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BACKGROUND AND AIM: Gastric intestinal metaplasia (GIM) is a high-risk factor for the development of gastric cancer. Narrow-band imaging (NBI) enables endoscopic grading of GIM (EGGIM). In the era of climate change, gastrointestinal endoscopists are expected to reduce greenhouse gas emissions and medical waste. Based on the diagnostic performance of NBI endoscopy, this study measured the environmental impact and reduced cost of implementing EGGIM during gastroscopy. METHODS: Using NBI endoscopy in 242 patients, EGGIM classification and operative link on GIM (OLGIM) staging were prospectively performed in five different areas (lesser and greater curvatures of the corpus and antrum, and the incisura angularis). We estimated the environmental impact and cost reduction of the biopsy procedures and pathological processing if EGGIM were used instead of OLGIM. RESULTS: The diagnostic accuracy of NBI endoscopy for GIM was 93.0-97.1% depending on the gastric area. When a high EGGIM score ≥ 5 was the cut-off value for predicting OLGIM stages III-IV, the area under the curve was 0.862, sensitivity was 81.9%, and specificity was 90.4%. The reduction in the carbon footprint by EGGIM was -0.4059 kg carbon dioxide equivalents per patient, equivalent to 1 mile driven by a gasoline-powered car. The cost savings were calculated to be $47.36 per patient. CONCLUSIONS: EGGIM is a reliable method for identifying high-risk gastric cancer patients, thereby reducing the carbon footprint and medical costs in endoscopy practice.
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Huella de Carbono , Gastroscopía , Metaplasia , Imagen de Banda Estrecha , Neoplasias Gástricas , Humanos , Imagen de Banda Estrecha/métodos , Imagen de Banda Estrecha/economía , Femenino , Masculino , Persona de Mediana Edad , Neoplasias Gástricas/patología , Neoplasias Gástricas/diagnóstico por imagen , Gastroscopía/economía , Gastroscopía/métodos , Huella de Carbono/economía , Anciano , Estudios Prospectivos , Adulto , Ahorro de CostoRESUMEN
BACKGROUND: There is few study evaluating the relationship between endoscopic submucosal dissection (ESD) resection speed and the lesion characteristics of gastric neoplasia. We investigated the learning curve of consecutive ESDs using cumulative sum (CUSUM) analysis. METHODS: A total of 356 ESDs performed by a single endoscopist were grouped chronologically into three learning periods. The ESD procedure was defined to be fast when resection speed was > 9.0 cm2/hour. The CUSUM method was used to assess the number of ESDs required for achieving proficiency and mastery. RESULTS: Mean resection speed was significantly faster in Phase III (15.1 cm2/hour) compared to those in Phase I (9.3 cm2/hour) and II (11.4 cm2/hour) (p < 0.001). Tumors in the stomach's upper and middle third location were significantly associated with difficulty in attaining the fast resection speed (odds ratios, 0.05 and 0.36) compared to the lower third location. The number of ESDs required to achieve a competency for fast resection was 15 for tumors in the lower third of the stomach and 98 for those in the upper/middle third location, respectively. In the lower third location of the tumor, the CUSUM curve revealed that 75 cases were needed to achieve proficiency and 174 cases to achieve mastery. However, mastery was not achieved in ESD for the upper/middle third tumor during the study period. CONCLUSION: The time required to achieve relevant competency in gastric ESD depends on the tumor location.
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Resección Endoscópica de la Mucosa , Neoplasias Gástricas , Humanos , Curva de Aprendizaje , Resección Endoscópica de la Mucosa/métodos , Mucosa Gástrica/cirugía , Mucosa Gástrica/patología , Neoplasias Gástricas/cirugía , Neoplasias Gástricas/patología , Resultado del TratamientoRESUMEN
Graphene has been the subject of much research, with structural engineering frequently used to harness its various properties. In particular, the concepts of graphene origami and kirigami have inspired the design of quasi-three-dimensional graphene structures, which possess intriguing mechanical, electronic, and optical properties. However, accurate controlling the folding process remains a big challenge. Here, we report the discovery of spontaneous folding growth of graphene on the h-BN substrate via adopting a simple chemical vapor deposition method. Folded edges are formed when two stacked graphene layers share a joint edge at a growth temperature up to 1300 °C. Using first-principles density functional theory calculations, the bilayer graphene with folded edges is demonstrated to be more stable than that with open edges. Utilizing this novel growth mode, hexagram bilayer graphene containing entirely sealed edges is eventually realized. Our findings provide a route for designing graphene devices with a new folding dimension.
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Recently, the experimental discovery of high-Tc superconductivity in compressed hydrides H3S and LaH10 at megabar pressures has triggered searches for various superconducting superhydrides. It was experimentally observed that thorium superhydrides, ThH10 and ThH9, are stabilized at much lower pressures than LaH10. Based on first-principles density functional theory calculations, we reveal that the isolated Th frameworks of ThH10 and ThH9 have relatively more excess electrons in interstitial regions than the La framework of LaH10. Such interstitial excess electrons easily participate in the formation of the anionic H cage surrounding the metal atom. The resulting Coulomb attraction between cationic Th atoms and anionic H cages is estimated to be stronger than the corresponding one of LaH10, thereby giving rise to larger chemical precompressions in ThH10 and ThH9. Such a formation mechanism of H clathrates can also be applied to other superhydrides such as CeH9, PrH9, and NdH9. Our findings demonstrate that interstitial excess electrons in the isolated metal frameworks of high-pressure superhydrides play an important role in generating the chemical precompression of H clathrates.
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BACKGROUND: The ABC test measures serum pepsinogen and anti-Helicobacter pylori IgG antibody levels to predict precancerous conditions in the stomach and gastric cancer. However, a limitation of this test is that the gastric cancer risk is not negligible in patients with a negative result. METHODS: Based on their ABC results, 1157 patients were classified into Groups A (n = 392), B (n = 479), C (n = 247), and D (n = 39). In Group A, 24.2% of patients had atrophic gastritis and/or intestinal metaplasia and had thus been incorrectly assigned to Group A. Patients in Group A were then assigned to derivation (n = 236) and validation (n = 156) cohorts by 3:2 random sampling. Logistic regression analyses were performed to identify the factors discriminating between a correct (true) and incorrect (false) Group A classification. RESULTS: A 4-point discriminative model was constructed based on a high-negative H. pylori IgG antibody titer and the patient's age (50-64 and ≥65 years). The areas under the receiver operating characteristic curve for the derivation and validation cohorts were 0.868 and 0.894, respectively. In the validation cohort, the addition of a discriminative model score ≥2 to the ABC method showed a similar accuracy for predicting gastric cancer risk compared with the ABC method alone (93.8% vs. 92.4%). CONCLUSION: The 4-point discriminative model may help identify patients with a normal serological test who are nonetheless at risk of developing gastric cancer.
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Neoplasias Gástricas , Anciano , Helicobacter pylori/inmunología , Humanos , Inmunoglobulina G/sangre , Persona de Mediana Edad , Pepsinógeno A/sangre , Medición de Riesgo , Neoplasias Gástricas/sangre , Neoplasias Gástricas/epidemiologíaRESUMEN
Recently, two-dimensional layered electrides have emerged as a new class of materials which possess anionic electrons in the interstitial spaces between cationic layers. Here, based on first-principles calculations, we discover a time-reversal-symmetry-breaking Weyl semimetal phase in a unique two-dimensional layered ferromagnetic (FM) electride Gd_{2}C. It is revealed that the crystal field mixes the interstitial electron states and Gd-5d orbitals near the Fermi energy to form band inversions. Meanwhile, the FM order induces two spinful Weyl nodal lines (WNLs), which are converted into multiple pairs of Weyl nodes through spin-orbit coupling. Further, we not only identify Fermi-arc surface states connecting the Weyl nodes but also predict a large intrinsic anomalous Hall conductivity due to the Berry curvature produced by the gapped WNLs. Our findings demonstrate the existence of Weyl fermions in the room-temperature FM electride Gd_{2}C, therefore offering a new platform to investigate the intriguing interplay between electride materials and magnetic Weyl physics.
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BACKGROUND AND AIM: This study investigated the usefulness of near-focus narrowband imaging (NF-NBI) for determining gastric tumor margins compared with indigo carmine chromoendoscopy (ICC) before endoscopic submucosal dissection (ESD). METHODS: This prospective randomized controlled trial was conducted at seven teaching hospitals in Korea. Patients with gastric adenoma or differentiated adenocarcinoma undergoing ESD were enrolled and randomly assigned to the NF-NBI or ICC group. A marking dot was placed on the most proximal margin of the tumor before ESD. The primary endpoint was delineation accuracy, which was defined as presence of marking dots within 1 mm of the tumor margin under microscopic observation. RESULTS: A total of 200 patients in the NF-NBI group and 195 patients in the ICC group were included. The delineation accuracy rate was 84.5% in the NF-NBI group and 81.0% in the ICC group (P = 0.44). However, the distance from the marking dot to the margin of the tumor was significantly shorter in the NF-NBI group than in the ICC group (0.8 ± 0.8 vs 1.2 ± 1.3 mm, P < 0.01). Even after adjustment of other clinicopathological factors that are associated with difficulty of tumor delineation, NF-NBI did not show significant association with accurate delineation (odds ratio of 0.86, P = 0.60). CONCLUSIONS: This prospective multicenter study showed that NF-NBI is not superior to ICC in terms of accurately delineating gastric tumors (NCT02661945).
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Resección Endoscópica de la Mucosa/métodos , Endoscopía Gastrointestinal/métodos , Márgenes de Escisión , Imagen de Banda Estrecha/métodos , Neoplasias Gástricas/diagnóstico por imagen , Neoplasias Gástricas/cirugía , Cirugía Asistida por Computador/métodos , Anciano , Femenino , Humanos , Carmin de Índigo , Masculino , Persona de Mediana Edad , Estudios Prospectivos , Neoplasias Gástricas/patología , Resultado del TratamientoRESUMEN
Objective: Serum levels of pepsinogen (PG) are related to Helicobacter pylori-induced inflammation of the gastric mucosa. This study aimed to examine the influence of H. pylori eradication on serum PG, analyze its associated factors, and evaluate the long-term outcomes.Methods: H. pylori-positive patients who underwent gastroscopy and serum PG measurement were enrolled in a single academic hospital. After H. pylori eradication, the measurement of serum PG level was performed. Recovery of serum PG I/II ratio was defined as a PG I/II ratio after eradication of >3.0 in patients with a PG I/II ratio ≤ 3.0 before eradication. Follow-up involved serum PG measurement and gastroscopy with a rapid urease test annually.Results: In all, 327 patients were eligible for study inclusion. Compared to those before H. pylori eradication, serum PG I (74.9 vs. 44.3 ng/mL, p < .001) and PG II (25.4 vs. 9.1 ng/mL, p < .001) levels significantly decreased after successful eradication. In addition, there was a significant increase in serum PG I/II ratio after eradication (3.07 vs. 4.98, p < .001). In multivariate analyses, the following were independently associated with failed recovery of serum PG I/II ratio despite successful eradication: age ≥ 60 years (odds ratio [OR] = 0.231, 95% confidence interval [CI] = 0.084-0.629, p = .004) and severe gastric atrophy (OR = 0.156, 95% CI = 0.055-0.440, p < .001).Conclusions: Recovery of serum PG I/II ratio after H. pylori eradication may be achieved in H. pylori-infected patients aged <60 years without severe gastric atrophy.
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Amoxicilina/uso terapéutico , Antibacterianos/uso terapéutico , Claritromicina/uso terapéutico , Infecciones por Helicobacter/sangre , Infecciones por Helicobacter/tratamiento farmacológico , Helicobacter pylori , Pepsinógeno A/sangre , Inhibidores de la Bomba de Protones/uso terapéutico , Adulto , Anciano , Femenino , Estudios de Seguimiento , Humanos , Masculino , Persona de Mediana Edad , Inducción de Remisión , República de Corea , Factores de TiempoRESUMEN
BACKGROUND AND AIM: The Helicobacter pylori eradication rate using conventional triple therapy has decreased due to clarithromycin (CAM) resistance in H. pylori. Recently, dual priming oligonucleotide (DPO)-based multiplex polymerase chain reaction (PCR) can be used to detect H. pylori and point mutations in the 23S ribosomal RNA gene causing CAM resistance. This study aimed to evaluate the success rate and cost-effectiveness of tailored H. pylori eradication using DPO-PCR. METHODS: The H. pylori-positive patients diagnosed by a rapid urease test or DPO-PCR were enrolled from a single academic hospital. The patients with positive rapid urease test results received a CAM-based triple regimen. In the tailored therapy group that underwent DPO-PCR testing, patients with A2142G and/or A2143G point mutations were treated with a bismuth-containing quadruple regimen. The cost-effectiveness of H. pylori eradication success was evaluated according to the average cost per patient and the incremental cost-effectiveness ratio. RESULTS: A total of 243 patients were allocated to the triple therapy group and 124 patients to the tailored therapy group. The first-line eradication rate of H. pylori was significantly higher in the tailored therapy group than in the conventional triple therapy group (92.7% vs 76.5%, P < 0.001). The average costs per patient for tailored therapy were $307.37 and $299.59 for first-line and second-line treatments, respectively. Compared with triple therapy, the incremental cost-effectiveness ratios of tailored therapy were $3.96 and -$3.81 per patient for first-line and second-line treatments, respectively. CONCLUSION: In Korea, tailored H. pylori eradication using DPO-PCR may be more cost-effective than conventional triple therapy.
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Antibacterianos/economía , Antibacterianos/farmacología , Claritromicina/economía , Claritromicina/farmacología , Análisis Costo-Beneficio , Farmacorresistencia Bacteriana/genética , Gastritis/tratamiento farmacológico , Gastritis/microbiología , Infecciones por Helicobacter , Helicobacter pylori , Mutación Puntual , Medicina de Precisión/economía , Medicina de Precisión/métodos , ARN Ribosómico 23S/genética , Adulto , Anciano , Anciano de 80 o más Años , Pueblo Asiatico , Quimioterapia Combinada/economía , Femenino , Gastritis/diagnóstico , Gastritis/economía , Helicobacter pylori/efectos de los fármacos , Helicobacter pylori/genética , Humanos , Masculino , Persona de Mediana Edad , Reacción en Cadena de la Polimerasa/métodos , Adulto JovenRESUMEN
A flatband representing a highly degenerate and dispersionless manifold state of electrons may offer unique opportunities for the emergence of exotic quantum phases. To date, definitive experimental demonstrations of flatbands remain to be accomplished in realistic materials. Here, we present the first experimental observation of a striking flatband near the Fermi level in the layered Fe_{3}Sn_{2} crystal consisting of two Fe kagome lattices separated by a Sn spacing layer. The band flatness is attributed to the local destructive interferences of Bloch wave functions within the kagome lattices, as confirmed through theoretical calculations and modelings. We also establish high-temperature ferromagnetic ordering in the system and interpret the observed collective phenomenon as a consequence of the synergetic effect of electron correlation and the peculiar lattice geometry. Specifically, local spin moments formed by intramolecular exchange interaction are ferromagnetically coupled through a unique network of the hexagonal units in the kagome lattice. Our findings have important implications to exploit emergent flat-band physics in special lattice geometries.
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BACKGROUND AND AIMS: Education on preparation is essential for successful colonoscopy. This study aimed to evaluate the impact of audiovisual (AV) re-education via a smartphone on bowel preparation quality before colonoscopy. METHODS: A prospective, endoscopist-blinded, randomized, controlled study was performed. Patients who underwent colonoscopy with 3 purgatives, including 4 L of polyethylene glycol (4-L PEG), 2 L of PEG with ascorbic acid (2-L PEG/Asc), and sodium picosulfate with magnesium citrate (SPMC), were enrolled and randomized into the AV re-education via smartphone group (AV group, n = 160) and a control group (n = 160). The primary outcome was the quality of the bowel preparation according to the Boston Bowel Preparation Scale (BBPS). The secondary outcomes included instruction adherence using adherence score (AS) and patient satisfaction with education using a visual analog scale (VAS). RESULTS: A total of 283 patients (AV group, n = 139; control group, n = 144) were analyzed per protocol. The mean BBPS (7.53 vs 6.29, P < .001) and the proportion with adequate preparation were higher in the AV group. The mean BBPS of the AV group was significantly higher than that of the control group for the 2-L PEG/Asc and SPMC preparations, but not for the 4-L PEG preparation. The mean AS and the mean VAS score were all significantly higher in the AV group. Among the 3 purgatives, the mean AS was lowest in the 4-L PEG group (P = .041). CONCLUSIONS: AV re-education via smartphone was easy and convenient, and enhanced preparation quality, patient adherence to instructions, and patient satisfaction.
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Catárticos/administración & dosificación , Colonoscopía/métodos , Cooperación del Paciente/estadística & datos numéricos , Educación del Paciente como Asunto/métodos , Adulto , Anciano , Anciano de 80 o más Años , Ácido Ascórbico/administración & dosificación , Citratos/administración & dosificación , Ácido Cítrico/administración & dosificación , Femenino , Humanos , Masculino , Persona de Mediana Edad , Compuestos Organometálicos/administración & dosificación , Satisfacción del Paciente/estadística & datos numéricos , Picolinas/administración & dosificación , Polietilenglicoles/administración & dosificación , Cuidados Preoperatorios/métodos , Estudios Prospectivos , Método Simple Ciego , Teléfono Inteligente , Grabación en Video/métodosRESUMEN
Bulk tellurium (Te) is composed of one-dimensional (1D) helical chains which have been considered to be coupled by van der Waals (vdW) interactions. However, on the basis of first-principles density functional theory calculations, we here propose a different bonding nature between neighboring chains: i.e., helical chains made of normal covalent bonds are connected together by coordinate covalent bonds. It is revealed that the lone pairs of electrons of Te atoms participate in forming coordinate covalent bonds between neighboring chains, where each Te atom behaves as both an electron donor to neighboring chains and an electron acceptor from neighboring chains. This ligand-metal-like bonding nature in bulk Te results in the same order of bulk moduli along the directions parallel and perpendicular to the chains, contrasting with the large anisotropy of bulk moduli in vdW crystals. We further find that the electron effective masses parallel and perpendicular to the chains are almost the same as each other, consistent with the observed nearly isotropic electrical resistivity. It is thus demonstrated that the normal/coordinate covalent bonds parallel/perpendicular to the chains in bulk Te lead to a minor anisotropy in structural and transport properties.
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Graphene is a promising material for designing next-generation electronic and valleytronic devices, which often demand the opening of a bandgap in the otherwise gapless pristine graphene. To date, several conceptually different mechanisms have been extensively exploited to induce bandgaps in graphene, including spin-orbit coupling and inversion symmetry breaking for monolayer graphene, and quantum confinement for graphene nanoribbons (GNRs). Here, we present a multiscale study of the competing gap opening mechanisms in a graphene overlayer and GNRs proximity-coupled to topological insulators (TIs). We obtain sizable graphene bandgaps even without inversion symmetry breaking and identify the Kekulé lattice distortions caused by the TI substrates to be the dominant gap opening mechanism. Furthermore, Kekulé distorted armchair GNRs display intriguing nonmonotonous gap dependence on the nanoribbon width, resulting from the coexistence of quantum confinement, edge passivation, and Kekulé distortions. The present study offers viable new approaches for tunable bandgap engineering in graphene and GNRs.
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Contemporary science is witnessing a rapid expansion of the two-dimensional (2D) materials family, each member possessing intriguing emergent properties of fundamental and practical importance. Using the particle-swarm optimization method in combination with first-principles density functional theory calculations, here we predict a new category of 2D monolayers named tellurene, composed of the metalloid element Te, with stable 1T-MoS_{2}-like (α-Te), and metastable tetragonal (ß-Te) and 2H-MoS_{2}-like (γ-Te) structures. The underlying formation mechanism is inherently rooted in the multivalent nature of Te, with the central-layer Te behaving more metal-like (e.g., Mo), and the two outer layers more semiconductorlike (e.g., S). We also show that the α-Te phase can be spontaneously obtained from the magic thicknesses divisible by three layers truncated along the [001] direction of the trigonal structure of bulk Te, and both the α- and ß-Te phases possess electron and hole mobilities much higher than MoS_{2}. Furthermore, we present preliminary but convincing experimental evidence for the layering behavior of Te on HOPG substrates, and predict the importance of multivalency in the layering behavior of Se. These findings effectively extend the realm of 2D materials to group-VI elements.
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OBJECTIVE: This study aimed to evaluate the optimal biopsy site for Helicobacter pylori detection by comparing the results of rapid urease test (RUT) between the gastric corpus and the antrum. METHODS: A biopsy specimen from each subject was obtained from the corpus and from the antrum. For each subject, the two specimens were separately immersed in two different RUT kits. Positive reaction times were measured at 20 minutes and 1, 3, and 24 hours. If either of the two RUT kits showed a positive reaction, H. pylori infection was confirmed. RESULTS: A total of 310 H. pylori-infected subjects were eligible for study inclusion. Compared with the antrum, positive RUT reaction times in the corpus were shorter when the degree of gastric atrophy was moderate or severe (p = .001 and p < .001, respectively). A multivariate analysis revealed that the factors resulting in a faster positive RUT reaction in the corpus were age ≥50 years (odds ratio [OR] = 1.84; 95% confidence interval [CI] = 1.10-3.08; p = .021) and severe gastric atrophy (OR = 2.41; 95% CI = 1.13-5.13; p = .023). Also, severe gastric atrophy was an independent factor associated with positive RUT reaction only in the corpus (OR = 5.12; 95% CI = 1.55-16.88; p = .007). CONCLUSIONS: In subjects aged ≥50 years or with severe gastric atrophy, biopsy of the corpus mucosa optimized the efficiency of H. pylori detection through a faster positive RUT reaction.
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Mucosa Gástrica/enzimología , Infecciones por Helicobacter/diagnóstico , Antro Pilórico/patología , Ureasa/análisis , Adulto , Atrofia , Biopsia , Femenino , Mucosa Gástrica/patología , Helicobacter pylori/aislamiento & purificación , Humanos , Modelos Logísticos , Masculino , Persona de Mediana Edad , Análisis Multivariante , Estudios ProspectivosRESUMEN
Chemical modification of graphene with adatoms is of importance for nanoelectronics applications. Based on first-principles density-functional theory calculations including van der Waals interactions, we present a comparative study of the diffusion characteristics of oxygen (O) and fluorine (F) atoms both on graphene and between the layers of bilayer graphene. We find that the calculated diffusion barrier for the O atom increases slightly from 0.81 eV on graphene to 0.85 eV within bilayer graphene, while that for the F atom largely decreases from 0.30 eV on graphene to 0.18 eV within bilayer graphene. Such contrasting behaviors of the O and F diffusions within bilayer graphene can be traced to their different bonding natures: i.e., the O adatom that shows strongly covalent C-O-C bonding on the bridge site of the C-C bond diffuses on one graphene layer with a slight interference of the other layer, while the F adatom that shows semi-ionic F-C bonding on top of a C atom easily diffuses by hopping between two graphene layers by accepting more electron charges from the two layers. The present findings have important implications for the understanding of the diffusion processes of F and O atoms on graphene and within bilayer graphene.
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Quantum growth refers to the phenomena in which the quantum mechanically confined motion of electrons in metallic wires, islands, and films determines their overall structural stability as well as their physical and chemical properties. Yet to date, there has been a lack of a unified understanding of quantum growth with respect to the dimensionality of the nanostructures as well as the valency of the constituent atoms. Based on a first-principles approach, we investigate the stability of nanowires, nanoislands, and ultrathin films of prototypical metal elements. We reveal that the Friedel oscillations generated at the edges (or surfaces) of the nanostructures cause corresponding oscillatory behaviors in their stability, leading to the existence of highly preferred lengths (or thicknesses). Such magic lengths of the nanowires are further found to depend on both the number of valence electrons and the radial size, with the oscillation period monotonously increasing for alkali and group IB metals, and monotonously decreasing for transition and group IIIA-VA metals. When the radial size of the nanowires increases to reach â¼10 Å, the systems equivalently become nanosize islands, and the oscillation period saturates to that of the corresponding ultrathin films. These findings offer a generic perspective of quantum growth of different classes of metallic nanostructures.
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Exploring the properties of noble metal atoms and nano- or subnano-clusters on the semiconductor surface is of great importance in many surface catalytic reactions, self-assembly processes, crystal growth, and thin film epitaxy. Here, the energetics and kinetic properties of a single Cu atom and previously reported Cu magic clusters on the Si(111)-(7 × 7) surface are re-examined by the state-of-the-art first-principles calculations based on density functional theory. First of all, the diffusion path and high diffusion rate of a Cu atom on the Si(111)-(7 × 7) surface are identified by mapping out the total potential energy surface of the Cu atom as a function of its positions on the surface, supporting previous experimental hypothesis that the apparent triangular light spots observed by scanning tunneling microscopy (STM) are resulted from a single Cu atom frequently hopping among adjacent adsorption sites. Furthermore, our findings confirm that in the low coverage of 0.15 monolayer (ML) the previously proposed hexagonal ring-like Cu6 cluster configuration assigned to the STM pattern is considerably unstable. Importantly, the most stable Cu6/Si(111) complex also possesses a distinct simulated STM pattern with the experimentally observed ones. Instead, an energetically preferred solid-centered Cu7 structure exhibits a reasonable agreement between the simulated STM patterns and the experimental images. Therefore, the present findings convincingly rule out the tentative six-atom model and provide new insights into the understanding of the well-defined Cu nanocluster arrays on the Si(111)-(7 × 7) surface.
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Exploration of the catalytic activity of low-dimensional transition metal (TM) or noble metal catalysts is a vital subject of modern materials science because of their instrumental role in numerous industrial applications. Recent experimental advances have demonstrated the utilization of single atoms on different substrates as effective catalysts, which exhibit amazing catalytic properties such as more efficient catalytic performance and higher selectivity in chemical reactions as compared to their nanostructured counterparts; however, the underlying microscopic mechanisms operative in these single atom catalysts still remain elusive. Based on first-principles calculations, herein, we present a comparative study of the key kinetic rate processes involved in CO oxidation using a monomer or dimer of two representative TMs (Pd and Ni) on defective TiO2(110) substrates (TMn@TiO2(110), n = 1, 2) to elucidate the underlying mechanism of single-atom catalysis. We reveal that the O2 activation rates of the single atom TM catalysts deposited on TiO2(110) are governed cooperatively by the classic spin-selection rule and the well-known frontier orbital theory (or generalized d-band picture) that emphasizes the energy gap between the frontier orbitals of the TM catalysts and O2 molecule. We further illuminate that the subsequent CO oxidation reactions proceed via the Langmuir-Hinshelwood mechanism with contrasting reaction barriers for the Pd monomer and dimer catalysts. These findings not only provide an explanation for existing observations of distinctly different catalytic activities of Pd@TiO2(110) and Pd2@TiO2(110) [Kaden et al., Science, 2009, 326, 826-829] but also shed new insights into future utilization and optimization of single-atom catalysis.
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BACKGROUND: Trucut biopsy (TCB) has been proposed to overcome the limitations of endoscopic ultrasonography (EUS)-guided fine-needle aspiration for the pathologic diagnosis of upper gastrointestinal (GI) subepithelial tumor (SET); however, it can be difficult to perform because the Trucut biopsy needle is very stiff. Although technical failures have been reported with the use of TCB, recently the forward-viewing echoendoscope showed a high diagnostic accuracy. We hypothesized that TCB under a conventional forward-viewing endoscope can be applied with higher yield of tissue diagnosis. METHODS: To evaluate the feasibility of TCB under a forward-looking endoscopy without cumbersome EUS guidance, we introduced a 19-gauge TCB needle into the working channel of a conventional upper endoscope in 27 patients with GI SET to make tissue diagnosis. Prospectively collected data were analyzed, including technical success rate, pathologic result, and adverse events. RESULTS: Twenty-seven patients with GI SET (18 esophageal tumors and nine gastric tumors) underwent TCB under a forward-looking endoscope. All procedures were performed safely without any TCB-related complications. Subsequently, histopathology examination revealed gastrointestinal stromal tumors (GISTs) in three cases and leiomyomas in 21 cases. Histologic assessment was completed in 24 out of 27 patients (88.9 %) because tissue obtained from three patients, whose tumors were located in the stomach, was not sufficient for the pathologic diagnosis. CONCLUSIONS: TCB using a conventional forward-viewing endoscope without EUS guidance provided an excellent pathologic diagnosis of upper GI SET.