A Convenient Method for the Preparation of 6,7-Methyl-Enedioxy-3-Alkyl-2-Hydroxy-1,4-Naphthoquinones from Natural Safrole and Carboxylic Acids

As part of our program to prepare substituted rtaphthoquinones with potential biological activity¹ we have synthetized 6, 7-methyleriedioxy-3-alky 1 lawsones (5a-g) from natural safrole (1) and carboxylic' acids (～50% overall yield).     

Removal efficiency of 75Se, 51Cr and 60Co from tidal water by mangrove sediments from Sepetiba Bay (SE Brazil)

Mangrove sediment cores sampled from Sepetiba Bay (SE Brazil) were covered with tidal water spiked with ⁷⁵Se, ⁵¹Cr and ⁶⁰Co to evaluate the removal efficiency of these radiotracers by underlying sediments. Variable time-evolution trends were observed along 115 h experiments, with significant differences between removal efficiencies of all radiotracers observed only after 70 h (⁵¹Cr > ⁶⁰Co > ⁷⁵Se). After an event of ⁶⁰Co release back to overlying water, there was a general trend of lower ⁶⁰Co removal than observed for other radiotracers during the period from 20 to 54 h. After this event, alternated periods of higher ⁶⁰Co and higher ⁷⁵Se removal trends were observed, attributed to behavioural differences expected for such anionic and cationic radiotracers. While ⁷⁵Se and ⁵¹Cr showed uniform time-evolution curves, as typically found in the literature for most radiotracers, ⁶⁰Co removal rates presented oscillations, probably due to sensitivity to changes in redox conditions within underlying sediments. Results evidenced the role of mangrove sediments as trace element sinks, which have implications for coastal water quality and for possible uses of such sediments in wastewater treatment systems.     

Impact of High-Pressure Homogenization on the Cell Integrity of Tetradesmus obliquus and Seed Germination

Microalgae have almost unlimited applications due to their versatility and robustness to grow in different environmental conditions, their biodiversity and variety of valuable bioactive compounds. Wastewater can be used as a low-cost and readily available medium for microalgae, while the latter removes the pollutants to produce clean water. Nevertheless, since the most valuable metabolites are mainly located inside the microalga cell, their release implies rupturing the cell wall. In this study, Tetradesmus obliquus grown in 5% piggery effluent was disrupted using high-pressure homogenization (HPH). Effects of HPH pressure (100, 300, and 600 bar) and cycles (1, 2 and 3) were tested on the membrane integrity and evaluated using flow cytometry and microscopy. In addition, wheat seed germination trials were carried out using the biomass at different conditions. Increased HPH pressure or number of cycles led to more cell disruption (75% at 600 bar and 3 cycles). However, the highest increase in wheat germination and growth (40–45%) was observed at the lowest pressure (100 bar), where only 46% of the microalga cells were permeabilised, but not disrupted. Non-treated T. obliquus cultures also revealed an enhancing effect on root and shoot length (up to 40%). The filtrate of the initial culture also promoted shoot development compared to water (21%), reinforcing the full use of all the process fractions. Thus, piggery wastewater can be used to produce microalgae biomass, and mild HPH conditions can promote cell permeabilization to release sufficient amounts of bioactive compounds with the ability to enhance plant germination and growth, converting an economic and environmental concern into environmentally sustainable applications.     

Bayesian modeling of financial returns: A relationship between volatility and trading volume

The modified mixture model with Markov switching volatility specification is introduced to analyze the relationship between stock return volatility and trading volume. We propose to construct an algorithm based on Markov chain Monte Carlo simulation methods to estimate all the parameters in the model using a Bayesian approach. The series of returns and trading volume of the British Petroleum stock will be analyzed. Copyright © 2009 John Wiley & Sons, Ltd.     

Index growth of hypersurfaces with constant mean curvature

In this paper we give the precise index growth for the embedded hypersurfaces of revolution with constant mean curvature (cmc) 1 in (Delaunay unduloids). When n=3, using the asymptotics result of Korevaar, Kusner and Solomon, we derive an explicit asymptotic index growth rate for finite topology cmc 1 surfaces with properly embedded ends. Similar results are obtained for hypersurfaces with cmc bigger than 1 in hyperbolic space. Received: 6 July 2000; in final form: 10 September 2000 / Published online: 25 June 2001     

A genetic algorithm with neural network fitness function evaluation for IMRT beam angle optimization

Intensity Modulated Radiotherapy Treatment (IMRT) is a technique used in the treatment of cancer, where the radiation beams are modulated by a multileaf collimator allowing the irradiation of the patient using non-uniform radiation fields from selected angles. Beam angle optimization consists in trying to find the best set of angles that should be used in IMRT planning. The choice of this set of angles is patient and pathology dependent and, in clinical practice, most of the times it is made using a trial and error procedure or simply using equidistantly distributed angles. In this paper we propose a genetic algorithm that aims at calculating good sets of angles in an automated way, given a predetermined number of angles. We consider the discretization of all possible angles in the interval [0 \(^{\circ }\) , 360 \(^{\circ }\) ], and each individual is represented by a chromosome with 360 binary genes. As the calculation of a given individual’s fitness is very expensive in terms of computational time, the genetic algorithm uses a neural network as a surrogate model to calculate the fitness of most of the individuals in the population. To explicitly consider the estimation error that can result from the use of this surrogate model, the fitness of each individual is represented by an interval of values and not by a single crisp value. The genetic algorithm is capable of finding improved solutions, when compared to the usual equidistant solution applied in clinical practice. The genetic algorithm will be described and computational results will be shown.     

Experimental and molecular dynamics simulation study of the sublimation energetics of cyclopentadienyltricarbonylmanganese (Cymantrene)

The standard molar enthalpy of sublimation of monoclinic cyclopentadienyltricarbonylmanganese, Mn(eta (5)-C 5H 5)(CO) 3, at 298.15 K, was determined as Delta sub H m (o)[Mn(eta (5)-C 5H 5)(CO) 3] = 75.97 +/- 0.37 kJ x mol (-1) from Knudsen effusion and Calvet-drop microcalorimetry measurements, thus considerably improving the very large inaccuracy (>10 kJ x mol (-1)) of the published data. The obtained value was used to assess the extension of the OPLS-based all-atom force field we previously developed for iron metallocenes to manganese organometallic compounds. The modified force field was able to reproduce the volumetric properties (density and unit-cell volume) of crystalline Mn(eta (5)-C 5H 5)(CO) 3 with a deviation of 0.6% and the experimentally determined enthalpy of sublimation with an accuracy of 1 kJ x mol (-1). The interaction (epsilon) and atomic-diameter (sigma) parameters of the Lennard-Jones (12-6) potential function used to calculate dispersion contributions within the framework of the force field were found to be transferable from iron to manganese.     

Determination of gatifloxacin in bulk and tablet preparations by high-performance liquid chromatography

A sensitive, precise, and specific high-performance liquid chromatographic (HPLC) method was developed for the assay of gatifloxacin (GATX) in raw material and tablets. The method validation parameters yielded good results and included the range, linearity, precision, accuracy, specificity, and recovery. It was also found that the excipients in the commercial tablet preparation did not interfere with the assay. The HPLC separation was carried out by reversed-phase chromatography on a C18 absorbosphere column (250 x 4.6 mm id, 5 microm particle size) with a mobile phase composed of acetic acid 5%-acetonitrile-methanol (70 + 15 + 15, v/v/v) pumped isocratically at a flow rate of 1.0 mL/min. The effluent was monitored at 287 nm. The calibration graph for GATX was linear from 4.0 to 14.0 microg/mL. The interday and intraday precisions (relative standard deviation) were less than 1.05%.     

Processing Parameters Matching Effects upon Rhizobium tropici Biopolymers’ Rheological Properties

The combined effects of the processing parameters upon rheological properties of biopolymers produced by Rhizobium tropici were studied as a function of the Ca(+2) ions' concentration variation, yeast extract concentration added to the medium, aeration, and agitation, maintaining the mannitol concentration in 10 g/L. The experiments were carried out using a fermenter with 20-L capacity as a reactor. All processing parameters were monitored online. The temperature [(30 +/- 1) degrees C] and pH values (7.0) were kept constant throughout the experimental time. As a statistical tool, a complete 2(3) factorial design with central point and response surface was used to investigate the interactions between relevant variables of the fermentation process: calcium carbonate concentration, yeast extract concentration, aeration, and agitation. The processing parameter setup for reaching the maximum response for rheological propriety production was obtained when applying mannitol concentration of 10.0 g/L, calcium carbonate concentration 1.0 g/L, yeast extract concentration 1.0 g/L, aeration 1.30 vvm, and agitation 800 rpm. The viscosimetric investigation of polysaccharide solutions exposed their shear-thinning behavior and polyelectrolytic feature.     

Luminescent Di‐ and Trinuclear Boron Complexes Based on Aromatic Iminopyrrolyl Spacer Ligands: Synthesis,Characterization, and Application in OLEDs

New bis‐ and tris(iminopyrrole)‐functionalized linear (1,2‐(HNC₄H₃‐C(H)?N)₂‐C₆H₄ ( 2 ), 1,3‐(HNC₄H₃‐C(H)?N)₂‐C₆H₄ ( 3 ), 1,4‐(HNC₄H₃‐C(H)?N)₂‐C₆H₄ ( 4 ), 4,4′‐(HNC₄H₃‐C(H)?N)₂‐(C₆H₄‐C₆H₄) ( 5 ), 1,5‐(HNC₄H₃C‐(H)?N)₂‐C₁₀H₆ ( 6 ), 2,6‐(HNC₄H₃C‐(H)?N)₂‐C₁₀H₆ ( 7 ), 2,6‐(HNC₄H₃C‐(H)?N)₂‐C₁₄H₈ ( 8 )) and star‐shaped (1,3,5‐(HNC₄H₃‐C(H)?N‐1,4‐C₆H₄)₃‐C₆H₃ ( 9 )) π‐conjugated molecules were synthesized by the condensation reactions of 2‐formylpyrrole ( 1 ) with several aromatic di‐ and triamines. The corresponding linear diboron chelate complexes (Ph₂B[1,3‐bis(iminopyrrolyl)‐phenyl]BPh₂ ( 10 ), Ph₂B[1,4‐bis(iminopyrrolyl)‐phenyl]BPh₂ ( 11 ), Ph₂B[4,4′‐bis(iminopyrrolyl)‐biphenyl]BPh₂ ( 12 ), Ph₂B[1,5‐bis(iminopyrrolyl)‐naphthyl]BPh₂ ( 13 ), Ph₂B[2,6‐bis(iminopyrrolyl)‐naphthyl]BPh₂ ( 14 ), Ph₂B[2,6‐bis(iminopyrrolyl)‐anthracenyl]BPh₂ ( 15 )) and the star‐shaped triboron complex ([4′,4′′,4′′′‐tris(iminopyrrolyl)‐1,3,5‐triphenylbenzene](BPh₂)₃ ( 16 )) were obtained in moderate to good yields, by the treatment of 3 – 9 with B(C₆H₅)₃. The ligand precursors are non‐emissive, whereas most of their boron complexes are highly fluorescent; their emission color depends on the π‐conjugation length. The photophysical properties of the luminescent polyboron compounds were measured, showing good solution fluorescence quantum yields ranging from 0.15 to 0.69. DFT and time‐dependent DFT calculations confirmed that molecules 10 and 16 are blue emitters, because only one of the iminopyrrolyl groups becomes planar in the singlet excited state, whereas the second (and third) keeps the same geometry. Compound 13 , in which planarity is not achieved in any of the groups, is poorly emissive. In the other examples ( 11 , 12 , 14 , and 15 ), the LUMO is stabilized, narrowing the gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital (HOMO–LUMO), and the two iminopyrrolyl groups become planar, extending the size of the π‐system, to afford green to yellow emissions. Organic light‐emitting diodes (OLEDs) were fabricated by using the new polyboron complexes and their luminance was found to be in the order of 2400 cd m^?2, for single layer devices, increasing to 4400 cd m^?2 when a hole‐transporting layer is used.