Absolute configuration reassignment of two chromanes from Peperomia obtusifolia (Piperaceae) using VCD and DFT calculations

Previous analysis of the ECD spectra of two prenylated benzopyrans isolated from Peperomia obtusifolia, by means of the helicity rule for the chromane chromophore, resulted in the incorrect assignment of their absolute configuration, (5) instead of (R) for a deduced P-helicity of the chromane ring for the (+)-enantiomers. This was discovered by the application of DFT calculations and VCD spectroscopy. Experimental and calculated (B3LYP/6-31G(d)) VCD and IR spectra were compared, and a definitive absolute configuration of (+)-1 and (+)-2 is reassigned directly in solution as (R). The assumption of equatorial positioning of bulky groups, shown here to be invalid for the title molecules, is the underlying cause of the previous incorrect assignment of absolute configuration. Moreover, TDDFT (B3LYP/6-311++G(2d,2p)//B3LYP/6-31G(d)) calculations of ECD spectra have shown that both P- and M-helicity of the heterocyclic ring, for a given absolute configuration, lead to the same sign for the (1)L(b) ECD band, thus bringing into question the validity of the empirical ECD helicity rule for chromane molecules. (C) 2010 Elsevier Ltd. All rights reserved.

Resolution and Absolute Configuration Assignment of a Natural Racemic Chromane from Peperomia obtusifolia (Piperaceae)

The resolution of the natural racemic chromane 3,4-dihydro-5-hydroxy-2,7-dimethyl-8-(3 ``-methyl-2 ``-butenyl)-2-(4`-methyl-1`,3`-pentadienyl)-2H-1-benzopyran-6-carboxylic acid (1) isolated from the leaves of Peperomia obtusifolia has been accomplished using stereoselective HPLC. The absolute coil figuration of the resolved enantiomers was determined by the analysis of optical rotations and CD spectra. The finding of a racemic mixture instead of an enantiomerically pure metabolite raises questions about the final steps in the biosynthesis of this class of natural products, suggesting that the intramolecular chromane ring formation step may not be enzymatically controlled at all in P. obtusifolia. Chirality 21:799-801, 2009. (C) 2008 Wiley-Liss, Inc.

(+)- and (-)-Mutisianthol: First Total Synthesis, Absolute Configuration, and Antitumor Activity

The first synthesis of the natural product (+)-mutisianthol was accomplished in 11 steps and in 21% overall yield from 2-methylanisole. The synthesis of its enantiomer was also performed in a similar overall yield. The absolute configuration of the sesquiterpene (+)-mutisianthol was assigned as (1S,3R). Key steps in the route are the asymmetric hydrogenation of a nonfunctionalized olefin using chiral iridium catalysts and the ring contraction of 1,2-dihydronaphthalenes using thallium(III) or iodine(III). The target molecules show moderate activity against the human tumor cell lines SF-295, HCT-8, and MDA-MB-435.

Absolute Configuration and Selective Trypanocidal Activity of Gaudichaudianic Acid Enantiomers

Gaudichaudianic acid, a prenylated chromene isolated from Piper gaudichaudianum, has been described as a potent trypanocidal compound against the Y-strain of Trypanosoma cruzi. We herein describe its isolation as a racemic mixture followed by enantiomeric resolution using chiral HPLC and determination of the absolute configuration of the enantiomers as (+)-S and (-)-R by means of a combination of electronic and vibrational circular dichroism using density functional theory calculations. Investigation of the EtOAc extract of the roots, stems, and leaves from both adult specimens and seedlings of P. gaudichaudianum revealed that gaudichaudianic acid is biosynthesized as a racemic mixture from the seedling stage onward. Moreover, gaudichaudianic acid was found exclusively in the roots of seedlings, while it is present in all organs of the adult plant. Trypanocidal assays indicated that the (+)-enantiomer was more active than its antipode. Interestingly, mixtures of enantiomers stowed a synergistic effect, with the racemic mixture being the most active.

Model Configuration And Data Management In The Short-Term Water Information Forecasting Tools

The Short-term Water Information and Forecasting Tools (SWIFT) is a suite of tools for flood and short-term streamflow forecasting, consisting of a collection of hydrologic model components and utilities. Catchments are modeled using conceptual subareas and a node-link structure for channel routing. The tools comprise modules for calibration, model state updating, output error correction, ensemble runs and data assimilation. Given the combinatorial nature of the modelling experiments and the sub-daily time steps typically used for simulations, the volume of model configurations and time series data is substantial and its management is not trivial. SWIFT is currently used mostly for research purposes but has also been used operationally, with intersecting but significantly different requirements. Early versions of SWIFT used mostly ad-hoc text files handled via Fortran code, with limited use of netCDF for time series data. The configuration and data handling modules have since been redesigned. The model configuration now follows a design where the data model is decoupled from the on-disk persistence mechanism. For research purposes the preferred on-disk format is JSON, to leverage numerous software libraries in a variety of languages, while retaining the legacy option of custom tab-separated text formats when it is a preferred access arrangement for the researcher. By decoupling data model and data persistence, it is much easier to interchangeably use for instance relational databases to provide stricter provenance and audit trail capabilities in an operational flood forecasting context. For the time series data, given the volume and required throughput, text based formats are usually inadequate. A schema derived from CF conventions has been designed to efficiently handle time series for SWIFT.

Testicular arteries systematization based on different levels of scrotal configuration in caprines

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

A doorway to Borromean halo nuclei: the Samba configuration

We exploit the possibility of new configurations in three-body halo nuclei, Samba type (the neutron-core form a bound system) as a doorway to Borromean systems. The nuclei Be-12, B-15, N-23 and F-27 are of such nature, in particular N-23 with a half-life of 37.7 s and a halo radius of 6.07 fm is an excellent example of Samba-halo configuration. The fusion below the barrier of the Samba halo nuclei with heavy targets could reveal the so far elusive enhancement and a dominance of one-neutron over two-neutron transfers, in contrast to what was found recently for the Borromean halo nucleus He-6 + U-238.

Resistivity in the dynamic current sheath of a field reversed configuration

The resistivity of a field reversed configuration in a theta-pinch with slow rising current was investigated during the turbulent phase from the moment of field reversal until end of plasma radial implosion. This transport coefficient was obtained in a hydrogen plasma by local measurements with magnetic probe and compared to numerical calculations with Chodura resistivity and evolution of lower hybrid drift instability. The values of resistivity are higher than those predicted by classical binary collision. During early phase of confinement, the doubly layer structure of current sheath in the low electric field machine was theoretically well reproduced with anomalous collision frequency calculated with Chodura resistivity that provides appropriate conditions for onset of lower hybrid drift instability and the regular evolution of pinch. The plasma dynamic, radial profiles of magnetic field during the radial compression and resistivity values were equally close to those observed by the measurements. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.3698405]

Neural network based on adaptive resonance theory with continuous training for multi-configuration transient stability analysis of electric power systems

This work presents a methodology to analyze electric power systems transient stability for first swing using a neural network based on adaptive resonance theory (ART) architecture, called Euclidean ARTMAP neural network. The ART architectures present plasticity and stability characteristics, which are very important for the training and to execute the analysis in a fast way. The Euclidean ARTMAP version provides more accurate and faster solutions, when compared to the fuzzy ARTMAP configuration. Three steps are necessary for the network working, training, analysis and continuous training. The training step requires much effort (processing) while the analysis is effectuated almost without computational effort. The proposed network allows approaching several topologies of the electric system at the same time; therefore it is an alternative for real time transient stability of electric power systems. To illustrate the proposed neural network an application is presented for a multi-machine electric power systems composed of 10 synchronous machines, 45 buses and 73 transmission lines. (C) 2010 Elsevier B.V. All rights reserved.

Influence of microgap location and configuration on the periimplant bone morphology in submerged implants. An experimental study in dogs

Objectives: The vertical location of the implant-abutment connection influences the periimplant bone morphology. It is unknown, however, whether different microgap configurations cause different bone reactions. Therefore, in this study the bone morphologies of two different implant systems were compared.Material and methods: Three months after tooth extraction in eight mongrel dogs, two grit-blasted screw implants with internal Morse taper connection (ANK group) were placed on one side whereas the contralateral side received two oxidized screw implants with external hex (TIU group). One implant on each side was placed level with the bone (equicrestal), the second implant was inserted 1.5mm below bone level (subcrestal). After 3 months the implants were uncovered. Three months after stage two surgery, histometrical evaluations were performed in order to assess the periimplant bone levels (PBL), the first bone-to-implant contact points (BICP), the width (HBD) and the steepness (SLO) of the bone defect.Results: All implants osseointegrated clinically and histologically. Bone overgrowth of the microgap was seen in ANK implants only. No significant differences between ANK and TIU could be detected in neither vertical position for PBL and BICP. However, a tendency in favor of ANK was visible when the implants were placed subcrestally. In the parameters HBD (ANK equicrestal -0.23mm; TIU equicrestal -0.51mm; ANK subcrestal +0.19mm; TIU subcrestal -0.57mm) and SLO (ANK equicrestal 35.36 degrees; TIU equicrestal 63.22 degrees; ANK subcrestal 20.40 degrees; TIU subcrestal 44.43 degrees) more pronounced and significant differences were noted.Conclusions: Within the limits of this study, it is concluded that different microgap designs cause different shapes and sizes of the periimplant ('dish-shaped') bone defect in submerged implants both in equicrestal and subcrestal positions.

Influence of Microgap Location and Configuration on Radiographic Bone Loss Around Submerged Implants: An Experimental Study in Dogs

Purpose: The vertical location of the implant-abutment connection influences the subsequent reaction of the peri-implant bone. It is not known, however, whether any additional influence is exerted by different microgap configurations. Therefore, the radiographic bone reactions of two different implant systems were monitored for 6 months. Materials and Methods: In eight mongrel dogs, two implants with an internal Morse-taper connection (INT group) were placed on one side of the mandible; the contralateral side received two implants with an external-hex connection (EXT group). on each side, one implant was aligned at the bone level (equicrestal) and the second implant was placed 1.5 mm subcrestal. Healing abutments were placed 3 months after submerged healing, and the implants were maintained for another 3 months without prosthetic loading. At implant placement and after 1, 2, 3, 4, 5, and 6 months, standardized radiographs were obtained, and peri-implant bone levels were measured with regard to microgap location and evaluated statistically. Results: All implants osseointegrated clinically and radiographically. The overall mean bone loss was 0.68 +/- 0.59 mm in the equicrestal INT group, 1.32 +/- 0.49 mm in the equicrestal EXT group, 0.76 +/- 0.49 mm in the subcrestal INT group, and 1.88 +/- 0.81 mm in the subcrestal EXT group. The differences between the INT and EXT groups were statistically significant (paired t tests). The first significant differences between the internal and external groups were seen at month 1 in the subcrestal groups and at 3 months in the equicrestal groups. Bone loss was most pronounced in the subcrestal EXT group. Conclusions: Within the limits of this study, different microgap configurations can cause different amounts of bone loss, even before prosthetic loading. Subcrestal placement of a butt-joint microgap design may lead to more pronounced radiographic bone loss. INT J ORAL MAXILLOFAC IMPLANTS 2011;26:941-946