Chemically Research Articles

Porous Materials for the heterogeneously catalyzed synthesis of high Value-Added products: latest trends and future prospects.

Heterogeneous catalysis currently stands as a foundational area in materials synthesis and applied chemistry. In this context, emphasizing the significance of heterogeneous catalysis in expediting chemical reactions and controlling the formation of desired products using porous materials represents an intriguing approach in the current technological landscape. This work delves into the synthesis and design of a variety of porous materials, encompassing microporous, mesoporous and macroporous materials (e.g. carbonaceous materials, metal oxides, MOFs, zeolites and functionalized analogues), alongside their properties and characteristics pivotal in heterogeneous catalysis. among others, and their subsequent modification, underscoring the significance of tailoring porous materials for specific catalytic applications.

The successive reduction of iodate to iodide driven by iron redox cycling

Ferrous iron (Fe(II)) produced by microbial Fe(III) reduction and reactive oxygen species (ROS) generated from aerobic Fe(II) oxidation can mediate iodate (IO3−) reduction and iodide (I−) oxidation, respectively. Nevertheless, how Fe redox cycling under redox fluctuating conditions drives transformation of iodine species remain unclear. In this study, Shewanella oneidensis MR-1 wildtype (WT) and its mutant △dmsEFAB, which lost the ability to enzymatically reduce IO3−, were chosen to conduct ferrihydrite/goethite/nontronite culture experiments under consecutive cycles of anoxic reduction of Fe(III) and re-oxidation of Fe(II) by O2 to reveal the role of Fe redox cycling in the transformation of iodine species. The results showed that both surface-adsorbed and mineral structural Fe(II) chemically reduced IO3−. Chemical IO3− reduction by biogenic Fe(II) was slower than enzymatic IO3− reduction by WT. Compared to △dmsEFAB cultures, WT cultures all showed higher Fe(II) concentrations under anoxic conditions but lower cumulative •OH under oxic conditions, which imply the chemical reaction between I− and ROS. I− oxidation by ROS, however, did not lead to a significant production of IO3− compared with I− formed under anoxic conditions. Consequently, Fe redox cycling successively reduced IO3− to I−, which highlights vital roles of Fe(III)-reducing bacteria in I− formation and mobilization in environments.

Characterization of the Physicochemical Properties of Salix psammophila Sand Barriers Degradation Under Ultraviolet Irradiation and Synergistic Water Environment

The degradation of Salix psammophila mechanical sand barriers in desert environments can lead to a reduction in their windbreak and sand-fixing benefits, thereby becoming a significant factor limiting the operational lifespan of these structures. Targeting the typical damage types of S. psammophila sand barriers in the desert, we conducted simulations of desert sunlight and rainfall phenomena and investigated the changing characteristics of the physical, mechanical, and chemical properties of sand barriers in the degradation process. The results clearly indicate that (1) accelerated aging for 288 h represents a critical time point for assessing changes in physical, mechanical, and chemical properties during the interaction between ultraviolet irradiation and water. Following 576 h of accelerated aging, compared with a fresh S. psammophila branch sample (CK), the mass loss percentage was 24.33%, while the basic density decreased by 35.87%, and the modulus of rupture and elasticity decreases by 24.93% and 23.03%, respectively. (2) After accelerated aging for 576 h, the contents of lignin, hemicellulose, and cellulose decreased by 35.93%, 33.84%, and 22.38%, respectively. The interaction between simulated ultraviolet irradiation and water under sunlight intensifies the vigorous physical and chemical reactions occurring within the S. psammophila sand barrier, alters its internal structure, diminishes its mechanical properties, and expedites the degradation of its protective capabilities.

Development of Software for Hydrometallurgical Calculation of Metal Extraction

Hydrometallurgy plays a critical role in the metallurgical industry by providing an efficient method for extracting metals from ores and secondary materials using aqueous solutions. This approach is particularly advantageous for processing low-grade and complex ores, as well as secondary resources that cannot be effectively processed by traditional pyrometallurgical methods. The objective of this study is to develop specialized software to automate and optimize the calculations necessary for metal extraction in hydrometallurgical processes. The software integrates a complete computational framework for automating the various stages of the hydrometallurgical process, including ore composition initialization, total element mass calculations, and the determination of metal concentrations in both metal products (matte) and by-products (slag). The methodology involves the design and implementation of a web-based application using Django for the user interface and MySQL for robust data storage. The computational module, written in Python, automates the mathematical operations required to simulate complex chemical reactions and metal extraction processes. This module supports real-time processing and ensures accurate calculations for each stage of metal extraction, including leaching, extraction, re-extraction, sorption, and electrolysis. The software also features detailed tables and dynamic graphs that allow users to analyze the distribution of valuable metals and assess the influence of key operational parameters on extraction efficiency. The results show that the developed software successfully manages large datasets, enhances the precision of hydrometallurgical calculations, and minimizes the risk of human error. The implementation of the software leads to significant improvements in the economic efficiency of production by optimizing metal recovery rates and reducing operational costs. Additionally, it supports comprehensive process control by providing actionable insights into each stage of extraction, thus improving the quality of the final metal product. Overall, the software represents a significant technological advancement in the field, offering a scalable solution for industries aiming to streamline hydrometallurgical processes.

In Situ Synthesis of NPC-Cu2O/CuO/rGO Composite via Dealloying and Microwave-Assisted Hydrothermal Technique

The nanoporous copper (NPC)-copper oxides (Cu2O/CuO)/reduced graphene oxide (rGO) composite structure was synthesized by combining the dealloying process of Cu48Zr47Al5 amorphous ribbons with a microwave-assisted hydrothermal technique at a temperature of 200 °C. The main advantage of the microwave-assisted hydrothermal process is the oxidation of nanoporous copper together with the in situ reduction of graphene oxide to form rGO. The integration of rGO with NPC improves electrical conductivity and streamlines the process of electron transfer. This composite exhibit considerable potential in electrochemical catalysis application, due to the combined catalytic activity of NPC and the chemical reactivity of rGO. Our study relates the transition to n-type rGO in microwave-assisted hydrothermal reactions, and also the development of an electrode material suitable for electrochemical applications based on the p-p-n junction NPC-Cu2O/CuO/rGO heterostructure. To confirm the formation of the composite structure, structural, morphological, and optical techniques as XRD, SEM/EDX, UV-Vis and Raman spectroscopy were used. The composite’s electrochemical properties were measured by EIS and Mott-Schottky analyses, showing a charge transfer resistance (Rp) of 250 Ω and indicating the type of the semiconductor properties. The calculated carrier densities of 4.2 × 1018 cm−3 confirms n-type semiconductor characteristic for rGO, and 7.22 × 1018 cm−3 for Cu2O/CuO indicating p-type characteristic.

Pressure enabled organic reactions via confinement between layers of 2D materials.

Confinement of reactants within nanoscale spaces of low-dimensional materials has been shown to provide reorientation of strained reactants or stabilization of unstable reactants for synthesis of molecules and tuning of chemical reactivity. While few studies have reported chemistry within zero-dimensional pores and one-dimensional nanotubes, organic reactions in confined spaces between two-dimensional materials have yet to be explored. Here, we demonstrate that reactants confined between atomically thin sheets of graphene or hexagonal boron nitride experience pressures as high as 7 gigapascal, which allows the propagation of solvent-free organic reactions that ordinarily do not occur under standard conditions. Specifically, we show that cyclodehydrogenation of hexaphenylbenzene without catalysts as a proof of concept and oxidative polymerization of dopamine into sheet-like crystalline structure are enabled by the effective high pressure experienced by the reactants between the graphene layers. Our results demonstrate a facile, general approach for performing high-pressure chemistry based on confinement of reactants within two-dimensional materials.

Catalytic Asymmetric Reactions of Ketimines and Alkenes via [2 + 2] Cycloaddition: Chemical Reactivity Controlled by Switching a Heteroatom.

Azetidine units are commonly found in natural products and biologically active drugs. The [2 + 2] cycloaddition of imines and alkenes has been extensively used in the synthesis of such structures, while enantioselective approaches remain elusive. Herein, an efficient B(C6F5)3/chiral phosphoric acid-catalyzed asymmetric [2 + 2] cycloaddition of ketimines and aryl vinyl selenides was presented, delivering valuable chiral azetidines with excellent stereoselectivities (>20:1 dr and up to 96:4 er). What's even more interesting was that when a "Se" atom was switched to an "S" atom, the reaction proceeded through a [2 + 2] cycloaddition/ring-opening cascade process, affording a range of chiral thioacetals with high enantioselectivities (up to 98:2 er), which were also important organic sulfur compounds. Mechanistic experiments, coupled with density functional theory (DFT) calculations, shed light on a mechanism involving stepwise [2 + 2] cycloaddition and ring-opening processes, with the initial alkenylation step identified as crucial for achieving stereoselective control.

Versatile Mechanochemical Reactions via Tailored Force Transmission in Mechanophores.

In polymer mechanochemistry, regulating the intrinsic mechanical reactivity of a mechanophore offers extensive opportunities in material science, enabling the development of hierarchical and multifunctional polymer-based materials. Recent advances have focused on innovating various types of mechanophores with inherent reactivity (e.g. regioselectivity and stereoselectivity). However, little attention has been given to modulating their reactivity by tailoring force transmission within mechanophores. Here, we introduce a novel approach through the implementation of a cyclic pulling geometry into an anthracene-maleimide (AM) mechanophore. This approach manipulates force transmission within the mechanophore and effectively regulates its reactivity from 0.0160 min-1 to 0.00133 min-1, achieving up to a 12-fold change. Mechanochemical coupling analysis suggests that the split force transmission within the ring may suppress the sequential bond rupture mechanism in AM mechanophores under applied forces. By leveraging the distinct force transmission pathways within cyclic and linear AM mechanophores, we covalently integrate them with a spiropyran mechanophore to design tandem mechanophore systems for hierarchical mechanochemical activation. These findings highlight the efficacy and versatility of the cyclic pulling strategy in modulating mechanophore reactivity, providing valuable insights for the design of tunable multifunctional polymer-based materials.

Versatile Mechanochemical Reactions via Tailored Force Transmission in Mechanophores

In polymer mechanochemistry, regulating the intrinsic mechanical reactivity of a mechanophore offers extensive opportunities in material science, enabling the development of hierarchical and multifunctional polymer‐based materials. Recent advances have focused on innovating various types of mechanophores with inherent reactivity (e.g. regioselectivity and stereoselectivity). However, little attention has been given to modulating their reactivity by tailoring force transmission within mechanophores. Here, we introduce a novel approach through the implementation of a cyclic pulling geometry into an anthracene‐maleimide (AM) mechanophore. This approach manipulates force transmission within the mechanophore and effectively regulates its reactivity from 0.0160 min‐1 to 0.00133 min‐1, achieving up to a 12‐fold change. Mechanochemical coupling analysis suggests that the split force transmission within the ring may suppress the sequential bond rupture mechanism in AM mechanophores under applied forces. By leveraging the distinct force transmission pathways within cyclic and linear AM mechanophores, we covalently integrate them with a spiropyran mechanophore to design tandem mechanophore systems for hierarchical mechanochemical activation. These findings highlight the efficacy and versatility of the cyclic pulling strategy in modulating mechanophore reactivity, providing valuable insights for the design of tunable multifunctional polymer‐based materials.

Solvent Dictated Organic Transformations.

Solvent plays an important role in many chemical reactions. The C-H activation has been one of the most powerful tools in organic synthesis. These reactions are often assisted by solvents which not only provide a medium for the chemical reactions but also facilitate reaching to the product stage. The solvent helps the reaction profile both chemically and energetically to reach the targeted product. Organic transformations via C-H activation from the solvent assistance perspective has been discussed in this review. Various solvents such as tetrahydrofuran (THF), MeCN, dichloromethane (DCM), dimethoxyethane (DME), 1,2-dichloroethane (1,2-DCE), dimethylformamide (DMF), dimethylsulfoxide (DMSO), isopropyl nitrile (iPrCN), 1,4-dioxane, AcOH, trifluoroacetic acid (TFA), Ac2O, PhCF3, chloroform (CHCl3), H2O, N-methylpyrrolidone (NMP), acetone, methyl tert-butyl ether (MTBE), toluene, p-xylene, alcohols, MeOH, 1,1,1-trifluoroethanol (TFE), 1,1,1,3,3,3-hexafluoroisopropanol (HFIP), tert-amyl alcohol and their roles are discussed. The exclusive role of the solvent in various transformations has been deliberated by highlighting the substrate scope, along with the proposed mechanisms. For easy classification, the review has been divided into three parts: (i) solvent-switched divergent C-H activation; (ii) C-H bond activation with solvent as the coupling reagent, and (iii) C-H activation with solvent caging and solvent-assisted electron donor acceptor (EDA) complex formation and autocatalysis.

The molecular structure, electronic properties, and decomposition mechanism of FOX-7 under external electric field were calculated based on density functional theory.

Based on the density functional theory (DFT), we analyzed the changes of the FOX-7 molecule under external electric field (EEF) from multiple perspectives, including molecular structure, electronic structure, decomposition mechanism, frontier molecular orbitals (FMOs), and density of states (DOS). The results revealed that as the intensity of the positive EEF increased, the detonation performance of the FOX-7 molecule was significantly enhanced, while its thermal stability was also improved. This discovery challenges the traditional concept that explosives are inherently dangerous under external electric fields and provides new insights for research in related fields. To further explore the impact of EEF on the thermal stability of FOX-7, we conducted a thorough analysis of the mechanism by which EEF affects the decomposition process. Our findings indicate that applying a positive EEF significantly increases the energy required to overcome intramolecular hydrogen transfer and C-NO2 bond rupture, while having a relatively minor effect on the nitro isomerization process. This observation further demonstrates that the appropriate application of a positive EEF can enhance the detonation performance of FOX-7 without compromising its thermal stability. Further research revealed that as the intensity of the positive EEF increased, the electronegativity of the nitro group gradually enhanced, leading to an increase in the electronegativity of the oxygen atoms within it. This made the oxygen atoms more prone to participating in chemical reactions. This phenomenon also explains why the energy barrier required for nitro isomerization in FOX-7 gradually decreases as the intensity of the positive EEF increases. Based on the density functional theory (DFT), the structural optimizations were performed both under applied EEF and without EEF at the B3LYP/6-311G (d, p) level. All optimized results were converged and exhibited no imaginary frequencies. Based on the optimized structures, single-point energy calculations were further conducted at the B3LYP/def2-TZVPP level. Subsequently, analyses of molecular structure, electronic structure, decomposition mechanism, frontier molecular orbitals, and density of states were carried out.

Entropy optimization in a radiative and chemically reactive EMHD flow of a nanofluid coexisting Ohmic dissipation and multiple slips

Purpose This research focuses on the controlling irreversibilities in a radiative, chemically reactive electromagnetohydrodynamics (EMHD) flow of a nanofluid toward a stagnation point. Key considerations include the presence of Ohmic dissipation, linear thermal radiation, second-order chemical reaction with the multiple slips. With these factors, this study aims to provide insights for practical applications where thermal management and energy efficiency are paramount. Design/methodology/approach Lie group transformation is used to revert the leading partial differential equations into nonlinear ODE form. Hence, the solutions are attained analytically through differential transformation method-Padé and numerically using the Runge–Kutta–Fehlberg method with shooting procedure, to ensure the precise and reliable determination of the solution. This dual approach highlights the robustness and versatility of the methods. Findings The system’s entropy generation is enhanced by incrementing the magnetic field parameter (M), while the electric field (E) and velocity slip parameters (ξ) control its growth. Mass transportation irreversibility and the Bejan number (Be) are significantly increased by the chemical reaction rate (Cr). In addition, there is a boost in the rate of heat transportation by 3.66% while 0.05⩽ξ⩽0.2; meanwhile for 0.2⩽ξ⩽1.1, the rate of mass transportation gets enhanced by 12.87%. Originality/value This paper presents a novel approach to analyzing the entropy optimization in a radiative, chemically reactive EMHD nanofluid flow near a stagnation point. Moreover, this research represents a significant advancement in the application of analytical techniques, complemented by numerical approaches to study boundary layer equations.

Electrochemical C−O and C−N Arylation using Alternating Polarity in flow for Compound Libraries

AbstractEtherification and amination of aryl halide scaffolds are commonly used reactions in parallel medicinal chemistry to rapidly scan structure–activity relationships with abundant building blocks. Electrochemical methods for aryl etherification and amination demonstrate broad functional group tolerance and extended nucleophile scope compared to traditional methods. Nevertheless, there is a need for robust and scale‐transferable workflows for electrochemical compound library synthesis. Herein we describe a platform for automated electrochemical synthesis of C−X arylation (X=NH, OH) in flow to access compound libraries. A comprehensive Design of Experiment (DoE) study identifies an optimal protocol which generates high yields across>30 aryl halide scaffolds, diverse amines (including electron‐deficient sulfonamides, sulfoximines, amides, and anilines) and alcohols (including serine residues within peptides). Reaction sequences are automated on commercially available equipment to generate libraries of anilines and aryl ethers. The unprecedented application of potentiostatic alternating polarity in flow is essential to avoid accumulating electrode passivation. Moreover, it enables reactions to be performed in air, without supporting electrolyte and with high reproducibility over consecutive runs. Our method represents a powerful means to rapidly generate nucleophile independent C−X arylation compound libraries using flow electrochemistry.

Comparing parameterized and self-consistent approaches to abinitio cavity quantum electrodynamics for electronic strong coupling.

Molecules under strong or ultra-strong light-matter coupling present an intriguing route to modify chemical structure, properties, and reactivity. A rigorous theoretical treatment of such systems requires handling matter and photon degrees of freedom on an equal quantum mechanical footing. In the regime of molecular electronic strong or ultra-strong coupling to one or a few molecules, it is desirable to treat the molecular electronic degrees of freedom using the tools of abinitio quantum chemistry, yielding an approach referred to as abinitio cavity quantum electrodynamics (ai-QED), where the photon degrees of freedom are treated at the level of cavity QED. We analyze two complementary approaches to ai-QED: (1) a parameterized ai-QED, a two-step approach where the matter degrees of freedom are computed using existing electronic structure theories, enabling the construction of rigorous ai-QED Hamiltonians in a basis of many-electron eigenstates, and (2) self-consistent ai-QED, a one-step approach where electronic structure methods are generalized to include coupling between electronic and photon degrees of freedom. Although these approaches are equivalent in their exact limits, we identify a disparity between the projection of the two-body dipole self-energy operator that appears in the parameterized approach and its exact counterpart in the self-consistent approach. We provide a theoretical argument that this disparity resolves only under the limit of a complete orbital basis and a complete many-electron basis for the projection. We present numerical results highlighting this disparity and its resolution in a particularly simple molecular system of helium hydride cation, where it is possible to approach these two complete basis limits simultaneously. In this same helium hydride system, we examine and compare the practical issue of the computational cost required to converge each approach toward the complete orbital and many-electron bases limit. Finally, we assess the aspect of photonic convergence for polar and charged species, finding comparable behavior between parameterized and self-consistent approaches.

Application of nucleophilic substitution reaction for sensitive determination of heptaminol hydrochloride in pharmaceuticals

A straightforward and sensitive spectrofluorimetric approach was established for the determination of heptaminol hydrochloride (HTM-HCl) based on the derivatization of the drug through its reaction with 5-dimethylaminonaphthalene-1-sulfonyl chloride (Dansyl chloride). The reagent underwent a nucleophilic substitution of its chlorine atom with HTM to give N-(5-dimethylaminonaphthalene-1-sulfonyl)-6-amino-2-methylheptan-2-ol. The highly luminescent derivative was extracted using methylene chloride and subjected to analysis at an excitation wavelength of 345 nm and an emission wavelength of 490 nm. The chemical reaction occurred within an aqueous environment buffered with a 0.1 M borate buffer solution adjusted to pH 10.5. Experimental findings indicate that the proposed method displays sensitivity and linearity across a concentration range from 0.03 to 2 µg mL− 1. The method achieves lower detection and quantification limits of 0.016 and 0.048 µg mL− 1, respectively. The analytical validation of this method followed the guidelines outlined by the International Council of Harmonization (ICH). This approach was applied effectively for quantifying the medication in both tablet and oral drops formulations available on the market, demonstrating excellent recovery of 98.95 ± 0.45 for tablets and 99.37 ± 0.24 for oral drops with no interference from excipients.

Noncanonical Amino Acid Tools and Their Application to Membrane Protein Studies.

Methods rooted in chemical biology have contributed significantly to studies of integral membrane proteins. One recent key approach has been the application of genetic code expansion (GCE), which enables the site-specific incorporation of noncanonical amino acids (ncAAs) with defined chemical properties into proteins. Efficient GCE is challenging, especially for membrane proteins, which have specialized biogenesis and cell trafficking machinery and tend to be expressed at low levels in cell membranes. Many eukaryotic membrane proteins cannot be expressed functionally in E. coli and are most effectively studied in mammalian cell culture systems. Recent advances have facilitated broader applications of GCE for studies of membrane proteins. First, AARS/tRNA pairs have been engineered to function efficiently in mammalian cells. Second, bioorthogonal chemical reactions, including cell-friendly copper-free "click" chemistry, have enabled linkage of small-molecule probes such as fluorophores to membrane proteins in live cells. Finally, in concert with advances in GCE methodology, the variety of available ncAAs has increased dramatically, thus enabling the investigation of protein structure and dynamics by multidisciplinary biochemical and biophysical approaches. These developments are reviewed in the historical framework of the development of GCE technology with a focus on applications to studies of membrane proteins.

Enhancement of the quality of mc-Si ingot grown by vacuum directional solidification furnace with growth rate increase reducing the cost of the wafer for PV application: Carbon and oxygen analysis

In this paper, we propose a numerical model to investigate the dissolution of oxygen atoms from the porous silica crucible, SiO gas formation, back diffusion of CO gas and segregation of carbon and oxygen during the growth of multi-crystalline silicon (mc-Si) by vacuum directional solidification (VDS) at different growth rates (3, 6 and 9 mm/h) by silt valve opening rate. The dissolution of oxygen decreases during the rapid growth of ingot because the reaction between the molten silicon and the porous silica crucible is constrained. This limitation on oxygen dissolution from the porous silica crucible further diminishes chemical reaction inside the VDS furnace. Consequently, the segregation pattern of the carbon and oxygen is affected at higher growth rate. During the VDS mc-Si growth, a growth rate of 9mm/h yields better quality of the VDS grown mc-Si ingots compared to other growth rates, this rate reduces SiC precipitation and SiO2 cluster formation due to lower concentration of carbon and oxygen. The obtained carbon concentration minimizes the wire saw defects. Based on these numerical results (9 mm/h), we have implemented experimental work. Prepared samples are analyzed using FTIR spectra and minority carrier lifetime measurements. The effect of oxygen concentration in the samples is analyzed in the minority carrier lifetime measurements. The oxygen and carbon concentrations are calculated by FTIR spectra and their results are compared with the numerical simulation.

Carbon Dioxide as a Sustainable Reagent in Circular Hydrometallurgy.

This review highlights the use of CO2 as a reagent in hydrometallurgy, with emphasis on the new concept of circular hydrometallurgy. It is shown how waste CO2 can be utilised in hydrometallurgical operations for pH control or regeneration of acids for leaching. Metal-rich raffinate solutions generated after removal of the valuable metals can serve as feedstocks for mineral carbonation, providing alternative avenues for CO2 sequestration. Furthermore, CO2 can also be used as a renewable feedstock for the production of chemical reagents that can find applications in hydrometallurgy as lixiviant, as precipitation reagent or for pH control. Mineral carbonation can be combined with chemical reactions involving metal complexation reagents, as well as with solvent extraction processes for the concurrent precipitation of metal carbonates and acid regeneration. An outlook for future research in the area is also presented.

Photoinduced Pd‐Catalyzed Direct Sulfonylation of Allylic C−H Bonds

AbstractAllylic sulfones are valuable motifs due to their medicinal and biological significance and their versatile chemical reactivities. While direct allylic C−H sulfonylation represents a straightforward and desirable approach, these methods are primarily restricted to terminal alkenes, leaving the engagement of the internal counterparts a formidable challenge. Herein we report a photocatalytic approach that accommodates both cyclic and acyclic internal alkenes with diverse substitution patterns and electronic properties. Importantly, the obtained allylic sulfones can be readily diversified into a wide range of products, thus enabling formal alkene transposition and all‐carbon quaternary center formation through the sequential C−H functionalization.

Experimental Insights into the Formation, Reactivity, and Crosstalk of Thionitrite (SNO−) and Perthionitrite (SSNO−)

AbstractHydrogen sulfide (H2S) and nitric oxide (NO) are important gaseous biological signaling molecules that are involved in complex cellular pathways. A number of physiological processes require both H2S and NO, which has led to the proposal that different H2S/NO⋅ crosstalk species, including thionitrite (SNO−) and perthionitrite (SSNO−), are responsible for this observed codependence. Despite the importance of these S/N hybrid species, the reported properties and characterization, as well as the fundamental pathways of formation and subsequent reactivity, remain poorly understood. Herein we report new experimental insights into the fundamental reaction chemistry of pathways to form SNO− and SSNO−, including mechanisms for proton‐mediated interconversion. In addition, we demonstrate new modes of reactivity with other sulfur‐containing potential crosstalk species, including carbonyl sulfide (COS).