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To investigate the factors that contribute to subjective quality of life (QOL) in adolescents with cerebral palsy (CP). We evaluated the subjective QOL in 51 adolescents with CP through interviews using the Japanese version of KIDSCREEN-27 (J-KIDSCREEN-27) and compared the scores with those of 60 typically developing adolescents. Correlations of subjective QOL with age, sex, the levels of functions (gross motor, manipulation, and communication), intelligence, the level of activity of daily living (ADL), and the type of educational support were examined. Thereafter, we investigated the predictors of the subjective QOL by multiple regression analysis. The total QOL scores and individual J-KIDSCREEN-27 domains were not significantly different from those of typically developing adolescents. Sex, manipulation and communication functions, and intelligence had no relationship with subjective QOL. Gross motor function and ADL level negatively correlated with satisfaction with the school environment. Multiple regression analysis revealed that higher age predicts lower psychological well-being, lower gross motor function predicts higher satisfaction with the school environment, and attending schools or classes for special needs predicts higher physical well-being. Seeking adequate support for mildly affected adolescents attending regular classes will be the key to further improving subjective QOL in adolescents with CP. [ABSTRACT FROM AUTHOR]

A new material concept of soft crystals is proposed. Soft crystals respond to gentle stimuli such as vapor exposure and rubbing but maintain their structural order and exhibit remarkable visual changes in their shape, color, and luminescence. Various interesting examples of soft crystals are introduced in the article. By exploring the interesting formation and phase‐transition phenomena of soft crystals through interdisciplinary collaboration, new materials having both the characteristics of ordered hard crystals and those of flexible soft matter are expected. Soft crystals respond to gentle stimuli such as vapor exposure and mechanical stimuli but maintain their structural order and exhibit remarkable visual changes in shape, color, and luminescence. [ABSTRACT FROM AUTHOR]

Double-decker platinum complexes with N -heteroaromatic ligands have attracted increasing interest due to their outstanding luminescent properties and rich redox behavior. In this review, the design principles and recent observations on luminescent and redox-active double-decker platinum complexes are discussed. Because these properties are precisely controlled by intra- and intermolecular Pt⋯Pt electronic interactions, double-decker platinum complexes have been also used to obtain phenomena driven by stimulus–responsive color and luminescence change, such as vapochromism, mechanochromism, thermochromism, and electrochromism. This review also summarizes chromic materials based on double-decker platinum complexes influenced by changes in the Pt⋯Pt electronic interactions. [ABSTRACT FROM AUTHOR]

A highly methanol-selective vapochromic response has been realized in a NiII-quinonoid complex, [Ni(HLMe)2] (H2LMe=4-methylamino-6-methyliminio-3-oxocyclohexa-1,4-dien-1-olate) which exhibits a reversible structural transformation including a coordination geometrical change between the square-planar and octahedral structure by the selective uptake of methanol vapor. This was accompanied by a remarkable color change between purple and orange, as well as temperature-robust spin-state switching in the solid state under ambient conditions. It is remarkable that the properties are derived by the fine structural modification of the quinonoid ligand such as methyl or ethyl analogues. Such a system has high potential for applications in memory devices as well as chemical sensors and smart responsive materials. [ABSTRACT FROM AUTHOR]

• The latest trends in multifunctional vapochromic materials are reviewed. • Studies on vapochromism coupled with conductivity and magnetism are discussed. • Single-crystal to single-crystal transformation in vapochromic systems is described. The latest trends in vapochromic materials that exhibit reversible color changes in response to gas or vapor are reviewed. Since the end of the 20th century, studies on vapochromic materials have significantly increased for environmental sensing, particularly those accompanied by the luminescence. In addition to the diversity of materials, vapochromic multifunctional systems that exhibit additional functions, such as conductivity and magnetic properties along with color and/or luminescence change by vapor, would be more attractive. In this context, recent developments in multifunctional vapochromic systems are discussed. Systems exhibiting single-crystal to single-crystal transformations are reviewed because these provide useful information on the structural dynamics, which is essential for understanding vapochromic phenomena. [ABSTRACT FROM AUTHOR]

Vapochromic materials that show reversible color change driven by vapor adsorption/desorption have drawn significant attention because of their potential applications in chemical sensors and chemical-switching modules. Among the vapochromic coordination complexes reported so far, a series of square-planar PtII complexes has been studied and represents one of the most promising systems for practical chemical sensors. For such systems, the color of the complexes strongly depends not only on the ligand-field splitting, but also on the intermolecular distance between the PtII ions. This microreview presents recent results of vapochromic complexes centered on one-dimensionally stacked PtII systems from the viewpoint of the origin of their vapochromic behavior. The design of vapochromic materials has been facilitated because several useful chromophores, including metallophilic interaction between PtII ions, have been developed. However, it is still challenging to realize a specifically sensitive and selective response to targeted vapors. This review focuses on strategies to achieve assembled PtII complexes with selective vapochromic responses. [ABSTRACT FROM AUTHOR]

Spinal cord tumors are rare in children. We report a novel case of pediatric intramedullary spinal cord tumor with unusual solid-cystic and papillary features. Clinically, the patient presented at the age of 3 years with motor deficit and urinary incontinence, and MRI demonstrated multilocular cystic lesions in the thoracic spine. Histologically the tumor consisted of solid, sheet-like components and branching papillary structures, and immunohistochemistry demonstrated positive reactivity for epithelial membrane antigen, cytokeratins (7, AE1/3, CAM5.2), E-cadherin and transthyretin, and negativity for GFAP, S-100 protein, synaptophysin and neurofilament. These histological and immunohistochemical findings appeared to be unique, and were not compatible with the features of classical ependymoma or choroid plexus papilloma. The clinical behavior, characterized by relatively rapid tumor regrowth after surgical resection and a relatively high MIB-1 labeling index, suggest that this tumor might have had moderate malignant potential. This pediatric case appears to be particularly informative with regard to the tumor biology or tumorigenesis of intramedullary spinal cord tumor with unusual solid-cystic and papillary features. [ABSTRACT FROM AUTHOR]

Abstract: The authors produced a monoclonal antibody (mAb) against dolphin neutrophils by fusing mouse myeloma cells with lymph node cells from a Wistar rat immunized with bottlenose dolphin (Tursiops truncatus) polymorphonuclear leukocytes (PMNs). This mAb (DN1) was reactive against 77.1±8.6% of dolphin peripheral blood PMN by flow cytometric analysis; furthermore, there was no cross-reactivity with human or bovine leukocytes. The DN1-positive cells isolated with a sorting cytometer were almost all (99.7%) neutrophils. By using DN1 in conjunction with magnetic-activated cell sorting (MACS), the authors isolated neutrophils and eosinophils from density gradient-fractionated PMN with 100% and 95.6±4.8% purities, respectively. These results suggest that this mAb specific for bottlenose dolphin neutrophils is useful as a potential reagent to study bottlenose dolphin neutrophils and eosinophils. [Copyright &y& Elsevier]

Seventy-three ostracode species from 38 genera were recovered from the 55 surface sediment samples in Lützow-Holm Bay, northeastern Antarctica. We investigated bathymetric and geographic distributions of modem benthic ostracode species in the bay and compared this fauna with published modem and fossil ostracode data of Antarctic and southern South American regions. The results show: (1) Four biotopes and three sub-biotopes are recognized based on Q-mode cluster analysis, which suggest distributions of modem ostracodes are mainly controlled by water-mass structure, ice scouring, and light availability. (2) Comparison between the Lützow-Holm Bay fauna and other ostracode faunas from Antarctica and southern South America shows high endemism and homogeneity of Antarctic ostracode fauna, suggesting in situ evolution of most extant Antarctic species. (3) Most species are endemic to the Antarctica, a few species also inhabit South American waters. [ABSTRACT FROM AUTHOR]

The title dinuclear platinum(III) complex, [Pt2(C11H2N)2(C5H4NS)4], forms two crystal structures, viz. the non-solvated and acetonitrile-solvated (C2H3N) forms. For both forms, two (2-pyridylphenyl)platinum units are bridged by two pyridine-2-thiolate (pyt) anions in a head-to-tail configuration, and the other two pyridine-2-thiolate anions occupy the axial position, coordinated through their S atoms. The most remarkable difference between the two forms is the orientation of the axial monodentate ligands. Those for the solvated form are located over the 2-pyridylphenyl ligands, being related by a twofold axis which lies through the centre of the Pt—Pt bond, while the axial pyt ligands for the non-solvated form are oriented irregularly, which is attributable to the dimeric arrangement in the crystal. [ABSTRACT FROM AUTHOR]

Discusses the thermal and photo control of the linkage isomerism of Bis(thiocyanato)(2,2'-bipyridine)platinum(II). Isolation and structural elucidation of three linkage isomers; Crystal data; Dependence of stacking structures on the coordination geometries based on the N- and S-coordination of the thiocyanato ligands; Isomerization behaviors of the complex in solution and in solid state.

Describes the compound, [(1R,2R)-1,2-diaminocyclohexane- κ²N,N'](alpha;-diimine-κ²N,N')platinum(II)bis(hexaf luorophosphate), where α-diimine is 2,2'-bipyridine and 1,10-phenanthroline. Aromatic alpha-diimine and a non-planar diaminocyclohexane which forms a ladder-type structure.

Background/Aims: The human proto-oncogene c-erbB-2 (also called HER-2/neu) is located on chromosome 17q21-22. There have been no studies on gene amplification or mRNA expression of c-erbB-2 in human intrahepatic cholangiocarcinoma (CC) hitherto.Methods: We investigated c-erbB-2 gene amplification by fluorescence in situ hybridization (FISH), c-erbB2 mRNA expression by ISH, and c-erbB-2 protein expression by immunohistochemistry in 22 archival cases of CC.Results: FISH revealed that c-erbB-2 gene signals were increased in CC. ISH showed that c-erbB-2 mRNA signals were located in the nuclei and cytoplasms of cancer cells and were increased in cancer cells compared with non-cancerous bile ducts where no signals were present. Immunohistochemistry showed that the c-erbB-2 protein was expressed in the cell membrane of cancer cells, and was increased compared with non-cancerous bile ducts where no expression was found. There was a positive significant correlation between c-erbB-2 mRNA and protein expression. Clinicopathologically, there were no correlations between the c-erbB-2 expression and various pathological features.Conclusions: These data suggest that c-erbB-2 gene amplification does occur in CC, and that there is an overexpressed c-erbB-2 protein through the enhanced mRNA expression. The c-erbB-2 gene amplification may be related to the oncogenesis or tumor progression of CC. [Copyright &y& Elsevier]

Vapochromic behavior of the crystal of dicyano(2,2′-bipyridine)platinum(II), [Pt(CN) 2 (bpy)], has been investigated structurally and emission spectroscopically. Red Form with an infinite Pt···Pt chain transforms to Yellow Form reversibly by taking up water vapor. The crystal structure of Yellow Form ([Pt(CN) 2 (bpy)]·H 2 O) was determined by X-ray analysis: the square-planar complexes form the inclined stack with short and long Pt···Pt distances (3.3279(3) and 4.6814(3) Å). The crystal water makes hydrogen bonds with CN - ligands connecting the stacks. The transformation is accompanied by the sensitive luminescence change as well as the color change, which reflects the change of the Pt⋯Pt electronic interactions. The sensitive vapochromism for this system is attributable to the slight deformation of the stacking structure induced by water molecules. platinum complex luminescence spectrum vapochromism metal-metal interaction crystal structure [ABSTRACT FROM AUTHOR]

Background/Aims: Midkine (MK) is a novel heparin-binding growth factor whose gene has been identified in embryonal carcinoma cells in early stages of retinoic acid-induced differentiation. In this study, we investigated the developmental expression of MK protein in the human fetal liver and kidney. Methods: Twenty-one specimens each of the liver and kidney from fetuses (gestational weeks from 9 to 40) and neonates less than 4 weeks old were examined. Immunohistochemical and Western blot analyses were performed using a rat IgG2a monoclonal antibody against the carboxyl terminal region of human MK. Results: Immunohistochemical analysis revealed MK expression in the human fetal liver and kidney. The MK expression in the fetal liver showed a strong reaction from 9 to 16 gestational weeks. MK was expressed in the ductal plate, migrating biliary cells and newly formed bile ducts, and in hepatocytes of the hilar region in all specimens in the first and second trimesters. By contrast, the MK expression decreased gradually and was weak or not detected in the third trimester and neonatal period. However, MK expression in the kidney was found at 16 gestational weeks, as well as during both gestation and the neonatal period. Conclusions: Divergent MK-expression was detected in the human fetal liver and kidney, and its expression may be related to fetal development, maturation, and functions of the liver and kidney. [ABSTRACT FROM AUTHOR]

A case of testicular yolk sac tumor (endodermal sinus tumor) consisting predominantly of hepatoid cells is documented. A mass measuring approximately 4 × 3 cm was noted in the left testis of a 64-year-old man. Preoperative examination revealed an elevated serum level of α-fetoprotein (5479 ng/mL). Histologically, the lesion was composed predominantly of sheet-like or trabecular proliferation of hepatocyte-like cells with eosinophilic or clear cytoplasm. The tumor cells were immunoreactive for α-fetoprotein, antimitochondrial antibody, cytokeratin (AE1/AE3), α-1-antichymotrypsin, α-1-antitrypsin, albumin, carcinoembryonic antigen and epithelial membrane antigen. It was necessary to distinguish this variant lesion from metastatic hepatocellular carcinoma, embryonal carcinoma and hepatoid carcinoma. [ABSTRACT FROM AUTHOR]

Aims/Background: Midkine (MK) is a novel heparin-binding growth factor whose gene was identified in embryonal carcinoma cells in the early stages of retinoic acid-induced differentiation. This study investigates the overexpression of MK in intrahepatic cholangiocarcinoma (CC). Methods: Forty-five primary CC specimens from patients (aged 19–81 years, 24 males and 21 females) were examined. Histologically, 17 cases of CC were classified as the well-differentiated type, 19 as moderately-differentiated and 9 as poorly-differentiated. Immunohistochemical analysis was performed using a rat IgG2a monoclonal antibody against the carboxyl terminal region of human MK. Results: We successfully applied this monoclonal antibody against MK to analyze archival paraffin sections. The cancer tissues showed a positive reaction to this antibody, and there was an intense reaction in their cytoplasm. Approximately 40% of individuals with CC (17/45) had tumor cells that expressed MK, and these were classified into the following types: moderately-differentiated type (9/19), well-differentiated type (8/17) and poorly-differentiated type (0/9). In situ hybridization analysis revealed that signals of MK transcripts were found in the cytoplasm of the cancer cells; the distribution and localization of the MK-transcript signals determined by in situ hybridization analysis were similar to those obtained by immunohistochemical analysis. Conclusions: These findings revealed that CC express increased MK at the messenger RNA and protein levels. [ABSTRACT FROM AUTHOR]

A case of peripheral primitive neuroectodermal tumor of the small bowel mesentery with an uncommon clinical onset is reported. A 40-year-old man was admitted to hospital because of acute severe abdominal pain. Chest X-ray revealed a free air sign beneath the diaphragm. At emergency surgery a mass measuring 11.0 × 8.0 cm with perforation was located in the jejunal mesenteric region. Histologically the resected lesion consisted of sheets of undifferentiated small round cells forming abortive Homer Wright rosettes. Some spindle-shaped cells showed perivascular pseudorosettes. Immunohistochemical study revealed that the tumor cells expressed positivity against CD99 (MIC2), neuron-specific enolase, synaptophysin and vimentin. To the authors’ knowledge this is the first documentation of peripheral primitive neuroectodermal tumor of the small bowel mesentery with perforation at onset. [ABSTRACT FROM AUTHOR]

A case of a uterus-like mass arising from the mesentery is reported. A mass measuring 14 × 11 cm was noted in the small bowel mesentery of a 59-year-old woman. Histologically, the lesion consisted of endometrial-type and fallopian tube-type mucosa surrounded by thick bundles of smooth muscle cells. Since the first report by Cozzutto in 1981, 10 cases of uterus-like mass, that included seven ovarian and three extraovarian cases, have been reported. To our knowledge, the present lesion was the first case originating from the mesenteric region. Three hypotheses of this rare lesion: (i) congenital anomaly; (ii) metaplasia; and (iii) heterotopia theories are reviewed. [ABSTRACT FROM AUTHOR]

A case of parotid juvenile hemangioma associated with cytomegalovirus infection is reported. A growing lobulated mass, measuring 30 × 20 mm, was extirpated from the left parotid gland in a 4-month-old male. Histologically, the tumor consisted of cellular plump endothelial cells, stromal cells and residual ductal and acinar elements of the parotid gland. Numerous intranuclear and cytoplasmic inclusions were observed in the ductal cells of the whole parenchymal part of the parotid gland and the residual part of the tumor. Immunohistochemically, some nuclei of the ductal cells possessing these inclusions were positive for the anti-cytomegalovirus antibody but there were no positive findings in the endothelial or stromal cells. Although the present lesion may suggest that the human cytomegalovirus plays some role in the etiology of juvenile hemangioma, it is unknown whether or not this association is incidental. [ABSTRACT FROM AUTHOR]

A case of pseudovascular squamous cell carcinoma in the uterine cervix of a 64-year-old woman was examined. Histologically, the lesion consisted of atypical, large, non-keratinizing squamous cells that exhibited not only acantholytic changes but also pseudovascular changes. Immunohistochemically, these tumor cells were positive for cytokeratin, epithelial membrane antigen and carcinoembryonic antigen, but none of them were positive for Factor VIII-related antigen or CD34. To our knowledge, pseudovascular carcinoma of the uterine cervix has not been described in the literature. Pathologists should be aware of this unusual form of cervical squamous cell carcinoma, particularly in the differential diagnosis of angiosarcoma. [ABSTRACT FROM AUTHOR]

Studies the temperature dependence of both emission spectrum and crystal structure of a liner-chain platinum complex. Correlation of the luminescence emission spectrum and the Pt---Pt distance for the platinum(II) complex; Behavior the platinum complex crystal; Pi-pi interactions of the complex.

Reports on the preparation of three platinum(II) complexes and their x-ray crystal structures and luminescence properties. Synthesis; Solution and refinement of structures; Physical measurements; Structural description; Emission and absorption properties.

Reports on the synthesis of a series of diiron(III) complexes containing alkoxo and carboxylato bridges. Molecular structures and magnetic properties; Crystallographic parameters; Atomic coordinates and thermal parameters; Fourier transforms; Relevant interatomic distances and angles; Magnetic properties.

Examines the reactivity of a noncoordinated hydroxyl group in the metal complex to acid anhydrides. Esterification of K[Co(dhpta)]; Description of structures; Absolute configuration and circular dichroism; Cobalt(III) complexes having a long alkyl chain.

• The luminescence properties of anionic cyclometalated Pt(II) complexes are controlled by the cations. • The systems surrounded by bulky organic cations realize intense molecular-based luminescence. • Non-innocent cations enhance emission intensity and control of energy through dative bonds or charge transfer. • The systems with adaptable cations exhibit characteristic luminescence and stimulus-response based on the Pt⋯Pt interactions. The characteristic luminescence properties of anionic cyclometalated Pt(II) complexes are discussed from the viewpoint of the counter cations. To date, various cyclometalated Pt(II) complexes have been developed as promising luminescent materials because cyclometalating ligands provide stable and strong ligand fields. In addition to the molecular design of cyclometalated Pt(II) complexes, control of the intermolecular interactions is particularly important for Pt(II) complexes with square-planar geometry. In this context, we focus on the effects of counter cations on anionic cyclometalated Pt(II) complexes by classifying such complexes into three categories, i.e., (i) systems with bulky organic cations, which enable the formation of isolated Pt(II) complexes, (ii) systems with non-innocent cations, which interact with anionic Pt(II) complexes through dative bonds or charge transfer, and (iii) systems including adaptable cations, which support the assembly of the Pt(II) complexes by cancelling out the electrostatic repulsion between Pt(II) complex anions that form stacking structures with Pt⋯Pt interactions. For this category, the formation and properties of ionic liquids using asymmetric cations is discussed. [ABSTRACT FROM AUTHOR]

Ten ionic manganese(II) complexes of [EMIm]2[MnX2Y2] (EMIm=1‐ethyl‐3‐methylimidazolium ion; X, Y=Cl, Br or I) and [BnMIm]2[MnX2Y2] (BnMIm=1‐benzyl‐3‐methylimidazolium ion; X, Y=Cl, Br or I) types were synthesized and studied in terms of their thermal and photophysical properties. Complexes with [BnMIm]+ cation were found to exhibit higher crystallinity, owing to the aromatic π‐stacking, and superior photoluminescent quantum yields, promoted by the increased Mn⋅⋅⋅Mn distance. For complexes with chlorine and bromine ligands efficient tunability of photophysical parameters was demonstrated. Out of all complexes, [BnMIm]2[MnBr4] was found to have the highest photoluminescence quantum yield at room temperature (Φ=0.59). To highlight the importance of a large Mn⋅⋅⋅Mn distance for achieving high Φ values, a mixed‐anion analog of complex [BnMIm]2[MnBr4] was prepared, with the suggested formula of [BnMIm]4[MnBr4]Br2. The latter have shown a significant improvement in d–d absorption efficiency and a reduction in nonradiative deactivation, which led to an outstanding Φ value of 0.97. Finally, the optical band gap of [BnMIm]4[MnBr4]Br2 was estimated to describe its applicability as light‐emitting material. [ABSTRACT FROM AUTHOR]

A coordination polymer, [Cu(SCN)(iqi)]n (iqi = isoquinoline), containing copper(I) thiocyanate and a nitrogen-containing π-conjugated ligand, iqi, has been synthesized and its physical properties were evaluated. This coordination polymer has a two-dimensional (2D) sheet structure consisting of copper(I) thiocyanate and shows photoluminescence derived from 3MLCT and photoconductive properties. [ABSTRACT FROM AUTHOR]

This article proposes the concept of soft crystals; flexible responsive systems with high structural order. Soft crystals are regular solids with stable and highly ordered structures. However, they undergo characteristic facile structural transformations and phase transitions in response to weak but specific stimuli. For more information, see the Concept article by M. Kato et al. on page 5105 ff. [ABSTRACT FROM AUTHOR]

Controlled self‐assembly of PtII complexes is key to the development of optical and stimuli‐responsive materials, but designing and precisely controlling them is still difficult owing to weak intermolecular interactions. Herein, we report the successful water‐vapor‐induced assembly of an anionic PtII complex [Pt(CN)2(ppy)]− (Hppy=2‐phenylpyridine) electrostatically loaded onto cationically charged layered double hydroxide (LDH) nanoparticles consisting of Mg2+ and Al3+ ions. When the PtII complexes were densely loaded onto the LDH nanoparticles, the assembly was maintained, even in dilute aqueous media. In the case of sparse loading, the PtII complexes were loaded discretely in the dry state; however, when water vapor was adsorbed, the increased mobility of the PtII complexes led to their assembly on the LDH nanoparticles. The presence of water vapor led to a drastic change in luminescence from green to orange. [ABSTRACT FROM AUTHOR]

Molecular crystals of Pt(II) complexes with metallophilic interactions can provide bright assembly-induced luminescence with colour tunability. However, the brittleness of many of these crystals makes their application in flexible optical materials difficult. Herein, we have achieved the elastic deformation of crystals of polyhalogenated Pt(II) complexes exhibiting bright assembly-induced luminescence. A crystal of [Pt(bpic)(dFppy)] (Hbpic = 5-bromopicolinic acid, HdFppy = 2-(2,4-difluorophenyl)pyridine) and a co-crystal of [Pt(bpic)(dFppy)] and [Pt(bpic)(ppy)] (Hppy = 2-phenylpyridine) were found to exhibit significant elastic deformation due to their highly anisotropic interaction topologies. While the crystal of [Pt(bpic)(dFppy)] exhibited monomer-based ligand-centred 3ππ* emission with an emission quantum yield of 0.40, the co-crystal exhibited bright, triplet metal–metal-to-ligand charge transfer (3MMLCT) emission owing to Pt⋯Pt interactions, thereby achieving a significantly higher emission quantum yield of 0.94. [ABSTRACT FROM AUTHOR]

A thermoresponsive structural change based on a disilane‐bridged bis(pyridine) ligand and CuI is reported. Single‐crystal X‐ray analysis revealed that there are two polymorphs in the Cu(I) complex: octanuclear copper(I) complex at 20 °C and 1D staircase copper(I) polymer complex at −173 °C. The formation of these polymorphs is due to the flexibility of the ligand. Cu−I bond formation is observed upon cooling the sample from −10 °C to −170 °C. The temperature‐induced phase transition progression was clarified by DSC, VT‐PXRD, and VT‐photoluminescence measurements and indicated a reversible temperature‐controlled crystal‐to‐crystal phase transition. Observation on a VT‐stage using a high‐speed camera showed crystal cracking during single‐crystal to single‐crystal transitions between these polymorphic forms. [ABSTRACT FROM AUTHOR]

Examines the crystal structure of dichloro(4,4-dinonyl-2,2'-bipyridine- kappa[sup 2]N,N')platinum(II). Bipyridine moiety with two long alkyl-chain substituents contained in the complex; Complex forming a segregated packing structure made up of the alkyl-chain layers and paired coordination sites.

A series of Pt(II) complexes bearing N-heterocyclic carbenes, [Pt(CN)2(Rim-Mepy)] (Rim-MepyH+ = 3-alkyl-1-(4-methyl-(2-pyridinyl))-1H-imidazolium, R = Me, Et, iPr, or tBu), exhibits triboluminescence in the visible range from blue to red, as well as the corresponding intense photoluminescence. Remarkably, among the complexes, the iPr-substituted one exhibits chromic triboluminescence behaviour during the process of rubbing and also vapour exposure. [ABSTRACT FROM AUTHOR]

Novel electrocatalysts for methanol oxidation were prepared from two Pt-Ni multinuclear complexes, [Pt 2 {Ni(NH 2 CH 2 CH 2 S) 2 } 4 ]Cl 4 and [Pt(bpy){Ni(NH 2 CH 2 CH 2 S) 2 (bpy)}](NO 3 ) 2 (bpy = 2,2′-bipyridine). They were adsorbed on a Au(111) surface by immersing the Au(111) electrode in solutions containing these complexes. The modified Au(111) electrodes were then subjected to potential cycling or heat-treatment at 200 °C and 300 °C so that organic ligands were decomposed and adsorbed complexes were converted to nanocomposites. For a comparison, Au(111) electrode modified by a Pt based nanocomposite prepared by using a di-platinum(II) complex ([Pt 2 (terpy) 2 (μ-otdst)] 2 + (terpy = 2.2′:6′,2″-terpyridine, H 2 otdst = 2-octylthio-4,6-disulfanyl-1,3,5-triazine)) as a starting molecule. The surface species were characterized by X-ray photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM) in addition to cyclic voltammetry (CV). Two-dimensional nanocomposites of monatomic height were observed by STM. The coverages of the nanocomposites were 2–8%. By repeating the complex adsorption and heat-treatment for five times, nanocomposites of higher coverage of 13–19% with monatomic height were formed on Au(111) surface. The resultant nanocomposites showed high activity for methanol oxidation reaction (MOR) with an improved CO-tolerance in a 0.1 M KOH aqueous solution containing 1 M CH 3 OH. [ABSTRACT FROM AUTHOR]

Dichloro­(4,4′-dipentyl-2,2′-bipyridine-κ2 N, N′)platinum(II), [PtCl2(C20H28N2)], adopts a discrete π–π stacking structure, where the alkyl chains are located in a random manner. In contrast, dichloro­(4,4′-diheptyl-2,2′-bipyridine-κ2 N, N′)platinum(II), [PtCl2(C24H36N2)], forms a layer structure comprised of alkyl chain layers and paired coordination sites, as observed for analogous complexes with longer alkyl chains. [ABSTRACT FROM AUTHOR]

A complex comprising one [Re(CO)3]+ unit and a phthalocyanine (Pc) ligand (Re1Pc) is shown to function as a photo‐induced CO‐releasing molecule (photoCORM) in the presence of O2 and a coordinative solvent under irradiation with red light, which can deeply penetrate living tissues. Transient absorption spectroscopic measurements indicate very short excited‐state lifetimes and ultrafast intersystem crossing for Re1Pc and Re2Pc, which contains two [Re(CO)3]+ units. The excited‐state properties are ascribed to efficient spin–orbit coupling and large Franck–Condon factors originating from the complexes' distorted structures, that is, unsymmetric coordination of [Re(CO)3]+ unit(s), one of which was confirmed by single‐crystal X‐ray analysis of a symmetrically substituted Pc with two [Re(CO)3]+ units. Re1Pc represents a promising red‐light‐driven photoCORM that can be applied in biological environments or therapeutic applications. [ABSTRACT FROM AUTHOR]

A series of mononuclear Cu(I)–halide complexes, [CuX(PPh 3 ) 2 (L)] (X = Cl − , Br − , I − ; PPh 3 = triphenylphosphine; L = pyridine (py), isoquinoline (iq), 1,6-naphthyridine (nap)), were synthesized. The emission color of [CuX(PPh 3 ) 2 (L)] varies from blue to red by changing the L ligands and the halide ions, and all the complexes exhibit high emission quantum yields (0.16–0.99) in the crystals. The emission studies revealed that the emissive states of [CuX(PPh 3 ) 2 (L)] differ depending on the L ligand. Complexes [CuX(PPh 3 ) 2 (py)] and [CuX(PPh 3 ) 2 (nap)] mainly emit from the singlet metal-to-ligand charge transfer mixed with the halide-to-ligand charge transfer ( 1 (M + X)LCT) state at room temperature. In contrast, emissions from [CuX(PPh 3 ) 2 (iq)] at room temperature originate from both 3 (M + X)LCT and 3 ππ* states. These results indicate that N -heteroaromatic ligands play an important role in the emission properties of mononuclear Cu(I)–halide complexes. [ABSTRACT FROM AUTHOR]

• We have synthesized disilane-bridged σ‒π frameworks, 1 and 2 , via Pd-mediated coupling. • These compounds showed higher fluorescence efficiency in the crystalline state than in n -hexane. • The single-crystal X-ray diffraction suggested that enhanced luminescence intensity is favored by crystal packing dominated by CH...π intermolecular interactions. • Theoretical calculations revealed that the HOMO‒LUMO gap of 1 and 2 decreases due to the σ‒π interactions. Introduction of Si‒Si σ bond into π-conjugated compounds expands the conjugated system through σ‒π interaction. In this work, disilane-bridged cyclic and linear σ‒π frameworks were synthesized by Pd-mediated coupling reaction between hydrosilane and 1,4-diiodobenzene. Their molecular structures were confirmed by NMR spectroscopy, mass spectrometry, and single-crystal X-ray diffraction analysis. The photophysical properties in n -hexane and in the crystalline state were investigated and theoretical calculations were carried out for additional evaluation. We considered cyclic and linear σ‒π conjugation evidenced in this study. [Display omitted] [ABSTRACT FROM AUTHOR]

The vapochromic single‐crystal‐to‐single‐crystal (SCSC) transformation of a highly luminescent PtII complex bearing an N‐heterocyclic carbene [Pt(CN)2(tBu‐impy)] (tBu‐impyH+=1‐tert‐butyl‐3‐(2‐pyridyl)‐1H‐imidazolium) is reported. The trihydrate form of the complex, which exhibits blue 3MMLCT emission owing to weak Pt⋅⋅⋅Pt interactions, changed its luminescence color from blue to yellowish‐green upon the desorption of water molecules while keeping the high emission quantum yield of more than 0.45. Variable‐temperature and continuous in‐situ tracking of single‐crystal X‐ray diffraction measurements revealed that the SCSC transformation proceeds reversibly by the release and reabsorption of water molecules, thereby changing the stacked structure slightly. As a result, the dynamics of vapor‐induced SCSC transformation were elucidated: that the anhydrous form returned to the original trihydrate form in a two‐step process under a water vapor atmosphere. In addition, the PtII complex exhibited a similar SCSC response accompanied by a luminescence color change in the presence of methanol vapor, while being inactive toward ethanol vapor. [ABSTRACT FROM AUTHOR]

Artificial intelligence algorithms utilizing deep learning are helpful tools for diagnostic imaging. A deep learning-based automatic detection algorithm was developed for rib fractures on computed tomography (CT) images of high-energy trauma patients. In this study, the clinical effectiveness of this algorithm was evaluated. A total of 56 cases were retrospectively examined, including 46 rib fractures and 10 control cases from our hospital, between January and June 2019. Two radiologists annotated the fracture lesions (complete or incomplete) for each CT image, which is considered the "ground truth." Thereafter, the algorithm's diagnostic results for all cases were compared with the ground truth, and the sensitivity and number of false positive (FP) results per case were assessed. The radiologists identified 199 images with a fracture. The sensitivity of the algorithm was 89.8%, and the number of FPs per case was 2.5. After additional learning, the sensitivity increased to 93.5%, and the number of FPs was 1.9 per case. FP results were found in the trabecular bone with the appearance of fracture, vascular grooves, and artifacts. The sensitivity of the algorithm used in this study was sufficient to aid the rapid detection of rib fractures within the evaluated validation set of CT images. [ABSTRACT FROM AUTHOR]

Trihexyltetradecylphosphonium (P6,6,6,14) salts of luminescent anionic Pt(II) complexes, (P6,6,6,14)[PtX2(ppy)] (X = Cl‐, Br‐; ppy = 2‐phenylpyridinate), are synthesized and photofunctional thin films with crystal/liquid bi‐stability are fabricated. In particular, the chloride complex provides a thin film exhibiting thermo‐ and mechano‐triggered luminescence ON/OFF switching at ambient temperature, which is based on the control of the supercooled liquid phase and bright luminescent crystalline phase. The photophysical properties of the complexes are investigated and compared with those of the bromide complex and tetra(n‐butyl)ammonium salts of the complexes. Furthermore, detailed photophysical analysis reveals a large contribution of the charge‐transfer character to the ligand‐centered 3π π* excited state, which results in intense phosphorescence in the crystal and high‐contrast luminescence ON/OFF by the phase transition of the chloride complex. [ABSTRACT FROM AUTHOR]

Ubiquitin-specific protease (USP)19 is a recently identified deubiquitinating enzyme (DUB) having multiple splice variants and cellular functions. One variant encodes an endoplasmic reticulum (ER)-anchored DUB that rescues misfolded transmembrane proteins from ER-associated degradation (ERAD), but the underlying mechanism remains to be elucidated. Here, we show that USP19 interacts with the ERAD-associated E3 ubiquitin ligase MARCH6. Overexpression of USP19 delayed the degradation of MARCH6, leading to an increase in its protein level. In contrast, USP19 depletion resulted in decreased expression of MARCH6. We also show that USP19 overexpression reduced ubiquitination of MARCH6, while its knockdown had the opposite effect. In particular, USP19 was found to protect MARCH6 by deubiquitination from the p97-dependent proteasomal degradation. In addition, USP19 knockdown leads to increased expression of mutant ABCB11, an ERAD substrate of MARCH6. Moreover, USP19 is itself subjected to endoproteolytic processing by DUB activity, and the processing cleaves off an N-terminal cytoplasmic region of unknown function. However, elimination of this processing had no evident effect on MARCH6 stabilization. These results suggest that USP19 is involved in the regulation of ERAD by controlling the stability of MARCH6 via deubiquitination. [ABSTRACT FROM AUTHOR]

The article titled "Front Cover: Photophysical Tuning of Imidazolium Tetrahalidomanganate(II) Complexes towards Highly Efficient Green Emitters with Near-Unity Quantum Yield" in the European Journal of Inorganic Chemistry discusses the achievement of bright green emission in a prepared material through rational structural design. The researchers lowered the concentration of [MnBr4]2− tetrahedra in the crystal structure to reduce non-radiative relaxation and increased the crystallinity of the material through π-π stacking between [BnMIm]+ cations. The article provides more detailed information on this research. [Extracted from the article]

We synthesized new oxygen-evolving molecular Ru(II) catalysts with one or two carbazole moieties on the axial pyridyl ligands, namely [Ru(bda)(cbz-py)(py)] and [Ru(bda)(cbz-py)2] [C1 and C2; bdaH2 = 2,2′-bipyridyl-6,6′-dicarboxylic acid, py = pyridine, and cbz-py = 9-(pyridin-4-yl)-9H-carbazole] to investigate the effect of cbz modification on the photophysical and catalytic properties of the well-known molecular catalyst [Ru(bda)(py)2] (C0). The initial oxygen-evolving catalytic activities of C1 and C2 were higher than that of C0 in both a chemical reaction driven by the strong oxidant (NH4)2[Ce(NO3)6] (CAN = ceric ammonium nitrate) and photochemical oxidation using a [Ru(bpy)3]2+ (bpy = 2,2′-bipyridine) photosensitizer with Na2S2O8 as the sacrificial oxidant. The higher activities were ascribed to the electron-withdrawing cbz groups, which promoted the radical coupling reaction to form a RuIV–O–O–RuIV species. A unique oxygen-evolution rate change behaviour was observed for both C1 and C2 in the presence of a large excess of CAN, suggesting the competitive oxidation of the cbz moiety during the chemical oxygen evolution reaction. This work suggests that the cbz modification of an oxygen evolution molecular catalyst is a promising approach for integrating the hole accumulator near the oxygen evolution catalytic centre. [ABSTRACT FROM AUTHOR]

Simple cysts of the testis are an uncommon lesion found in adults as well as infants. Only a few histological and immunohistochemical studies for this lesion have been reported because the lesion have rarely undergone surgical excision or histological confirmation. Herein is reported an autopsy case of simple cysts of the right testis found incidentally in an 84-year-old man who died of hepatocellular carcinoma. The cysts were multilocular, 12 × 8 mm in size, separated from the tunica albuginea and filled with transparent and colorless serous fluid. Histology and immunohistochemistry showed that the cystic lesion had flattened or cuboidal single-layered lining cells that were positive for cytokeratin AE1/AE3, calretinin, D2-40, HBME-1, mesothelin and thrombomodulin, indicating its mesothelial origin. To the authors' knowledge this is the first English-language report describing the origin of simple cysts of the testis. Although the exact pathogenesis of simple cysts of the testis is as yet unknown and there seems to be more than one etiology, at least in the present case the cysts were confirmed to correspond to mesothelial inclusions. [ABSTRACT FROM AUTHOR]

Abstract: To estimate the effects of changes in body posture on sudomotor function, sweat rates on the forearm, chest and thigh, tympanic temperature (T ty), and skin temperatures were recorded in an upright sitting and a supine position under a hot environment of 40 °C T a and 40% relative humidity for 60 min. Sweat expulsions were identified on sweat rate curves and their rates (F sw) were calculated. T ty was higher, and its initial fall was greater, in the supine position than in the sitting position. On the forearm and the chest, the regression line relating sweat rate to mean body temperature (T mb) had a gentler slope in the supine position, whereas on the thigh, it showed a steeper slope. The regression line relating F sw to T mb had a steeper slope in the supine position than in the sitting position, suggesting that the gain in the mechanisms for central integration and rhythm-generation was enhanced in the supine position. The parameter of sweat rate divided by F sw was lower on the forearm and the chest, whereas it was higher on the thigh in the supine position than in the sitting position, suggesting that sudomotor outflow was modified at the spinal cord in association with skin pressure. It was concluded that body posture affects sudomotor functions through both brain and spinal mechanisms. [Copyright &y& Elsevier]

Single crystals showing elastic flexibility have attracted increasing attention as next-generation soft materials. Herein, we successfully developed a series of polyhalogenated platinum(II)–bipyridine complexes showing solvent-of-crystallisation-dependent elastic flexibility. Notably, methanol-solvated crystals were the first examples of flexible crystals showing assembly-induced luminescence arising from the triplet metal–metal-to-ligand charge transfer (3MMLCT) excited state. Furthermore, factors inducing elastic deformability based on the packing structures of the crystals were explored. [ABSTRACT FROM AUTHOR]

The nickel(II)–chloranilato complex {Ni(ca)(VM)2}n (H2ca = chloranilic acid, VM = coordinated vapour molecules, such as water) shows reversible vapochromism upon exposure to various vapours and subsequent drying by heating. In contrast to the Ni(II)-quinonoid complex, [Ni(HLMe)2] (H2LMe = 4-methylamino-6-methyliminio-3-oxocyclohexa-1,4-dien-1-olate), which was reported to exhibit vapochromic spin-state switching between high and low spin states, the chloranilato complex does not change its spin state even after the removal of coordinated vapour molecules. X-ray absorption fine structure (XAFS) analysis revealed that the six-coordinate geometry of {Ni(ca)(VM)2}n was maintained even after the removal of vapour molecules, in contrast to the [Ni(HLMe)2] complex. The unique vapochromism that follows the dimensional change between 1D and higher is influenced by the relatively weaker ligand field of the chloranilate ligand. [ABSTRACT FROM AUTHOR]