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.

Selective Allylic oxidation of Cyclohexene by a Magnetically Recoverable Cobalt Oxide Catalyst

In this work, we prepared a new magnetically recoverable CoO catalyst through the deposition of the catalytic active metal nanoparticles of 2-3 nm on silica-coated magnetite nanoparticles to facilitate the solid separation from liquid media. The catalyst was fully characterized and presented interesting properties in the oxidation of cyclohexene, as for example, selectivity to the allylic oxidation product. It was also observed that CoO is the most active species when compared to Co(2+), Co(3)O(4) and Fe(3)O(4) in the catalytic conditions studied.

Electrocatalytic behavior of glassy carbon electrodes modified with multiwalled carbon nanotubes and cobalt phthalocyanine for selective analysis of dopamine in presence of ascorbic acid

This work describes the development, electrochemical characterization and utilization of a cobalt phthalocyanine modified carbon nanotube electrode for the quantitative determination of dopamine in 0.2 mol L-1 phosphate buffer contaminated with high concentration of ascorbic acid. The electrode surface was analyzed by cyclic voltammetry and electrochemical impedance spectroscopy which showed a modified surface presenting a charge transfer resistance of 500 Omega, against the 16.46 k Omega value found for the bare glassy carbon surface. A pseudo rate constant value of 5.4 x 10(-4) cm s(-1) for dopamine oxidation was calculated. Voltammetric experiments showed a shift of the peak potential of DA oxidation to less positive value at 390 mV as compared with that of a bare GC electrode at 570 mV. The electrochemical determination of dopamine, in presence of ascorbic acid in concentrations up to 0.1 mol L-1 by differential pulse voltarnmetry, yielded a detection limit as low as 2.56 x 10(-7) mol L-1.

Selective photoinactivation of C. albicans and C. dubliniensis with hypericin

The genus Candida includes different species that have the potential to invade and colonize the human body and C. albicans is the most common cause of skin, nail and mucous infections. The increasing resistance against antifungal drugs has renewed the search for new treatment procedures and antimicrobial photodynamic inactivation (PDI) is a propitious candidate. Hypericin (HY) has several wanted properties to be used as a photosensitizer in this technique including a high quantum yield of singlet oxygen generation, a high extinction coefficient near 600 nm, and a relatively low dark toxicity. Although the phototoxicity of HY on several tumor cells has been reported, the data concerning its photoactivity on microorganisms are scarce. The aim of this study was to obtain the experimental parameters to achieve an acceptable selective hypericinphotoinactivation of two species of Candida comparing with fibroblasts and epithelial cells which are the constituents of some potential host tissues, such mucosas, skin and cavities. Microorganisms and cells were incubated with the same HY concentrations and short incubation time followed by irradiation with equal dose of light. The best conditions to kill just Candida were very low HY concentration (0.1-0.4 mu g ml(-1)) incubated by 10 min and irradiated with LED 590 nm with 6 J cm(-2).

Development and Application of a Highly Selective Biomimetic Sensor for Detection of Captopril, an Important Ally in Hypertension Control

A biomimetic sensor is proposed as a promising new analytical method for determination of captopril in different classes of samples. The sensor was prepared by modifying a carbon paste electrode with iron (II) phthalocyanine bis(pyridine) [FePe(dipy)] complex. Amperometric measurements in a batch analytical mode were first carried out in order to optimize the sensor response. An applied potential lower than 0.2 V vs Ag vertical bar AgCl in 0.1 mol L(-1) of TRIS buffer at pH 8.0 provided the best response, with a linear range of 2.5 x 10(-5) to 1.7 x 10(-4) mol L(-1). A detailed investigation of the selectivity of the sensor, employing seventeen other drugs, was also performed. Recovery studies were carried out using biological and environment samples in order to evaluate the sensor`s potential for use with these sample classes. Finally, the performance of the biomimetic sensor was optimized in a flow injection (FIA) system using a wall jet electrochemical cell. Under optimized flow conditions, a broad linear response range, from 5.0 x 10(-4) to 2.5 x 10(-2) mol L(-1), was obtained for captopril, with a sensitivity of 210 +/- 1 mu A L mol(-1).

Fast separation of selective serotonin reuptake inhibitors antidepressants in plasma sample by nonaqueous capillary electrophoresis

A simple, fast, and sensitive liquid-liquid extraction method followed by nonaqueous capillary electrophoresis (LLE/NACE) was developed and validated for Simultaneous determination of four antidepressants (fluoxetine, sertraline, citalopram and paroxetine) in human plasma. Several experimental separation conditions using aqueous and nonaqueous media separation were tested by varying the electrolyte pH value (for aqueous medium) and the ionic strength concentration considering the similar mobility of the compounds. High-resolution separation was achieved with a mixture of 1.25 mol L(-1) of phosphoric acid in acetonitrile. The quantification limits of the LLE/CE method varied between 15 and 30 ng mL(-1), with a relative standard deviation (RSD) lower than 10.3%. The method was successfully applied in therapeutic drug monitoring and should be employed in the evaluation of plasma levels in urgent toxicological analysis. (C) 2009 Elsevier B.V. All rights reserved.

Immobilized analogues of sunflower trypsin inhibitor-1 constitute a versatile group of affinity sorbents for selective isolation of serine proteases

Sunflower trypsin inhibitor-1 (SFI-1), a natural 14-residue cyclic peptide, and some of its synthetic acyclic variants are potent protease inhibitors displaying peculiar inhibitory profiles. Here we describe the synthesis and use of affinity sorbents prepared by coupling SFTI-1 analogues to agarose resin. Chymotrypsinand trypsin-like proteases could then be selectively isolated from pancreatin; similarly, other proteases were obtained from distinct biological sources. The binding capacity of [Lys5]-SFTI-1-agarose for trypsin was estimated at over 10 mg/mL of packed gel. SFTI-1-based resins could find application either to improve the performance of current purification protocols or as novel protease-discovery tools in different areas of biological investigation. (C) 2009 Elsevier B.V. All rights reserved.

New 2,N6-Disubstituted adenosines: Potent and selective A1 adenosine receptor agonists

A number of adenosine analogues substituted in the 2- and N⁶-positions were synthesized and evaluated for affinity, functional potency and intrinsic activity at the A₁ and A_2A adenosine receptors (AR). Three classes of N⁶-substituents were tested; norbornen-2-yl (series 1), norborn-2-yl (series 2) and 5,6-epoxynorborn-2-yl (series 3). The halogens; fluoro, bromo, and iodo were evaluated as C-2 substituents. All compounds showed relatively high affinity (nanomolar) for the A₁AR and high potency for inhibiting (−)isoproterenol-stimulated cAMP accumulation in hamster smooth muscle DDT1 MF-2 cells with the 2-fluoro derivatives from each series having the highest affinity. All of the derivatives showed the same intrinsic activity as CPA. At the A2AAR, all of the derivatives showed relatively low affinity and potency (micromolar) for stimulating cAMP accumulation in rat pheochromocytoma PC-12 cells. The intrinsic activity of the derivatives compared to CGS 21680 was dependent upon the halogen substituent in the C-2 position with most showing partial agonist activity. Of particular interest is 2-iodo-N⁶-(2S-endo-norborn-2-yl)adenosine (5e), which is over 100-fold selective for the A₁AR, is a full agonist at this receptor subtype and has no detectable agonist activity at the A_2AAR.

Selective determination of amino acids using flow injection analysis coupled with chemiluminescence detection

The determination of the amino acids proline, histidine, tyrosine, arginine, phenylalanine and tryptophan using flow injection analysis (FIA) with chemiluminescence detection is described. Proline was the only amino acid to exhibit chemiluminescence with the tris(2,2-bipyridyl)ruthenium(III) reaction at pH 10. While, histidine was found to selectively enhance the reaction of luminol with Mn(II) salts in a basic medium. Acidic potassium permanganate chemiluminescence was able to selectively determine tyrosine at pH 6.75. Low pressure separations using a C18 guard column allowed the simultaneous determination of tyrosine and tryptophan or phenylalanine and tryptophan with acidic potassium permanganate and copper(II)–amino acid–hydrogen peroxide chemiluminescence, respectively. Precision for each method was less than 3.9% (R.S.D.) for five replicates of a standard (1×10−5 M) and the detection limits ranged between 4×10−9 and 7×10−6 M. Preliminary investigations revealed that the methodology developed was able to selectively determine the individual amino acids in an equimolar mixture of the 20 naturally occurring amino acids.

Comparative analysis of two selective bleaching methods on alpaca fibers

Dark brown Alpaca fiber was reduced in shade via selective bleaching with peroxide. Two selective oxidative bleaching methods were tested on alpaca top to assess their effectiveness for color removal and fiber quality properties. Color change, bundle strength, weight loss, fiber diameter, surface modification, dye-ability and dye wash fastness were assessed for both methods and compared with the original brown top. Bleach method 1 (BL-I) showed little surface modification, 5.8 % weight loss and 2.4 % strength loss. D1925 yellowness index was reduced to 74.3 from 83.1 and provided a good base for the dyeing of medium to deep shades. Bleach method 2 (BL-II) displayed considerable surface modification, 7.8 % weight loss and 18 % strength loss. BL-II also resulted in a mean diameter reduction of 1.9 micron during bleaching. Yellow-ness was reduced to 64.5 from 83.1 and provided a very good base for the dyeing of medium to deep shades. BL-I showed better exhaustion of the pre-metallised dye Lanaset Violet B than BL-II. Wash fastness for BL-II was 1 grey scale unit poorer than BL-I. BL-II showed far better color clarity at pale depths however the wash fastness of the finished product was not good enough to maintain the depth or clarity of the color. BL-I showed poorer clarity of color but exhibited better wash fastness results.

On the production of randomly-oriented recrystallization nuclei for selective growth experiments

The ideal starting condition for selective growth experiments is one having a layer of randomly-oriented nuclei adjacent to a matrix with negligible orientational variation but sufficient stored energy to promote growth. In practice, cutting or deformation processes are used in an attempt to approximate these ideal conditions, but the degree to which this is achieved has not been rigorously quantified. In this work, Fe-3wt%Si single crystals were cut or deformed using six different processes. The variation in texture with distance from the cut or deformed surface was measured using electron backscatter diffraction (EBSD) in a field emission gun scanning electron microscope (FEG-SEM) in order to assess the ability of each process to create conditions suitable for selective growth experiments. While grooving with a machine tool produced the best spread of orientations at the cut surface, the suitability of this process is diminished by the presence of a differently-textured deformed layer between the cut surface and the single crystal matrix. Grinding produced a less ideal distribution of orientations at the cut surface, but the presence of these orientations in a very thin layer adjacent to the matrix makes this process preferable for preparing crystals for selective growth experiments, provided the results are corrected for the deviation in the distribution of nuclei orientations from a random distribution.

The trouble with woon: the selective answering of police questions and the right to pre-trial silence

The 1964 High Court decision in Woon v The Queen is commonly understood to permit the drawing of an inference of a ‘consciousness of guilt’ when a suspect selectively responds to police questions. It is the author’s contention that, in the light of the emphatic endorsement of the right to pre-trial silence by the High Court in 1993 in Petty v The Queen; Maiden v The Queen, Woon should now be regarded as bad law and should no longer be followed.

Polyhedral combinatorics of the cardinality constrained quadratic knapsack problem and the quadratic selective travelling salesman problem

This paper considers the Cardinality Constrained Quadratic Knapsack Problem (QKP) and the Quadratic Selective Travelling Salesman Problem (QSTSP). The QKP is a generalization of the Knapsack Problem and the QSTSP is a generalization of the Travelling Salesman Problem. Thus, both problems are NP hard. The QSTSP and the QKP can be solved using branch-and-cut methods. Good bounds can be obtained if strong constraints are used. Hence it is important to identify strong or even facet-defining constraints. This paper studies the polyhedral combinatorics of the QSTSP and the QKP, i.e. amongst others we identify facet-defining constraints for the QSTSP and the QKP, and provide mathematical proofs that they do indeed define facets.

Selective feeding centres in refugee settings: evaluation framework protocol

Selective feeding programs are centres for the treatment of persons suffering from acute malnutrition. Unlike chronic malnutrition, acute malnutrition reflects recent problems. In a crisis situation, wasting is preferred above other indicators because it is sensitive to rapid change, indicates present change, can be used to monitor the impact of interventions and is a good predictor of immediate mortality risk. This paper reviews the current approach being used in the field to evaluate the effectiveness of feeding programs. There is no comprehensive evaluation framework in place to assess the impact of feeding programs on mortality due to malnutrition. Some loose outcome measures, such as the number of children enrolled in a feeding centre, are being used to determine if a feeding centre should continue. In addition, malnutrition prevalence and crude mortality rates determined through nutritional and mortality surveys are used to assess the impact of feeding programs. This procedure does not take into account potential confounding factors that impact on malnutrition prevalence, including access to non-relief foods and the general food ration. Therefore, one could not confidently say that the reduction of malnutrition prevalence is a result of feeding programs. This paper presents an alternative approach to evaluating feeding centres.

The case for selective ICT outsourcing : it`s easier for "green field" sites

This paper examines published research on Information and Communications Technology (ICT) Outsourcing and uses this as a framework through which to examine the delivery of ICT services at the South West Alliance of Rural Hospitals, an environment not without challenges. Right from the beginning the CIO appointed to the Alliance decided to address these challenges by implementing a high speed telecommunications network to reduce the costs of data, voice and video communications within the Alliance. The emergence of the truly virtual health care network in Victoria’s South West supported by external service providers but managed by a small yet powerful central ICT team holds a number of useful lessons for the delivery of services in start up cooperative organizations, particularly regional, rural and remote (R3) organizations.