Geometries of stacking interactions between phenanthroline ligands in crystal structures of square-planar metal complexes

Stacking interactions of phenanthroline square-planar complexes in crystal structures were studied by analyzing data from the Cambridge Structural Database. In most of the crystal structures, two phenanthroline complexes were oriented “head to tail.” Phenanthroline complexes show a wide range of overlap geometries in stacking interactions, while short metal–metal distances were not observed. Stacking chains with alternating overlaps were the predominant type of packing in the crystal structures.     

Theoretical study of 1-(4-hexylcyclohexyl)-4-isothiocyanatobenzene: molecular properties and spectral characteristics

The mesogenic species 4-(4-hexylcyclohexyl) isothiocyanatobenzene (6CHBT) was studied with density functional theory and molecular mechanics in order to investigate the molecular properties, interactions between dimers and to interpret the IR spectrum. Two types of calculations were performed for model systems containing single and double molecules of 6CHBT. Calculations (involving conformation analysis) for isolated species indicated that the trans isomer, in the equatorial–equatorial conformation, is the most energetically stable. The 6CHBT molecule is polar, with a rather high (4.43 D) dipole moment with negatively charged isothiocyanato (NCS) ligand. The dimer–dimer interaction energies show that the head-to-head configuration (where van der Waals attraction forces play the major role) is the most energetically stable. Vibrational analysis provided detailed assignment of the experimental infra-red (IR) spectrum. Figure Most favorite 6CHBT head to head interaction - ESP mapped to electron density surface Dedication  This paper is dedicated to the memory of Dr. Wacław Witko, who introduced us to research on mesogenic systems.     

Measurement of Dynamic Interfacial Tension in a Carbohydrate Melt at High Temperature Using a Drop Volume Tensiometer

Many food and encapsulation products are dispersed systems with a highly viscous concentrated carbohydrate solution or melt as the continuous phase and for which interfacial properties are important at high temperatures. A drop volume interfacial tensiometer was utilized to provide objective characterization of surfactant behavior in such systems at temperatures typical of food production processes. Interfacial tension was measured over a range of flow rates within a maltodextrin–sucrose–water melt at 105 °C using limonene as the oil phase and a sucrose ester surfactant. The results showed that the kinetics of surfactant adsorption were faster when the surfactant was dissolved in the oil phase. However, the low critical micelle concentration in the oil phase resulted in a lower than expected diffusion coefficient.     

NMR studies on interaction of lauryl maltoside with cytochrome c oxidase: a model for surfactant interaction with the membrane protein

Interaction of lauryl maltoside (LM) surfactant with bovine heart cytochrome c oxidase (CcO) has been studied by NMR techniques. Detailed 2-D (1)H and (13)C NMR techniques were used to assign the NMR signals of the surfactant nuclei. Paramagnetic dipolar shift of the surfactant (13)C NMR signals were used to identify the atoms close to the enzyme. The diamagnetic carbon monoxide complex of CcO did not cause any shift in the surfactant NMR spectra suggesting that the paramagnetic centres of the native CcO cause the shifts by dipolar interactions. The results showed that the polar head groups of the surfactant comprised of two maltoside rings are more affected, while the hydrophobic tail groups did not show any significant change on binding of the surfactant to the enzyme. This indicated that surfactant head groups possibly bind to the enzyme surface and the hydrophobic tail of the surfactant forms micelles and remains away from the enzyme. Based on the results, we propose that the membrane bound enzyme is possibly stabilised in aqueous solution by association with the micelles of the neutral surfactant so that the polar heads of the micelles bind to the polar surface of the enzyme. These micelles might form a 'belt like' structure around the enzyme helping it to remain monodispersed in the active form.     

Cubic phases of ternary amphiphile–water systems

The reversed cubic phases (Q_II) are a class of self-assembled amphiphile–water structures that are rich in diversity and structural complexity. These nanostructured liquid crystalline materials are generating much interest owing to their unique surface morphology, biological relevance and potential technological and medical applications. The structure of Q_II phases in binary amphiphile–water systems is affected by the molecular structure of surfactant, water content, temperature and pressure. The presence of additives also plays an important role. The structure and phase behaviour of ternary Q_II phases, which are comprised of two miscible amphiphiles and water, significantly differ from the binary system alone. The modulation of the phase behaviour through the addition of a second amphiphile offers an opportunity to control the size and shape of the nanostructures using a ‘bottom-up’ approach. In this mini-review, we discuss the structure of reversed cubic phases of amphiphile–water systems and highlight the modulation of cubic-phase structure in ternary-phase systems. We also extend this review to bulk cubic phases and the corresponding nanoscale dispersions, cubic-phase nanoparticles.     

Diclofenac-β-cyclodextrin binary systems: Physicochemical characterization and in vitro dissolution and diffusion studies

The aim of this work was to study the influence of β-cyclodextrin (β-CD) on the biopharmaceutic properties of diclofenac (DCF). To this purpose the physicochemical characterization of diclofenac-β-cyclodextrin binary systems was performed both in solution and solid state. Solid phase characterization was performed using differential scanning calorimetry (DSC), powder x-ray diffractometry (XRD), and Fourier transform infrared spectroscopy (FTIR). Phase solubility analyses, and in vitro permeation experiments through a synthetic membrane were performed in solution. Moreover, DCF/β-CD interactions were studied in DMSO by¹H nuclear magnetic resonance (NMR) spectroscopy. The effects of different preparation methods and drug-to-β-CD molar ratios were also evaluated. Phase solubility studies revealed 1∶1 M complexation of DCF when the freeze-drying method was used for the preparation of the binary system. The true inclusion for the freeze-dried binary system was confirmed by¹H NMR spectroscopy, DSC, powder XRD, and IR studies. The dissolution study revealed that the drug dissolution rate was improved by the presence of CDs and the highest and promptest release was obtained with the freeze-dried binary system. Diffusion experiments through a silicone membrane showed that DCF diffusion was higher from the saturated drug solution (control) than the freeze-dried inclusion complexes, prepared using different DCF-β-CD molar ratios. However, the presence of the inclusion complex was able to stabilize the system giving rise to a more regular diffusion profile. Published: October 22, 2005     

Seeing through the lizard’s trick: do avian predators avoid autotomous tails?

Counter-adaptations of predators towards their prey are a far less investigated phenomenon in predator-prey interactions. Caudal autotomy is generally considered an effective last-resort mechanism for evading predators. However, in victim-exploiter relationships, the efficacy of a strategy will obviously depend on the antagonist’s ability to counter it. In the logic of the predator-prey arms race, one would expect predators to develop attack strategies that minimize the chance of autotomy of the prey and damage on the predator. We tested whether avian predators preferred grasping lizards by their head. We constructed plasticine models of the Italian wall lizard (Podarcis sicula) and placed them in natural habitat of the species. Judging from counts of beak marks on the models, birds preferentially attack the head and might also avoid the tail and limb regions. While a preference for the head might not necessarily demonstrate tail and limb avoidance, this topic needs further exploration because it suggests that even unspecialised avian predators may see through the lizard’s trick-of-the-tail. This result may have implications for our understanding of the evolution of this peculiar defensive system and the loss or decreased tendency to shed the tail on island systems with the absence of terrestrial predators.     

Perturbation of DPPC/POPG bilayers by the N-terminal helix of lung surfactant protein SP-B: a <Superscript>2</Superscript>H NMR study

SP-B_8–25 is a synthetic peptide comprising the N-terminal helix of the essential lung surfactant protein SP-B. Rat lung oxygenation studies have shown that SP-B_8–25 retains some of the function of full-length SP-B. We have used deuterium nuclear magnetic resonance (²H-NMR) to examine the influence of SP-B_8–25 on the mixing properties of saturated PC and unsaturated PG lipids in model mixed lipid bilayers containing dipalmitoylphosphatidylcholine (DPPC) and palmitoyl-oleoyl-phosphatidylglycerol (POPG), in a molar ratio of 7:3. In the absence of the peptide, ²H-NMR spectra of DPPC/POPG mixtures, with one or the other lipid component deuterated, indicate coexistence of large liquid crystal and gel domains over a range of about 10°C through the liquid crystal to gel transition of the bilayer. Addition of SP-B_8–25 has little effect on the width of the transition but the spectra through the transition range cannot be resolved into distinct liquid crystal and gel spectral components suggesting that the peptide interferes with the tendency of the DPPC and POPG lipid components in this mixture to phase separate near the bilayer transition temperature. Quadrupole echo decay observations suggest that the peptide may also reduce differences in the correlation times for local reorientation of the two lipids. These observations suggest that SP-B_8–25 promotes a more thorough mixing of saturated PC and unsaturated PG components and may be relevant to understanding the behaviour of lung surfactant material under conditions of lateral compression which might be expected to enhance the propensity for saturated and unsaturated surfactant lipid components to segregate.     

Evaluation of SLS: APG Mixed Surfactant Systems as Carrier for Solid Dispersion

The present investigation aims at studying the effect of mixed surfactant system of sodium lauryl sulphate (SLS) and alkyl polyglucosides (C₁₀APG, C₁₂APG and C_12/14APG) on dissolution rate enhancement of poorly water soluble drug. Aceclofenac—a non-steroidal anti-inflammatory agent was used as a model drug as it has limited water solubility. The influence of the surfactant concentration in various blends on dissolution rate of Solid Dispersion (SD), prepared using solution method with ethanol as the solvent was studied and the advantage of mixed surfactant systems over the individual surfactants was illustrated by differences in the in-vitro dissolution profiles of SD. Physico chemical evaluation (critical micellar concentration, zeta potential and β-parameter calculations) was carried out to study the mixed surfactant systems. Solid mixtures were characterized by Infrared spectroscopy (FT-IR); X-ray diffraction studies (XRD) and scanning electron microscopy (SEM). It was seen that the dissolution rate of aceclofenac from SD increased with the increase in the APG proportion relative to SLS with the optimum ratio of 0.2 SLS:0.8 APG showing the best effect in all cases. Results obtained from physico-chemical evaluation (the decrease in the value of critical micelle concentration and higher negative value of β-parameters) suggested the existence of synergism between surfactants blends. The observed results in the dissolution rate enhancement could be attributed to the drug—surfactant interactions as evident from FT-IR, SEM and XRD results.     

Indirect interactions in aphid–parasitoid communities

Indirect interactions between populations of different species can be important in structuring natural communities. Indirect effects are either mediated by changes in population densities (trophic or density-mediated effects) or by changes in the behavior of species that are not trophically connected (behavioral or trait-mediated effects). We reviewed the literature on aphids and their parasitoids to explore the various possible indirect interactions that can occur in such communities. The review was motivated by our study of a particular aphid–parasitoid community in a natural (i.e., nonagricultural) habitat, and by the wealth of information that exists about aphid–parasitoid systems in agricultural settings. We focused our review on aphid–parasitoid interactions, but considered how these were influenced by the other aphid natural enemies and also by aphid mutualists and host plants. We conclude that indirect effects are likely to have a major effect in structuring aphid–parasitoid communities, and that the latter are a valuable model system for testing ideas about community interactions. Received: December 20, 1998 / Accepted: January 12, 1999     

Solubilization and interaction of α-tocopherol in water-aerosol OT-isooctane systems

Solubilization and interaction of α-tocopherol into bis(2-ethylhexyl)sulphosuc cinate sodium salt microemulsion systems have been studied by temperature dependent phase transition, viscosity and nuclear magnetic resonance studies. Tocopherol being an amphiphilic molecule dissolves into the interfacial surfactant monolayer of the microemul sion droplets. The dissolution leads to an enhancement of the rigidity of the surfactant monolayer as studied by the increase in mixing and phase transition temperatures of the microemulsion droplets. Solubilization of tocopherol into microemulsion droplets causes an increase in the effective size of the droplet and as a consequence, the inter-droplet interactions are also increased. The water binding capacity of the surfactant (bis(2-ethylhexyl)sulphosuccinate sodium salt) is reduced due to solubilization of tocopherol as is evidenced from the downfield shifts of water proton magnetic resonances. In the presence of the dissolved electrolytes into the aqueous core, tocopherol is squeezed out of the microemulsion droplets increasing the membrane fluidity and permeability.     

The effect of sedimentation and microbial nitrogen regeneration in a plankton community: a simulation investigation

A computer simulation model was developed to investigate nitrogenfluxes associated with microbial interactions in plankton communities.A short time scale was used, appropriate to the build-up anddecline of phytoplankton blooms in temperate shelf waters aftera mixing or upwelling event. The model depicts a continuum ofevents, many of which have been observed in coastal, upwellingand oceanic systems, including two phytoplankton peaks correspondingto ‘new production’ and ‘regenerated production’.It predicts that nitrogen loss through sedimentation of phytoplanktonand faeces may result in a smaller bloom with a delayed onsetand prolonged duration. Microbial regeneration of nitrogen wasfound to be important in sustaining the middle stages of a phytoplanktonbloom, whereas micro- and meso-zooplankton regeneration occurredtowards the end of the bloom.     

Protein–protein interactions within peroxiredoxin systems

Peroxiredoxin systems in plants were demonstrated involved in crucial roles related to reactive oxygenated species (ROS) metabolism and the linked cell signalling to ROS. Peroxiredoxins function as peroxidasic systems that combine at least a reactivating reductant agent like thioredoxins, and sometimes glutaredoxins and glutathion. In the past three years a number of peroxiredoxin structures were solved by crystallography in different experimental crystallisation conditions. The structures have revealed a significant propensity of peroxiredoxins for oligomerism that was confirmed by biophysical studies in solution using NMR and other methods as analytical ultra-centrifugation. These studies showed that quaternary structures of peroxiredoxins involve specific protein–protein interaction interfaces that rely upon the peroxiredoxin types and/or their redox conditions. The protein–protein interactions with the reactivating redoxins essentially lead to transient unstable complexes. We review herein the different protein–protein interactions characterized or deduced from those reports.VNM is recipient of a PhD fellowship of the French Ministère de l’Enseignement Supérieur de la Recherche et des Nouvelles Technologies for the year 2003–2006 and the Research Doctorate School of Chemistry of Lyon.     

Degeneracy-Driven Self-Structuring Dynamics in Selective Repertoires

Numerous biological interactions, such as interactions between T cell receptors or antibodies with antigens, interactions between enzymes and substrates, or interactions between predators and prey are often not strictly specific. In such less specific, or “sloppy,” systems, referred to here as degenerate systems, a given unit of a diverse resource (antigens, enzymatic substrates, prey) is at risk of being recognized and consumed by multiple consumers (lymphocytes, enzymes, predators). In this study, we model generalized degenerate consumer-resource systems of Lotka–Volterra and Verhulst types. In the degenerate systems of Lotka–Volterra, there is a continuum of types of consumer and resource based on variation of a single trait (characteristic, or preference). The consumers experience competition for a continuum of resource types. This non-local interaction system is modeled with partial differential-integral equations and shows spontaneous self-structuring of the consumer population that depends on the degree of interaction degeneracy between resource and consumer, but does not mirror the distribution of resource. We also show that the classical Verhulst (i.e. logistic) single population model can be generalized to a degenerate model, which shows qualitative behavior similar to that in the degenerate Lotka–Volterra model. These results provide better insight into the dynamics of selective systems in biology, suggesting that adaptation of degenerate repertoires is not a simple “mirroring” of the environment by the “fittest” elements of population.     

Food Webs and Disease: Is Pathogen Diversity Limited by Vector Diversity?

Classical predator–prey and host–parasite systems have been extensively studied in a food web context. Less attention has been paid to communities that include pathogens and their vectors. We present a coarse-grained, pan-African analysis of the relationships between the abiotic environment (location, precipitation, temperature), the species richness and community composition of ixodid ticks, and the species richness and community composition of pathogens that ticks transmit to humans. We found strong correlations between the abiotic environment and tick species richness, and a weak but significant correlation between the abiotic environment and pathogen species richness. A substantial amount of variation in community composition of parasites and pathogens was not explained by the variables that we considered. A structural equation model that compensated for the indirect effects of climate on the pathogen community via tick community composition suggested that while the environment strongly regulates tick community composition and tick community composition strongly regulates pathogen community composition, abiotic influences on pathogen species richness and community composition are weak. Our results support the view that changes in the broader environment will influence tick-borne pathogens primarily via the influence of the environment on ticks. The interactions that regulate host–vector–pathogen dynamics are of particular relevance in understanding the relationships between environmental change and health concerns, such as the impact of climate change on the occurrence of vector-borne diseases.     

Modelling the phase equilibria in two-component membranes of phospholipids with different acyl-chain lengths

A phenomenological model is proposed to describe the membrane phase equilibria in binary mixtures of saturated phospholipids with different acyl-chain lengths. The model is formulated in terms of thermodynamic and thermomechanic properties of the pure lipid bilayers, specifically the chain-melting transition temperature and enthalpy, the hydrophobic bilayer thickness, and the lateral area compressibility modulus. The model is studied using a regular solution theory made up of a set of interaction parameters which directly identify that part of the lipid-lipid interaction which is due to hydrophobic mismatch of saturated chains of different lengths. It is then found that there is effectively a single universal interaction parameter which, in the full composition range, describes the phase equilibria in mixtures of DMPC/DPPC, DPPC/DSPC, DMPC/DSPC, and DLPC/DSPC, in excellent agreement with experimental measurements. The model is used to predict the variation with temperature and composition of the specific heat, as well as of the average membrane thickness and area in each of the phases. Given the value of the universal interaction parameter, the model is then used to predict the phase diagrams of binary mixtures of phospholipids with different polar head groups, e.g., DPPC/DPPE, DMPC/DPPE and DMPE/DSPC. By comparison with experimental results for these mixtures, it is shown that difference in acyl-chain lengths gives the major contribution to deviation from ideal mixing. Application of the model to mixtures with non-saturated lipids is also discussed.     

Investigation of extractive microbial transformation in nonionic surfactant micelle aqueous solution using response surface methodology

Extractive microbial transformation of L-phenylacetylcarbinol (L-PAC) in nonionic surfactant Triton X-100 micelle aqueous solution was investigated by response surface methodology. Based on the Box–Behnken design, a mathematical model was developed for the predication of mutual interactions between benzaldehyde, Triton X-100, and glucose on L-PAC production. It indicated that the negative or positive effect of nonionic surfactant strongly depended on the substrate concentration. The model predicted that the optimal concentration of benzaldehyde, Triton X-100, and glucose was 1.2 ml, 15 g, and 2.76 g per 100 ml, respectively. Under the optimal condition, the maximum L-PAC production was 27.6 mM, which was verified by a time course of extractive microbial transformation. A discrete fed-batch process for verification of cell activity was also presented.     

Bistability and regular spatial patterns in arid ecosystems

A variety of patterns observed in ecosystems can be explained by resource–concentration mechanisms. A resource–concentration mechanism occurs when organisms increase the lateral flow of a resource toward them, leading to a local concentration of this resource and to its depletion from areas farther away. In resource–concentration systems, it has been proposed that certain spatial patterns could indicate proximity to discontinuous transitions where an ecosystem abruptly shifts from one stable state to another. Here, we test this hypothesis using a model of vegetation dynamics in arid ecosystems. In this model, a resource–concentration mechanism drives a positive feedback between vegetation and soil water availability. We derived the conditions leading to bistability and pattern formation. Our analysis revealed that bistability and regular pattern formation are linked in our model. This means that, when regular vegetation patterns occur, they indicate that the system is along a discontinuous transition to desertification. Yet, in real systems, only observing regular vegetation patterns without identifying the pattern-driving mechanism might not be enough to conclude that an ecosystem is along a discontinuous transition because similar patterns can emerge from different ecological mechanisms.     

A new sea catfish,Netuma patriciae (Siluriformes: Ariidae), from the Philippines

A new sea catfish (Ariidae), Netuma patriciae, is described based on the holotype and nine paratypes, 127.3–303.4 mm in standard length, collected from Panay and Luzon islands, Philippines. The new species most resembles N. thalassina (Rüppell 1837), in sharing counts of anal-fin rays (17–19 in N. patriciae, 15–17 in N. thalassina) and a distinct dorsomedian head groove (longitudinal length of the groove, 33.7–40.1% of head length, 22.3–31.0%). However, the new species can be easily distinguished from the latter in having fused vomerine tooth patches, and more numerous free vertebrae (43–44 vs. 41–42 in N. thalassina). Although N. bilineata (Valenciennes in Cuvier and Valenciennes 1840a) has also fused vomerine tooth patches, the new species is distinguished by having fewer free vertebrae (43–44 vs. 47–51 in N. bilineata) and longer dorsomedian head groove (33.7–40.1% of head length vs. 0–9.7%). The new species can also be easily distinguished from both N. thalassina and N. bilineata by having a filamentous dorsal-fin ray (longest dorsal-fin ray 26.9–35.9% of standard length vs 20.3–23.3% in N. thalassina, 20.9–25.3% in N. bilineata, standard length > 127 mm) and a U-shaped junction of dorsomedian head ridge (vs. V-shaped in both species).