of states of the sample at E(F). These effects give rise to the enhanced STHM resolution.

Physical and chemical nature of the scaling relations between adsorption energies of atoms on metal surfaces.

Despite their importance in physics and chemistry, the origin and extent of the scaling relations between the energetics of adsorbed species on surfaces remain elusive. We demonstrate here that scalability is not exclusive to adsorbed atoms and their hydrogenated species but rather a general phenomenon between any set of adsorbates bound similarly to the surface. On the example of the near-surface alloys of Pt, we show that scalability is a result of identical variations of adsorption energies with respect to the valence configuration of both the surface components and the adsorbates.

C6H6/Au(111): interface dipoles, band alignment, charging energy, and van der Waals interaction.

We analyze the benzene/Au(111) interface taking into account charging energy effects to properly describe the electronic structure of the interface and van der Waals interactions to obtain the adsorption energy and geometry. We also analyze the interface dipoles and discuss the barrier formation as a function of the metal work-function. We interpret our DFT calculations within the induced density of interface states (IDIS) model. Our results compare well with experimental and other theoretical results, showing that the dipole formation of these interfaces is due to the charge transfer between the metal and benzene, as described in the IDIS model.

On the behavior of Brønsted-Evans-Polanyi relations for transition metal oxides.

Versatile Brønsted-Evans-Polanyi (BEP) relations are found from density functional theory for a wide range of transition metal oxides including rutiles and perovskites. For oxides, the relation depends on the type of oxide, the active site, and the dissociating molecule. The slope of the BEP relation is strongly coupled to the adsorbate geometry in the transition state. If it is final state-like the dissociative chemisorption energy can be considered as a descriptor for the dissociation. If it is initial state-like, on the other hand, the dissociative chemisorption energy is not suitable as descriptor for the dissociation. Dissociation of molecules with strong intramolecular bonds belong to the former and molecules with weak intramolecular bonds to the latter group. We show, for the prototype system La-perovskites, that there is a "cyclic" behavior in the transition state characteristics upon change of the active transition metal of the oxide.

Lanthanide-porphyrin species as Kondo irreversible switches through tip-induced coordination chemistry.

Metallosupramolecular chemical protocols are applied to in situ design dysprosium porphyrin complexes on Au(111) by sequential deposition of 2H-4FTPP species and Dy, resulting in the production of premetallated Dy-2H-4FTPP, partially metallated Dy-1H-4FTPP and fully metallated Dy-0H-4FTPP complexes, as determined by scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. A zero bias resonance is found in the Dy-2H-4FTPP species which, upon study of its spatial distribution and behavior with temperature, is assigned to a Kondo resonance resulting from an unpaired spin in the molecular backbone, featuring a Kondo temperature (TK) of ≈ 21 K. Notably, the Kondo resonance can be switched off by removing one hydrogen atom of the macrocycle through tip-induced voltage pulses with submolecular precision. The species with this Kondo resonance can be laterally manipulated illustrating the potential to assemble artificial Kondo lattices. Our study demonstrates that the pre-metallation of macrocycles by lanthanides and their controlled manipulation is a novel strategy to engineer in situ tunable Kondo nanoarchitectures, enhancing the potential of coordination chemistry for spintronics.

Optical to ultraviolet spectra of sandwiches of benzene and transition metal atoms: Time dependent density functional theory and many-body calculations.

The optical spectra of sandwich clusters formed by transition metal atoms (titanium, vanadium, and chromium) intercalated between parallel benzene molecules have been studied by time-dependent density functional theory (TDDFT) and many-body perturbation theory. Sandwiches with different number of layers, including infinite chains, are considered. The lowest excitation energy peaks in the spectra are characteristic of the robust bonding in these complexes. The excitation energies vary in a systematic way with the metal atoms and with the cluster size, and so these materials could be used to tune the optical properties according to specific functionality targets. The differences in the spectra could be used to identify relative abundances of isomers with different spins in experimental studies. As a salient feature, this theoretical spectroscopic analysis predicts the metallization of the infinite (TiBz)(infinity) chain, which is not the case of (CrBz)(infinity).

A New Species of Moth Lacewing from the Mesoamerican Genus Adamsiana Penny 1996 (Neuroptera: Ithonidae).

The poorly studied Mesoamerican genus Adamsiana Penny, 1996 (Neuroptera: Ithonidae) was considered monotypic for more than 20 years, containing only Adamsiana curoei Penny. However, a second species was recently discovered in the southern region of Guatemala and is described here as Adamsiana alux Ardila-Camacho, Castillo-Argaez & Martinez, sp. nov. A key to the Adamsiana species and a list of the extant New World Ithonidae species are provided. This work emphasizes the necessity for more studies about not only Ithonidae but also all entomological fauna in the Neotropics.