Site-selective and direct C–F bond transformation of perfluoroalkylarenes was achieved with allylic stannanes via an iridium photoredox catalyst system. The present defluoroallylation proceeds ...exclusively at the benzylic position through perfluoroalkyl radicals generated by a single-electron transfer from an excited photoredox catalyst to perfluoroalkylarenes. A variety of perfluoroalkyl groups are applicable: linear perfluoroalkyl-substituted arenes such as Ar– n C4F9 and Ar– n C6F13 and heptafluoroisopropylarenes (Ar–CF(CF3)2) underwent site-selective defluoroallylation. DFT calculation studies revealed that the in situ generated Bu3SnF traps F– to prevent a retroreaction from the unstable perfluoroalkyl radical intermediate, and the radical intermediate favorably reacts with allylic stannanes. The synthesis of a bis(trifluoromethyl)methylene unit containing compound, which is an analog that is useful as a pharmaceutical agent for the prophylaxis or treatment of diabetes and inflammatory diseases, demonstrated the utility of this reaction.
Public perceptions and personal characteristics are heterogeneous between countries and subgroups, which may have different impacts on health-protective behaviors during the coronavirus disease 2019 ...(COVID-19) pandemic. To assess whether self-reported perceptions of COVID-19 and personal characteristics are associated with protective behaviors among general adults and to compare patterns in six different countries.
This cross-sectional study uses the secondary data collected through an online survey between 15 and 23 April 2020 across six countries (China, Italy, Japan, Korea, the UK, and the USA). A total of 5945 adults aged 18 years or older were eligible for our analysis. A logistic regression model was used to estimate odds ratios (OR) and 95% confidence intervals (95%CI) of three recommended behaviors (wearing a mask, handwashing, and avoiding social gatherings).
In most countries except for China, the participants who perceived wearing a mask as being extremely effective to curtail the pandemic were more likely to wear a mask (OR, 95%CI: Italy: 4.14, 2.08-8.02; Japan: 3.59, 1.75-7.30; Korea: 7.89, 1.91-31.63: UK: 9.23, 5.14-17.31; USA: 4.81, 2.61-8.92). Those who perceived that handwashing was extremely effective had higher ORs of this preventive behavior (OR, 95%CI: Italy: 16.39, 3.56-70.18; Japan: 12.24, 4.03-37.35; Korea: 12.41, 2.02-76.39; UK: 18.04, 2.60-152.78; USA: 10.56, 2.21-44.32). The participants who perceived avoiding social gathering as being extremely effective to curtail the pandemic were more likely to take this type of preventive behavior (OR, 95%CI: China: 3.79, 1.28-10.23; Korea: 6.18, 1.77-20.60; UK: 4.45, 1.63-11.63; USA: 4.34, 1.84-9.95). The associations between personal characteristics, living environment, psychological status, and preventive behaviors varied across different countries. Individuals who changed their behavior because of recommendations from doctors/public health officials were more likely to take preventive behaviors in many countries.
These findings suggest that higher perceived effectiveness may be a common factor to encourage preventive behaviors in response to the COVID-19 pandemic. These results may provide a better understanding of the homogeneity and heterogeneity of factors related to preventive behaviors and improve public health policies in various countries and groups.
The efficacy of flow diversion (FD) in the treatment of paraclinoid aneurysms has been established. The pipeline embolization device (PED) is one of the most commonly used FD devices. Coil ...embolization is also useful for treating paraclinoid aneurysms. This study aimed to compare the efficacy and safety of PED treatment and coil embolization for large unruptured paraclinoid aneurysms. This was a single-center, retrospective study of large unruptured paraclinoid aneurysms treated endovascularly between 2009 and 2019 (coil embolization between 2009 and 2015, and PED between 2015 and 2019). Cases with a follow-up period of less than 1 year and recurrence after coil embolization were excluded. The treatment outcomes between coil embolization and PED were compared. We investigated 45 patients with 45 large unruptured paraclinoid aneurysms treated by endovascular surgery in our institution. Twenty-four patients were treated with coil embolization and 21 with PED. In the PED group, the device cost was significantly lower (2,770.4 ± 699.5 vs. 1941.2 ± 552.8 1000 yen, P = 0.03), procedure duration was significantly shorter (155.4 ± 66.7 vs. 95.1 ± 35.4 min, P <0.01), and the numbers of re-treatments were lower than those in the coil embolization group (41.7 vs. 14.3%, P = 0.05). Both PED and coil embolization were effective and safe for large unruptured paraclinoid aneurysms, and their treatment results were similar. The PED is more beneficial because of its lower cost, shorter procedure duration, and fewer retreatments, and is therefore more useful for the treatment of large unruptured paraclinoid aneurysms.
Eosinophils not only play a critical role in the pathogenesis of eosinophil-associated diseases, but they also have multiple important biological functions, including the maintenance of homeostasis, ...host defense against infections, immune regulation through canonical Th1/Th2 balance modulation, and anti-inflammatory and anti-tumorigenic activities. Recent studies have elucidated some emerging roles of eosinophils in steady-state conditions; for example, eosinophils contribute to adipose tissue metabolism and metabolic health through alternatively activated macrophages and the maintenance of plasma cells in intestinal tissue and bone marrow. Moreover, eosinophils exert tissue damage through eosinophil-derived cytotoxic mediators that are involved in eosinophilic airway inflammation, leading to diseases including asthma and chronic rhinosinusitis with nasal polyps characterized by fibrin deposition through excessive response by eosinophils-induced. Thus, eosinophils possessing these various effects reflect the heterogenous features of these cells, which suggests the existence of distinct different subpopulations of eosinophils between steady-state and pathological conditions. Indeed, a recent study demonstrated that instead of dividing eosinophils by classical morphological changes into normodense and hypodense eosinophils, murine eosinophils from lung tissue can be phenotypically divided into two distinct subtypes: resident eosinophils and inducible eosinophils gated by Siglec-Fint CD62L+ CD101low and Siglec-Fhigh CD62L– CD101high, respectively. However, it is difficult to explain every function of eosinophils by rEos and iEos, and the relationship between the functions and subpopulations of eosinophils remains controversial. Here, we overview the multiple roles of eosinophils in the tissue and their biological behavior in steady-state and pathological conditions. We also discuss eosinophil subpopulations.
(o‐Phenylenediamino)borylstannanes were newly synthesized to achieve radical boryl substitutions of a variety of alkyl radical precursors. Dehalogenative, deaminative, decharcogenative, and ...decarboxylative borylations proceeded in the presence of a radical initiator to give the corresponding organic boron compounds. Radical clock experiments and computational studies have provided insights into the mechanism of the homolytic substitution (SH2) of the borylstannanes with alkyl radical intermediates. DFT calculation disclosed that the phenylenediamino structure lowered the LUMO level including the vacant p‐orbital on the boron atom to enhance the reactivity to alkyl radicals in SH2. Moreover, C(sp3)‐H borylation of THF was accomplished using the triplet state of xanthone.
Newly synthesized (o‐phenylenediamino)borylstannanes were utilized for radical borylations. Various alkyl radical precursors were applicable to dehalogenative‐, deaminative‐, dechalgenative‐, decarboxylative‐, and C−H borylation. The interaction of the p‐orbital on the boron atom with the SOMO of the alkyl radical was a key to this reaction.
We describe two transient slow slip events that occurred before the 2011 Tohoku-Oki earthquake. The first transient crustal deformation, which occurred over a period of a week in November 2008, was ...recorded simultaneously using ocean-bottom pressure gauges and an on-shore volumetric strainmeter; this deformation has been interpreted as being an M6.8 episodic slow slip event. The second had a duration exceeding 1month and was observed in February 2011, just before the 2011 Tohoku-Oki earthquake; the moment magnitude of this event reached 7.0. The two events preceded interplate earthquakes of magnitudes M6.1 (December 2008) and M7.3 (March 9, 2011), respectively; the latter is the largest foreshock of the 2011 Tohoku-Oki earthquake. Our findings indicate that these slow slip events induced increases in shear stress, which in turn triggered the interplate earthquakes. The slow slip event source area on the fault is also located within the downdip portion of the huge-coseismic-slip area of the 2011 earthquake. This demonstrates episodic slow slip and seismic behavior occurring on the same portions of the megathrust fault, suggesting that the faults undergo slip in slow slip events can also rupture seismically.
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► Transient crustal deformations were seen in 2008 and 2011 near the Japan Trench. ► The observed deformations are explained by M6.8 and M7.0 slow slip events. ► The slow slip events preceded moderate or large interplate earthquakes. ► The fault is located in the coseismic slip area of the 2011 Tohoku-Oki earthquake.
A low-velocity zone (LVZ) has been detected by seismic exploration surveys within the Nankai accretionary prism toe off the Kii Peninsula, southwestern Japan, and is considered to be a mechanically ...weak volume at depth. Such mechanical heterogeneities potentially influence seismic and tsunamigenic slips on megathrust earthquakes in the subduction zone. However, the spatial distribution of the LVZ along the trough-parallel direction is still elusive. Here we show sporadic LVZs in the prism toe from one-dimensional shear wave velocity (Vs) profiles obtained at 49 cabled ocean bottom stations, which were estimated by a nonlinear inversion technique, simulated annealing, using the displacement-pressure ratios of the Rayleigh wave. The estimated distribution of LVZs along the trough widely correlates with the epicentres of shallow very low frequency earthquakes (sVLFEs), which suggests that sVLFEs are activated in the sporadically distributed low-velocity and mechanically weak volumes where fluids significantly reduce the shear strength of faults.
Eosinophilic chronic rhinosinusitis (ECRS) is a subtype of chronic rhinosinusitis associated with asthma. CD69 is an important marker of activation for eosinophils. But, whether a correlation exist ...between the CD69 expression on eosinophils and clinical findings is unclear.
We performed quantitative PCR and/or flow cytometry using tissue and purified eosinophils from the blood and nasal polyps of 12 patients with ECRS and from 8 patients without ECRS (controls). We assessed clinical findings including nasal polyp (NP) scores, sinus CT findings, and pulmonary function test results, and examined their possible association with the CD69 expression. We also performed CD69 cross-linking experiments in mouse eosinophils to investigate the functional role of CD69.
Levels of cytokine mRNAs (IL-4, -5, -10, and -13) were significantly higher in purified NP eosinophils and tissues from patients with ECRS than the levels of those in controls. The expressions of major basic protein (MBP), eosinophilic cationic protein (ECP), eosinophilic-derived neurotoxin (EDN), eosinophil peroxidase (EPX) in cytotoxic granules, and CD69 mRNA were significantly higher in purified eosinophils from NPs than in those from blood. We also found a correlation between expression of CD69 and clinical findings. Moreover, we found EPX release from mouse eosinophils following CD69 cross-linking.
These data suggest that increased CD69 expression by eosinophils is not only a biomarker for nasal obstruction and pulmonary dysfunction, but also a potential therapeutic target for patients with ECRS and asthma.
Lower limb lymphedema (LLL) is a chronic and incapacitating condition afflicting patients who undergo lymphadenectomy for gynecologic cancer. This study aimed to identify risk factors for LLL and to ...develop a prediction model for its occurrence.
Pelvic lymphadenectomy (PLA) with or without para-aortic lymphadenectomy (PALA) was performed on 366 patients with gynecologic malignancies at Yaizu City Hospital between April 2002 and July 2014; we retrospectively analyzed 264 eligible patients. The intervals between surgery and diagnosis of LLL were calculated; the prevalence and risk factors were evaluated using the Kaplan-Meier and Cox proportional hazards methods. We developed a prediction model with which patients were scored and classified as low-risk or high-risk.
The cumulative incidence of LLL was 23.1% at 1 year, 32.8% at 3 years, and 47.7% at 10 years post-surgery. LLL developed after a median 13.5 months. Using regression analysis, body mass index (BMI) ≥25 kg/m
(hazard ratio HR, 1.616; 95% confidence interval CI, 1.030-2.535), PLA + PALA (HR, 2.323; 95% CI, 1.126-4.794), postoperative radiation therapy (HR, 2.469; 95% CI, 1.148-5.310), and lymphocyst formation (HR, 1.718; 95% CI, 1.120-2.635) were found to be independently associated with LLL; age, type of cancer, number of lymph nodes, retroperitoneal suture, chemotherapy, lymph node metastasis, herbal medicine, self-management education, or infection were not associated with LLL. The predictive score was based on the 4 associated variables; patients were classified as high-risk (scores 3-6) and low-risk (scores 0-2). LLL incidence was significantly greater in the high-risk group than in the low-risk group (HR, 2.19; 95% CI, 1.440-3.324). The cumulative incidence at 5 years was 52.1% 95% CI, 42.9-62.1% for the high-risk group and 28.9% 95% CI, 21.1-38.7% for the low-risk group. The area under the receiver operator characteristics curve for the prediction model was 0.631 at 1 year, 0.632 at 3 years, 0.640 at 5 years, and 0.637 at 10 years.
BMI ≥25 kg/m
, PLA + PALA, lymphocyst formation, and postoperative radiation therapy are significant predictive factors for LLL. Our prediction model may be useful for identifying patients at risk of LLL following lymphadenectomy. Providing an intensive therapeutic strategy for high-risk patients may help reduce the incidence of LLL and conserve the quality of life.
BACKGROUND AND PURPOSE—Reperfusion therapy by mechanical thrombectomy is used to treat acute ischemic stroke. However, reactive oxygen species generation after reperfusion therapy causes cerebral ...ischemia–reperfusion injury, which aggravates cerebral infarction. There is limited evidence for clinical efficacy in stroke for antioxidants. Here, we developed a novel core-shell type nanoparticle containing 4-amino-4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (nitroxide radical-containing nanoparticles RNPs) and investigated its ability to scavenge reactive oxygen species and confer neuroprotection.
METHODS—C57BL/6J mice underwent transient middle cerebral artery occlusion and then received RNPs (9 mg/kg) through the common carotid artery. Infarction size, neurological scale, and blood-brain barrier damage were visualized by Evans blue extravasation 24 hours after reperfusion. RNP distribution was detected by rhodamine labeling. Blood-brain barrier damage, neuronal apoptosis, and oxidative neuronal cell damage were evaluated in ischemic brains. Multiple free radical-scavenging capacities were analyzed by an electron paramagnetic resonance–based method.
RESULTS—RNPs were detected in endothelial cells and around neuronal cells in the ischemic lesion. Infarction size, neurological scale, and Evans blue extravasation were significantly lower after RNP treatment. RNP treatment preserved the endothelium and endothelial tight junctions in the ischemic brain; neuronal apoptosis, O2 production, and gene oxidation were significantly suppressed. Reactive oxygen species scavenging capacities against OH, ROO, and O2 improved by RNP treatment.
CONCLUSIONS—An intra-arterial RNP injection after cerebral ischemia–reperfusion injury reduced blood-brain barrier damage and infarction volume by improving multiple reactive oxygen species scavenging capacities. Therefore, RNPs can provide neurovascular unit protection.
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