Hooker’s ‘lapachol peroxide’ revisited

The structure of ‘lapachol peroxide’ was published by Hooker in 1936; however, we recently discovered a mistake in the originally proposed structure; the correct structure, according to X-ray spectroscopy, is given here.     

Chemometrically Assisted Development and Validation of LC for Simultaneous Determination of Carbamazepine and Its Impurities Iminostilbene and Iminodibenzyl in Solid Dosage Form

A chemometrical approach was applied to develop a reversed-phase liquid chromatographic method for simultaneous determination of carbamazepine and its impurities iminostilbene and iminodibenzyl in solid dosage form. According to contemporary literature, no method was developed for simultaneous determination of carbamazepine and these impurities by chemometrical approach. The fractional factorial design was used for selection of variables significantly influencing the chromatographic separation of the investigated substances. The investigated variables were: temperature of the column, the percentage of organic modifier, the acetate buffer concentration and pH of water phase. The first three variables were proved to be significant and were optimized by face centered, central composite design. Investigation was performed using C18 XBridge Shield analytical column (50 mm × 4.6 mm i.d., particle size 3.5 µm). The optimal conditions for the separation were established with the mobile phase composition of methanol–10 mM acetate buffer (pH adjusted to 2.21 with glacial acetic acid) (50:50, v/v) at a flow rate of 1.5 mL min^?1, 25 °C column temperature and detection at 260 nm. Total analysis time was shortened to about 8 min. Finally, the method was successfully validated and subsequently applied to the analysis of commercially available carbamazepine tablets.     

A Comparison Between Shaker and Bioreactor Performance Based on the Kinetic Parameters of Xanthan Gum Production

Xanthan gum production was studied using sugarcane broth as the raw material and batch fermentation by Xanthomonas campestris pv. campestris NRRL B-1459. The purpose of this study was to optimize the variables of sucrose, yeast extract, and ammonium nitrate concentrations and to determine the kinetic parameters of this bioreaction under optimized conditions. The effects of yeast extract and ammonium nitrate concentrations for a given sucrose concentration (12.1–37.8 g L^?1) were evaluated by central composite design to maximize the conversion efficiency. In a bioreactor, the maximum conversion efficiency was achieved using 27.0 g L^?1 sucrose, 2.7 g L^?1 yeast extract, and 0.9 g L^?1 NH₄NO₃. This point was assayed in a shaker and in a bioreactor to compare bioreaction parameters. These parameters were estimated by the unstructured kinetic model of Weiss and Ollis (Biotechnol Bioeng 22:859–873, 1980) to determinate the yields (Y _P/S), the maximum growth specific rate (μ _max), and the saturation cellular concentration (X*). The parameters of the model (μ _max, X*, m, λ, α, and β) were obtained by nonlinear regression. For production of xanthan gum in a shaker, the values of μ _max and Y _P/S obtained were 0.119 h^?1 and 0.34 g g^?1, respectively, while in a bioreactor, they were 0.411 h^?1 and 0.63 g g^?1, respectively.     

Green approaches for the synthesis of nucleotides,their conjugates and analogues

Abstract

We have developed original one-pot and protecting group-free approaches, which are also user-friendly and reliable, to synthesize nucleotides and derivatives starting from nucleoside 5’-monophosphates. Both methods present convenient set-up, i.e., non-dry solvents and reagents, substrates in their sodium or acid form, and commercially available and cheap phosphorus reagents as sodium and potassium salts.     

Essential oil and fractions isolated of Laurel to control adults and larvae of cattle ticks

Abstract

This study, was to evaluate the acaricidal effect of the essential oil (EO) and fractions (FR) obtained from Laurus nobilis leaves on Rhipicephalus (Boophilus) microplus. Eight fractions were obtained, however FR1: sabinene (37.83%), β-pinene (13.50%), 1,8-cineole (12.66%), α-pinene (12.56%) and FR8: α-terpineol (79.19%) were highlighted as to the larvicidal potential when submitted by Larval Packet Test. The EO was tested by the Adult Immersion Test, at concentrations of 200.00; 100.00 and 50.00?µL/mL caused mortality of engorged females, egg mass reduction and hatching inhibition. Two fractions are shown to be efficient in controlling larvae FR8 (LC₅₀?=?0.13?µL/mL, LC₉₉?=?0.51?µL/mL) and FR1 (LC₅₀?=?0.20?µL/mL, LC₉₉?=?0.56?µL/mL). The fractionation of EO was determinant to elucidate which compounds were responsible for the larvicidal potential. This study opens new perspectives to direct new bioassays with the compounds obtained in the fractionation, since they present high potential on cattle tick larvae.     

Determination of phenolic compounds,in vitro antioxidant activity and characterization of secondary metabolites in different parts of Passiflora cincinnata by HPLC-DAD-MS/MS analysis

Abstract

Ethanol extracts of different parts of Passiflora cincinnata were obtained by maceration. The total phenolic and flavonoid contents were evaluated. The antioxidant activities were determined by β-carotene-linoleic acid bleaching test, 2,2-diphenyl-1-picrylhydrazil (DPPH), and 2,2’-azinobis-3-ethylbenzothiazoline-6-sulfonic acid (ABTS) radical scavenging. The crude ethanol stem extract showed the highest amount of total polyphenols (45.53?mg gallic acid equivalent/g) while the highest total flavonoid contents (1.42?mg of quercetin equivalent/g) were observed in the leaf extract. The lowest IC₅₀ (25.65?μg/ml) by the DPPH method was observed for the stem extract. The ABTS method showed a significant antioxidant activity for all investigated extracts. The secondary metabolite composition of ethanol extracts was assessed by HPLC-DAD-MS/MS analysis, leading to the identification of fourteen secondary metabolites in P. cincinnata extracts. These results showed the potentiality of this species as a source of phenolic compounds and antioxidants.     

Anisotropic Electron Conductance Driven by Reaction Byproducts on a Porous Network of Dibromobenzothiadiazole on Cu(110)

Efficiency in charge‐transport is a fundamental but demanding prerequisite to allow better exploitation of molecular functionalities in organic electronics and energy‐conversion systems. Here, we report on a mechanism that enables a one‐dimensional conductance structure by connecting discrete molecular states at 2.1 eV through the pores of a metal–organic network on Cu(110). Two adjacent, periodic and isoenergetic contributions, namely a molecular resonance and the confined surface‐state, add‐up leading to anisotropic structures, as channels, observable in real‐space conductance images. The adsorption configurations of Br atoms, inorganic byproduct of the redox‐reacted 4,7‐dibromobenzo[c]‐1,2,5‐thiadiazole (2Br‐BTD) molecules on the copper surface, drive the confinement of the Cu surface state within the pores and critically control the channel continuity. Small displacements of the Br atoms change the local surface potential misaligning the energy levels. This work visualizes the effect of order‐disorder transitions caused by the movement of single atoms in the electronic properties of two‐dimensional organic networks.     

Unambiguous Intracellular Localization and Quantification of a Potent Iridium Anticancer Compound by Correlative 3D Cryo X‐Ray Imaging

The iridium half‐sandwich complex [Ir(η⁵:κ¹‐C₅Me₄CH₂py)(2‐phenylpyridine)]PF₆ is highly cytotoxic: 15–250× more potent than clinically used cisplatin in several cancer cell lines. We have developed a correlative 3D cryo X‐ray imaging approach to specifically localize and quantify iridium within the whole hydrated cell at nanometer resolution. By means of cryo soft X‐ray tomography (cryo‐SXT), which provides the cellular ultrastructure at 50 nm resolution, and cryo hard X‐ray fluorescence tomography (cryo‐XRF), which provides the elemental sensitivity with a 70 nm step size, we have located the iridium anticancer agent exclusively in the mitochondria. Our methodology provides unique information on the intracellular fate of the metallodrug, without chemical fixation, labeling, or mechanical manipulation of the cells. This cryo‐3D correlative imaging method can be applied to a number of biochemical processes for specific elemental localization within the native cellular landscape.     

A simple adsorptive chronopotentiometric stripping method for determination of vitamin B 1 in pharmaceutical products

A new electroanalytical method for vitamin B1 determination, based on adsorptive chronopotentiometric stripping analysis and non-specific adsorption onto mercury film electrode, was developed and validated. Stripping chronopotentiograms showed a single well-defined oxidation wave corresponding to vitamin B1 at about − 0.43 V in citrate buffer pH 6.0. The most important experimental factors affecting the monitored electroanalytical response of vitamin B1 were investigated and optimised. Under the optimal experimental conditions, linear response of vitamin B1 was obtained in the concentration range of 5–50 mg dm−3, with the achieved limit of detection of 1.64 mg dm−3, and the limit of quantitation of 4.97 mg dm−3. A mean recovery of 97.1% and relative standard deviations of 3.75% were achieved. The developed electrochemical procedure was successfully applied for the determination of vitamin B1 in pharmaceutical products. The results of the proposed method were in good agreement with those obtained by parallel HPLC analyses, confirming an accuracy of the developed method.     

Determination of personal care products in water using UHPLC–MS after solid phase extraction with mesoporous silica‐based MCM‐41 functionalized with cyanopropyl groups

A silica‐based MCM‐41 mesoporous material functionalized with cyanopropyl groups has been synthesized by cocondensation, characterized and applied to preconcentrate six parabens and three UV filters in river and swimming‐pool waters. The analytes were quantified by ultra‐high performance liquid chromatography‐tandem mass spectrometry, according to the Directive 96/23/EC. Even though matrix effect was negligible, quantification in river water samples with the standard addition approach improved the recoveries obtained using solvent‐based and even with matrix‐matched calibration. The method quantification limits in river water samples were 0.05 ng/mL for 2,4‐dihydroxybenzophenone and 0.01 ng/mL for the rest. Recoveries, evaluated for a concentration level of 0.5 ng/L, were in the range 93.5‐107.6% for parabens and in the range 64.2‐85.8% for UV filters, with relative standard deviations intraday ≤10.2 and 10.8%, respectively. This parameter, evaluated for a concentration level of 0.1 ng/L, ranged between 98.3 and 110.4% for parabens and between 61.9 and 89.9% for UV filters, with relative standard deviation intraday ≤15.3 and 15.5%, respectively. The two UV filters with lower recoveries were the most affected by the addition of sodium chloride. River and swimming pool waters were analyzed and all the personal care products were found in the swimming pool water, whereas only methylparaben was detected in the river water.