Effect of porphyrin ligands on the catalytic CH4 oxidation activity of monocationic µ-nitrido-bridged iron porphyrinoid dimers by using H2O2 as an oxidant.

The µ-nitrido-bridged iron phthalocyanine homodimer is a potent molecule-based CH4 oxidation catalyst that can effectively oxidize chemically stable CH4 under mild reaction conditions in an acidic aqueous solution including an oxidant such as H2O2. The reactive intermediate is a high-valent iron-oxo species generated upon reaction with H2O2. However, a detailed comparison of the CH4 oxidation activity of the µ-nitrido-bridged iron phthalocyanine dimer with those of µ-nitrido-bridged iron porphyrinoid dimers containing one or two porphyrin ring(s) has not been yet reported, although porphyrins are the most important class of porphyrinoids. Herein, we compare the catalytic CH4 and CH3CH3 oxidation activities of a monocationic µ-nitrido-bridged iron porphyrin homodimer and a monocationic µ-nitrido-bridged heterodimer of an iron porphyrin and an iron phthalocyanine with those of a monocationic µ-nitrido-bridged iron phthalocyanine homodimer in an acidic aqueous solution containing H2O2 as an oxidant. It was demonstrated that the CH4 oxidation activities of monocationic µ-nitrido-bridged iron porphyrinoid dimers containing porphyrin ring(s) were much lower than that of a monocationic µ-nitrido-bridged iron phthalocyanine homodimer. These findings suggested that the difference in the electronic structure of the porphyrinoid rings of monocationic µ-nitrido-bridged iron porphyrinoid dimers strongly affected their catalytic light alkane oxidation activities.

[Surgical Treatment for Ruptured Thoracoabdominal Aneurysm Following Descending Aortic Replacement with Double Barrel Anastomosis].

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.

[Delayed Type â ¢b Endoleak After Thoracic Endovascular Aortic Repair for Thoracic Aortic Aneurysm: Report of a Case].

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 Ⅲb endoleak. TEVAR was performed to close a type Ⅲb endoleak with a relining technique uneventfully. Intraoperative completion aortography and postoperative CT confirmed the disappearance of a type Ⅲb endoleak. She was discharged 27 days after the treatment.

[Acute Type A Aortic Dissection Complicated by Cerebral Malperfusion and Leg Ischemia:Report of a Case].

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.

[Surgical Treatment of the Perforation of the Right Ventricle and Diaphragm by a Permanent Pacing Lead:Report of a Case].

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.

Enhanced Co-culture System Using Escherichia coli and Pichia pastoris (Komagataella phaffii) for Improved Microbial Production of Valuable Plant Alkaloids.

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.

Simulation to determine the approach of transcatheter aortic valve implantation in patients undergoing hemodialysis.

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.

Correction: Ishihara et al. Association between Daily Physical Activity and Locomotive Syndrome in Community-Dwelling Japanese Older Adults: A Cross-Sectional Study. Int. J. Environ. Res. Public Health 2022, 19, 8164.

There was an error in the "d-value of the first paragraph in Section 3 (Results)" in the original publication (Page 5, Line 41) [...].

[Compartment Syndrome After Stanford Type A Acute Aortic Dissection Surgery:Report of a Case].

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.

Design and Synthesis of Poly(2,2'-Bipyridyl) Ligands for Induction of Cell Death in Cancer Cells: Control of Anticancer Activity by Complexation/Decomplexation with Biorelevant Metal Cations.

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.

Optical Resolution of Carboxylic Acid Derivatives of Homoleptic Cyclometalated Iridium(III) Complexes via Diastereomers Formed with Chiral Auxiliaries.

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.

[Amyloidosis Diagnosed Following Aortic Valve Replacement:Report of a Case].

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.

[Stanford Type A Acute Aortic Dissection Complicated by Right Lung Hemorrhage:Report of a Case].

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.

Stacking of a Cofacially Stacked Iron Phthalocyanine Dimer on Graphite Achieved High Catalytic CH4 Oxidation Activity Comparable to That of pMMO.

Numerous biomimetic molecular catalysts inspired by methane monooxygenases (MMOs) that utilize iron or copper-oxo species as key intermediates have been developed. However, the catalytic methane oxidation activities of biomimetic molecule-based catalysts are still much lower than those of MMOs. Herein, we report that the close stacking of a µ-nitrido-bridged iron phthalocyanine dimer onto a graphite surface is effective in achieving high catalytic methane oxidation activity. The activity is almost 50 times higher than that of other potent molecule-based methane oxidation catalysts and comparable to those of certain MMOs, in an aqueous solution containing H2O2. It was demonstrated that the graphite-supported µ-nitrido-bridged iron phthalocyanine dimer oxidized methane, even at room temperature. Electrochemical investigation and density functional theory calculations suggested that the stacking of the catalyst onto graphite induced partial charge transfer from the reactive oxo species of the µ-nitrido-bridged iron phthalocyanine dimer and significantly lowered the singly occupied molecular orbital level, thereby facilitating electron transfer from methane to the catalyst in the proton-coupled electron-transfer process. The cofacially stacked structure is advantageous for stable adhesion of the catalyst molecule on the graphite surface in the oxidative reaction condition and for preventing decreases in the oxo-basicity and generation rate of the terminal iron-oxo species. We also demonstrated that the graphite-supported catalyst exhibited appreciably enhanced activity under photoirradiation owing to the photothermal effect.

California poppy (Eschscholzia californica), the Papaveraceae golden girl model organism for evodevo and specialized metabolism.

California poppy or golden poppy (Eschscholzia californica) is the iconic state flower of California, with native ranges from Northern California to Southwestern Mexico. It grows well as an ornamental plant in Mediterranean climates, but it might be invasive in many parts of the world. California poppy was also highly prized by Native Americans for its medicinal value, mainly due to its various specialized metabolites, especially benzylisoquinoline alkaloids (BIAs). As a member of the Ranunculales, the sister lineage of core eudicots it occupies an interesting phylogenetic position. California poppy has a short-lived life cycle but can be maintained as a perennial. It has a comparatively simple floral and vegetative morphology. Several genetic resources, including options for genetic manipulation and a draft genome sequence have been established already with many more to come. Efficient cell and tissue culture protocols are established to study secondary metabolite biosynthesis and its regulation. Here, we review the use of California poppy as a model organism for plant genetics, with particular emphasis on the evolution of development and BIA biosynthesis. In the future, California poppy may serve as a model organism to combine two formerly separated lines of research: the regulation of morphogenesis and the regulation of secondary metabolism. This can provide insights into how these two integral aspects of plant biology interact with each other.

[Very Late Stent Thrombosis during Perioperative Period of Aortic Valve Replacement:Report of a Case].

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.

[Gallbladder Necrosis after Surgery for Stanford Type A Aortic Dissection in an Elderly Patient:Report of a Case].

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.

Synthesis of Isomeric Tb3+ -Phthalocyanine Double-Decker Complexes Depending on the Difference in the Direction of Coordination Plane and Their Magnetic Properties.

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.

Synthesis of Isomeric Tb3+ -Phthalocyanine Double-Decker Complexes Depending on the Difference in the Direction of Coordination Plane and Their Magnetic Properties.

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.