Loss Of Chloride Research Articles

Investigation of Phosphazene Superbase Interactions with [PCl2N]3.

In this study, the reaction between phosphazene superbases and a chlorophosphazene trimer ([PCl2N]3) has been investigated. In this room temperature reaction, the phosphazene superbase (Me2N)3PN(Me2N)2P═NEt, commonly known as P2Et, was shown to behave as a nucleophile, displacing one of the chlorides from [PCl2N]3 and producing the tadpole-like structure 1. The reaction described herein is one of the few instances of a phosphazene superbase behaving as a nucleophile rather than a Brønsted base. Once formed, this structure contains contrasting reactivity, containing a weakly basic phosphazene head while maintaining a highly basic phosphazene tail of the tadpole. The mechanism of the reaction was explored by investigating the potential energy surface through density functional theory calculations at the B3LYP/6-311+G(d,p) level of quantum mechanical theory. It was determined that the reaction of P2Et with [PCl2N]3 followed a stepwise process beginning with the substitution of P2Et onto [PCl2N]3 with the concurrent loss of chloride. Subsequently, the chloride attacks the ethyl group of the P2Et moiety, and ethyl chloride is released, producing 1. Compound 1 was further characterized via 31P NMR spectroscopy, mass spectrometry, and X-ray crystallography.

Metabolic alkalosis in cystic fibrosis: from vascular volume depletion to impaired bicarbonate excretion.

Cystic fibrosis (CF) is the most common life-threatening genetic disease in the United States and among people of European descent. Despite the widespread distribution of the cystic fibrosis transmembrane conductance regulator (CFTR) along kidney tubules, specific renal phenotypes attributable to CF have not been well documented. Recent studies have demonstrated the downregulation of the apical Cl-/HCO3 - exchanger pendrin (Slc26a4) in kidney B-intercalated cells of CF mouse models. These studies have shown that kidneys of both mice and humans with CF have an impaired ability to excrete excess HCO3 -, thus developing metabolic alkalosis when subjected to excess HCO3 - intake. The purpose of this minireview is to discuss the latest advances on the role of pendrin as a molecule with dual critical roles in acid base regulation and systemic vascular volume homeostasis, specifically in CF. Given the immense prevalence of vascular volume depletion, which is primarily precipitated via enhanced chloride loss through perspiration, we suggest that the dominant presentation of metabolic alkalosis in CF is due to the impaired function of pendrin, which plays a critical role in systemic vascular volume and acid base homeostasis.

Macrophage WNK1 senses intracellular hypo-chlorine to regulate vulnerability to sepsis attack during hypochloremia

Sepsis is one of the leading causes of death in critical patients worldwide and its occurrence is related to the excessive activation of macrophages. Chloride loss worsens the prognosis of patients with sepsis but the underlying mechanism is currently unclear. In this study, we founded that macrophages deficient in intracellular Cl- secrete more inflammatory cytokines such as IL-1β, IL-6 and TNF-α compared with control group. The intracellular chloride level decreased in WNK1 deficiency or activity inhibited macrophages with more severe inflammatory response after LPS treatment. Remimazolam, as classic GABAa receptor agonist, alleviates excessive inflammation cascade by promoting macrophage chloride influx during sepsis progression. Collectively, this study proves that macrophage WNK1 acts as a negative regulator of inflammatory response by sensing chloride to maintain intracellular chloride balance during sepsis coupled with hypochloremia.

Optimization of ultrasonic enhanced chloride-hydrogen peroxide system for leaching platinum from propane dehydrogenation spent catalyst by response surface methodology

Based on the environmental pressure and the resource wastage caused by the spent catalyst of propane dehydrogenation, a novel approach for the comprehensive treatment of spent catalyst was proposed, which first pulverizing the waste catalyst, and then recovered platinum by chloride-hydrogen peroxide system. The results show that in the HCl-H2O2-NaClO3-AlCl3 system, the addition of AlCl3 can supplement the loss of chloride ions during the reaction. The addition of H2O2 and NaClO3 to HCl not only significantly increases the electrode potential of the reaction system, but also produces Cl2, which promotes the reaction between Pt and Cl2 and dissolves in the form of [PtCl6]2−. In addition, the addition of NaClO3 can also reduce the concentration of HCl and avoid waste. In the actual experimental process, a maximum platinum leaching rate of 96.91 % was achieved, representing a 15.00 % increase compared to conventional leaching methods. The results of Box–Behnken design (BBD) optimization showed that under the conditions of hydrochloric acid concentration of 5 mol/L, reaction temperature of 90 °C, reaction time of 150 min and ultrasonic power of 400 W, the actual leaching rate of Pt and the leaching rate predicted by the quadratic regression model were 97.17 % and 97.26 %, respectively, and the error between the two was less than 0.10 %. The characterization results of the residue showed that the process significantly reduced the toxicity of the residue while increasing the leaching rate of Pt, alleviated the environmental pressure caused by waste stacking, and enriched Al2O3 in the slag phase with high purity for further recycling.

Study on the Influence of Etchant Composition and Etching Process on the Precision of Stainless‐Steel Microchannel and Etching Mechanism

The chemical etching method has the advantages of high precision and low cost for the preparation of steel surface microchannel, but the composition of the etching solution and the etching process have a great influence on the precision of the microstructure. In this article, the influence of etching solution composition and the etching time on the etching precision of stainless steel using a mixture of HCl and H2O2 as an etching solution is studied. The reactions and passivation processes that occur during the etching process are analyzed. The etching mechanism is revealed. The sample prepared with HCl:H2O2 = 1:2 can obtain better etching precision and high‐dimensional stability. The amount of lateral erosion and the depth of etching increases with the increase of etching time, resulting in a decrease in the etching factor and precision. Pitting and intergranular corrosion mainly occur during the etching process, and the loss of metal chloride formed in the process forms holes, which become rapid diffusion channels for corrosive Cl and O elements, and promotes the etching process. The etching reaction forms a passivation film on the surface of the substrate, which reduces the rate of the etching reaction.

Heterocyclic Diammonium Dion‐Jacobson Perovskite Blue Light‐Emitting Diodes with Nonshift Emission Peak Under High Bias Voltage

AbstractThe emission peak shift caused by ion motion, especially under high bias voltage, is an obstacle to the development of blue perovskite light‐emitting diodes (PeLEDs). In this work, 3‐Aminopiperidine dihydrochloride (3AP) to construct heterocyclic dication Dion‐Jacobson (DJ) PeLEDs is introduced, and found that 3AP incorporation can retard the halide segregation and chloride loss, leading to the improvement of the emission spectral stability. By increasing the amount of 3AP (DJ phase), emission centers can be tuned from green to blue but the excitonic peak abnormally disappears, indicative of exciton delocalization. Photoluminescence quantum yield (PLQY) and ultrafast spectroscopy indicated that the introduction of 3AP can passivate defects and control the exciton delocalization to facilitate interlayer charge transfer. The external quantum efficiencies (EQE) of the obtained green (513 nm), sky blue (488 nm), and blue (478 nm) PeLEDs reached 3.0%, 7.1%, and 4.8%, respectively, and the maximum luminance is 10956, 1093 and 782 cd m−2, respectively. Most importantly, under high operating voltages from 3 to 10 V, the PeLEDs delivered outstanding spectral stability free of peak shift.

Comparison of seasonality of urban grime in three southern Ontario cities

Urban grime refers to films made of a complex chemical mixture of organics and inorganics deposited on outdoor surfaces. The specific chemical composition of such films can vary considerably due to geographic and seasonal influences. We compared the seasonal change of grime’s water-soluble inorganic ion content in a rural (Thamesford), suburban (Oshawa), and urban city (Toronto) in southern Ontario, Canada. Sodium, calcium, chloride, nitrate, and sulfate amounts in grime were collected and quantified over four seasons in Oshawa, ON and Thamesford, ON and compared with results from a previous study in Toronto to elucidate differences. We found that all three regions displayed a clear seasonality in sodium and chloride consistent with winter road salt inputs and chloride loss in summer. Mole fractions of sulfate were consistently the lowest of the measured ions, and NO3 −/SO4 2− ratios showed a winter–spring minimum and summer–fall maximum. Urban–rural differences in the seasonal changes of ionic mole ratios suggest that additional chloride displacement by nitrate occurs within grime in Toronto that is not present in the two other rural/suburban cities in the same region.

Acute Kidney Injury with Severe Metabolic Alkalosis Caused by Habitual Vomiting in an Alcohol Abuser with Pyloric Stenosis.

A 47-year-old man was complaining of consciousness disorder. He had acute kidney injury, hypokalemia, and severe metabolic alkalosis. Initial treatment using intravenous infusion of 0.9% saline and potassium chloride improved his consciousness. It was clarified that he was a severe alcohol abuser who habitually self-vomited. We diagnosed him with volume depletion and pseudo-Bartter's syndrome due to loss of chloride by habitual vomiting. Gastrointestinal endoscopy demonstrated pyloric stenosis, which was ameliorated by Helicobacter pylori eradication therapy. We should consider volume depletion and pseudo-Bartter's syndrome as differential diagnoses when we encounter patients with acute kidney injury and severe metabolic alkalosis.

A Comprehensive and Updated Review of MicroRNA Pathogenesis and Gene Expression in Cystic Fibrosis

MicroRNAs (miRNAs) are short (~22 nucleotides) non-coding sequences that regulate gene expression. It has been recently identified that miR-145 regulates cystic fibrosis transmembrane regulator (CFTR) expression, and response to first-generation miRNAs is recognized as major biomedical research in CF. Abnormal miRNA activity causes numerous diseases, thus the critical role of miRNA is to focus on miRNA bindings to target proteins. miRNA classifications depend on their genomic location and gene structure, and they include intergenic and intronic regions. Intronic miRNA location is in the introns of annotated genes. Intergenic and intronic miRNA genes are controlled with their promoters. Some miRNAs negatively regulate the cystic fibrosis transmembrane conductance regulator (CFTR) gene expression (e.g., miR-101) in adult lung cells and have no effect on fetal epithelial cells. MiR-145, miR-223, and miR-494 directly regulate the CFTR gene expression. MiR-509-3p and miR-494 regulate CFTR more strongly than the other miRNAs. MiR-138 enhances CFTR channels on the cell surface of epithelial cells. Polymorphisms in the 3′-UTR region of CFTR decrease the expression of CFTR. Mutations in the CF (CFTR) gene, located on chromosome 7, diminish ion transport. The consequent loss of chloride and bicarbonate secretion and absorption lead to a multi-organ disease called CF marked by mucus inspissation, chronic inflammation, and tissue destruction. The most affected organs are the lung and pancreas, but the liver, bowel, sinuses, and vas deferens, among others, are prominently involved as well. The loss of CFTR also results in an altered miRNA profile that regulates the response to therapy and disease pathogenesis. This review summarizes miRNA alterations in the CF tissue, the role of miRNA in disease pathogenesis, and the therapeutic opportunity for oligotherapeutic manipulation to improve CF outcomes.

An Unusual Case of BSND Gene–Related (Type IV) Bartter Syndrome Presenting as Antenatal Bartter Syndrome: A Case Report and Review of Literature

Abstract Bartter syndrome is a group of autosomal recessive renal tubular disorders; it has two types of presentation: antenatal and classic. The antenatal type presents as severe unexplained polyhydramnios in the second trimester. This is due to fetal urinary losses of sodium, chloride, and potassium, leading to fetal polyuria. The classic type presents in the late neonatal or infancy stage, with dehydration, dyselectrolytemia, failure to thrive, and nephrocalcinosis. Antenatal scans are normal in such cases. Type I and II Bartter syndrome presents in the antenatal period, whereas type IV has a classic presentation. We describe an unusual case of type IVa Bartter syndrome presenting in the antenatal period, with severe polyhydramnios. The initial diagnosis was made based on amniotic fluid chloride levels and later confirmed by performing a genetic test. Genetic testing is important for confirming diagnosis and prognostication regarding the condition.

Mechanisms of paracellular transport of magnesium in intestinal and renal epithelia.

Magnesium is the fourth most abundant cation in the body. It plays a critical role in many biological processes, including the process of energy release. Paracellular transport of magnesium is mandatory for magnesium homeostasis. In addition to intestinal absorption that occurs in part across the paracellular pathway, magnesium is reabsorbed by the kidney tubule. The bulk of magnesium is reabsorbed through the paracellular pathway in the proximal tubule and the thick ascending limb of the loop of Henle. The finding that rare genetic diseases due to pathogenic variants in genes encoding specific claudins (CLDNs), proteins located at the tight junction that determine the selectivity and the permeability of the paracellular pathway, led to an awareness of their importance in magnesium homeostasis. Familial hypomagnesemia with hypercalciuria and nephrocalcinosis is caused by a loss of function of CLDN16 or CLDN19. Pathogenic CLDN10 variants cause HELIX syndrome, which is associated with a severe renal loss of sodium chloride and hypermagnesemia. The present review summarizes the current knowledge of the mechanisms and factors involved in paracellular magnesium permeability. The review also highlights some of the unresolved questions that need to be addressed.

Direct quantification of changes in pH within single levitated microdroplets and the kinetics of nitrate and chloride depletion.

The hygroscopicity and pH of aqueous microdroplets and smaller aerosols control their impacts on human health and the climate. Nitrate depletion and chloride depletion through the partitioning of HNO3 and HCl into the gas phase are processes that are enhanced in micron-sized and smaller aqueous droplets and this depletion influences both hygroscopicity and pH. Despite a number of studies, uncertainties remain about these processes. While acid evaporation and the loss of HCl or HNO3 have been observed during dehydration, there is a question as to the rate of acid evaporation and whether this can occur in fully hydrated droplets at higher relative humidity (RH). To directly elucidate the kinetics of nitrate and chloride depletion through evaporation of HNO3 and HCl, respectively at high RH, single levitated microdroplets are probed with cavity-enhanced Raman spectroscopy. Using glycine as a novel in situ pH probe, we are able to simultaneously measure changes in microdroplet composition and pH over timescales of hours. We find that the loss of chloride from the microdroplet is faster than that of nitrate, and the calculated rate constants infer that depletion is limited by the formation of HCl or HNO3 at the air-water interface and subsequent partitioning into the gas phase.

Kinetics of hypochlorous acid reactions with organic and chloride-containing tropospheric aerosol.

Chlorine plays an important role in tropospheric oxidation processes, in both marine and continental environments. Although modeling studies have explored the importance of halogen chemistry, uncertainty remains in associated chemical mechanisms and fundamental kinetics parameters. Prior kinetics measurements of multiphase halogen recycling reactions have been largely performed with dilute, bulk solutions, leaving unexplored more realistic chemical systems which have high solute concentrations and are internally mixed with both halide and organic components. Here, we address the multiphase kinetics of gaseous HOCl using an aerosol flow tube and aerosol mass spectrometer to study its reactions with particulate chloride, using atmospherically relevant particle acidity, solute concentrations, and ionic strength. We also investigate the chemistry that results when biomass burning (BB) aerosol components and chloride are internally mixed. Using pH-buffered deliquesced particles, we show that the rate constant for reaction of dissolved HOCl with H+ and Cl- at high relative humidity (RH) (80-85%) is within a factor of two of the literature value for bulk phase conditions. However, at lower RH values (60-70%) where the particles are considerably more concentrated, the rate constant for chloride loss from the particles is an order of magnitude higher. For pure organic compounds commonly found in biomass burning (BB) aerosol, such as coniferaldehyde, salicylic acid and furfural, an increase in the aerosol chlorine content occurs with HOCl exposure, indicating the formation of organochlorine species. Together, these independent findings explain results for internally mixed aerosol particles with both chloride and BB components present where we observed behavior consistent with both chloride loss and organochlorine formation occurring simultaneously upon HOCl exposure. Our results indicate that chlorine recycling via HOCl uptake by chloride-containing particles will occur in the atmosphere efficiently over a wide range of RH conditions, even when reactive organic compounds are present in the same particles as chloride. Simultaneously, formation of organochlorine compounds, which are commonly toxic, is likely occurring when reactive organic components are present.

Pseudo-Bartter syndrome in an infant without obvious underlying conditions: A case report

Pseudo-Bartter syndrome (PBS) develops owing to renal or extrarenal chloride loss, leading to hypokalemic alkalosis. Whereas most adult cases result from diuretic/laxative abuse, many infantile cases occur secondary to cystic fibrosis. Rarely, infantile PBS is caused by renal salt loss with anomalies of the kidney/urinary tract or genetic disorders, such as Dent disease. Here, we report the case of a 10-mo-old girl with a one-month history of decreased formula intake and 5.6% body weight loss. She showed typical laboratory findings as PBS, including hypokalemia (2.7 mEq/L) and high levels of bicarbonate (32.7 mEq/L) with a plasma renin activity of 399 ng/mL/h. With minimum supplementation of potassium and sodium, an improvement in body mass index, from –1.13 SD to +0.52 SD, with complete resolution of laboratory data was obtained in approximately one month. No causative mutations were identified in candidate genes for Bartter–Gitelman syndrome. Due to profound hypochloruria (< 15 mEq/L), PBS of renal origin was unlikely. In addition, extrarenal chloride loss did not seem to be the case, because the patient never manifested gastrointestinal symptoms. Therefore, we speculate that a temporary decrease in chloride intake, coupled with the putative genetic/epigenetic disadvantage of chloride retention, such as a subtle renal leak, may be responsible for the PBS in our patient.

FC018: The B1 H+-ATPASE (ATP6V1B1) Subunit is Required for Non-Type a Intercalated Cell Function During Alkalosis

Abstract BACKGROUND AND AIMS Non-type A intercalated cells (IC) in the connecting tubule (CNT) and cortical collecting duct (CCD) express the luminal Cl−/HCO3− exchanger pendrin and apical and/or basolateral vacuolar H+-ATPases containing the B1 subunit isoform. One of the main functions of non-type A ICs is the secretion of bicarbonate during metabolic alkalosis. Mutations in the B1 subunit (ATP6V1B1) in man cause distal renal tubular acidosis due to its importance in acid secretion by type A ICs. However, the function of the B1 isoform in non-type A ICs has remained elusive. In this work, we investigated the role of the B1 H+-ATPase subunit in non-type A intercalated in the control of alkalosis. METHOD Acid-base metabolism of Atp6v1b1 mice was studied during an alkali load (0.28 M NaHCO3 in drinking water and 2 mg deoxycorticosterone i.p for 4 days) or during a chronic furosemide treatment (20 mg i.p. injection daily for 9 days). RESULTS Induction of metabolic alkalosis by 0.28 M NaHCO3 resulted in a more pronounced alkalosis in ATP6v1b1−/− mice with increased blood bicarbonate, hypokalaemia and hypochloraemia despite a reduced lung minute volume. Determination of the relative abundance of the different subtypes of cells in the collecting duct system revealed a remodelling of CNT and CCD in the cortex with an increase of type A ICs and a compensatory increase of non-type A ICs in collecting ducts of the outer medullary in ATP6v1b1−/− kidneys. Total pendrin expression in the kidney and activity in non-type A cells of ex vivo microperfused CCD were reduced in ATP6v1b1−/− mice. Moreover, the stimulating effect of Isoproterenol, a β2-adrenergic receptor agonist stimulating cAMP production, on pendrin activity was blunted in non-type A ICs from ATP6v1b1−/− mice. Basolateral H+-ATPase activity in pendrin-expressing cells was strongly reduced, even though the expression of the B2 isoform was increased at their basolateral side. Moreover, the E1 and A H+-ATPase subunits of the V0 domain did only partially colocalize with the a4 H+-ATPase subunit of the V1 domain of H+-ATPases at the basolateral pole of ATP6v1b1−/− non-type A ICs, indicating impaired assembly of V0 and V1 H+-ATPase domains. Finally, when exposed to a chronic furosemide treatment, a treatment associated with a high risk to develop metabolic alkalosis in patients, ATP6v1b1−/− mice developed a more pronounced hypokalaemic hypochloraemic alkalosis with polyuria and loss of urine chloride compared with their wildtype littermates. In ATP6v1b1−/− kidneys, pendrin expression was drastically reduced as well as the water channel AQP2 and the α and γ subunits of the sodium channel ENaC. An increase of BUN and a decrease of kidney klotho expression were also observed in ATP6v1b1−/− mice which might indicate a worsening of their kidney function. CONCLUSION Thus, this study demonstrates for the first time that i) the B1 H+-ATPase subunit is critical for normal non-type A ICs function and protects against alkalosis. ii) Moreover, the B1 subunit is required for the assembly of complete and functional basolateral vacuolar H+-ATPases complexes in intercalated cells.

Methane Pyrolysis in Molten Potassium Chloride: An Experimental and Economic Analysis

Although steam methane reforming (CH4 + 2H2O → 4H2 + CO2) is the most commercialized process for producing hydrogen from methane, more than 10 kg of carbon dioxide is emitted to produce 1 kg of hydrogen. Methane pyrolysis (CH4 → 2H2 + C) has attracted much attention as an alternative to steam methane reforming because the co-product of hydrogen is solid carbon. In this study, the simultaneous production of hydrogen and separable solid carbon from methane was experimentally achieved in a bubble column filled with molten potassium chloride. The melt acted as a carbon-separating agent and as a pyrolytic catalyst, and enabled 40 h of continuous running without catalytic deactivation with an apparent activation energy of 277 kJ/mole. The resultant solid was purified by water washing or acid washing, or heating at high temperature to remove salt residues from the carbon. Heating the solid product at 1200 °C produced the highest purity carbon (97.2 at%). The economic feasibility of methane pyrolysis was evaluated by varying key parameters, that is, melt loss, melt price, and carbon revenue. Given a potassium chloride loss of &lt;0.1 kg of salt per kg of produced carbon, the carbon revenue was calculated to be USD &gt; 0.45 per kg of produced carbon. In this case, methane pyrolysis using molten potassium chloride may be comparable to steam methane reforming with carbon capture storage.

Exertional heat stress and sodium balance: Leaders, followers, and adaptations.

Exertional heat stress presents a different acute challenge to salt balance compared to at rest. Sodium (Na+) and chloride (Cl-) losses during exercise are overwhelmingly driven by eccrine sweat glands (the "leader"), with minimal urinary excretion. Total salt losses are therefore largely influenced by thermoregulatory need, although adaptations from prior heat exposure or altered dietary intake influences sweat gland ion reabsorption, and therefore sweat Na+ ([Na+]sweat) and Cl- concentrations. The hypotheses that body Na+ and Cl- conservation, or their release from osmotically inactive stores, can occur during the timeframe of a single bout of exertional heat stress, has not been studied to date. The consequences of unreplaced Na+ and Cl- losses during exertional heat stress appear limited primarily to their interactions with water balance. However, the water volume ingested is substantially more influential than salt intake on total body water, plasma volume, osmolality, and thermoregulation during exercise. Acute salt and water loading 1-3h prior to exercise can induce isosmotic hyperhydration in situations where this is deemed beneficial. During exercise, only scenarios of whole body [Na+]sweat>75th centile, combined with fluid replacement >80% of losses, are likely to require significant replacement to prevent hyponatremia. Post-exercise, natriuresis resumes as the main regulator of salt losses, with the kidneys (the "follower") working to restore salt balance incurred from any exercise-induced deficit. If such a deficit exceeds usual dietary intake, and rapid restoration of hydration status is desirable, a deliberate increase in salt intake may assist in volume restoration.

Catalytic Reduction of Dioxygen to Water by a Bioinspired Non-Heme Iron Complex via a 2+2 Mechanism.

We report a bioinspired non-heme Fe complex with a tripodal [N3O]- ligand framework (Fe(PMG)(Cl)2) that is electrocatalytically active toward dioxygen reduction with acetic acid as a proton source in acetonitrile solution. Under electrochemical and chemical conditions, Fe(PMG)(Cl)2 selectively produces water via a 2+2 mechanism, where H2O2 is generated as a discrete intermediate species before further reduction to two equivalents of H2O. Mechanistic studies support a catalytic cycle for dioxygen reduction where an off-cycle peroxo dimer species is the resting state of the catalyst. Spectroscopic analysis of the reduced complex FeII(PMG)Cl shows the stoichiometric formation of an Fe(III)-hydroxide species following exposure to H2O2; no catalytic activity for H2O2 disproportionation is observed, although the complex is electrochemically active for H2O2 reduction to H2O. Electrochemical studies, spectrochemical experiments, and DFT calculations suggest that the carboxylate moiety of the ligand is sensitive to hydrogen-bonding interactions with the acetic acid proton donor upon reduction from Fe(III)/(II), favoring chloride loss trans to the tris-alkyl amine moiety of the ligand framework. These results offer insight into how mononuclear non-heme Fe active sites in metalloproteins distribute added charge and poise proton donors during reactions with dioxygen.

Strong Acids or Bases Displaced by Weak Acids or Bases in Aerosols: Reactions Driven by the Continuous Partitioning of Volatile Products into the Gas Phase

Aerosols are ubiquitous in the atmosphere and profoundly affect climate systems and human health. To gain more insights on their broad impacts, we need to comprehensively understand the fundamental properties of atmospheric aerosols. Since aerosols are multiphase, a dispersion of condensed matter (solid particles or liquid droplets, hereafter particles) in gas, partitioning of volatile matter between the condensed and the gas phases is one defining characteristic of aerosols. For example, water content partitioning under different relative humidity conditions, known as aerosol hygroscopicity, has been extensively investigated in the past decades. Meanwhile, partitioning of volatile organic or inorganic components, which is referred to as aerosol volatility, remains understudied. Commonly, a bulk solution system is treated as a single phase, with volatility mainly determined by the nature of its components, and the composition partitioning between solution and gas phase is limited. Aerosols, however, comprise an extensive gas phase, and their volatility can also be induced by component reactions. These reactions occurring within aerosols are driven by the formation of volatile products and their continuous partitioning into the gas phase. As a consequence, the overall aerosol systems exhibit prominent volatility. Noteworthily, such volatility induced by reactions is a phenomenon exclusively observed in the multiphase aerosol systems, and it is trivial in bulk solutions due to the limited extent of liquid-gas partitioning. Take the chloride depletion in sea salt particles as an example. Recent findings have revealed that chloride depletion can be caused by reactions between NaCl and weak organic acids, which release HCl into the gas phase. Such a reaction can be described as a strong acid displaced by a weak acid, which is hardly observed in bulk phase. Generally, this unique partitioning behavior of aerosol systems and its potential to alter aerosol composition, size, reactivity, and other physicochemical properties merits more attention by atmospheric community.This Account focuses on the recent advancements in the research of component reactions that induce aerosol volatility. These reactions can be categorized into four types: chloride depletion, nitrate depletion, ammonium depletion, and salt hydrolysis. The depletion of chloride or nitrate can be regarded as a displacement reaction, in which a strong acid is displaced by a weak acid. Such a reaction releases highly volatile HCl or HNO3 into the gas phase and leads to a loss of chloride or nitrate within the particles. Likewise, ammonium depletion is a displacement reaction in which a strong base is displaced by a weak base, resulting in release of ammonia and substantial changes in aerosol hygroscopicity. In addition, aerosol volatility can also be induced by salt hydrolysis in a specific case, which is sustained by the coexistence of proton acceptor and hydroxide ion acceptor within particles. Furthermore, we quantitatively discuss these displacement reactions from both thermodynamic and kinetic perspectives, by using the extended aerosol inorganic model (E-AIM) and Maxwell steady-state diffusive mass transfer equation, respectively. Given the ubiquity of component partitioning in aerosol systems, our discussion may provide a new perspective on the underlying mechanisms of aerosol aging and relevant climate effects.

Rate and Product Studies with 1-Adamantyl Chlorothioformate under Solvolytic Conditions.

A study was carried out on the solvolysis of 1-adamantyl chlorothioformate (1-AdSCOCl, 1) in hydroxylic solvents. The rate constants of the solvolysis of 1 were well correlated using the Grunwald–Winstein equation in all of the 20 solvents (R = 0.985). The solvolyses of 1 were analyzed as the following two competing reactions: the solvolysis ionization pathway through the intermediate (1-AdSCO)+ (carboxylium ion) stabilized by the loss of chloride ions due to nucleophilic solvation and the solvolysis–decomposition pathway through the intermediate 1-Ad+Cl− ion pairs (carbocation) with the loss of carbonyl sulfide. In addition, the rate constants (kexp) for the solvolysis of 1 were separated into k1-Ad+Cl− and k1-AdSCO+Cl− through a product study and applied to the Grunwald–Winstein equation to obtain the sensitivity (m-value) to change in solvent ionizing power. For binary hydroxylic solvents, the selectivities (S) for the formation of solvolysis products were very similar to those of the 1-adamantyl derivatives discussed previously. The kinetic solvent isotope effects (KSIEs), salt effects and activation parameters for the solvolyses of 1 were also determined. These observations are compared with those previously reported for the solvolyses of 1-adamantyl chloroformate (1-AdOCOCl, 2). The reasons for change in reaction channels are discussed in terms of the gas-phase stabilities of acylium ions calculated using Gaussian 03.