Quantum confinement of surface electrons in two-dimensional metal-organic networks offers a powerful route to engineer electronic states for quantum and spintronic technologies. Here, we demonstrate the pivotal role of vertical variations in the surface potential on the quantum confinement of surface electrons. We investigate the confinement of both Shockley surface state and image-potential state electrons with their distinct vertical electron density distributions in a Cu-T4PT network on Cu(111). We find a substantial renormalization of the band mass of the image state, whereas the Shockley state remains almost unchanged. This notable divergence arises from the distinct three-dimensional potential landscape of the Cu-T4PT network, with a strong repulsive potential at the vertical position of the molecular backbone and leaky channels beneath the Cu coordination spheres. Our findings demonstrate the essential role of vertical potential engineering in designing quantum-confined states, thereby advancing control over electronic properties and quantum phenomena at the nanoscale.

Introduction Eosinophilia is a rare disease characterized by an increase in eosinophils. Suplatast tosilate is a selective Th2 cytokine inhibitor that can reduce eosinophils. There is currently a lack of clinical studies of suplatast tosilate in the treatment of eosinophilia. Research objective To explore whether suplatast tosilate can reduce blood eosinophil levels in eosinophilia and the factors that might influence the improvement. Methods A real-world retrospective study of 20 patients with eosinophilia was conducted using electronic medical record information. The main outcome measure was the difference in peripheral blood absolute eosinophil count (AEC) and percentage (EOS%) before suplatast tosilate (baseline) and the lowest AEC during the 1-year period of suplatast tosilate treatment (post-treatment). Data on age, gender, disease duration, involved organs, and concomitant medication were collected, and subgroup analysis and linear regression analysiswere performed. Results Subjects were predominantly male, with a mean age of 33 years and a disease duration of approximately 30 months. After treatment with suplatast tosilate, the patient's AEC (p=0.029) and EOS% (p=0.016) significantly decreased. The decline in eosinophils was more pronounced in patients who were male, age < 33 years, disease duration < 30 months and gastrointestinal system involvement. In addition, the shorter the course of the disease, the greater the relative decrease in eosinophils after suplatast tosilate treatment (β=-0.018, p<0.001). Conclusions Suplatast tosilate is effective in reducing peripheral blood eosinophil levels in patients with eosinophilia. Large-scale prospective cohort studies are needed for further confirmation.

Background Hypereosinophilia (HE) is a rare disease characterized by an increase in eosinophils. Suplatast tosilate is a selective Th2 cytokine inhibitor. This case report presents the course and prognosis of a patient with hypereosinophilia treated with suplatast tosilate monotherapy. Case presentation A 41-year-old female patient who complained of "Elevated blood eosinophils were found during physical examination for more than 2 months" visited the Allergy Department. The systematic screening results of parasites, autoantibodies spectrum, tumor markers, peripheral blood morphology analysis, and leukemia fusion gene (FIP1L1-PDGFR α) were all negative. Gastrointestinal endoscopy only indicated mild gastritis. The dust mites and multiple fungal mixtures were weakly positive in intradermal tests. Finally diagnosed HE. After treatment with suplatast tosilate 2 months of 100mg three times daily, the blood eosinophils decreased to normal. Then, maintenance treatment with 50mg three times a day for 3 months. And without recurrence during nearly five years of follow-up. Conclusion The report indicates that suplatast tosilate can reduce peripheral blood eosinophils levels in patients with HE, and may be a reliable option for individualized treatment of HE. However, there is still no consensus on whether suplatast tosilate can be used as a first-line treatment or as an adjuvant therapy to reduce the corticosteroids dosage for patients with eosinophilia, and further research is needed.

Two-dimensional metal-organic porous networks (2D-MOPNs) have been identified as versatile nanoarchitectures to tailor surface electronic and magnetic properties on noble metals. In this context, we propose a protocol to redecorate a ferromagnetic surface potential landscape using a 2D-MOPN. Ultrathin cobalt (Co) films grown on Au(111) exhibit a well-ordered surface triangular reconstruction. On the ferromagnetic surface, the adsorbed 2,4,6-tris(4-pyridyl)-1,3,5triazine (T4PT) molecules can coordinate with the native Co atoms to form a large-scale Co-T4PT porous network. The Co-T4PT network with periodic nanocavities serves as a templating layer to reshape the ferromagnetic surface potential. The subsequently deposited C60 molecules are steered by the network porous potential and the neighboring C60 interactions. The prototype of the ferromagnetic-supported 2D-MOPN is a promising template for the tailoring of molecular electronic and spin properties.

Two-dimensional organic porous networks (2DOPNs) have opened new vistas for tailoring the physicochemical characteristics of metallic surfaces. These typically chemically bound nanoporous structures act as periodical quantum wells leading to the 2D confinements of surface electron gases, adatoms and molecular guests. Here we propose a new type of porous network with weakly interacting 2,4,6-triphenyl-1,3,5-triazine (TPT) molecules on a Cu(111) surface, in which a temperature-driven (T-driven) phase transition can reversibly alter the supramolecular structures from a close-packed (CP-TPT) phase to a porous-network (PN-TPT) phase. Crucially, only the low-temperature PN-TPT exhibits subnano-scale cavities that can confine the surface state electrons and metal adatoms. The confined surface electrons undergo a significant electronic band renormalization. To activate the spin degree of freedom, the T-driven PN-TPT structure can additionally trap Co atoms within the cavities, forming highly ordered quantum dots. Our theoretical simulation reveals a complex spin carrier transfer from the confined Co cluster to the neighbouring TPT molecules via the underlying substrate. Our results demonstrate that weakly interacting 2DOPN offers a unique quantum switch capable of steering and controlling electrons and spin at surfaces via tailored quantum confinements.

Surface alloys are a highly tunable class of low dimensional materials with the opportunity to tune and control the spin and charge carrier functionalities on the nanoscale. Here, we focus on the atomic and mesoscopic structural details of three distinctive binary rare-earth-noble metals (RE/NM) surface alloys by employing scanning tunneling microscopy (STM) and low energy electron diffraction (LEED). Using Dysprosium as the guest element on fcc(111) noble metal substrates, we identify the formation of non-commensurate surface alloy superstructures which exhibit homogeneous moiré patterns for DyCu2/Cu (111) and DyAu2/Au(111), while an inhomogeneous one is found for DyAg2/Ag(111). The variations in the local structure are analyzed for all three surface alloys and the observed differences are discussed in the light of the lattice mismatches of the alloy layer with respect to the underlying substrate. For the particularly intriguing case of a Dy-Ag surface alloy, the surface alloy layer does not show a uniform long-range periodic structure, but consists of local hexagonal tiles separated by extended domain walls. These domain walls exist to relief the in-plane strain within the DyAg2 surface alloy layer. Our findings clearly demonstrate that surface alloying is an intriguing tool to tailor both the local atomic, but also the mesoscopic moiré structures of metallic heterostructures.

Context: The hemoglobin glycation index (HGI) is correlated with metabolic diseases and inflammation. Whether the HGI is associated with the aging process and how inflammation and oxidative stress affect the relationship remain unclear. Objective: We aimed to analyze links between the HGI and aging biomarkers, and to explore a potential role of inflammation and oxidative stress in the correlations. Methods: A cross-sectional study of 434 subjects with different glucose intolerances in a rural community was enrolled. The HGI was calculated as the difference between the measured and predicted hemoglobin A1c (HbA1c). The population was categorized into tertiles of the HGI. Telomere length (LTL) and mitochondrial DNA copy number (mtDNAcn) determined by polymerase chain reaction assay.Tumor necrosis factor (TNF) alpha and interleukin (IL) 6, 8-oxo-2'-deoxyguanosine (8-oxo-dG), superoxide dismutase (SOD) activities, and glutathione reductase (GR) were measured. Results: Participants in the high HGI group were older and reported a shorter LTL, higher levels of TNF alpha, SOD activities, and HbA1c. Correlation analyses demonstrated that HGI was correlated with LTL (r = -0.25, P < .001) and TNF alpha (r = 0.19, P < .001) regardless of HbA1c levels. No relationship was found between HGI and mtDNAcn. HGI (beta = -0.238, 95% CI -0.430, -0.046, P= .015) and TNF alpha (beta =-0.02, 95% CI -0.030, -0.014, P< .001) were proved to be correlated with LTL independently, using multiple linear regression analysis. Ordinal logistic regression models showed that compared with subjects the high HGI group, the possibilities of a higher-level LTL was 5.29-fold in the low HGI group (OR 5.29, 95% CI (2.45, 11.41), P< .001), 2.41-fold in the moderate HGI group (OR 2.41, 95% CI 1.35, 4.30, P= .003) after controlling for confounding variables. Mediation analyses indicated that TNF alpha accounted for 30.39% of the effects of the HGI on LTL. Conclusion: HGI was negatively related to telomere attrition, independent of HbA1c. TNF alpha acted as a mediator of the relationship between HGI and LTL.

Purpose:An end-of-fast insulin level ≥ 3 µIU/ml, C-peptide level ≥ 0.6 ng/ml, and proinsulin level ≥ 5 pmol/l with end-of-fast glucose level ≤ 3.0 mmol/l have been established as the criteria for endogenous hyperinsulinemic hypoglycemia. However, all these criteria have been proposed based on patients in Western populations. This study aimed to determine the optimal criteria using a large series of Chinese patients.Methods:This retrospective study comprised 144 patients with surgically proven insulinoma and 40 controls who underwent a 72-h fasting test at the Peking Union Medical College Hospital(PUMCH) from 2000 to 2020. Receiver operating characteristic curves were used for analysis.Results:In this series of patients, the optimal diagnostic criteria for endogenous hyperinsulinemic hypoglycemia were insulin  ≥ 5.5 μIU/ml, C-peptide ≥ 0.7 ng/ml, and proinsulin ≥ 12 pmol/l with end-of-fast glucose ≤ 2.8 mmol/l; the sensitivity and specificity were 99% and 100% for insulin, 100% and 100% for C-peptide, and 93% and 100% for proinsulin, respectively. The diagnostic efficacy of the criteria based on Western populations was then tested. The sensitivity and specificity of end-of-fast insulin ≥ 3 μIU/ml, C-peptide ≥ 0.6 ng/ml, and proinsulin ≥ 5 pmol/l with end-of-fast glucose ≤ 3.0 mmol/l were 100% and 83%, 100% and 80%, and 97% and 78%, respectively.Conclusions:New and optimized diagnostic criteria for endogenous hyperinsulinemic hypoglycemia in Chinese populations have been proposed, and these criteria yield satisfactory accuracy.

Mobilisierung beim Abkühlen Auf einer Kupferoberfläche adsorbierte Dimolybdäntetraacetat-Moleküle bilden bei Raumtemperatur eine geordnete Struktur aus aufrecht stehenden Molekülen. Beim Abkühlen auf 220 K werden die Moleküle auf der Oberfläche beweglich. Dieser kontraintuitive Phasenübergang von einer geordneten Struktur bei hohen Temperaturen zu einer mobilen Phase bei tiefen Temperaturen lässt sich durch eine geringere molare Entropie in der mobilen Phase im Vergleich zur geordneten Phase erklären, wie Angelika Kühnle et al. in ihrer Zuschrift auf S. 19265 berichten.

Phase transitions between different aggregate states are omnipresent in nature and technology. Conventionally, a crystalline phase melts upon heating as we use ice to cool a drink. Already in 1903, Gustav Tammann speculated about the opposite process, namely melting upon cooling. So far, evidence for such "inverse" transitions in real materials is rare and limited to few systems or extreme conditions. Here, we demonstrate an inverse phase transition for molecules adsorbed on a surface. Molybdenum tetraacetate on copper(111) forms an ordered structure at room temperature, which dissolves upon cooling. This transition is mediated by molecules becoming mobile, i.e., by mobilization upon cooling. This unexpected phenomenon is ascribed to the larger number of internal degrees of freedom in the ordered phase compared to the mobile phase at low temperatures.

AbstractPhasenübergänge zwischen unterschiedlichen Aggregatzuständen sind in Natur und Technik allgegenwärtig. Üblicherweise schmilzt ein Kristall, wenn er erwärmt wird. Daher nutzen wir Eis, um einen Drink zu kühlen. Bereits im Jahre 1903 spekulierte Gustav Tammann über den umgekehrten Prozess des Schmelzens durch Kühlen. Bisher gibt es allerdings nur sehr wenige Beispiele für solche “inversen” Phasenübergänge, die meist auch auf extreme Bedingungen beschränkt sind. Hier zeigen wir einen inversen Phasenübergang von adsorbierten Molekülen auf einer Oberfläche. Molybdänacetat bildet bei Zimmertemperatur eine geordnete Struktur auf der (111)‐Oberfläche von Kupfer, die sich beim Kühlen auflöst. Dieser Übergang entsteht dadurch, dass die Moleküle mobil werden, d. h., wir beobachten die Mobilisierung durch Kühlen. Dieses unerwartete Phänomen kann durch die große Zahl an internen Freiheitsgraden der geordneten Phase im Vergleich zur mobilen Phase erklärt werden.

Controlling the structure formation of molecules on surfaces is fundamental for creating molecular nanostructures with tailored properties and functionalities and relies on tuning the subtle balance between intermolecular and molecule-surface interactions. So far, however, reliable rules of design are largely lacking, preventing the controlled fabrication of self-assembled functional structures on surfaces. In addition, while so far many studies focused on varying the molecular building blocks, the impact of systematically adjusting the underlying substrate has been less frequently addressed. Here, we elucidate the potential of tailoring the mesoscopic island shape by tuning the interactions at the molecular level. As a model system, we have selected the molecule dimolybdenum tetraacetate on three prototypical surfaces, Cu(111), Au(111) and CaF 2 (111). While providing the same hexagonal geometry, compared to Cu(111), the lattice constants of Au(111) and CaF 2 (111) differ by a factor of 1.1 and 1.5, respectively. Our high-resolution scanning probe microscopy images reveal molecular-level information on the resulting islands and elucidate the molecular-level design principles for the observed mesoscopic island shapes. Our study demonstrates the capability to tailor the mesoscopic island shape by exclusively tuning the substrate lattice constant, in spite of the very different electronic structure of the substrates involved. This work provides insights for developing general design strategies for controlling molecular mesostructures on surfaces.

The interface between organic semiconductors and Co thin film has been studied by spin-resolved photoemission spectroscopy. We found that the spin-polarized states of cobalt still exist when 1.0 nm rubrene or 0.7 nm C60 or 1.0 nm DBBA molecules deposited on Co, while 0.4 nm C8-BTBT eliminates the highly spin-polarized states of cobalt due to the desulfurization reaction occurred at the interface. The mode and strength of the interfacial interaction between organic semiconductors and magnetic electrode affect the spin-polarized states of magnetic electrode greatly. Our observations provide assistance in device design, fabrication and performance improvement in Co-based organic spintronic devices.

Designing exotic structures in low dimensions is key in today’s quest to tailor novel quantum states in materials with unique symmetries. Particularly intriguing materials in this regard are low dimensional aperiodic structures with non-conventional symmetries that are otherwise forbidden in translation symmetric crystals. In our work, we focus on the link between the structural and electronic properties of aperiodically ordered aromatic molecules on a quasicrystalline surface, which has largely been neglected so far. As an exemplary case, we investigate the self-assembly and the interfacial electronic properties of the nano-graphene-like molecule coronene on the bulk truncated icosahedral (i) Al–Pd–Mn quasicrystalline surface using multiple surface sensitive techniques. We find an aperiodically ordered coronene monolayer (ML) film on the i-Al–Pd–Mn surface that is characterized by the same local motifs of the P1 Penrose tiling model as the bare i-Al–Pd–Mn surface. The electronic valence band structure of the coronene/i-Al–Pd–Mn system is characterized by the pseudogap of thebare i-Al–Pd–Mn, which persists the adsorption of coronene confirming the quasiperiodic nature of the interface. In addition, we find a newly formed interface state of partial molecular character that suggests an at least partial chemical interaction between the molecule and the quasicrystalline surface. We propose that this partial chemical molecule–surface interaction is responsible for imprinting the quasicrystalline order of the surface onto the molecular film.

The discovery and realization of graphene as an ideal two-dimensional (2D) material has triggered extensive efforts to create similar 2D materials with exciting spin-dependent properties. Here, we report on a novel Sn 2D superstructure on Au(111) that shows similarities and differences to the expected electronic features of ideal stanene. Using spin- and angle-resolved photoemission spectroscopy, we find that a particular Sn/Au superstructure reveals a linearly dispersing band centered at the Γ̅ -point and below the Fermi level with anti-parallel spin polarization and a Fermi velocity of v F ≈ 1×10 6 m/s, the same value as for graphene. We attribute the origin of the band structure to the hybridization between the Sn and the Au orbitals at the 2D Sn-Au interface. Considering that free-standing stanene simply cannot exist, our investigated structure is an important step towards the search of useful stanene-like overstructures for future technological applications.

We have observed breaking down and reconstruction of islands in the film growth of a copper phthalocyanine (CuPc) film on highly ordered pyrolytic graphite using photoelectron spectroscopy (PES) and atomic force microscopy (AFM). At the initial deposition of CuPc, the film adopts the Stranski-Krastanov mode and the islands increase normally with the nominate film thickness. At a critical thickness around 6nm, the islands break down suddenly into small clusters. Further deposition drives the reunion of clusters to form large islands again and makes the film coverage smaller at a nominate thickness of 13nm. The nonmonotonic PES data and AFM morphology confirmed the re-exposure of the substrate and the first layer CuPc during the island reconstruction process. This nonmonotonic growth behavior may exist widely in many anisotropic molecular film growth processes where the thin film phases are confined or restricted by the symmetry of the substrate and different from their bulk phases.

Comprehensive measurements of ultraviolet photoemission spectroscopy, X-ray photoemission spectroscopy, X-ray diffraction, and atomic force microscopy are adopted to investigate the corelevance of energy level alignment, molecular orientation, and film growth of Au/C8BTBT/perovskite interfaces. A small energy offset of valence band maximum of 0.06 eV between perovskite and C8BTBT makes hole transportation feasible. About 0.65 eV upward shift of energy levels is observed with the deposition of the Au film on C8BTBT, which enhances hole transportation to the Au electrode. The observations from the interface analysis are supported by a prototype photodetector of Au (80 nm)/C8BTBT (20 nm)/perovskite (100 nm) that exhibits excellent performances whose responsivity can reach up to 2.65 A W-1, 4 times higher than the best CH3NH3PbI3 photodetectors.

The bimetallic molecular compound Dimolybdenum tetraacetate (MoMo-Methyl) is grown on a Cu(111) surface with submonolayer coverage. Scanning tunneling microscopy experiments reveal that the compound forms two different structural phases on the Cu surface, whose ratio can be reversibly controlled by changing the sample temperature. The so-called chain-phase is characterized by tilted Mo-Mo dimers bonded to the Cu surface via the methyl groups. In the so-called mesh-phase, on the other hand, the molecules adsorb in a flat lying adsorption configuration with one of the Mo-atoms in direct contact with the Cu surface. Crucially, the different structural properties of the two phases reflect the different inter- and intramolecular interactions between the Mo metal centers, as well as the different interactions between Mo and the Cu surface atoms. In this way, the structural changes result in a modification of the cooperative effects in the system. Therefore, it is proposed that the observed reversible structural phase transition could be used to control the strength of cooperative effects in MoMo-Methyl on Cu(111).

We have investigated the atomic and electronic structure of the (root 3x root 3)R30 degrees SnAu2/Au(111) surface alloy. Low-energy electron diffraction and scanning tunneling microscopy measurements show that the native herringbone reconstruction of bare Au(111) surface remains intact after formation of a long-range ordered (root 3x root 3)R30 degrees SnAu2/Au(111) surface alloy. Angle-resolved photoemission and two-photon photoemission spectroscopy techniques reveal Rashba-type spin-split bands in the occupied valence band with comparable momentum space splitting as observed for the Au(111) surface state, but with a hole-like parabolic dispersion. Our experimental findings are compared with density functional theory (DFT) calculation that fully support our experimental findings Taking advantage of the good agreement between our DFT calculations and the experimental results, we are able to extract that the occupied Sn-Au hybrid band is of (s, d)-orbital character, while the unoccupied Sn-Au hybrid bands are of (p, d)-orbital character. Hence we can conclude that the Rashba-type spin splitting of the hole-like Sn-Au hybrid surface state is caused by the significant mixing of Au d with Sn s states in conjunction with the strong atomic spin-orbit coupling of Au. i.e., of the substrate.

We have investigated the atomic and electronic structure of the $(\sqrt{3}\ifmmode\times\else\texttimes\fi{}\sqrt{3})R{30}^{\ensuremath{\circ}}\phantom{\rule{4pt}{0ex}}\mathrm{SnA}{\mathrm{u}}_{2}\text{/}\mathrm{Au}(111)$ surface alloy. Low-energy electron diffraction and scanning tunneling microscopy measurements show that the native herringbone reconstruction of bare Au(111) surface remains intact after formation of a long-range ordered $(\sqrt{3}\ifmmode\times\else\texttimes\fi{}\sqrt{3})R{30}^{\ensuremath{\circ}}\mathrm{SnA}{\mathrm{u}}_{2}\text{/}\mathrm{Au}(111)$ surface alloy. Angle-resolved photoemission and two-photon photoemission spectroscopy techniques reveal Rashba-type spin-split bands in the occupied valence band with comparable momentum space splitting as observed for the Au(111) surface state, but with a hole-like parabolic dispersion. Our experimental findings are compared with density functional theory (DFT) calculation that fully support our experimental findings. Taking advantage of the good agreement between our DFT calculations and the experimental results, we are able to extract that the occupied Sn-Au hybrid band is of $(s,\phantom{\rule{0.28em}{0ex}}d)$-orbital character, while the unoccupied Sn-Au hybrid bands are of $(p,\phantom{\rule{0.28em}{0ex}}d)$-orbital character. Hence we can conclude that the Rashba-type spin splitting of the hole-like Sn-Au hybrid surface state is caused by the significant mixing of Au $d$ with Sn $s$ states in conjunction with the strong atomic spin-orbit coupling of Au, i.e., of the substrate.