A Concise Diastereoselective Total Synthesis of α-Ambrinol.

(-)-cis-α-Ambrinol is a natural product present in ambergris, a substance of marine origin that has been highly valued by perfumers. In this paper, we present a new approach to its total synthesis. The starting material is commercially available α-ionone and the key step is an intramolecular Barbier-type cyclization induced by CpTiCl2, an organometallic compound prepared in situ by a CpTiCl3 reduction with Mn.

Screening of Lesser-Known Salted-Dried Fish Species for Fatty Acids, Tocols, and Squalene.

The fillets and roes of 29 species of dry-salted fishes consumed in Eurasian countries were analyzed for fatty acids (FAs), tocols, and squalene, looking for derived health benefits. FAs were analyzed by GC-FID, and tocols and squalene were analyzed by HPLC-DAD. With some exceptions, docosahexaenoic (DHA, 22:6n-3), eicosapentaenoic (EPA, 20:5n-3), and arachidonic (ARA, 20:4n-6) acids were the prominent polyunsaturated fatty acids (PUFAs). The fillets of Scardinius erythrophthalmus reached the highest amounts of total FAs, ARA, and DHA (23.1, 1.82, and 2.49 mg/100 g). The fillets of Seriola quinqueradiata showed the highest percentages of DHA (34.4% of total FAs). Nutritional quality indices for fish lipids were favorable in all samples, especially the n-6/n-3 PUFA ratio, which was below 1 in most cases. α-Tocopherol was found in all fillets and roes, especially in Cyprinidae and Pleuronectidae species, and the highest value was found in the roes of Abramis brama (5.43 mg/100 g). Most samples contained tocotrienols at trace levels. The fillets of Clupeonella cultriventris contained the highest amounts of squalene (1.83 mg/100 g). Overall, dry-salted fish stand out due to their high concentrations of ARA, EPA, and DHA, as well as for α-tocopherol concentrations in roes.

Fatty acid profiling in the genus Pinus in relation to its chemotaxonomy and nutritional or pharmaceutical properties.

To develop and utilize the oil of Pinus seeds and explore natural resources rich in pinolenic acid (PNLA), twenty-one Pinus taxa were evaluated in a search of Δ5-unsaturated polymethylene-interrupted fatty acids (Δ5-UPIFA)-rich oils. While the fatty acid (FA) composition was determined by GC-FID and GC-MS, NMR of crude oils proved to be a fast method for establishing the ratio between Δ5-UPIFA and total FA. For all analyzed taxa, both the geographical origin and the concentration of total FA in the seeds are provided. PNLA and sciadonic acids occurred in all samples, while taxoleic and bishomopinolenic acids were present in most taxa. PNLA reached a maximum of 28.3% of total FA in P. mugo, and P. koraiensis showed the highest total FA amount (66.8 g/100 g seeds). The previously unanalyzed taxon P. ponderosa var. scopulorum can be considered a new PNLA source (17.1%). Principal Component Analysis showed that the similarities in FA profiles allow the grouping of the various taxa within Pinus subsections and confirmed the differential metabolic activities of Δ5 and Δ9 desaturase enzymes. This study showed that several underutilized Pinus taxa could be developed into renewable woody oil species, and their seeds could be used as raw materials for Δ5-UPIFA-rich oils extraction.

Enantioselective total synthesis of putative dihydrorosefuran, a monoterpene with an unique 2,5-dihydrofuran structure.

An original synthesis of the structure of dihydrorosefuran, a compound allegedly identified in Artemisia pallens and Tagetes mendocina, has been developed. The key steps in the five-step 36% overall yield synthesis are a CpTiIIICl2 mediated Barbier-type allenylation of a linear aldehyde and the formation of a 2,5-dihydrofuran scaffold through a Ag(I)-mediated cyclization. Neither of the reported spectral data for dihydrorosefuran match those of the synthetic product, suggesting that the isolated compound from Tagetes mendocina is in fact the natural product rosiridol, while the real structure of the product from Artemisia pallens remains unknown.

Emotional intelligence abilities of caregivers of patients with acquired brain injury and cognitive impairment: are they related to overload or resilience?

Introduction: Acquired brain injury entails stressful situations of emotional complexity. Objective: To evaluate possible relationship among emotional intelligence, emotional status, resilience, and burden sensation of caregivers of patients with cognitive-behavioral impairment due to acquired brain injury in isolation circumstances because of COVID-19 pandemic. Material and methods: An observational descriptive cross-sectional study of prevalence was designed with a sample of 17 caregivers of patients with cognitive-behavioral impairment due to acquired brain injury. Main outcome measures: Caregiver Burden Interview, the 10-item Connor-Davidson Resilience Scale, Emotional Health, the Trait Meta-Mood Scale and the Positive and Negative Affect Schedule. Results: The median age of the 17 caregivers was 47.5 years, 71% of women had a median care-time of 3.5 years, and 65% of the total sample were spouses of the patients. 70% of the patients were affected by stroke (hemorrhagic or ischemic cause). 59% of the caregivers presented a low level of emotional attention and emotional clarity, and 47 %, low emotional repair ability. 82% of them did not report overload, 53% showed low resilience level. Emotional intelligence showed strong correlation with resilience and mental health of caregivers. All of them were positively correlated with daily positive emotions and negatively correlated with negative emotions and overload. Conclusions: Emotional intelligence, resilience, and mental health of caregivers are strongly correlated. All of them increase positive emotions and reduce negative emotions and overload.

Introducción: el daño cerebral adquirido crea situaciones estresantes y de gran complejidad emocional. Objetivo: evaluar relación entre inteligencia emocional, resiliencia, estado emocional y sobrecarga de los cuidadores de pacientes con daño cerebral adquirido y afectación cognitivo-conductual en circunstancias de aislamiento por pandemia COVID-19. Materiales y métodos: estudio observacional descriptivo transversal de prevalencia. Participantes: 17 cuidadores de pacientes con daño cerebral adquirido y afectación cognitivo- conductual. Principales medidas: Cuestionario sobre Carga del Cuidador, Medida de Resiliencia Connor- Davidson, Cuestionario de Salud Emocional, Escala Trait Meta-Mood y Escala de Afecto Positivo y Negativo. Resultados: mediana de edad 47,5 años, 71% mujeres, mediana de tiempo siendo cuidador 3,5 años y 65% de la muestra eran cónyuges. El 70% de los pacientes habían sufrido un ictus y el principal deterioro cognitivo de ellos, referido por familiares, fue el déficit de memoria. El 59% de los cuidadores presentó bajo nivel de atención emocional y claridad emocional, y el 47%, baja capacidad de reparación emocional. El 82% no informó sobrecarga, el 53% mostró un bajo nivel de resiliencia y un afecto positivo en el mes previo ligeramente más alto que el afecto negativo. La inteligencia emocional mostró una fuerte correlación con la resiliencia y la salud mental. Además, estas tres variables correlacionaron positivamente con las emociones positivas y negativamente con las negativas y la sobrecarga. Conclusiones: Inteligencia emocional, resiliencia y salud mental están fuertemente correlacionadas. Las tres aumentan las emociones positivas y reducen las negativas y la sobrecarga. La sobrecarga asocia peor resiliencia, reparación emocional y salud mental.

Marine Terpenic Endoperoxides.

Organic extracts of marine invertebrates, mainly sponges, from seas all over the world are well known for their high in vitro anticancer and antibiotic activities which make them promising sources of compounds with potential use as pharmaceutical leads. Most of the structures discovered so far have a peculiar structural feature in common: a 1,2-dioxane ring. This is a highly reactive heterocycle that can be considered as an endoperoxide function. Together with other structural features, this group could be responsible for the strong biological activities of the substances present in the extracts. Numerous research programs have focused on their structural elucidation and total synthesis since the seventies. As a consequence, the number of established chiral centres and the similarity between different naturally occurring substances is increasingly higher. Most of these compounds have a terpenoid nature, mainly diterpene and sesterterpene, with several peculiar structural features, such as the loss of one carbon atom. Although there are many reviews dealing with the occurrence of marine peroxides, their activities, or potential pharmaceutical uses, no one has focused on those having a terpene origin and the endoperoxide function. We present here a comprehensive review of these compounds paying special attention to their structural features and their biological activity.

Protocolo sedoanalgésico para la infiltración de toxina botulínica A en parálisis cerebral / Sedation-analgesia protocol for the injection of botulinum toxin A in cerebral palsy

Objetivo: Evaluar el impacto de la técnica sedoanalgésica en el dolor experimentado por el paciente. Métodos: Estudio transversal realizado en pacientes consecutivos con parálisis cerebral (PC) que se infiltraron con toxina botulínica A (OnabotA). Los pacientes fueron divididos en 4 grupos según la estrategia analgésica asignada: Grupo I, sin sedación o crema anestésica tópica; Grupo II, inhalación de óxido nitroso; Grupo III, sedación intravenosa profunda y Grupo IV, sedación ligera con benzodiacepinas. El dolor se evaluó con diferentes escalas según la edad del paciente. Los padres clasificaron su satisfacción con la comodidad de su hijo mediante una escala tipo Likert de 5 puntos. La variable primaria de eficacia fue la proporción de pacientes que experimentaron un nivel de dolor ≤ 2, según las escalas de dolor, en los diferentes grupos de estudio. Resultados: De los 124 pacientes incluidos en el estudio, 56 (45,2%) experimentaron un nivel de dolor ≤ 2. En el Grupo III, una proporción significativamente mayor de pacientes presentó un nivel de dolor ≤ 2, p < 0,001, en comparación con todos los grupos de estudio, respectivamente. La inyección de OnabotA fue guiada por ultrasonografía en 109 (87,9%) pacientes y por referencia anatómica en 15 (12,1%). Conclusión: En los pacientes con PC tratados con infiltraciones de OnabotA, la estrategia sedoanalgésica tuvo un impacto significativo en el dolor experimentado por el sujeto. Seleccionar una estrategia analgésica apropiada es crucial para reducir el estrés asociado con la administración de inyecciones de OnabotA en niños con PC

Objective: To evaluate the impact of the sedation-analgesia technique on the pain experienced by the patient. Methods: This cross-sectional study was conducted on consecutive patients with cerebral palsy (CP) who underwent infiltration with botulinum toxin A (BoTNA). The patients were divided into 4 different groups according to the analgesic strategy assigned: Group I, without sedation or topical anaesthetic cream; Group II, inhalation of nitrous oxide; Group III, deep intravenous sedation; and Group IV, light sedation with benzodiazepines. Pain was assessed with different scales depending on patient age. Parents were asked to rate their satisfaction with their child's comfort by using a 5-point Likert-type scale. The primary end-point was the proportion of patients that experienced a pain level equal or lower than 2, according to pain scales, in the different study groups. Results: Of the 124 patients included in the study, 56 (45.2%) experienced a pain level ≤ 2. In the Group III a significantly greater proportion of patients were classified with a pain level score ≤ 2, P < .001, as compared with all the study groups, respectively. The BoTNA injection was guided by ultrasonography in 109 (87.9%) patients, and by palpation in 15 (12.1%). Conclusion: The results of this study suggested that, in patients with CP treated with BoTNA injections, the sedation-analgesic strategy had a significant impact on the pain experienced by the subject. Selecting an appropriate analgesic strategy is crucial for reducing the stress associated with the administration of BoTNA injections in children with CP

[Sedation-analgesia protocol for the injection of botulinum toxin A in cerebral palsy]. / Protocolo sedoanalgésico para la infiltración de toxina botulínica A en parálisis cerebral.

OBJECTIVE: To evaluate the impact of the sedation-analgesia technique on the pain experienced by the patient. METHODS: This cross-sectional study was conducted on consecutive patients with cerebral palsy (CP) who underwent infiltration with botulinum toxin A (BoTNA). The patients were divided into 4 different groups according to the analgesic strategy assigned: Group I, without sedation or topical anaesthetic cream; Group II, inhalation of nitrous oxide; Group III, deep intravenous sedation; and Group IV, light sedation with benzodiazepines. Pain was assessed with different scales depending on patient age. Parents were asked to rate their satisfaction with their child's comfort by using a 5-point Likert-type scale. The primary end-point was the proportion of patients that experienced a pain level equal or lower than 2, according to pain scales, in the different study groups. RESULTS: Of the 124 patients included in the study, 56 (45.2%) experienced a pain level ≤2. In the Group III a significantly greater proportion of patients were classified with a pain level score ≤2, P<.001, as compared with all the study groups, respectively. The BoTNA injection was guided by ultrasonography in 109 (87.9%) patients, and by palpation in 15 (12.1%). CONCLUSION: The results of this study suggested that, in patients with CP treated with BoTNA injections, the sedation-analgesic strategy had a significant impact on the pain experienced by the subject. Selecting an appropriate analgesic strategy is crucial for reducing the stress associated with the administration of BoTNA injections in children with CP.

Stereoselective Barbier-Type Allylations and Propargylations Mediated by CpTiCl3.

CpTiCl2, prepared in situ by manganese reduction of CpTiCl3, is an excellent new system for the Barbier-type allylation and propargylation of carbonyl compounds. It can be used in catalytic amounts when combined with Et3N·HBr/TMSBr, which acts as a regenerating system. The high regio- and stereoselectivity shown by this system makes it useful for prenylation and crotylation processes in the synthesis of natural products.

Extrinsic bronchial obstruction caused by scoliosis.

STUDY DESIGN: A case report. OBJECTIVE: To emphasize the importance of monitoring the breathing capacity in patients with moderate to severe scoliosis, even in adulthood. SUMMARY OF BACKGROUND DATA: Diseases that disturb the structure of the chest wall affect the function of the respiratory pump. Restrictive respiratory pattern is caused by severe scoliosis. However, scoliosis may provoke obstructive changes due to compression of the airways. It can be a direct compression because of imprinting of vertebral bodies, or an indirect one, due to rotation forces. METHODS.: We have collected data from the patients' clinical history and have reviewed similar published cases. CASE PRESENTATION: a white female, with frequent respiratory tract infections during her childhood. She was diagnosed as having 55° right T5-T11 scoliosis. At age of 26, an increase of her pulmonary symptoms appeared with difficulty to expel mucus and medium efforts dyspnea. A computed axial tomographic scan showed T8 vertebral body pushing against the right intermediate bronchus. A bronchoscopy found a decrease in the bronchial area, with near contact between the walls. Lung function test: 41% forced vital capacity (FVC), 43% forced expiratory volume in 1 second (FEV1), and 91 FEV1/FVC1. The patient underwent surgical correction using rods and pedicle screws; she had improvement of symptoms, image tests, and pulmonary function (70% FVC, 71% FEV1, and 101 FEV1/FVC). CONCLUSION: Increased frequency and severity of respiratory tract infections, difficulty in expelling mucus and dyspnea are warning signs of compromised airways. Spirometry tests and image tests such as computed axial tomography and bronchoscopy are essential for diagnosis. Surgical approach may be the treatment of choice.