Extended Tripodal Hydrotris(indazol-1-yl)borate Ligands as Ruthenium-Supported Cogwheels for On-Surface Gearing Motions.

This paper reports the synthesis of ruthenium-based molecular gear prototypes composed of a brominated or non-brominated pentaphenylcyclopentadienyl ligand as an anchoring unit and a tripodal ligand with aryl-functionalized indazoles as a rotating cogwheel. Single crystal structures of the ruthenium complexes revealed that the appended aryl groups increase the apparent diameter of the cogwheel rendering them larger than the diameter of the anchoring units and consequently making them suitable for intermolecular gearing motions once the complexes will be adsorbed on a surface.

Phase-Dependent Reactivity and Host-Guest Behaviors of a Metallo-Macrocycle in Liquid and Solid-State Photosensitized Oxygenation Reactions.

The photochemical oxygenation reactions of a host-guest complex, pCp⊂[Ag2L0](SbF6)2 (pCp = [2.2]paracyclophane) have been investigated in solution and in the solid state, using the macrocyclic ligand L0 having four anthracene moieties in the framework. As a result, it was found that the reactivity and host-guest functions show remarkable phase dependence. In solution, the photosensitized oxygenation of all the anthracene moieties of L0 resulted in a fully oxygenated macrocycle [Ag2L4](SbF6)2 as the final product, while simultaneously the guest molecule was dissociated from the macrocyclic cavity. On the other hand, in an amorphous solid of pCp⊂[Ag2L0](SbF6)2 prepared by decomposing single crystals through the removal of the crystalline solvent, the oxygenated site of L0 was significantly controlled to provide a site-selectively oxygenated inclusion complex, pCp⊂[Ag2L1](SbF6)2, possessing a mono-oxygenated Cs-symmetrical macrocyclic skeleton.

[A Case of Brain Metastasis of Gastric Cancer Successfully Treated with Nivolumab].

A 68‒year‒old man was referred to our hospital due to vomiting and light‒headedness. The patient was diagnosed with advanced gastric cancer. Neoadjuvant chemotherapy(S‒1 plus oxaliplatin)was initiated resulting in a partial response(PR) after 5 courses. Total gastrectomy and D1 dissection was performed. The tumor was diagnosed as poorly differentiated adenocarcinoma and the pathological Stage was ypT3, N3b, M1[CY1], ypStage Ⅳ. Ramucirumab plus nab‒paclitaxel was administered due to the appearance of swollen lymph nodes post‒operatively. This treatment maintained PR for 6 courses. However, after an evaluation of progressive disease(PD), nivolumab was initiated as third‒line chemotherapy. After 3 courses, a sudden seizure occurred and a brain metastasis with a diameter of 6 mm was observed. Considering the decrease in CEA level and that the brain metastasis presented as a small lesion, the tumor was inferred to be highly sensitive to nivolumab. We continued nivolumab monotherapy as chemotherapy. Radiotherapy was not performed. Both intra and extra‒cranial metastatic lesions maintained PR for 17 courses. The treatment was changed to irinotecan after evidence of PD was observed. However, after 2 courses(2 years and 3 months from his first visit), the patient died of an unknown cause. To our knowledge, this is the first case of brain metastasis of gastric cancer successfully treated with nivolumab.

Thermosalience in Macrocycle-Based Soft Crystals via Anisotropic Deformation of Disilanyl Architecture.

We describe here the preparation of soft crystals using disilanyl macrocycle C4 possessing four p-phenylenes circularly connected by four flexible disilane bonds. Single crystals of C4 exhibited a reversible thermal single-crystal-to-single-crystal (SCSC) phase transition behavior between two crystal phases accompanied by remarkable mechanical motion (thermosalient effect), as revealed by thermal analyses and X-ray diffraction measurements. Detailed structural analyses implied that flexibility of the parallelogram disilanyl architecture and molecular packing mode via weak intermolecular interactions facilitated a concerted structural transformation (parallel crank motion) of macrocycles in the crystal, thus resulting in the SCSC phase transition accompanied by anisotropic shrinking/elongation of the cells to induce the thermosalient effect. This work explores a new area of organosilicon chemistry and presents the potential utility of disilanyl macrocycles as soft crystals.

Enhancement of the Photofunction of Phosphorescent Pt(II) Cyclometalated Complexes Driven by Substituents: Solid-State Luminescence and Circularly Polarized Luminescence.

Ligand functionalization is an attractive strategy for enhancing the performance of metal-based phosphorescent emitters. Here, we report the synthesis and characterization of cyclometalated Pt(II) complexes Pt3 and Pt4 containing organosilyl-substituted (2-(2-thienyl)pyridine) ligands and compare their properties with those of Pt1 (no substituent) and Pt2 (organocarbon substituent). The photophysical characteristics of these molecules, including their absorption and phosphorescence spectra, phosphorescence quantum yield and lifetime, were investigated. The molecular structures were revealed by X-ray diffraction analysis. Under UV light irradiation, Pt2-Pt4 emitted intense orange phosphorescence in the solid state because of the bulkiness of their side chains (up to ΦP: 0.49). Optically pure (-)-(S)Si-Pt4 and (+)-(R)Si-Pt4 were prepared using the optically active ligands (+)-L4 and (-)-L4, respectively. The chiroptical properties of (+)-(R)Si-Pt4, which has an asymmetric silicon atom, were investigated. Circular dichroism and circularly polarized luminescence measurements showed that these structural motifs are suitable for applications in chiroptical phosphorescent materials.

Effects of Substituents on the Blue Luminescence of Disilane-Linked Donor‒Acceptor‒Donor Triads.

A series of disilane-linked donor‒acceptor‒donor triads (D‒Si‒Si‒A‒Si‒Si‒D) was synthesized to investigate the effects of substituents on the photophysical properties. The triads were prepared by metal-catalyzed diiodosilylation of aryl iodides using a Pd(P(t-Bu)3)2/(i-Pr)2EtN/toluene system that we previously developed. Optical measurements, X-ray diffraction analysis, and density functional theory calculations revealed relationships between the photophysical properties and molecular structures of these triads in solution and in the solid state. The compounds emitted blue to green fluorescence in CH2Cl2 solution and in the solid state. Notably, compound 2 showed fluorescence with an absolute quantum yield of 0.17 in the solid state but showed no fluorescence in CH2Cl2. Our findings confirmed that the substituent adjacent to the disilane moiety affects the conformations and emission efficiencies of compounds in solution and in the solid state.

Multifunctional Octamethyltetrasila[2.2]cyclophanes: Conformational Variations, Circularly Polarized Luminescence, and Organic Electroluminescence.

Both symmetrical and unsymmetrical cyclophanes containing disilane units, tetrasila[2.2]cyclophanes 1-9, were synthesized. The syn and anti conformations and the kinetics of inversion between two anti-isomers were investigated by X-ray diffraction and variable-temperature NMR analysis, respectively. The flipping motion of two aromatic rings was affected by the bulkiness of the aromatic moiety (1 vs 6), the phase (solid vs solution), and the inclusion by host molecules (1 vs 1⊂[Ag2L]2+). The photophysical, electrochemical, and structural properties of the compounds were thoroughly investigated. Unsymmetrical tetrasila[2.2]cyclophanes 5-8 displayed blue-green emission arising from intramolecular charge transfer. Compound 6 emitted a brilliant green light in the solid state under 365 nm irradiation and showed a higher fluorescence quantum yield in the solid state (Φ = 0.49) than in solution (Φ = 0.05). We also obtained planar chiral tetrasila[2.2]cyclophane 9, which showed interesting chiroptical properties, such as a circularly polarized luminescence (CPL) with a dissymmetry factor of |glum| = ca. 2 × 10-3 at 500 nm. Moreover, an organic green light-emitting diode that showed a maximum external quantum efficiency (ηext) of ca. 0.4% was fabricated by doping 4,4'-bis(2,2'-diphenylvinyl)-1,1'-biphenyl with 6.

Multipoint recognition of ditopic aromatic guest molecules via Ag-π interactions within a dimetal macrocycle.

A macrocyclic host molecule possessing a nanocavity with two Ag(I) centers for guest binding and four anthracene walls has been developed. This dimetal-macrocycle forms stable inclusion complexes with ditopic aromatic guest molecules, [2.2]paracyclophane, and ferrocene, in solution and/or in the solid state through Ag-π interactions within the nanocavity. The binding constants for the inclusion complexes were found to range roughly from 10(4) to 10(9) M(-1). Electrochemical measurement revealed that the oxidized form of the included cationic ferrocene was less stabilized due to the direct binding to the cationic two Ag(I) centers.

Lipid cubic phase with an organic-inorganic hybrid structure formed by organoalkoxysilane lipid.

A lipid cubic phase encompassing a cross-linked siloxane structure was formed by the self-assembly of a synthetic organoalkoxysilane lipid in water. The spontaneous sol-gel reaction of the alkoxysilane moiety on the lipid head group produced an organic-inorganic hybrid material with a double gyroid Ia3d cubic structure.

Airway obstruction caused by achalasia: A case report.

We report a rare case of airway obstruction caused by megaesophagus associated with achalasia. A 78-year-old man was admitted with post meal dyspnea, decreased consciousness, expiratory and inspiratory wheezing, and respiratory distress. Arterial blood gas analysis showed findings of marked acute respiratory acidosis (pH 7.18, PaCO2 75 mmHg, PaO2 225 mm Hg, HCO3- 22 mmol/L). An emergency laryngoscopy was performed because of a suspected airway obstruction, but no abnormalities were observed from the airway to the glottis. Noninvasive positive pressure ventilation (NPPV) was immediately introduced, and the respiratory rate and breathing pattern was normalized. A chest X-ray showed an enlarged upper mediastinal outline and an ill-defined border of the trachea. A computed tomography (CT) scan showed an enlarged esophagus with a maximum diameter of 9.90 cm, compressing the trachea to the back of the sternal notch. Following removal of the esophageal contents using a nasogastric tube, NPPV was discontinued with no respiratory episodes. After he was stabilized, he was transferred to another hospital for endoscopic myotomy. In a review of the literature, we identified 66 cases of airway obstruction due to achalasia, mainly in older women. None of the patients received NPPV. As a differential diagnosis for acute airway obstruction, achalasia-related airway obstruction should be considered, particularly in older women. Furthermore, since this condition is suspected to involve tracheomalacia, NPPV may be a useful respiratory support therapy.

Comparison of the effectiveness of pericardiocentesis and surgical pericardiotomy in the prognosis of patients with blunt traumatic cardiac tamponade: a multicenter study using the Japan Trauma Data Bank.

Aim: To compare the prognostic impact of pericardiocentesis (PCC) and surgical pericardiotomy (SP) in blunt traumatic pericardial tamponade. Methods: Among 361,706 trauma patients registered in the Japan Trauma Data Bank from January 2004 to December 2018, we included those with blunt traumatic cardiac tamponade who underwent PCC and/or SP. We excluded patients with penetrating trauma, age younger than 15 years, Injury Severity Score (ISS) equal to 75, blood pressure 0 mmHg at the time of admission, head Abbreviated Injury Scale (AIS) score 5 or more, and those with missing data for outcomes. To examine the effect of SP, patients were divided into a PCC group and an SP-only group. Missing values of age, sex, systolic blood pressure, respiratory rate, pulse rate, time from emergency call to hospital arrival, head AIS, chest AIS, abdomen/pelvis AIS, Glasgow Coma Scale score, and ISS were estimated using multiple imputation. In-hospital mortality was analyzed using multivariable analysis, and we undertook a survival analysis. Results: We analyzed 305 patients, 150 (49.2%) in the PCC group and 155 (50.8%) in the SP-only group. The in-hospital mortality rate was 40.7% in the PCC group and 76.8% in the SP-only group. Multivariable analysis after multiple imputation showed an odds ratio of SP for in-hospital mortality 5.34 (95% confidence interval, 2.80-10.18; P < 0.01) compared with PCC. Using the Kaplan-Meier method, SP showed a significant risk of mortality (hazard ratio 2.16; 95% confidence interval, 1.58-2.95; P < 0.01). Conclusions: In patients with blunt traumatic cardiac tamponade, SP was associated with poor prognosis.

Thermally responsive morphological changes of layered coordination polymers induced by disordering/ordering of flexible alkyl chains.

The search for a method to control structural transformations of layered coordination polymers is highly desirable to modulate their properties and functions. Herein, we report the construction of a novel coordination polymer named ZnC16 with Zn(II) ions coordinated to isophthalate ligands bearing an n-hexadecyloxy chain (C162-). Its structure consists of a layer-by-layer structure of a rigid two-dimensional coordination network and an assembly of alkyl chains as a thermally responsive moiety. Single crystals of ZnC16 exhibit a thermal crystal-to-crystal phase transition behaviour dominated by disordering/ordering of alkyl chains, which induces the expansion and shrinkage of the distance within the rigid 2D coordination networks. Microscopic observation revealed that the thermal phase transition of ZnC16 induces a significant change in their crystal morphology: a reversible macroscopic elongation/shrinkage of crystal dimensions driven by the displacement of interlayer distances and an irreversible delamination and polycrystal slippage driven by constraints generated from this phase transition. Our result provides a new direction to modulate the dynamic behaviour and related properties and functions of layered coordination polymers where the thermally responsive character of flexible alkyl chains plays an important role in tuning interlayer interactions.

Comorbid rectus abdominis diastasis is a risk factor for recurrence of umbilical hernia in Japanese patients.

INTRODUCTION: Rectus abdominis diastasis (RAD) is characterized by thinning and widening of the linea alba and laxity of the ventral abdominal muscle. RAD, when coexistent with umbilical hernia, is considered a risk factor for hernia recurrence. We investigated the impact of comorbid RAD in patients with umbilical hernia who had undergone hernia repair. METHODS: We enrolled 30 patients who had undergone umbilical hernia repair using either a laparoscopic or anterior approach between April 2006 and May 2018. We diagnosed RAD according to preoperative CT. The outcomes of patients with umbilical hernia, the RAD group, and the non-RAD group were compared, especially in terms of recurrence. RESULTS: Twenty-five patients (83%) presented with RAD, including three patients (12%) with postoperative recurrence who were allocated to the RAD group. The median BMI in the RAD group was 27.2 kg/m2 . In the RAD group, a prosthesis mesh was used in 12 patients (48%), and nonabsorbable suture material was used in four patients (16%). There was no statistically significant difference between the two groups in terms of age, hernial orifice diameter, surgical technique, or operative time. CONCLUSION: The rate of comorbid umbilical hernia in Japanese patients with RAD was high, as was the recurrence rate of umbilical hernia. We strongly recommend preoperative detection of RAD. We also recommend mesh-based repair of the midline and nonabsorbable suture material to decrease the recurrence rate, irrespective of hernia size.

Observation of an exotic state of water in the hydrophilic nanospace of porous coordination polymers.

Fundamental understanding of the confinement of water in porous coordination polymers (PCPs) is important not only with respect to their application, such as in gas storage and separation, but also for exploring confinement effects in nanoscale spaces. Here, we report the observation of water in an exotic state in the well-designed hydrophilic nanopores of PCPs. Single-crystal X-ray diffraction finds that nanoconfined water has an ordered structure that is characteristic in ices, but infrared spectroscopy reveals a significant number of broken hydrogen bonds that is characteristic in liquids. We find that their structural properties are quite similar to those of solid-liquid supercritical water predicted in hydrophobic nanospace at extremely high pressure. Our results will open up not only new potential applications of water in an exotic state in PCPs to control chemical reactions, but also experimental systems to clarify the existence of solid-liquid critical points.

Molecular recognition of planar and non-planar aromatic hydrocarbons through multipoint Ag-π bonding in a dinuclear metallo-macrocycle.

Exploration of a novel structural motif of host-guest interactions is one of the most fundamental topics to develop macrocycle-based host-guest/supramolecular systems. Herein, we present an unprecedented mode of inclusion of aromatic hydrocarbons into a macrocyclic cavity via multipoint Ag-π bonding as a driving force. A dinuclear AgI-macrocycle encapsulated one molecule of anthracene, a typical planar aromatic hydrocarbon, in solution and in the solid state. Single-crystal X-ray diffraction analysis of the host-guest inclusion complex revealed the binding of anthracene via multipoint Ag-π bonding to both AgI ions arranged within the open-ended nano-cavity of the dinuclear AgI-macrocycle. Notably, this binding motif based on Ag-π bonding was also applied to the inclusion of triptycene, a non-planar aromatic hydrocarbon with a steric tripodal structure, to evaluate the rotational motion of the molecular paddle-wheel in the AgI-macrocycle.

Paraffinic metal-organic polyhedrons: solution-processable porous modules exhibiting three-dimensional molecular order.

Metal-organic polyhedral cages substituted with paraffinic side chains were designed as solution-processable porous modules, which provide soft materials possessing self-organized cavity structures with three-dimensional molecular order in a lyotropic mesophase. The macroscopic shape of the resulting soft materials can be easily modified through solution-based processes.

Anisotropic convergence of dendritic macromolecules facilitated by a heteroleptic metal-organic polyhedron scaffold.

Anisotropic dendrimers with bipolar shapes were systematically obtained using a heteroleptic metal-organic polyhedron (MOP) as a robust core scaffold. The structure of one of these polyhedral shapes was unambiguously determined by single-crystal X-ray analysis, which revealed that the bulky dendrons converge to both axial positions of the heteroleptic MOP core.

Anisotropic coordination star polymers realized by self-sorting core modulation.

End-functionalized polymeric ligands (macroligands) and azobenzene-3,3'-dicarboxylic acid with Cu2+ self-sort into anisotropic coordination star polymers with polymeric chains on the arms, grafted from each polar position of the metal-organic polyhedral core.

Laparoscopic orchidopexy with transabdominal preperitoneal hernia repair in an adult.

We report an adult who underwent laparoscopic orchidopexy and transabdominal preperitoneal hernia repair. The patient was a 53-year-old man who was referred to our hospital for a bulge and pain in his left inguinal area. An abdominal CT scan revealed that the greater omentum was incarcerated in a left inguinal hernia. The patient underwent emergency laparoscopic surgery immediately. After reduction, he was diagnosed with bilateral cryptorchidism and inguinal hernia. After adequate mobilization, pneumoperitoneum was discontinued, and orchidopexy was performed with the Lichtenstein tension-free hernioplasty. One month later, the patient underwent elective laparoscopic orchidopexy with transabdominal preperitoneal hernia repair on his right side. The patient's postoperative course has been uneventful, with no evidence of hernia recurrence to date. This procedure is safe and may be an option for adult patients who desire testis preservation. This may be the first report of laparoscopic hernia repair with orchidopexy.

Immediate postoperative angiographic embolization after damage control surgery for liver injury: report of a case.

A multimodality strategy, including damage control and angioembolization techniques, has been reported to reduce the mortality associated with surgery for complex blunt hepatic injuries. However, the indications for angiographic evaluation and embolization in patients who require surgery for hepatic injury remain unclear. We report a case of blunt hepatic injury requiring emergency laparotomy, which we treated by damage control surgery because of an inaccessible major venous injury and the fact that coagulopathy was stopping hemostasis. The decision to perform immediate postoperative angiography was based on the hemorrhagic response to Pringle's maneuver and its release after perihepatic packing during surgery. Hepatic angiography revealed extravasation from a branch of the middle hepatic artery, which was embolized successfully. Although the definitive indications for immediate postoperative angioembolization for hepatic injury have not been established, the hemorrhagic response to Pringle's maneuver and its release after perihepatic packing during damage control surgery is an indication for immediate postoperative angioembolization.