Highly Efficient and Thermally Durable Luminescence of 1D Eu3+ Coordination Polymers with Arsenic Bridging Ligands.

In this work, bisarsine oxides were evaluated as novel bridging ligands, aiming to develop practical and efficient luminescent lanthanide coordination polymers. We have synthesized one-dimensional (1D) Eu3+ coordination polymers that incorporate bisarsine oxide bridging ligands and hexafluoroacetylacetonate anions. These polymers exhibited a denser packing of chains compared to analogous polymers bridged with bisphosphine oxides. The coordination polymers demonstrated exceptional thermal stability and substantial emission quantum yields. Additionally, the bisarsine oxides induced a pronounced polarization effect, facilitating a sensitive electric dipole transition that yields considerably narrow band red emission. Remarkably, the Eu3+ coordination polymers with bisarsine oxides maintained intense emission even at 550 K. A distinctive feature of these polymers is their heating-induced emission enhancement observed when the temperature was increased from 300 K to 400 K.

Effects of Central Elements on the Properties of Group 13 Dialdiminate Complexes.

Novel luminescent dialdiminate complexes of the Group 13 elements were prepared to evaluate the effects of the central element on their properties. We demonstrate that their absorption wavelength and the response to Lewis bases apparently depend on the central atom. The aluminum complex exhibited the absorption band in the higher-energy region than the gallium and indium congeners. Theoretical calculations suggest that the aluminum complex has a lower-lying highest-occupied molecular orbital than the other complexes. Additionally, the emission intensity of the aluminum complex clearly changed in response to a Lewis base. Quantum chemical calculations suggest that these element-dependent optical properties could originate from the difference in the electric charges on the central elements. Interestingly, the ligand exchange reactions were observed in the indium complexes together with the changes in the optical properties and controlled by the addition of InCl3 and InMe3 . Furthermore, all the complexes showed aggregation-induced emission enhancement (AIEE) and crystallization-induced emission enhancement (CIEE) properties. These results lead to proposing a practical strategy for manipulating the optoelectronic properties coupled with the reactivities of complexes by choosing the central elements in the same group.

Effects of Central Elements on the Properties of Group 13 Dialdiminate Complexes.

Invited for the cover of this issue is the group of Kazuo Tanaka at Kyoto University. The image depicts the element-dependent properties of group 13 dialdiminate complexes Read the full text of the article at 10.1002/chem.202300654.

Modulation of Properties by Ion Changing Based on Luminescent Ionic Salts Consisting of Spirobi(boron ketoiminate).

We report development of luminescent ionic salts consisting of the boron ketoiminate structure, which is one of the robust skeletons for expressing aggregation-induced emission (AIE) properties. From the formation of the boron-centered spiro structure with the ketoiminate ligands, we obtained stable ionic salts with variable anions. Since the ionic salts show Tms below 100 °C, it was shown that these salts can be classified as an ionic liquid. By using PF6 anion, the single crystal-which is applicable for X-ray crystallography-was obtained. According to the optical measurements, it was proposed that electronic interaction should occur through the boron center. Moreover, intense emission was observed both in solution and solid. Finally, we demonstrated that the emission color of the PF6 salt was altered from crystal to amorphous by adding mechanical forces. Based on boron complexation and intrinsic solid-state luminescent characters, we achieved obtainment of emissive ionic materials with environmental responsivity.

Reversible Vapochromic Luminescence Accompanied by Planar Half-Chair Conformational Change of a Propeller-Shaped Boron ß-Diketiminate Complex.

Leakage of volatile organic compounds (VOCs) is one of the most severe industrial problems, because it can cause environmental pollution, global warming, fire, and explosion. Hence, the visualization of leakage is an essential technology to detect it at an early stage. Molecular crystals, fluorescence color of which can be changed by the exposure to VOCs could potentially serve as the sensing materials for realizing rapid and facile VOC detection. However, these materials usually require harsh conditions, such as heating or a vacuum, to recover their initial phases for reuse. Therefore, it remains a challenge to obtain completely reversible sensing systems without such energy-consuming recycling processes. Herein, the reversible color change of fluorescence from the crystals of a propeller-shaped boron ß-diketiminate complex is reported. The complex was crystallized in distinct crystalline phases having different luminescent colors. Importantly, these phases were interconverted very rapidly (time constant <60 s) and repeatedly upon exposure to the vapors of the appropriate VOCs. The small energy differences between conformers of the complex could lead to this pseudopolymorphic behavior. This finding could be applied for the development of further eco-friendly reversible sensing materials based on four-coordinated boron complexes.

A three-dimensional computed tomography angiography study of the anatomy of the accessory middle colic artery and implications for colorectal cancer surgery.

PURPOSE: In the present study, we focused on the accessory middle colic artery and aimed to increase the safety and curative value of colorectal cancer surgery by investigating the artery course and branching patterns. METHODS: We included 143 cases (mean age, 70.4 ± 11.2 years; 86 males) that had undergone surgery for neoplastic large intestinal lesions at the First Department of Surgery at Yamagata University Hospital between August 2015 and July 2018. We constructed three-dimensional (3D) computed tomography (CT) angiograms and fused them with reconstructions of the large intestines. We investigated the prevalence of the accessory middle colic artery, the variability of its origin, and the prevalence and anatomy of the arteries accompanying the inferior mesenteric vein at the same level as the origin of the inferior mesenteric artery. RESULTS: Accessory middle colic artery was observed in 48.9% (70/143) cases. This arose from the superior mesenteric artery in 47, from the inferior mesenteric artery in 21, and from the celiac artery in two cases. In 78.2% (112/143) cases, an artery accompanying the inferior mesenteric vein was present at the same level as the origin of the inferior mesenteric artery; this artery was the left colic artery in 92, the accessory middle colic artery in 11, and it divided and became the left colic artery and the accessory middle colic artery in 10 cases. CONCLUSION: 3D CT angiograms are useful for preoperative evaluation. Accessory middle colic arteries exist and were observed in 14.9% of cases.

[A Case of Large-Cell Neuroendocrine Carcinoma of the Stomach with Multiple Liver Metastases That Show Complete Response to Multidisciplinary Therapy].

A 64-year-old man was diagnosed with advanced gastric cancer based on an endoscopic examination in June 2009; histological findings indicated poorly differentiated adenocarcinoma.Computed tomography revealed multiple liver metastases and bulky lymph node metastases of LN#7.The multiple liver metastases of the gastric cancer were not considered to be candidates for surgical resection, and S-1/CDDP chemotherapy was initiated in July 2009. After 6 courses of this regimen, liver and lymph node metastases showed partial response(PR), but the gastric tumor showed progressive disease(PD).Therefore, we switched this regimen to bi-weekly CPT-11/CDDP in March 2010. However, because the gastric tumor had increased in size and presented with bleeding, we performed distal gastrectomy.The pathological diagnosis based on the resected speci- men was large-cell neuroendocrine carcinoma.After surgery, CPT-11/CDDP was continued but was switched to CPT-11 in June 2011 because of induced renal dysfunction.In November 2011, the regimen was switched to weekly paclitaxel because of a progressive increase in size of a solitary liver metastatic lesion located in S4-5.Two courses of this regimen were administered, but they were ineffective; therefore, we performed partial hepatectomy.No other recurrent lesions were observed during the surgery, and the patient was estimated to have achieved complete response(CR).After the surgery, no further adjuvant chemotherapy was administered.Four years after hepatectomy, the patient was diagnosed with esophageal cancer but exhibited no recurrence of the gastric cancer.We performed esophagectomy for the esophageal cancer in May 2016.T he patient is currently well without any relapse.

Arene-Inserted Extended Germa[n]pericyclynes: Synthesis, Structure, and Phosphorescence Properties.

This report describes the synthesis and characterization of arene-inserted extended (ArEx) germa[n]pericyclynes composed of germanium and 1,4-diethynylbenzene units. These novel cyclic germanium-π unit materials were synthesized with diethynylbenzene and germanium dichloride. X-ray crystallographic analysis revealed their structures, and the planar conformation of ArEx germa[4]pericyclyne along with the regular aromatic rings. UV/Vis absorption spectra and fluorescence emission spectra showed considerably unique and highly improved character compared to previously reported germa[n]pericyclynes. Even in the absence of transition metal components, phosphorescence emissions were observed, and the emission lifetimes were dramatically improved. ArEx germa[n]pericyclynes showed high photoluminescence quantum yields, whereas low photoluminescence quantum yields were observed for acyclic compounds. Density functional theory calculations show delocalized orbitals between skipped alkyne units through a germanium tether, and an increase in the HOMO energy level, leading to a small HOMO-LUMO energy gap.

Development of solid-state emissive o-carboranes and theoretical investigation of the mechanism of the aggregation-induced emission behaviors of organoboron "element-blocks".

This paper presents the aggregation-induced emission (AIE) properties of o-carborane derivatives and proposes a potential strategy for constructing AIE-active organoboron complexes via the enhancement of freedom of intramolecular mobility. Initially, the optical properties of o-carborane derivatives with or without the fused ring structure at the C-C bond in o-carborane in which elongation should be induced by photo-excitation according to theoretical calculations were compared. Accordingly, it was shown that large mobility at the C-C bond in o-carborane should be responsible for the annihilation of emission in solution, leading to the AIE property. From this result, it was presumed that by enhancing the freedom of intramolecular mobility in conventional luminescent organoboron complexes, the deactivation of the excited state in solution and emission recovery in the aggregate can be induced. Based on this idea, we have performed several studies and introduce two representative results. Firstly, the decrease in luminescent properties of boron dipyrromethene (BODIPY) in solution by introducing a movable functional group is explained. Next, the AIE behaviors of boron ketoiminates and the potential mechanism concerning conformational changes for the deactivation of the excited state in the solution state are illustrated. It is proposed that enhancement of the freedom of mobility in the excited state of luminescent organoboron complexes could be a potential strategy for realizing AIE behaviors.

Effects of a central element on the photoluminescence properties of ß-diketiminate complexes composed of group 13 elements.

Various kinds of boron complexes have been utilized as functional luminescent materials. However, only a limited number of emissive complexes containing other group 13 elements have been reported. Herein, we report the synthesis and optical properties of luminescent ß-diketiminate complexes containing a series of group 13 elements. The synthesized complexes exhibited crystallization-induced emission properties. It was indicated that the heavier group 13 elements accelerate intersystem crossing from the singlet to the triplet excited state because of the strong heavy atom effect. Finally, we discovered that aluminum and gallium complexes can work as solid-state luminescent materials with high emission efficiencies.

Effects of childhood experiences of parental attitude, depressive rumination, and sleep disturbances on adulthood depressive symptoms.

Aim: Various factors are thought to be involved in the development of depression, but the mechanisms are not yet clear. Although several reports have demonstrated that parental attitude experienced in childhood, depressive rumination, and sleep disturbances each influence depressive symptoms, and the association between two of these four variables, to our knowledge, no reports to date have investigated the association among the four variables. Methods: A questionnaire survey was administered to 576 adults who agreed to participate in this study between April 2017 and April 2018. Questionnaires assessed parental attitudes experienced in childhood, depressive rumination, sleep disturbances, and depressive symptoms in adulthood. The associations among the four variables were tested by structural equation modeling. Results: Regarding the direct effects, the parental attitude of "care" had a negative influence on depressive rumination and depressive symptoms, whereas "overprotection" had a positive influence on depressive rumination. Depressive rumination had a positive influence on sleep disturbance and depressive symptoms, whereas sleep disturbances had a positive influence on depressive symptoms. Regarding indirect effects, depressive rumination mediated the association between parental attitudes and sleep disturbances or depressive symptoms. Furthermore, sleep disturbances mediated the association between depressive rumination and depressive symptoms. Care and overprotection showed opposite effects. The goodness of fit of this model was high. Conclusion: The results of this study demonstrated that there were associations among the four variables. Clinical assessment and intervention of depressive rumination and sleep disturbances that are closely associated with previous parental attitudes may lead to an improvement of depressive symptoms.

Effects of Inappropriate Nurturing Experiences, Depressive Rumination, and Trait Anxiety on Depressive Symptoms.

Background: Prior research has shown that inappropriate childhood nurturing experiences (low care and high overprotection), trait anxiety, and depressive rumination are risk factors for depression. However, no studies to date have analyzed the overall association between these factors and depressive symptoms. In the present study, we hypothesized that depressive rumination mediates the impacts of inappropriate childhood nurturing experiences on depressive symptoms, and that these mediating effects are moderated by trait anxiety, and tested these hypotheses in adult volunteers. Methods: The subjects were adult volunteers who were investigated between April 2017 and April 2018. A self-report questionnaire on demographic data, childhood nurturing experiences, trait anxiety, depressive rumination, and depressive symptoms was distributed to conduct the survey, and written informed consent and valid responses were obtained from 585 subjects. Mediation and moderated-mediation analyses were performed by SPSS 28 and macro PROCESS 4.0 software. This study was approved by the Ethics Committee of Tokyo Medical University. Results: Parental care showed a significant negative indirect effect on depressive symptoms via its effect on depressive rumination (p < 0.01), whereas parental overprotection showed the opposite effect (p < 0.01). Furthermore, the mediation effect of depressive rumination on depressive symptoms was increased by trait anxiety (p < 0.05). Conclusion: Our present study demonstrated that the main factor affecting depressive symptoms is inappropriate childhood nurturing experiences, which indirectly enhance depression by intensifying depressive rumination, and that depressive rumination and trait anxiety mutually reinforce each other to enhance depressive symptoms. These findings may be useful for the prevention of depressive symptoms. Large-scale prospective studies are needed to confirm the causal associations among these factors in the future.

Effects of Peer Victimization in Childhood and Trait Anxiety on Job Stress in Adulthood.

Background: The experience of peer victimization in childhood increases the risk of developing anxiety disorders and depression, risk of suicide, as well as sensitivity to stress, in adulthood. Various personality traits are known to be associated with these effects. However, the influence of trait anxiety on job stress has not yet been reported. In the present study, we tested the hypothesis that the experience of peer victimization in childhood and trait anxiety influence job stress in adulthood. Methods: A questionnaire survey, including State-Trait Anxiety Inventory, Childhood Victimization Rating Scale, and Brief Job Stress Questionnaire, was administered to 566 adult workers. The interrelationship between multiple variables was analyzed by multiple regression analysis and path analysis. Results: In the path model, childhood peer victimization had a positive direct effect on trait anxiety and the psychological and physical stress response (PPSR). Trait anxiety had a positive direct effect on job stressors and PPSR, and job stressors had a positive direct effect on PPSR. Regarding indirect effects, childhood peer victimization had a significant adverse effect on job stressors and PPSR via trait anxiety. Conclusion: Our results showed that childhood peer victimization has a negative impact on job stress in adulthood, which is influenced by trait anxiety. Interventions to address peer victimization in childhood and trait anxiety may reduce job stress in adulthood, and thus contribute to improved occupational mental health and productivity in the workplace.

Design and Synthesis of Far-Red to Near-Infrared Chromophores with Pyrazine-Based Boron Complexes.

We synthesized new binuclear boron complexes based on pyrazine with ortho and para substitution patterns. It was demonstrated that the para-linked complexes possess a significantly narrow energy gap between highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO), leading to their far-red to near-infrared emission properties. Meanwhile, the ortho-substituted complex showed orange emission. Considering the HOMO and LUMO distributions of pyrazine, the boron complexation to the nitrogen atoms would stabilize its LUMO more efficiently than its HOMO because a nodal plane in the HOMO passes through the two nitrogen atoms. The theoretical study suggests that the para-substitution would not significantly perturb such a characteristic HOMO distribution originating from pyrazine in stark contrast to the ortho-substituted one. As a result, the HOMO-LUMO gap of the para-linked complex is dramatically narrower than that of the ortho-linked one.

The disparity of utilization rate among specific groups for a rapid spreading telehealth application called LEBER during the COVID-19 state of emergency in Japan.

Objectives: The purpose of this research is to describe the social demographics and chief complaints of users of a free medical consultation application in Ibaraki Prefecture, where a free medical consultation application was released. Methods: The present study included users of a telehealth application in Ibaraki Prefecture between April 9 and May 17, 2020, during the state of emergency. User background characteristics were descriptively analyzed to clarify individual factors with the potential to act as barriers to equally using innovative solutions. Additionally, the age and consultation time distribution by sex were examined for those who used the application for COVID-19 and non-COVID-19 issues. Results: Most of the participants were in their thirties. Moreover, 72% were female, with most being in their thirties (86%) and the least being in their sixties (45%). The number of consultations was concentrated between 6 p.m. and 10 p.m., with the least between 1 a.m. and 5 a.m. The telehealth application users were mainly females in their thirties and forties. Conclusions: To prevent the widening of health disparities due to the rapid introduction of telehealth, further research is required to identify why the use of the application did not spread beyond the aforementioned user groups.

Optimal Physical Activity Is Associated with the Reduction of Depressive Symptoms via Neuroticism and Resilience.

BACKGROUND: Personality traits, such as neuroticism, that results in vulnerability to stress, and resilience, a measure of stress coping, are closely associated with the onset of depressive symptoms, whereas regular physical activity habits have been shown to reduce depressive symptoms. In this study, the mediating effects of neuroticism and resilience between physical activity duration and depressive symptoms were investigated by a covariance structure analysis. METHODS: Between April 2017 and April 2018, 526 adult volunteers were surveyed using self-administered questionnaires. Demographic information, habitual physical activity duration (PAD), neuroticism, and resilience were investigated. The effects of these factors on depressive symptoms were analyzed by a covariance structure analysis. This study was conducted with the approval of the Medical Ethics Committee of Tokyo Medical University. RESULTS: The dose-response curves of physical activity duration and depression scores were U-shaped: the optimal physical activity duration for the lowest depression score was 25.7 h/week. We found that the greater the difference from the optimal PAD, the higher the neuroticism and the lower the resilience, and the more severe the depressive symptoms. Covariance structure analysis demonstrated that neuroticism and resilience significantly and completely mediated the effects of the difference from the optimal PAD on depressive symptoms (coefficient of determination R2 = 0.349). CONCLUSION: Our study suggests that there is an optimal PAD that reduces depressive symptoms, and that a greater difference from the optimal PAD increases depressive symptoms through neuroticism and resilience.

[Investigation of rescued cases with cardiac rupture caused by blunt trauma].

The mortality of cardiac rupture by blunt trauma is so high that quick diagnosis and appropriate treatment are essential for saving patients. Based on 8 such cases rescued in our hospital and on 70 other rescued cases reported in Japan, we review its treatment strategy. Ultrasound examination, particularly focused assessment with sonography for trauma (FAST), was useful for diagnosing traumatic cardiac rupture. It was, however, impossible to detect the exact site of rupture before surgery. Three quarters of the rescued cases suffered from right cardiac rupture and more than 95% of those were treated successfully without extracorporeal circulation. All the cases with multiple cardiac rupture needed cardiopulmonary bypass or percutaneous cardiopulmonary support (PCPS) for their surgeries. And so did a quarter of the cases with left cardiac rupture. The standard treatment strategy seems to be as follows:to release cardiac tamponade as slowly as possible, to set up an extracorporeal circulation for surgery, and to repair the ruptured heart via median sternotomy.

Moderating and Mediating Effects of Resilience Together with Neuroticism on Depressive Symptoms in Adult Volunteers.

Background: Parenting quality experienced in childhood affects depressive symptoms in adulthood, and neuroticism and resilience are attracting attention as personality traits that mediate the effects of parental rearing quality experienced in childhood on adulthood depressive symptoms. However, the interaction between neuroticism and resilience remains unclear. In this study, we hypothesized that resilience and neuroticism are mediators between parental rearing quality experienced in childhood and depressive symptoms in adulthood, and furthermore, that resilience and neuroticism interact with each other in their effects on depressive symptoms. To test these hypotheses, we conducted structural equation modeling and hierarchical multiple regression analysis including interactions in adult volunteers. Methods: A self-administered questionnaire survey was conducted on 528 adult volunteers recruited at Tokyo Medical University for 1 year from April 2017 to April 2018. The Parental Bonding Instrument (PBI), Eysenck Personality Questionnaire-revised short version, Connor-Davidson Resilience Scale, and Patient Health Questionnaire-9 were used as questionnaires, and their scores were analyzed using structure equation modeling. The interaction between resilience and neuroticism was analyzed using hierarchical multiple regression analysis. Results: Structural equation modeling showed that parenting quality (care and overprotection) experienced in childhood had a significant indirect effect on the severity of depressive symptoms in adulthood, mediated by both neuroticism and resilience. Among the subscores of the PBI, "care" showed opposite effects to "overprotection". Structural equation modeling of "care" and "overprotection" explained 36.9% and 36.6% of the variability in depressive symptoms in adulthood, respectively. Hierarchical multiple regression analysis showed that the negative interaction between neuroticism and resilience had a significant effect on depressive symptom severity in adulthood. Conclusion: The results of this study show that resilience and neuroticism are mediators of the effects from parental child-rearing to depressive symptoms in adulthood. Furthermore, resilience antagonizes the effect of neuroticism on adulthood depressive symptoms.

[Comparative study between landiolol and amiodarone for therapeutic efficacy after open heart surgery].

Tachyarrhythmia, especially atrial fibrillation, remains as a common complication after open heart surgery and sometimes leads to fatal condition. Many reports showed that landiolol (ultra short-acting beta one blocker) and amiodarone were effective against postoperative atrial fibrillation (POAF). However, there were few comparative studies between these 2 drugs as prophylactic agents, and no report mentioned the therapeutic efficacy. Our study suggests that landiolol be the 1st choice for rate control of tachyarrhythmia because of easy dose adjustment and mild side effects. Amiodarone may be useful for the patients whose left ventricular function is poor.

Molecular design and application of luminescent materials composed of group 13 elements with an aggregation-induced emission property.

Complexation of π-conjugated ligands by metal or semimetal ions leads to the enhancement of the planarity and rigidity of π-conjugated systems. Boron, especially, has played a central role in the design of luminescent main-group complexes. However, these complexes still suffer the disadvantage of aggregation-caused quenching as well as typical organic fluorophores. It has recently been reported that some types of boron complexes exhibit the aggregation-induced emission (AIE) property. Moreover, AIE behavior from complexes and organometallic compounds composed of the other group 13 elements, such as aluminum and gallium, has emerged in this decade. These observations greatly encourage us to develop advanced functional materials based on the group 13 elements. Indeed, recent research has demonstrated that these classes of materials are potentially versatile scaffolds for constructing chromic luminophores, efficiently emissive π-conjugated polymers and so on. This review mainly describes AIE-active group 13 complexes with four-coordinate structures and their application as photo-functional materials. Proposed mechanisms of the origins of AIE behavior are briefly discussed.