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.

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.

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.

Chemical equilibrium in AGB atmospheres: Successes, failures, and prospects for small molecules, clusters, and condensates.

Chemical equilibrium has proven extremely useful for predicting the chemical composition of AGB atmospheres. Here we use a recently developed code and an updated thermochemical database that includes gaseous and condensed species involving 34 elements to compute the chemical equilibrium composition of AGB atmospheres of M-, S-, and C-type stars. We include for the first time Ti x C y clusters, with x = 1-4 and y = 1-4, and selected larger clusters ranging up to Ti13C22, for which thermochemical data are obtained from quantum-chemical calculations. Our main aims are to systematically survey the main reservoirs of each element in AGB atmospheres, review the successes and failures of chemical equilibrium by comparing it with the latest observational data, identify potentially detectable molecules that have not yet been observed, and diagnose the most likely gas-phase precursors of dust and determine which clusters might act as building blocks of dust grains. We find that in general, chemical equilibrium reproduces the observed abundances of parent molecules in circumstellar envelopes of AGB stars well. There are, however, severe discrepancies of several orders of magnitude for some parent molecules that are observed to be anomalously overabundant with respect to the predictions of chemical equilibrium. These are HCN, CS, NH3, and SO2 in M-type stars, H2O and NH3 in S-type stars, and the hydrides H2O, NH3, SiH4, and PH3 in C-type stars. Several molecules have not yet been observed in AGB atmospheres but are predicted with non-negligible abundances and are good candidates for detection with observatories such as ALMA. The most interesting ones are SiC5, SiNH, SiCl, PS, HBO, and the metal-containing molecules MgS, CaS, CaOH, CaCl, CaF, ScO, ZrO, VO, FeS, CoH, and NiS. In agreement with previous studies, the first condensates predicted to appear in C-rich atmospheres are found to be carbon, TiC, and SiC, while Al2O3 is the first major condensate expected in O-rich outflows. According to our chemical equilibrium calculations, the gas-phase precursors of carbon dust are probably acetylene, atomic carbon, and/or C3, while for silicon carbide dust, the most likely precursors are the molecules SiC2 and Si2C. In the case of titanium carbide dust, atomic Ti is the major reservoir of this element in the inner regions of AGB atmospheres, and therefore it is probably the main supplier of titanium during the formation of TiC dust. However, chemical equilibrium predicts that large titanium-carbon clusters such as Ti8C12 and Ti13C22 become the major reservoirs of titanium at the expense of atomic Ti in the region where condensation of TiC is expected to occur. This suggests that the assembly of large Ti x C y clusters might be related to the formation of the first condensation nuclei of TiC. In the case of Al2O3 dust, chemical equilibrium indicates that atomic Al and the carriers of Al-O bonds AlOH, AlO, and Al2O are the most likely gas-phase precursors.

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.

Aperture design for the third neutron and first gamma-ray imaging systems for the National Ignition Facility.

The current construction of a new nuclear-imaging view at the National Ignition Facility will provide a third line of sight for hotspot and cold fuel imaging and the first dedicated line of sight for 4.4-MeV γ-ray imaging of the remaining carbon ablator. To minimize the effort required to hold and align apertures inside the vacuum chamber, the apertures for the two lines of sight will be contained in the same array. In this work, we discuss the system requirements for neutron and γ-ray imaging and the resulting aperture array design.

Mexican consensus on lysosomal acid lipase deficiency diagnosis. / Consenso mexicano sobre el diagnóstico de la deficiencia de lipasa ácida lisosomal.

INTRODUCTION: Lysosomal acid lipase deficiency (LAL-D) causes progressive cholesteryl ester and triglyceride accumulation in the lysosomes of hepatocytes and monocyte-macrophage system cells, resulting in a systemic disease with various manifestations that may go unnoticed. It is indispensable to recognize the deficiency, which can present in patients at any age, so that specific treatment can be given. The aim of the present review was to offer a guide for physicians in understanding the fundamental diagnostic aspects of LAL-D, to successfully aid in its identification. METHODS: The review was designed by a group of Mexican experts and is presented as an orienting algorithm for the pediatrician, internist, gastroenterologist, endocrinologist, geneticist, pathologist, radiologist, and other specialists that could come across this disease in their patients. An up-to-date review of the literature in relation to the clinical manifestations of LAL-D and its diagnosis was performed. The statements were formulated based on said review and were then voted upon. The structured quantitative method employed for reaching consensus was the nominal group technique. RESULTS: A practical algorithm of the diagnostic process in LAL-D patients was proposed, based on clinical and laboratory data indicative of the disease and in accordance with the consensus established for each recommendation. CONCLUSION: The algorithm provides a sequence of clinical actions from different studies for optimizing the diagnostic process of patients suspected of having LAL-D.

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.

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.

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.

Low Temperature Metal Free Growth of Graphene on Insulating Substrates by Plasma Assisted Chemical Vapor Deposition.

Direct growth of graphene films on dielectric substrates (quartz and silica) is reported, by means of remote electron cyclotron resonance plasma assisted chemical vapor deposition r-(ECR-CVD) at low temperature (650°C). Using a two step deposition process- nucleation and growth- by changing the partial pressure of the gas precursors at constant temperature, mostly monolayer continuous films, with grain sizes up to 500 nm are grown, exhibiting transmittance larger than 92% and sheet resistance as low as 900 Ω·sq-1. The grain size and nucleation density of the resulting graphene sheets can be controlled varying the deposition time and pressure. In additon, first-principles DFT-based calculations have been carried out in order to rationalize the oxygen reduction in the quartz surface experimentally observed. This method is easily scalable and avoids damaging and expensive transfer steps of graphene films, improving compatibility with current fabrication technologies.

Design of the polar neutron-imaging aperture for use at the National Ignition Facility.

The installation of a neutron imaging diagnostic with a polar view at the National Ignition Facility (NIF) required design of a new aperture, an extended pinhole array (PHA). This PHA is different from the pinhole array for the existing equatorial system due to significant changes in the alignment and recording systems. The complex set of component requirements, as well as significant space constraints in its intended location, makes the design of this aperture challenging. In addition, lessons learned from development of prior apertures mandate careful aperture metrology prior to first use. This paper discusses the PHA requirements, constraints, and the final design. The PHA design is complex due to size constraints, machining precision, assembly tolerances, and design requirements. When fully assembled, the aperture is a 15 mm × 15 mm × 200 mm tungsten and gold assembly. The PHA body is made from 2 layers of tungsten and 11 layers of gold. The gold layers include 4 layers containing penumbral openings, 4 layers containing pinholes and 3 spacer layers. In total, there are 64 individual, triangular pinholes with a field of view (FOV) of 200 µm and 6 penumbral apertures. Each pinhole is pointed to a slightly different location in the target plane, making the effective FOV of this PHA a 700 µm square in the target plane. The large FOV of the PHA reduces the alignment requirements both for the PHA and the target, allowing for alignment with a laser tracking system at NIF.

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.

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.

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.

Reversible stimulus-responsive Cu(I) iodide pyridine coordination polymer.

We present a structurally flexible copper-iodide-pyridine-based coordination polymer showing drastic variations in its electrical conductivity driven by temperature and sorption of acetic acid molecules. The dramatic effect on the electrical conductivity enables the fabrication of a simple and robust device for gas detection. X-ray diffraction studies and DFT calculations allow the rationalisation of these observations.

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.

Simultaneous neutron and x-ray imaging of inertial confinement fusion experiments along a single line of sight at Omega.

Neutron and x-ray imaging provide critical information about the geometry and hydrodynamics of inertial confinement fusion implosions. However, existing diagnostics at Omega and the National Ignition Facility (NIF) cannot produce images in both neutrons and x-rays along the same line of sight. This leads to difficulty comparing these images, which capture different parts of the plasma geometry, for the asymmetric implosions seen in present experiments. Further, even when opposing port neutron and x-ray images are available, they use different detectors and cannot provide positive information about the relative positions of the neutron and x-ray sources. A technique has been demonstrated on implosions at Omega that can capture x-ray images along the same line of sight as the neutron images. The technique is described, and data from a set of experiments are presented, along with a discussion of techniques for coregistration of the various images. It is concluded that the technique is viable and could provide valuable information if implemented on NIF in the near future.

Magnetic properties of a Kramers doublet. An univocal bridge between experimental results and theoretical predictions.

The magnetic response of a Kramers doublet is analyzed in a general case taking into account only the formal properties derived from time reversal operation. It leads to a definition of a matrix G (gyromagnetic matrix) whose expression depends on the chosen reference frame and on the Kramers conjugate basis used to describe the physical system. It is shown that there exists a reference frame and a suitable Kramers conjugate basis that gives a diagonal form for the G-matrix with all non-null elements having the same sign. A detailed procedure for obtaining this canonical expression of G is presented when the electronic structure of the KD is known regardless the level of the used theory. This procedure provides a univocal way to compare the theoretical predictions with the experimental results obtained from a complete set of magnetic experiments. In this way the problems arising from ambiguities in the g-tensor definition are overcome. This procedure is extended to find a spin-Hamiltonian suitable for describing the magnetic behavior of a pair of weakly coupled Kramers systems in the multispin scheme when the interaction between the two moieties as well as the individual Zeeman interaction are small enough as compared with ligand field splitting. Explicit relations between the physical interaction and the parameters of such a spin-Hamiltonian are also obtained.