Stoichiometry Of Reaction Research Articles

Decreasing the Uncertainty in the Comparison of Molecular Fingerprints of Organic Aerosols with H/D Exchange Mass Spectrometry.

High-resolution mass spectrometry (HRMS) has become an indispensable tool in the characterization of organic aerosols (OA) providing information on air quality, health assessment, climate trends, reactions, and source apportionment. Spectra-derived lists of formulas and their relative abundances are used to compare ambient OA from different sources or to monitor secondary OA formation under controlled laboratory conditions in smog chamber experiments. Various techniques are implemented to visualize common and unique features, series of precursors, and products. The disadvantage of this conventional approach is in associating elemental compositions to specific compounds, while due to several analytical limitations, the structural information remains hidden. We argue that some of the conclusions derived from this data analysis can be misleading. In this study, we applied in-ESI source H/D exchange (HDX), which facilitated enumeration of labile protons in molecules behind elemental compositions of OA. We applied this technique to compare OA from three different locations representing urban, forest, and marine environments and to examine tentative chemical information derived from Kendrick mass defect (KMD) series analysis. Significant discrepancies were found between numbers of labile protons in protogenic functional groups and the stoichiometry of chemical reactions, which are associated with KMD series. Only a portion of chemical pairs matched target stoichiometries, which highlights the existing limitations in environmental applications of conventional formula-based HRMS data interpretation strategies.

Kinetic Modeling of Brilliant Blue Discoloration by Ozonation

This paper presents the results of investigations on the kinetic modeling of Brilliant Blue FCF (BB) discoloration reactions in aqueous solutions with different ozone concentrations and pH conditions. Kinetic studies involve knowledge of the structure and properties of dye and ozone, as well as of the experimental conditions. In general, scientists admit that the predominant oxidation pathway is direct (by free oxygen atoms) or indirect (by free hydroxyl radicals); this will depend on influencing factors such as the physicochemical properties of the dye, the pH of the aqueous solution, ozone concentration, reaction time, and the contact mode with/without stirring. In this experimental research, two pathways were chosen following CBB = f(t)—1. a constant dye concentration and different ozone concentrations, in the concentration range of 100–250 mg/L, in three pH media (acidic, neutral, and basic), with and without stirring; 2. a constant concentration of ozone and different dyes in the concentration range of 2.5–10 mg/L, under the conditions of point 1. With the obtained experimental data, the curves CBB = f(t) were drawn and processed according to the integral method of classical kinetics, based on first- and second-order equations. Unfortunately, this simple procedure did not give any results for the pH values studied. The rate constants were negative, and/or the reaction order depended on the initial conditions. Due to its structure, the BB dye has several chromophore groups, and thus multiple attack centers, resulting in several oxidation by-products, which is why the 1H-NMR spectrum was recorded for the discoloration of BB with ozone. Since the stoichiometry of the overall oxidation reaction, as well as the relationship between the rate constant and the reaction conditions mentioned above, is not known, a kinetic model based on mass transfer coupled with a chain reaction in the bulk liquid phase was proposed and successfully tested at pH = 7. This research approach also involves the consolidation of the theoretical bases of the ozonation process through the kinetic study carried out, as well as the proposal of a kinetic model. These systematics lead to results that are applicable to other aqueous systems that are impure with dyes, allowing for generalizations and the development of the field, ensuring the sustainability of the research.

Numerical investigation of the influence of thermal runaway modelling on car park fire hazard and application to a Lithium-ion Manganese Oxide battery

This article presents numerical simulations of a Nissan LEAF 2011 electric car fire inside a concrete parking facility. Variations in the thermo-chemical properties of thermal runaway are analysed, and the way they affect the heat received by the concrete structure and a nearby parked vehicle is evaluated. Three key parameters are identified: the composition of the gas flowing through the pressure vent, the associated flow rate, and the peak heat release rate. These parameters are established independently, and the model is closed by adjusting the stoichiometry of the combustion reaction of the vented gas. Four simulations are conducted to capture the uncertainty. The net heat flux and surface temperature on the concrete and on a neighbouring parked car are monitored during each simulation. The study includes a sensitivity analysis of the impact of input variables on the net heat fluxes and surface temperatures, and investigations are carried out to understand the role of internal heat release. Variations in the gaseous mixture composition, heat release rate, and internal heat release have little impact on the resulting thermal conditions around the burning car because the combustion of the polymers in the passenger cabin drives the total heat release rate.

An Overview of H2 and CH4 as Environmentally Sustainable Alternative Reductants to C for Chromite Smelting

The application of hydrogen (H2) and methane (CH4) as gaseous reductants for pure chromite (FeCr2O4) is reviewed in four theoretical approaches. These approaches are evaluated against the conventional process, where the sole reductant is a solid carbon (C) source. The sustainability is measured by gaseous carbon monoxide (CO(g)) formation, determined by the reaction stoichiometry of each theoretical approach. Decreased CO(g) formation is critical for alleviating the adverse environmental impact of ferroalloy production. The prereduction of FeCr2O4 by H2, followed by reduction by CH4 shows the largest decrease in CO(g) formation, i.e., a 75% decrease, compared to the conventional process. Furthermore, the H2‐based prereduction and CH4‐based primary reduction occur at lower temperatures than C‐based reduction, due to kinetic advantages, and thus decrease energy consumption. The overview discusses the environmental impact of substituting C with H2 and CH4 and briefly discusses how it can be implemented in industry.

Insight in sulfadiazine degradation by peroxymonosulfate activated by polydopamine-derived nitrogen-doped carbon supported CoFe2O4: Co leaching inhibition and degradation enhancement

Heterogeneous catalyst-mediated sulfate radical-based advanced oxidation processes (SR-AOPs) showed excellent performance during antibiotics degradation. Spinel was a promising catalyst for SR-AOPs, but the secondary contamination due to metal ions leaching needed to be addressed. And the destruction of catalyst structure could lead to the reduction of catalytic activity and the difficulty of recovery. Thus, a novel nitrogen-doped carbon (NC)-supported CoFe2O4 (CoFe2O4@NC) was synthesized as the activator of PMS for sulfadiazine (SDZ) degradation under low Co leaching conditions. The consequences indicated that the CoFe2O4@NC/PMS system exhibited higher PMS decomposition efficiency and reaction stoichiometry efficiency than the bare CoFe2O4/PMS systems (CoFe2O4-180 and CoFe2O4-800), which in turn demonstrated a better SDZ removal performance. Under the condition of CoFe2O4@NC dosage 0.1 g/L, PMS concentration 0.5 mM, solution pH 6.8 and temperature 25°C, SDZ (20 mg/L) was almost completely degraded within 60 min. XPS analysis showed that the NC not only protected and stabilized CoFe2O4, but also provided additional active sites for PMS activation. During SDZ degradation, SO4•−, HO•, •O2− and 1O2 were involved in the reaction, among which SO4• and HO• made the main contribution. Meanwhile, CoFe2O4@NC could be recovered by magnetic separation, and showed great stability (Co leaching 0.852 mg/L) and reusability. In the fifth cycle experiment, 85.02 % SDZ degradation was obtained. Based on the detected intermediates (12 intermediates were identified) and DFT calculations, possible degradation pathways for SDZ in CoFe2O4@NC/PMS were proposed. The condensed dual descriptor indicated that the N7, N11, and C15 atoms on SDZ molecule were the main sites of electrophilic attack, which was consistent with the detected intermediates. The degradation of SDZ involved hydroxylation of NH2, cleavage of S−N and extrusion of SO2. This study explored the improvements made in NC support material to catalytic performance and resistance to dissolution of spinel, providing new insights for subsequent researches.

Clostridium autoethanogenum alters cofactor synthesis, redox metabolism, and lysine-acetylation in response to elevated H2:CO feedstock ratios for enhancing carbon capture efficiency

BackgroundClostridium autoethanogenum is an acetogenic bacterium that autotrophically converts carbon monoxide (CO) and carbon dioxide (CO2) gases into bioproducts and fuels via the Wood–Ljungdahl pathway (WLP). To facilitate overall carbon capture efficiency, the reaction stoichiometry requires supplementation of hydrogen at an increased ratio of H2:CO to maximize CO2 utilization; however, the molecular details and thus the ability to understand the mechanism of this supplementation are largely unknown.ResultsIn order to elucidate the microbial physiology and fermentation where at least 75% of the carbon in ethanol comes from CO2, we established controlled chemostats that facilitated a novel and high (11:1) H2:CO uptake ratio. We compared and contrasted proteomic and metabolomics profiles to replicate continuous stirred tank reactors (CSTRs) at the same growth rate from a lower (5:1) H2:CO condition where ~ 50% of the carbon in ethanol is derived from CO2. Our hypothesis was that major changes would be observed in the hydrogenases and/or redox-related proteins and the WLP to compensate for the elevated hydrogen feed gas. Our analyses did reveal protein abundance differences between the two conditions largely related to reduction–oxidation (redox) pathways and cofactor biosynthesis, but the changes were more minor than we would have expected. While the Wood–Ljungdahl pathway proteins remained consistent across the conditions, other post-translational regulatory processes, such as lysine-acetylation, were observed and appeared to be more important for fine-tuning this carbon metabolism pathway. Metabolomic analyses showed that the increase in H2:CO ratio drives the organism to higher carbon dioxide utilization resulting in lower carbon storages and accumulated fatty acid metabolite levels.ConclusionsThis research delves into the intricate dynamics of carbon fixation in C. autoethanogenum, examining the influence of highly elevated H2:CO ratios on metabolic processes and product outcomes. The study underscores the significance of optimizing gas feed composition for enhanced industrial efficiency, shedding light on potential mechanisms, such as post-translational modifications (PTMs), to fine-tune enzymatic activities and improve desired product yields.

Low-Temperature Water Electrolysis Under a Sustained pH-Gradient for Electrochemically-Induced Decarbonation of Limestone into Hydrated Lime

Lime holds considerable potential in diverse environmental applications. However, its current production remains highly carbon-intensive, emitting more than one ton of CO2 per ton of lime. To address this issue, recent studies have explored the concept of electrifying the decarbonation of limestone to produce hydrated lime. In this work, a two-compartment electrolysis cell capable of producing Ca(OH)2 has been tested at different currents. Precise pH and Ca2+ concentration measurements demonstrate that the electrolysis setup is able to dissolve CaCO3 and precipitate Ca(OH)2 with near-perfect efficiencies. Notably, it highlights that Faraday’s law and the concept of transport number can be applied to predict both the equilibrium and kinetic behavior of each step of the process in each of the two cell compartments. Moreover, the use of controlled batch additions of CaCO3 in the system, as opposed to one-time excess addition, was assessed to mitigate the fouling of the cationic exchange membrane used to separate the compartments. Finally, based on the experimental findings, key guidelines are proposed to achieve a perfect reaction stoichiometry for each step. These findings pave the way for a more sustainable and environmentally friendly approach to lime production.

Valorization of hemicellulose waste streams for moisture barrier coatings and hydrophobic films

Replacing plastics with renewable and environmentally friendly substitutes is becoming ever more critical as we begin to realize the consequences of their negative impacts on the environment. Plant polysaccharides are the most abundant biopolymers on Earth, and hemicelluloses like xylan that are enriched in many agro-industrial waste streams have vast potential as eco-friendly building blocks for polymer science and engineering. However, xylan is one of the less studied natural polymers for applications that are relevant to the synthetic plastics and polymeric materials markets. Hemicellulose isolated from viscose and Lyocell fiber mills is largely seen as a waste product due to difficulties arising from the potential for structural heterogeneity and its lack of solubility after enrichment. In this work, we developed a strategy to valorize hemicellulose by functionalization with octyl isocyanate to achieve solubility and thermoplastic/hydrophobic properties. Xylan isolated from dissolving pulp waste streams was successfully functionalized with octyl isocyanate in DMSO at an estimated 79% hydroxyl conversion. Reaction parameters, including temperature, time, and stoichiometry were optimized for each reaction. The resultant carbamates of xylan oligo- and monosaccharides have good solubility in chloroform and impressive hydrophobic film forming properties yet retain the composability properties desired for renewable materials that are envisioned to enter the circular bioeconomy. Functionalization of xylan with an aliphatic chain through formation of an aliphatic carbamate is not expected to harbor the same toxicity or carcinogenic characteristics as the reactive isocyanate it is derived from, and thus should not inherently restrict these materials for use in diverse packaging applications. These modified physical properties show that xylan from agro-industrial waste streams has considerable potential to replace petroleum-based feedstocks in the existing packaging industry. In the future, we will continue to further develop strategies for valorization of these materials.Graphical

Low-Temperature Water Electrolysis Under a Sustained pH-Gradient for the Electrochemically-Induced Decarbonation of Limestone into Hydrated Lime

Conventional low-temperature water electrolysis processes operate either at high or low pH to enhance conductivity, minimizing electrical resistance. Neutral water electrolysis in a buffer solution is considered non-competitive due to higher energy consumption. Nevertheless, interest in water electrolysis using a salt-based electrolyte has grown due to its ability to generate a pH gradient inside the cell. Electrolysis using a neutral salt-based electrolyte has higher operating costs due to its higher standard equilibrium potential (due to the pH gradient) and lower conductivity. Although this approach incurs higher operating costs, it presents a unique advantage: the production of additional valuable elements thanks to the pH gradient generated.In 2019, Ellis & al. [1] highlighted the possibility to use this pH gradient to electrify the production of hydrated lime (calcium hydroxide). Lime has applications in different areas such as the removal of impurities during steel production and aqueous or gaseous effluent treatments. It can also be used as a precursor of cement. Cement production is accounting for 8% of global CO2 emissions. The acidity generated by water oxidation at the anode dissolves the calcium carbonate inserted. Carbon dioxide from the dissolution is recovered with the oxygen generated. The calcium cations migrate through the cationic membrane towards the cathodic compartment to react with the hydroxide ions generated by water reduction at the cathode. Calcium hydroxide is finally collected after precipitation. Figure 1 compares the conventional process with the electrochemical way and describes more precisely the steps involved in Figure 1. More recently, another way of exploiting this gradient has been proposed by Ni & al. [2] for the recycling of spent Li-ion batteries. With the growing interest in process electrification, other applications may emerge.In this paper, this hybrid electrochemical system for the simultaneous production of hydrogen, oxygen and calcium hydroxide has been intensively studied. Water electrolysis has been performed in a two-compartment cell at different applied currents. Calcium concentration and pH measurement enabled the study of the sub-step efficiencies and equilibria in anodic and cathodic chambers. Perfect faradic efficiencies were obtained with perchlorate salt electrolytes and platinum-free electrodes. The establishment of the pH gradient has been proven and correlated with the transport number of protons through the cationic membrane. Finally, the kinetics of calcium ion migration and calcium hydroxide precipitation have been investigated as well. Continuous addition of calcium carbonate as opposed to a single excess addition was shown to be able to tune the working pH in the anodic compartment and thereby reducing the risk of precipitation on the membrane. Our experimental results lead to the formulation of practical recommendations for achieving optimal reaction stoichiometry in each stage. These findings pave the way for scaling up a promising new sustainable process for lime and cement production.[1] L. D. Ellis, A. F. Badel and M. L. Chiang, "Toward electrochemical synthesis of cement," PNAS, vol. 117, no. 23, pp. 12584-12591, 2019.[2] N. Jihong, Z. Jiayin, B. Jinhong and G. Xiaofei, "Recycling the cathode materials of spent Li-ion batteries in a H-Shaped neutral water electrolysis cell," Separation and Putification Technology , vol. 278, p. 119485, 2022. Figure 1 - Conventional and electrochemical production route of Ca(OH)2 and a simplified scheme of the hybrid electrolyzer used in this work, with the reactions involved. Figure 1

Integrated spectroscopic approaches for the facile one pot quantification of olanzapine in pharmaceutical formulation and spiked human plasma

In this work, the xanthene dye, erythrosine B, was employed as a probe for the determination of olanzapine using two fast and highly simple analytical approaches. The assay was based on the formation of a binary complex between the drug and erythrosine B in a slightly acidic aqueous buffered solution. In the first method, the absorbance of the formed product was monitored at 558 nm. The reaction stoichiometry was investigated, and the stability constant of the formed complex was estimated. The linear range of the method that obeyed Beer's law was in the concentration range of 0.6–8.0 µg/ml. The calculated detection and quantitation limits were 0.2 and 0.6 µg/mL. Upon adding the drug solution to erythrosine B, the native fluorescence of the dye was quenched and monitored at 550 nm after excitation at 528 nm. Thus, the fluorescence quenching was utilized as the quantitative signal in the spectrofluorimetric approach. The extent of quenching in the fluorescence intensity was rectilinear with the drug concentration in a range of 0.1–2.5 µg/ml with a detection limit of 0.032 µg/ml. Both approaches were analytically validated based on the guiding rules of the ICH with acceptable results, and were utilized efficiently in the analysis of olanzapine in commercial tablets containing the cited drug. In addition, owing to its high sensitivity and selectivity, the spectrofluorimetric method was applied for drug analysis in spiked human plasma with satisfactory % recoveries. Finally, the greenness of the methods was confirmed using eco-score scale and Analytical Green Evaluation metrics.

Host-Guest Complexes of Flavanone and 4'-Chloroflavanone with Naturals and Modified Cyclodextrin: A Calorimetric and Spectroscopy Investigations.

The aim of the research was to investigate and compare the interaction between flavanones (flavanone, 4-chloro-flavanone) with potential anticancer activity and selected cyclodextrins. Measurements were made using calorimetric (ITC, DSC) and spectrophotometric (UV-Vis spectroscopy, FT-IR, 1H NMR) methods. The increase in the solubility in aqueous medium caused by the complexation process was determined by the Higuchi-Connors method. As a result of the study, the stoichiometry and thermodynamics of the complexation reaction were determined. The formation of stable inclusion complexes at a 1:1 M ratio between flavanone and 4-chloroflavanone and the cyclodextrins selected for research was also confirmed.

Estimating nitroxynil residues in food samples and surface water using two different sustainable chemical sensing techniques: Comparative greenness, whiteness, and blueness study

The presence of veterinary drug residues in edible animal tissues endangers human health and safety, accordingly, global nations enacted legislative restrictions to monitor their concentrations in food. In this work, we introduce two fluorimetric sensors for determining nitroxynil (NXL), a crucial veterinary medication, in various matrices. Sensor I, novel nitrogen and sulfur-doped carbon quantum dots (S,N-CQDs), was fabricated from strawberry and leek juices as cheap and sustainable natural resources. Only five minutes of microwave radiation were required as a rapid synthesizing technique without any drastic conditions or organic solvents. The S,N-CQDs manifest blue emission using λex/em of 340/418 nm. The synthesized nanosensor was characterized using UV Spectroscopy, transmission electron microscopy (TEM), and Fourier-transform infrared spectrometry (FTIR). Sensor II was the acriflavine reagent (AV) that exhibits native fluorescence using λex/em of 265/505 nm. Both sensors displayed quantitative turning off in their native fluorescence by increasing concentrations of NXL (1.0–10.0 and 0.5–8.0 µg mL−1) with correlation coefficients r = 0.9998 and 0.9999 for sensors I and II, respectively. The two probes achieved satisfactory percentage recoveries and standard deviation (SD < 4) for NXL assessing in complex matrices of diverse food samples (bovine muscle, kidney, and fat) and Fasciolar® veterinary formulation. Additionally, they have been successfully used to detect the investigated drug in river ecosystems with a mean %recovery of 100.10 ± 1.70, and 99.95 ± 1.31 for sensors I and II, respectively. The two constructed sensors’ specificity has been confirmed for all tested matrices reflecting their feasibility as promising platforms in therapeutic drug monitoring, livestock ecosystems, food safety assurance, quality control of drugs, and environmental pollution monitoring. Quenching mechanisms for both methodologies were studied and the reaction stoichiometry for NXL − AV complex was calculated in two ways. Lastly, a comprehensive comparison was performed between the suggested methodologies and published fluorimetric works. The greenness feature was assessed by the Analytical Eco-scale (AES), Green Analytical Procedure Index (GAPI), and Analytical GREEnness Metric Approach (AGREE). In addition, white analytical chemistry principles were checked to assess sustainability criteria using the RGB 12 algorithm. The recently launched Blue Applicability Grade Index (BAGI) metric tool was also employed to assess the practicality (Blueness) character.

Performance of ammonia catalytic combustion over Cu-CeOx catalyst and the impact of oxygen concentration

Ammonia has long been regarded as a high-quality zero-carbon fuel; however, limitations in its combustion characteristics have restricted its practical applications. Catalytic combustion is considered an effective solution to overcome the challenges associated with ammonia combustion. In this study, we successfully synthesized a copper-cerium binary catalyst (Cu-CeOx) using the sol-gel method, demonstrating outstanding performance for NH3 catalytic combustion. Through in-situ DRIFTS results, we observed that the 15Cu-CeOx catalyst exhibits both i-SCR and -NH mechanisms. The oxygen concentration affects the N2 selectivity by modulating the overoxidation of NH3. Under high oxygen concentrations, high temperatures promote the excessive oxidation of NH3, and ammonia combustion through the i-SCR mechanism. Conversely, the oxygen concentration was equal to NH3 reaction stoichiometry, the overoxidation of NH3 is limited, and ammonia combustion proceeds through the NH mechanism, resulting in higher N2 selectivity.

Anti-oxidative reactivity and mechanism of formic hydrazide, acethydrazide and butyrohydrazide towards reduction of single electron oxidant iridium(IV)

Reduction of a well-known single electron oxidant [IrCl6]2– by aliphatic hydrazides, viz. formic hydrazide, acethydrazide and butyrohydrazide, was investigated by use of several techniques including 1H NMR and rapid scan spectroscopies. It was demonstrated that the redox reactions exclusively follow second-order kinetics over a wide pH range; the observed second-order rate constants k' versus pH profiles have been established. When the features revealed by the rapid scan spectra, the reaction stoichiometry and the oxidation products were considered together, a reaction mechanism was proposed involving three parallel rate-determining steps in which [IrCl6]2– reacted with all the three protolytic forms of the hydrazides. Rate constants of the rate-determining steps and the dissociation constants of hydrazides at 25.0 °C and 1.0 M ionic strength were derived from the kinetic data. Activation parameters were determined for the reactions of [IrCl6]2– with the neutral forms of the hydrazides, and an outer-sphere electron transfer mode was implied. The reactivity of each protolytic form of the hydrazides was elucidated and its distribution versus pH was calculated. The reactivity of the protolytic forms was compared with that of the corresponding forms of aryl hydrazides, revealing that both the neutral and enolate forms of aliphatic hydrazides are less reactive than those of the aryl hydrazides towards reduction of [IrCl6]2–. It was concluded that aryl hydrazides are more important than aliphatic ones in the development of new hydrazide-based antioxidants in the future. Additionally, the protolysis equilibria of these aliphatic hydrazides in aqueous solution and their redox properties have been characterized and the dissociation constants in the case of butyrohydrazide are reported for the first time.

An eco-friendly spectrophotometric analysis tool with whiteness assessment to assay erythromycin in pharmaceutical formulation through metal complexation with Ni2+: application to the microbiological activity using agar diffusion method

A new, facile and eco-friendly spectrophotometric method for estimating erythromycin (ERY) in its dosage form has been proposed and validated. It depends on the formation of a complex between the drug and nickel at pH 7, using distilled water as a diluent, where the absorbance of the generated complex was measured at 228.5 nm. The formed complex followed a linear response over the concentration range of 80.0 to 300.0 µg/mL of ERY. The proposed method was fully validated according to international conference of harmonization (ICH) and was used to estimate the relevant concentration of the drug in its oral suspension formulation providing mean percentage recovery of 100.0±1.08 with a limit of detection and limit of quantification of 60 µg/mL and 80 µg/mL, respectively. the reaction stoichiometry was investigated and a reaction mechanism proposal was offered. Eventually, the antimicrobial effect of ERY and its metal complex with Ni2+ were compared using agar diffusion method, where no significant difference in their activities was observed.

Spatial, Seasonal, and Diel Controls of Nitrogen‐Carbon‐Oxygen Cycling During Lake‐Water Infiltration to an Aquifer

AbstractMany freshwater lakes are groundwater flow‐through systems. Although lakes commonly are considered to be sinks for nitrogen inputs, relatively little is known about carbon and nitrogen export from lakes to groundwater. The current study focused on lake‐bottom biogeochemical processes accompanying the transport of nitrogen, dissolved oxygen (O2), and dissolved organic carbon (DOC) during lake‐water recharge from a groundwater flow‐through lake. Lake‐water and porewater (15–100 cm below lakebed) samples were collected along transects within the lake downwelling zone. Infiltrating porewater O2 and DOC concentrations decreased with depth while nitrate (NO3−) concentrations increased, indicating nitrification of organic matter within the profiles. The depth of NO3− production and transport was seasonally dependent. In winter, NO3− and O2 were exported beyond 100‐cm depth; whereas in summer, shallow nitrification zones were underlain by deeper NO3− reduction zones, and diel patterns of O2 and NO3− penetration depths were observed. Microbial community compositions and stable isotope profiles (δ15N[NO3−], δ18O[NO3−], δ18O[O2]) were consistent with apparent C–N–O reaction stoichiometries indicating O2 reduction and nitrification in shallower porewater, followed by varying NO3− reduction at depth. Maximum porewater NO3− concentrations (∼10–20 μM) were limited by infiltrating O2 concentrations and C/N ratios of reacting organic matter. Lake‐water level variations caused changes in shoreline position and porewater velocities, while variations in lake‐water temperature, DOC, and O2 contributed to changes in reaction rates and depth of O2 and NO3− penetration into the lakebed. The quality of groundwater recharged by lake water reflected temporally and spatially varying physical and biogeochemical processes in the sediment porewater.

The Sensitivity of Structure to Ionic Radius and Reaction Stoichiometry: A Crystallographic Study of Metal Coordination and Hydrogen Bonding in Barbiturate Complexes of All Five Alkali Metals Li-Cs.

A systematic study has been conducted on barbiturate complexes of all five alkali metals, Li-Cs, prepared from metal carbonates or hydroxides in an aqueous solution without other potential ligands present, varying the stoichiometric ratio of metal ion to barbituric acid (BAH). Eight polymeric coordination compounds (two each for Na, K, and Rb and one each for Li and Cs) have been characterised by single-crystal X-ray diffraction. All contain some combination of barbiturate anion BA- (necessarily in a 1:1 ratio with the metal cation M+), barbituric acid, and water. All organic species and water molecules are coordinated to the metal centres via oxygen atoms as either terminal or bridging ligands. Coordination numbers range from 4 (for the Li complex) to 8 (for the Cs complex). Extensive hydrogen bonding plays a significant role in all the crystal structures, almost all of which include pairs of N-H···O hydrogen bonds linking BA- and/or BAH components into ribbons extending in one dimension. Factors influencing the structure adopted by each compound include cation size and reaction stoichiometry as well as hydrogen bonding.

Interpreting biogeochemical processes through the relationship between total alkalinity and dissolved inorganic carbon: Theoretical basis and limitations

AbstractThe marine carbonate system is influenced by anthropogenic CO2 uptake, biogeochemical processes, and physical changes that involve freshwater input and removal. Two frequently used parameters to quantify seawater carbonate system are total alkalinity (TA) and total dissolved inorganic carbon (DIC). To account for the physical changes, both TA and DIC are usually normalized to a reference salinity (i.e., nTA and nDIC), and then the relationship between nTA and nDIC is used to identify major biogeochemical processes that regulate the carbonate system, based on process‐specific reaction stoichiometry. However, the theoretical basis of this interpretation has not been holistically examined. In this study, we validated this method under idealized conditions and discussed the associated assumptions and limitations. Furthermore, we applied this method to interpret field TA and DIC data from a lagoonal estuary in the northwestern Gulf of Mexico. Our results demonstrated that evaluating field data that encompass multiple stations and time periods could be problematic. In addition, various combinations of biogeochemical processes can lead to the same nTA–nDIC relationship, even though the relative importance of each individual process may vary significantly. Therefore, the stoichiometric relationship relying solely on TA and DIC data is not a definitive approach for uncovering dominant biogeochemical processes. Instead, measurements of process‐specific parameters are necessary.

Reduced 2,2’‐Bipyridine Lanthanide Metallocenes Provide Access to Mono‐C5Me5 and Polyazide Complexes

AbstractExploration of the reduction chemistry of the 2,2’‐bipyridine (bipy) lanthanide metallocene complexes Cp*2LnCl(bipy) and Cp*2Ln(bipy) (Cp* = C5Me5) resulted in the isolation of a series of complexes with unusual composition and structure including complexes with a single Cp* ligand, multiple azide ligands, and bipy ligands with close parallel orientations. These results not only reveal new structural types, but they also show the diverse chemistry displayed by this redox‐active platform. Treatment of Cp*2NdCl(bipy) with excess KC8 resulted in the formation of the mono‐Cp* Nd(III) complex, [K(crypt)]2[Cp*Nd(bipy)2], 1, as well as [K(crypt)][Cp*2NdCl2], 2, and the previously reported [K(crypt)][Cp*2Nd(bipy)]. A mono‐Cp* Lu(III) complex, Cp*Lu(bipy)2, 3, was also found in an attempt to make Cp*2Lu(bipy) from LuCl3, 2 equiv. of KCp*, bipy, and K/KI. Surprisingly, the (bipy)1− ligands in neighboring molecules in the structure of 3 are oriented in a parallel fashion with intermolecular C⋅⋅⋅C distances of 3.289(4) Å, which are shorter than the sum of van der Waals radii of two carbon atoms, 3.4 Å. Another product with one Cp* ligand per lanthanide was isolated from the reaction of [K(crypt)][Cp*2Eu(bipy)] with azobenzene, which afforded the dimeric Eu(II) complex, [K(crypt)]2[Cp*Eu(THF)(PhNNPh)]2, 4. Attempts to make 4 from the reaction between Cp*2Eu(THF)2 and a reduced azobenzene anion generated instead the mixed‐valent Eu(III)/Eu(II) complex, [K(crypt)][Cp*Eu(THF)(PhNNPh)]2, 5, which allows direct comparison with the bimetallic Eu(II) complex 4. Mono‐Cp* complexes of Yb(III) are obtained from reactions of the Yb(II) complex, [K(crypt)][Cp*2Yb(bipy)], with trimethylsilylazide, which afforded the tetra‐azido [K(crypt)]2[Cp*Yb(N3)4], 6, or the di‐azido complex [K(crypt)]2[Cp*Yb(N3)2(bipy)], 7 a, depending on the reaction stoichiometry. A mono‐Cp* Yb(III) complex is also isolated from reaction of [K(crypt)][Cp*2Yb(bipy)] with elemental sulfur which forms the mixed polysulfido Yb(III) complex [K(crypt)]2[Cp*Yb(S4)(S5)], 8 a. In contrast to these reactions that form mono‐Cp* products, reduction of Cp*2Yb(bipy) with 1 equiv. of KC8 in the presence of 18‐crown‐6 resulted in the complete loss of Cp* ligands and the formation of [K(18‐c‐6)(THF)][Yb(bipy)4], 9. The (bipy)1− ligands of 9 are arranged in a parallel orientation, as observed in the structure of 3, except in this case this interaction is intramolecular and involves pairs of ligands bound to the same Yb atom. Attempts to reduce further the Sm(II) (bipy)1− complex, Cp*2Sm(bipy) with 2 equiv. of KC8 in the presence of excess 18‐crown‐6 led to the isolation of a Sm(III) salt of (bipy)2− with an inverse sandwich Cp* counter‐cation and a co‐crystallized K(18‐c‐6)Cp* unit, [K2(18‐c‐6)2Cp*]2[Cp*2Sm(bipy)]2 ⋅ [K(18‐c‐6)Cp*], 10.

Reversible chirality inversion of an AuAgx-cysteine coordination polymer by pH change

Responsive chiral systems have attracted considerable attention, given their potential for diverse applications in biology, optoelectronics, photonics, and related fields. Here we show the reversible chirality inversion of an AuAgx-cysteine (AuAgx-cys) coordination polymer (CP) by pH changes. The polymer can be obtained by mixing HAuCl4 and AgNO3 with L-cysteine (or D-cysteine) in appropriate proportions in H2O (or other surfactant solutions). Circular dichroism (CD) spectrum is used to record the strong optical activity of the AuAg0.06-L-cys enantiomer (denoted as L0.06), which can be switched to that of the corresponding D0.06 enantiomer by alkalization (final dispersion pH > 13) and can be switched back after neutralization (final dispersion pH <8). Multiple structural changes at different pH values (≈9.6, ≈13) are observed through UV-Vis and CD spectral measurements, as well as other controlled experiments. Exploration of the CP synthesis kinetics suggests that the covalent bond formation is rapid and then the conformation of the CP materials would continuously evolve. The reaction stoichiometry investigation shows that the formation of CP materials with chirality inversion behavior requires the balancing between different coordination and polymerization processes. This study provides insights into the potential of inorganic stereochemistry in developing promising functional materials.