Response of microbial communities to nutrient removal in coastal sediment by using ecological concrete.

Ecological concrete (eco-concrete) is a kind of environment-friendly material with porous characteristics. In this study, the eco-concrete was used to remove the total nitrogen (TN), total phosphorus (TP), and total organic carbon (TOC) in marine coastal sediment. The bacterial communities in sediment and on eco-concrete surface were also investigated by using high-throughput sequencing and quantitative PCR of 16S rRNA gene. We found that the mean removal efficiencies of TN, TP, and TOC in treatment group were 8.3%, 8.4%, and 12.3% after 28 days. The bacterial community composition in the treatment group was significantly different from that in the control group on day 28. In addition, the bacterial community composition on eco-concrete surface was slightly different from that in sediment, and the copy numbers of 16S rRNA gene were higher on eco-concrete surface than in sediment. The types of eco-concrete aggregates (gravel, pebble, and zeolite) also had effects on the bacterial community composition and 16S rRNA gene copy numbers. Furthermore, we found the abundant genus Sulfurovum increased significantly on eco-concrete surface in the treatment group after 28 days. Bacteria belonging to this genus were found having denitrification ability and were commonly detected in bioreactors for nitrate removal. Overall, our study expands the application scopes of eco-concrete and suggests that the bacterial communities in eco-concrete can potentially enhance the removal efficiency of nutrients in coastal sediment.

Use of ecological concrete for nutrient removal in coastal sediment and its effects on sediment microbial communities.

Ecological concrete (eco-concrete) can reduce excess nutrients (nitrogen and phosphorus) in water, but its effectiveness in removing nutrients in marine coastal sediments and the response of sediment microbial communities to its use are largely unknown. In this study, eco-concrete planted with Bruguiera gymnorrhiza was used to remove nutrients in marine coastal sediment. We found that the mean removal efficiencies of sediment total nitrogen and total phosphorus by using planted eco-concrete were 11.50% and 30.31% on day 60, and were higher than those obtained by only using B. gymnorrhiza (7.14% and 7.36%). the Diatoms and bacterial genera Fusibacter and Anoxynatronum (which belong to Firmicutes) increased and became the abundant microbes by day 60 when using planted eco-concrete, indicating their potential roles in nutrient removal. Moreover, the eco-concrete did not endanger the core microbes in sediment suggesting its environment-friendly character. Our results suggest a potential method to control marine coastal eutrophication.

Characteristics of microbial eukaryotic community recovery in eutrophic water by using ecological floating beds.

Ecological floating beds can rapidly remove nutrients (nitrogen and phosphorus) from eutrophic water, but we still know little about whether this process can simultaneously recover microbial eukaryotic communities. To fill this gap, planktonic microbial eukaryotic communities were investigated using 18S rRNA high-throughput gene sequencing during nutrient removal by floating beds of Canna indica L. We found that nutrient concentrations were high in both the control and treatment groups during period 1 (days 0-5) but rapidly decreased in the treatment group during period 2 (days 6-9) and period 3 (days 10-18). However, the microbial eukaryotic species richness and community compositions were similar between the control and treatment groups during periods 1 and 2 but showed small differences during period 3. The microbial eukaryotic co-occurrence networks between the control and treatment groups also showed similar degree centrality and interconnected eukaryotic members. We found that some abundant fungi species significantly responded to nutrient variations, but a large number of abundant ciliates were insensitive to nutrient removal. Our findings suggest that ecological floating beds can rapidly remove nutrients in eutrophic waters but that it is difficult to quickly and simultaneously improve microbial eukaryotic communities. This result reveals the critical influence of nutrient pollution on aquatic ecosystems and therefore on long-term and comprehensive aquatic habitat restoration, as aquatic macrophyte recoveries should be conducted after nutrient controls have been implemented.

Asymmetric abstraction of two chemically-equivalent methylene hydrogens: significant enantioselectivity of endoperoxide presented by fumitremorgin B endoperoxidase.

The combination of the inert C-H bond activation and asymmetric synthesis, especially the transformation of prochiral sp3 precursors to chiral sp3 centers, is a profound challenge. In the present DFT calculations, the unique enantioselectivity in verruculogen biosynthesis catalyzed by fumitremorgin B endoperoxidase (FtmOx1) has been mechanistically investigated, where a prochiral methylene in fumitremorgin B is dominantly converted to an R-chiral eight-membered endoperoxy ring. FtmOx1 is the first-reported mononuclear α-ketoglutarate-dependent non-heme iron enzyme responsible for chiral endoperoxide formation, which handles the substrate using a Tyr224 radical resulting from the hydrogen abstraction by an FeIV[double bond, length as m-dash]O species. It is demonstrated that the perfect enantioselectivity of the R-endoperoxy ring originates from the asymmetric abstraction of two chemically-equivalent methylene hydrogens from substrate chain A by the Tyr224 radical and the high conformation stability of the resultant chain A radical due to steric effects. The barrier difference in the abstraction of two hydrogens is 5.6 kcal mol-1. The hydrogen abstraction by the Tyr224 radical is rate-limiting in the FtmOx1 reaction with an overall barrier of 18.6 kcal mol-1. The results obtained here advance the understanding of the chemistry in enantioselectivity, providing a potentially general way for the transformation of prochiral sp3 precursors to chiral sp3 centers.

µ3-Oxo stabilized by three metal cations is a sufficient nucleophile for enzymatic hydrolysis of phosphate monoesters.

Diverse species have previously been proposed to be effective nucleophiles in the enzymatic hydrolysis of phosphate esters. A novel penta-metal cluster (two Fe(3+) and three Ca(2+)) was recently discovered in the active site of PhoX alkaline phosphatase, with the revelation of the architecture of µ3-oxo bridging one Ca(2+) and two antiferromagnetically coupled Fe(3+). In this work, using density functional theory calculations, the µ3-oxo stabilized by three cations has been demonstrated to be a new type of effective nucleophile. The calculations give strong support to the "ping-pong" mechanism involving the nucleophilic attack of the µ3-oxo on the substrate phosphor and the subsequent hydrolysis of the covalent phospho-enzyme intermediate. A base mechanism with the µ3-oxo acting as a general base to activate an additional water molecule has further been demonstrated to be inaccessible. The results advance the understanding of the enzymatic hydrolysis of phosphate esters and may give important inspiration for the exploration of multinuclear biomimetic catalysts.

Enhancing effects of hydrogen/halogen bonds on σ-hole interactions involving ylide.

Cooperativity between the H/Cl···C bonds of XH/XCl···CH2PH3 and the P···N interaction of CH2PH3···NH3 in XH/XCl···CH2PH3···NH3 (X = F, N3, CN, CCCN, CCF) was investigated by performing second-order Møller-Plesset perturbation theory (MP2) calculations and quantum theory of atoms in molecules (QTAIM) studies. The formation of a hydrogen/halogen bond greatly extends the scope and increases the most positive electrostatic potential of the σ-hole on the outer surface of the phosphorus atom. This increases the P···N interaction energy, the electron density at the P···N bond critical point, the electrostatic character of the P···N interaction, and it decreases the P···N interaction distance. The net result is that the formation of a hydrogen/halogen bond enhances the P···N interaction, and vice versa. However, the P···N interaction is enhanced by the presence of the hydrogen or halogen bond to a much greater degree than the hydrogen or halogen bond is enhanced by the P···N interaction.

Discovery of σ-hole interactions involving ylides.

The positive electrostatic potentials (σ-hole) have been found in ylides CH2XH3 (X = P, As, Sb) and CH2YH2 (Y = S, Se, Te), on the outer surfaces of group VA and VIA atoms, approximately along the extensions of the C-X and C-Y bonds, respectively. These electrostatic potentials suggest that the above ylides can interact with nucleophiles to form weak, directional noncovalent interactions similar to halogen bonding interactions. MP2 calculations have confirmed the formation of CH2XH3···HM complexes (X = P, As, Sb; M = BeH, ZnH, MgH, Li, Na). The interaction energies, interaction distances, topological properties (electron density and its Laplacian), and energy properties (kinetic electron energy density and potential electron energy density) at the X(1)···H(10) bond critical points are all correlated with the most negative electrostatic potential value of HM, indicating that electrostatic interactions play an important role in these weak X···H interactions. Similar to the halogen bonding interactions, weak interactions involving ylides may be significant in several areas such as organic synthesis, crystal engineering, and design of new materials.