Angew Chem Int Ed Engl
December 2024
The ML cage, self-assembling from six Pd(II) or Pt(II) 90-degree blocks and four triazine-cored triangular ligands, has an effective hydrophobic cavity of about 450 Å capable of encapsulating one or more small molecules. Here, from the same components, we successfully constructed an ML cage with an internal volume expanded to 1540 Å via the self-assembly of an ML precursor using pillar[5]arene as a template. This cage retains the high molecular recognition ability of the ML cage while recognizing medium-sized guest molecules with molecular weights of up to ∼1600.
View Article and Find Full Text PDFBackground: Carotid artery stenting (CAS) is commonly performed to treat internal carotid artery (ICA) stenosis;however, it is associated with high recurrence rates. The treatment of in-stent restenosis (ISR) following CAS poses several challenges, and percutaneous transluminal angioplasty (PTA) is a possible treatment option. Scoring balloons used in the cardiovascular field can prevent slipping and plaque incisions during balloon expansion;however, their efficacy in treating cervical ICA ISR remains uncertain.
View Article and Find Full Text PDFBackground: Treatment of chronic subdural hematoma (CSDH) with middle meningeal artery embolization (MMAE) is becoming well established. Transradial artery access (TRA) is considered less invasive than transfemoral artery access (TFA) and is increasingly indicated in the field of endovascular therapy. Therefore, this study focused on postoperative delirium and compared access routes.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
February 2024
Arene-formaldehyde condensation is a versatile reaction for producing various oligomeric/polymeric materials. However, the precise control of oligomerization degree is still challenging because the starting materials and intermediates have similar reactivities. Here, we demonstrate the selective synthesis of a methylene-bridged arene trimer using the confined cavity of a coordination cage.
View Article and Find Full Text PDFEndovascular therapy (EVT) for real-world patients after extended time frames is associated with concerns about its efficacy and safety. We conducted a prospective registry at 77 centers between November 2019 and October 2020. The registry criteria included patients treated with Trevo Retriever alone or in combined therapy with an aspiration catheter.
View Article and Find Full Text PDFThe tetradehydro-Diels-Alder (TDDA) reaction is a useful transformation for the rapid assembly of polycyclic scaffolds from simple linear precursors in a single synthetic step. However, the reaction requires careful substrate design and harsh reaction conditions to overcome the inherent entropic cost for this transformation. Herein we report an efficient site-selective TDDA transformation within a self-assembled PdL cage.
View Article and Find Full Text PDFNumerous indole alkaloids such as the iboga- and aspidosperma-type are believed to be biosynthesized via a common hypothetical intermediate, dehydrosecodine. The highly reactive nature of dehydrosecodine-type compounds has hampered their isolation and structural elucidation. In this study, we achieved the first X-ray structural determination of a dehydrosecodine-type compound by integrating synthetic optimization of the reactivity and stabilizing the fragile molecule by encapsulation into a supramolecular host.
View Article and Find Full Text PDFBackground: The Spetzler-Martin Grade (SMG) is widely used to evaluate the risk of resection of cerebral arteriovenous malformation (AVM), and direct surgery is strongly recommended for low SMG lesions. Micro-AVMs are defined as AVMs with a nidus <1 cm in diameter, and sometimes, the challenge is identifying the exact lesion site during AVM resection, although identification of the site is very important in the procedure. Here, we present two cases in which the sites of micro-AVM were marked using presurgical embolization and easily confirmed by intraoperative ultrasonography (IUS) and discuss the benefits of IUS in combination with presurgical embolization for low-grade micro-AVM.
View Article and Find Full Text PDFSelf-assembled coordination cages composed of metal cations and ligands can enhance the hydrolysis of non-covalently trapped amides in mild conditions as demonstrated in recent experiments. Here, we reveal the mechanism that accelerates base-catalyzed amide hydrolysis inside the octahedral coordination cage, by means of a quantum mechanics/molecular mechanics/polarizable continuum model. The calculated activation barrier of the nucleophilic OH addition to a planar diaryl amide drastically decreases in the cage because of mechanical bond-twisting due to host-guest π-stacking.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2022
The properties of rare-earth-metal ions in aqueous media often depend on their various hydration modes, which allow them to exist as monomeric or oligomeric species with different coordination numbers. Capturing rare-earth-metal ions in a confined cavity can fix their hydration modes and thus enable their intrinsic properties to be distinguished. However, the isolation of ionic species from bulk aqueous media is not an easy task due to competitive interaction with bulk water.
View Article and Find Full Text PDFA 2-biphenylacetylene was fixed into a specific conformation within the confined cavity of a hollow cage, where it underwent a regioselective spirocyclization in the presence of an electrophile. A 5-endo-dig cyclization proceeded selectively in the cage, which stands in sharp contrast to the 6-endo-dig cyclization that normally occurs in common organic media. The folded conformation adopted by the substrate within the cage was examined by H NMR spectroscopy and X-ray crystallographic analysis.
View Article and Find Full Text PDFThe creaming behavior of an oil-in-water (O/W) emulsion was quantitatively evaluated via resonance-enhanced multiphoton ionization time-of-flight mass spectrometry. Styrene O/W emulsions were prepared with initial styrene concentrations of 1 and 4 g/L, and the height at the center of the sample was monitored. A peak area of the molecular ion of styrene was set as the signal intensity, for which a time profile was constructed from a series of mass spectra.
View Article and Find Full Text PDFA molecular host with photosensitizing centers provides photo-responsive host-guest properties based on its molecular recognition ability. Here, we construct a self-assembled photoactive Ir() cage-shaped complex that contains anion binding pockets on its rim. The anion recognition ability of the complex enables efficient catalysis of the visible-light-induced - isomerization of an anionic styrene derivative.
View Article and Find Full Text PDFAll three patients were men in their 70s. All cases were solitary onset and the chief complaint was gait disturbance. All patients had miosis and limb and trunk ataxia, MMSE score was declined in two patients, and FAB score was declined in all patients.
View Article and Find Full Text PDFThe ability of a cationic coordination cage to encapsulate molecular guests is enhanced by non-covalent capping of the cage portals with tripodal anions. The capped cage provides new cation binding sites at the portals, which enable accommodation of cationic substrates within the cationic cage. In addition, non-covalent capping allows neutral guests in the cage to be exchanged for cationic ones on demand.
View Article and Find Full Text PDFThe most preferred treatment for organized chronic subdural hematoma (OSDH) remains controversial. Although a large craniotomy has been reported to be necessary and effective for the treatment of an OSDH, a craniotomy is associated with postoperative hemorrhagic complications and recurrence. Although middle meningeal artery (MMA) embolization has been reported to be effective for a refractory chronic subdural hematoma (CSDH), its efficacy for an OSDH remains unclear.
View Article and Find Full Text PDFIn microthermoelectric generators (μTEGs), parasitic thermal resistance must be suppressed to increase the temperature difference across thermocouples for optimum power generation. A thermally conductive (TC) layer is typically used in μTEGs to guide the heat flow from the heat source to the hot junction of each thermocouple. In this study, we investigate the effect of the thermal boundary resistance (TBR) in metal/dielectric TC layers on the power generation of silicon nanowire (SiNW) μTEGs.
View Article and Find Full Text PDFA small centrum ovale infarct in the territory of the white matter medullary artery can be caused not only by embolism but also small-vessel disease. In our study, thorough screening for emboligenic diseases was performed, including the modality of transesophageal echocardiography (TEE), in patients with an acute, isolated, small (less than 1.5 cm) infarct in the centrum ovale.
View Article and Find Full Text PDFTemperature increase in the continuously narrowing interconnects accelerates the performance and reliability degradation of very large scale integration (VLSI). Thermal boundary resistance (TBR) between an interconnect metal and dielectric interlayer has been neglected or treated approximately in conventional thermal analyses, resulting in significant uncertainties in performance and reliability. In this study, we investigated the effects of TBR between an interconnect metal and dielectric interlayer on temperature increase of Cu, Co, and Ru interconnects in deeply scaled VLSI.
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