Organometallics in molecular junctions: conductance, functions, and reactions.

Molecular junctions, which involve sandwiching molecular structures between electrodes, play a crucial role in molecular electronics. Recent advances in this field have revealed the vital role of organometallic chemistry in the investigation of molecular junctions, which has added to their well-known contributions to catalysis and materials chemistry. This review summarizes the recent examples of organometallic chemistry applications in molecular junctions, which can be categorized into three types, i.e., class I encompassing molecular junctions with bridging organometallic complexes, class II involving molecular junctions with covalent and noncovalent metal electrode-carbon bonds, and class III comprising organometallic reactions within molecular junctions.

Intraorbital Dural Arteriovenous Fistula Treated by Transarterial Embolization Using Onyx: A Case Report.

Objective: Intraorbital dural arteriovenous fistula (IO-dAVF) is a rare condition, and treatment options vary from case to case. We report a case of transarterial embolization (TAE) for IO-dAVF. Case Presentation: A 62-year-old male complained of gradually worsening pain, hyperemia, and visual impairment in the right eye. He did not exhibit diplopia or exophthalmos. Cerebral angiography revealed an arteriovenous fistula in the right orbit. The feeding arteries were the ophthalmic artery (OphA) and the artery of the superior orbital fissure (ASOF), with the superior ophthalmic vein (SOV) as the main draining vein. The venous pathway from the SOV was not clearly visible, and considering the risk of blindness with TAE from the OphA, TAE from the ASOF was performed. Onyx 18 was selected as the liquid embolic material and injected through a microcatheter placed in the internal maxillary artery. Occlusion up to the SOV was achieved, and the shunt flow completely disappeared. Normal blood flow in the OphA was maintained, hyperemia improved, and no complications were observed. Conclusion: In cases of IO-dAVF, when transvenous embolization is difficult to perform, TAE using Onyx from the vessel of the external carotid artery system may be preferred over OphA.

Aortoesophageal fistula due to esophageal cancer: a case report of successful management.

BACKGROUND: Aortoesophageal fistula (AEF) is a rare but potentially life-threatening condition. The best treatment for the AEF due to esophageal carcinoma is still unresolved. Here, we report a rare case of AEF caused by esophageal cancer, that was successfully treated with emergency thoracic endovascular aortic repair (TEVAR), followed by esophagectomy and gastric tube reconstruction. CASE PRESENTATION: A 64-year-old man presented with loss of consciousness and hypotension during chemoradiotherapy for advanced esophageal cancer. Enhanced computed tomography showed extravasation from the descending aorta into the esophagus at the tumor site. We performed emergency TEVAR for the AEF, which stabilized the hemodynamics. We then performed thoracoscopic subtotal esophagectomy on day 4 after TEVAR to prevent graft infection, followed by gastric tube reconstruction on day 30 after TEVAR. At 9 months after the onset of AEF, the patient continues to receive outpatient chemotherapy and leads a normal daily life. CONCLUSION: TEVAR is a useful hemostatic procedure for AEF. If the patient is in good condition and can continue treatment for esophageal cancer, esophagectomy and reconstruction after TEVAR should be performed to prevent graft infection and maintain quality of life.

Performance changes due to differences among annotating radiologists for training data in computerized lesion detection.

PURPOSE: The quality and bias of annotations by annotators (e.g., radiologists) affect the performance changes in computer-aided detection (CAD) software using machine learning. We hypothesized that the difference in the years of experience in image interpretation among radiologists contributes to annotation variability. In this study, we focused on how the performance of CAD software changes with retraining by incorporating cases annotated by radiologists with varying experience. METHODS: We used two types of CAD software for lung nodule detection in chest computed tomography images and cerebral aneurysm detection in magnetic resonance angiography images. Twelve radiologists with different years of experience independently annotated the lesions, and the performance changes were investigated by repeating the retraining of the CAD software twice, with the addition of cases annotated by each radiologist. Additionally, we investigated the effects of retraining using integrated annotations from multiple radiologists. RESULTS: The performance of the CAD software after retraining differed among annotating radiologists. In some cases, the performance was degraded compared to that of the initial software. Retraining using integrated annotations showed different performance trends depending on the target CAD software, notably in cerebral aneurysm detection, where the performance decreased compared to using annotations from a single radiologist. CONCLUSIONS: Although the performance of the CAD software after retraining varied among the annotating radiologists, no direct correlation with their experience was found. The performance trends differed according to the type of CAD software used when integrated annotations from multiple radiologists were used.

A Role in 15-Deacetylcalonectrin Acetylation in the Non-Enzymatic Cyclization of an Earlier Bicyclic Intermediate in Fusarium Trichothecene Biosynthesis.

The trichothecene biosynthesis in Fusarium begins with the cyclization of farnesyl pyrophosphate to trichodiene, followed by subsequent oxygenation to isotrichotriol. This initial bicyclic intermediate is further cyclized to isotrichodermol (ITDmol), a tricyclic precursor with a toxic trichothecene skeleton. Although the first cyclization and subsequent oxygenation are catalyzed by enzymes encoded by Tri5 and Tri4, the second cyclization occurs non-enzymatically. Following ITDmol formation, the enzymes encoded by Tri101, Tri11, Tri3, and Tri1 catalyze 3-O-acetylation, 15-hydroxylation, 15-O-acetylation, and A-ring oxygenation, respectively. In this study, we extensively analyzed the metabolites of the corresponding pathway-blocked mutants of Fusarium graminearum. The disruption of these Tri genes, except Tri3, led to the accumulation of tricyclic trichothecenes as the main products: ITDmol due to Tri101 disruption; a mixture of isotrichodermin (ITD), 7-hydroxyisotrichodermin (7-HIT), and 8-hydroxyisotrichodermin (8-HIT) due to Tri11 disruption; and a mixture of calonectrin and 3-deacetylcalonectrin due to Tri1 disruption. However, the ΔFgtri3 mutant accumulated substantial amounts of bicyclic metabolites, isotrichotriol and trichotriol, in addition to tricyclic 15-deacetylcalonectrin (15-deCAL). The ΔFgtri5ΔFgtri3 double gene disruptant transformed ITD into 7-HIT, 8-HIT, and 15-deCAL. The deletion of FgTri3 and overexpression of Tri6 and Tri10 trichothecene regulatory genes did not result in the accumulation of 15-deCAL in the transgenic strain. Thus, the absence of Tri3p and/or the presence of a small amount of 15-deCAL adversely affected the non-enzymatic second cyclization and C-15 hydroxylation steps.

Prediction of antenatal bleeding and preterm deliveries using placental magnetic resonance imaging in patients with placenta previa.

PURPOSE: This study aimed to clarify associations between subacute hematoma on placental magnetic resonance imaging (MRI), antenatal bleeding, and preterm deliveries in patients with placenta previa (PP) without placenta accreta spectrum (PAS). MATERIALS AND METHODS: This retrospective study investigated 78 consecutive patients with PP (median age, 34.5 years; interquartile range [IQR], 31-37 years) who underwent placental MRI in the third trimester. Patients with PAS detected intraoperatively or pathologically were excluded. Two radiologists evaluated the presence of subacute hematomas and their locations on placental MRI. We examined associations between presence of subacute hematoma and antenatal bleeding, emergency cesarean section (CS), hysterectomy, gestational age (GA) at delivery, birth weight, and amount of blood loss at CS. We also examined the association between perinatal outcome and subacute hematoma location: marginal, retro-placental, or intra-placental. Inter-observer agreement for the detection of subacute hematoma was calculated using kappa analysis. RESULTS: Subacute hematomas were identified on MRI in 39 of the 78 patients (50.0%). Antenatal bleeding and emergency CS were more prevalent in patients with subacute hematoma on MRI (20 patients [51.3%] and 18 patients [46.2%], respectively) than in patients without (7 patients [17.9%], Fisher's exact test, p = 0.004 and 7 patients [17.9%], p = 0.014, respectively). GA at delivery was significantly lower in patients with subacute hematoma (median 36w3d, IQR 35w4d-37w1d) than in patients without (median 37w1d, IQR 36w4d-37w2d; Mann-Whitney test: p = 0.048). Marginal hematoma was significantly associated with antenatal bleeding and emergency CS. Inter-observer agreement for the presence of subacute hematoma was moderate (κ = 0.573). CONCLUSION: Subacute hematoma on placental MRI was associated with antenatal bleeding, emergency CS and shorter GA at delivery in patients with PP. Marginal hematoma was also associated with antenatal bleeding and emergency CS. Placental MRI appears useful for predicting antenatal bleeding and preterm delivery in patients with PP.

Efficacy of an oscillating positive expiratory pressure device in patients with Mycobacterium avium complex pulmonary disease.

Patients with Mycobacterium avium complex pulmonary disease (MAC-PD) often suffer from chronic symptoms such as sputum production, which reduces quality of life. Oscillatory positive expiratory pressure (OPEP) devices are used in physiotherapy to promote the clearance of respiratory secretions. We report two cases of improved lung function and improved scores on the Leicester Cough Questionnaire (LCQ) and the Breathlessness, Cough and Sputum Scale (BCSS) after the use of OPEP in patients with MAC-PD where treatment with guideline-based therapy, including amikacin liposome inhalation suspension, had proved ineffective for symptoms. Use of OPEP might maximize the efficacy of therapy and thereby improves outcomes in patients with MAC-PD. It is important to use both guideline-based therapy and OPEP, especially in patients whose health-related quality of life is affected by sputum symptoms. Further prospective studies are warranted to assess the benefit of adding OPEP to guidelines concerning therapy for patients with MAC-PD and sputum symptoms.

Factors Associated with Perioperative Edema in Patients with Stage I Gastric Cancer Using a Body Composition Analyzer.

PURPOSE: Assessment of nutritional status and nutritional interventions is important in gastric cancer patients. We investigated the factors associated with perioperative edema in patients with stage I gastric cancer using a body composition analyzer. METHODS: The study included 106 patients with stage I gastric cancer who underwent distal gastrectomy. The body composition of each patient was evaluated by bioelectrical impedance analysis (BIA) using an InBody 720 body composition analyzer. Patients with an extracellular water to total body water ratio of ≥ 0.4 before and 1 week after gastrectomy were considered to have edema, the cause of which was determined retrospectively. RESULTS: Patients with preoperative edema were significantly older, had a significantly higher lymph node metastasis rate and disease stage, and had a significantly poorer Controlling Nutritional Status (CONUT) score, and Prognostic Nutritional Index (PNI) compared with patients without preoperative edema. The group with postoperative edema had significantly higher proportions of elderly and female patients as well as a higher rate of Billroth-II reconstruction compared with the group without postoperative edema. The group with postoperative edema also had significantly lower intracellular water content, total body water content, protein content, skeletal muscle mass, and PNI. CONCLUSIONS: Preoperative edema occurs in elderly patients with poor nutritional status, and postoperative edema occurs in elderly patients with a shorter operative time. Perioperative edema status assessed by BIA is thought to be related to perioperative nutritional status.

Endovascular Treatment May Be Effective in Preventing Recurrence of Ischemic Stroke in Vertebral Artery Stump Syndrome: A Case Series.

Vertebral artery stump syndrome (VASS) is a rare condition that can cause posterior circulation ischemic stroke due to occlusion of the ipsilateral vertebral artery (VA) orifice, resulting in blood flow stagnation and embolus formation. Although there is no established treatment for this condition, we observed 3 cases of VASS out of 326 acute ischemic stroke cases at a single institution from April 2021 to October 2022. Despite the best possible antithrombotic treatment, all 3 patients had recurrent ischemic strokes. One patient underwent drug-eluting stenting of the VA orifice to relieve occlusive flow. The other 2 patients received coil embolization, which resulted in the disappearance of their culprit collateral flow. None of the patients had recurrent ischemic strokes after endovascular intervention. Based on our observations, stenting and coil embolization are effective methods for preventing future recurrences of VASS.

Pregnancy outcomes following radical trachelectomy for early-stage cervical cancer: A retrospective observational study in the Kanto area, Japan.

OBJECTIVE: The authors aimed to investigate the prevalence of pregnancy and obstetric outcomes in patients who underwent radical trachelectomy (RT) for early-stage cervical cancer in the Kanto area, Japan. METHOD: A survey among 113 perinatal centers affiliated with the Kanto Society of Obstetrics and Gynecology was conducted to investigate their experience in managing pregnancies following RT, between 2010 and 2020. The association between preterm delivery (before 34 gestational weeks) and a midtrimester short cervix (<13 mm) was evaluated. RESULTS: The authors retrospectively collected maternal and perinatal data from 13 hospitals. There were 135 pregnancies among 115 women following RT. Of the 135 pregnancies, 32 were miscarriages (<12 gestational weeks: n = 22; >12 gestational weeks: n = 10), and 103 were delivered after 22 gestational weeks. The incidences of preterm delivery before 28 and 34 gestational weeks were 8.7% and 30.1%, respectively. A midtrimester short residual cervix was associated with preterm delivery (P = 0.046). CONCLUSION: Since more than 100 pregnancies were recorded after RT in the Kanto area, many physicians had more opportunities to manage pregnancy after RT. Pregnancy following RT is associated with increased risk of preterm delivery, and midtrimester short residual cervix is a good predictor of preterm delivery.

Impact of Intermittent Deposition on Spontaneous Orientation Polarization of Organic Amorphous Films Revealed by Rotary Kelvin Probe.

The control of the molecular orientation and resultant polarization is essential for improving the performance of organic optoelectronic devices. Conventionally, the substrate temperature and deposition rate are tuned to control the molecular orientation of vapor-deposited films. In this study, we proposed a novel method, referred to as "intermittent deposition", in which the polarization direction and magnitude are controlled by introducing intervals during physical vapor deposition. The rotary Kelvin probe measurement of the Alq3 and TPBi films clearly showed a time-dependent decrease in the surface potential owing to the surface relaxation of the molecular orientation immediately after deposition. Through a series of intermittent depositions, in which the deposition shutter is repeatedly opened and closed at certain intervals, a relaxed surface layer was built up, and we could control the polarization magnitude. For the Alq3 film, even the polarization direction was switched. The proposed new deposition method is applicable to general organic molecules, not limited to polar molecules, thereby potentially tuning the conduction properties of organic devices and fabricating novel devices.

Solution-state mechanochromic luminescence of Pt(ii)-complexes displayed within micellar aromatic capsules.

Mechanochromic luminescence (MCL) is an intrinsic phenomenon in the solid state and thus has been hardly observed in solution so far. Here we report that arylethynyl Pt(ii)-complexes with an NCN-pincer ligand are efficiently encapsulated by micellar aromatic capsules in water, through a simple grinding protocol with bent amphiphiles. When a bent pentamethylbenzene-based amphiphile is employed as an optimized capsule component, the resultant host-guest composite, with an average diameter of ∼4 nm, is obtained in water at room temperature. Notably, the nanocomposite displays strong red emission (Φ = 33%, λmax = 700 nm) derived from MCL via intermolecular Pt(ii)⋯Pt(ii) interactions even under aerobic aqueous conditions, in sharp contrast to the free Pt(ii)-complex with weak green emission (Φ = 4%, λmax = 500 nm) in CH2Cl2. Moreover, enhancement of the solution-state MCL (up to Φ = 48%) can be achieved by coencapsulation of the Pt(ii)-complexes with carbazole derivatives by the capsule in water. This study provides the first example of "solution-state" mechanochromic luminescence, capable of facilely tuning its intensity and wavelength, among the intensive studies of various solid-state MCL reported previously.

Pediatric allergies in Japan: Coronavirus disease pandemic-related risk factors.

Background: The coronavirus disease 2019 (COVID-19) pandemic impacted various parts of society, including Japanese children with allergies. Objective: This study investigated risk factors for pediatric allergic diseases associated with the state of emergency owing to the COVID-19 pandemic in Japan, including during school closures. Methods: Parents of pediatric patients (0-15 years) with allergies were enrolled and queried regarding the impact of school closure on pediatric allergies compared to that before the COVID-19 pandemic. Results: A valid response was obtained from 2302 parents; 1740 of them had children with food allergies. Approximately 4% (62/1740) of the parents reported accidental food allergen ingestion was increased compared to that before the COVID-19 pandemic. Accidental ingestion during school closures was associated with increased contact with meals containing allergens meant for siblings or other members of the family at home. The exacerbation rate during the pandemic was highest for atopic dermatitis at 13% (127/976), followed by allergic rhinitis at 8% (58/697), and bronchial asthma at 4% (27/757). The main risk factors for worsening atopic dermatitis, allergic rhinitis, and bronchial asthma were contact dermatitis of the mask area (34/120 total comments); home allergens, such as mites, dogs, and cats (15/51 total comments); and seasonal changes (6/25 total comments), respectively. Conclusion: The main factors affecting allergic diseases were likely related to increased time at home, preventive measures against COVID-19, and refraining from doctor visits. Children with allergies were affected by changes in social conditions; however, some factors, such as preventing accidental ingestion and the management of allergens at home, were similar to those before the COVID-19 pandemic. Patients who had received instructions on allergen avoidance at home before the pandemic were able to manage their disease better even when their social conditions changed.

Transformation of Highly Hydrophobic Triarylphosphines into Amphiphiles via Staudinger Reaction with Hydrophilic Trichlorophenyl Azide.

Owing to its hydrophobic properties and reactivity, triarylphosphines (PAr3 ) are promising precursors for the development of new amphiphiles. However, an efficient and reliable synthetic method for amphiphiles based on highly hydrophobic PAr3 is still required. Herein, a straightforward transformation of highly hydrophobic PAr3 into amphiphiles via the Staudinger reaction is reported. By simply mixing PAr3 and a hydrophilic trichlorophenyl azide containing two hydrophilic chains, amphiphiles bearing a N=P bond (i. e., an azaylide moiety) were quantitatively formed. The obtained azaylide-based amphiphiles were remarkably water-soluble, enabling their spontaneous self-assembly into 2 nm-sized micelles composed of 4-5 molecules in water with a low critical micelle concentration (up to 0.05 mM or less) due to the effective intermolecular interactions among the hydrophobic surfaces. Although the azaylide moiety is easily hydrolyzed in the presence of water, the azaylide in the amphiphiles displayed notable stability in water even at 60 h, which stems from the LUMO modulation induced by the presence of three electron-withdrawing chloro groups and two twisted alkoxycarbonyl groups, according to DFT calculations. An amphiphile having a large hydrophobic surface solubilized various hydrophobic organic dyes through efficient intermolecular interactions, resulting in the dyes exhibiting either monomer or excimer emissions in water.

[A CASE OF SUSPECTED ALLERGIC BRONCHOPULMONARY MYCOSIS CAUSED BY SCEDOSPORIUM APIOSPERMUM THAT SHOWED CLINICAL IMPROVEMENT AFTER BRONCHOSCOPIC REMOVAL OF A MUCUS PLUG].

A 69-year-old woman presented with a persistent cough and high fever. Thoracic computed tomography revealed atelectasis and high-attenuation mucus. The blood test results showed eosinophils at 18.2%, an absolute eosinophil count of 980 cells/µL, and a total serum immunoglobulin E of 1980IU/mL. Bronchoscopy revealed a mucous plug, which upon photomicrograph examination, showed eosinophils. A culture study of the mucus yielded Scedosporium apiospermum, leading to the suspicion of allergic bronchopulmonary mycosis (ABPM) caused by the fungus. After the bronchoscopic removal of the mucous plug, her symptoms quickly diminished. She was successfully treated without medication, and ABPM has not recurred for 2 years. To our knowledge, ABPM caused by Scedosporium apiospermum is rare, and close follow-up was effective without the administration of systemic steroids or antifungal drugs.

A Redox-Responsive Ferrocene-Based Capsule Displaying Unusual Encapsulation-Induced Charge-Transfer Interactions.

A ferrocene-based capsule is spontaneously and quantitatively formed in water by the assembly of bent amphiphiles carrying two ferrocene units. The disassembly and assembly of the new organometallic capsule, with a well-defined and highly condensed ferrocene core, are demonstrated by chemical redox stimuli in a fully reversible fashion under ambient conditions. In contrast to previously reported multiferrocene assemblies, only the present capsule efficiently encapsulates typical organic/inorganic dyes as well as electron-accepting molecules in water. As a result, unusual host-guest charge-transfer (CT) interactions, displaying relatively wide absorption bands in the visible to near-infrared region (λ=650-1350 nm), are observed upon the encapsulation of acceptors (i.e., chloranil and TCNQ). The resultant encapsulation-induced CT interactions can be released by a redox stimulus through the disassembly of the capsule.