A Three-Dimensionally Extended Metal-Organic Ladder Compound Exhibiting Proton Conduction.

Ladder systems situated in the dimensional crossover region have attracted much attention because their electronic states and physical properties depend strongly on the electronic correlations among the constituent legs. Generally, two-/three-legged transition metal-oxide ladder compounds are studied as representative ladder systems, but two-/three-dimensional (2D/3D) extensions based on such ladder systems with a few numbers of legs are difficult because of the extreme synthesis conditions. Here, for the first time, we report the successful creation of a 3D extended two-legged ladder compound, [Pt(en)(dpye)I]2(NO3)4 ⋅ 2H2O (en=ethylenediamine; dpye=1,2-Di(4-pyridyl)ethane), which is obtained by simple oxidative polymerization of a small Pt macrocyclic complex using elemental I2. The unique 3D extended lattice consists of 1D mixed-valence halogen-bridged metal chains (⋅⋅⋅Pt-I-Pt-I⋅⋅⋅) and helically arranged macrocyclic units as the constituent legs and rungs, as confirmed by single-crystal X-ray diffraction. Diffuse X-ray scattering analyses and optical measurements revealed that the out-of-phase mixed-valence Pt2+/Pt4+ arrangement arises from the weak interchain correlation among adjacent legs. In addition, this compound shows an increase in proton conductivity by a factor of up to 1000, depending on humidity.

Life-threatening coronary vasospasm in patients with type 2 diabetes with SGLT2 inhibitor-induced euglycemic ketoacidosis: a report of two consecutive cases.

Euglycemic diabetic ketoacidosis (eDKA) has emerged as an adverse event associated with sodium-glucose transporter-2 inhibitors (SGLT2i). We present two consecutive cases of SGLT2i-induced eDKA, both manifested as life-threatening coronary vasospastic angina (VSA). Case 1: A 64-year-old male overweight patient with type 2 diabetes (BMI 28.2 kg/m2), treated with dapagliflozin 5 mg daily for 6 months and a restricted diet for 2 months, experienced loss of consciousness following severe chest pain while driving, resulting in a traffic accident: plasma glucose, 163 mg/dL; urine ketones, (+++); bicarbonate (HCO3-), 13.2 mmol/L; and total ketone body, 1539 µmol/L. Coronary angiography (CAG) performed on day 5 revealed diffusely spastic coronary arteries with 90% stenosis in the right coronary artery, leading to the diagnosis of VSA in the presence of coronary atherosclerosis. Case 2: A 63-year-old male patient with type 2 diabetes (BMI 22.2 kg/m2) experienced severe chest discomfort and faintness following 2 months of chest pain while on dapagliflozin 10 mg daily for 1 year: plasma glucose, 112 mg/dL; urine ketones, (+++); HCO3-, 15.3 mmol/L; and total ketone body, 10,883 µmol/L. CAG performed on day 10 revealed no organic stenosis but diffusely spastic coronary arteries in response to coronary ergonovine infusion, confirming the diagnosis of VSA. SGLT2i has the potential to inhibit acetylcholine and butyrylcholine esterase activities, leading to reduced scavenging of acetylcholine and possible induction of coronary vasospasm. These cases highlight the association between life-threatening VSA and SGLT2i-induced eDKA.

Topological charge of soft X-ray vortex beam determined by inline holography.

A Laguerre-Gaussian (LG) vortex beam having a spiral wavefront can be characterized by its topological charge (TC). The TC gives the number of times that the beam phase passes through the interval [Formula: see text] following a closed loop surrounding the propagation axis. Here, the TC spectra of soft X-ray vortex beams are acquired using the in-line holography technique, where interference between vortex waves produced from a fork grating and divergent waves from a Fresnel zone plate is observed as a holographic image. The analyses revealed the phase distributions and the TC for the LG vortex waves, which reflects topological number of the fork gratings, as well as for the Hermite-Gaussian (HG) mode waves generated from the other gratings. We also conducted a simulation of the present technique for pair annihilation of topological defects in a magnetic texture. These results may pave the way for development of probes capable of characterizing the topological numbers of magnetic defects.

[Actual state of injection techniques and effect of medical treatment instructions in elderly patients with diabetes using insulin].

AIM: Support for elderly patients using insulin to continue self-injection safely is required for clinical settings. The aim of this study was 1) to clarify the actual state of self-injection procedures for elderly people injecting insulin and 2) to verify whether or not the injection procedures can be improved by nurses' medical treatment instructions. SUBJECTS AND METHODS: The subjects were outpatients at an educational facility certified by the Japan Diabetes Society. Basic clinical characteristics, the Mini-Cog cognitive function test, basic ADL and instrumental ADL, and 24 items of the self-injection procedure were evaluated by nurses. After receiving a 30-minute face-to-face session of individual instructions from trained nurses two or more times, the injection procedure was re-evaluated. RESULTS: Of the 63 study subjects, 10 were injecting insulin with the support of others (supported injection group). The median age in the self-injection group was 72 years old, while that in the supported injection group was 82 years old. The supported injection group was older, the female ratio higher, and the Mini-Cog and ADL indices lower than in the self-injection group (p <0.05). The median history of the use of insulin was over 10 years in both groups. In the self-injection group, the degree of proficiency with the injection technique was significantly improved after receiving the instructions (p <0.05). The biggest improvement was in response to the question, "Do you know that you need to shift the site of injections?", which doubled (p <0.05). The correct answer rate for "Do you know the name of your insulin formulation?" was less than half, and it remained unchanged even after receiving instructions. In the supported injection group, 90% had a Mini-Cog of ≤2 points, but 6 subjects (60%) were able to perform an injection by themselves with others supporting the adjustments made to the amount of insulin. CONCLUSIONS: The self-injection technique improved significantly, even in elderly people, following the delivery of medical treatment instructions by nurses, and the item with the highest improvement effect was subjects' understanding of the need to shift the injection site. Our study showed that even in elderly people with cognitive dysfunction who are performing injections with the support of others, some of the injection procedures were retained by relying on procedural memory acquired in the past.

Associations between Sleep-Disordered Breathing and Metabolic Risk Factors beyond Obesity.

OBJECTIVE: Individuals with multiple metabolic risk factors often experience concomitant sleep-disordered breathing (SDB). We aimed to determine the associations of SDB with individual components of metabolic syndrome independent of obesity. METHODS: A cross-sectional study was conducted in 1137 employees aged 30-64 years. Apnea-hypopnea index (AHI) was assessed using a portable monitor for obstructive sleep apnea by admission. Of these, 451 participants took an oral glucose tolerance test to assess homeostatic model assessment of insulin resistance (HOMA-IR) and Matsuda insulin sensitivity index (ISI). RESULTS: The odds ratio (OR) of the highest category of the AHI (≥15 episodes per hour) compared to the lowest one (<5 episodes per hour) was significantly elevated for hypertension, for hypertriglyceridemia, and for low HDL-cholesterolemia when adjusted for age, sex, and alcohol and smoking status (p < 0.05). After further adjustment for body mass index (BMI) or waist circumference, the associations for hypertension still remained statistically significant (p < 0.05) while those for hypertriglyceridemia and low HDL-cholesterolemia were no longer significant. The association between higher insulin resistance as assessed by HOMA-IR and Matsuda ISI and higher categories of the AHI was also lost after adjustment for BMI. CONCLUSION: Obesity was a strong confounding factor in the association between SDB and most metabolic risk factors including insulin resistance, except for hypertension. Further longitudinal study is needed to examine the temporal or causal relationships between SDB and metabolic risk factors. This trial is registered with UMIN-CTR UMIN000028067.

Surface Structure of Organic Semiconductor [ n]Phenacene Single Crystals.

Surface structure relaxation of organic semiconductors affects the properties of organic devices, although such relaxation has not been well explored. Only two examples have been experimentally reported; tetracene shows a large surface relaxation, while rubrene exhibits no relaxation. Therefore, a systematic investigation of the surface relaxation is conducted on [ n]phenacenes ( n = 5, 7, and 9). Electron density analyses are performed based on the synchrotron surface X-ray scattering with the aid of first-principles calculations. The results show little surface relaxation in [ n]phenacenes.

Spin-orbital entangled liquid state in the copper oxide Ba3CuSb2O9.

Structure with orbital degeneracy is unstable toward spontaneous distortion. Such orbital correlation usually has a much higher energy scale than spins, and therefore, magnetic transition takes place at a much lower temperature, almost independently from orbital ordering. However, when the energy scales of orbitals and spins meet, there is a possibility of spin-orbital entanglement that would stabilize novel ground state such as spin-orbital liquid and random singlet state. Here we review on such a novel spin-orbital magnetism found in the hexagonal perovskite oxide Ba3CuSb2O9, which hosts a self-organized honeycomblike short-range order of a strong Jahn-Teller ion Cu2+. Comprehensive structural and magnetic measurements have revealed that the system has neither magnetic nor Jahn-Teller transition down to the lowest temperatures, and Cu spins and orbitals retain the hexagonal symmetry and paramagnetic state. Various macroscopic and microscopic measurements all indicate that spins and orbitals remain fluctuating down to low temperatures without freezing, forming a spin-orbital entangled liquid state.

Ventricular Fibrillation Associated With Dynamic Changes in J-Point Elevation in a Patient With Silent Thyroiditis.

A J wave is a common electrocardiographic finding in the general population. Individuals with prominent J waves in multiple electrocardiogram (ECG) leads have a higher risk of lethal arrhythmias than those with low-amplitude J waves. There are few reports about the relationship between thyroid function and J-wave amplitude. We report the case of a 45-year-old man who had unexpected ventricular fibrillation (VF). He had dynamic J-point elevation in multiple ECG leads. Possible early repolarization syndrome was diagnosed. He also had thyrotoxicosis caused by silent thyroiditis, and his J-wave amplitude decreased according to changes in thyroid function because of spontaneous remission of silent thyroiditis. There was a positive correlation between serum triiodothyronine levels and J-wave amplitudes. The findings in case suggested silent thyroiditis may contribute to the occurrence of VF in a patient with dynamic changes in J-point elevation in multiple ECG leads. Thyrotoxicosis is a relatively common endocrine disease; therefore, clinicians should pay attention to J-wave amplitude in the ECG of patients with thyrotoxicosis.

Bayesian inference of metal oxide ultrathin film structure based on crystal truncation rod measurements.

Monte Carlo (MC)-based refinement software to analyze the atomic arrangements of perovskite oxide ultrathin films from the crystal truncation rod intensity is developed on the basis of Bayesian inference. The advantages of the MC approach are (i) it is applicable to multi-domain structures, (ii) it provides the posterior probability of structures through Bayes' theorem, which allows one to evaluate the uncertainty of estimated structural parameters, and (iii) one can involve any information provided by other experiments and theories. The simulated annealing procedure efficiently searches for the optimum model owing to its stochastic updates, regardless of the initial values, without being trapped by local optima. The performance of the software is examined with a five-unit-cell-thick LaAlO3 film fabricated on top of SrTiO3. The software successfully found the global optima from an initial model prepared by a small grid search calculation. The standard deviations of the atomic positions derived from a dataset taken at a second-generation synchrotron are ±0.02 Šfor metal sites and ±0.03 Šfor oxygen sites.

Direct Estimation of the Surface Location of Immobilized Functional Groups for Concerted Catalysis Using a Probe Molecule.

The location of active sites during concerted catalysis by a metal complex and tertiary amine on a SiO2 surface is discussed based on the interaction between the functionalized SiO2 surface and a probe molecule, p-formyl phenylboronic acid. The interactions of the probe molecule with the surface functionalities, diamine ligand, and tertiary amine, were analyzed by FT-IR and solid-state (13)C and (11)B MAS NMR. For the catalyst exhibiting high 1,4-addition activity, the diamine ligand and tertiary amine base exist in closer proximity than in the catalyst with low activity.

Absence of Jahn-Teller transition in the hexagonal Ba3CuSb2O9 single crystal.

With decreasing temperature, liquids generally freeze into a solid state, losing entropy in the process. However, exceptions to this trend exist, such as quantum liquids, which may remain unfrozen down to absolute zero owing to strong quantum entanglement effects that stabilize a disordered state with zero entropy. Examples of such liquids include Bose-Einstein condensation of cold atoms, superconductivity, quantum Hall state of electron systems, and quantum spin liquid state in the frustrated magnets. Moreover, recent studies have clarified the possibility of another exotic quantum liquid state based on the spin-orbital entanglement in FeSc2S4. To confirm this exotic ground state, experiments based on single-crystalline samples are essential. However, no such single-crystal study has been reported to date. Here, we report, to our knowledge, the first single-crystal study on the spin-orbital liquid candidate, 6H-Ba3CuSb2O9, and we have confirmed the absence of an orbital frozen state. In strongly correlated electron systems, orbital ordering usually appears at high temperatures in a process accompanied by a lattice deformation, called a static Jahn-Teller distortion. By combining synchrotron X-ray diffraction, electron spin resonance, Raman spectroscopy, and ultrasound measurements, we find that the static Jahn-Teller distortion is absent in the present material, which indicates that orbital ordering is suppressed down to the lowest temperatures measured. We discuss how such an unusual feature is realized with the help of spin degree of freedom, leading to a spin-orbital entangled quantum liquid state.

Large surface relaxation in the organic semiconductor tetracene.

Organic crystals are likely to have a large degree of structural relaxation near their surfaces because of the weak inter-molecular interactions. The design of organic field-effect transistors requires a detailed knowledge of the surface relaxation as the carriers usually transfer within the first few molecular layers at the semiconductor surfaces, and their transport properties reflect the structural changes through the transfer integral. Here, we report the direct observation of the surface relaxation of an organic semiconductor, a tetracene single crystal, by means of X-ray crystal truncation rod scattering measurements. A significant degree of surface relaxation is observed, taking place only in the first monolayer at the semiconductor surface. First principles calculations show that the resultant transfer integrals are completely different between the bulk and surface of the semiconductor.

Malignant melanoma with probable smooth muscle differentiation.

Malignant melanomas occasionally exhibit various divergent differentiation types. Of these, smooth muscle differentiation is extremely rare; only 1 case has been reported in the literature until recently. We report an extremely rare case of malignant melanoma with smooth muscle differentiation, which appeared as an amelanotic reddish nodule on the left toe.

Dynamical spin-orbital correlation in the frustrated magnet Ba3CuSb2O9.

At low temperatures, atomic magnetic moments usually exhibit some order, for example ferromagnetic order. An exception is frustrated magnets, in which the symmetry impedes the minimization of energy by pairwise magnetic interactions. In such frustrated magnets, new quantum phases, such as spin liquids, are expected. Theoretically, a quantum liquid based on the orbital degree of freedom has also been considered possible when spin and orbital degrees of freedom are entangled. However, to date, experimental observation of such a dynamic spin-orbital state has been a challenge. Here we report an X-ray scattering study of a dynamic spin-orbital state in the frustrated magnet Ba3CuSb2O9. Orbital dynamical motion and increasing short-range orbital correlation with cooling are observed. The most significant feature is that the temperature variation of the orbital correlation is clearly affected by the magnetic interaction. This finding strongly supports a new quantum state in which spins and orbitals are entangled.

Smallest optical gap for quasi-one-dimensional iodo-bridged platinum compounds.

We synthesized a series of one-dimensional (1D) iodo-bridged platinum compounds with long alkyl chains on the counterions. In the compounds, the shortest Pt···Pt distance and the smallest band gap thus far reported were achieved. These compounds were found to be in a CDW state by using synchrotron X-ray diffraction measurements.