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This research addresses the rapid aging phenomenon prevalent in Asian societies, which has led to a significant increase in elderly individuals relocating to nursing homes due to health-related issues. This trend has resulted in social isolation and loneliness among the elderly, contributing to physical and mental ailments such as hypertension and cardiovascular diseases, as highlighted by the World Health Organization (WHO). To mitigate these issues, the research proposes leveraging technology, specifically the integration of robotics, to alleviate the caregiver shortage and enhance human interaction for the elderly. The novel approach involves developing a social robot designed to bridge the gap between humans and machines, combining knowledge from embedded systems, robotics, and essential soft skills for effective interaction. The authors found that this technological solution holds promise in addressing the caregiver shortage and improving the well-being of elderly individuals by reducing their sense of isolation, fostering better mental and physical health outcomes, and potentially transforming the landscape of elderly care through innovative technological applications. Future work includes expanding pilot studies and collaborating with healthcare institutions to further validate the effectiveness of the solution.
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Envejecimiento , Servicios de Atención de Salud a Domicilio , Robótica , Humanos , Robótica/métodos , Anciano , Envejecimiento/fisiología , Cuidadores/psicología , Soledad/psicologíaRESUMEN
Background Aortic valve (AV) repair is a challenging procedure due to its complexity, lower reproducibility, and steep learning curve. To examine its durability and validity, we investigated mid-term outcomes following AV repair without aortic root replacement. Methods Between March 2007 and May 2018, we retrospectively identified 14 patients who underwent AV repair without aortic root replacement at our institution. We investigated their baseline characteristics and postoperative outcomes, including the reoperation rate due to aortic regurgitation (AR) recurrence. Furthermore, we divided them into two groups: those who required reoperation due to AR recurrence (Group R) and those who did not require reoperation (Group F), and statistically compared them. Results The median age was 52.5 years (IQR: 42.0-60.8), with 11 male patients (78.6%). Eight patients (57.1%) had a bicuspid AV. Five cases (35.7%) underwent reoperation due to AR recurrence during a median follow-up period of 5.5 years. There were no significant differences in baseline characteristics between Group R (n=5, 35.7%) and Group F (n=9, 64.3%), including AR etiology, AV repair procedure, and intraoperative AR grade after the final declamp. All cases in Group R had at least mild to moderate AR on the echocardiogram before discharge. Regarding the AR grade before discharge, Group R had a significantly higher grade than Group F (p = 0.013). Conclusions The indication for AV repair for AR might need to be reassessed due to the considerable mid-term reoperation rate. Cases of AV repair with more than mild AR at discharge should be carefully monitored, as they are likely to require future reoperation for AR.
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Macrocyclic molecules have characteristic properties different from linear ones, such as high symmetry and guest-inclusion ability. To bring drastic changes to these properties, direct introduction of many substituents is a challenging but effective tool. Herein, we attain direct installation of ten six-membered-ring aromatic π-units into both rims of a pillar[5]arene. In contrast to previous pillar[n]arenes with less hindered five-membered-ring units, which showed conformational complexity and crushed crystal structures, the per-phenyl-substituted pillar[5]arene has a cylinder-shaped crystal structure with a dichloromethane inside the cavity and is obtained as a single pair of D 5-symmetric enantiomers. The average dihedral angles between the core and peripheral benzene rings sharply increase from 38° to 66°. These differences indicate the importance of local steric repulsion on both rims for determining the structures and properties of macrocycles.
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BACKGROUND: Cardiac metastasis including the right ventricle from renal cell carcinoma is rare. No standard treatment for cardiac metastasis and recurrence in renal cell carcinoma has been established. CASE PRESENTATION: We present the case of a 61-year-old man who underwent the resection of recurrent right ventricular metastasis caused by renal cell carcinoma following molecular targeted therapy. The first cardiac operation was performed for right ventricular metastasis due to renal cell carcinoma. The patient had a good postoperative course. Two years after the first operation, however, follow-up computed tomography revealed the recurrence of the right ventricular tumor and metastases in both lungs. Molecular targeted therapy was carried out and effectively controlled the lung metastasis but the right ventricular lesion remained unchanged, leading to reoperation. The recurrent right ventricular tumor was completely resected through a redo median sternotomy assisted by cardiopulmonary bypass. The patient had an uneventful postoperative course and was discharged on the 13th postoperative day. Follow-ups at 2 years showed no cardiac recurrence. CONCLUSION: Surgical intervention was considered useful in managing the recurrence of right ventricular metastasis from renal cell carcinoma after molecular targeted therapy.
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We present a novel system, a liquid-state pillar[5]arene decorated with tri(ethylene oxide) chains, that brings electron-donor and electron-acceptor molecules into proximity for efficient exciplex formation. The electron-accepting guests exhibit a blue-purple emission from a localized excited state upon excitation in common solvents. However, directly dissolving the guests in the electron-donating pillar[5]arene liquid (a bulk system) results in visible green emission from the formed exciplexes. In the bulk system, the guest molecules are always surrounded by excess pillar[5]arene molecules, resulting in the formation of mainly inclusion-type exciplexes. In the bulk system, energy migration occurs between the pillar[5]arene molecules. Excitation of the pillar[5]arenes results in a more intense green exciplex emission than that observed upon direct excitation of the guests. In summary, the pillar[5]arene liquid is a novel system for achieving efficient exciplex formation and energy migration that is different from typical solvent and solid systems.
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Self-inclusion complexes consisting of host-guest conjugates are one of the unique supramolecular structures because they form in-state and out-state depending on the external stimuli. Despite many reports of the stimuli-responsive self-inclusion complex formation, study of the structural relaxation from out-state to in-state by photoexcitation has been unexplored. Herein, we report that an electron-donating host and an electron-accepting guest conjugate exhibits the structural relaxation from out-state to in-state by photoexcitation. Formation of the in-state in the excited state resulted in exciplex emission along with the locally excited emission from the out-state. Moreover, this structural relaxation by photoexcitation was suppressed not only by temperature, but also by the presence of guest molecules, resulting in changes in the ratio of the dual emission intensities.
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Macrocyclic arenes show conformational adaptability, which allows host-guest complexations with the size-matched guest molecules. However, their emission properties are often poor in the solid states due to the self-absorption. Herein, we newly synthesized pillar[6]arene derivatives having alternate methylene and nitrogen bridging structures. Solvatochromic study reveals that the nitrogen-embedding into the cyclic structures can strengthen the intramolecular charge transfer (CT) nature compared to that of the linear nitrogen-bridged precursor. Owing to the large Stokes shift in the solid state, one of the nitrogen-embedded pillar[6]arenes shows high absolute photoluminescence quantum yield (ΦPL=0.36). Furthermore, it displays a turn-off sensing ability toward nitrobenzene (NB) vapor; a fluorescence quenching is observed when exposed to the NB vapor. From the structural analysis before and after the exposure of NB vapor, the amorphous nitrogen-embedded pillar[6]arene efficiently co-crystallize with NB and formed non-emissive intermolecular CT complexes with NB.
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Solid-state assembling modes are as crucial as the chemical structures of single molecules for real applications. In this work, solid-state structures and phase-transition temperatures are investigated for a series of fluoranthene-fused [3.3.3]propellanes consisting of a rigid three-dimensional (3D) π-core and varying lengths of alkoxy groups. Compounds in this series with n-butoxy or longer alkoxy groups take an amorphous state at room temperature. In these molecules, rotatable biaryl-type bonds are not incorporated and high D3h molecular symmetry is retained. Therefore, π-fused [3.3.3]propellanes present a unique platform for amorphous molecular materials with low ratios of flexible alkoxy atoms to rigid π-core ones.
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During recent decades, methylene-bridged macrocyclic arenes have been widely used in supramolecular chemistry. However, their π-conjugations are very weak, as the methylene bridges disrupt the electronic communication between π orbitals of the aromatic units. Herein, we successfully synthesized a series of silapillar[n]arenes (n = 4, 6, and 8) using silylene bridging. These showed enhanced electronic conjugation compared with the parent pillar[n]arenes because of σ*-π* conjugation between σ* (Si-C) orbitals and π* orbitals of the benzenes. Owing to the longer Si-C bond compared with the C-C bond, silylene-bridging provides additional structural flexibility into the pillar[n]arene scaffolds; a strained silapillar[4]arene was formed, which is unavailable in the parent pillar[n]arenes because of the steric requirements. Furthermore, silapillar[n]arenes displayed interesting size-dependent structural and optical properties.
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We report on the synthesis and selective adsorption property of a novel threefold interpenetrated Zr-based metal-organic framework (MOF), [Zr12O8(OH)8(HCOO)15(BPT)3] (BPT3- = [1,1'-biphenyl]-3,4',5-tricarboxylate) (abbreviated as Zr-BPT). This MOF shows a high tolerance to acidic conditions and has permanent pores, the size of which (approx. <5.6 Å) is the smallest ever reported among porous Zr-based MOFs with high acid tolerance. Zr-BPT selectively adsorbs aryl acids due to its strong affinity for them and exhibits separation ability, even between strong acid molecules, such as sulfonic and phosphonic acids. This is the first demonstration of a MOF exhibiting selective adsorption and separation ability for strong acids.
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Pillar[n]arenes can be constructed using a Friedel-Crafts alkylation process. However, due to the reversible nature of the alkylation, mixture of large pillar[n]arenes (n≥7) are obtained as minor products, and thus laborious purification are necessary to isolate the larger pillar[n]arenes. Moreover, inert methylene bridges are introduced during the alkylation process, and the multi-functionalization of the bridges has never been investigated. Herein, an irreversible Friedel-Crafts acylation is used to prepare pillar[n]arenes. Due to the irreversible nature of the acylation, the reaction of precursors bearing carboxylic acids and electron-rich arene rings results in a size-exclusive formation of pillar[n]arenes, in which the ring-size is determined by the precursor length. Because of this size-selective formation, laborious separation of undesired macrocycles is not necessary. Moreover, the bridges of pillar[n]arenes are selectively installed with reactive carbonyl groups using the acylation method, whose positions are determined by the precursor used. The carbonyl bridges can be easily converted into versatile functional groups, leading to various laterally modified pillar[n]arenes, which cannot be accessed by the alkylation strategy.
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Femoral pseudoaneurysms are typically associated with femoral arterial catheterisation. Treating iatrogenic morbidity requires curing the disease, without causing any additional complications. Occlusion of the aneurysmal neck is ideal to seal post-catheterised pseudoaneurysms along with maintaining the femoral arterial flow. However, few reports have suggested neck embolisation for post-catheterised pseudoaneurysms. We describe five cases of iatrogenic femoral pseudoaneurysms in patients successfully treated with embolisation through the aneurysmal neck. This technique may be an alternative therapeutic option in managing femoral pseudoaneurysms.
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BACKGROUND: Iatrogenic aortic dissection during cardiac surgery is a rare but critical complication. At present, no strategies have been developed to prevent it. We herein report a case of intraoperative aortic dissection during aortic root replacement in an older patient with Loeys-Dietz syndrome type III who had no family history of aortic disease. CASE PRESENTATION: A 60-year-old man was admitted to the hospital for Stanford type B acute aortic dissection and given conservative treatment. He was found to have aortic root dilatation and severe aortic regurgitation. Thus, elective Bentall procedure was performed. Postoperative computed tomography showed new Stanford type A aortic dissection that may have developed due to aortic cannulation during surgery. The patient was given conservative treatment and successfully discharged to home at postoperative day 34. Although he had no family history of aortic disease, a genetic test revealed an unreported SMAD3 frameshift mutation (c.742_749dup, p. Gln252ThrfsTer7), and the patient was diagnosed with Loeys-Dietz syndrome type III. CONCLUSION: In patients with connective tissue disorder, aortic manipulations may become the cause of critical complications. Avoiding the use of invasive techniques, such as cannulation and cross-clamping, and implementing treatment strategies, such as perfusion from other sites than the aorta and open distal anastomosis, can prevent these complications, and may be useful treatment modalities. The possibility of connective tissue disease should be considered even if the patient is older and has no family history of aortic disease.
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Disección Aórtica , Síndrome de Loeys-Dietz , Masculino , Humanos , Persona de Mediana Edad , Síndrome de Loeys-Dietz/complicaciones , Síndrome de Loeys-Dietz/genética , Síndrome de Loeys-Dietz/cirugía , Válvula Aórtica , Aorta , Disección Aórtica/etiología , Disección Aórtica/cirugía , Enfermedad IatrogénicaRESUMEN
PURPOSE: To clarify the role of dynamic computed tomography (CT) in diagnosing extrahepatic cholangiocarcinoma (eCCA) involving adjacent organs. MATERIAL AND METHODS: We retrospectively analyzed patients diagnosed with eCCA in Iwate Medical University Hospital (Morioka, Japan) during January 2011-December 2021 who underwent dynamic contrast-enhanced CT before biliary intervention, surgery, or chemotherapy. For surgical cases, two radiologists independently reviewed CT images in the portal, dual (adding arterial phase), and triple (adding delayed phase) phases. The mean attenuations of the abdominal aorta, portal vein (PV), hepatic parenchyma, pancreatic parenchyma, and eCCA were measured. The biliary segment-wise longitudinal tumour extent, arterial and PV invasion, organ invasion (liver, pancreas, and duodenum), and regional lymph node metastasis were assessed on a five-point scale. Image performances were compared using the sensitivity, specificity, and area under the curve (AUC). RESULTS: We included 120 patients (mean age, 71.7 ± 8.9; 84 males). The PV and liver differed most from the bile duct tumour in the portal phase. The abdominal aorta and pancreas differed most from eCCA in the arterial phase. For 80 patients evaluated on the five-point scale, adding phases increased the AUC for pancreatic, duodenal, and arterial invasion for each observer (observer 1, 0.79-0.93, p<0.01, 0.71-0.86, p = 0.04, 0.74-0.99, p = 0.02; observer 2, 0.88-0.96, p = 0.01, 0.73-0.94, p<0.01, 0.80-0.99 p = 0.04; respectively). The AUC for biliary segment-wise longitudinal tumor extent, hepatic, and PV invasion remained unchanged with additional phases. CONCLUSIONS: Portal-phase information is sufficient to evaluate the segmental extent of bile duct and liver/PV invasion. Arterial- and delayed-phase information can help evaluate pancreatic, duodenal, and arterial invasion.
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Metals typically crystallize in highly symmetric structures due to their nondirectional and nonsaturated metallic bonds. Here, we report that terbium metal in its ferromagnetic state adopts an unusual low-symmetry orthorhombic structure with a Cmcm space group. A similar structure has been previously observed only in a few actinide metals with bonding 5f electrons at ambient pressure, such as uranium, neptunium, and plutonium, but with different nearest coordination numbers and bond-length variations. The Tb atom occupies the 4c site (0, â¼0.1661, 1/4), building up -[Tb-Tb]- layers stacking along the b-axis. Our first-principles many-body calculations of the crystal field splitting in the correlated Tb 4f-shell demonstrate that the Cmcm structure for ferromagnetic terbium is stabilized by magneto-elastic forces due to a secondary order of quadrupolar moments in the ferromagnetic state. These findings are significant for further understanding of the nature of terbium, including its electron structure, energy bands, phonons, and magnetism.
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Pillar[n]arenes are symmetrical macrocyclic compounds composed of benzene panels with para-methylene linkages. Each panel usually exhibits planar chirality and prefers chirality-aligned states. Because of this feature, pillar[n]arenes are attractive scaffolds for chiroptical materials that are easy to prepare and optically resolve and show intense circular dichroism (CD) signals. In addition, rotation of the panels endows the chirality of pillar[n]arenes with a dynamic nature. The chirality in tubular oligomers and supramolecular assemblies sometimes show time- and procedure-dependent alignment phenomena. Furthermore, the CD signals of some pillar[n]arenes respond to the addition of chiral guests when their dynamic chirality is coupled with host-guest properties. By using diastereomeric pillar[n]arenes with additional chiral structures, the response can also be caused by achiral guests and changes of the environment, providing molecular sensors.
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Chiral rotaxanes have attracted much attention in recent decades for their unique chirality based on their interlocked structures. Thus, selective synthesis methods of chiral rotaxanes have been developed. The introduction of substituents with chiral centers to produce diastereomers is a powerful strategy for the construction of chiral rotaxanes. However, in case of a small energy difference between the diastereomers, diastereoselective synthesis is extremely difficult. Herein, we report a new diastereoselective rotaxane synthesis method using solid-phase diastereoselective [3]pseudorotaxane formation and mechanochemical solid-phase end-capping reactions of the [3]pseudorotaxanes. By co-crystallization of stereodynamic planar chiral pillar[5]arene with stereogenic carbons at both rims and axles with suitable end groups and lengths, the [3]pseudorotaxane with a high diastereomeric excess (ca. 92% de) was generated in the solid state because of higher effective molarity with aid by packing effects and significant energy differences between [3]pseudorotaxane diastereomers. In contrast, the de of the pillar[5]arene was low in solution (ca. 10% de) because of a small energy difference between diastereomers. Subsequent end-capping reactions of the polycrystalline [3]pseudorotaxane with high de in solvent-free conditions successfully yielded rotaxanes while maintaining the high de generated by the co-crystallization.
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Rapid progress in modern technologies demands zero thermal expansion (ZTE) materials with multi-property profiles to withstand harsh service conditions. Thus far, the majority of documented ZTE materials have shortcomings in different aspects that limit their practical utilization. Here, we report on a superior isotropic ZTE alloy with collective properties regarding wide operating temperature windows, high strength-stiffness, and cyclic thermal stability. A boron-migration-mediated solid-state reaction (BMSR) constructs a salient "plum pudding" structure in a dual-phase Er-Fe-B alloy, where the precursor ErFe10 phase reacts with the migrated boron and transforms into the target Er2Fe14B (pudding) and α-Fe phases (plum). The formation of such microstructure helps to eliminate apparent crystallographic texture, tailor and form isotropic ZTE, and simultaneously enhance the strength and toughness of the alloy. These findings suggest a promising design paradigm for comprehensive performance ZTE alloys.
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We report on high Mg2+ conduction in a metal-organic framework (MOF), UiO-66, under organic vapors. We prepared a Mg2+-containing MOF, UiO-66â{Mg(TFSI)2}1.0 (TFSI- = bis(trifluoromethanesulfonyl)imide), including Mg2+ carriers in three-dimensional pores. The compound showed a superionic conductivity above 10-4 S cm-1 under MeCN and MeOH vapors.
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A three-dimensional skeleton, π-fused [4.3.3]propellane, was constructed and derivatized by selective π-extension at the two naphthalene units. The obtained propellanes existed as stereoisomers different in spatial arrangement, one of which displayed a chiroptical response originating from through-space interactions between 5-azachrysenes in a skew position.