Evolutionary acquisition and loss of saxitoxin biosynthesis in dinoflagellates: The second "core" gene, sxtG

Saxitoxin and its derivatives are potent neurotoxins produced by several cyanobacteria and dinoflagellate species. SxtA is the initial enzyme in the biosynthesis of saxitoxin. The dinoflagellate full mRNA and partial genomic sequences have previously been characterized, and it appears that sxtA originated in dinoflagellates through a horizontal gene transfer from a bacterium. So far, little is known about the remaining genes involved in this pathway in dinoflagellates. Here we characterize sxtG, an amidinotransferase enzyme gene that putatively encodes the second step in saxitoxin biosynthesis. In this study, the entire sxtG transcripts from Alexandrium fundyense CCMP1719 and Alexandrium minutum CCMP113 were amplified and sequenced. The transcripts contained typical dinoflagellate spliced leader sequences and eukaryotic poly(A) tails. In addition, partial sxtG transcript fragments were amplified from four additional Alexandrium species and Gymnodinium catenatum. The phylogenetic inference of dinoflagellate sxtG, congruent with sxtA, revealed a bacterial origin. However, it is not known if sxtG was acquired independently of sxtA. Amplification and sequencing of the corresponding genomic sxtG region revealed noncanonical introns. These introns show a high interspecies and low intraspecies variance, suggesting multiple independent acquisitions and losses. Unlike sxtA, sxtG was also amplified from Alexandrium species not known to synthesize saxitoxin. However, amplification was not observed for 22 non-saxitoxin-producing dinoflagellate species other than those of the genus Alexandrium or G. catenatum. This result strengthens our hypothesis that saxitoxin synthesis has been secondarily lost in conjunction with sxtA for some descendant species. © 2013, American Society for Microbiology

Exploring potential mechanisms involved in the relationship between eudaimonic wellbeing and nature connection

ArticleThis is the author accepted manuscript. The final version is available from Elsevier via the DOI in this record.A growing body of research demonstrates associations between nature connection and a wide variety of positive health and wellbeing outcomes. Yet, the interpretation of this research is restricted because underpinning mechanisms − particularly the psychological mechanisms of wellbeing enhancement as opposed to wellbeing restoration − remain largely unexplored. Understanding such mechanisms is important for theory development and for assisting policy-makers and urban planners to translate this theory into practice effectively. This essay examines the limitations in our current understanding of the psychological mechanisms involved in the relationship between nature connection and eudaimonic wellbeing. It also advances opportunities to move the field forward through exploring two potential mechanisms, namely satisfying the psychological need of relatedness and fostering intrinsic value orientation. These mechanisms may explain how an individual’s level of nature connection enhances their psychological wellbeing. Understanding such mechanisms could improve the implementation of targeted nature connection policies and interventions designed to enhance psychological wellbeing among complex urban populations with diverse needs

Advances in the use of microgels as emulsion stabilisers and as a strategy for cellulose functionalisation

Microgel particles have recently emerged as an alternative route to emulsion stabilisation. Classed as soft colloidal particles, their ability to swell to differing degrees in certain solvents and to rearrange once attached to an interface makes them highly suitable for systems requiring long-term stabilization, such as formulations in the food, agricultural, cosmetic and pharmaceutical industries. Microgels made with biocompatible polymers such as proteins and polysaccharides in particular offer an environmental advantage and currently form a very active area of research. Cellulose, being a natural, biodegradable polymer, is an attractive ingredient for gels and microgels. However, its use as a functional material is often somewhat hindered by its insolubility in water and most other organic solvents. Furthermore, the surface activity of cellulose has proven difficult to harness and therefore its ability to act as an emulsion stabiliser has been almost exclusively applied to oil-in-water (O/W) emulsions, with very few reports on its water in oil (W/O) activity. This review aims to summarise some of the recent progress made in the microgel field including their ability to act as emulsion stabilisers, with a focus on cellulose microgels (CMGs). A brief overview of cellulose processing is also given, describing the dissolution and reprecipitation routes used to functionalise cellulose without covalent modification and the potential for cellulose particles and CMGs to act as O/W and W/O emulsion stabilisers

Opinion: Cloud-phase climate feedback and the importance of ice-nucleating particles

Shallow clouds covering vast areas of the world's middle- and high-latitude oceans play a key role in dampening the global temperature rise associated with CO2. These clouds, which contain both ice and supercooled water, respond to a warming world by transitioning to a state with more liquid water and a greater albedo, resulting in a negative “cloud-phase” climate feedback component. Here we argue that the magnitude of the negative cloud-phase feedback component depends on the amount and nature of the small fraction of aerosol particles that can nucleate ice crystals. We propose that a concerted research effort is required to reduce substantial uncertainties related to the poorly understood sources, concentration, seasonal cycles and nature of these ice-nucleating particles (INPs) and their rudimentary treatment in climate models. The topic is important because many climate models may have overestimated the magnitude of the cloud-phase feedback, and those with better representation of shallow oceanic clouds predict a substantially larger climate warming. We make the case that understanding the present-day INP population in shallow clouds in the cold sector of cyclone systems is particularly critical for defining present-day cloud phase and therefore how the clouds respond to warming. We also need to develop a predictive capability for future INP emissions and sinks in a warmer world with less ice and snow and potentially stronger INP sources

Effect of Oil on Cellulose Dissolution in the Ionic Liquid 1-Butyl-3-methyl Imidazolium Acetate

While ionic liquids (ILs) are well known to be excellent solvents for cellulose, the exact mechanism of dissolution has been a much disputed topic in recent years and is still not completely clear. In this work, we add to the current understanding and highlight the importance of hydrophobic interactions, through studying cellulose dissolution in mixtures of 1-butyl-3-methyl imidazolium acetate (BmimAc) and medium-chain triglyceride (MCT) oil. We demonstrate that the order in which constituents are mixed together plays a key role, through nuclear magnetic resonance (NMR) spectroscopic analysis. When small quantities of MCT oil (0.25–1 wt %) were introduced to BmimAc before cellulose, the effect on BmimAc chemical shift values was much more significant compared to when the cellulose was dissolved first, followed by oil addition. Rheological analysis also showed small differences in the viscosities of oil–cellulose–BmimAc solutions, depending on the order the constituents were added. On the other hand, no such order effect on the NMR results was observed when cellulose was replaced with cellobiose, suggesting that this observation is unique to the macromolecule. We propose that a cellulose–oil interaction develops but only when the cellulose structure has a sufficient degree of order and not when the cellulose is molecularly dispersed, since the hydrophobic cellulose plane is no longer intact. In all cases, cellulose–BmimAc–oil solutions were stable for at least 4 months. To our knowledge, this is the first work that investigates the effect of oil addition on the dissolving capacity of BmimAc and highlights the need for further re-evaluation of accepted mechanisms for cellulose dissolution in ILs

Relationship between size and cellulose content of cellulose microgels (CMGs) and their water-in-oil emulsifying capacity

Soluble polysaccharides have been used extensively as gelling/thickening agents in emulsions, but they generally display weak surface activity. Insoluble polysaccharides such as cellulose can be converted to thickening agents and even emulsifiers, but generally only after considerable chemical modification. Here we use the ionic liquid (IL) 1-butyl-3-methyl imidazolium acetate (BmimAc) to dissolve and reprecipitate cellulose in the presence of oil, i.e., a physical process, to tune the cellulose properties. ILs have previously been used in this way to form hydrophobic (‘oily’) cellulose microgels (CMGs), potentially capable of stabilizing water-in-oil (W/O) emulsions. However, these previous CMGs were made via a ‘top-down’ method and were relatively large and polydisperse, giving limited stability to the W/O emulsions formed. Here we demonstrate how the CMG size can be drastically reduced via a ‘bottom-up’ approach and employing high-pressure homogenization (HPH), thus achieving sub-micron CMG particle sizes. This has previously been impossible with other reported IL-cellulose coagulation methods and the corresponding W/O emulsions were more stable. In addition, confocal and cryo-scanning electron microscopy (SEM) revealed that the surface coverage of these CMGs on droplets increased over time, which led to the formation of even thicker interfacial layers and further enhanced emulsion stability (at least 2 months). We also demonstrate unequivocally that the stability of the W/O emulsions is indeed due to the CMGs adsorbing via the Pickering mechanism, rather than forming a stabilizing cellulosic network in the continuous phase, thus providing a novel route to ‘green’ Pickering emulsions

Mononuclear dysprosium(III) complexes with triphenylphosphine oxide ligands: controlling the coordination environment and magnetic anisotropy

We report the synthesis, structural and magnetic characterization of five mononuclear DyIII ion complexes using triphenylphosphine oxide as a monodentate ligand. They have formulae [DyIII(OPPh3)3(NO3)3] (1), [DyIII(OPPh3)4(NO3)2](NO3) (2), [DyIII(OPPh3)3Cl3] (3), [DyIII(OPPh3)4Cl2]Cl (4) and [DyIII(OPPh3)4Cl2](FeCl4) (5). These complexes are characterized using single crystal X-ray diffraction, which revealed that each complex has a unique coordination environment around the DyIII ion, which results in varying dynamic magnetic behavior. Ab initio calculations are performed to rationalize the observed magnetic behavior and to understand the effect that the ligand and coordination geometry around the DyIII ion has on the single-molecule magnet (SMM) behavior. In recent years, seven coordinate DyIII complexes possessing pseudo ~D5h symmetry are found to yield attractive blocking temperatures for the development of new SMM complexes. However, here we show that the strength of the donor ligand plays a critical role in determining the effective energy barrier and is not simply dependent on the geometry and the symmetry around the DyIII ion. Seven coordinate molecules possessing pseudo D5h symmetry with strong equatorial ligation and weak axial ligation are found to be inferior, exhibiting no SMM characteristics under zero-field conditions. Thus, this comprehensive study offers insight on improving the blocking temperature of mononuclear SMMs

Exploring the Influence of Diamagnetic Ions on the Mechanism of Magnetization Relaxation in {CoIII2LnIII2} (Ln = Dy, Tb, Ho) “Butterfly” Complexes

© 2017 American Chemical Society. The synthesis and magnetic and theoretical studies of three isostructural heterometallic [CoIII2LnIII2(μ3-OH)2(o-tol)4(mdea)2(NO3)2] (Ln = Dy (1), Tb (2), Ho (3)) "butterfly" complexes are reported (o-tol = o-toluate, (mdea)2- = doubly deprotonated N-methyldiethanolamine). The CoIII ions are diamagnetic in these complexes. Analysis of the dc magnetic susceptibility measurements reveal antiferromagnetic exchange coupling between the two LnIII ions for all three complexes. ac magnetic susceptibility measurements reveal single-molecule magnet (SMM) behavior for complex 1, in the absence of an external magnetic field, with an anisotropy barrier Ueff of 81.2 cm-1, while complexes 2 and 3 exhibit field induced SMM behavior, with a Ueff value of 34.2 cm-1 for 2. The barrier height for 3 could not be quantified. To understand the experimental observations, we performed DFT and ab initio CASSCF+RASSI-SO calculations to probe the single-ion properties and the nature and magnitude of the LnIII-LnIII magnetic coupling and to develop an understanding of the role the diamagnetic CoIII ion plays in the magnetization relaxation. The calculations were able to rationalize the experimental relaxation data for all complexes and strongly suggest that the CoIII ion is integral to the observation of SMM behavior in these systems. Thus, we explored further the effect that the diamagnetic CoIII ions have on the magnetization blocking of 1. We did this by modeling a dinuclear {DyIII2} complex (1a), with the removal of the diamagnetic ions, and three complexes of the types {KI2DyIII2} (1b), {ZnII2DyIII2} (1c), and {TiIV2DyIII2} (1d), each containing a different diamagnetic ion. We found that the presence of the diamagnetic ions results in larger negative charges on the bridging hydroxides (1b > 1c > 1 > 1d), in comparison to 1a (no diamagnetic ion), which reduces quantum tunneling of magnetization effects, allowing for more desirable SMM characteristics. The results indicate very strong dependence of diamagnetic ions in the magnetization blocking and the magnitude of the energy barriers. Here we propose a synthetic strategy to enhance the energy barrier in lanthanide-based SMMs by incorporating s- and d-block diamagnetic ions. The presented strategy is likely to have implications beyond the single-molecule magnets studied here

Counterflow dielectrophoresis for trypanosome enrichment and detection in blood

Human African trypanosomiasis or sleeping sickness is a deadly disease endemic in sub-Saharan Africa, caused by single-celled protozoan parasites. Although it has been targeted for elimination by 2020, this will only be realized if diagnosis can be improved to enable identification and treatment of afflicted patients. Existing techniques of detection are restricted by their limited field-applicability, sensitivity and capacity for automation. Microfluidic-based technologies offer the potential for highly sensitive automated devices that could achieve detection at the lowest levels of parasitemia and consequently help in the elimination programme. In this work we implement an electrokinetic technique for the separation of trypanosomes from both mouse and human blood. This technique utilises differences in polarisability between the blood cells and trypanosomes to achieve separation through opposed bi-directional movement (cell counterflow). We combine this enrichment technique with an automated image analysis detection algorithm, negating the need for a human operator

Strong control of Southern Ocean cloud reflectivity by ice-nucleating particles

Large biases in climate model simulations of cloud radiative properties over the Southern Ocean cause large errors in modeled sea surface temperatures, atmospheric circulation, and climate sensitivity. Here, we combine cloud-resolving model simulations with estimates of the concentration of ice-nucleating particles in this region to show that our simulated Southern Ocean clouds reflect far more radiation than predicted by global models, in agreement with satellite observations. Specifically, we show that the clouds that are most sensitive to the concentration of ice-nucleating particles are low-level mixed-phase clouds in the cold sectors of extratropical cyclones, which have previously been identified as a main contributor to the Southern Ocean radiation bias. The very low ice-nucleating particle concentrations that prevail over the Southern Ocean strongly suppress cloud droplet freezing, reduce precipitation, and enhance cloud reflectivity. The results help explain why a strong radiation bias occurs mainly in this remote region away from major sources of ice-nucleating particles. The results present a substantial challenge to climate models to be able to simulate realistic ice-nucleating particle concentrations and their effects under specific meteorological conditions