Preparation and characterization of scleroglucan drug delivery films: The effect of freeze‐thaw cycling

This study examined the effect of the freeze‐thaw process on the physical properties of films prepared from scleroglucan (Scl) hydrogels, suitable for drug delivery applications. Films made from Scl, using glycerol as plasticizer, were prepared from hydrogels by two procedures: a room temperature drying (RTD) method and a freeze‐thaw cyclic process, before the application of RTD, which results in a reinforced physically cross‐linked network. Films were characterized by studies of water vapor transmission (WVT), swelling, tensile tests, ESEM microscopy, FTIR, and drug release measurements. These determinations showed significant differences between films obtained by both treatments. The films prepared through freeze‐thaw cycles showed an important increase of the tensile strength with respect to those corresponding to films only air dried and a decreasing swelling degree in direct relationship to the number of freeze‐thaw cycles. A model drug, Theophylline, was included in these biocompatible films for in vitro drug release measurements, using a flat Franz cell. The physical differences observed between Scl films prepared with both methods can be explained proposing that the number of crosslinking points by hydrogen bonding increase when increasing the number of freezing and thawing cycles used for film preparation. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis,Inhibition Potency,Binding Mode,and Antiprotozoal Activities of Fluorescent Inhibitors of Trypanothione Reductase Based on Mepacrine‐Conjugated Diaryl Sulfide Scaffolds

Trypanothione reductase (TR) is a flavoenzyme unique to trypanosomatid parasites and a target for lead discovery programs. Various inhibitor scaffolds have emerged in the past, exhibiting moderate affinity for the parasite enzyme. Herein we show that the combination of two structural motifs of known TR inhibitors — diaryl sulfides and mepacrine — enables the simultaneous addressing of two hydrophobic patches in the active site. The binding efficacy of these conjugates is enhanced over that of the respective parent inhibitors. They show K_ic values for the parasite enzyme down to 0.9±0.1 μm and exhibit high selectivity for TR over human glutathione reductase (GR). Despite their considerable molecular mass and in some cases permanent positive charges, in vitro studies revealed IC₅₀ values in the low micromolar to sub‐micromolar range against Trypanosoma brucei rhodesiense and Trypanosoma cruzi, as well as the malaria parasite Plasmodium falciparum, which lack trypanothione metabolism. The inhibitors exhibit strong fluorescence due to their aminoacridine moiety. This feature allows visualization of the drugs in the parasite where high accumulation was observed by fluorescence microscopy even after short exposure times.     

Methods to Investigate the Adhesion of Soft Nano‐Coatings on Metal Substrates – Application to Polymer‐Coated Stents

Soft coatings are widely used to tailor the surface chemistry of materials without altering their bulk properties. However, the strength of adhesion between the coating and the substrate must be high enough for long‐term applications. This has become a major challenge in the medical field, especially for polymer‐coated stents, mainly due to several coating failures reported after mechanical expansion during clinical implantation. In this work, the applicability of current polymer‐metal adhesion tests to polymer‐coated stents is discussed. The small punch test was proposed as an adhesion test that allows fundamental studies on the adhesion and coating properties. This adhesion test was applied to thin fluorocarbon coatings deposited by plasma on 316L stainless steel.

     

In situ active chlorine generation for the treatment of dye-containing effluents

This study examined the possibility to remove colour causing-compounds from synthetic effluent by indirect electrochemical oxidation using iridium oxide anode electrodes. Using a high concentration of chloride ions (17.1 mM) and various current densities, it was possible to produce high concentration of active chlorine with a specific production rate of 2.8 mg min⁻¹ A⁻¹. The best performance for acid methyl violet 2B dye (MV2B) decomposition was obtained using Ti/IrO₂ anodes operated at a current density of 15 mA cm⁻² during 40 min of treatment in the presence of 3.42 mM of chloride ions. Under these conditions, more than 99% of MV2B was removed (with a reaction rate apparent constant of 0.20 min⁻¹), whereas COD and TOC removal were 51% and 75%, respectively. The electrolytic cell was then used for the degradation of three other synthetic dye solutions: Eosin yellowish (EOY), Trypan Blue (TRB), Acridine Orange (ACO). TRB was the most difficult dye to remove from solution with a value reaction rate constant of 0.12 min⁻¹, compared to 0.19 min⁻¹ and 0.24 min⁻¹ recorded for ACO and EOY dyes, respectively. More than 99% of these dyes were removed by electrochemical oxidation.     

Nitrogen balances in farmers fields under alternative uses of a cover crop legume: a case study from Nicaragua

Canavalia brasiliensis (canavalia), a drought tolerant legume, was introduced into the smallholder traditional crop-livestock production system of the Nicaraguan hillsides as green manure to improve soil fertility or as forage during the dry season for improving milk production. Since nitrogen (N) is considered the most limiting nutrient for agricultural production in the target area, the objective of this study was to quantify the soil surface N budgets at plot level in farmers fields over two cropping years for the traditional maize/bean rotation and the alternative maize/canavalia rotation. Mineral fertilizer N, seed N and symbiotically fixed N were summed up as N input to the system. Symbiotic N₂ fixation was assessed using the ¹⁵N natural abundance method. Nitrogen output was quantified as N export via harvested products. Canavalia derived in average 69% of its N from the atmosphere. The amount of N fixed per hectare varied highly according to the biomass production, which ranged from 0 to 5,700 kg ha^?1. When used as green manure, canavalia increased the N balance of the maize/canavalia rotation but had no effect on the N uptake of the following maize crop. When used as forage, it bears the risk of a soil N depletion up to 41 kg N ha^?1 unless N would be recycled to the plot by animal manure. Without N mineral fertilizer application, the N budget remains negative even if canavalia was used as green manure. Therefore, the replenishment of soil N stocks by using canavalia may need a few years, during which the application of mineral N fertilizer needs to be maintained to sustain agricultural production.     

Complexation of Tolane by Fluorinated Organomercurials—Structures and Luminescence Properties of an Unusual Class of Supramolecular π-Coordination Polymers

The interaction of the Hg(II) derivatives bis(pentafluoro)phenyl mercury (1), (pentafluoro)phenyl mercury chloride (2) and trimeric perfluoro-ortho-phenylene mercury (3) with tolane (diphenylacetylene) in CH₂Cl₂ leads to the formation of [1·tolane], [2 ₂·tolane], and [3·tolane·CH₂Cl₂]. These adducts have been characterized by elemental analysis, X-ray crystallography, and luminescence spectroscopy. In the solid state of these adducts, the tolane molecules interact with the molecules of 1, 2 and 3 via secondary Hg–π interactions and arene–fluoroarene interactions. As a result of an external mercury heavy atom effect, adducts [1·tolane] and [2 ₂·tolane] are phosphorescent at room temperature.     

Synthesis and characterization of cytidine derivatives that inhibit the kinase IspE of the non-mevalonate pathway for isoprenoid biosynthesis

The enzymes of the non-mevalonate pathway for isoprenoid biosynthesis are attractive targets for the development of novel drugs against malaria and tuberculosis. This pathway is used exclusively by the corresponding pathogens, but not by humans. A series of water-soluble, cytidine-based inhibitors that were originally designed for the fourth enzyme in the pathway, IspD, were shown to inhibit the subsequent enzyme, the kinase IspE (from Escherichia coli). The binding mode of the inhibitors was verified by co-crystal structure analysis, using Aquifex aeolicus IspE. The crystal structures represent the first reported example of a co-crystal structure of IspE with a synthetic ligand and confirmed that ligand binding affinity originates mainly from the interactions of the nucleobase moiety in the cytidine binding pocket of the enzyme. In contrast, the appended benzimidazole moieties of the ligands adopt various orientations in the active site and establish only poor intermolecular contacts with the protein. Defined binding sites for sulfate ions and glycerol molecules, components in the crystallization buffer, near the well-conserved ATP-binding Gly-rich loop of IspE were observed. The crystal structures of A. aeolicus IspE nicely complement the one from E. coli IspE for use in structure-based design, namely by providing invaluable structural information for the design of inhibitors targeting IspE from Mycobacterium tuberculosis and Plasmodium falciparum. Similar to the enzymes from these pathogens, A. aeolicus IspE directs the OH group of a tyrosine residue into a pocket in the active site. In the E. coli enzyme, on the other hand, this pocket is lined by phenylalanine and has a more pronounced hydrophobic character.     

Performance characteristics of a new structured packing

A new structured packing using carbon fibres, called Sepcarb^® 4D, is presented. This packing has several attractive properties, such as high voidage (ε=94%) and high effective area (a=420 m² m^?3). These properties are advantageous for packing used as a gas–liquid contactor for separation units. To determine the internal characteristics of this packing, we performed several experiments using a 150-mm-internal-diameter column. Firstly, hydrodynamics experiments were conducted using an air–water counter current flow to determine the pressure drop (for both dry and wet packing) and flooding point. Secondly, the mass transfer efficiency was determined in terms of HETP (height equivalent to theoretical plate) by total reflux experiments with an n-heptane/cyclohexane mixture at atmospheric pressure. Hydrodynamic performance and mass transfer efficiency were compared with those of packings generally used in distillation and absorption.     

Microwave analysis of PACVD diamond deposition reactor based on electromagnetic modelling

The production of high quality diamond films by microwave plasma assisted CVD, with rapid growth rates and good uniformity over large surfaces, requires perfectly optimized reactors from the microwave design point of view. Most MW plasma assisted CVD reactors used for diamond film deposition work on the resonant cavity principle. The design of such reactors relies on 3 choices: i) choice of a suitable resonant mode (i.e. with an electric field structure conducive to plasma ignition), ii) choice of a MW coupling system to excite the cavity, and iii) choice of a quartz window to delimit a reduced pressure zone inside the cavity, so as to obtain the plasma in front of the substrate [1].In this paper, we present an analysis method for MW plasma reactors relying on EM modelling, which allows for the identification of a resonant mode responsible for plasma ignition, applied to an existing reactor exhibiting plasma instabilities and requiring constant supervision.This analysis method, which can be generalised to any resonant cavity reactor, can describe the device behaviour (shape and location of the plasma, occurrence of instabilities) as a function of the various cavity geometrical configurations and to get a first estimate of the process performance.On the basis of such an analysis, it was possible to propose modifications to the reactor considered in order to improve process stability, and obtain higher growth rates. First growth tests done on diamond mono- and nano-crystalline films show excellent material quality and an increase in growth rate by more than an order of magnitude.     

Phenolic Composition and Antioxidant Capacity of Bilberry (<Emphasis Type=Italic>Vaccinium myrtillus</Emphasis>) Leaves in Northern Europe Following Foliar Development and Along Environmental Gradients

Bilberry is a characteristic field layer species in the boreal forests and is an important forage plant for herbivores of the North European ecosystem. Bilberry leaves contain high levels of phenolic compounds, especially hydroxycinnamic acids, flavonols, catechins, and proanthocyanidins. We investigated the phenolic composition of bilberry leaves in two studies, one following foliar development in forest and open areas, and the other along a wide geographical gradient from south to north boreal forests in Finland. An analysis of bilberry leaves collected in open and forest areas showed that major phenolic changes appeared in the first stages of leaf development, but, most importantly, synthesis and accumulation of flavonoids was delayed in the forest compared to the high light sites. Sampling along a geographical gradient in the boreal zone indicated that leaves from higher latitudes and higher altitudes had greater soluble phenolic and flavonol levels, higher antioxidant capacity, and lower contents of chlorogenic acid derivatives. The ecological significance of the results is discussed.