Synthesis and characterization of diiron dithiolate complexes containing a quinoxaline bridge

A potential model complex for the hydrogenase active site, [Fe(2){(μ-CH(2)S)(2)R}(CO)(6)] (1) (R = quinoxaline), was synthesized by condensation of [(μ-LiS)(2)Fe(2)(CO)(6)] with 2,3-bis(bromomethyl)quinoxaline. Reactions of 1 with bis(diphenylphosphino)methane (dppm) under a range of conditions yielded substituted complexes [Fe(2){(μ-CH(2)S)(2)R}(CO)(5)(dppm)] (2), [Fe(2){(μ-CH(2)S)(2)R}(CO)(4)(k(2)-dppm)] (3) and [Fe(2){(μ-CH(2)S)(2)R}(CO)(4)(μ-dppm)] (4). X-ray crystallography confirms that in 2, the dppm is terminally bonded to an iron atom via one phosphorus atom, whereas in 3, it acts as a chelating ligand to coordinate to an iron center in a dibasal-substituted manner. In 4, the dppm bridges the two iron atoms in a cis basal/basal fashion with one phosphorus bonded to each iron atom. Treatment of 1 with various tertiary phosphines at room temperature in acetonitrile (MeCN) generates a range of mono-substituted products [Fe(2){(μ-CH(2)S)(2)R}(CO)(5)L] (5, L = PEt(3); 6, PMe(3); 7, PPh(3); 8, Me(2)PPh). With Bu(t)NC, mono- and di-substituted [Fe(2){(μ-CH(2)S)(2)R}(CO)(5)(Bu(t)NC)] (9) and [Fe(2){(μ-CH(2)S)(2)R}(CO)(4)(Bu(t)NC)(2)] (10) complexes are generated. All the complexes were characterized by elemental analysis, IR, MS and NMR spectroscopy. IR and NMR spectroscopic studies suggest that addition of excess HBF(4)·OEt(2) acid to 1-4 led to the protonation of quinoxaline nitrogen atoms. In contrast, 5-10 were not stable in acidic media. Electrochemistry of 1-4 was investigated in the acetonitrile medium (0.1 M Bu(4)NPF(6)). The electrochemical instability of the reduced ligand, quinoxaline, and the reduced forms of these complexes revealed from the electrochemical studies suggests that they do not provide ideal models of the hydrogenase active site.     

Circadian variations in biologically closed electrochemical circuits in Aloe vera and Mimosa pudica

The circadian clock regulates a wide range of electrophysiological and developmental processes in plants. This paper presents, for the first time, the direct influence of a circadian clock on biologically closed electrochemical circuits in vivo. Here we show circadian variation of the plant responses to electrical stimulation. The biologically closed electrochemical circuits in the leaves of Aloe vera and Mimosa pudica, which regulate their physiology, were analyzed using the charge stimulation method. The electrostimulation was provided with different timing and different voltages. Resistance between Ag/AgCl electrodes in the leaf of Aloe vera was higher during the day than at night. Discharge of the capacitor in Aloe vera at night was faster than during the day. Discharge of the capacitor in a pulvinus of Mimosa pudica was faster during the day. The biologically closed electrical circuits with voltage gated ion channels in Mimosa pudica are also activated the next day, even in the darkness. These results show that the circadian clock can be maintained endogenously and has electrochemical oscillators, which can activate ion channels in biologically closed electrochemical circuits. We present the equivalent electrical circuits in both plants and their circadian variation to explain the experimental data.     

A Zinc Oxide Carbon Nanotube Based Sensor for In Situ Monitoring of Hydrogen Peroxide in Swimming Pools

Zinc oxide nanoparticles were tethered to carbon nanotubes to form an electrochemical sensing composite, which was characterized using transmission electron microscopy, and X‐ray photoelectron and attenuated total reflectance infrared spectroscopies. The sensor′s electrocatalytic response for measuring hydrogen peroxide was investigated using cyclic voltammetry and chronoamperometry in a dynamic, well defined swimming pool environment. A wide, linear response in the concentration range of 0.025–7.0 mM at a potential of ?0.360 V was shown, with rapid response time (<5 s). The sensor had excellent reproducibility, exhibited stability and selectivity, and was able to measure concentrations in a dynamic environment as they varied.     

A Simple,High‐Yield Synthesis of DNA Duplexes Containing a Covalent,Thermally Cleavable Interstrand Cross‐Link at a Defined Location

Interstrand DNA–DNA cross‐links are highly toxic to cells because these lesions block the extraction of information from the genetic material. The pathways by which cells repair cross‐links are important, but not well understood. The preparation of chemically well‐defined cross‐linked DNA substrates represents a significant challenge in the study of cross‐link repair. Here a simple method is reported that employs “post‐synthetic” modifications of commercially available 2′‐deoxyoligonucleotides to install a single cross‐link in high yield at a specified location within a DNA duplex. The cross‐linking process exploits the formation of a hydrazone between a non‐natural N⁴‐amino‐2′‐deoxycytidine nucleobase and the aldehyde residue of an abasic site in duplex DNA. The resulting cross‐link is stable under physiological conditions, but can be readily dissociated and re‐formed through heating–cooling cycles.     

Independent components analysis coupled with 3D-front-face fluorescence spectroscopy to study the interaction between plastic food packaging and olive oil

Olive oil is one of the most valued sources of fats in the Mediterranean diet. Its storage was generally done using glass or metallic packaging materials. Nowadays, plastic packaging has gained worldwide spread for the storage of olive oil. However, plastics are not inert and interaction phenomena may occur between packaging materials and olive oil. In this study, extra virgin olive oil samples were submitted to accelerated interaction conditions, in contact with polypropylene (PP) and polylactide (PLA) plastic packaging materials. 3D-front-face fluorescence spectroscopy, being a simple, fast and non destructive analytical technique, was used to study this interaction. Independent components analysis (ICA) was used to analyze raw 3D-front-face fluorescence spectra of olive oil. ICA was able to highlight a probable effect of a migration of substances with antioxidant activity. The signals extracted by ICA corresponded to natural olive oil fluorophores (tocopherols and polyphenols) as well as newly formed ones which were tentatively identified as fluorescent oxidation products. Based on the extracted fluorescent signals, olive oil in contact with plastics had slower aging rates in comparison with reference oils. Peroxide and free acidity values validated the results obtained by ICA, related to olive oil oxidation rates. Sorbed olive oil in plastic was also quantified given that this sorption could induce a swelling of the polymer thus promoting migration.     

A Closer Look at 3,5-Dinitrotoluene

The dinitrotoluenes (DNT) are some widely used compounds despite the first general impression one might have. They are the intermediates of several economically important industrial reactions such as the continuous nitration process of trinitrotoluene (TNT).^3,4 As we were interested in the spectral characteristics of the various isomers of DNT⁵, we realized that the 3,5 isomer was not u-sually obtained during the nitration process of toluene⁶, thus making its availability quite restricted. It appeared relevant to find a useful and practical way to synthesize that particular isomer as it could also lead to the formation of new polyurethanes⁷, many polymerization processes uses DNT (mainly the 2,4 isomer because of its availability and its low price).     

Colloidal Nanocrystals of Lithiated Group 14 Elements

The synthesis of colloidal nanocrystals (NCs) of lithiated group 14 elements (Z=Si, Ge, and Sn) is reported, which are Li_4.4Si, Li_3.75Si, Li_4.4Ge, and Li_4.4Sn. Li_xZ compounds are highly reactive and cannot be synthesized by existing methods. The success relied on separating the surface protection from the crystal formation and using a unique passivating ligand. Bare Li_xZ crystals were first produced by milling elemental Li and Z in an argon‐filled jar. Then, under the assistance of additional milling, hexyllithium was added to passivate the freshly generated Li_xZ NCs. This ball‐milling‐assisted surface protection method may be generalized to similar systems, such as Na_xZ and K_xZ. Moreover, Li_4.4Si and Li_4.4Ge NCs were conformally encapsulated in carbon fibers, providing great opportunities for studying the potential of using Li_xZ to mitigate the volume‐fluctuation‐induced poor cyclability problem confronted by Z anodes in lithium‐ion batteries.     

Improving Site‐Directed RNA Editing In Vitro and in Cell Culture by Chemical Modification of the GuideRNA

Adenosine‐to‐inosine deamination can be re‐addressed to user‐defined mRNAs by applying phosphothioate/2′‐methoxy‐modified guideRNAs. Dense chemical modification of the guideRNA clearly improves performance of the covalent conjugates inside the living cell. Furthermore, careful positioning of a few modifications controls editing selectivity in vitro and was exploited for the challenging repair of the Factor 5 Leiden missense mutation.     

New di‐ and triorganotin(IV) carboxylates derived from a Schiff base: synthesis,characterization and in vitro antimicrobial activities

A new carboxylic acid, 2‐{[5‐(2‐nitrophenyl)furan‐2‐yl]methyleneamino}benzoic acid (HOBZ), has been produced by reacting 5‐(2‐nitrophenyl)furfural with 2‐aminobenzoic acid. Reactions of NaOBZ with organotin chlorides led to formation of [Me₃Sn(OBZ)] ( 1 ), [Bu₃Sn(OBZ)] ( 2 ), [Me₂Sn(OBZ)₂] ( 3 ) and [Bu₂Sn(OBZ)₂] ( 4 ). Complexes 1 , 2 , 3 , 4 have been characterized using elemental analyses and infrared, ¹H NMR, ¹³C NMR, ¹¹⁹Sn NMR and ¹¹⁹Sn Mössbauer spectroscopies. In the solid state, the OBZ ligands might coordinate to tin in an anisobidentate fashion via the carboxylate group. The in vitro antimicrobial activity of all compounds has been screened against the following fungi: Aspergillus niger, A. flavus, A. parasiticus, Penicillium citrinum, Candida dubliniensis, C. lusitaniae, C. albicans, C. tropicalis, C. parapsilosis and C. glabrata; and against the following bacteria: Staphylococcus aureus, Listeria monocytogenes, Bacillus cereus, Streptococcus sanguinis, Escherichia coli, Citrobacter frendii, Salmonella typhimurium and Pseudomonas aeruginosa. Complexes 2 and 4 exhibited higher biocide activity in comparison to 1 and 3 and to the control drugs nystatin and miconazole nitrate for the yeasts, and chloramphenicol and ampicillin for the bacteria. The biological activity of 2 was superior to that of 4 . In addition, the toxicity of HOBZ, NaOBz and 1 , 2 , 3 , 4 were determined using Chlorella vulgaris, revealing low toxicity of the complexes at MIC₅₀ concentrations. We also performed cell viability studies, using XTT assay, displaying no change in the mitochondrial function after 2–4 h of exposure of the microorganism to the complexes at MIC₅₀ concentrations. The butyl‐containing complexes 2 and 4 display greater lipophilicities than do the methyl analogues 1 and 3 , thereby endowing 2 and 4 with superior abilities to cross the microbe cell membrane, the possible mechanism of action. Copyright © 2015 John Wiley & Sons, Ltd.