RESUMEN
Metal-ligand delocalization of metal porphyrin complexes in aqueous solutions was investigated by analyzing the electronic structure of both the metal and ligand sides using soft X-ray absorption spectroscopy (XAS) at the metal L2,3-edges and nitrogen K-edge, respectively. In the N K-edge XAS spectra of the ligands, the energies of the CîN π* peaks of cobalt protoporphyrin IX (CoPPIX) are higher than iron protoporphyrin IX (FePPIX). The energy difference between the two lowest peaks in the XAS spectrum of CoPPIX is also larger than that of FePPIX. Nitrogen K-edge inner-shell calculations of metalloporphyrins with different central metals indicate that the energy differences between these peaks reflect the electronic configurations and spin multiplicities of metalloporphyrins. We also investigated the hydration structure of CoPPIX in aqueous solution by analyzing the electronic structure of the ligand and revealed that CoPPIX maintains its five-coordination geometry in aqueous solution. The present study shows high performance of N K-edge XAS of ligands for studying the coordination structures of metalloporphyrins in solutions rather than the metal L2,3-edges of central metals.
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PURPOSE: The present study investigated potential access vessels in patients receiving hemodialysis who underwent surgical aortic valve replacement and determined which approaches were most suitable for performing transcatheter aortic valve implantation. METHODS: Consecutive patients undergoing hemodialysis with aortic valve stenosis who underwent surgical aortic valve replacement were included. Preoperative computed tomography data were analyzed to assess the vessel diameter and calcification. Simulations were conducted to determine the feasibility of inserting the 14-F eSheath of Sapien 3 via transfemoral, trans-cervical, trans-subclavian, and direct aorta approaches. RESULTS: A total of 72 patients were included in this study. The access route was characterized by severe calcification of the common iliac artery. The transfemoral approach was feasible in 77.8% of the cases, but the rate decreased to 33% when the calculations were based on the maximum sheath extension diameter. The trans-cervical, trans-subclavian, and direct aortic approaches were suitable for many patients. Lower extremity artery disease was identified as a risk factor for the unsuitability of the transfemoral approach. CONCLUSIONS: Common iliac artery calcification in patients undergoing hemodialysis restricts the use of the transfemoral approach. Therefore, some patients require alternative approaches.
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Estenosis de la Válvula Aórtica , Prótesis Valvulares Cardíacas , Reemplazo de la Válvula Aórtica Transcatéter , Humanos , Reemplazo de la Válvula Aórtica Transcatéter/métodos , Resultado del Tratamiento , Válvula Aórtica/cirugía , Estenosis de la Válvula Aórtica/cirugía , Diálisis Renal , Arteria Femoral/cirugíaRESUMEN
A 75-year-old woman was diagnosed with type B acute aortic dissection 14 years ago and 3-channeled aortic dissection 7 years ago. She received total arch replacement 6 years ago and descending aortic replacement with double barrel anastomosis technique for distal anastomosis 5 years ago. Computed tomography( CT) revealed giant thyroid tumor and thoracoabdominal aortic aneurysm( 58 mm in diameter). She suffered from back pain during her follow-up period. CT revealed ruptured thoracoabdominal aortic aneurysm. First, the false lumen of descending aorta was closed by thoracic endovascular aortic repair, and then thoracoabdominal aortic replacement was performed uneventfully.
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Aneurisma de la Aorta Torácica , Aneurisma de la Aorta Toracoabdominal , Disección Aórtica , Rotura de la Aorta , Implantación de Prótesis Vascular , Procedimientos Endovasculares , Humanos , Femenino , Anciano , Aneurisma de la Aorta Torácica/diagnóstico por imagen , Aneurisma de la Aorta Torácica/cirugía , Disección Aórtica/diagnóstico por imagen , Disección Aórtica/cirugía , Aorta/cirugía , Rotura de la Aorta/diagnóstico por imagen , Rotura de la Aorta/cirugía , Implantación de Prótesis Vascular/métodos , Anastomosis Quirúrgica , Resultado del TratamientoRESUMEN
Persistent sciatic artery( PSA) is a rare congenital anomaly and often results in aneurismal or occlusive changes. A 82-year-old woman was reffered with diagnosis of Stanford type A acute aortic dissection complicated cardiac tamponade. Emergent aortic arch replacement was performed. Cardiopulmonary bypass was established by central cannulation into true lumen of aortic arch because of asceding aortic rupture during the operation, axillary arteries dissection and hypoplastic femoral arteries. Post-operative course was uneventful. She was transferred to the local hospital 32 days after the operation for the purpose of rehabilitation.
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Disección Aórtica , Humanos , Femenino , Anciano de 80 o más Años , Disección Aórtica/cirugía , Disección Aórtica/complicaciones , Disección Aórtica/diagnóstico por imagen , Enfermedad Aguda , Rotura de la Aorta/cirugía , Rotura de la Aorta/diagnóstico por imagen , Rotura de la Aorta/complicaciones , Aneurisma de la Aorta Torácica/cirugía , Aneurisma de la Aorta Torácica/diagnóstico por imagen , Aneurisma de la Aorta Torácica/complicaciones , Resultado del TratamientoRESUMEN
An 81-year-old man underwent total arch replacement for thoracic aortic aneurysm 8 years ago and catheter ablation for paroxysmal atrial fibrillation 1 year ago. Transthoracic echocardiography revealed a mass in the right atrium, and the patient was admitted for close examination and treatment. Transesophageal echocardiography revealed a 23×17 mm large well-defined mass above the cavotricuspid isthmus. Two venous drainage cannulas were inserted directly to the superior vena cava and to the inferior vena cava via the right femoral vein, in order to avoid the direct contact with the right atrium prior to institution of cardiopulmonary bypass. The right atrial tumor was found attached to the cavotricuspid isthmus, and was resected together with the right atrial wall. Pathological examination showed myxomatous tissue. Postoperative course was uneventful. He was discharged 23 days after the operation.
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Ablación por Catéter , Atrios Cardíacos , Neoplasias Cardíacas , Mixoma , Humanos , Mixoma/cirugía , Mixoma/diagnóstico por imagen , Masculino , Anciano de 80 o más Años , Neoplasias Cardíacas/cirugía , Neoplasias Cardíacas/diagnóstico por imagen , Atrios Cardíacos/cirugíaRESUMEN
A C4h symmetrically substituted phthalocyanine, 1,8,15,22-tertrakis(2,4-dimethylpent-3-oxy)phthalocyanine (H2 TdMPPc), was used to synthesize Tb3+ -phthalocyanine double-decker complexes ([Tb(TdMPPc)2 ]s). Because H2 TdMPPc has C4h symmetry, S,S, R,R, and meso isomers of [Tb(TdMPPc)2 ] were obtained depending on the difference in the direction of the coordination plane of two C4h -type phthalocyanines with respect to a central Tb3+ ion. We investigated the physical properties of these [Tb(TdMPPc)2 ] isomers, including their single-ion magnetic properties, and found that the spin-reversal energy barrier (Ueff ) of the meso isomer was apparently higher than that of the enantiomers. Detailed crystal structural analyses indicated that the meso isomer has a more symmetrical structure than do the enantiomers, thereby suggesting that the higher Ueff of the meso isomer originated from the more highly symmetrical structure.
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Invited for the cover of this issue are Kentaro Tanaka at Nagoya University and co-workers. The image depicts three isomers of a terbium(III) phthalocyanine double-decker complex made from C4h symmetrically substituted phthalocyanines and their magnetic properties. Read the full text of the article at 10.1002/chem.202203272.
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Chelation therapy is a medical procedure for removing toxic metals from human organs and tissues and for the treatment of diseases by using metal-chelating agents. For example, iron chelation therapy is designed not only for the treatment of metal poisoning but also for some diseases that are induced by iron overload, cancer chemotherapy, and related diseases. However, the use of such metal chelators needs to be generally carried out very carefully, because of the side effects possibly due to the non-specific complexation with intracellular metal cations. Herein, we report on the preparation and characterization of some new poly(bpy) ligands (bpy: 2,2'-bipyridyl) that contain one-three bpy ligand moieties and their anticancer activity against Jurkat, MOLT-4, U937, HeLa S3, and A549 cell lines. The results of MTT assays revealed that the tris(bpy) and bis(bpy) ligands exhibit potent activity for inducing the cell death in cancer cells. Mechanistic studies suggest that the main pathway responsible for the cell death by these poly(bpy) ligands is apoptotic cell death. It was also found that the anticancer activity of the poly(bpy) ligands could be controlled by the complexation (anticancer activity is turned OFF) and decomplexation (anticancer activity is turned ON) with biorelevant metal cations. In this paper, these results will be described.
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2,2'-Dipiridil , Neoplasias , Humanos , Ligandos , Muerte Celular , Metales , Quelantes , Cationes/farmacología , Poli ARESUMEN
We report on a facile method for the optical resolution of cyclometalated iridium(III) (Ir(III)) complexes via diastereomers formed with chiral auxiliaries. The racemic carboxylic acids of Ir(III) complexes (fac-4 (fac-Ir(ppyCO2H)3 (ppy: 2-phenylpyridine)), fac-6 (fac-Ir(tpyCO2H)3 (tpy: 2-(4'-tolyl)pyridine)), and fac-13 (fac-Ir(mpiqCO2H)3 (mpiq: 1-(4'-methylphenyl)isoquinoline))) were converted into the diastereomers, Δ- and Λ-forms of fac-9 (from fac-6), fac-10 (from fac-4), fac-11 (from fac-6), and fac-14 (from fac-13), respectively, by the condensation with (1R,2R)-1,2-diaminocyclohexane or (1R,2R)-2-aminocyclohexanol. The resulting diastereomers were separated by HPLC (with a nonchiral column) or silica gel column chromatography, and their absolute stereochemistry was determined by X-ray single-crystal structure analysis and CD (circular dichroism) spectra. Spectra of all diastereomers of the Ir(III) complexes are reported. Hydrolysis of the ester moieties of Δ- and Λ-forms of fac-10, fac-11, and fac-14 gave both enantiomers of the corresponding carboxylic acid derivatives in the optically pure forms, Δ-fac and Λ-fac-4, -6, and -13, respectively.
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Advancements in synthetic biology have facilitated the microbial production of valuable plant metabolites. However, constructing complete biosynthetic pathways within a single host organism remains challenging. To solve this problem, modular co-culture systems involving host organisms with partial pathways have been developed. We focused on Escherichia coli, a general host for metabolite production, and Pichia pastoris (Komagataella phaffii), a novel synthetic biology host due to its high expression of biosynthetic enzymes. Previously, we reported the co-culture of E. coli cells, which produce reticuline (an important intermediate for various alkaloids) from glycerol, with P. pastoris cells, which produce the valuable alkaloid stylopine from reticuline. However, Pichia cells inhibited E. coli growth and reticuline production. Therefore, we aimed to improve this co-culture system. We investigated the pre-culture time before co-culture to enhance E. coli growth and reticuline production. Additionally, we examined the optimal concentration of Pichia cells inoculated for co-culture and methanol addition during co-culture for the continuous expression of biosynthetic enzymes in Pichia cells. We successfully established an improved co-culture system that exhibited an 80-fold increase in productivity compared to previous methods. This enhanced system holds great potential for the rapid and large-scale production of various valuable plant metabolites.
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Escherichia coli , Pichia , Escherichia coli/genética , Técnicas de Cocultivo , Pichia/genética , Proteínas Recombinantes/metabolismoRESUMEN
A 73-year-old man underwent drug eluting stent (DES) implantation in the left anterior descending artery (LAD) 11 years ago and in the right coronary artery (RCA) 8 years ago. He suffered from chest tightness and was diagnosed with severe aortic valve stenosis. Perioperative coronary angiography revealed no significant stenosis and thrombotic occlusion of the DES. Five days before operation, antiplatelet therapy was discontinued. Aortic valve replacement was performed uneventfully. But he developed chest pain and transient loss of consciousness, electrocardiographic changes were observed on the 8th postoperative day. Emergency coronary angiography revealed thrombotic occlusion of the drug eluting stent in the RCA, despite the postoperative oral adoministration of warfarin and aspirin. Percutaneous catheter intervention (PCI) restored the stent patency. Dual antiplatelet therapy (DAPT) was initiated immediately after the PCI, and anticoagulation therapy with warfarin was continued. Clinical symptons of stent thrombosis disappeared immediately after the PCI. He was discharged 7 days after the PCI.
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Stents Liberadores de Fármacos , Intervención Coronaria Percutánea , Masculino , Humanos , Anciano , Válvula Aórtica/cirugía , Stents Liberadores de Fármacos/efectos adversos , Intervención Coronaria Percutánea/efectos adversos , Warfarina , Periodo PerioperatorioRESUMEN
A 76-year-old man had been under observation for nephrotic syndrome. He suffered from hypotension and transient loss of consciousness. He was diagnosed with thoracic aortic aneurysm and severe aortic valve stenosis. Ascending aorta replacement concomitant with aortic valve replacement was performed uneventfully. He was diagnosed with light chain amyloidosis by pathological examination of the resected ascending aorta. He was received referral treatment for amyloidosis.
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Aneurisma de la Aorta Torácica , Aneurisma de la Aorta , Estenosis de la Válvula Aórtica , Masculino , Humanos , Anciano , Válvula Aórtica/diagnóstico por imagen , Válvula Aórtica/cirugía , Aneurisma de la Aorta/cirugía , Aorta/cirugía , Aneurisma de la Aorta Torácica/diagnóstico por imagen , Aneurisma de la Aorta Torácica/cirugía , Aneurisma de la Aorta Torácica/complicaciones , Estenosis de la Válvula Aórtica/diagnóstico por imagen , Estenosis de la Válvula Aórtica/cirugía , Estenosis de la Válvula Aórtica/complicacionesRESUMEN
A 59-year-old woman was transferred to our hospital because of a sudden onset of chest and back pain. Computed tomography (CT) demonstrated Stanford type A acute aortic dissection with cardiac tamponade and right airway bleeding. Hemorrhage from ruptured false lumen extended along the pulmonary artery (PA), compression of the right PA were recognized due to hematoma surrounding the PA. An emergency operation was performed. The primary tear was located at the distal aortic arch, and total arch replacement with frozen elephant trunk was performed. During the operation, she had airway bleeding. The bleeding was thought to be due to the hematoma extending along the pulmonary artery. She was extubated 7th postopratively. She was discharged 44 days after the operation.
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Aneurisma de la Aorta Torácica , Disección Aórtica , Implantación de Prótesis Vascular , Femenino , Humanos , Persona de Mediana Edad , Aneurisma de la Aorta Torácica/complicaciones , Aneurisma de la Aorta Torácica/diagnóstico por imagen , Aneurisma de la Aorta Torácica/cirugía , Implantación de Prótesis Vascular/métodos , Disección Aórtica/complicaciones , Disección Aórtica/diagnóstico por imagen , Disección Aórtica/cirugía , Aorta Torácica/cirugía , Hemorragia/diagnóstico por imagen , Hemorragia/etiología , Hemorragia/cirugía , Hematoma/cirugía , Pulmón/cirugíaRESUMEN
An 97-year-old woman was diagnosed with complete atrioventricular block and underwent pacemaker implantation( PMI). Three days after the PMI, computed tomography revealed cardiac perforation and migration of the lead to the abdominal cavity. Surgical procedure through median sternotomy was performed, and the penetrated lead was removed. The holes of the right ventricle and diaphragm were repaired. Abdominal organ was not injured. She was discharged 14 days after the surgical procedure.
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Lesiones Cardíacas , Marcapaso Artificial , Femenino , Humanos , Anciano de 80 o más Años , Ventrículos Cardíacos/diagnóstico por imagen , Ventrículos Cardíacos/cirugía , Diafragma/diagnóstico por imagen , Diafragma/cirugía , Marcapaso Artificial/efectos adversos , Tórax , Lesiones Cardíacas/diagnóstico por imagen , Lesiones Cardíacas/etiología , Lesiones Cardíacas/cirugíaRESUMEN
An 85-year-old woman underwent aortic arch replacement and thoracic endovascular aortic repair (TEVAR) 5 years ago. She suffered from chest and back pain. Computed tomography (CT) demonstrated enlargement of the aortic aneurysm by a type â ¢b endoleak. TEVAR was performed to close a type â ¢b endoleak with a relining technique uneventfully. Intraoperative completion aortography and postoperative CT confirmed the disappearance of a type â ¢b endoleak. She was discharged 27 days after the treatment.
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Aneurisma de la Aorta Torácica , Implantación de Prótesis Vascular , Procedimientos Endovasculares , Femenino , Humanos , Anciano de 80 o más Años , Prótesis Vascular , Endofuga/diagnóstico por imagen , Endofuga/etiología , Endofuga/cirugía , Implantación de Prótesis Vascular/efectos adversos , Implantación de Prótesis Vascular/métodos , Reparación Endovascular de Aneurismas , Stents , Aorta Torácica/diagnóstico por imagen , Aorta Torácica/cirugía , Resultado del Tratamiento , Procedimientos Endovasculares/efectos adversos , Procedimientos Endovasculares/métodos , Aneurisma de la Aorta Torácica/diagnóstico por imagen , Aneurisma de la Aorta Torácica/cirugía , Estudios RetrospectivosRESUMEN
An 82-year-old woman suddenly developed chest pain and apoplexy. Computed tomography (CT) showed acute type A aortic dissection, the true lumen in the brachicephalic artery was severely compressed by the faulse lumen. Pulsation in the either leg was not detected during induction of anesthesia. We evaluated the cerebral blood flow and lower extremity blood flow using near infrared spectroscopy (NIRS) during the operation, tissue oxygenation index (TOI) was continuously monitored during the operation. Cardiopulmonary bypass( CPB) was established by puncturing the true lumen in the ascending aorta and bicaval venous drainage. TOI was returned to normal range by CPB. Although the central repair (ascending aorta replacement) was performed, leg ischemia persisted. We performed ascending aorta-bifemoral bypass. After the operation, leg ischemia disappeared and CT revealed patency of the bypass graft. Postoperative course was uneventful without deterioration of neurological function. She was discharged 49 days after the operation.
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Disección Aórtica , Pierna , Femenino , Humanos , Anciano de 80 o más Años , Pierna/irrigación sanguínea , Disección Aórtica/complicaciones , Disección Aórtica/diagnóstico por imagen , Disección Aórtica/cirugía , Aorta/cirugía , Isquemia/diagnóstico por imagen , Isquemia/etiología , Isquemia/cirugía , Extremidad Inferior/cirugíaRESUMEN
A 53-year-old man presented to the emergency department with chest and back pain. Contrast-enhanced computed tomography( CT) revealed a Stanford type A acute aortic dissection with a pseudo-lumen occlusion. On the same day, the patient underwent emergent aortic arch replacement with frozen elephant trunk. When introducing cardiopulmonary bypass, arterial cannula was inserted into the right femoral artery. The day after surgery, swelling of the right lower leg appeared with CK and intramuscular compartment pressure elevation. Thus, the patient was diagnosed with compartment syndrome and decompressive fasciotomy was performed. Although there was no preoperative blood flow disturbance in the lower extremities on preoperative CT, lower limbs ischemia happened. Necrotic muscles in his right leg required debridement, but amputation was not needed. The patient was discharged unaided utilising orthotics on the day 120. In muscular, young male patients, care should be taken in the method of blood delivery.
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Disección Aórtica , Síndromes Compartimentales , Humanos , Masculino , Persona de Mediana Edad , Síndromes Compartimentales/diagnóstico por imagen , Síndromes Compartimentales/etiología , Síndromes Compartimentales/cirugía , Pierna , Disección Aórtica/diagnóstico por imagen , Disección Aórtica/cirugía , Puente Cardiopulmonar , Arteria Femoral/diagnóstico por imagen , Arteria Femoral/cirugíaRESUMEN
An 86-year-old woman who suffered from cardiac tamponade due to acute Stanford type A aortic dissection was admitted to our hospital. An emergency operation was performed uneventfully. She suffered from abdominal pain 13 days after the operation. Computed tomography( CT) scan revealed pericholecystic fluid and unclear gallbladder wall, revealing acalculous necrotizing cholecystitis. We performed open cholecystectomy and abdominal cavity drainage. No gallstones were observed. She underwent intensive treatment. She was discharged without complications 44 days after the cholecystectomy.
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Disección Aórtica , Vesícula Biliar , Femenino , Humanos , Anciano , Anciano de 80 o más Años , Disección Aórtica/diagnóstico por imagen , Disección Aórtica/cirugía , Tomografía Computarizada por Rayos X , NecrosisRESUMEN
We report on the design and synthesis of triptycene-peptide hybrids (TPHs), 5, syn-6, and anti-6, which are conjugates of a triptycene core unit with two or three cationic KKKGG peptides (K: lysine and G: glycine) through a C8 alkyl chain. It was discovered that syn-6 and anti-6 induce paraptosis, a type of programmed cell death (PCD), in Jurkat cells (leukemia T-lymphocytes). Mechanistic studies indicate that these TPHs induce the transfer of Ca2+ from the endoplasmic reticulum (ER) to mitochondria, a loss of mitochondrial membrane potential (ΔΨm), tethering of the ER and mitochondria, and cytoplasmic vacuolization in the paraptosis processes.
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Retículo Endoplásmico , Neoplasias , Antracenos , Apoptosis , Muerte Celular , Línea Celular Tumoral , Retículo Endoplásmico/metabolismo , Humanos , Neoplasias/metabolismo , Péptidos/metabolismo , Péptidos/farmacologíaRESUMEN
Spatial distance is an important factor in controlling the functional interactions between molecular units in a conjugate; therefore, the bridging unit has been closely examined. Here, we examined the effect of the flexibility of bridging alkyl chains on the proximity of stacked porphyrin and phthalocyanine conjugated with a fourfold rotaxane linkage. We found that closely stacking two π systems requires bridging alkyl chains above a certain length, and the shorter bridges hinder stacking because of their lower flexibility. The stacking distance between porphyrin and phthalocyanine in the conjugate with decyl (C10 ) chains was estimated to be 4.03â Å and showed a unique physical character arising from short-distance interactions. The longer alkyl chains minimized steric restriction inside the fourfold rotaxane and allowed efficient communication between the porphyrin and phthalocyanine units. This is due to the flexibility of the side chains.