Anion Binding to Ammonium and Guanidinium Hosts: Implications for the Reverse Hofmeister Effects Induced by Lysine and Arginine Residues.

Anions have a profound effect on the properties of soluble proteins. Such Hofmeister effects have implications in biologics stability, protein aggregation, amyloidogenesis, and crystallization. However, the interplay between the important noncovalent interactions (NCIs) responsible for Hofmeister effects is poorly understood. To contribute to improving this state of affairs, we report on the NCIs between anions and ammonium and guanidinium hosts 1 and 2, and the consequences of these. Specifically, we investigate the properties of cavitands designed to mimic two prime residues for anion-protein NCIs─lysines and arginines─and the solubility consequences of complex formation. Thus, we report NMR and ITC affinity studies, X-ray analysis, MD simulations, and anion-induced critical precipitation concentrations. Our findings emphasize the multitude of NCIs that guanidiniums can form and how this repertoire qualitatively surpasses that of ammoniums. Additionally, our studies demonstrate the ease by which anions can dispense with a fraction of their hydration-shell waters, rearrange those that remain, and form direct NCIs with the hosts. This raises many questions concerning how solvent shell plasticity varies as a function of anion, how the energetics of this impact the different NCIs between anions and ammoniums/guanidiniums, and how this affects the aggregation of solutes at high anion concentrations.

Ammonium carboxylates in the ammonia-Ugi reaction: one-pot synthesis of α,α-disubstituted amino acid derivatives including unnatural dipeptides.

Despite the remarkable developments of the Ugi reaction and its variants, the use of ammonia in the Ugi reaction has long been recognized as impractical and unsuccessful. Indeed, the ammonia-Ugi reaction often requires harsh reaction conditions, such as heating and microwave irradiation, and competes with the Passerini reaction, thereby resulting in low yields. This study describes a robust and practical ammonia-Ugi reaction protocol. Using originally prepared ammonium carboxylates in trifluoroethanol, the ammonia-Ugi reaction proceeded at room temperature in high yields and showed a broad substrate scope, thus synthesizing a variety of α,α-disubstituted amino acid derivatives, including unnatural dipeptides. The reaction required no condensing agents and proceeded without racemization of the chiral stereocenter of α-amino acids. Furthermore, using this protocol, we quickly synthesized a novel dipeptide, D-Leu-Aic-NH-CH2Ph(p-F), which exhibited a potent inhibitory activity against α-chymotrypsin with a Ki value of 0.091 µM.

Nitrate Chemodenitrification by Iron Sulfides to Ammonium under Mild Conditions and Transformation Mechanism.

Autotrophic denitrification utilizing iron sulfides as electron donors has been well studied, but the occurrence and mechanism of abiotic nitrate (NO3-) chemodenitrification by iron sulfides have not yet been thoroughly investigated. In this study, NO3- chemodenitrification by three types of iron sulfides (FeS, FeS2, and pyrrhotite) at pH 6.37 and ambient temperature of 30 °C was investigated. FeS chemically reduced NO3- to ammonium (NH4+), with a high reduction efficiency of 97.5% and NH4+ formation selectivity of 82.6%, but FeS2 and pyrrhotite did not reduce NO3- abiotically. Electrochemical Tafel characterization confirmed that the electron release rate from FeS was higher than that from FeS2 and pyrrhotite. Quenching experiments and density functional theory calculations further elucidated the heterogeneous chemodenitrification mechanism of NO3- by FeS. Fe(II) on the FeS surface was the primary site for NO3- reduction. FeS possessing sulfur vacancies can selectively adsorb oxygen atoms from NO3- and water molecules and promote water dissociation to form adsorbed hydrogen, thereby forming NH4+. Collectively, these findings suggest that the NO3- chemodenitrification by iron sulfides cannot be ignored, which has great implications for the nitrogen, sulfur, and iron cycles in soil and water ecosystems.

Potential electron acceptors for ammonium oxidation in wastewater treatment system under anoxic condition: A review.

Anaerobic ammonium oxidation has been considered as an environmental-friendly and energy-efficient biological nitrogen removal (BNR) technology. Recently, new reaction pathway for ammonium oxidation under anaerobic condition had been discovered. In addition to nitrite, iron trivalent, sulfate, manganese and electrons from electrode might be potential electron acceptors for ammonium oxidation, which can be coupled to traditional BNR process for wastewater treatment. In this paper, the pathway and mechanism for ammonium oxidation with various electron acceptors under anaerobic condition is studied comprehensively, and the research progress of potentially functional microbes is summarized. The potential application of various electron acceptors for ammonium oxidation in wastewater is addressed, and the N2O emission during nitrogen removal is also discussed, which was important greenhouse gas for global climate change. The problems remained unclear for ammonium oxidation by multi-electron acceptors and potential interactions are also discussed in this review.

Potassium and ammonium recovery in treated urine by zeolite based mixed matrix membranes.

Nitrogen, phosphorus and potassium are essential for crop growth, which are abundant in urine. Although numerous studies have developed techniques to recover ammonium and phosphorus from urine, limited research made efforts on the recovery of potassium, which is a non-renewable resource with uneven global distribution. In this study, we explored the possibility of zeolite based mixed matrix membranes (MMMs) to selectively recover ammonium and potassium from urine, with minimal detention of sodium. The findings demonstrated that upon the pre-treatment of zeolites with sodium chloride solution, a 70 wt% zeolite loaded MMM could achieve 69.3 % recovery of potassium and almost full recovery of ammonium. By varying the desorption temperatures and MMMs production process, it was discovered that stepwise backwash at low temperature (276 K) greatly lowered sodium recovery whilst simultaneously enhancing the recovery of potassium and ammonium. This study demonstrates the potential of recovering potassium and ammonium from urine using zeolite-loaded MMMs, coupled with achieving low-sodium recovery.

Boosting nutrient recovery from AnMBR effluent by means of electrodialysis technology: Operating parameters assessing.

This work describes a comprehensive assessment of operating parameters of a bench-scale electrodialysis (ED) plant for nutrient concentration from an Anaerobic Membrane BioReactor (AnMBR) effluent. The ED bench-scale plant serves a dual purpose. Firstly, to generate a concentrated stream with a high nutrient content, and secondly, to produce high-quality reclaimed water in the diluted stream, both sourced from real wastewater coming from the effluent of an AnMBR. Two sets of experiments were conducted: 1) short-term experiments to study the effect of some parameters such as the applied current and the type of anionic exchange membrane (AEM), among others, and 2) a long-term experiment to verify the feasibility of the process using the selected parameters. The results showed that ED produced concentrated ammonium and phosphate streams using a 10-cell pair stack with 64 cm2 of unitary effective membrane area, working in galvanostatic mode at 0.24 A, and operating with an Acid-100-OT anionic exchange membrane. Concentrations up to 740 mg/L and 50 mg/L for NH4-N and PO4-P, respectively, were achieved in the concentrated stream along with removal efficiencies of 70% for ammonium and 60% for phosphate in the diluted stream. The average energy consumption was around 0.47 kWh·m-3.

Ammonium addition reduces phosphorus leaching in a long-term mineral or organic fertilized calcareous soil during flooding conditions.

Organic amendment substitutes mineral fertilizers has been proven to increase the organic matter content of soils, which in turn may induce phosphorus (P) mobilization by triggering the redox reaction. However, under flooded conditions according to local agricultural practices, as one of the factors restricting the decomposition of organic matter, the role ammonium plays in P transformation and leaching from soils with different organic matter remains unclear. To address the knowledge gap, the calcareous soils were collected from a long-term field trial (>13 years) containing two treatments with equal P inputs: a long-term mineral fertilization and a long-term organic amendment. Both long-term mineral fertilized soil and long-term organic amended soil were split into ammonium applications or no ammonium applications. A series of column devices were deployed to create flooded conditions and monitor the P leaching from the collected soils. The K-edge X-ray absorption near-edge structure and sequential extraction method were employed jointly to detect soil P fractions and speciation, and the P sorption/desorption characteristics of soil were evaluated by Langmuir fitting. The results showed a reduction of cumulative leached P from soils by 33.2%-43.3% after ammonium addition, regardless of previous long-term mineral fertilization or organic amendment history. A significant enhancement of soil labile P pool (indicated by the H2O-P fraction and NaHCO3-P fraction) after ammonium addition results in the reduction in soil P leaching. The reduced P sorption capacity coupled with the transformation from hydroxyapatite to ß-tricalcium phosphate indicated that the phosphate retention is attributed to the precipitation formation rather than phosphate sorption by soil. The present study highlights that the ammonium addition could affect the phosphate precipitation transformation. This may be attributed to the effect of ammonium addition on the calcium and magnesium ion content and molar ratio in this soil, thereby regulating the form of soil phosphate precipitation. The mechanisms revealed in this study can support developing optimized agricultural management practices to alleviate soil P loss.

Monitoring Ammonium Polyphosphate (APP) Biodegradation by Acinetobacter nosocomialis D-3 Using DAPI.

Ammonium polyphosphate (APP), a pivotal constituent within environmentally friendly flame retardants, exhibits notable decomposition susceptibility and potentially engenders ecological peril. Consequently, monitoring the APP concentration to ensure product integrity and facilitate the efficacious management of wastewater from production processes is of great significance. A fluorescent assay was devised to swiftly discern APP utilizing 4',6'-diamino-2-phenylindole (DAPI). With increasing APP concentrations, DAPI undergoes intercalation within its structure, emitting pronounced fluorescence. Notably, the flame retardant JLS-PNA220-A, predominantly comprising APP, was employed as the test substrate. Establishing a linear relationship between fluorescence intensity (F-F0) and JLS-PNA220-A concentration yielded the equation y = 76.08x + 463.2 (R2 = 0.9992), with a LOD determined to be 0.853 mg/L. The method was used to assess the degradation capacity of APP-degrading bacteria. Strain D-3 was isolated, and subsequent analysis of its 16S DNA sequence classified it as belonging to the Acinetobacter genus. Acinetobacter nosocomialis D-3 demonstrated superior APP degradation capabilities under pH 7 at 37 °C, with degradation rates exceeding 85% over a four-day cultivation period. It underscores the sensitivity and efficacy of the proposed method for APP detection. Furthermore, Acinetobacter nosocomialis D-3 exhibits promising potential for remediation of residual APP through environmental biodegradation processes.

Sugarcane bagasse-derived biochar modified by alkali for enriching surface functional groups to effectively treat ammonium-contaminated water.

In this study, sugarcane bagasse (SB), which was preliminarily treated with H3PO4, was utilized to produce biochar (SB-BC). The SB-BC was subsequently modified with KOH to enrich oxygen-containing functional groups (OCFGs) for the enhanced adsorption of NH4+ from wastewater. Batch tests revealed that KOH-modified SB-BC (SB-MBC) increased the maximum Langmuir adsorption capacity of NH4+ by approximately twofold, from 27.1 mg/g for SB-BC to 53.1 mg/g for SB-MBC. The optimal operational conditions for NH4+ adsorption onto SB-MBC were pH of 7.0 and a biochar dose of 3.0 g/L for the removal of 50 mg/L NH4+ at room temperature (25 ± 2 °C) over 180 min of contact. The enhanced adsorption capacity of NH4+ onto SB-MBC was due to the important contribution of the OCFGs enriched on the surface of biochar, which was increased by about fourfold, after being modified by KOH. The NH4+ adsorption dynamics were better fitted by the Elovich and the NH4+ adsorption isotherms were better described by Langmuir and Sips models, showing that the adsorption process was dominated by monolayer chemisorption. The properties of the adsorption materials before and after adsorption of NH4+ confirmed that cation exchange, electrostatic attraction and surface complexation were the main mechanisms controlling the adsorption process. The desorption and reusability tests of NH4+-saturated SB-MBC revealed that NH4+ adsorption slightly decreased after three successive sorption‒desorption cycles. The findings suggested that SB-MBC is a promising and feasible adsorbent for the effective treatment of NH4+-contaminated water sources. Future work should conduct tests for treatment of NH4+-rich real wastewater and utilize NH4+-saturated SB-MBC as slow releasing fertilizer for plants growth.

Comparing Mn-based oxides filters started by KMnO4 versus K2FeO4 for ammonium and manganese removal: Formation mechanism of active species.

A pilot-scale filtration system was adopted to prepare filter media with catalytic activity to remove manganese (Mn2+) and ammonium (NH4+-N). Three different combinations of oxidants (KMnO4 and K2FeO4) and reductants (MnSO4 and FeCl2) were used during the start-up period. Filter R3 started up by KMnO4 and FeCl2 (Mn7+→MnOx) exhibited excellent catalytic property, and the NH4+-N and Mn2+ removal efficiency reached over 80% on the 10th and 35th days, respectively. Filter R1 started up by K2FeO4 and MnSO4 (MnOx←Mn2+) exhibited the worst catalytic property. Filter R2 started up by KMnO4 and MnSO4 (Mn7+→MnOx←Mn2+) were in between. According to Zeta potential results, the Mn-based oxides (MnOx) formed by Mn7+→MnOx performed the highest pHIEP and pHPZC. The higher the pHIEP and pHPZC, the more unfavorable the cation adsorption. However, it was inconsistent with its excellent Mn2+ and NH4+-N removal abilities, implying that catalytic oxidation played a key role. Combined with XRD and XPS analysis, the results showed that the MnOx produced by the reduction of KMnO4 showed early formation of buserite crystals, high degree of amorphous, high content of Mn3+ and lattice oxygen with the higher activity to form defects. The above results showed that MnOx produced by the reduction of KMnO4 was more conducive to the formation of active species for catalytic oxidation of NH4+-N and Mn2+ removal. This study provides new insights on the formation mechanisms of the active MnOx that could catalytic oxidation of NH4+-N and Mn2+.

Selective Arylation of RNA 2'-OH Groups via SNAr Reaction with Trialkylammonium Heterocycles.

Small-molecule reactions at the 2'-OH groups of RNA enable useful applications for transcriptome technology and biology. To date, all reactions have involved carbonyl acylation and mechanistically related sulfonylation, limiting the types of modifications and properties that can be achieved. Here we report that electron-deficient heteroaryl species selectively react with 2'-OH groups of RNA in water via SNAr chemistry. In particular, trialkyl-ammonium (TAA)-activated aromatic heterocycles, prepared in one step from aryl chloride precursors, give high conversions to aryl ether adducts with RNAs in aqueous buffer in ~2-3 h. Remarkably, a TAA triazine previously used only for reaction with carboxylic acids, shows unprecedented selectivity for RNA over water, reacting rapidly with 2'-OH groups while exhibiting a half-life in water of >10 days. We further show that a triazine aryl species can be used as a probe at trace-level yields to map RNA structure in vitro. Finally, we prepare a number of functionalized trialkylammonium triazine reagents and show that they can be used to covalently label RNA efficiently for use in vitro and in living cells. This direct arylation chemistry offers a simple and distinct structural scaffold for post-synthetic RNA modification, with potential utility in multiple applications in transcriptome research.

Rh(II)/Pd(0) Dual Catalysis: Interception of Ammonium Ylide with Allyl Palladium to Construct 2,2-Disubstituted Tetrahydroquinoline Derivatives.

New synthetic methods to construct 2,2-disubstituted tetrahydroquinoline derivatives are of significant value in pharmaceutical chemistry. Herein, a Rh(II)/Pd(0) dual-catalyzed diazo α-aminoallylation reaction has been developed between allylpalladium(II) and ammonium ylides derived from the Rh2(OAc)4-mediated intramolecular N-H bond insertion reaction of diazo compounds, affording various 2,2-disubstituted tetrahydroquinoline derivatives in good yields up to 93% with high chemoselectivities under mild reaction conditions. A substrate scope investigation reveals broad ester substituent tolerance, and control experiments provide the basis for a proposed reaction mechanism.

Enhancement of Ammonium Oxidation at Microoxic Bioanodes.

Bioelectrochemical systems (BESs) are considered to be energy-efficient to convert ammonium, which is present in wastewater. The application of BESs as a technology to treat wastewater on an industrial scale is hindered by the slow removal rate and lack of understanding of the underlying ammonium conversion pathways. This study shows ammonium oxidation rates up to 228 ± 0.4 g-N m-3 d-1 under microoxic conditions (dissolved oxygen at 0.02-0.2 mg-O2/L), which is a significant improvement compared to anoxic conditions (120 ± 21 g-N m-3 d-1). We found that this enhancement was related to the formation of hydroxylamine (NH2OH), which is rate limiting in ammonium oxidation by ammonia-oxidizing microorganisms. NH2OH was intermediate in both the absence and presence of oxygen. The dominant end-product of ammonium oxidation was dinitrogen gas, with about 75% conversion efficiency in the presence of a microoxic level of dissolved oxygen and 100% conversion efficiency in the absence of oxygen. This work elucidates the dominant pathways under microoxic and anoxic conditions which is a step toward the application of BESs for ammonium removal in wastewater treatment.

Simple and Low-Cost Electroactive Membranes for Ammonia Recovery.

Ammonia is considered a contaminant to be removed from wastewater. However, ammonia is a valuable commodity chemical used as the primary feedstock for fertilizer manufacturing. Here we describe a simple and low-cost ammonia gas stripping membrane capable of recovering ammonia from wastewater. The material is composed of an electrically conducting porous carbon cloth coupled to a porous hydrophobic polypropylene support, that together form an electrically conductive membrane (ECM). When a cathodic potential is applied to the ECM surface, hydroxide ions are produced at the water-ECM interface, which transforms ammonium ions into higher-volatility ammonia that is stripped across the hydrophobic membrane material using an acid-stripping solution. The simple structure, low cost, and easy fabrication process make the ECM an attractive material for ammonia recovery from dilute aqueous streams, such as wastewater. When paired with an anode and immersed into a reactor containing synthetic wastewater (with an acid-stripping solution providing the driving force for ammonia transport), the ECM achieved an ammonia flux of 141.3 ± 14.0 g.cm-2.day-1 at a current density of 6.25 mA.cm-2 (69.2 ± 5.3 kg(NH3-N)/kWh). It was found that the ammonia flux was sensitive to the current density and acid circulation rate.

Long-term effect of light rare earth element neodymium on Anammox process.

During the mining of rare earth minerals, the application of neodymium-containing manures, and the treatment of spent neodymium iron boron magnet, the generation of ammonia wastewater containing neodymium is increasing. Thus, the effects of neodymium (Nd(III)) on anaerobic ammonium oxidation (Anammox) were investigated from the aspects of performance, kinetics, statistics, microbial community and sludge morphology, and the recovery strategy of EDTA-2Na wash was discussed. The nitrogen removal efficiency of the Anammox reactor decreased significantly and eventually collapsed at the Nd(III) dosing levels of 20 and 40 mg L-1, respectively. And the toxicity of Nd(III) to AnAOB was determined by the amount internalized into the cells. The EDTA-2Na wash successfully increased the total nitrogen removal rate (TNRR) of Nd(III)-inhibited Anammox to 41.60% of its initial value within 30 days, and the modified Boltzmann model accurately simulated this recovery process. The transient and extended effects of Nd(III), self-recovery, and EDTA-2Na wash on Anammox were effectively assessed using a one-sample t-test. 16S rRNA gene sequencing indicated that Nd(III) remarkably decreased the relative abundance of Planctomycetes and Candidatus Brocadia. The scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS) revealed crystal-like neodymium particles on the surface of Anammox sludge. The above-mentioned results demonstrate that the concentration of Nd(III) should be below the toxicity threshold (20 mg L-1) when treating ammonia wastewater containing neodymium by Anammox, and also emphasize the importance of an appropriate recovery strategy.

Non-rhizosphere reinforces the contributions of Feammox and anammox to nitrogen loss than rhizosphere in riparian zones.

The emergence of anaerobic ammonium oxidation (anammox) coupled to iron reduction (named Feammox) refreshes the microbial pathways for nitrogen (N) loss. However, the ecological role of Feammox, compared with conventional denitrification and anammox, in microbial N attenuation in ecosystems remains unclear. Here, the specific contribution of Feammox to N loss and the underlying microbiome interactive characteristics in a riparian ecosystem were investigated through 15N isotope tracing and molecular analysis. Feammox was highlighted in the riparian interface soils and maximally contributed 14.2% of N loss. Denitrification remained the dominant contributor to N loss (68.0%-95.3%), followed by anammox (5.7%-19.1%) and Feammox (0-14.2%). The rates of Feammox and anammox significantly decreased in rhizosphere soils (0.15 ± 0.08 µg N g-1 d -1 for Feammox, 0.80 ± 0.39 µg N g-1 d -1 for anammox) compared with those in non-rhizosphere soils; however, the activities of denitrification remarkably increased in the rhizosphere (13.17 ± 3.71 µg N g-1 d -1). In rhizosphere soils, the competition between bioavailable organic matter (e.g., amino acids and carbohydrates) and ammonium for electron acceptor [i.e., Fe(III)] was the vital inducement for restricted Feammox, while the nitrite consumption boosted by heterotrophic denitrifiers was responsible for weakened anammox. The functional gene of autotrophic Acidimicrobiaceae bacterium A6, instead of heterotrophic Geobacteraceae spp., was significantly positively correlated with Feammox activity. Rare iron-reducing bacteria showed higher node degrees in the non-rhizosphere network than in the rhizosphere network. A syntrophic relationship was found between iron-reducing bacteria (e.g., Anaeromyxobacter, Geobacter) and iron-oxidizing bacteria (e.g., Sideroxydans) in the non-rhizosphere network and facilitated the Feammox pathway. This study provides an in-depth exploration of microbial driven N loss in a riparian ecosystem and introduces new insights into riparian management practices toward high-efficient N pollution alleviation.

Microbial ecological responses of partial nitritation/anammox granular sludge to real water matrices and its potential application.

Granular sludges are commonly microbial aggregates used to apply partial nitritation/anammox (PN/A) processes during efficient biological nitrogen removal from ammonium-rich wastewater. Considering keystone taxa of anammox bacteria (AnAOB) in granules and their sensitivity to unfavorable environments, it is essential to investigate microbial responses of autotrophic PN/A granules to real water matrices containing organic and inorganic pollutants. In this study, tap water, surface water, and biotreated wastewater effluents were fed into a series of continuous PN/A granular reactors, respectively, and the differentiation in functional activity, sludge morphology, microbial community structure, and nitrogen metabolic pathways was analyzed by integrating kinetic batch testing, size characterization, and metagenomic sequencing. The results showed that feeding of biotreated wastewater effluents causes significant decreases in nitrogen removal activity and washout of AnAOB (dominated by Candidatus Kuenenia) from autotrophic PN/A granules due to the accumulation of heavy metals and formation of cavities. Microbial co-occurrence networks and nitrogen cycle-related genes provided evidence for the high dependence of symbiotic heterotrophs (such as Proteobacteria, Chloroflexi, and Bacteroidetes) on anammox metabolism. The enhancement of Nitrosomonas nitritation in the granules would be considered as an important contributor to greenhouse gas (N2O) emissions from real water matrices. In a novel view on the application of microbial responses, we suggest a bioassay of PN/A granules by size characterization of red-color cores in ecological risk assessment of water environments.

Geochemical transition zone powering microbial growth in subsurface sediments.

No other environment hosts as many microbial cells as the marine sedimentary biosphere. While the majority of these cells are expected to be alive, they are speculated to be persisting in a state of maintenance without net growth due to extreme starvation. Here, we report evidence for in situ growth of anaerobic ammonium-oxidizing (anammox) bacteria in ∼80,000-y-old subsurface sediments from the Arctic Mid-Ocean Ridge. The growth is confined to the nitrate-ammonium transition zone (NATZ), a widespread geochemical transition zone where most of the upward ammonium flux from deep anoxic sediments is being consumed. In this zone the anammox bacteria abundances, assessed by quantification of marker genes, consistently displayed a four order of magnitude increase relative to adjacent layers in four cores. This subsurface cell increase coincides with a markedly higher power supply driven mainly by intensified anammox reaction rates, thereby providing a quantitative link between microbial proliferation and energy availability. The reconstructed draft genome of the dominant anammox bacterium showed an index of replication (iRep) of 1.32, suggesting that 32% of this population was actively replicating. The genome belongs to a Scalindua species which we name Candidatus Scalindua sediminis, so far exclusively found in marine sediments. It has the capacity to utilize urea and cyanate and a mixotrophic lifestyle. Our results demonstrate that specific microbial groups are not only able to survive unfavorable conditions over geological timescales, but can proliferate in situ when encountering ideal conditions with significant consequences for biogeochemical nitrogen cycling.

Integrated effects of operational temperature, HRT, and influent ammonium concentration on a CANON coupling with denitrification process treating for digested piggery wastewater: performance and microbial community.

In this study, an improved system called the completely autotrophic nitrogen removal over nitrite (CANON) process was presented and coupled with denitrification for the treatment of digested piggery wastewater (DPW). The effects of operating parameters, including hydraulic retention time (HRT) (1.6 d → 1.0 d), influent NH4+-N concentration (350 mg L-1 → 600 mg L-1), and temperature (41 â„ƒ → 17 â„ƒ), on the nitrogen removal performance and response characteristics of microbial population were investigated. Results showed that all considered parameters caused a remarkable effect on NH4+-N and total nitrogen removal efficiencies, and the chemical oxygen demand was more markedly affected by temperature. Candidatus_Kuenenia, Candidatus_Brocadia, Denitratisoma, norank_o_Xanthmonadales, norank_p_WWE3, and SM1A02 were the dominant genera influencing nitrogen removal in the improved CANON system for treating DPW. Redundancy discriminant analysis showed that the biological structure was positively correlated with the influent ammonium concentration, temperature, and HRT. The relative abundance of Candidatus_Kuenenia was perfectly correlated with HRT and temperature. However, environmental factors did not affect Candidatus_Brocadia and norank_p_WWE3. norank_c_Ardenticatenia, SM1A02, and norank_f_SJA-28 were all positively correlated with influent ammonium nitrogen concentration, but not correlated with HRT and temperature. The improved CANON process realized the nitrogen removal under high ammonium (NH4+-N) concentration and low C/N wastewater.

Comparative Analysis of Sulfonium-π, Ammonium-π, and Sulfur-π Interactions and Relevance to SAM-Dependent Methyltransferases.

We report the measurement and analysis of sulfonium-π, thioether-π, and ammonium-π interactions in a ß-hairpin peptide model system, coupled with computational investigation and PDB analysis. These studies indicated that the sulfonium-π interaction is the strongest and that polarizability contributes to the stronger interaction with sulfonium relative to ammonium. Computational studies demonstrate that differences in solvation of the trimethylsulfonium versus the trimethylammonium group also contribute to the stronger sulfonium-π interaction. In comparing sulfonium-π versus sulfur-π interactions in proteins, analysis of SAM- and SAH-bound enzymes in the PDB suggests that aromatic residues are enriched in close proximity to the sulfur of both SAM and SAH, but the populations of aromatic interactions of the two cofactors are not significantly different, with the exception of the Me-π interactions in SAM, which are the most prevalent interaction in SAM but are not possible for SAH. This suggests that the weaker interaction energies due to loss of the cation-π interaction in going from SAM to SAH may contribute to turnover of the cofactor.