Nitrate Upcycling Mediated by Organonickel Catalysis.

Nitrogen oxides (NOx) are major environmental pollutants and to neutralize this long-term environmental threat, new catalytic methods are needed. Although there are biological denitrification processes involving four different enzymatic reactions to convert nitrate (NO3 -) into dinitrogen (N2), it is unfortunately difficult to apply in industry due to the complexity of the processes. In particular, nitrate is difficult to functionalize because of its chemical stability. Thus, there is no organometallic catalysis to convert nitrate into useful chemicals. Herein, we present a nickel pincer complex that is effective as a bifunctional catalyst to stepwise deoxygenate NO3 - by carbonylation and further through C-N coupling. By using this nickel catalysis, nitrate salts can be selectively transformed into various oximes (>20 substrates) with excellent conversion (>90 %). Here, we demonstrate for the first time that the highly inert nitrate ion can be functionalized to produce useful chemicals by a new organonickel catalysis. Our results show that the NOx conversion and utilization (NCU) technology is a successful pathway for environmental restoration coupled with value-added chemical generation.

A conjugate of chlorin e6 and cationic amphipathic peptoid: a dual antimicrobial and anticancer photodynamic therapy agent.

Cationic amphipathic structures are often utilized in natural membrane-active host-defense peptides. Negatively charged surface membranes of rapidly proliferating bacterial and cancer cells have been targeted by various synthetic peptides and peptidomimetics adopting the structural motif. Herein, we synthesized a set of conjugates composed of cationic amphipathic peptoids (i.e., oligo-N-substituted glycines) and a chlorin photosensitizer, named chlorin e6 (Ce6)-peptoid conjugates (CPCs). Among the nine CPCs, CPC 7, composed of Ce6, a PEG linker, and guanidine-rich helical amphipathic peptoids, exhibited a distinct photoresponsive inactivation of Gram-positive and Gram-negative bacteria. Subsequent studies showed that CPC 7 effectively killed various cancer cells after irradiation with red light (655 nm), suggesting the potential of CPC 7 as a dual antimicrobial and anticancer agent. Confocal laser scanning microscopy and flow cytometry data suggested that CPC 7 could induce apoptotic cell death. Our results show the potential of peptoid-based photosensitizer conjugates as a versatile platform for antimicrobial and anticancer photodynamic therapy agents and peptoid therapeutics.

Electronic Effect on Phenoxide Migration at a Nickel(II) Center Supported by a Tridentate Bis(phosphinophenyl)phosphido Ligand.

A phosphide nickel(II) phenoxide pincer complex (2) reacts with CO(g) to give a pseudo-tetrahedral nickel(0) monocarbonyl complex (3) possessing a phosphinite moiety. This metal-ligand cooperative (MLC) transformation occurs with a (PPP)Ni scaffold (PPP- = P[2-PiPr2-C6H4]2-), which can accommodate both square planar and tetrahedral geometries. The 2-electron reduction of a nickel(II) species induced by CO coordination involves group transfer to generate a P-O bond. For better mechanistic understanding, a series of nickel(II) phenolate complexes (2a-2e, XC6H4O- (X = OMe, Me, H, and CF3) and pentafluorophenolate) were prepared. Kinetic experimental data reveal that a phenolate species with an electron-withdrawing group reacts faster than those with electron-donating groups. The reaction kinetic experiments were conducted in pseudo-first order conditions at room temperature monitored by UV-vis spectroscopy. A pentafluorophenolate nickel(II) complex (2e) reveals instantaneous reactions even at -40 °C to give a nickel(0) monocarbonyl species (3e) and the reverse reaction is also possible. According to kinetic experiments, the rate determining step (RDS) would be the formation of a 5-coordinate intermediate 4 with a negative entropy value (ΔS‡ < 0), and a positive ρ value based on the Hammett plot indicates that the electron-deficient phenolate leads to a faster CO association. Furthermore, scramble experiments suggest that phenolate de-coordinates from the intermediate 4, which gives a (PPP)Ni-CO species 6. The cationic nickel monocarbonyl intermediate can possess a P--Ni(II), P•-Ni(I), or even a P+-Ni(0) character. Such an inner-sphere electron transfer is suggested when a π-acidic ligand such as CO coordinates to a metal ion. Another possible reaction is homolysis of a Ni-O bond to give P--Ni(I) or P•-Ni(0), when a phenoxyl radical is liberated. Considering the P-O bond formation, closed-shell nucleophilic and open-shell radical pathways are suggested. A phenolate pathway reveals a lower energy state for 2e relative to other complexes (2c and 2d), while its radical pathway undergoes via a higher energy state. Therefore, the formation of a P-O bond may occur with the binding of a closed-shell phenolate to the electron-deficient P center.

Highly Distorted Bismuth-Nickel(II) Complex.

The synthesis and characterization of a series of nickel complexes bearing a bismuth-containing pincer ligand are presented herein. In particular, synthesis of a 4-coordinate Bi-Ni(II) complex allows the influence of bismuth on a d8 Ni(II) ion to be investigated. A trigonal-bipyramidal complex, (BiP2)Ni(PPh) (1), possessing an anionic bismuth donor was prepared via the Bi-C bond cleavage of a BiP3 ligand (BiP3 = Bi(o-PiPr2-C6H4)3) mediated by Ni(0). To remove a PPh moiety, compound 1 was treated with MeI to give a 5-coordinate nickel(II) complex (MeBiP2)Ni(PPh)(I) (2), followed by its exposure to heat or UV irradiation, resulting in the formation of a nickel halide complex, (BiP2)Ni(I) (3). The X-ray crystal structure of 2 revealed that the methyl moiety binds to a bismuth site, providing a neutral MeBiP2 ligand, while the iodide anion is bound to the nickel(II) center, displacing one phosphine donor. Because of the methylation on a Bi site, the Bi-Ni bond in 2 is clearly elongated relative to that of 1, which indicates that the bonding interactions between Bi and Ni are substantially different. Interestingly, compound 3 revealing a sawhorse geometry is significantly distorted away from a square-planar structure compared to the previously reported nickel(II) pincer complexes, (NP2)Ni(Cl) and (PP2)Ni(I). Such difference indicates that a bismuth donor can be a structurally influencing cooperative site for a nickel(II) ion, leading to have a Ni(I)-Bi(II) character. Migratory insertion of CO into a Ni-C bond of 1 gives (BiP2)Ni(COPPh) (4), which further leads to an analogous methylated product (MeBiP2)Ni(COPPh)(I) (5) from reaction with MeI. Due to the structural influence of a carbonyl group in each step, the total reaction time from 1 to 3 was dramatically reduced. The bimetallic cooperativity of the complexes and unusual bonding properties presented here highlight the potential of a bismuth-nickel moiety as a new type of heterobimetallic site for the design of bimetallic complexes to facilitate a variety of chemical transformations.

Reaction of Amino Acids with Ferrate(VI): Impact of the Carboxylic Group on the Primary Amine Oxidation Kinetics and Mechanism.

Ferrate (Fe(VI)) is a novel oxidant that can be used to mitigate disinfection byproduct (DBP) precursors. However, the reaction of Fe(VI) with organic nitrogen, which is a potential precursor of potent nitrogenous DBPs, remains largely unexplored. The present work aimed to identify the kinetics and products for the reaction of Fe(VI) with primary amines, notably amino acids. A new kinetic model involving ionizable intermediates was proposed and can describe the unusual pH effect on the Fe(VI) reactivity toward primary amines and amino acids. The Fe(VI) oxidation of phenylalanine produced a mixture of nitrile, nitrite/nitrate, amide, and ammonia, while nitroalkane was an additional product in the case of glycine. The product distribution for amino acids significantly differed from that of uncarboxylated primary amines that mainly generate nitriles. A general reaction pathway for primary amines and amino acids was proposed and notably involved the formation of imines, the degradation of which was affected by the presence of a carboxylic group. In comparison, ozonation led to higher yields of nitroalkanes that could be readily converted to potent halonitroalkanes during chlor(am)ination. Based on this study, Fe(VI) can effectively mitigate primary amine-based, nitrogenous DBP precursors with little formation of toxic halonitroalkanes.

Assessment of the recycling potential of valuable metals by mapping the elemental composition in discarded light-emitting diodes (LEDs).

Electronic waste (e-waste) is the world's fastest-growing type of waste, with lighting accounting for 9% of the total. Light-emitting diodes (LEDs) are composed of the most concentrated critical elements (Ag and Au) and recovery of these metals could generate economic benefits and reduce the burdens of environmental pollution; nevertheless, the absence of information about their composition currently presents a challenge in recycling these metals with minimal prospects for recovery. This study assessed the distribution and variation of elemental concentrations of 16 different elements in three generations of LEDs (12 different LED units): sub-mounted-device (SMD #10), chip-on-board (COB #1), and positive-intrinsic-negative (PIN #1). The SMD LEDs contained a considerable amount of Au with a median average concentration of 1204 mg/kg (ranging from 323 - 3687 mg/kg), which was similar to that of COB (1550 mg/kg), but higher than that of PIN LED (175 mg/kg). Based on the total threshold limiting concentration (TTLC), the Cu levels (605,823 mg/kg) in the SMD package exceeded the regulatory limits (2500 mg/kg). Concentrations of the hazardous elements Cr (29 mg/kg), Pb (12 mg/kg), Cd (0.1 mg/kg), and As (1 mg/kg) in the LED packages were within the regulatory limits. To recycle precious metals and other technological metals, a well-organized and dedicated optimized assessment of the value of metals is required especially in accordance with the concept of criticality and recyclability. Two factors, i.e., a high resource index (RI) and technology index (TI), suggest the importance of waste to the economy and has a significant potential for recycling with less processing burdens. Present findings indicated that the COB and a few of the studied SMD LEDs (3020, 4014, 5630, and 7020), exhibit high criticality and recyclability. For the RI and TI index, the contribution of metals such as Cu, Fe, Al, and Au were dominant. These findings can serve as a reference for the development of a viable approach for the recycling and recovery of targeted metals from LED e-waste.

Versatile Post-synthetic Modifications of Helical ß-Peptide Foldamers Derived from a Thioether-Containing Cyclic ß-Amino Acid.

We introduce a novel cyclic ß-amino acid, trans-(3S,4R)-4-aminotetrahydrothiophene-3-carboxylic acid (ATTC), as a versatile building block for designing peptide foldamers with controlled secondary structures. We synthesized and characterized a series of ß-peptide hexamers containing ATTC using various techniques, including X-ray crystallography, circular dichroism, and NMR spectroscopy. Our findings reveal that ATTC-containing foldamers can adopt 12-helical conformations similar to their isosteres and offer the possibility of fine-tuning their properties via post-synthetic modifications. In particular, chemoselective conjugation strategies demonstrate that ATTC provides unique post-synthetic modification opportunities, which expand their potential applications across diverse research areas. Collectively, our study highlights the versatility and utility of ATTC as an alternative to previously reported cyclic ß-amino acid building blocks in both structural and functional aspects, paving the way for future research in the realm of peptide foldamers and beyond.

Nickel-Catalyzed NO Group Transfer Coupled with NOx Conversion.

Nitrogen oxide (NOx) conversion is an important process for balancing the global nitrogen cycle. Distinct from the biological NOx transformation, we have devised a synthetic approach to this issue by utilizing a bifunctional metal catalyst for producing value-added products from NOx. Here, we present a novel catalysis based on a Ni pincer system, effectively converting Ni-NOx to Ni-NO via deoxygenation with CO(g). This is followed by transfer of the in situ generated nitroso group to organic substrates, which favorably occurs at the flattened Ni(I)-NO site via its nucleophilic reaction. Successful catalytic production of oximes from benzyl halides using NaNO2 is presented with a turnover number of >200 under mild conditions. In a key step of the catalysis, a nickel(I)-•NO species effectively activates alkyl halides, which is carefully evaluated by both experimental and theoretical methods. Our nickel catalyst effectively fulfills a dual purpose, namely, deoxygenating NOx anions and catalyzing C-N coupling.

Reductive Carbonylation of Nitroarenes Using a Heterogenized Phen-Pd Catalyst.

The reductive carbonylation of nitroarenes in the presence of MeOH and CO(g) is one of the interesting alternative routes without utilizing toxic phosgene and corrosive HCl generation for the synthesis of industrially useful carbamate compounds that serve as important intermediates for polyurethane production. Since homogeneous palladium catalysts supported by phen (phen = 1,10-phenanthroline) are known to be effective for this catalysis, the heterogenized Pd catalyst was developed using the phen-containing solid support. In this study, we report the synthesis of a phen-based heterogeneous Pd catalyst, Pd@phen-POP, which involves the solvent knitting of a phen scaffold via the Lewis-acid-catalyzed Friedel-Crafts reaction using dichloromethane as a source for linker in the presence of AlCl3 as a catalyst. The resulting solid material has been thoroughly characterized by various physical methods revealing high porosity and surface area. Similar to the homogeneous pallidum catalyst, this heterogeneous catalyst shows efficient reductive carbonylation of various nitroarenes. The catalytic reaction using nitrobenzene as a model compound presents a high turnover number (TON = 530) and a reasonable turnover frequency (TOF = 45 h-1), with a high selectivity (92%) for the carbamate formation. According to the recycling study, the heterogeneous catalyst is recyclable and retains ∼90% of the original reactivity in each cycle.

Application of Nucleotide-Based Kinetic Modeling Approaches to Predict Antibiotic Resistance Gene Degradation during UV- and Chlorine-Based Wastewater Disinfection Processes: From Bench- to Full-Scale.

This study investigated antibiotic resistance gene (ARG) degradation kinetics in wastewaters during bench- and full-scale treatment with UV light and chlorine─with the latter maintained as free available chlorine (FAC) in low-ammonia wastewater and converted into monochloramine (NH2Cl) in high-ammonia wastewater. Twenty-three 142-1509 bp segments (i.e., amplicons) of seven ARGs (blt, mecA, vanA, tet(A), ampC, blaNDM, blaKPC) and the 16S rRNA gene from antibiotic resistant bacteria (ARB) strains Bacillus subtilis, Staphylococcus aureus, Enterococcus faecium, Escherichia coli, Pseudomonas aeruginosa, and Klebsiella pneumoniae were monitored as disinfection targets by qPCR. Rate constants for ARG and 16S rRNA gene amplicon degradation by UV, FAC, and NH2Cl were measured in phosphate buffer and used to expand and validate several recently developed approaches to predict DNA segment degradation rate constants based solely on their nucleotide contents, which were then applied to model ARG degradation during bench-scale treatment in buffer and wastewater matrixes. Kinetics of extracellular and intracellular ARG degradation by UV and FAC were well predicted up to ∼1-2-log10 elimination, although with decreasing accuracy at higher levels for intracellular genes, while NH2Cl yielded minimal degradation under all conditions (agreeing with predictions). ARB inactivation kinetics varied substantially across strains, with intracellular gene degradation lagging cell inactivation in each case. ARG degradation levels observed during full-scale disinfection at two wastewater treatment facilities were consistent with bench-scale measurements and predictions, where UV provided ∼1-log10 ARG degradation, and chlorination of high-ammonia wastewater (dominated by NH2Cl) yielded minimal ARG degradation.

Conformational Adaptation of ß-Peptide Foldamers for the Formation of Metal-Peptide Frameworks.

Metal-coordinated frameworks derived from small peptidic ligands have received much attention thanks to peptides' vast structural and functional diversity. Various peptides with partial conformational preferences have been used to build metal-peptide frameworks, however, the use of conformationally constrained ß-peptide foldamers has not been explored yet. Herein we report the first metal-coordination-mediated assembly of ß-peptide foldamers with 12-helical folding propensity. The coordination of Ag+ to the terminal pyridyl moieties afforded a set of metal-peptide frameworks with unique entangled topologies. Interestingly, formation of the network structures was accompanied by notable conformational distortions of the foldamer ligands. As the first demonstration of new metal-peptide frameworks built from modular ß-peptide foldamers, we anticipate that this work will be an important benchmark for further structural evolution and mechanistic investigation.

Axial Redox Tuning at a Tetragonal Cobalt Center.

Square pyramidal cobalt complexes were prepared to study their multielectron redox properties. To build a stable redox-active cobalt complex, the combination of a tridentate acriPNP (acriPNP- = 4,5-bis(diisopropylphosphino)-2,7,9,9-tetramethyl-9H-acridin-10-ide) ligand with a bidentate ligand, such as 2,2'-bipyridine, 2-(o-phenyl)pyridine, biphenylene, and their analogues, was employed. In a cobalt complex having a tetragonal structure, the dx2-y2 orbital possesses an antibonding character and must remain empty for its structural integrity, while the dz2 orbital acts as a redox-active frontier molecular orbital (FMO). Tuning the redox potential of the Co(II/I) couple was successfully achieved by introducing a different axial donor. The reduction of Co(II) to Co(I) occurs at -2.6 V for a neutral donor but shifts to -3.4 V for an anionic donor. Since the redox-active dz2 orbital is close in energy to other ligand-based orbitals, multielectron redox activity is also observed. Electrochemical measurements indicate three reversible redox events within a window of -3.0-0.0 V vs Fc/Fc+ in tetrahydrofuran (THF). These redox processes are fully reversible for over 100 cycles, reflecting the electrochemical stability of these cobalt complexes. Surprisingly, the oxidation potential of the acriPNP ligand varies dramatically from +0.15 to -2.4 V, which is probably due to the cobalt contribution on the amido-based molecular orbital. The electronic structure of the cobalt complexes was examined structurally, spectroscopically, and theoretically.

Photosensitizer-peptoid conjugates for photoinactivation of Gram-negative bacteria: structure-activity relationship and mechanistic studies.

Multitarget engagement is considered an effective strategy to overcome the threat of bacterial infection, and antimicrobials with multiple mechanisms of action have been successful as natural chemical weaponry. Here, we synthesized a library of photosensitizer-peptoid conjugates (PsPCs) as novel antimicrobial photodynamic therapy (aPDT) agents. The peptoids, linkers, and photosensitizers were varied, and their structure-antimicrobial activity relationships against Escherichia coli were evaluated; PsPC 9 was indicated to be the most promising photoresponsive antimicrobial agent among the synthesized PsPCs. Spectroscopic analyses indicated that 9 generated singlet oxygen upon absorption of visible light (420 nm) while maintaining the weakly helical conformation of the peptoid. Mechanistic studies suggested that damage to the bacterial membrane and cleavage of DNA upon light irradiation were the main causes of bactericidal activity, which was supported by flow cytometry and DNA gel electrophoresis experiments. We demonstrated that the optimal combination of membrane-active peptoids and photosensitizers can generate an efficient aPDT agent that targets multiple sites of bacterial components and kills bacteria by membrane disruption and reactive oxygen species generation.

Degradation Kinetics of Antibiotic Resistance Gene mecA of Methicillin-Resistant Staphylococcus aureus (MRSA) during Water Disinfection with Chlorine, Ozone, and Ultraviolet Light.

Degradation kinetics of antibiotic resistance genes (ARGs) by free available chlorine (FAC), ozone (O3), and UV254 light (UV) were investigated in phosphate buffered solutions at pH 7 using a chromosomal ARG (mecA) of methicillin-resistant Staphylococcus aureus (MRSA). For FAC, the degradation rates of extracellular mecA (extra-mecA) were accelerated with increasing FAC exposure, which could be explained by a two-step FAC reaction model. The degradation of extra-mecA by O3 followed second-order reaction kinetics. The degradation of extra-mecA by UV exhibited tailing kinetics, which could be described by a newly proposed kinetic model considering cyclobutane pyrimidine dimer (CPD) formation, its photoreversal, and irreversible (6-4) photoproduct formation. Measured rate constants for extra-mecA increased linearly with amplicon length for FAC and O3, or with number of intrastrand pyrimidine doublets for UV, which enabled prediction of degradation rate constants of extra-mecA amplicons based on sequence length and/or composition. In comparison to those of extra-mecA, the observed degradation rates of intracellular mecA (intra-mecA) were faster for FAC and O3 at low oxidant exposures but significantly slower at high exposures for FAC and UV. Differences in observed extra- and intracellular kinetics could be due to decreased DNA recovery efficiency and/or the presence of MRSA aggregates protected from disinfectants.

Recent Update on UV Disinfection to Fulfill the Disinfection Credit Value for Enteric Viruses in Water.

Ultraviolet (UV) radiation alone or in combination with other oxidation processes is increasingly being considered for water disinfection because of stringent regulatory requirements for pathogen inactivation. To fulfill this requirement, an appropriate UV dose or fluence (mJ/cm2) is applied to combat enteric viruses in surface or treated water. There is a need for a cumulative review on the effectiveness of current and emerging UV technologies against various types of human enteric viruses. We extracted the kinetics data from 52 selected experimental studies on enteric virus inactivation using low pressure (LP-UV), medium pressure (MP-UV), UV-LED, and advanced oxidation processes (AOPs) and applied a simple linear regression analysis to calculate the range of UV fluence (mJ/cm2) needed for 4-log10 inactivation. The inactivation of adenoviruses with LP-UV, MP-UV, and UV/H2O2 (10 mg/L) required the highest fluence, which ranged from 159 to 337, 45, and 115 mJ/cm2, respectively. By contrast, when using LP-UV, the inactivation of other enteric viruses, such as the Caliciviridae and Picornaviridae family and rotavirus, required fluence that ranged from 19 to 69, 18 to 43, and 38 mJ/cm2, respectively. ssRNA viruses exhibit higher sensitivity to UV radiation than dsRNA and DNA viruses. In general, as an upgrade to LP-UV, MP-UV is a more promising strategy for eliminating enteric viruses compared to AOP involving LP-UV with added H2O2 or TiO2. The UV-LED technology showed potential because a lower UV fluence (at 260 and/or 280 nm wavelength) was required for 4-log10 inactivation compared to that of LP-UV for most strains examined in this critical review. However, more studies evaluating the inactivation of enteric viruses by means of UV-LEDs and UV-AOP are needed to ascertain these observations.

Photophysical Tuning of σ-SiH Copper-Carbazolide Complexes To Give Deep-Blue Emission.

A series of σ-SiH copper complexes with different carbazole derivatives have been synthesized and characterized that adopt a neutral SiHP2 ligand (SiHP2 = (2-iPr2PC6H4)2SiHMe) and present photophysical properties. A previously reported copper complex (SiHP2)Cu(carbazolide), and its derivatives showed that tuning of the emission properties is possible by incorporating various substituents on the carbazolide moiety. Newly synthesized copper complexes (2-6) having 3,6-dichlorocarbazolide, 3,6-dibromocarbazolide, 1-fluorocarbazolide, 3,6-dimethylcarbazolide, and 3,6-diphenylcarbazolide show a range of λmax values of emission from 418 to 511 nm. Detailed analysis supports that their emission bands originate from excited states with Cu metal-ligand charge transfer (MLCT) and/or ligand-centered (LC) π-π* transitions. Substitution of a methyl or trifluoromethyl group at the 1-position of the carbazolide moiety was also investigated to regulate the structural tuning of the copper emitters. From the X-ray crystallographic data of (SiHP2)Cu(1-methylcarbazolide) (7) and (SiHP2)Cu(1,3-di(trifluoromethyl)carbazolide) (8), unusual structural features, arising from the interaction of a SiH moiety with CH3 and CF3, respectively, were recognized. Such interaction forces the carbazolide moiety to tilt, while the copper geometry remains consistent with the other complexes. In the case of 8, a SiH···F3C interaction locks the carbazolide moiety in place, restricting its orbital overlapping with a copper-based orbital, according to the theoretical analysis by using density functional theory (DFT) computations. Thus, the unusual tilting results in deep-blue emission with a λmax of 430 nm.

Mechanistic and Kinetic Understanding of the UV254 Photolysis of Chlorine and Bromine Species in Water and Formation of Oxyhalides.

This study investigated the UV254 photolysis of free available chlorine and bromine species in water. The intrinsic quantum yields for •OH and X• (X = Cl or Br) generation were determined by model fitting of formaldehyde formation using a tert-butanol assay to be 0.61/0.45 for HOCl/OCl- and 0.32/0.43 for HOBr/OBr-. The steady-state •OH concentration in UV/HOX was higher than that in UV/OX- by a factor of 23.3 and 7.8 for Cl and Br, respectively. This was attributed to the different •OH consumption rate by HOCl versus OCl-, while for HOBr/OBr-, both the •OH formation and consumption rates were implied. This was supported by a k of 1.4 × 108 M-1 s-1 for the •OH reaction with HOCl, which was >14 times less than the k for •OH reactions with OCl-, HOBr, and OBr-. Formation of ClO3- and BrO3- was found to be significant with apparent quantum yields of 0.12-0.23. A detailed mechanistic study on the formation of XO3- including a new pathway involving XO• is presented, which has important implications as the level of XO3- can exceed the regulation (BrO3-) or guideline (ClO3-) values during UV/halogen oxidant water treatment. Our new kinetic models well simulate the experimental results for the halogen oxidant decomposition, probe compound degradation, and formation of ClO3- and BrO3-.

Coexposure Degradation of Purine Derivatives in the Sulfate Radical-Mediated Oxidation Process.

Purines are the most widely occurring heterocyclic-N compounds. The degradation behaviors of purine derivatives, theophylline (TPL) and adenine (ADN) as representatives, in both single-component and mixture systems during UV/peroxydisulfate (PDS) treatment were explored. In the mixture system when the concentrations of SO4•- and HO• were reduced by more than half in comparison to a single-component system, the observed first-order rate constant of TPL was reduced by 11%, whereas ADN degradation was almost completely inhibited. An ADN "revert" pathway, that is, back transformation of ADN(-H)• to ADN by TPL via single electron-transfer reactions, was found. The second-order rate constant of ADN(-H)• with TPL was determined to be (1.94 ± 0.21) × 108 M-1 s-1. A kinetic model was developed, which successfully quantifies the contribution of each reaction pathway at various target compound concentrations. In the copresence of 0.1 µM TPL, 58% ADN (3.0 µM) was reduced back to ADN at the PDS dose of 290 µM. The ADN revert pathway's effectiveness is governed by the relative reduction potentials of the reactants. Purines and phenols with lower reduction potentials are able to react via the ADN revert pathway. These findings improve the understanding of the removal of mixture pollutants from real water media in advanced oxidation processes.

Selective Transformation of CO2 to CO at a Single Nickel Center.

Carbon dioxide conversion mediated by transition metal complexes continues to attract much attention because of its future potential utilization as a nontoxic and inexpensive C1 source for the chemical industry. Given the presence of nickel in natural systems that allow for extremely efficient catalysis, albeit in an Fe cluster arrangement, studies that focus on selective CO2 conversion with synthetic nickel species are currently of considerable interest in our group. In this Account, the selective conversion of CO2 to carbon monoxide occurring at a single nickel center is discussed. The chemistry is based on a series of related nickel pincer complexes with attention to the uniqueness of the coordination geometry, which is crucial in allowing for particular reactivity toward CO2. Our research is inspired by the efficient enzymatic CO2 catalysis occurring at the active site of carbon monoxide dehydrogenase. Since the binding and reactivity toward CO2 are controlled in part by the geometry of a L3Ni scaffold, we have explored the chemistry of low-valent nickel supported by PPMeP and PNP ligands, in which a pseudotetrahedral or square-planar geometry is accommodated. Two isolated nickel-CO2 adducts, (PPMeP)Ni(η2-CO2-κ C) (2) and {Na(12-C-4)2}{(PNP)Ni(η1-CO2-κ C)} (7), clearly demonstrate that the geometry of the nickel ion is crucial in the binding of CO2 and its level of activation. In the case of a square-planar nickel center supported by a PNP ligand, a series of bimetallic metallacarboxylate Ni-µ-CO2-κ C, O-M species (M = H, Na, Ni, Fe) were synthesized, and their structural features and reactivity were studied. Protonation cleaves the C-O bond, resulting in the formation of a nickel(II) monocarbonyl complex. By sequential reduction, the corresponding mono- and zero-valent Ni-CO species were produced. The reactivities of three nickel carbonyl species toward various iodoalkanes and CO2 were explored to address whether their corresponding reactivities could be controlled by the number of valence d electrons. In particular, a (PNP)Ni(0)-CO species (13) shows immediate reactivity toward CO2 but displays multiple product formation. By incorporation of a -CMe2- bridging unit, a structurally rigidified acriPNP ligand was newly designed and produced. This ligand modification was successful in preparing the T-shaped nickel(I) metalloradical species 9 exhibiting open-shell reactivity due to the sterically exposed nickel center possessing a half-filled d x2- y2 orbital. More importantly, the selective addition of CO2 to a nickel(0)-CO species was enabled to afford a nickel(II)-carboxylate species (22) with the expulsion of CO(g). Finally, the (acriPNP)Ni system provides a synthetic cycle in the study of the selective conversion of CO2 to CO that involves two-electron reduction of Ni-CO followed by the direct addition of CO2 to release the coordinated CO ligand.

Zavarzinia aquatilis sp. nov., isolated from a freshwater river.

A Gram-stain-negative, strictly aerobic, catalase-positive and oxidase-positive bacterium, designated strain HR-AST, was isolated from a water sample of the Han River located in the Republic of Korea. Cells were motile rods with a polar flagellum. Growth was observed at 5-35 °C (optimum of 25 °C) and pH 6-8 (optimum of pH 7) and in the presence of 0-2 % (w/v) NaCl (optimum of 0 %). Phylogenetic analysis based on 16S rRNA gene sequences revealed that strain HR-AST formed a tight phylogenic lineage with Zavarzinia compransoris LMG 5821T. Strain HR-AST was most closely related to Z. compransoris LMG 5821T with a 98.7 % 16S rRNA gene sequence similarity and had very low similarities (below 91.0 %) to other type strains with validly published names. Average nucleotide identity and in silico DNA-DNA hybridization values between strain HR-AST and Z. compransoris DSM 1231T were 80.4 and 23.1 %, respectively. Strain HR-AST contained ubiquinone-10 as the major quinone and homospermidine and putrescine as the major polyamines. The major fatty acids were summed feature 8 (C18 : 1 ω6c and/or C18 : 1 ω7c), C16 : 0 and C18 : 1 2-OH. Strain HR-AST contained diphosphatidylglycerol, an unidentified aminolipid and two unidentified phospholipids as major polar lipids. The DNA G+C content of strain HR-AST was 67.2 mol%. Based on the genotypic, chemotaxonomic and phenotypic analyses, strain HR-AST represents a novel species of the genus Zavarzinia, for which the name Zavarziniaaquatilis sp. nov. is proposed. The type strain is HR-AST (=KACC 19412T=JCM 32263T).