One-pot synthesis of novel mesoporous FeOOH modified NaZrH(PO4)2·H2O for the enhanced removal of Co(II) from aqueous solution.

One-pot synthesis of a novel mesoporous hydroxyl oxidize iron functional Na-zirconium phosphate (FeOOH-NaZrH(PO4)2·H2O) composites was firstly characterized and investigated its Co(II) adsorption from aqueous solution. Compared to NaZrH(PO4)2·H2O (65.7 mg⋅g-1), the maximum Co(II) adsorption capacity of FeOOH-NaZrH(PO4)2·H2O was improved to be 95.1 mg⋅g-1. BET verified the mesoporous structures of FeOOH-NaZrH(PO4)2·H2O with a larger pore volume than NaZrH(PO4)2·H2O. High pH values, initial Co(II) concentration, and temperature benefited the Co(II) adsorption. Kinetics, isotherms, and thermodynamics indicated an endothermic, spontaneous chemisorption process. FeOOH-NaZrH(PO4)2·H2O has a better Co(II) adsorption selectivity than that of NaZrH(PO4)2·H2O. In particular, FeOOH-NaZrH(PO4)2·H2O exhibited an outstanding reusability after ten cycles of tests. The main possible mechanism for adsorbents uptake Co(II) involved in ion exchange, electrostatic interaction, and -OH, Zr-O bond coordination based on FTIR and XPS analysis. This work presents a feasible strategy to prepare novel modified zirconium phosphate composites for extracting Co(II) from solutions and providing a new insight into the understanding of Co(II) adsorption in the real nuclear Co(II)-containing wastewater.

Bioinspired Macrocyclic Molecule Supported Two-Dimensional Lamellar Membrane with Robust Interlayer Structure for High-Efficiency Nanofiltration.

2D lamellar membranes (2DLMs) are used for efficient desalination and nanofiltration. However, weak interactions between adjacent stacked nanosheets result in susceptibility to swelling that limits practical applicability. Inspired by the super adhesion of multi-point suction cups on octopus tentacles, a 2DLM is constructed from Ti3 C2 Tx MXene supported by the macrocyclic "multi-point" molecule cucurbit[5]uril (CB5) and demonstrated for nanofiltration of methyl blue (MB) and enrichment of uranyl carbonate. Experimental results and density functional theory calculations indicate that CB5 rivets to the surface of the nanoflakes through strong stable interactions between its multiple binding sites and surface hydroxyl functional groups on MXene nanosheets. This novel 2DLM exhibits excellent nanofiltration performance (69 L m-2 h-1 bar-1 permeance with 93.6% rejection for MB) and can be recycled at least 30 times without significant degradation. The 2DLM exhibits excellent swelling resistance at high salinity, with a demonstration of selective enrichment of uranyl carbonate from artificial water and natural seawater. The results provide a new strategy for constructing highly stable 2DLMs with interlayer spacing controllable from sub-nano to nanometer scales, for size-selective sieving of molecules and ions, high-efficiency nanofiltration, and other applications.

Solar-Driven Nitrogen Fixation Catalyzed by Stable Radical-Containing MOFs: Improved Efficiency Induced by a Structural Transformation.

Herein we present a new viologen-based radical-containing metal-organic framework (RMOF) Gd-IHEP-7, which upon heating in air undergoes a single-crystal-to-single-crystal transformation to generate Gd-IHEP-8. Both RMOFs exhibit excellent air and water stability as a result of favorable radical-radical interactions, and their long-lifetime radicals result in wide spectral absorption in the range 200-2500 nm. Gd-IHEP-7 and Gd-IHEP-8 show excellent activity toward solar-driven nitrogen fixation, with ammonia production rates of 128 and 220 µmol h-1 g-1 , respectively. Experiments and theoretical calculations indicate that both RMOFs have similar nitrogen fixation pathways. The enhanced catalytic efficiency of Gd-IHEP-8 versus Gd-IHEP-7 is attributed to intermediates stabilized by enhanced hydrogen bonding.

Molecular Spring-like Triple-Helix Coordination Polymers as Dual-Stress and Thermally Responsive Crystalline Metal-Organic Materials.

Elastic metal-organic materials (MOMs) capable of multiple stimuli-responsiveness based on dual-stress and thermally responsive triple-helix coordination polymers are presented. The strong metal-coordination linkage and the flexibility of organic linkers in these MOMs, rather than the 4 Šstacking interactions observed in organic crystals, causes the helical chain to act like a molecular spring and thus accounts for their macroscopic elasticity. The thermosalient effect of elastic MOMs is reported for the first time. Crystal structure analyses at different temperatures reveal that this thermoresponsiveness is achieved by adaptive regulation of the triple-helix chains by fine-tuning the opening angle of flexible V-shaped organic linkers and rotation of its lateral conjugated groups to resist possible expansion, thus demonstrating the vital role of adaptive reorganization of triple-helix metal-organic chains as a molecular spring-like motif in crystal jumping.

Kinked-Helix Actinide Polyrotaxanes from Weakly Bound Pseudorotaxane Linkers with Variable Conformations.

The incorporation of a mechanically interlocked molecule such as pseudorotaxane into metal-organic coordination polymers has afforded plenty of new hybrid materials with special structures and unique properties. In this work, we employ a weakly bound cucurbit[6]uril (CB[6])-bipyridinium pseudorotaxane as a supramolecular precursor to assemble with uranyl, aiming to construct uranyl-rotaxane coordination polymers (URCPs) with intriguing structures. By adjusting the synthetic conditions, a new kinked-helix uranyl rotaxane compound (URCP3), together with three other compounds URCP1, URCP2, and URCP4 varying from 1D chains to 2D interwoven networks, was obtained. Detailed structural analyses indicate that the pseudorotaxane ligand (C8BPCA@CB[6]) shows great configuration diversity in the construction of URCPs, which is most probably due to the weak binding strength between the host and guest molecules. Specifically, based on the monodentate coordination of the end carboxyl groups of C8BPCA forced by the surrounding unilaterally-chelated oxalate, the entire flexible pseudorotaxane linker will be more likely to undergo conformational change, thereby binding to the uranyl center from both sides of the uranyl equatorial plane and promoting the formation of a kinked helix structure of URCP3 that is shaped like a Chinese knot along [001]. This work enriches the library of actinide-rotaxane compounds and provides a new approach to construct metal-organic compounds with complicated structures using weakly bonded pseudorotaxanes as well.

Noncomplexed Cucurbituril-Mediated Structural Evolution of Layered Uranyl Terephthalate Compounds.

Template synthesis is one of the most feasible ways to explore new uranyl compounds with intriguing structures and properties. Here we demonstrate the preparation of six novel "sandwichlike" uranyl coordination polymers (UCPs) based on two-dimensional uranyl-terephthalate acid (H2TP) networks using CBn (n = 5, 6, 8) as template ligands in the presence of different cations (Na+, K+, Cs+, or H2N(CH3)2+). Compound 1 ([UO2(TP)2][Na2(CB5)(H2O)](H2O)5) is composed of layered uranyl-TP networks with the complex of CB5 and sodium cations as template ligands. In compound 2 ([(UO2)2(TP)3]2(CB6)(H2O)10), CB6 located between uranyl-TP networks contacts them by π-π interactions and hydrogen bonds. Compound 3 ([(UO2)2(TP)3]2[Na2(H2O)10(CB6)]) is the same as compound 2 except for sodium cations bonding with CB6. Similarly in compound 4 ([(UO2)2(TP)3][Cs(H2O)3(CB6)]), CB6 is a capsulelike structure capped with two cesium cations and interacts with uranyl-TP networks through π-π and C-H···π interactions. Compound 5 ([(UO2)2(TP)3(HCOO)2][K(H2O)2(CB5)]2[H2N(CH3)2]2(CB6)(H2O)6) consists of both templates of CB6 and CB5 in which each CB5 is capped with one potassium cation while the H2N(CH3)2+ cation is held at CB6 portals. In compound 6 ([(UO2)2(TP)3]2[UO2(TP)2(H2O)2][Cs(CB8)3(H2O)4](H2O)16), CB8 ligands are connected by cesium cations to form a triangle motif and are further located between the uranyl-TP networks as template agents. All of the 2D layered structures with free CBn or cation-anchored CBn intercalate into the laminates of uranyl-terephthalate and shows a cucurbituril-mediated structural evolution. The regulating role of CBn as structure-directing template agents for the construction of layered UCPs through outer-surface interactions with layers of uranyl terephthalate is demonstrated, especially for the case of CB6 with contractive interlayer spacing.

Structural Diversity of Bipyridinium-Based Uranyl Coordination Polymers: Synthesis, Characterization, and Ion-Exchange Application.

As well-known functional groups with excellent electro/photochromic and ion-exchange properties, bipyridinium motifs have been used in functionalized metal-organic coordination polymers, but they are still rarely applied to construct actinide coordination polymers. In this work, we utilized a bipyridinium-based carboxylic acid, 1,1'-bis(4-carboxyphenyl)-4,4'-bipyridinium bis(chloride) ([H2bcbp]Cl2), as the organic ligand to assemble with uranyl cations. By the introduction of different kinds of auxiliary ligands and adjustment of the pH, five novel uranyl coordination compounds, 1-5, have been synthesized through hydrothermal reactions. Starting from uranyl ions and terephthalic acid (H2TP) and H2bcbp ligands, [(UO2)2(bcbp)(TP)2]·3H2O (1) has a wave-shaped two-dimensional (2D) structure consisting of dinuclear units connected by terephthalate linkers and further supported by the longer H2bcbp ligands. [(UO2)2(bcbp)(PA)2]·4H2O (2) has a zigzag chain of dimeric uranium units, and [(UO2)2(bcbp)(bpdc)2]·5H2O (3) forms a one-dimensional ribbonlike structure. The 2D structures of [(UO2)(bcbp)(OH)(H2O)]·Cl (4) and [(UO2)(bcbp)Cl]·Cl (5) are similar, both of which are constructed from dinuclear uranyl units and bcbp2- ligands. Furthermore, the performance for perrhenate removal of compound 4 with a cationic framework is assessed, and we found that compound 4 can efficiently remove ReO4- from an aqueous solution in a wide range of pH values. This work extends the library of viologen derivative-based uranyl coordination polymers, provides to some extent broader insights into actinide coordination chemistry of functionalized ligands, and may facilitate the ion-exchange applications of related coordination polymers.

Bipyridine-Directed Syntheses of Uranyl Compounds Containing Semirigid Dicarboxylate Linkers: Diversity and Consistency in Uranyl Speciation.

Bipyridine organic bases are beneficial to the synthesis of novel uranyl-organic hybrid materials, but the relationship between their molecular structures and specific roles as structure-directing agents, especially for the semirigid dicarboxylate systems, is still unclear. Here we demonstrate how the bipyridine ligands direct the coordination assembly of uranyl-organic compounds with a semirigid dicarboxylate linker, 4,4'-dicarboxybiphenyl sulfone (H2dbsf), by utilizing a series of bipyridine ligands, 1,10-phenanthroline (phen), 2,2'-bipyridine (2,2'-bpy), 5,5'-dimethylbipyridine (5,5'-dmbpy), 4,4'-bipyridine (4,4'-bpy), or 1,3-di(4-pyridyl)propane (bpp). Under hydrothermal conditions, eight uranyl-organic coordination polymers (UCPs), four of which [[UO2(dbsf)(phen)] (1), [UO2(dbsf)(phen)]·H2O (1'), [U4O10(dbsf)3]2[H2bpp]2 (6), and [U4O10(dbsf)3]2[H2bpp] (6')] were reported previously, were synthesized and divided into two types based on the chelate or template effect of these bipyridine ligands. 1, 1', [UO2(dbsf)(2,2'-bpy)] (2), and [(UO2)2(dbsf)2(5,5'-dmbpy)2] (3) are springlike triple helices with bipyridine ligands (phen, 2,2'-bpy, or 5,5'-dmbpy) as chelate ligands, while [U4O10(dbsf)3][H2(4,4'-bpy)] (4), [U4O10(dbsf)3]2[H(4,4'-bpy)]2[Ni(H2O)6] (5), 6, and 6' are tetranuclear uranyl-mediated 2-fold-interpenetrating networks with 4,4'-bpy or bpp as template ligands and charge-balancing agents. The participation or not in uranyl coordination of different bipyridine ligands promotes not only diversity in uranyl speciation and final topological structures among different classes of organic bases but also consistency for the same types of bipyridine ligands, which thus endows the possibility of the rational design of UCPs based on semirigid dicarboxylate ligands with the aid of cautiously selected bipyridine ligands.

The fate of rhenium in polyaminocarboxy solution: Hourglass crystal and its speciation study.

This paper studied the fate of Re in the presence of polyaminocarboxy ligand (DTPA, EDTA and NTA) under reducing condition. When SnCl2 as reducing agent, the results indicated the low valent Re was formed. And batch experiments studied the effect of pH and different ligands on the formation of low valent Re complex, the acid condition was favoured for the formation of low valent Re complex, and the order of complexing toward the low valent Re was the following: DTPA > EDTA > NTA. In the condition of pH = 1, DTPA as ligand, the hourglass crystal was obtained. Using ESI-MS, solid-state UV-Vis-NIR spectra, EXAFS, DFT calculation et al, the darkened patch of the hourglass crystal was demonstrated to be Re, and its speciation was dimeric Re2(µ-O)2DTPA.

Uranyl Compounds Involving a Weakly Bonded Pseudorotaxane Linker: Combined Effect of pH and Competing Ligands on Uranyl Coordination and Speciation.

Pseudorotaxane-type ligands with tunable structural dynamics offer an opportunity in the exploration of new actinide hybrid materials. In this work, we utilized a weakly bonded pseudorotaxane ligand involving CB[6] and 1, 1'-(heptane-1, 7-diyl)bis(4-(ethoxycarbonyl)pyridin-1-ium) bromides ([C7BPCEt]Br2@CB[6]) to assemble with uranyl ion, and we systematically investigated the effect of different factors including pH and competing ligands on the hydrothermal synthesis of URCPs. Nine uranyl-rotaxane coordination polymers (URCPs) with diversity in coordination mode and topological structure were successfully prepared (two previously reported complexes, URCP1 and URCP2 are also included). The results indicate that sulfate, bromide, CB[6], and C7BPCA (the hydrolyzate of [C7BPCEt]Br2) show a combined influence on the obtained URCPs. At low pH, both CB[6] and C7BPCA can bond with uranyl centers and produce interwoven structures in URCP1, URCP2, and URCP6; at high pH, C7BPCA and competing anions (sulfate and bromide) have priority to coordinate with uranyl ions in URCP3-URCP5 and URCP7-URCP9. Notably, for the first time, bromide anion with lower affinity to uranyl ions is also observed in solid-state uranyl coordination polymer (URCP7-URCP9), which has been demonstrated by both energy dispersive X-ray spectroscopy and single-crystal X-ray structure analysis. In addition, a spontaneously single-crystal-to-single-crystal transformation from URCP3 to URCP4, which is driven by thermodynamics, was observed and explained by computational study. Moreover, it reveals that sulfate with stronger coordination ability can inhibit the hydrolysis of uranyl ion to some extent with only a rarely reported pentanuclear uranyl center found in URCP5 obtained at pH 5.67. These results indicate that the combined effect of competing ligands and pH has great significance in the formation of URCPs in terms of uranyl coordination and speciation and can be an alternative way to design and synthesize uranyl coordination polymers with new topologies.

Uranyl-Organic Coordination Compounds Incorporating Photoactive Vinylpyridine Moieties: Synthesis, Structural Characterization, and Light-Induced Fluorescence Attenuation.

The fluorescence of uranyl originated from electronic transitions (S11-S00 and S10-S0v, v = 0-4) of the ligand-to-metal charge transfer (LMCT) process is an intrinsic property of many uranyl coordination compounds. However, light-induced regulation on fluorescence features of uranyl hybrid materials through photoactive functional groups is less investigated. In this work, the photoactive vinyl group-containing ligands, ( E)-methyl 3-(pyridin-4-yl)acrylate and ( E)-methyl 3-(pyridin-3-yl)acrylate, have been used in the construction of uranyl coordination polymers in the presence of 1,10-phenanthroline (phen). Five compounds (UO2)3(µ3-O)(µ2-OH)2(L1)2( phen)2(1), (UO2)3(µ3-O)(µ2-OH)3(L1)( phen)2 (2), (UO2)3(µ3-O)(µ2-OH)3(L2)( phen)2 (3), [(UO2)2(µ2-OH)2(L2)2( phen)2]·2H2O (4), and (UO2)Zn(SO4)(phen)(H2O)(OH)2(5) were obtained under hydrothermal conditions. Compounds 1-4 are polynuclear uranyl structures with abundant π-π interactions and hydrogen bonds contributed to the 3D crystal packing of them. As model compounds, 1 and 3 are selected for exploring photoresponsive behaviors. The emission intensities of these two compounds are found to decrease gradually over the exposure time of UV irradiation. X-ray single crystal structural analysis suggests that the fluorescence attenuation can be explained by the slight rotation of pyridinyl groups around the carbon-carbon double bond during UV irradiation, which is accompanied by the change of weak interactions, i.e., π-π interactions and hydrogen bonds in strength and density. This feature of light-induced fluorescence attenuation may enable these two compounds to act as potential photoresponsive sensor materials.

Releasing Metal-Coordination Capacity of Cucurbit[6]uril Macrocycle in Pseudorotaxane Ligands for the Construction of Interwoven Uranyl-Rotaxane Coordination Polymers.

As an emerging type of actinide hybrid material, uranyl-rotaxane coordination polymers (URCPs) with new coordination patterns and topological structures are still desired. In this work, we propose a new strategy to construct URCPs by promoting the simultaneous coordination of both the wheel and axle moieties in pseudorotaxane linkers with metal nodes. Starting from a series of cucurbit[6]uril (CB[6])-based pseudorotaxane ligands, C nBPCA@CB[6] [C nBPCA = 1,1-(α,ω-diyl)bis[4-(ethoxycarbonyl)pyridin-1-ium] bromides, where n = 5-8] with slightly deformed CB[6], four new URCPs (URCP1, URCP3, URCP4, and URCP5) with interwoven network structures, as well as another noninterwoven polymer(URCP2), have been successfully prepared. According to single-crystal structure analysis, we attribute the interwoven structures of the URCPs to the distortion of CB[6] in pseudorotaxane ligands with shorter or longer spacers (C5, C7, and C8). This indicates that the deformation could effectively diminish the steric hindrance around the portals, thus endowing the "inert" CB[6] host with coordination ability like the string molecule. Besides, the participation of water molecules and sulfate anions in the uranyl coordination sphere is also found to have a great influence on the final structures of the obtained URCPs. The successful preparation of interwoven URCPs in this work gives some new insights into the metal coordination of supramolecular entities and could facilitate other new applications of CB[6]-based pseudorotaxane ligands. Most importantly, the strategy proposed in this work provides some hints in the controllable design of metal-organic rotaxane frameworks with unique topologies.

Stepwise ortho Chlorination of Carboxyl Groups for Promoting Structure Variance of Heterometallic Uranyl-Silver Coordination Polymers of Isonicotinate.

We report the syntheses and characterization of four new heterometallic uranyl-silver compounds from isonicotinic acid derivatives with a stepwise ortho chlorination of carboxyl group, that is, isonicotinic acid (H-PCA), 3-chloroisonicotinic acid (H-3-MCPCA), and 3,5-dichloroisonicotinic acid (H-3,5-DCPCA). Compound 1, (UO2)Ag4(3,5-DCPCA)6(3,5-DCPy)2, from H-3,5-DCPCA displays a heterometallic three-dimensional (3D) framework through the connection of 3,5-DCPCA and in situ-formed 3,5-dichloropyridine (3,5-DCPy) with the aid of multiple argentophilic interactions. Compounds 2 ((UO2)Ag(3-MCPCA)3) and 3 ((UO2)Ag2(3-MCPCA)4), which differ from each other in coordination modes of uranyl center, are both heterometallic 3D reticular frameworks from 3-MCPCA based on highly coordinated silver nodes. All these heterometallic uranyl-silver compounds are different from the hydrothermal products from chlorine-free H-PCA ligand in the presence of uranyl and silver ions, U-Ag-PCA ((UO2Ag(OH)(PCA)2)) and 4 ((UO2)Ag2(OH)(H2O)2(PCA)4) due to highly coordinated silver ions found in 1-3, among which carboxyl groups of isonicotinate expected to coordinate with uranyl are the biggest contributors. Detailed structural analysis reveals that the inclination of the carboxyl group of isonicotinate driven by large steric hindrance from bulky ortho chlorine atoms at its ortho positions enables it to participate in the coordination sphere of silver ion and promote the formation and structure variance of 3D heterometallic uranyl-silver frameworks.

An Unprecedented Two-Fold Nested Super-Polyrotaxane: Sulfate-Directed Hierarchical Polythreading Assembly of Uranyl Polyrotaxane Moieties.

The hierarchical assembly of well-organized submoieties could lead to more complicated superstructures with intriguing properties. We describe herein an unprecedented polyrotaxane polythreading framework containing a two-fold nested super-polyrotaxane substructure, which was synthesized through a uranyl-directed hierarchical polythreading assembly of one-dimensional polyrotaxane chains and two-dimensional polyrotaxane networks. This special assembly mode actually affords a new way of supramolecular chemistry instead of covalently linked bulky stoppers to construct stable interlocked rotaxane moieties. An investigation of the synthesis condition shows that sulfate can assume a vital role in mediating the formation of different uranyl species, especially the unique trinuclear uranyl moiety [(UO2 )3 O(OH)2 ](2+) , involving a notable bent [O=U=O] bond with a bond angle of 172.0(9)°. Detailed analysis of the coordination features, the thermal stability as well as a fluorescence, and electrochemical characterization demonstrate that the uniqueness of this super-polyrotaxane structure is mainly closely related to the trinuclear uranyl moiety, which is confirmed by quantum chemical calculations.

The templated synthesis of a unique type of tetra-nuclear uranyl-mediated two-fold interpenetrating uranyl-organic framework.

Two novel tetra-nuclear uranyl-mediated two-fold interpenetrating networks, [U4O10(dbsf)3]2[H2bpp]2 and [U4O10(dbsf)3][H2bpp], have been hydrothermally synthesized from a semi-rigid carboxylic acid, H2dbsf, with the organic base, bpp, as the charge balancing agent and stacking template (H2dbsf = 4,4'-dicarboxybiphenyl sulfone, bpp = 1,3-di(4-pyridyl)propane).

Silver Ion-Mediated Heterometallic Three-Fold Interpenetrating Uranyl-Organic Framework.

A unique case of a uranyl-silver heterometallic 3-fold interpenetrating network (U-Ag-2,6-DCPCA) from a multifunctionalized organic ligand, 2,6-dichloroisonicotinic acid, in the presence of uranyl and silver ions is reported. It is the first report of a heterometallic uranyl-organic interpenetrating network or framework. Notably, a (4,4)-connected uranyl building unit in U-Ag-2,6-DCPCA, which is available through combined influences of structural halogenation and silver ion additive on uranyl coordination, plays a vital role in the formation of a 3-fold interpenetrating network. Halogen substitution effectively changes structural features and coordination behaviors of isonicotinate ligand and contributes to the control of uranyl coordination. Meanwhile, it exerts influence on the stabilization of 3-fold interpenetrating networks by halogen-halogen interactions. Theoretical calculation suggests that the silver ion should mainly serve as an inductive factor of uranyl species through strong Ag-N binding affinity, directly leading to the formation of a (4,4)-connected uranyl building unit and finally a heterometallic 3-fold interpenetrating network. Related experimental results, especially an interesting postsynthetic metalation, afford further evidence of this induction effect.

Supramolecular inclusion-based molecular integral rigidity: a feasible strategy for controlling the structural connectivity of uranyl polyrotaxane networks.

The assembly of two-dimensional (2D) large channel uranyl-organic polyrotaxane networks as well as structural regulation of uranyl-bearing units using jointed cucurbit[6]uril-based pseudorotaxanes with integral rigidity based on supramolecular inclusion is presented for the first time. This construction strategy concerning controlling molecular integral rigidity based on supramolecular inclusion may afford an entirely new methodology for coordination chemistry.

The first case of actinide triple helices: pH-dependent structural evolution and kinetically-controlled transformation of two supramolecular conformational isomers.

The first actinide triple helices, including two supramolecular conformational isomers of uranium(VI), have been synthesized with the aid of a flexible V-shaped ligand and a rigid aromatic base. The isomers exhibit an intriguing pH-dependent structural evolution and a kinetically-controlled transformation via a novel conformational rearrangement of the organic base.

Production of novel antibiotics zeamines through optimizing Dickeya zeae fermentation conditions.

Dickeya zeae strain EC1 was recently shown to produce a new type of phytotoxins designated as zeamine and zeamine II, which are potent wide-spectrum antibiotics against Gram-positive and Gram-negative bacterial pathogens, suggesting their promising potential as clinical medicines. In this study, the optimized medium composition and culture conditions for biosynthesis of novel antibiotics zeamines have been established by using response surface methodology, largely increasing the yield of zeamines from original about 7.35 µg · mL(-1) in minimal medium to about 150 µg · mL(-1) in LS5 medium. The study identified the major factors contributing to zeamines production, which include nitrate, sucrose, asparaginate, mineral elements Mg2+ and K+, and optimized amount of phosphate. In addition, the results showed that overexpression of zmsK in D. zeae strain EC1 could further increase zeamines yield to about 180 µg · mL(-1) in LS5 medium. The findings from this study could facilitate further characterization and utilization of these two novel antibiotics, and also provide useful clues for understanding the regulatory mechanisms that govern D. zeae virulence.

Fenpropathrin biodegradation pathway in Bacillus sp. DG-02 and its potential for bioremediation of pyrethroid-contaminated soils.

The widely used insecticide fenpropathrin in agriculture has become a public concern because of its heavy environmental contamination and toxic effects on mammals, yet little is known about the kinetic and metabolic behaviors of this pesticide. This study reports the degradation kinetics and metabolic pathway of fenpropathrin in Bacillus sp. DG-02, previously isolated from the pyrethroid-manufacturing wastewater treatment system. Up to 93.3% of 50 mg L(-1) fenpropathrin was degraded by Bacillus sp. DG-02 within 72 h, and the degradation rate parameters qmax, Ks, and Ki were determined to be 0.05 h(-1), 9.0 mg L(-1), and 694.8 mg L(-1), respectively. Analysis of the degradation products by gas chromatography-mass spectrometry led to identification of seven metabolites of fenpropathrin, which suggest that fenpropathrin could be degraded first by cleavage of its carboxylester linkage and diaryl bond, followed by degradation of the aromatic ring and subsequent metabolism. In addition to degradation of fenpropathrin, this strain was also found to be capable of degrading a wide range of synthetic pyrethroids including deltamethrin, λ-cyhalothrin, ß-cypermethrin, ß-cyfluthrin, bifenthrin, and permethrin, which are also widely used insecticides with environmental contamination problems with the degradation process following the first-order kinetic model. Bioaugmentation of fenpropathrin-contaminated soils with strain DG-02 significantly enhanced the disappearance rate of fenpropathrin, and its half-life was sharply reduced in the soils. Taken together, these results depict the biodegradation mechanisms of fenpropathrin and also highlight the promising potentials of Bacillus sp. DG-02 in bioremediation of pyrethroid-contaminated soils.