High-Temperature Atomic Diffusion and Specific Heat in Quasicrystals.

A quasicrystal is an ordered but nonperiodic structure understood as a projection from a higher-dimensional periodic structure. Some physical properties of quasicrystals are different from those of conventional solids. An anomalous increase in heat capacity at high temperatures has been discussed for over two decades as a manifestation of a hidden high dimensionality of quasicrystals. A plausible candidate for this origin has been the phason, which has excitation modes originating from the additional atomic rearrangements introduced by the quasiperiodic order, which can be understood in terms of shifting a higher-dimensional lattice. However, most theoretical studies of phasons have used toy models. A theoretical study of the heat capacity of realistic quasicrystals or their approximants has yet to be conducted because of the huge computational complexity. To bridge this gap between experiment and theory, we show experiments and molecular simulations on the same material, an Al-Pd-Ru quasicrystal, and its approximants. We show that at high temperatures, aluminum atoms diffuse with discontinuouslike jumps, and the diffusion paths of the aluminum can be understood in terms of jumps corresponding to hyperatomic-fluctuations-associated atomic rearrangements of the phason degrees of freedom. It is concluded that the anomaly in the heat capacity of quasicrystals arises from the hyperatomic fluctuations that play a role in diffusive Nambu-Goldstone modes.

Deep Learning Enables Rapid Identification of a New Quasicrystal from Multiphase Powder Diffraction Patterns.

Since the discovery of the quasicrystal, approximately 100 stable quasicrystals are identified. To date, the existence of quasicrystals is verified using transmission electron microscopy; however, this technique requires significantly more elaboration than rapid and automatic powder X-ray diffraction. Therefore, to facilitate the search for novel quasicrystals, developing a rapid technique for phase-identification from powder diffraction patterns is desirable. This paper reports the identification of a new Al-Si-Ru quasicrystal using deep learning technologies from multiphase powder patterns, from which it is difficult to discriminate the presence of quasicrystalline phases even for well-trained human experts. Deep neural networks trained with artificially generated multiphase powder patterns determine the presence of quasicrystals with an accuracy >92% from actual powder patterns. Specifically, 440 powder patterns are screened using the trained classifier, from which the Al-Si-Ru quasicrystal is identified. This study demonstrates an excellent potential of deep learning to identify an unknown phase of a targeted structure from powder patterns even when existing in a multiphase sample.

Crystal structures of five compounds in the aluminium-ruthenium-silicon system.

Single crystals of five compounds with approximate compositions ∼Ru16(Al0.78Si0.22)47, (I), ∼Ru9(Al0.70Si0.30)32, (II), ∼Ru10(Al0.67Si0.33)41, (III), ∼Ru(Al0.57Si0.43)5, (IV), and ∼Ru2(Al0.46Si0.54)9, (V), were obtained from polycrystalline lumps mainly composed of the target compounds, and their crystal structures were determined by means of single-crystal X-ray diffraction. The crystal structure of (I) can be related to that of a cubic rational crystalline approximant to an icosa-hedral quasicrystal through crystallographic shear and then unit-cell twinning. The crystal structure of (II) is isotypic with that of a phase with composition ∼Fe9(Al,Si)32. The crystal structure of (III) is comprised of edge-sharing Ru(Al,Si)9-11 polyhedra with disordered chains along edges of polyhedra. The crystal structure of (IV) is of the LiIrSn4 type. The crystal structure of (V) can be viewed as a crystallographic shear structure derived from that of (IV).

Half-Heusler phase TmNiSb under pressure: intrinsic phase separation, thermoelectric performance and structural transition.

Half-Heusler (HH) phase TmNiSb was obtained by arc-melting combined with high-pressure high-temperature sintering in conditions: p = 5.5 GPa, [Formula: see text] = 20, 250, 500, 750, and 1000 [Formula: see text]C. Within pressing temperatures 20-750 [Formula: see text]C the samples maintained HH structure, however, we observed intrinsic phase separation. The material divided into three phases: stoichiometric TmNiSb, nickel-deficient phase TmNi[Formula: see text]Sb, and thulium-rich phase Tm(NiSb)[Formula: see text]. For TmNiSb sample sintered at 1000 [Formula: see text]C, we report structural transition to LiGaGe-type structure (P[Formula: see text]mc, a = 4.367(3) Å, c = 7.138(7) Å). Interpretation of the transition is supported by X-ray powder diffraction, electron back-scattered diffraction, ab-initio calculations of Gibbs energy and phonon dispersion relations. Electrical resistivity measured for HH samples with phase separation shown non-degenerate behavior. Obtained energy gaps for HH samples were narrow ([Formula: see text] 260 meV), while the average hole effective masses in range 0.8-2.5[Formula: see text]. TmNiSb sample pressed at 750 [Formula: see text]C achieved the biggest power factor among the series, 13 [Formula: see text]WK[Formula: see text]cm[Formula: see text], which proves that the intrinsic phase separation is not detrimental for the electronic transport.

Successful case of olaparib treatment for castration-resistant prostate cancer with multiple DNA repair gene mutations: Use of comprehensive genome profiling for treatment-refractory cases.

Herein, we report a case of a 59-year-old man with advanced castration-resistant prostate cancer with rectal invasion. Multimodal treatment, including drug therapy, surgery, and radiation therapy was sequentially performed; however, lymph node metastases repeatedly occurred. Tumor genomic profiling using FoundationOne CDx identified pathogenic alterations in three DNA repair genes, including BRCA2 frameshift mutation. Olaparib, a poly-ADP ribose polymerase inhibitor, showed marked response. Castration-resistant prostate cancer with multiple DNA repair genes was successfully treated with olaparib; comprehensive genome profiling can lead to its optimal clinical management.

Division of dorsal vascular complex using soft coagulation without suture ligation during robot-assisted laparoscopic radical prostatectomy: a propensity score-matched study in a single-center experience.

Introduction: Apical dissection and control of the dorsal vascular complex (DVC) affects blood loss, positive surgical margins, and urinary control during robot-assisted laparoscopic radical prostatectomy. Soft coagulation is widely used for hemostasis. However, using soft coagulation to the DVC may affect the continence outcomes. In this study, we described technique and outcomes for division of the DVC after soft coagulation (DVC-SC) compared with delayed ligation of the DVC (D-DVC). Material and methods: Medical records of 170 patients who underwent robot-assisted laparoscopic radical prostatectomy from June 2016 to March 2020 were retrospectively reviewed. To reduce the selection bias, the two groups were matched in a 1:1 ratio on the basis of propensity scores. Perioperative data and results were compared in both groups. Results: Patients undergoing DVC-SC experienced less estimated blood loss compared to patients undergoing D-DVC (median: 105.5 vs 225 ml, p = 0.017). Postoperative continence rates at 1 week, 1, 3, 6 months in DVC-SC group and D-DVC group were 32.5% versus 15%, 62.5% versus 32.5%, 85% versus 67.5%, 95% versus 90%, respectively. Continence was significantly better at 1 month with DVC-SC versus D-DVC (p = 0.013). Conclusions: Division of the DVC after soft coagulation technique did not affect continence after robot-assisted laparoscopic radical prostatectomy despite the thermal division and gave the surgeon good hemostasis with simple procedure.

Machine Learning to Predict Quasicrystals from Chemical Compositions.

Quasicrystals have emerged as the third class of solid-state materials, distinguished from periodic crystals and amorphous solids, which have long-range order without periodicity exhibiting rotational symmetries that are disallowed for periodic crystals in most cases. To date, more than one hundred stable quasicrystals have been reported, leading to the discovery of many new and exciting phenomena. However, the pace of the discovery of new quasicrystals has lowered in recent years, largely owing to the lack of clear guiding principles for the synthesis of new quasicrystals. Here, it is shown that the discovery of new quasicrystals can be accelerated with a simple machine-learning workflow. With a list of the chemical compositions of known stable quasicrystals, approximant crystals, and ordinary crystals, a prediction model is trained to solve the three-class classification task and its predictability compared to the observed phase diagrams of ternary aluminum systems is evaluated. The validation experiments strongly support the superior predictive power of machine learning, with the overall prediction accuracy of the phase prediction task reaching ≈0.728. Furthermore, analyzing the input-output relationships black-boxed into the model, nontrivial empirical equations interpretable by humans that describe conditions necessary for stable quasicrystal formation are identified.

A case of primary retroperitoneal amyloidoma resected laparoscopically.

Amyloidosis is known as a group of diseases that causes various disorders because of deposition of amyloid protein in various organs. Amyloidosis occurring in the retroperitoneum is a rare disease. We report a 75-year-old male patient presented to our hospital because he was identified with a retroperitoneal mass incidentally by CT. Laparoscopic surgery was performed to resect the tumor. In the histopathological specimen, amyloid was found in the fibrous soft tissue by Congo red staining. This is the first report to document a primary solitary amyloidosis of the retroperitoneum without systemic amyloidosis, which was resected using the laparoscopic approach.

Phase stability and thermoelectric properties of semiconductor-like tetragonal FeAl2.

Tetragonal FeAl2 is a high-pressure phase and is predicted to exhibit semiconductor-like behavior. We investigated the pressure and temperature synthesizing conditions of tetragonal FeAl2, supported by in situ X-ray diffractions, using synchrotron radiation during heating the sample under a pressure of 20 GPa. Based on the determined optimal conditions, we synthesized the bulk polycrystalline samples of tetragonal FeAl2 at 7.5 GPa and 873 K, using a multi-anvil press and measured its thermoelectric properties. The Seebeck coefficient of tetragonal FeAl2 showed a large negative value of - 105 µV/K at 155 K and rapidly changed to a positive value of 75 µV/K at 400 K. Although these values are the largest among those of Fe-Al alloys, the maximum power factor remained at 0.41 mW/mK2 because the carrier concentration was not tuned. A comparison of the Gibbs free energy of tetragonal FeAl2, triclinic FeAl2 and FeAl+Fe2Al5 revealed that tetragonal FeAl2 became unstable as the temperature increased, because of its smaller contribution of vibrational entropy.

Cathepsin K activity controls cardiotoxin-induced skeletal muscle repair in mice.

BACKGROUND: Cathepsin K (CatK) is a widely expressed cysteine protease that has gained attention because of its enzymatic and non-enzymatic functions in signalling. Here, we examined whether CatK-deficiency (CatK-/- ) would mitigate injury-related skeletal muscle remodelling and fibrosis in mice, with a special focus on inflammation and muscle cell apoptosis. METHODS: Cardiotoxin (CTX, 20 µM/200 µL) was injected into the left gastrocnemius muscle of male wild-type (CatK+/+ ) and CatK-/- mice, and the mice were processed for morphological and biochemical studies. RESULTS: On post-injection Day 14, CatK deletion ameliorated muscle interstitial fibrosis and remodelling and performance. At an early time point (Day 3), CatK-/- reduced the lesion macrophage and leucocyte contents and cell apoptosis, the mRNA levels of monocyte chemoattractant protein-1, toll-like receptor-2 and toll-like receptor-4, and the gelatinolytic activity related to matrix metalloproteinase-2/-9. CatK deletion also restored the protein levels of caspase-3 and cleaved caspase-8 and the ratio of the BAX to the Bcl-2. Moreover, CatK deficiency protected muscle fibre laminin and desmin disorder in response to CTX injury. These beneficial muscle effects were mimicked by CatK-specific inhibitor treatment. In vitro experiments demonstrated that pharmacological CatK inhibition reduced the apoptosis of C2C12 mouse myoblasts and the levels of BAX and caspase-3 proteins induced by CTX. CONCLUSIONS: These results demonstrate that CatK plays an essential role in skeletal muscle loss and fibrosis in response to CTX injury, possibly via a reduction of inflammation and cell apoptosis, suggesting a novel therapeutic strategy for the control of skeletal muscle diseases by regulating CatK activity.

Structures and photophysical properties of copper(I) complexes bearing diphenylphenanthroline and bis(diphenylphosphino)alkane: the effect of phenyl groups on the phenanthroline ligand.

A series of copper(I) complexes bearing 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (dmpp) and a diphosphine ligand have been prepared. The diphosphine ligands used have two, three or four methylene carbons between the two phosphorus atoms. The crystallographic study has revealed that two of the three complexes have the mononuclear structure bearing dmpp and a bidentate diphosphine ligand, and one is a diphosphine-bridged binuclear complex. The photoluminescence of the complexes in solution was studied and compared with the previously reported complexes bearing 2,9-dimethyl-1,10-phenanthroline (dmp). It was found that the two phenyl groups on the phenanthroline ligand have a marked effect on the photophysical properties of the complexes; the intensity of the emission of the complexes is greatly enhanced by the phenyl groups. The photophysics of the complexes is discussed with the results of DFT and TDDFT calculations.

ß-Hydroxy-ß-methylbutyrate facilitates PI3K/Akt-dependent mammalian target of rapamycin and FoxO1/3a phosphorylations and alleviates tumor necrosis factor α/interferon γ-induced MuRF-1 expression in C2C12 cells.

ß-Hydroxy-ß-methylbutyrate (HMB) prevents deleterious muscle responses under pathological conditions, including tumor- and chronic steroid therapy-related muscle losses. Here, we investigated the hypothesis that HMB may modulate the balance between protein synthesis and degradation in the PI3K/Akt-mediated mammalian target of rapamycin (mTOR) and FoxO1/FoxO3a-dependent mechanisms in differentiated C2C12 muscle cells. We also tested the effect of HMB on the expression of MuRF-1 and atrogin-1 in response to the inflammatory stress. ß-Hydroxy-ß-methylbutyrate up-regulated phosphorylation of Akt and mTOR, and these effects were completely abolished in the presence of PI3K inhibitor LY294002. ß-Hydroxy-ß-methylbutyrate also up-regulated FoxO1 and FoxO3a phosphorylation, and these changes were inhibited by LY294002. Although, unexpectedly, HMB failed to reduce the expressions of atrophy-related atrogin-1 messenger RNA and the protein response to the proinflammatory cytokines tumor necrosis factor α plus interferon γ, HMB did attenuate the MuRF-1 expression. Thus, HMB appears to restore the balance between intracellular protein synthesis and proteolysis, likely via activation of the PI3K/Akt-dependent mTOR and FoxO1/FoxO3a signaling pathway and the reduction of tumor necrosis factor α/interferon γ-induced MuRF-1 expression, thereby ameliorating aging-related muscle atrophy.

Thermoelectric properties and electronic structure of the Zintl phase Sr5Al2Sb6.

The Zintl phase Sr5Al2Sb6 has a large, complex unit cell and is composed of relatively earth-abundant and non-toxic elements, making it an attractive candidate for thermoelectric applications. The structure of Sr5Al2Sb6 is characterized by infinite oscillating chains of AlSb4 tetrahedra. It is distinct from the structure type of the previously studied Ca5M2Sb6 compounds (M = Al, Ga or In), all of which have been shown to have promising thermoelectric performance. The lattice thermal conductivity of Sr5Al2Sb6 (~0.55 W mK(-1) at 1000 K) was found to be lower than that of the related Ca5M2Sb6 compounds due to its larger unit cell (54 atoms per primitive cell). Density functional theory predicts a relatively large band gap in Sr5Al2Sb6, in agreement with the experimentally determined band gap of E(g) ~ 0.5 eV. High temperature electronic transport measurements reveal high resistivity and high Seebeck coefficients in Sr5Al2Sb6, consistent with the large band gap and valence-precise structure. Doping with Zn(2+) on the Al(3+) site was attempted, but did not lead to the expected increase in carrier concentration. The low lattice thermal conductivity and large band gap in Sr5Al2Sb6 suggest that, if the carrier concentration can be increased, thermoelectric performance comparable to that of Ca5Al2Sb6 could be achieved in this system.

Metallic-covalent bonding conversion and thermoelectric properties of Al-based icosahedral quasicrystals and approximants.

In this article, we review the characteristic features of icosahedral cluster solids, metallic-covalent bonding conversion (MCBC), and the thermoelectric properties of Al-based icosahedral quasicrystals and approximants. MCBC is clearly distinguishable from and closely related to the well-known metal-insulator transition. This unique bonding conversion has been experimentally verified in 1/1-AlReSi and 1/0-Al12Re approximants by the maximum entropy method and Rietveld refinement for powder x-ray diffraction data, and is caused by a central atom inside the icosahedral clusters. This helps to understand pseudogap formation in the vicinity of the Fermi energy and establish a guiding principle for tuning the thermoelectric properties. From the electron density distribution analysis, rigid heavy clusters weakly bonded with glue atoms are observed in the 1/1-AlReSi approximant crystal, whose physical properties are close to icosahedral Al-Pd-TM (TM: Re, Mn) quasicrystals. They are considered to be an intermediate state among the three typical solids: metals, covalently bonded networks (semiconductor), and molecular solids. Using the above picture and detailed effective mass analysis, we propose a guiding principle of weakly bonded rigid heavy clusters to increase the thermoelectric figure of merit (ZT) by optimizing the bond strengths of intra- and inter-icosahedral clusters. Through element substitutions that mainly weaken the inter-cluster bonds, a dramatic increase of ZT from less than 0.01 to 0.26 was achieved. To further increase ZT, materials should form a real gap to obtain a higher Seebeck coefficient.

Matrix metalloproteinase-2 regulates the expression of tissue inhibitor of matrix metalloproteinase-2.

1. Matrix metalloproteinases (MMP) are associated with the vascular remodelling seen in atherosclerosis and aneurysm. The activation and activity of MMP-2 are regulated by the intrinsic tissue inhibitor of MMP-2 (TIMP-2). The aim of the present study was to examine whether, conversely, MMP-2 can affect the gene and protein expression of TIMP-2. 2. In the present study, we examined the mRNA and protein expression of MMP-2 and TIMP-2 in cultured smooth muscle cells (SMC) from the aortas of MMP-2(+/+) and MMP-2(-/-) mice. We also examined the roles of MMP-2 in SMC cellular events. 3. Western blotting showed that less TIMP-2 protein was present in the conditioned medium of MMP-2(-/-) SMC than in that of MMP-2(+/+) SMC. Real-time reverse transcription polymerase chain reaction analysis showed that MMP-2 deficiency reduced TIMP-2 mRNA expression in SMC. Recombinant MMP-2 enhanced the expression of TIMP-2 protein in cultured SMC from MMP-2(-/-) mice. Furthermore, a siRNA targeting MMP-2 impaired the gene and protein expression of MMP-2 in cultured SMC from MMP-2(+/+) mice. MMP-2 deficiency impaired SMC invasion, but not their proliferation, adhesion or migration. 4. Our findings suggest that MMP-2 is likely to be responsible, at least in part, for regulating TIMP-2 expression and is thus a potential target, in addition to TIMP-2, for therapeutics aimed at preventing cardiovascular remodelling in response to injury.

Synthesis and formation mechanism of hydrogenated boron clusters B(12)H(n) with controlled hydrogen content.

We present the formation of hydrogen-content-controlled B(12)H(n) (+) clusters through the decomposition and ion-molecule reactions of the decaborane (B(10)H(14)) and diborane (B(2)H(6)) molecules in an external quadrupole static attraction ion trap. The hydrogen- and boron-contents of the B(10-y)H(x) (+) cluster are controlled by charge transfer from ambient gas ions. In the process of ionization, a certain number of hydrogen and boron atoms are detached from decaborane ions by the energy caused by charge transfer. The energy caused by the ion-molecule reactions also induces H atom detachment. Ambient gas of Ar leads to the selective generation of B(10)H(6) (+). The B(10)H(6) (+) clusters react with B(2)H(6) molecules, resulting in the selective formation of B(12)H(8) (+) clusters. Ambient gas of Ne (He) leads to the generation of B(10-y)H(x) (+) clusters with x=4-10 and y=0-1 (with x=2-10 and y=0-2), resulting in the formation of B(12)H(n) (+) clusters with n=4-8 (n=2,4-8). The introduction of ambient gas also increases the production of clusters. PBE0/6-311+G(d)//B3LYP/6-31G(d)-level density functional theory calculations are conducted to investigate the structure and the mechanism of formation of B(10-y)H(x) (+) and B(12)H(n) (+) clusters.

Co(OH)3 nanobelts: synthesis, characterization and shape-preserved transformation to pseudo-single-crystalline Co3O4 nanobelts.

In this paper, we demonstrated a facile hydrothermal route leading to the generation of a new cobalt hydroxide, Co(OH)(3), nanobelt. This new product of Co(OH)(3) nanobelts was well characterized and identified by SEM, TEM, XRD, EDX, XPS, EXAFS, Raman, TGA and SQUID. Additionally, through systematic investigations on morphological evolution, it was found that the size and shape of Co(OH)(3) nanobelts were adjustable in large scale, e.g. from 50 to 1.5 microm in length and 5 microm to 20 nm in width, by means of fine experimental parameter control. Furthermore, the unique pseudo-single-crystalline Co(3)O(4) nanobelts were produced from Co(OH)(3) precursors via heating treatment. This is the first synthesis of Co(OH)(3) with tunable shapes and sizes, which may find important applications as gas sensors, catalysts, and electrode materials, owing to the specific large surface-to-volume ratio and other unique properties endowed by typical 1D nanobelts.

Formation of hydrogenated boron clusters in an external quadrupole static attraction ion trap.

We report the formation of icosahedral B(12)H(8) (+) through ion-molecule reactions of the decaborane ion [B(10)H(x)(+) (x=6-14)] with diborane (B(2)H(6)) molecules in an external quadrupole static attraction ion trap. The hydrogen content n of B(12)H(n)(+) is determined by the analysis of the mass spectrum. The result reveals that B(12)H(8)(+) is the main product. Ab initio calculations indicate that B(12)H(8)(+) preferentially forms an icosahedral structure rather than a quasiplanar structure. The energies of the formation reactions of B(12)H(14)(+) and B(12)H(12)(+) between B(10)H(x)(+) (x=6,8) ions, which are considered to be involved in the formation of B(12)H(n)(+), and a B(2)H(6) molecule are calculated. The calculations of the detachment pathway of H(2) molecules and H atoms from the product ions, B(12)H(14)(+) and B(12)H(12) (+), indicate that the intermediate state has a relatively low energy, enabling the detachment reaction to proceed owing to the sufficient reaction energy. This autodetachment of H(2) accounts for the experimental result that B(12)H(8)(+) is the most abundant product, even though it does not have the lowest energy among B(12)H(n)(+).

Cystic clear cell tumor of borderline malignancy of the ovary lacking fibromatous components: report of two cases and a possible new histological subtype.

BACKGROUND: All of the ovarian borderline clear cell tumors ever reported had, without exception, an adenofibromatous pattern. CASE: We report two cases of borderline cystic clear cell tumor of the ovary without apparent invasive lesions or adenofibromatous components. CONCLUSION: This is the first report of cystic clear cell tumors of borderline malignancy, indicating a possible new histological subtype.

Primary retroperitoneal mucinous cystadenoma of borderline malignancy: a case report and review of the literature.

A case of primary retroperitoneal mucinous cystic tumor of borderline malignancy is reported. A 36-year-old, nulliparous woman complained of abdominal fullness. Physical examination revealed a cystic mass 12-cm x 8-cm in size. At laparotomy, a cystic tumor was observed in the right retroperitoneal space. Both ovaries appeared normal and the uterus was almost normal except for small myomatous nodules. Removal of the retroperitoneal tumor, an appendectomy, and a myomectomy were performed. The histologic diagnosis was a primary retroperitoneal mucinous cystic tumor of borderline malignancy, similar to findings for ovarian tumor. There was no evidence of disease 6 months after the surgery.