Diterpenos tipo abietano isolados de Plectranthus barbatus Andrews

Plectranthus barbatus is largely used in the Northeast region of Brazil by the local population for treatment of digestive problems as substitute of boldo (Pneumus boldus). Phytochemical analysis of the leaf extracts of Plectranthus barbatus (Labiatae) cultivated in this region yielded two abietane diterpenoids, cyclobubatusin (1) and barbatusin (2) and a new one named 7beta-acetyl-12-deacetoxycyclobutatusin (3). The structures of the isolated compounds were established by spectral analysis, using mainly mass spectra and ¹H and 13CNMR (1D and 2D). These procedures permitted the assignment of all chemical shifts in the diterpenoids.

Sobre uma degenerescência acidental nos deslocamentos químicos de RMN de 31P{¹H} em complexos difosfínicos de rutênio

The [RuCl(bipy)(dppb)(4-pic)]PF6 complex was prepared and fully characterized. The X-ray crystal structure of this complex was determined in order to make an unambiguous distinction between the two possible positions of the 4-methylpyridine ligand (4-pic) in the compound: trans to phosphorus atom or trans to nitrogen atom. The [RuCl(bipy)(dppb)(4-pic)]PF6 complex exhibits an unusual temperature-dependent accidental degeneracy of the 31P chemical shifts in its solution NMR spectrum.

Effect of temperature on the electro-oxidation of ethanol on platinum

We present in this work an experimental investigation of the effect of temperature (from 25 to 180 ºC) in the electro-oxidation of ethanol on platinum in two different phosphoric acid concentrations. We observed that the onset potential for ethanol electro-oxidation shifts to lower values and the reaction rates increase as temperature is increased for both electrolytes. The results were rationalized in terms of the effect of temperature on the adsorption of reaction intermediates, poisons, and anions. The formation of oxygenated species at high potentials, mainly in the more diluted electrolyte, also contributes to increase the electro-oxidation reaction rate.

Characterization of the antibiotic doripenem using physicochemical methods: chromatography, spectrophotometry, spectroscopy and thermal analysis

Doripenem was characterized through physicochemical and spectroscopic techniques, as well as thermal analysis. TLC (Rf = 0.62) and HPLC (rt = 7.4 min) were found to be adequate to identify the drug. UV and infrared spectra showed similar profile between doripenem bulk and standard. The ¹H and 13C NMR analysis revealed chemical shifts that allowed identifying the drug. Thermal analysis demonstrated three steps with mass loss, at 128, 178 and 276 ºC. The work was successfully applied to qualitative analysis of doripenem, showing the reported methods can be used for physicochemical characterization of doripenem

A regra de Bent contextualiza a força da ligação de hidrogênio em clusters trimoleculares

This article presents a theoretical study of the molecular properties of trimolecular clusters of CnHm∙∙∙HCN∙∙∙HX formed by the ϖ∙∙∙H and n∙∙∙H hydrogen bonds. The interaction strengths of these interactions are in line with the variations in s-character, and independently, the red-shift rise whether stronger or weaker bound systems are carried out. This behavior was justified via NBO analysis and supported by Bent´s rule, wherein the greater variations in s-character of X are in good agreement with larger red-shifts and vice-versa. To conclude, the refinement of the supermolecule approach and NBO binding energies also corroborate in this regard.

Modulating the electronic structure of amino acids: interaction of model lewis acids with anthranilic acid

On the basis of theoretical B3LYP calculations, Yáñez and co-workers (J. Chem. Theory Comput. 2012, 8, 2293) illustrated that beryllium ions are capable of significantly modulating (changing) the electronic structures of imidazole. In this computational organic chemistry study, the interaction of this β-amino acid and five model Lewis acids (BeF1+, Be2+, AlF2(1+), AlF2+, and Al3+) were investigated. Several aspects were addressed: natural bond orbitals, including second order perturbation analysis of intra-molecular charge delocalization and the natural population analysis atomic charges; molecular geometries; selected infrared stretching frequencies (C-N, C-O, and N-H), and selected ¹H-NMR chemical shifts. The data illustrate that this interaction can weaken the H-O bond and goes beyond strengthening the intra-molecular hydrogen bond (N...H-O) to cause a spontaneous transfer of the proton to the nitrogen atom in five cases generating zwitterion structures. Many new features are observed. Most importantly, the zwitterion structures include a stabilizing hydrogen bond (N-H...O) that varies in relative strength according to the Lewis acid. These findings explain the experimental observations of α-amino acids (for example: J. Am. Chem. Soc. 2001, 123, 3577) and are the first reported fundamental electronic structure characterization of β-amino acids in zwitterion form.

A FORMAÇÃO DE LIGAÇÕES DE HIDROGÊNIO π‧‧‧H, F‧‧‧H E C‧‧‧H NOS COMPLEXOS C2H2‧‧‧(HF), C2H2‧‧‧2(HF) E C2H2‧‧‧3(HF)

In this work, a theoretical study on the basis of structural, vibrational, electronic and topological parameters of the C2H2‧‧‧(HF), C2H2‧‧‧2(HF) and C2H2‧‧‧3(HF) complexes concerning the formation of π‧‧‧H, F‧‧‧H and C‧‧‧H hydrogen bonds is presented. The main difference among these complexes is not properly the interaction strength, but the hydrogen bond type whose benchmark is ruled justly by the structure. Meanwhile, the occurrence of π‧‧‧H hydrogen bonds was unveiled in both C2H2‧‧‧(HF) dimer and C2H2‧‧‧3(HF) tetramer, although in latter, this interaction is stronger than C‧‧‧H of the C2H2‧‧‧2(HF) trimer. However, the F‧‧‧H hydrogen bonds within the subunits of hydrofluoric acid are the strongest ones, reaching a partial covalent limit, and thereby contribute decisively to the stabilization of the tetramer structure. In line with this, the largest red-shifts were observed on the hydrofluoric acid trimer of the C2H2‧‧‧3(HF) complex.

Evaluation of group electronegativities and hardness (softness) of group 14 elements and containing functional groups through density functional theory and correlation with NMR spectra data

Quantum Chemical calculations for group 14 elements of Periodic Table (C, Si, Ge, Sn, Pb) and their functional groups have been carried out using Density Functional Theory (DFT) based reactivity descriptors such as group electronegativities, hardness and softness. DFT calculations were performed for a large series of tetracoordinated Sn compounds of the CH3SnRR'X type, where X is a halogen and R and R' are alkyl, halogenated alkyl, alkoxy, or alkyl thio groups. The results were interpreted in terms of calculated electronegativity and hardness of the SnRR'X groups, applying a methodology previously developed by Geerlings and coworkers (J. Phys. Chem. 1993, 97, 1826). These calculations allowed to see the regularities concerning the influence of the nature of organic groups RR' and inorganic group X on electronegativities and hardness of the SnRR'X groups; in this case, it was found a very good correlation between the electronegativity of the fragment and experimental 119Sn chemical shifts, a property that sensitively reflects the change in the valence electronic structure of molecules. This work was complemented with the study of some compounds of the EX and ER types, where E= C, Si, Ge, Sn and R= CH3, H, which was performed to study the influence that the central atom has on the electronegativity and hardness of molecules, or whether these properties are mainly affected for the type of ligand bound to the central atom. All these calculations were performed using the B3PW91 functional together with the 6-311++G** basis set level for H, C, Si, Ge, F, Cl and Br atoms and the 3-21G for Sn and I atoms.

Cirurgia de tikhoff-linberg para tratamento de condrossarcoma localmente avançado da região escápulo-umeral

Chondrosarcoma is a rare malignant neoplasia that most of the time affects young adults. Its location is preferentially the pelvic and scapular girdle and surgery is its treatment of choice. There are no role for chemo or radiation therapy, because of their low index of response. We describe a case of a 45 year-old male patient with an extensive low grade right umerus chondrosarcoma. In spite of the local extension, there was no invasion of the shoulder neurovascular structures. Treatment proposed was the Tikhoff-Linberg procedure, and the operation was performed with success, with no complications. Free margins were obtained. The patient is now on two years follow-up with no evidence of recurrent disease and is able to drive, fish and carry packs. He can not abduct his arm, but he could not do that even before surgery, due to severe pain. We believe this is an excellent conservative approach to such tumors, that otherwise would require a forequarter amputation, and strongly recommend the technique.

Amputação interescapulotorácica sob anestesia locorregional

Forequarter amputations are an uncommon option for the treatment of upper limb and shoulder girdle tumors nowadays. This procedure can be done by different approaches and general anesthesia is commonly used. The authors report a case of forequarter amputation by the posterior approach performed for treatment of a soft-tissue sarcoma under a brachial plexus block associated with venous sedation and local anesthesia.

Medico-legal litigation in Obstetrics: a characterization analysis of a decade in Portugal

PURPOSE: It was to analyse the most critical areas in Obstetrics and to suggest measures to reduce or avoid the situations most often involved in these disputes. METHODS: Obstetrics cases submitted to the Medico-legal Council since the creation of the National Institute of Legal Medicine and Forensic Sciences in 2001 until 2011 were evaluated. A comprehensive characterization, determination of absolute/relative frequencies, hypothesis of a linear trend over the years and the association between each parameter was done. RESULTS: The analysis has shown no significantly linear trend. The most common reasons for disputes were perinatal asphyxia (50%), traumatic injuries of the newborn (24%), maternal sequelae (19%) and issues related to prenatal diagnosis and/or obstetric ultrasound (5.4%). Perinatal asphyxia showed no significantly linear trend (p=0.58) and was usually related to perinatal deaths or permanent neurologic sequelae in newborn children. Traumatic injuries of the newborn, mostly related to instrumented deliveries, shoulder dystocia or vaginal delivery in breech presentation, has shown a significantly increased linear trend (p<0.001), especially related to instrumented deliveries. The delay/absence of cesarean section was the clinical procedure questioned in a significantly higher number of cases of perinatal asphyxia (68.7%) and of traumatic lesions of the newborn due to instrumented deliveries (20.5%). CONCLUSION: It is important to improve and correct theoretical/practical daily clinical performance in these highlighted areas, in order to reduce or even avoid situations that could end up in medico-legal litigations.

Influence of the bipartite scrotum on the testicular and scrotal temperatures in goats

The influence of the scrotal bipartition and of the year period on the scrotal-testicular thermal regulation was evaluated in male goats raised in Piaui State, Brazil. Eighteen male goats at mating age were accomplished in this study and arranged into three Groups (6 animals each) obeying the classification as goats presenting no scrotal bipartition (Group I), goats showing scrotal bipartition at 50% of the testicular length (Group II), and goats with more than 50% of scrotal bipartition (Group III). The scrotal, testicular and spermatic funiculi temperatures were evaluated invasively with the aid of a digital thermometer and non-invasive with a pyrometer in the proximal, medial and distal portion. The data were acquired during the dry (October-November) and rainy (February-March) period of the year, measured in two shifts: morning (6h00-7h00) and afternoon (14h00-15h00). The results were submitted to variance analysis (ANOVA) following the SNK test for average comparison (p<0.05). The year period interfered on the scrotal-testicular thermal regulation, due to increased temperatures of the scrotal, testicular and spermatic funiculi during the dry period in comparison with the rainy period. The bipartition level was also a factor which contributed to the influence of scrotal-testicular temperature regulation, due to lower average scrotal-testicular temperature rates observed during both periods in the goats with higher levels of scrotal bipartition (>50%). It is possible to conclude that with the experimental conditions applied on this study, the level of scrotal bipartition and the climatic conditions interfere with the scrotal-testicular thermal regulation in goats.

Kinematic gait analyses in healthy Golden Retrievers

Kinematic analysis relates to the relative movement between rigid bodies and finds application in gait analysis and other body movements, interpretation of their data when there is change, determines the choice of treatment to be instituted. The objective of this study was to standardize the march of Dog Golden Retriever Healthy to assist in the diagnosis and treatment of musculoskeletal disorders. We used a kinematic analysis system to analyse the gait of seven dogs Golden Retriever, female, aged between 2 and 4 years, weighing 21.5 to 28 kg, clinically normal. Flexion and extension were described for shoulder, elbow, carpal, hip, femorotibialis and tarsal joints. The gait was characterized lateral and had accepted hypothesis of normality for all variables, except for the stance of hip and elbow, considering a confidence level of 95%, significance level α = 0.05. Variations have been attributed to displacement of the stripes during movement and the duplicated number of reviews. The kinematic analysis proved to be a consistent method of evaluation of the movement during canine gait and the data can be used in the diagnosis and evaluation of canine gait in comparison to other studies and treatment of dogs with musculoskeletal disorders.

Variations in weed population densities, rate of change and community diversity in RR-soybeans and RR-maize strip crops under two herbicide strategies

Concerns about the sustainability of large-scale, direct-drilled RR-soybeans (Glycine max), and RR-maize (Zea mays) under monoculture in central Argentina are growing steadily. An experiment was conducted during three consecutive years to determine the effects of crops and systems (monocultures and strips) and herbicide strategy on weed density, population rate of change (l), b community diversity (H´), crop yields and Land Equivalent Ratio (LER). Not only crops but also crop systems differentially influenced weed densities along their growth and development. For crop harvests, weed densities increased in both maize crop systems as compared to in the one for soybeans, but the lowest increase occurred in soybean strips. Differences were leveled by both herbicide strategies, which achieved 73% efficacy during the critical periods in both crops. l of annual monocotyledonous increased, thus shifting the weed community composition. Species richness and H´ were not affected by crop systems, but both herbicide strategies, particularly POST, either in soybeans in monoculture or in maize strips, significantly enhanced H´. Crop yields significantly increased in the maize-strip system with POST (Year 1) or PRE (Years 2 and 3) strategies, thus increasing LER above 1. Herbicide Environmental Load treatments fall within very low or low field use rating.

Juvenile dynamics of the endemic and rare Enterolobium glaziovii Benth. (Mimosaceae) around reproductive trees in the Atlantic forest, Brazil

Studies on the regeneration and seedling mortality of rare tree species are important, but scarce. The aim of this study was to investigate the annual variation in recruitment, growth and mortality of juveniles of Enterolobium glaziovii Benth., a rare tree species from the Brazilian Atlantic Rain Forest. All seedlings and juveniles around four reproductive trees were labeled and their fate was followed from 1996 to 1999. There were no annual differences in juveniles' recruitment below and beyond the parental crown, but juveniles' survival and growth were lower below than beyond of the parental tree crowns. Small individuals (< 15 cm tall) showed the greatest mortality and the lowest growth, followed by medium (from 15 to 50 cm tall) and large ones (> 50 cm tall). Large juveniles were more widely dispersed from the conspecific parental tree than were medium and small ones. This suggests that distance dependent mortality of juveniles mediated by the parental tree is an important cause of spacing shifts associated with the growth of small individuals of E. glaziovii into large ones. Widely dispersed juveniles may escape the high mortality associated with pathogens, herbivores or seed predators concentrated around adult conspecifics. The negative influence of the parental tree on its juveniles may explain the sparse distribution of its adults in the forest.