Helices on Interdomain Interface Couple Catalysis in the ATPPase Domain with Allostery in Plasmodium falciparum GMP Synthetase

GMP synthetase catalyses the conversion of XMP to GMP through a series of reactions that include hydrolysis of Gln to generate ammonia in the glutamine amidotransferase (GATase) domain, activation of XMP to adenyl-XMP intermediate in the ATP pyrophosphatase (ATPPase) domain and reaction of ammonia with the intermediate to generate GMP. The functioning of GMP synthetases entails bidirectional domain crosstalk, which leads to allosteric activation of the GATase domain, synchronization of catalytic events and tunnelling of ammonia. Herein, we have taken recourse to the analysis of structures of GMP synthetases, site-directed mutagenesis and steady-state and transient kinetics on the Plasmodium falciparum enzyme to decipher the molecular basis of catalysis in the ATPPase domain and domain crosstalk. Our results suggest an arrangement at the interdomain interface, of helices with residues that play roles in ATPPase catalysis as well as domain crosstalk enabling the coupling of ATPPase catalysis with GATase activation. Overall, the study enhances our understanding of GMP synthetases, which are drug targets in many infectious pathogens.     

Structural evolution at short and medium range distances during crystallization of a P2O5-Li2O-Al2O3-SiO2 glass

Li₂O-Al₂O₃-SiO₂ (LAS) glass-ceramics have important industrial applications and bulk nucleation is usually achieved by using nucleating agents. In particular, P₂O₅ is an efficient agent in glasses containing a low level of Al₂O₃ but its role in the first stages of nucleation is not well established. In this study, we combine structural investigations from local to mesoscales to describe the structural evolution during crystallization of LAS glass-ceramics. Local environment is probed using ²⁹Si and ³¹P MAS-NMR, indicating organization of P in poorly crystallized Li₃PO₄ species prior to any crystallization. To better understand the detailed nanoscale changes of the glass structure, ³¹P-³¹P DQ-DRENAR homonuclear correlation experiments have been carried out, revealing the gradual segregation of P atoms associated with the formation of disordered Li₃PO₄. Small-angle neutron scattering data also show the apparition of nanoscale heterogeneities associated with Li₃PO₄ species upon heating treatments and allow the determination of their average sizes. These new structural information enhance our understanding of the role of P in nucleation mechanisms. Nucleation is initiated by gradual change in P environment implying P segregation upon heating treatments, forming disordered Li₃PO₄ heterogeneities. The segregation of P atoms enables the precipitation of meta- and disilicate phases.     

Influence of the character of NOM on the ozonation of MIB and geosmin

Tastes and odours (T&Os) are a major concern in drinking water as they are not efficiently removed by conventional water treatment. Ozonation has been effective for their destruction in some studies. However, the natural organic matter (NOM) in waters can affect the ozonation process and subsequently affect the destruction of T&Os. Five NOM fractions were isolated and ozonated in synthetic waters. The fraction containing the more highly coloured, higher molecular weight compounds exhibited the highest ozone (O3) demand, whereas the low aromatic fraction exhibited the lowest O3 demand. The character of the NOM fractions influenced the ozonation of MIB and geosmin. The destruction of MIB and geosmin was significantly higher in the fraction with the highest colour and UV/visible absorbance at all O3 doses. The destruction of the compounds in the other fractions showed the same trends, increasing MIB and geosmin destruction with increasing UV/visible absorbing character of the NOM. MIB was also ozonated in two real waters. with results showing a competing effect between NOM concentration and NOM character. The O3 reaction time was shown to be important for the destruction of both compounds.     

Raft crystals of poly(isoprene)-block-poly(ferrocenyldimethylsilane) and their surface wetting behavior during melting as observed by AFM and NanoTA

We report on the morphology evolution during heating and melting of lamellar poly(isoprene)-block-poly(ferrocenyldimethylsilane) (PI₇₆-b-PFDMS₇₆) raft crystals deposited at the native oxide surface of silicon (SiO₂) or at a highly ordered pyrolytic graphite (HOPG) surface, studied by in situ temperature controlled atomic force microscopy. Crystals deposited on hydrophilic SiO₂ surfaces revealed an irreversible decrease in length at temperatures of up to tens of degrees above their expected melting temperature, while maintaining their platelet-like structure. Crystals deposited on hydrophobic HOPG surfaces initially decreased in length below their expected melting temperature, while at 120 °C and above a typical molten morphology was observed. In addition, the irreversible formation of a PI₇₆-b-PFDMS₇₆ wetting layer around the crystals was observed upon increasing the temperature. These observations in the morphological behavior upon heating emphasize the role of interfacial energy between a surface deposited block copolymer based macromolecular nanostructure and its supporting substrate.     

Simulation analysis of producing xylitol from hemicelluloses of pre-hydrolysis liquor

The pre-hydrolysis liquor (PHL) of the kraft-based dissolving pulp production process is currently sent to the recovery boiler and incinerated. However, PHL contains about 5–8% lignocelluloses that can be utilized in the production of value-added chemicals. In this study, a process for producing xylitol from hemicelluloses in PHL is developed. This process involves several acidification, neutralization, adsorption (along with reactivation) and evaporation stages. The mass balance indicates that 533 kg/h xylitol (with 99% purity), 187 kg/h lignin, 806 kg/h basic ferric acetate, and 1600 kg/h gypsum can be produced from 41,670 kg/h PHL. The energy balance shows that the evaporators are the largest consumers of energy, while the reactivation kiln, acidification, neutralization, and precipitation processes generate some heat. Overall, 41% conversion of xylose to xylitol is achieved.     

Mosquito sound communication: are male swarms loud enough to attract females?

Given the unsurpassed sound sensitivity of mosquitoes among arthropods and the sound source power required for long-range hearing, we investigated the distance over which female mosquitoes detect species-specific cues in the sound of station-keeping mating swarms. A common misunderstanding, that mosquitoes cannot hear at long range because their hearing organs are ‘particle-velocity’ receptors, has clouded the fact that particle velocity is an intrinsic component of sound whatever the distance to the sound source. We exposed free-flying Anopheles coluzzii females to pre-recorded sounds of male An. coluzzii and An. gambiae s.s. swarms over a range of natural sound levels. Sound levels tested were related to equivalent distances between the female and the swarm for a given number of males, enabling us to infer distances over which females might hear large male swarms. We show that females do not respond to swarm sound up to 48 dB sound pressure level (SPL) and that louder SPLs are not ecologically relevant for a swarm. Considering that swarms are the only mosquito sound source that would be loud enough to be heard at long range, we conclude that inter-mosquito acoustic communication is restricted to close-range pair interactions. We also showed that the sensitivity to sound in free-flying males is much enhanced compared to that of tethered ones.