FORMATION AND MORPHOLOGY OF AN IRON PLAQUE ON THE ROOTS OF TYPHA LATIFOLIA L. GROWN IN SOLUTION CULTURE

Roots of Typha latifolia L. exposed to Fe²⁺ under reduced conditions in solution culture developed visible coatings (plaques) of an oxidized Fe compound that extended as much as 15-17 μm into the rhizosphere. Iron concentrations were significantly less and discoloration was not apparent on the surface of roots exposed to Fe-(BPDS)₃, Fe³⁺, Fe-EDDHA, and Fe-EDTA. The extent of plaque formation increased with the concentration of Fe²⁺ in solution and with pH of the solution in the range of 3.0 to 4.6. Above pH 4.6, oxidation of Fe²⁺ in the culture solution may have reduced precipitation of Fe on the root surface. Plaque development was most extensive approximately 1.0 cm from the root tip, but all root surfaces showed some Fe staining. Scanning electron micrographs of plaqued roots, grown both in solution culture and in the field, provided support for a model of cast formation by oxidation and precipitation of Fe on external cell surfaces.     

Hybrid MC/QC simulations of water-assisted proton transfer in nucleosides. Guanosine and its analog acyclovir

To provide an in-depth insight into the molecular basis of spontaneous tautomerism in DNA and RNA base pairs, a hybrid Monte Carlo (MC)–quantum chemical (QC) methodology is implemented to map two-dimensional potential energy surfaces along the reaction coordinates of solvent-assisted proton transfer processes in guanosine and its analog acyclovir in aqueous solution. The solvent effects were simulated by explicit inclusion of water molecules that model the relevant part of the first hydration shell around the solute. The position of these water molecules was estimated by carrying out a classical Metropolis Monte Carlo simulation of dilute water solutions of the guanosine (Gs) and acyclovir (ACV) and subsequently analyzing solute–solvent intermolecular interactions in the statistically-independent MC-generated configurations. The solvent-assisted proton transfer processes were further investigated using two different ab initio MP2 quantum chemical approaches. In the first one, potential energy surfaces of the ‘bare’ finite solute–solvent clusters containing Gs/ACV and four water molecules (MP2/6-31+G(d,p) level) were explored, while within the second approach, these clusters were embedded in ‘bulk’ solvent treated as polarizable continuum (C-PCM/MP2/6-31+G(d,p) level of theory). It was found that in the gas phase and in water solution, the most stable tautomer for guanosine and acyclovir is the 1H-2-amino-6-oxo form followed by the 2-amino-6-(sZ)-hydroxy form. The energy barriers of the water-assisted proton transfer reaction in guanosine and in acyclovir are found to be very similar – 11.74 kcal mol^?1 for guanosine and 11.16 kcal mol^?1 for acyclovir, and the respective rate constants (k = 1.5?×?10¹ s^?1, guanosine and k = 4.09?×?10¹ s^?1, acyclovir), are sufficiently large to generate the 2-amino-6-(sZ)-hydroxy tautomer. The analysis of the reaction profiles in both compounds shows that the proton transfer processes occur through the asynchronous concerted mechanism.     

Reactive oxygen species generated in the presence of fine pyrite particles and its implication in thermophilic mineral bioleaching

In the tank bioleaching process, maximising solid loading and mineral availability, the latter through decreasing particle size, are key to maximising metal extraction. In this study, the effect of particle size distribution on bioleaching performance and microbial growth was studied through applying knowledge based on medical geology research to understand the adverse effects of suspended fine pyrite particles. Small-scale leaching studies, using pyrite concentrate fractions (106–75, 75–25, ?25 μm fines), were used to confirm decreasing performance with decreasing particle size (D ₅₀ <40 μm). Under equivalent experimental conditions, the generation of the reactive oxygen species (ROS), hydrogen peroxide and hydroxyl radicals from pyrite was illustrated. ROS generation measured from the different pyrite fractions was found to increase with increasing pyrite surface area loading (1.79–74.01 m² L^?1) and Fe²⁺ concentration (0.1–2.8 g?L^?1) in solution. The highest concentration of ROS was measured from the finest fraction of pyrite (0.85 mM) and from the largest concentration of Fe²⁺ (0.78 mM). No ROS was detected from solutions containing only Fe³⁺ under the same conditions tested. The potential of ROS to inhibit microbial performance under bioleaching conditions was demonstrated. Pyrite-free Sulfolobus metallicus cultures challenged with hydrogen peroxide (0.5–2.5 mM) showed significant decrease in both cell growth and Fe²⁺ oxidation rates within the concentration range 1.5–2.5 mM. In combination, the results from this study suggest that conditions of large pyrite surface area loading, coupled with high concentrations of dissolved Fe²⁺, can lead to the generation of ROS, resulting in oxidative stress of the microorganisms.     

Pyrazolone as a recognition site: Rhodamine 6G‐based fluorescent probe for the selective recognition of Fe3+ in acetonitrile–aqueous solution

Two novel Rhodamine–pyrazolone‐based colorimetric off–on fluorescent chemosensors for Fe³⁺ ions were designed and synthesized using pyrazolone as the recognition moiety and Rhodamine 6G as the signalling moiety. The photophysical properties and Fe³⁺‐binding properties of sensors L¹ and L² in acetonitrile–aqueous solution were also investigated. Both sensors successfully exhibit a remarkably ‘turn‐on’ response, toward Fe³⁺, which was attributed to 1: 2 complex formation between Fe³⁺ and L¹/L². The fluorescent and colorimetric response to Fe³⁺ can be detected by the naked eye, which provides a facile method for the visual detection of Fe³⁺. Copyright © 2014 John Wiley & Sons, Ltd.     

Bioleaching of Lizardite by Magnesium- and Nickel-Resistant Fungal Isolate from Serpentinite Soils—Implication for Carbon Capture and Storage

The major goal of this study was to evaluate the potential of fungal species indigenous to mine tailing soils in accelerating Mg release from lizardite (a polymorph of serpentine) at ambient T/P conditions. We characterized the culturable fungal isolates at three sampling sites representative of different degrees of mineral weathering by isolating the genomic subunits and internal transcribed spacer (ITS) rRNA genes using PCR and sequencing of cloned fragments. We chose the specific strain primarily identified as Talaromyces sp. for the further experiments with lizardite because of this strain's remarkable tolerance to high [Mg²⁺] (1 mol·L^?1) and [Ni²⁺] (10 mM·L^?1) levels in the screening test and its ubiquity in the most severely weathered samples. Results of dissolution experiments revealed that both magnesium-release rate and efficiency were significantly increased (e.g., by a factor of up to 15) in the presence of fungal cells than those in the abiotic controls. The enhanced dissolution of lizardite was mainly attributed to the fungal production of organic acids including oxalic acid, gluconic acid, formic acid, and fumaric acid added to the solution. The proton-promoted dissolution, however, was indicated not to be the only mechanism for fungus-lizardite interactions as much lesser Mg (in wt.%) was recovered in the abiotic system where the solution pH was constantly adjusted to match that of the fungal system. We also explored the dependence of fungal dissolution (of lizardite) on temperature and mineral particle sizes. In particular, we found that up to ～ 50 wt.% of Mg was released from mineral particles of ～ 50 μm within 30 days at 38°C, ～ 26% and 8% higher than that at 18°C and 28°C, respectively. At the same temperature of 28°C, the Mg-release efficiency increased from 12.2 wt% for particles of ～ 270 μm to 38.4 wt% for those of ～100 μm although no apparent difference was recognized when the particle size decreased below 100 μm. The nonlinear correlation of dissolution rates with particle surface areas suggested that the dissolution process was controlled by mineral surface-structural modification along with Mg release and by fungal cells’ interaction with these surface structures. An amorphous layer of Mg-depleted silica was detected at the reacted mineral surface by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). Formation of glushinskite (MgC₂O₄·2H₂O) was also observed when oxalate was accumulated to certain concentrations in the solution. Overall, this study showed that the isolated Talaromyces sp. was a promising bioagent to improve the efficacy of cation release from serpentine minerals for the purpose of carbon sequestration and resource recovery.     

Illite transformation and potassium release upon changes in composition of the rhizophere soil solution

Aims and background

Release of ‘non-exchangeable’ potassium (K) from interlayers of illite is diffusion-controlled and has been shown to depend on the solution concentration of K and other cations (Ca²⁺, Mg²⁺, NH₄ ⁺).

Methods

We analysed changes in soil solution concentrations of K and competing cations in situ at different distances from the root surface over time and related them to the transformation of illite, as revealed by X-ray diffraction, and chemical measures of differently bound K.

Results and Conclusions

Within 49 and 98 days, respectively, 6.4 and 14.4 % of the illite’s total K was released upon contact with the root system. Mixed layered minerals increased from 33 (0 d) to 35 (49 d) to 40 % (98 d). Release of K from interlayers and the transformation of illite occurred at soil solution K concentrations close to the threshold of 80 μM suggested earlier. Concentrations of Ca and Mg increased with decreasing distance from the root surface, promoting the release of K. The NaBPh₄ method supposed to determine ‘non-exchangeable’ K extracted only 1/3 of the total K from illite.     

Coordinating subdomains of ferritin protein cages with catalysis and biomineralization viewed from the C 4 cage axes

Integrated ferritin protein cage function is the reversible synthesis of protein-caged, solid Fe₂O₃·H₂O minerals from Fe²⁺ for metabolic iron concentrates and oxidant protection; biomineral order differs in different ferritin proteins. The conserved 432 geometric symmetry of ferritin protein cages parallels the subunit dimer, trimer, and tetramer interfaces, and coincides with function at several cage axes. Multiple subdomains distributed in the self-assembling ferritin nanocages have functional relationships to cage symmetry such as Fe²⁺ transport though ion channels (threefold symmetry), biomineral nucleation/order (fourfold symmetry), and mineral dissolution (threefold symmetry) studied in ferritin variants. On the basis of the effects of natural or synthetic subunit dimer cross-links, cage subunit dimers (twofold symmetry) influence iron oxidation and mineral dissolution. 2Fe²⁺/O₂ catalysis in ferritin occurs in single subunits, but with cooperativity (n = 3) that is possibly related to the structure/function of the ion channels, which are constructed from segments of three subunits. Here, we study 2Fe²⁺ + O₂ protein catalysis (diferric peroxo formation) and dissolution of ferritin Fe₂O₃·H₂O biominerals in variants with altered subunit interfaces for trimers (ion channels), E130I, and external dimer surfaces (E88A) as controls, and altered tetramer subunit interfaces (L165I and H169F). The results extend observations on the functional importance of structure at ferritin protein twofold and threefold cage axes to show function at ferritin fourfold cage axes. Here, conserved amino acids facilitate dissolution of ferritin-protein-caged iron biominerals. Biological and nanotechnological uses of ferritin protein cage fourfold symmetry and solid-state mineral properties remain largely unexplored.     

A model that predicts the attachment behavior of Ulva linza zoospores on surface topography

A predictive model for the attachment of spores of the green alga Ulva on patterned topographical surfaces was developed using a constant refinement approach. This ‘attachment model’ incorporated two historical data sets and a modified version of the previously-described Engineered Roughness Index. Two sets of newly-designed surfaces were used to evaluate the effect of two components of the model on spore settlement. Spores attached in fewer numbers when the area fraction of feature tops increased or when the number of distinct features in the design increased, as predicted by the model. The model correctly predicted the spore attachment density on three previously-untested surfaces relative to a smooth surface. The two historical data sets and two new data sets showed high correlation (R ² = 0.88) with the model. This model may be useful for designing new antifouling topographies.     

Green synthesis of fluorescence carbon nanoparticles from yum and application in sensitive and selective detection of ATP

Fluorescent carbon nanoparticles (CPs), a fascinating class of recently discovered nanocarbons, have been widely known as some of the most promising sensing probes in biological or chemical analysis. In this study, we demonstrate a green synthetic methodology for generating water‐soluble CPs with a quantum yield of approximately 24% via a simple heating process using yum mucilage as a carbon source. The prepared carbon nanoparticles with an ~10 nm size possessed excellent fluorescence properties, and the fluorescence of the CPs was strongly quenched by Fe³⁺, and recovered by adenosine triphosphate (ATP), thus, an ‘off’ and ‘on’ system can be easily established. This ‘CPs‐Fe³⁺‐ATP’ strategy was sensitive and selective at detecting ATP with the linear range of 0.5 µmol L^?1 to 50 µmol L^?1 and with a detection limit of 0.48 µmol L^?1. Copyright © 2015 John Wiley & Sons, Ltd.     

Process for biological oxidation and control of dissolved iron in bioleach liquors

Iron has a central role in bioleaching and biooxidation processes. Fe²⁺ produced in the dissolution of sulfidic minerals is re-oxidized to Fe³⁺ mostly by biological action in acid bioleaching processes. To control the concentration of iron in solution, it is important to precipitate the excess as part of the process circuit. In this study, a bioprocess was developed based on a fluidized-bed reactor (FBR) for Fe²⁺ oxidation coupled with a gravity settler for precipitative removal of ferric iron. Biological iron oxidation and partial removal of iron by precipitation from a barren heap leaching solution was optimized in relation to the performance and retention time (τ_FBR) of the FBR. The biofilm in the FBR was dominated by Leptospirillum ferriphilum and “Ferromicrobium acidiphilum.” The FBR was operated at pH 2.0 ± 0.2 and at 37 °C. The feed was a barren leach solution following metal recovery, with all iron in the ferrous form. 98–99% of the Fe²⁺ in the barren heap leaching solution was oxidized in the FBR at loading rates below 10 g Fe²⁺/L h (τ_FBR of 1 h). The optimal performance with the oxidation rate of 8.2 g Fe²⁺/L h was achieved at τ_FBR of 1 h. Below the τ_FBR of 1 h the oxygen mass transfer from air to liquid limited the iron oxidation rate. The precipitation of ferric iron ranged from 5% to 40%. The concurrent Fe²⁺ oxidation and partial precipitative iron removal was maximized at τ_FBR of 1.5 h, with Fe²⁺ oxidation rate of 5.1 g Fe²⁺/L h and Fe³⁺ precipitation rate of 25 mg Fe³⁺/L h, which corresponded to 37% iron removal. The precipitates had good settling properties as indicated by the sludge volume indices of 3–15 mL/g but this step needs additional characterization of the properties of the solids and optimization to maximize the precipitation and to manage sludge disposal.     

The mechanism of (+) taxifolin’s protective antioxidant effect for •OH-treated bone marrow-derived mesenchymal stem cells

The natural dihydroflavonol (+) taxifolin was investigated for its protective effect on Fenton reagent-treated bone marrow-derived mesenchymal stem cells (bmMSCs). Various antioxidant assays were used to determine the possible mechanism. These included ?OH-scavenging, 2-phenyl-4, 4, 5, 5-tetramethylimidazoline-1-oxyl-3-oxide radical-scavenging (PTIO?-scavenging), 1, 1-diphenyl-2-picryl-hydrazl radical-scavenging (DPPH?-scavenging), 2, 2′-azino-bis (3-ethylbenzo-thiazoline-6-sulfonic acid) radical-scavenging (ABTS⁺?-scavenging), Fe³⁺-reducing, and Cu²⁺-reducing assays. The Fe²⁺-binding reaction was also investigated using UV-Vis spectra. The results revealed that cell viability was fully restored, even increasing to 142.9?±?9.3% after treatment with (+) taxifolin. In the antioxidant assays, (+) taxifolin was observed to efficiently scavenge ?OH, DPPH? and ABTS⁺? radicals, and to increase the relative Cu²⁺- and Fe³⁺-reducing levels. In the PTIO?-scavenging assay, its IC₅₀ values varied with pH. In the Fe²⁺-binding reaction, (+) taxifolin was found to yield a green solution with two UV-Vis absorbance peaks: λ_max =?433 nm (ε =5.2?×?10² L mol^?1 cm ^?1) and λ_max =?721 nm (ε?=?5.1?×?10² L mol^?1 cm ^?1). These results indicate that (+) taxifolin can act as an effective ?OH-scavenger, protecting bmMSCs from ?OH-induced damage. Its ?OH-scavenging action consists of direct and indirect antioxidant effects. Direct antioxidation occurs via multiple pathways, including ET, PCET or HAT. Indirect antioxidation involves binding to Fe²⁺.     

<Emphasis Type="Italic">Agrobacterium</Emphasis>-mediated transformation and shoot regeneration in elite breeding lines of western shipper cantaloupe and honeydew melons (<Emphasis Type="Italic">Cucumis melo</Emphasis> L.)

A reliable Agrobacterium-mediated transformation and shoot regeneration protocol was developed for breeding lines of commercially important western-shipper cantaloupe and honeydew melons, ‘F39’ and ‘150’, respectively. Different media were tested to select a shoot regeneration system for each of three elite breeding lines ‘F39’, ‘141’ and ‘TMS’. Murashige &; Skoog (MS) basal medium supplemented with 1 mg l^?1 benzyladenine (BA), 0.26 mg l^?1 abscisic acid (ABA) and 0.8 mg l^?1 indole-3-acetic acid (IAA) was used for shoot regeneration from cotyledonary explants in ‘F39’ and ‘150’. Kanamycin sensitivity as well as Timentin^? and Clavamox^® were evaluated using wild-type ‘F39’ and ‘150’ cotyledons. Kanamycin concentrations of 200 and 150 mg l^?1 were chosen as the threshold levels for ‘F39’ and ‘150’, respectively. No significant differences were found between Timentin^? and Clavamox^® in ‘F39’; however, Clavamox^® reduced the incidence of vitrification and increased the frequency of shoot elongation in ‘150’. A. tumefaciens strain EHA105, harboring pCNL56 carrying neomycin phosphotransferase II (nptII) and gusA reporter genes, was selected to establish a transformation protocol for ‘F39’ and ‘150’. Putative transformants were evaluated using β-glucuronidase (GUS) histochemical assay, polymerase chain reaction (PCR) and Southern blot analyses. Based on these parameters, the transformation efficiency for cantaloupe ‘F39’ was 0.3% and that for honeydew ‘150’ was 0.5%.     

Quantification of algal biofilms colonising building materials: chlorophyll a measured by PAM-fluorometry as a biomass parameter

Abstract

The aim of this study was to quantify algal colonisation on anthropogenic surfaces (viz. building facades and roof tiles) using chlorophyll a (chl a) as a specific biomarker. Chl a was estimated as the initial fluorescence F₀ of ‘dark adapted’ algae using a pulse-modulated fluorometer (PAM-2000). Four isolates of aeroterrestrial green algae and one aquatic isolate were included in this study. The chl a concentration and F₀ showed an exponential relationship in the tested range between 0 and 400 mg chl a m^?2. The relationship was linear at chl a concentrations <20 mg m^?2. Exponential and linear models are presented for the single isolates with large coefficients of determination (exponential: r² > 0.94, linear: r² > 0.92). The specific power of this fluorometric method is the detection of initial algal colonisation on surfaces in thin or young biofilms down to 3.5 mg chl a m^?2, which corresponds to an abundances of the investigated isolates between 0.2 and 1.5 million cells cm^?2.     

Barnacle settlement and the adhesion of protein and diatom microfouling to xerogel films with varying surface energy and water wettability

Previous work has shown that organosilica-based xerogels have the potential to control biofouling. In this study, modifications of chemistry were investigated with respect to their resistance to marine slimes and to settlement of barnacle cyprids. Adhesion force measurements of bovine serum albumin (BSA)-coated atomic force microscopy (AFM) tips to xerogel surfaces prepared from aminopropylsilyl-, fluorocarbonsilyl-, and hydrocarbonsilyl-containing precursors, indicated that adhesion was significantly less on the xerogel surfaces in comparison to a poly(dimethylsiloxane) elastomer (PDMSE) standard. The strength of adhesion of BSA on the xerogels was highest on surfaces with the highest and the lowest critical surface tensions, γ_C and surface energies, γ_S, and duplicated the ‘Baier curve’. The attachment to and removal of cells of the diatom Navicula perminuta from a similar series of xerogel surfaces were examined. Initial attachment of cells was comparable on all of the xerogel surfaces, but the percentage removal of attached cells by hydrodynamic shear stress increased with γ_C and increased wettability as measured by the static water contact angle, θ_Ws, of the xerogel surfaces. The percentage removal of cells of Navicula was linearly correlated with both properties (R ² = 0.74 for percentage removal as a function of θ_Ws and R ² = 0.69 for percentage removal as a function of γ_C). Several of the aminopropylsilyl-containing xerogels showed significantly greater removal of Navicula compared to a PDMSE standard. Cypris larvae of the barnacle B. amphitrite showed preferred settlement on hydrophilic/higher energy surfaces. Settlement was linearly correlated with θ_Ws (R ² = 0.84) and γ_C (R ² = 0.84). Hydrophilic xerogels should prove useful as coatings for boats in regions where fouling is dominated by microfouling (protein and diatom slimes).     

Carbonate and Phosphate Precipitation by Saline Soil Bacteria in a Monitored Culture Medium

Carbonate and phosphate precipitation by bacteria isolated from a saline soil was studied in vitro in a liquid culture medium over 45 days. Physicochemical parameters of this medium were continuously monitored using both selective electrodes (continuous monitoring, CM) and individual measurements by other techniques on days 5, 10, 15, 20, 25, 35 and 45 (discontinuous monitoring, DM). In DM, the precipitated minerals were studied (XRD and SEM-EDX) and the saturation index of the mineral phases was analyzed (PHREEQC program). Using the CM and DM data it was possible to distinguish several temporary stages in which both the medium and the mineralogy changed: 1) 0 to 10 days: pH reaches 8.4; significant loss of Mg²⁺ (incorporated into the bacterial biomass) and Ca²⁺ (through mineral precipitation); formation of crystals, although not in sufficient quantity to be studied until day 10. 2) 10 to 25 days: pH decreases but remains above 8; appreciable loss of Mg²⁺ and Ca²⁺ due to formation of spherical carbonate bioliths with traces of phosphates occluded within these carbonates. 3) After 25 days: biomineralization slow down; pH returns to initial values and struvite is formed (idiomorphic prismatic crystals). These trends are in agreement with the findings of other workers, although with some peculiarities regarding stages and types of mineral precipitated. In some cases the struvite contained small quantities of K and Ca, possibly because these are intermediate mineral species between typic-struvite, K-struvite and Ca-struvite. The bacteria-mediated precipitation of carbonates of Ca and/or Mg and phosphates (struvite) by the bacteria from a saline soil is demonstrated. However, struvite was not found in the soils of origin of the bacteria, possibly because it is a metastable mineral in most soils.     

Rapid treatment of vessels fouled with an invasive polychaete,Sabella spallanzanii,using a floating dock and chlorine as a biocide

Chlorine solution was added to the water encapsulated within a proprietary ‘floating dock’ to treat a vessel infested with the invasive polychaete Sabella spallanzanii. The chlorine was added as sodium dichloroisocyanurate (‘dichlor’) at an initial concentration of 200 mg l^?1 of free available chlorine (FAC). This concentration killed 99% of S. spallanzanii in their tubes during a 4-h exposure in laboratory tests (EC₉₉ 160 mg FAC l^?1). The concentration of FAC in the floating dock declined to ~50 mg l^?1 after 4 h and < 10 mg l^–1 after 16 h. Residual FAC was neutralised with thiosulphate at completion of exposure. A sample of 30 S. spallanzanii individuals collected from the hull after treatment all showed morphological damage and 28 showed no response to touch. Re-examination of the hull after 6 d found no live worms or other fouling organisms. This method provides a cost-effective, rapid means of treating hull fouling.     

Metal-Dependent Root Iron Plaque Effects on Distribution and Translocation of Chromium and Nickel in Yellow Flag (Iris pseudacorus L.)

Iris pseudacorus L. (yellow flag) is a wide-use wetland plant for constructed wetlands for removing metals from wastewater. This study aims to understand effects of root iron plaque on sequestration and translocation of Cr and Ni in yellow flag seedlings using a hydroponic experiment. Yellow flag seedlings (4-week-old seedlings with 4–6 leaves) with or without iron plaque induction (at 50 mg Fe²⁺ L^?1 for 72 hours) were spiked for 6 days in the Hoagland solution with Cr or Ni at 0.5, 5, and 50 mg L^?1, equivalent to 1, 10, 100 times of thresholds of surface water quality, respectively. Results indicated that root iron plaque significantly reduced translocation of Cr and Ni to root but increased from root to shoot. Root iron plaque formation counteracted Cr toxicity to yellow flag seedlings while the control showed Cr toxicity to root at 5 mg L^?1and to shoot at 50 mg L^?1 with significant biomass loss. Neither Ni exposures caused significant biomass loss nor root iron plaque formation significantly changed Ni distribution among plant parts. Our study suggests that root iron plaque effects on metal sequestration and translocation in yellow flag seedlings were metal-dependent.     

Subnanomolar indazole-5-carboxamide inhibitors of monoamine oxidase B (MAO-B) continued: indications of iron binding,experimental evidence for optimised solubility and brain penetration

Pharmacological and physicochemical studies of N-unsubstituted indazole-5-carboxamides (subclass I) and their structurally optimised N1-methylated analogues (subclass II), initially developed as drug and radioligand candidates for the treatment and diagnosis of Parkinson’s disease (PD), are presented. The compounds are highly brain permeable, selective, reversible, and competitive monoamine oxidase B (MAO-B) inhibitors with improved water-solubility and subnanomolar potency (pIC₅₀ >8.8). Using a well-validated, combined X-ray/modelling technology platform, we performed a semi-quantitative analysis of the binding modes of all compounds and investigated the role of the indazole N1 position for their MAO-B inhibitory activity. Moreover, compounds NTZ-1006, 1032, and 1441 were investigated for their ability to bind Fe²⁺ and Fe³⁺ ions using UV-visible spectroscopy.     

Spin concentration measurements of high-spin (g′ = 4.3) rhombic iron(III) ions in biological samples: theory and application

Electron paramagnetic resonance (EPR) signals at g′ = 4.3 are commonly encountered in biological samples owing to mononuclear high-spin (S = 5/2) Fe³⁺ ions in sites of low symmetry. The present study was undertaken to develop the experimental method and a suitable g′ = 4.3 intensity standard and for accurately quantifying the amount of Fe³⁺ responsible for such signals. By following the work of Aasa and Vänngård (J. Magn. Reson. 19:308–315, 1975), we present equations relating the EPR intensity of S = 5/2 ions to the intensities of S = 1/2 standards more commonly employed in EPR spectrometry. Of the chelates tested, Fe³⁺–EDTA (1:3 ratio) in 1:3 glycerol/water (v/v), pH 2, was found to be an excellent standard for frozen-solution S = 5/2 samples at 77 K. The spin concentrations of Cu²⁺–EDTA and aqua VO²⁺, both S = 1/2 ions, and of Fe³⁺–transferrin, an S = 5/2 ion, were measured against this standard and found to agree within 2.2% of their known metal ion concentrations. Relative standard deviations of ±3.6, ±5.3 and ±2.9% in spin concentration were obtained for the three samples, respectively. The spin concentration determined for Fe³⁺–desferrioxamine of known Fe³⁺ concentration was anomalously low suggesting the presence of EPR-silent multimeric iron species in solution.     

Impact of Progerbalin LG® on the apple fruit physical attributes

During two consecutive years (2010 and 2011) we evaluated the impact of Progerbalin LG^® (mixture of gibberellins (GA₄₊₇) and N ⁶-benzyladenine) on fruit weight, fruit dimensions, elongation, geometric mean diameter or fruit size, aspect ratio, surface area and fruit volume of five apple cultivars belonging to ‘Red Delicious’ group (‘Hapke’ grafted on M.9 and M.26, ‘Hi Red’, ‘Starking’ and ‘Top Red’ on M.9, and ‘Red Chief Camspur’ on MM.106 rootstock). Trees were sprayed twice with 30, 50 or 100 ml L^?1 i.e. between 80 % of open flowers and the following petal fall (first treatment), and 10 days after first application (second treatment); control trees were not sprayed. Results showed that the lowest dose increased fruit weight in all cultivars, except ‘Top Red’ and ‘Red Chief Camspur’; this dose promoted fruit dimensions, fruit size and elongation in ‘Hapke’ on both rootstocks, and also fruit dimensions, surface area and fruit volume in ‘Hi Red’. Regarding ‘Starking’, different doses of Progerbalin LG^® did not affect other properties evaluated, but season played an important role in these cases. In contrast, the highest dose of this hormone improved all physical attributes in ‘Top Red’ and ‘Red Chief Camspur’, except elongation and/or aspect ratio. In some cases, good values were found in control treatment.