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1.
Vet Surg ; 53(4): 630-641, 2024 May.
Artículo en Inglés | MEDLINE | ID: mdl-38519449

RESUMEN

OBJECTIVE: To analyze risk factors for complicated perioperative recovery of dogs undergoing either staphylectomy or folded flap palatoplasty. STUDY DESIGN: Retrospective study. ANIMALS: Seventy-six client-owned dogs. METHODS: Medical records of dogs that underwent either staphylectomy or folded flap palatoplasty were reviewed for signalment, brachycephalic risk (BRisk) score, history of gastrointestinal signs, laryngeal collapse grade, presence of preoperative aspiration pneumonia, intraoperative respiratory and cardiovascular complications, length of general anesthesia, number of corrected brachycephalic obstructive airway syndrome (BOAS) components, and gastrointestinal and respiratory postoperative complications. Complicated recovery was defined as requirement for prolonged oxygen treatment and/or tracheostomy or perioperative death. Penalized logistic regression was used to identify risk factors. RESULTS: Seventy-six dogs were enrolled in the study. Multivariate penalized logistic regression identified four risk factors for complicated recovery. These include surgery type (p = .0002), age (p = .0113), laryngeal collapse grade >2 (p < .0001) and length of general anesthesia (p = .0051). CONCLUSIONS: In this population, dogs that had staphylectomy, increasing age, laryngeal collapse grade >2 and increasing length of general anesthesia were at increased risk for perioperative complicated recovery. CLINICAL SIGNIFICANCE: The results of this study identified risk factors for perioperative complicated recovery in dogs undergoing elongated soft palate correction and may assist in surgical planning and early prediction of complications.


Asunto(s)
Enfermedades de los Perros , Complicaciones Posoperatorias , Perros , Animales , Factores de Riesgo , Estudios Retrospectivos , Masculino , Femenino , Complicaciones Posoperatorias/veterinaria , Enfermedades de los Perros/cirugía , Paladar Blando/cirugía , Colgajos Quirúrgicos/veterinaria , Procedimientos de Cirugía Plástica/veterinaria , Procedimientos de Cirugía Plástica/métodos , Anestesia General/veterinaria , Anestesia General/efectos adversos
2.
Chempluschem ; 84(6): 665-672, 2019 06.
Artículo en Inglés | MEDLINE | ID: mdl-31944015

RESUMEN

The serendipitous isolation of very small amounts of two naphthocyclobutadiene (NCB) derivatives has led to the computational re-examination of the electrocyclization of Z,Z-3,5-octadiene-1,7-diyne as well as the experimental and computational study of diethynylindeno[2,1-a]fluorene derivatives that contain the 3,5-octadiene-1,7-diyne motif as part of a larger π-framework. In both cases the calculated potential energy surface strongly implicates two successive electrocyclic reactions to afford the antiaromatic products. With the octadienediyne fragment locked in the reactive conformation, the postulated diethynylindeno[2,1-a]fluorene intermediates afford the NCBs in modest to good yields. X-ray crystallography of four NCBs as well as NICS-XY scan calculations show that the paratropic motif is located primarily in the benzocyclobutadiene fragment within the larger π-scaffold.

3.
J Org Chem ; 82(24): 13076-13083, 2017 12 15.
Artículo en Inglés | MEDLINE | ID: mdl-29134806

RESUMEN

In 1 M triflic acid/dichloroethane, anthracene is protonated at C9, and the resulting 9-anthracenium ion is easily observed by NMR at ambient temperature. When heated as a dilute solution in triflic acid/dichloroethane, anthracene undergoes conversion to phenanthrene as the major volatile product. Minor dihydro and tetrahydro products are also observed. MALDI analysis supports the simultaneous formation of oligomers, which represent 10-60% of the product. Phenanthrene is nearly inert to the same superacid conditions. DFT and CCSD(T)//DFT computational models were constructed for isomerization and automerization mechanisms. These reactions are believed to occur by cationic ring pirouettes which pass through spirocyclic intermediates. The direct aryl pirouette mechanism for anthracene has a predicted DFT barrier of 33.6 kcal/mol; this is too high to be consistent with experiment. The ensemble of experimental and computational models supports a multistep isomerization process, which proceeds by reduction to 1,2,3,4-tetrahydroanthracene, acid-catalyzed isomerization to 1,2,3,4-tetrahydrophenanthrene with a predicted DFT barrier of 19.7 kcal/mol, and then reoxidation to phenanthrene. By contrast, DFT computations support a direct pirouette mechanism for automerization of outer ring carbons in phenanthrene, a reaction demonstrated previously by Balaban through isotopic labeling.

4.
J Am Chem Soc ; 139(40): 14053-14056, 2017 10 11.
Artículo en Inglés | MEDLINE | ID: mdl-28942643

RESUMEN

We report the concise, biomimetic total synthesis of the dimeric, Diels-Alder natural product griffipavixanthone from a readily accessible prenylated xanthone monomer. The key step utilizes a novel intermolecular [4+2] cycloaddition-cyclization cascade between a vinyl p-quinone methide and an in situ generated isomeric diene promoted by either Lewis or Brønsted acids. Experimental and computational studies of the reaction pathway suggest that a stepwise, cationic Diels-Alder cycloaddition is operative.


Asunto(s)
Productos Biológicos/síntesis química , Xantonas/síntesis química , Productos Biológicos/química , Biomimética/métodos , Cristalografía por Rayos X , Ciclización , Reacción de Cicloadición/métodos , Modelos Moleculares , Estereoisomerismo , Xantonas/química
5.
Br J Pharmacol ; 165(1): 4-19, 2012 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-21480863

RESUMEN

Diabetic retinopathy (DR) is one of the most common microvascular complications of diabetes and remains a major cause of preventable blindness among adults at working age. DR involves an abnormal pathology of major retinal cells, including retinal pigment epithelium, microaneurysms, inter-retinal oedema, haemorrhage, exudates (hard exudates) and intraocular neovascularization. The biochemical mechanisms associated with hyperglycaemic-induced DR are through multifactorial processes. Peroxisome proliferator-activated receptor-γ (PPAR-γ) plays an important role in the pathogenesis of DR by inhibiting diabetes-induced retinal leukostasis and leakage. Despite DR causing eventual blindness, only a few visual or ophthalmic symptoms are observed until visual loss develops. Therefore, early medical interventions and prevention are the current management strategies. Laser photocoagulation therapy is the most common treatment. However, this therapy may cause retinal damage and scarring. Herbal and traditional natural medicines may provide an alternative to prevent or delay the progression of DR. This review provides an analysis of the therapeutic potential of herbal and traditional natural medicines or their active components for the slowdown of progression of DR and their possible mechanism through the PPAR-γ pathway.


Asunto(s)
Productos Biológicos/uso terapéutico , Retinopatía Diabética/genética , Retinopatía Diabética/fisiopatología , PPAR gamma/genética , PPAR gamma/metabolismo , Productos Biológicos/química , Retinopatía Diabética/tratamiento farmacológico , Humanos , Plantas Medicinales/química , Retina/metabolismo , Retina/patología
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