NH Cl Research Articles

Application of Cu@Cu foam and RuO2@Ti for removal of nitrogen compounds and organic matters from non-standard treated municipal wastewater by continuous electrochemical process: Optimization and mechanism

Public health, potable water supplies, and ecosystems are endangered by the disposal or reuse of non-standard effluents of wastewater treatment plants. To achieve the Sustainable Development Goals (SDG 6) and USEPA quality standards, this work utilized an innovative electrochemical technique with continuous flow. Cu@Cu foam and RuO2@Ti were prepared for NO3 reduction and NH4 and COD oxidation, respectively. The characterization of electrodes was performed by XRD, EDS, FTIR, FE-SEM, and CV analysis. The effects of parameters including NH4 concentration (10–30 mg N/L), NO3 concentration (4–12 mg N/L), current (0.5–1.5 A), and Cl- concentration (100–400 mg/L) were examined for the removal of NH4, NO3, and COD. Characterization results confirmed that Cu and RuO2 were successfully coated on the surface of electrodes. Operating parameters were optimized using response surface methodology. The ideal conditions for current, Cl- concentration, and HRT were 1.5 A, 347.7 mg/L, and 120 min, respectively for concentrations of 9 mg /L NO3-N, 30 mg/L NH4-N, and 30 mg/L COD. Under these conditions, NO3-N, NH4-N, and COD removal efficiencies were 78 %, 97.8 %, and 61.2 %, respectively. The proposed electrochemical process was a sustainable technology for the concurrently removal nitrogen and carbon with advantages including environmental compatibility, versatility merits, and simplicity.

Theoretical and experimental study on the recovery of bromide by crystallization from pesticide production wastewater

Brominated wastewater from the propyl bromide pesticide production rich in ammonium, sodium and bromine salts at a high concentration of 11 %. For the recycling of chemical resources of this mixed brine salt system, this paper proposes a method for the separation of bromide from bromine-containing chemical wastewater by crystallization. According to the process design needs of the new method, and because 298 K and 323 K are two common temperatures in industrial practice, in this paper, the solubility data of the NaCl-NH4Cl-NaBr-NH4Br-H2O quaternary system at 298 K and 323 K, as well as its ternary subsystems, NaBr-NH4Br-H2O and NH4Cl-NH4Br-H2O at 323 K were determined by the isothermal solubilization method, and the corresponding phase diagrams were drawn. The solubility of the NaCl-NH4Cl-NaBr-NH4Br-H2O quaternary system at 298 K was also calculated using the Pitzer model, and the calculated results were in good agreement with the experimental measurements. Finally, based on the theoretical analysis of the phase diagrams of the 298 K and 323 K NaCl-NH4Cl-NaBr-NH4Br-H2O quaternary systems and combined with the phase diagrams of the 298 K NaBr-NaCl-CH3OH system, this paper proposes and designs a salt extraction process route for the brominated wastewater of the propyl bromide pesticide production. Through the separation experiment, the new process proved to be technically feasible and produced NaCl with 100 % purity, Na(Br,Cl) with 98.23 % NaBr, and NH4(Cl,Br) with 99.18 % and 97.57 % NH4Cl, respectively. The new process realizes the resourceful utilization of bromine-containing wastewater, and has the significant advantages of production safety and no emission of three wastes.

Development of an Enzyme Cascade System for the Synthesis of Enantiomerically Pure D-Amino Acids Utilizing Ancestral L-Amino Acid Oxidase.

Enantiomerically pure D-amino acids hold significant potential as precursors for synthesizing various fine chemicals, including peptide-based drugs and other pharmaceuticals. This study focuses on establishing an enzymatic cascade system capable of converting various L-amino acids into their D-isomers. The system integrates four enzymes: ancestral L-amino acid oxidase (AncLAAO-N4), D-amino acid dehydrogenase (DAADH), D-glucose dehydrogenase (GDH), and catalase. AncLAAO-N4 initiates the process by converting L-amino acids to corresponding keto acids, which are then stereo-selectively aminated to D-amino acids by DAADH using NADPH and NH4Cl. Concurrently, any generated H2O2 is decomposed into O2 and H2O by catalase, while GDH regenerates NADPH from D-glucose. Optimization of reaction conditions and substrate concentrations enabled the successful synthesis of five D-amino acids, including a D-Phe derivative, three D-Trp derivatives, and D-phenylglycine, all with high enantiopurity (>99 % ee) at a preparative scale (>100 mg). This system demonstrates a versatile approach for producing a diverse array of D-amino acids.

Platycodin D ameliorates ammonia-induced pulmonary fibrosis by repressing TGF-β1-mediated extracellular matrix remodeling.

Ammonia can induce pulmonary fibrosis in humans and animals. Platycodin D (PLD) possesses various bioactive activities including anti-fibrotic properties. In this study, we aimed to explore the activity and mechanism of PLD in pulmonary fibrosis induced by ammonia. The mouse model of ammonia-induced lung fibrosis was established, and the role of PLD was assessed by H&E and Masson's trichrome staining. The differentially expressed genes (DEGs) were identified by RNA-seq and subjected to GO and KEGG pathway analyses. BEAS-2B cells were treated with NH4 Cl alone or along with PLD. Results showed that PLD attenuated ammonia-induced pulmonary inflammation and fibrosis invivo. The extracellular matrix (ECM)-receptor interaction pathway was predicted as a prominent pathway underlying the anti-fibrotic function of PLD. In ammonia-induced mouse models and NH4 Cl-treated BEAS-2B cells, PLD could repress the activation of the TGF-β1 pathway. By incubating lung fibroblast HFL1 cells with the conditioned medium of BEAS-2B cells treated with NH4Cl alone or along with PLD, PLD was confirmed to attenuate NH4 Cl-induced ECM deposition in HFL1 cells. Our findings demonstrate that PLD exerts a protective function in ammonia-induced pulmonary fibrosis by repressing TGF-β1-mediated ECM remodeling, suggesting the potential therapeutic value of PLD in this disease.

Effect of electron donors on CO2 fixation from a model cement industry flue gas by non-photosynthetic microbial communities in batch and continuous reactors.

The aim of this work was to evaluate the effect of different inorganic compounds as electron donors for the capture of CO2 from a model cement flue gas CO2 /O2 /N2 (4.2:13.5:82.3% v/v) using a non-photosynthetic microbial community. The inoculum obtained from a H2 -producing reactor was acclimated to CO2 consumption achieving 100% of CO2 removal after 45 days. Na2 S, MnCl2 , NaNO2 , NH4 Cl, Na2 S2 O3 , and FeCl2 were used as energy source for CO2 fixation by the acclimated microbial community showing different efficiencies, being Na2 S the best electron donor evaluated (100% of CO2 consumption) and FeCl2 the less effective (28% of CO2 consumption). In all treatments, acetate and propionate were the main endpoint metabolites. Moreover, scaling the process to a continuous laboratory biotrickling filter using Na2 S as energy source showed a CO2 consumption of up to 77%. Analysis of the microbial community showed that Na2 S and FeCl2 exerted a strong selection on the microbial members in the community showing significant differences (PERMANOVA, p = 0.0001) compared to the control and the other treatments. Results suggest that the CO2 fixing pathways used by the microbial community in all treatments were the 3-hydroxypropionate-4-hydroxybutyrate cycle and the Wood-Ljungdahl pathway.

Limited role for hyperammonemia in the progression of diet-induced nonalcoholic steatohepatitis.

To determine whether hyperammonemia has a direct impact on steatohepatitis in mice fed with a high-fat diet (HFD). Male C57BL/6 mice were divided into two groups receiving either chow diet or HFD. After 12-week NASH modeling, hyperammonemia was induced by intragastric administration of ammonium chloride solution (NH4 Cl) or liver-specific carbamoyl phosphate synthetase 1 (Cps1) knockdown. In vitro experiments were performed in HepG2 cells induced by free fatty acid (FFA) and NH4 Cl. NH4 Cl administration led to increased levels of plasma and hepatic ammonia in NASH mice. NH4 Cl-induced hyperammonemia did not influence liver histological changes in mice fed with HFD; however, elevated plasma cholesterol level, and an increasing trend of liver lipid content were observed. No significant effect of hyperammonemia on hepatic inflammation and fibrosis in NASH mice was found. In vitro cell experiments showed that NH4 Cl treatment failed to increase the lipid droplet content and the expressions of de novo lipogenesis genes in HepG2 cells induced by FFA. The knockdown of Cps1 in HFD-fed mice resulted in elevated plasma ammonia levels but did not cause histological change in the liver. Our study revealed a limited role of ammonia in aggravating the progression of NASH. Further studies are needed to clarify the role and mechanism of ammonia in NASH development.

Real-time influence of intracellular acidification and Na+ /H+ exchanger inhibition on in-cell pyruvate metabolism in the perfused mouse heart: A 31 P-NMR and hyperpolarized 13 C-NMR study.

Disruption of acid-base balance is linked to various diseases and conditions. In the heart, intracellular acidification is associated with heart failure, maladaptive cardiac hypertrophy, and myocardial ischemia. Previously, we have reported that the ratio of the in-cell lactate dehydrogenase (LDH) to pyruvate dehydrogenase (PDH) activities is correlated with cardiac pH. To further characterize the basis for this correlation, these in-cell activities were investigated under induced intracellular acidification without and with Na+ /H+ exchanger (NHE1) inhibition by zoniporide. Male mouse hearts (n= 30) were isolated and perfused retrogradely. Intracellular acidification was performed in two ways: (1) with the NH4 Cl prepulse methodology; and (2) by combining the NH4 Cl prepulse with zoniporide. 31 P NMR spectroscopy was used to determine the intracellular cardiac pH and to quantify the adenosine triphosphate and phosphocreatine content. Hyperpolarized [1-13 C]pyruvate was obtained using dissolution dynamic nuclear polarization. 13 C NMR spectroscopy was used to monitor hyperpolarized [1-13 C]pyruvate metabolism and determine enzyme activities in real time at a temporal resolution of a few seconds using the product-selective saturating excitation approach. The intracellular acidification induced by the NH4 Cl prepulse led to reduced LDH and PDH activities (-16% and -39%, respectively). This finding is in line with previous evidence of reduced myocardial contraction and therefore reduced metabolic activity upon intracellular acidification. Concomitantly, the LDH/PDH activity ratio increased with the reduction in pH, as previously reported. Combining the NH4 Cl prepulse with zoniporide led to a greater reduction in LDH activity (-29%) and to increased PDH activity (+40%). These changes resulted in a surprising decrease in the LDH/PDH ratio, as opposed to previous predictions. Zoniporide alone (without intracellular acidification) did not change these enzyme activities. A possible explanation for the enzymatic changes observed during the combination of the NH4 Cl prepulse and NHE1 inhibition may be related to mitochondrial NHE1 inhibition, which likely negates the mitochondrial matrix acidification. This effect, combined with the increased acidity in the cytosol, would result in an enhanced H+ gradient across the mitochondrial membrane and a temporarily higher pyruvate transport into the mitochondria, thereby increasing the PDH activity at the expense of the cytosolic LDH activity. These findings demonstrate the complexity of in-cell cardiac metabolism and its dependence on intracellular acidification. This study demonstrates the capabilities and limitations of hyperpolarized [1-13 C]pyruvate in the characterization of intracellular acidification as regards cardiac pathologies.

Sustainable and Scalable Synthesis of 2D Ultrathin Hierarchical Porous Carbon Nanosheets for High-Performance Supercapacitor.

2D carbon nanomaterials such as graphene, carbon nanosheets, and their derivatives, representing the emerging class of advanced multifunctional materials, have gained great research interest because of their extensive applications ranging from electrochemistry to catalysis. However, sustainable and scalable synthesis of 2D carbon nanosheets (CNs) with hierarchical architecture and irregular structure via a green and low-cost strategy remains a great challenge. Herein, prehydrolysis liquor (PHL), an industrial byproduct of the pulping industry, is first employed to synthesize CNs via a simple hydrothermal carbonization technique. After mild activation with NH4 Cl and FeCl3 , the as-prepared activated CNs (A-CN@NFe) display an ultrathin structure (≈3 nm) and a desirable specific surface area (1021 m2 g-1 ) with hierarchical porous structure, which enables it to be both electroactive materials and structural support materials in nanofibrillated cellulose/A-CN@NFe/polypyrrole (NCP) nanocomposite, and thus endowing nanocomposite with impressive capacitance properties of 2546.3 mF cm-2 at 1 mA cm-2 . Furthermore, the resultant all-solid-state symmetric supercapacitor delivers a satisfactory energy storage ability of 90.1 µWh cm-2 at 250.0 µW cm-2 . Thus, this work not only opens a new window for sustainable and scalable synthesis of CNs, but also offers a double profits strategy for energy storage and biorefinery industry.

MAEL facilitates metabolic reprogramming and breast cancer progression by promoting the degradation of citrate synthase and fumarate hydratase via chaperone-mediated autophagy.

Metabolic reprogramming is a hallmark of cancer. Several studies have shown that inactivation of Krebs cycle enzymes, such as citrate synthase (CS) and fumarate hydratase (FH), facilitates aerobic glycolysis and cancer progression. MAEL has been shown to play an oncogenic role in bladder, liver, colon, and gastric cancers, but its role in breast cancer and metabolism is still unknown. Here, we demonstrated that MAEL promoted malignant behaviours and aerobic glycolysis in breast cancer cells. Mechanistically, MAEL interacted with CS/FH and HSAP8 via its MAEL domain and HMG domain, respectively, and then enhanced the binding affinity of CS/FH with HSPA8, facilitating the transport of CS/FH to the lysosome for degradation. MAEL-induced degradation of CS and FH could be suppressed by the lysosome inhibitors leupeptin and NH4 Cl, but not by the macroautophagy inhibitor 3-MA or the proteasome inhibitor MG132. These results suggested that MAEL promoted the degradation of CS and FH via chaperone-mediated autophagy (CMA). Further studies showed that the expression of MAEL was significantly and negatively correlated with CS and FH in breast cancer. Moreover, overexpression of CS or/and FH could reverse the oncogenic effects of MAEL. Taken together, MAEL promotes a metabolic shift from oxidative phosphorylation to glycolysis by inducing CMA-dependent degradation of CS and FH, thereby promoting breast cancer progression. These findings have elucidated a novel molecular mechanism of MAEL in cancer.

Bile duct ligation increased dopamine levels in the cerebral cortex of rats partly due to induction of tyrosine hydroxylase.

Liver failure is associated with psychiatric alterations, partly resulting from the increased brain dopamine levels. We investigated the relationship between increased dopamine levels and mental abnormalities using bile duct ligation (BDL) rats and the mechanism by which liver failure increased dopamine levels in SH-SY5Y cells. Behavioural tests were carried out on day 13 and 27 following BDL, along with measurements of dopamine and metabolites, expressions of enzymes and transporters related to dopamine metabolism, and its transport into the cortex and the hippocampus. SH-SY5Y cells were used to investigate whether NH4 Cl, bile acids and bilirubin affected expression of tyrosine hydroxylase or not. Tyrosine hydroxylase (TH) expression in SH-SY5Y cells co-incubated with bilirubin and signal pathway inhibitors was measured. Open-field test results demonstrated BDL rats showed anxiety-like behaviour, accompanied by increased dopamine levels and expression of TH protein in the cortex. Membrane bound long form (MB)-COMT, slightly but significantly decreased. SH-SY5Y cells indicated that increased bilirubin levels was a factor in inducing TH expression. Both inhibitor of NF-κB pathway BAY 11-7082 and silencing NF-κB p65 reversed bilirubin-induced upregulation of TH protein. NF-κB activator TNF-α increased expression of TH protein. Roles of bilirubin in increases of TH protein expressions and dopamine levels were measured using hyperbilirubinemia rats. Anxiety-like behaviour, was associated with increased dopamine levels and TH protein expressions in hyperbilirubinemia rats. BDL significantly increased dopamine levels in rat cortex partly due to bilirubin-mediated TH induction. Increased bilirubin induced TH expression via activating NF-κB signalling pathway.

Surface Modification of PAN-Derived Commercial Graphite Felts Using Deep Eutectic Solvents for their Application as Electrodes in All-Vanadium Redox Flow Batteries.

All-vanadium redox flow batteries are promising large-scale energy storage solutions to support intermittent power generation. Commercial graphite felts are among the most used materials as electrodes for these batteries due to their cheap price, high conductivity, and large surface area. However, these materials exhibit poor wettability and electrochemical activity towards vanadium redox reactions, which translates into overpotentials and lower efficiencies. Deep eutectic solvents (DES) are mixtures of Lewis acids and bases that exhibit lower melting points than their original components. Here, a DES composed of choline chloride and urea, and a DES composed of FeCl3 and NH4 Cl have been employed to modify the surface of graphite felts alongside a series of re-carbonization steps. The resulting materials were compared against pristine, thermally activated, and oxidatively activated graphite felts. Our results indicated that the treatments introduced new oxygen and nitrogen functionalities to the carbonaceous surface and increased the surface area, the degree of disorder and defects in the graphitic layers of the fibres. Cyclic voltammetry studies demonstrated higher electrochemical activity towards vanadium redox reactions and electrochemical impedance spectroscopy experiments showed the modified materials exhibited significantly lower charge transfer resistances. When tested in full cell configuration the electrode modified with the urea-based DES exhibited comparable coulombic efficiencies and superior energy storage capacity retention than the thermally oxidized felt used as benchmark, suggesting that the introduction of oxygen- and nitrogen-rich functional groups had a positive effect on the overall electrochemical performance of graphite felts.

Two-pore channel protein TPC1 is a determining factor for the adaptation of proximal tubular phosphate handling.

Two-pore channels (TPCs) constitute a small family of cation channels expressed in endo-lysosomal compartments. TPCs have been characterized as critical elements controlling Ca2+ -mediated vesicular membrane fusion and thereby regulating endo-lysosomal vesicle trafficking. Exo- and endocytotic trafficking and lysosomal degradation are major mechanisms of adaption of epithelial transport. A prime example of highly regulated epithelial transport is the tubular system of the kidney. We therefore studied the localization of TPC protein 1 (TPC1) in the kidney and its functional role in the dynamic regulation of tubular transport. Immunohistochemistry in combination with tubular markers were used to investigate TPC1 expression in proximal and distal tubules. The excretion of phosphate and ammonium, as well as urine volume and pH were studied in vivo, in response to dynamic challenges induced by bolus injection of parathyroid hormone or acid-base transitions via consecutive infusion of NaCl, Na2 CO3 , and NH4 Cl. In TPC1-deficient mice, the PTH-induced rise in phosphate excretion was prolonged and exaggerated, and its recovery delayed in comparison with wildtype littermates. In the acid-base transition experiment, TPC1-deficient mice showed an identical rise in phosphate excretion in response to Na2 CO3 compared with wildtypes, but a delayed NH4Cl-induced recovery. Ammonium-excretion decreased with Na2 CO3 , and increased with NH4 Cl, but without differences between genotypes. We conclude that TPC1 is expressed subapically in the proximal but not distal tubule and plays an important role in the dynamic adaptation of proximal tubular phosphate reabsorption towards enhanced, but not reduced absorption.

Fungicide smoke generated by electrical heating effectively controls gray mold of Chinese chives and reduces residue risk through adequate environmental sterilization.

Labor-saving pesticide application technology is eagerly pursued in the planting system of Chinese chives. In this study, we developed a set of application approaches by turning fungicides into smoke to achieve this goal. The fungicides fludioxonil, fluopyram, boscalid, procymidone, and prochloraz could be vaporized into smoke at temperatures below 300 °C. The SFR (smoke formation rate) decreased with the increasing temperature. At 300 °C, the SFR of fludioxonil, fluopyram, boscalid and procymidone were all higher than 80%. At 300 °C and 600 °C, there were no significant differences in the smoke particle state of these five fungicides. However, the inhibition rate of these five fungicides against the growth of Botrytis squamosa generally decreased with the temperature. At 600 °C, only fludioxonil and boscalid had inhibition rates higher than 80%. The deposition uniformity of fungicide smoke increased with the increasing amounts of NH4 Cl. When the amount of NH4 Cl reached 80% of the total content, the smoke of fungicide was uniformly deposited throughout each glass slide. In the greenhouse experiment, the control efficacy of fungicide application by smoke was significantly better than that of spraying application, whereas its residue was much lower. It is feasible to control air-borne disease through the vaporization of fungicides into smoke by electrical heating. Smoke application would effectively inhibit the spores in the air and would not increase the humidity of the environment. These findings indicate that smoke application is a labor-saving pesticide application technology viable in production. © 2022 Society of Chemical Industry.

Mesoporous N-rich Carbon with Single-Ni Atoms as a Multifunctional Sulfur Host for Li-S Batteries.

Physicochemical confinement and catalytic conversion of lithium polysulfides (LiPSs) are crucial to suppress the shuttle effect and enhance the redox kinetics of lithium-sulfur (Li-S) batteries. In this study, a NH4 Cl-assisted pyrolysis strategy is developed to fabricate highly mesoporous N-rich carbon (designed as NC(p)) featuring thin outer shells and porous inner networks, on which single-Ni atoms are anchored to form an excellent sulfur host (designed as Ni-NC(p)) for Li-S batteries. During pyrolysis, the pyrolytic HCl from confined NH4 Cl within ZIF-8 will in situ etch ZIF-8 to produce rich mesoporous in the carbonized product NC(p). The mesoporous Ni-NC(p) enables favorable electron/ion transfer, high sulfur loading, and effective confinement of LiPSs, while the catalytic effect of single-Ni species enhances the redox kinetics of LiPSs. As a result, the sulfur cathode based on the Ni-NC(p) host delivers obviously improved Li-S battery performance with high specific capacity, good rate capability, and cycling stability.

Nanoarchitectonics in the Ionothermal Synthesis for Nucleation of Crystalline Potassium Poly (heptazine imide) Towards an Enhanced Solar-Driven H2 O2 Production.

Solar-driven selective oxygen reduction reaction on polymeric carbon nitride framework is one of the most promising approaches toward sustainable H2 O2 production. Potassium poly(heptazine imide) (PHI), with regular metal sites in the framework and favorable crystalline structure, is highly active for photocatalytic selective 2e oxygen reduction to produce H2 O2 . By introducing NH4 Cl into the eutectic KCl-LiCl salt mixture, the PHI framework exhibits a remarkable performance for photocatalytic production of H2 O2 , for example, a record high H2 O2 photo-production rate of 29.5 μmol h-1 mg-1 . The efficient photocatalytic performance is attributed to the favorable properties of the new PHI framework, such as improved porosity, negatively shifted LUMO position, enhanced exciton dissociation and charges migration properties. A mechanistic investigation by quenching and electron spin resonance technique reveals the critical role of superoxide radicals for the formation singlet oxygen, and the singlet oxygen is one of the critical intermediates towards the formation of the H2 O2 by proton extraction from the ethanol.

Moving towards a novel therapeutic strategy for hyperammonemia that targets glutamine metabolism.

Patients with urea cycle disorders intermittently develop episodes of decompensation with hyperammonemia. Although such an episode is often associated with starvation and catabolism, its molecular basis is not fully understood. First, we attempted to elucidate the mechanism of such starvation-associated hyperammonemia. Using a mouse embryonic fibroblast (MEF) culture system, we found that glucose starvation increases ammonia production, and that this increase is associated with enhanced glutaminolysis. These results led us to focus on α-ketoglutarate (AKG), a glutamate dehydrogenase inhibitor, and a major anaplerotic metabolite. Hence, we sought to determine the effect of dimethyl α-ketoglutarate (DKG), a cell-permeable AKG analog, on MEFs and found that DKG mitigates ammonia production primarily by reducing flux through glutamate dehydrogenase. We also verified that DKG reduces ammonia in an NH4 Cl-challenged hyperammonemia mouse model and observed that DKG administration reduces plasma ammonia concentration to 22.8% of the mean value for control mice that received only NH4 Cl. In addition, we detected increases in ornithine concentration and in the ratio of ornithine to arginine following DKG treatment. We subsequently administered DKG intravenously to a newborn pig with hyperammonemia due to ornithine transcarbamylase deficiency and found that blood ammonia concentration declined significantly over time. We determined that this effect is associated with facilitated reductive amination and glutamine synthesis. Our present data indicate that energy starvation triggers hyperammonemia through enhanced glutaminolysis and that DKG reduces ammonia accumulation via pleiotropic mechanisms both in vitro and in vivo. Thus, cell-permeable forms of AKG are feasible candidates for a novel hyperammonemia treatment.

Signal enhancement of hyperpolarized 15 N sites in solution-increase in solid-state polarization at 3.35 T and prolongation of relaxation in deuterated water mixtures.

Hyperpolarized 15 N sites have been found to be promising for generating long-lived hyperpolarized states in solution, and present a promising approach for utilizing dissolution-dynamic nuclear polarization (dDNP)-driven hyperpolarized MRI for imaging in biology and medicine. Specifically, 15 N sites with directly bound protons were shown to be useful when dissolved in D2 O. The purpose of the current study was to further characterize and increase the visibility of such 15 N sites in solutions that mimic an intravenous injection during the first cardiac pass in terms of their H2 O:D2 O composition. The T1 values of hyperpolarized 15 N in [15 N2 ]urea and [15 N]NH4 Cl demonstrated similar dependences on the H2 O:D2 O composition of the solution, with a T1 of about 140 s in 100% D2 O, about twofold shortening in 90% and 80% D2 O, and about threefold shortening in 50% D2 O. [13 C]urea was found to be a useful solid-state 13 C marker for qualitative monitoring of the 15 N polarization process in a commercial pre-clinical dDNP device. Adding trace amounts of Gd3+ to the polarization formulation led to higher solid-state polarization of [13 C]urea and to higher polarization levels of [15 N2 ]urea in solution.

Dinitrogen Binding at a Trititanium Chloride Complex and Its Conversion to Ammonia under Ambient Conditions.

Reaction of [TiCp*Cl3] (Cp*=η5‐C5Me5) with one equivalent of magnesium in tetrahydrofuran at room temperature affords the paramagnetic trinuclear complex [{TiCp*(μ‐Cl)}3(μ3‐Cl)], which reacts with dinitrogen under ambient conditions to give the diamagnetic derivative [{TiCp*(μ‐Cl)}3(μ3‐η1 : η2 : η2‐N2)] and the titanium(III) dimer [{TiCp*Cl(μ‐Cl)}2]. The structure of the trinuclear mixed‐valence complexes has been studied by experimental and theoretical methods and the latter compound represents the first well‐defined example of the μ3‐η1 : η2 : η2 coordination mode of the dinitrogen molecule. The reaction of [{TiCp*(μ‐Cl)}3(μ3‐η1 : η2 : η2‐N2)] with excess HCl in tetrahydrofuran results in clean NH4Cl formation with regeneration of the starting material [TiCp*Cl3]. Therefore, a cyclic ammonia synthesis under ambient conditions can be envisioned by alternating N2/HCl atmospheres in a [TiCp*Cl3]/Mg(excess) reaction mixture in tetrahydrofuran.

Screening and identifying cucurbitacins and cucurbitacin glycosides in Cucumis sativus using high-performance liquid chromatography/quadrupole-time-of-flight mass spectrometry combined with in-source fragmentation and alkali adduct ions.

Cucumber, as a popular fruit and vegetable, has tremendously contributed to providing a sufficient and high-quality food supply. However, the cucumber plant metabolites, which may possess potential benefits for human health, were rarely reported. In addition, rapid detection of these metabolites from the complex biological matrix of cucumber samples is a tremendous challenge. A rapid detection method was established to systematically screen cucurbitacins and cucurbitacin glycosides in cucumber plants by combining high-performance liquid chromatography/quadrupole-time-of-flight mass spectrometry (HPLC-Q-TOF-MS) with in-source fragmentation (ISF). Moreover, the alkali cations, including acetic acid, 0.1% LiCl, 0.1% NH4 Cl, 0.1% NaCl, and 0.1% KCl, were added to the mobile phase for improving the ion response. The fragmentation pathways of seven cucurbitacins and cucurbitacin glycosides were primarily investigated. The characteristic ISF ions at m/z 501.3211 and 503.3367 were identified and employed to screen 40 cucurbitacins and cucurbitacinglycosides from the complex biological matrix. Their structures were identified by their tandem mass spectrometry (MS/MS) spectra and fragmentation pathways of references. Finally, the metabolic distribution and network of cucurbitacins and cucurbitacin glycosides in cucumber plants were also proposed. This work marks the first systematic and comprehensive study of the metabolites in cucumber plants using HPLC-Q-TOF-MS technology, providing a template for screening and identifying the triterpenoids from other plant-derived medicines or food.

Synergetic Chemistry and Interface Engineering of Hydrogel Electrolyte to Strengthen Durability of Solid-State Zn-Air Batteries.

For the challenging pursuit of high energy efficiency and mechanical tolerance in flexible solid-state Zn-air batteries (FSZABs), a hydrogel electrolyte (HE) consisting of dual-network crosslinked polyacrylic acid-Fe3+ -chitosan (PAA-Fe3+ -CS) polymer host infiltrated with a mixed aqueous electrolyte of NH4 Cl and ZnCl2 is developed. The absorbed near-neutral electrolyte renders the HE high ionic conductivity but low corrosiveness to both electrocatalysts and Zn metal anode (ZMA), ensuring more stable Zn-OH-O2 chemistry compared to that in strong alkaline electrolyte and thus endowing the assembled FSZABs with a landmark cycle life up to 120 h (5 mA cm-2 ). More intriguingly, the CS molecular beams introduced into the PAA hydrogel backbone will precipitate and fold subjecting to the Hofmeister effect when saturated with the near-neutral electrolyte, which can effectively enhance the interfacial adhesion strength of the HE on both air cathode and ZMA, achieving reliable and robust bonding between them. Thus, the FSZABs simultaneously exhibited a superior tolerance to repeated mechanical deformation during operation, allowing more than 360 continuous bending-recovery cycles without any decline in voltage efficiency. The ingenious chemistry and interface synergetic engineering on the crucial HEs provides a rational methodology to realize boosted electrochemical and mechanical durability of FSZABs forward for future practical implementation.