RESUMO
The cycloaddition of nitrile oxides with ethynyl-B(dan) (dan=naphthalene-1,8-diaminato) allowed the facile preparation of diverse isoxazolyl-B(dan) compounds, all of which displayed excellent protodeborylation-resistant properties. The dan-installation on the boron center proves vital to the high stability of the products as well as the perfect regioselectivity arising from hydrogen bond-directed orientation in the cycloaddition. The diminished boron-Lewis acidity of ethynyl-B(dan) also renders it amenable to azide-alkyne cycloaddition, Larock indole synthesis and related heteroannulations. The obtained boron-containing triazole, indoles, benzofuran and indenone exhibit sufficient resistance toward protodeborylation. Despite the commonly accepted transmetalation-inactive property derived from the diminished Lewis acidity, the synthesized heteroaryl-B(dan) compound was still found to be convertible to the oligoarene via sequential Suzuki-Miyaura coupling.
RESUMO
We report a rare case of ventricular septal perforation (VSP) after inferior myocardial infarction. Surgical repair of VSP after inferior infarction is technically difficult because of its anatomical location. An 81-year-old female presented with dyspnea on the 8th day after percutaneous coronary intervention for acute inferior myocardial infarction. Echocardiography revealed a ventricular septal perforation. Urgent operation was performed. There was a VSP around the base of the ventricular septum. The myocardial infarction extended to the adjacent muscle of the mitral valve annulus. Two bovine pericardial patches were used in the left ventricular cavity. The patches were sewn on the mitral valve annulus which was the only normal tissue in the region. The 1st patch was used to close the VSP directly, and the 2nd patch was sutured to the normal myocardium to exclude the infracted area. No residual shunt flow was observed. The postoperative course was uneventful.
Assuntos
Procedimentos Cirúrgicos Cardíacos/métodos , Valva Mitral/cirurgia , Infarto do Miocárdio/complicações , Pericárdio/transplante , Implantação de Prótese/métodos , Ruptura do Septo Ventricular/etiologia , Ruptura do Septo Ventricular/cirurgia , Idoso de 80 Anos ou mais , Animais , Bovinos , Feminino , Xenoenxertos , Humanos , Balão Intra-Aórtico , Valva Mitral/patologia , Infarto do Miocárdio/terapia , Resultado do Tratamento , Ruptura do Septo Ventricular/patologiaRESUMO
Lewis acidity of organoboronates [B(pin), B(neop), B(cat), B(eg), B(nad)] and organoboronamides [B(dan), B(aam), B(mdan)] has been found to be unifiedly evaluated by computed ammonia affinity (AA), while other methods [LUMO energies, global electrophilicity index (GEI), fluoride ion affinity (FIA)] were only partially applicable. The relationships between the AA values and such structural characters including the B-X bond lengths, the X-B-X angles, and the changes in the B-X bond lengths in the formation of the ammonia adducts were also described.
RESUMO
The patient was a 77-year-old man. In 2004, he developed thrombosed aortic dissection extending from the distal aortic arch to the renal artery bifurcation. He was discharged after his condition improved with conservative treatment. He was followed up as an outpatient because there was an aneurysm, which measured 50 mm in diameter, at the aortic arch. Thereafter the aneurysm gradually enlarged. In May 2009, computed tomography (CT) showed that the aneurysm had increased to 10 cm in diameter and the patient began to have back pain. Thus, surgery was planned. CT revealed that the right subclavian artery originated distal to the left subclavian artery and coursed posterior to the esophagus and trachea. Surgery was performed using median sternotomy. Arch replacement and right subclavian artery reconstruction were performed under hypothermic circulatory arrest with selective cerebral perfusion. The right subclavian artery was controlled at the right border of the trachea, and cerebral perfusion was performed at this site. An end-to-side anastomosis to the reconstructed right common carotid artery was performed by an anterior tracheal approach. The patient had no cerebral complications and his postoperative course was uneventful.
Assuntos
Aorta Torácica/cirurgia , Aneurisma da Aorta Torácica/cirurgia , Esterno/cirurgia , Artéria Subclávia/anormalidades , Idoso , Dissecção Aórtica/cirurgia , Humanos , Masculino , Artéria Subclávia/cirurgia , Procedimentos Cirúrgicos Vasculares/métodosRESUMO
This case report describes a partial aortic root remodeling, which applied a valve-sparing technique, with an adventitial inversion technique for an acute type A aortic dissection with intimal tear extending into the noncoronary sinus of Valsalva. Postoperative computed tomography at six months showed no dissection or pseudoaneurysm in the aortic root.
Assuntos
Doenças da Aorta/cirurgia , Dissecção Aórtica/cirurgia , Ruptura Aórtica/cirurgia , Valva Aórtica/patologia , Seio Aórtico/cirurgia , Adulto , Dissecção Aórtica/diagnóstico por imagem , Dissecção Aórtica/patologia , Doenças da Aorta/diagnóstico por imagem , Doenças da Aorta/patologia , Ruptura Aórtica/diagnóstico por imagem , Ruptura Aórtica/patologia , Valva Aórtica/diagnóstico por imagem , Valva Aórtica/cirurgia , Implante de Prótese Vascular/instrumentação , Implante de Prótese Vascular/métodos , Dor no Peito , Humanos , Masculino , Período Pós-Operatório , Seio Aórtico/diagnóstico por imagem , Seio Aórtico/patologia , Tomografia Computadorizada por Raios X , UltrassonografiaRESUMO
Copper-catalyzed arylstannylation of arynes has been developed. This transformation enables variously substituted ortho-stannylbiaryls and teraryls to be constructed straightforwardly. An electron-deficient tin center is the key, and thus the single or dual insertion of arynes into arylstannanes is precisely controllable by simply changing the equivalence of aryne precursors.
RESUMO
A new anthranilamide-substituted borane [H-B(aam)] was synthesized and found to serve as a stable, easy-to-handle substitute for H-B(pin). It was applied to the direct synthesis of diverse linear (E)-alkenyl-B(aam)s via regio- and stereoselective hydroboration of terminal alkynes under iridium catalysis. A boryliridium hydride complex arising from the oxidative addition of H-B(aam) to the Ir catalyst was isolated and characterized via NMR studies.
RESUMO
A sensitive and specific method for quantifying a genotoxic hydrazine, agaritine, has been developed using liquid chromatography-electrospray ionization tandem mass spectrometry (MS). Synthetic agaritine was structurally assigned by (1)H, (13)C and two-dimensional nuclear magnetic resonance (NMR) analysis (heteronuclear multiple-bond correlation [HMBC] and heteronuclear multiple-quantum coherence [HMQC]), high-resolution fast-atom-bombardment (HR-FAB) MS. Agaritine was separated on an ODS column using 0.01% AcOH-MeOH (99:1) as an eluent with a simple solid-phase-extraction cleanup for mushroom samples and with acetonitrile and methanol deprotenization for plasma samples. There were no interference peaks in any of the mushrooms or mouse plasma samples. The recoveries of agaritine from the spiked mushroom samples and spiked mouse plasma were 60.3-114 and 74.4%, respectively. The intra-day precision values for the spiked mushrooms were 5.5 and 4.2%, and the inter-day precision values were 15.0 and 23.0%, respectively. The limit of quantification was 0.01 microg/g (in mushrooms) and 0.01 microg/ml (in plasma). A precursor ion scan confirmed that agaritine derivatives, which can exert a similar toxicity, were absent. These results indicate that this analytical method for quantifying agaritine could help to evaluate the risk of mushroom hydrazines to humans.
Assuntos
Agaricales/química , Cromatografia Líquida de Alta Pressão/métodos , Fenil-Hidrazinas/análise , Espectrometria de Massas por Ionização por Electrospray/métodos , Espectrometria de Massas de Bombardeamento Rápido de Átomos/métodos , Animais , Espectroscopia de Ressonância Magnética , Camundongos , Padrões de Referência , Reprodutibilidade dos Testes , Sensibilidade e EspecificidadeRESUMO
[reaction: see text] Two indole-containing substrate analogues, in which a C20 isoprene unit is connected to indole (3-(geranylgeranyl)indole and 3-(farnesyldimethylallyl)indole), were synthesized and tested for enzymatic cyclization by squalene:hopene cyclase from Alicyclobacillus acidocaldarius. Interestingly, 3-(geranylgeranyl)indole was not a substrate for the bacterial squalene cyclase, while 3-(farnesyldimethylallyl)indole was efficiently converted to a 2:1 mixture of unnatural novel products.
Assuntos
Bacillus/enzimologia , Indóis/metabolismo , Liases/metabolismo , Hidrocarbonetos Policíclicos Aromáticos/metabolismo , Ciclização , Indóis/química , Estrutura Molecular , Hidrocarbonetos Policíclicos Aromáticos/química , Esqualeno/química , Esqualeno/metabolismoRESUMO
BACKGROUND: In thoracoabdominal aneurysm (TAAA) repair, our technical modification of visceral reconstruction using longer cut pre-sewn side branches has provided good surgical outcomes. Here, we assessed the long-term durability and patency of revascularized branches using computed tomography (CT) to confirm the validity of our approach. METHODS: Early and late CT evaluations were performed in 11 TAAA patients (males: 5; mean age: 60.6 years) using the Coselli graft to evaluate the position of main graft and the diverging pattern and patency of side branches. Seven of 11 were sutured in an extra-anatomical fashion using longer cut side branches. RESULTS: In Anatomical (n = 4) and Extra-anatomical (n = 7) groups, the early patency of side branches was not significantly different. Although the late patency of right renal artery (RA) was 100% in both groups, the one of left RA was 60% in Extra-anatomical, while 100% in Anatomical. Furthermore, the main graft in Extra-anatomical was significantly posterior and leftward to the spine with left RA side branch diverging at an acute angle. CONCLUSIONS: When a pre-sewn branched graft designed for TAAA is used, the graft should be sutured in a fashion similar to normal patient anatomy to minimize the possibility of kinking of RA side branch for the patency.
Assuntos
Aorta Torácica/cirurgia , Aneurisma da Aorta Torácica/cirurgia , Aortografia/métodos , Implante de Prótese Vascular/métodos , Tomografia Computadorizada por Raios X , Adulto , Idoso , Aorta Torácica/diagnóstico por imagem , Aorta Torácica/fisiopatologia , Aneurisma da Aorta Torácica/diagnóstico por imagem , Aneurisma da Aorta Torácica/fisiopatologia , Prótese Vascular , Implante de Prótese Vascular/instrumentação , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Valor Preditivo dos Testes , Desenho de Prótese , Estudos Retrospectivos , Técnicas de Sutura , Fatores de Tempo , Resultado do Tratamento , Grau de Desobstrução VascularRESUMO
1-methylidenesqualene and 25-methylidenesqualene were converted to 30-methylidenehop-22(29)-ene by squalene:hopene cyclase from Alicyclobacillus acidocaldarius. It was remarkable that both analogues generated the same product. The hopanyl intermediate cation, stabilized by the methylidene residue, enabled a rotation of the isobutenyl group at C-21 prior to the final proton elimination. In contrast, in the formation of hop-22(29)-ene, the final proton abstraction takes place regiospecifically from the Z-methyl group, which was verified by cyclization of (1,1,1,24,24,24-(2)H(6))squalene into (23,23,23,30,30,30-(2)H(6))hop-22(29)-ene. [reaction: see text]
Assuntos
Bacillus/enzimologia , Bacilos Gram-Positivos Formadores de Endosporo/enzimologia , Transferases Intramoleculares/análise , Sondas Moleculares , Esqualeno/síntese química , Sítios de Ligação , Estrutura Molecular , Esqualeno/análogos & derivados , Esqualeno/metabolismoRESUMO
Retroaortic left renal vein is a malformation in which the left renal vein courses dorsal to the abdominal aorta. In patients with abdominal aortic aneurysm, an aorto-left renal vein fistula can form if the left renal vein is sandwiched between the aneurysm wall and lumbar vertebrae. The patient was an 84-year-old man with lower back pain. We performed a contrast-enhanced computed tomography (CT), although renal dysfunction was noted. The CT showed a ruptured juxta-renal abdominal aortic with aorto-left renal vein fistula. This clinical condition can cause severe renal dysfunction, in spite of which an enhanced contrasted CT scan would be extremely informative preoperatively.
RESUMO
A cDNA encoding adenylate isopentenyltransferase (AIPT) was cloned from young leaves of mulberry (Morus alba) by a homology-based RT-PCR. A recombinant enzyme expressed in Escherichia coli catalyzed prenyl transfer from DMAPP to the N6 amino group of ADP and ATP, respectively, while AMP was a poor substrate of the enzyme. Interestingly, M. alba AIPT also accepted dADP, dATP, CDP, and GDP as the prenyl acceptors, and IPP, HMBPP, and GPP as the prenyl donors, to produce a series of cytokinin analogs. In particular, it was remarkable that the enzyme accepted HMBPP to produce trans-zeatin riboside phosphates, which suggested that trans-zeatin may be also produced from adenosine phosphates and HMBPP. Finally, alanine-scanning mutagenesis of conserved D49, Y54, F93, F120, Y153, F157, W159, Y170, Y217, and Q255, resulted in significant loss of enzyme activity except Y170A, confirming the functional and structural importance of the residues.
Assuntos
Alquil e Aril Transferases/química , Citocininas/biossíntese , Morus/enzimologia , Proteínas de Plantas/química , Alquil e Aril Transferases/genética , Alquil e Aril Transferases/isolamento & purificação , Sequência de Aminoácidos , Clonagem Molecular , Dados de Sequência Molecular , Morus/genética , Mutagênese , Mutação , Nucleotídeos/química , Folhas de Planta/enzimologia , Folhas de Planta/genética , Proteínas de Plantas/genética , Proteínas de Plantas/isolamento & purificação , Proteínas Recombinantes/biossíntese , Proteínas Recombinantes/química , Proteínas Recombinantes/isolamento & purificação , Análise de Sequência de DNA , Especificidade por SubstratoRESUMO
A new method with good sensitivity and specificity for detecting and quantifying genotoxic hydrazines, agaritine and 4-(hydroxymethyl)phenylhydrazine (HMPH), was developed using liquid chromatography-electrospray tandem mass spectrometry (MS). Synthetic agaritine and HMPH were structurally assigned by 1H-, 13C- and two-dimensional nuclear magnetic resonance (NMR) analysis (HMBC and HMQC), high-resolution fast-atom bombardment (HR-FAB) MS and time of flight (TOF) MS. The polar molecule agaritine was separated on an ODS column using 0.01% AcOH-MeOH (99:1, v/v) as an eluent with a simple solid-phase extraction cleanup. There were no interference peaks for any of the mushrooms. Agaricus spp. contained 1247 and 2017 microg g-1 agaritine. Other species of mushroom had no agaritine. Recoveries of agaritine from spiked mushroom samples were 60.3-114%. Intra-day precision values were 5.5 and 4.2%, and the inter-day precision values were acceptable (15.0 and 23.0%), as agaritine is unstable. The limit of quantification was 0.003 microg g-1. Even a trace amount of agaritine in mushrooms can, therefore, be determined using this method. We also directly analysed HMPH, an active free hydrazine form of genotoxic agaritine, and obtained direct evidence of its absence from mushrooms. A precursor ion scan confirmed that agaritine derivatives, which could exert similar toxicity, were absent. The results indicate that this specific and sensitive analytical method for detecting and quantifying agaritine and its derivatives could help evaluate the risk of mushroom hydrazines to humans.
Assuntos
Agaricales/química , Cromatografia Líquida de Alta Pressão/métodos , Fenil-Hidrazinas/análise , Espectrometria de Massas por Ionização por Electrospray/métodos , Espectrometria de Massas de Bombardeamento Rápido de Átomos/métodos , Reprodutibilidade dos Testes , Sensibilidade e EspecificidadeRESUMO
A C35 polyprene in which a farnesyl C15 unit is connected in a head-to-head fashion to a geranylgeranyl C20 unit was enzymatically converted to an unnatural hexacyclic polyprenoid by squalene:hopene cyclase from Alicyclobacillus acidocaldarius. This is the first demonstration of the remarkable ability of the squalene cyclizing enzyme to perform construction of unnatural hexacyclic skeleton. The cyclization of the C35 polyprene was initiated by a proton attack on the terminal double bond of the C15 unit and proceeded without rearrangement of carbon and hydrogen. The substrate should be folded in chair-chair-chair-chair-boat-boat conformation to achieve the stereochemistry of the cyclization product.
Assuntos
Liases/química , Terpenos/síntese química , Bacillus/enzimologia , Liases/metabolismo , Ressonância Magnética Nuclear Biomolecular , EstereoisomerismoRESUMO
Recombinant beta-amyrin synthase from Pisum sativum converted 22,23-dihydro-2,3-oxidosqualene, a substrate analogue lacking the terminal double bond of 2,3-oxidosqualene, into a 4:1 mixture of euph-7-en-3beta-ol and bacchar-12-en-3beta-ol. This is the first demonstration of the enzymatic formation of the baccharene skeleton with a six-membered D-ring. In the absence of the terminal double bond, the proton-initiated cyclization first generated the tetracyclic dammarenyl cation, followed by a backbone rearrangement with loss of H-7alpha leading to the formation of euph-7-en-3beta-ol, while D-ring expansion to the baccharenyl cation and subsequent 1,2-hydride shifts with H-12alpha elimination yielded bacchar-12-en-3beta-ol. It is remarkable that the formation of the anti-Markovnikov six-membered D-ring did not depend on the participation of the terminal pi-electrons.
Assuntos
Transferases Intramoleculares/química , Lanosterol/análogos & derivados , Lanosterol/síntese química , Esqualeno/análogos & derivados , Esqualeno/síntese química , Triterpenos/síntese química , Ciclização , Transferases Intramoleculares/metabolismo , Lanosterol/metabolismo , Pisum sativum/enzimologia , Proteínas Recombinantes/química , Proteínas Recombinantes/metabolismo , Esqualeno/metabolismo , Triterpenos/metabolismoRESUMO
Recombinant beta-amyrin synthase from Pisum sativum converted 24,30-bisnor-2,3-oxidosqualene into a 3:1:0.2 mixture of 29,30-bisnor-beta-amyrin, 29,30-bisnorgermanicol, and 29,30-bisnor-delta-amyrin. Further, enzyme reactions with [23-13C]- and [23,23-2H]-labeled isotopomers demonstrated that the cyclization did not proceed through formation of a lupanyl primary cation with a five-membered E-ring, but an electrophilic addition of the tetracyclic C-18 cation on to the terminal double bond directly generated a thermodynamically favored pentacyclic secondary cation with a less-strained six-membered E-ring. Interestingly, the formation of the three regioisomers suggested that the absence of the terminal methyl groups resulted in a structural perturbation in the folding conformation of the E-ring of the oleanyl cation at the active site of the enzyme.