Protonated Form Research Articles

Diphenylacetylene-Incorporating Octaphyrin: A Rigid Macrocycle with Readily Separable Conformational Isomers.

An expanded carbaporphyrinoid analogue, octaphyrin(2,1,1,1,2,1,1,1), containing two rigid diphenylacetylene moieties is reported. In contrast to traditional pyrrolic macrocycles where flexible conformers coexist in dynamic equilibrium, this macrocycle exists as two separable, conformationally stable stereoisomers, denoted as 1A and 1B. The conformational effect of both conformers, as well as their protonated forms, were thoroughly studied using NMR spectroscopy, UV-Vis, and single crystal X-ray diffraction analyses. Importantly, heating conformer 1B leads to its irreversible conversion to 1A, whereas in its protonated form, 1A·2MSA undergoes irreversible transformation to 1B·2MSA at lower temperatures. These temperature-dependent features establish a foundation for developing new accumulated heat sensors, as demonstrated by the use of the present octaphyrins as a customized thermochromic indicator in steam sterilization. The present study thus underscores how the conformational rigidity of these new polypyrrolic macrocycles imparts properties that are distinct from historically flexible expanded porphyrinoids.

In-depth study of a newly synthesized imidazole derivative as an eco-friendly corrosion inhibitor for mild steel in 1 M HCl: Theoretical, electrochemical, and surface analysis perspectives

The present study is concerned with the corrosion inhibition and adsorption behaviour of a series of novel imidazole derivatives. The compounds under investigation are 5,5-diphenyl-3-propyl-2-(propylthio)-3,5-dihydro-4 H-imidazol-4-one (AM3) and 3-allyl-2-(allylthio)-5,5-diphenyl-3,5-dihydro-4 H-imidazol-4-one (AM6). The objective of this study is to evaluate the efficacy of 5,5-diphenyl-3,5-dihydro-4 H-imidazol-4-one (AM6) as a corrosion inhibitor on mild steel immersed in a 1.0 M hydrochloric acid medium. This comprehensive study assesses the efficacy of these derivatives through a range of electrochemical and spectroscopic analysis techniques. Additionally, polarisation curves, electrochemical impedance spectroscopy and advanced computer simulations were employed to evaluate the efficacy and inhibition mechanism of imidazole derivatives, thereby facilitating a more profound understanding of their anticorrosive capacity. The results obtained from potentiodynamic polarisation (PDP), electrochemical frequency modulation (EFM) and electrochemical impedance spectroscopy (EIS) measurements demonstrate that the inhibition efficiency increases with increasing imidazole derivative concentration. Conversely, an inverse relationship is observed between inhibition efficiency and temperature. The thermodynamic parameters ΔG°_ads and ΔH°_ads corroborate the conclusion that the adsorption process is predominantly chemical in nature. Scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and X-ray photoelectron spectroscopy (XPS) were employed to characterise the surface morphology. The maximum protection afforded by imidazole derivatives was 95.2 % and 93 % for compounds AM3 and AM6, respectively. Polarisation curves indicated that imidazole derivatives exhibited mixed inhibition behaviour. Surface analysis demonstrated that imidazole derivatives were effectively adsorbed onto the carbon surface, thereby significantly reducing acid damage. This finding was corroborated by DFT calculations, as well as Monte Carlo (MC) and molecular dynamics (MD) simulations. These simulations provided a comprehensive insight into the adsorption of imidazole and its protonated form onto the carbon surface, offering valuable insight into the corrosion inhibition mechanism.

Correlation between Na-Cs Ion Exchange Properties in the Alkaline Form and Acid Strength in the Proton Form of Zeolite.

The ion exchange function of zeolite is useful for such a purpose as the removal of radioactive Cs species from water. In the very early days of zeolite science, the affinity of zeolites for metal cations was explained based on geometry. After the explanation presented above was proposed, many new zeolites and related materials were discovered or synthesized. Furthermore, it has become clear that the chemical nature of the ion exchange sites is strongly dependent on the framework topology. In this study, the ion exchange behavior between Na-form zeolites with different framework topologies and Cs-containing aqueous solutions was analyzed, and the equilibrium constant was calculated based on the Langmuir type equation to investigate the influence of the chemical nature of the zeolite framework on ion selectivity. The equilibrium constants at room temperature were in the order FAU < LTA < MFI < YFI < MOR. This order is the same as the order of Bro̷nsted acid strengths in the corresponding proton form zeolites. It is suggested that the delocalization of charge around the ion exchange site stabilizes a large cation whose charge is delocalized. In contrast, the equilibrium constant was not related to the pore and cavity size. This opens new insight into the influence of the chemical nature of zeolite on the affinity to cation.

Molecular Properties of Monoaminergic Catecholamines in Water.

Three neurotransmitters belonging to catecholamines (dopamine, noradrenaline, adrenaline) and related α-amino acids (DOPA and tyrosine) were studied by quantum-chemical ab initio and DFT calculations using B3LYP and DLPNO-CCSD(T) methods in water. In addition to the three canonical forms, zwitterionic forms were also investigated, each in three oxidation states (molecular cation L+, electroneutral molecule L0, and molecular anion L-). Each species was subjected to geometry optimization followed by vibrational analysis. Electronic properties (adiabatic ionization energy, electron affinity, chemical hardness, molecular electronegativity, electrophilicity index, dipole moment, electric polarizability, and quadrupole moment) and standard thermodynamic quantities (inner energy, entropy, enthalpy, and Gibbs energy) were evaluated, which allows the absolute oxidation and reduction potentials to be calculated. The absolute reduction potential (ARP) was found to correlate with the electrophilicity index ω along a straight line. Moreover, in addition to the standard expression for the absolute redox potential using reaction Gibbs energy, an approximation based on ionization energy and/or electron affinity was also tested. The main finding is that dopamine is a much weaker oxidizing agent with the ARP = 0.99 V relative to tyrosine with ARP = 1.38 V for canonical structures in water. This is also true for the zwitterionic structures in water: for dopamine ARP = 0.63 V is much lower relative to tyrosine with ARP = 1.31 V. The protonated form (DOPAH+) has the highest ARP = 2.02 V. Prediction of the redox potentials is an important factor influencing antioxidant (EC50) and/or antireductant activity. Based on 16 molecular properties for 20 molecules (320 entries), advanced statistical methods (cluster analysis, principal component analysis, pair-correlation) reveal that several groups of similarity exist: {dopamine-noradrenaline}, different from {adrenaline-DOPA-(tyrosine)} and zwitterionic forms of {dopamine-noradrenaline-adrenaline}.

FTIR study of light-induced proton transfer and Ca2+ binding in T82D mutant of TAT rhodopsin

Proton transfer reactions play important functional roles in many proteins, such as enzymes and transporters, which is also the case in rhodopsins. In fact, functional expression of rhodopsins accompanies intramolecular proton transfer reactions in many cases. One of the exceptional cases can be seen in the protonated form of marine bacterial TAT rhodopsin, which isomerizes the retinal by light but returns to the original state within 10−5 s. Thus, light energy is converted into heat without any function. In contrast, the T82D mutant of TAT rhodopsin conducts the light-induced deprotonation of the Schiff base at high pH. In this article, we report the structural analysis of T82D by means of difference Fourier transform infrared (FTIR) spectroscopy. In the light-induced difference FTIR spectra at 77 K, we observed little hydrogen out-of-plane vibrations for T82D as well as the wild-type (WT), suggesting that the planar chromophore structure itself is not the origin of the reversion from the K intermediate in WT TAT rhodopsin. Upon relaxation of the K intermediate, T82D forms the following intermediate, such as M, whereas K of WT returns to the original state. Present FTIR analysis revealed the proton transfer from the Schiff base to D82 in T82D upon formation of the M intermediate. It is accompanied by the second proton transfer from E54 to the Schiff base, forming the N intermediate, particularly in membranes. The equilibrium between the M and N intermediates corresponds to the protonation equilibrium between E54 and the Schiff base. We also found that Ca2+ binding takes place in T82D as well as WT but with 6 times lower affinity. An altered hydrogen-bonding network would be the origin of low affinity in T82D, where deprotonation of E54 is involved in the Ca2+ binding.

Determination of Nicotine Protonation State in E-Liquids by Low-Resolution Benchtop NMR Spectroscopy.

Over several years, e-liquids with "nicotine salts" have gained considerable popularity. These e-liquids have a low pH, at which nicotine occurs mostly in its monoprotonated form. Manufacturers usually accomplish this by the addition of an organic acid, such as levulinic acid, benzoic acid, or lactic acid. Nicotine in its protonated form can be more easily inhaled, enhancing the addictiveness and attractiveness of products. Several techniques have been described for measuring the protonation state of nicotine in e-liquids. However, nuclear magnetic resonance (NMR) spectroscopy is particularly suited for this purpose because it can be performed on unaltered e-liquids. In this article, we demonstrate the suitability of a benchtop NMR (60 MHz) instrument for determining the protonation state of nicotine in e-liquids. The method is subsequently applied to measure the protonation state of 33 commercially available e-liquids and to investigate whether the vaping process alters the protonation state of nicotine. For this purpose, the protonation state in the condensed aerosol obtained by automated vaping of different e-liquids was compared with that of the original e-liquids. Two distinct populations were observed in the protonation state of nicotine in commercial e-liquids: free-base (fraction of free-base nicotine αfb > 0.80) and protonated (αfb < 0.40). For 30 e-liquids out of 33, the information on the packaging regarding the presence of nicotine salt was in agreement with the observed protonation state. Three e-liquids contained nicotine salt, even though this was not stated on the packaging. Measuring the protonation state of nicotine before and after (machine) vaping revealed that the protonation state of e-liquids is not affected by vaping. In conclusion, it is possible to determine the nicotine protonation state with the described method. Two clusters can be distinguished in the protonation state of commercial e-liquids, and the protonation state of nicotine remains unchanged after vaping.

Development of a Cone Homooxacalix[3]arene-Based Fluorescent Chemosensor for the Selective Detection of Biogenic Ammonium Ions in Protic Solvents.

We report here on the development of a fluorescent cone homooxacalix[3]arene-based receptor with a pyrene unit on the wide rim of the macrocycle (Ox3F) for the selective detection of primary ammonium ions, including those of biological importance. Ox3F was synthesized efficiently via an innovative strategy that enables the regio- and iteroselective wide rim functionalization of the readily available p-tBu-substituted homooxacalix[3]arene precursor. Nuclear magnetic resonance studies and in silico methods highlighted the endo-complexation of primary ammonium ions, including the protonated form of biogenic dopamine, tryptamine, serotonin, mexamine, and 3-iodothyronamine. The binding mode is similar for all guests with the ion deeply inserted into the polyaromatic cavity, enabling the NH3+ head to establish three hydrogen bonds with the ethereal oxygens of the macrocycle. Fluorescence quenching of the pyrene unit was observed following the π-π interaction between the pyrene moiety and the aromatic groups of serotonin, mexamine, and 3-iodothyronamine. No quenching was observed upon complexation of the smaller aromatic neurotransmitter dopamine as well as aliphatic amines and polyamines. This study presents a novel approach for biologically relevant ammonium ion chemosensing with ongoing efforts focused on translating these systems for aqueous environment applications.

Pentaphosphorylation via the Anhydride of Dihydrogen Pentametaphosphate: Access to Nucleoside Hexa- and Heptaphosphates and Study of Their Interaction with RibonucleaseA.

Pentametaphosphate is the little studied cyclic pentamer of the metaphosphate ion, [PO3]5 5-. We show that the doubly protonated form of this pentamer can be selectively dehydrated to provide the anhydride [P5O14]3- (1). This trianion is the well-defined condensed phosphate component of a novel reagent for attachment of a pentaphosphate chain to biomolecules all in one go. Here, we demonstrate by extending adenosine monophosphate (AMP) and uridine monophosphate (UMP) to their corresponding nucleoside hexaphosphates, while adenosine diphosphate (ADP) and uridine diphosphate (UDP) are phosphate chain-extended to the corresponding nucleoside heptaphosphates. Such constructs are of interest for their potential biological function with respect to RNA-processing enzymes. Thus, we go on to investigate in detail the interaction of the polyanionic constructs with ribonuclease A, a model protein containing a polycationic active site and for which X-ray crystal structures are relatively straightforward to obtain. This work presents a combined experimental and quantum chemical approach to understanding the interactions of RNase A with the new nucleoside hexa- and heptaphosphate constructs.

Structural, computational, docking and biological studies of a triaminopyrimidine caspase-1 inhibitor

In order to more fully characterize the binding properties and activities of a potent, low nanomolar IC50 (half maximal inhibitory concentration) inhibitor of caspase-1, CK-1–41, a series of experiments were designed to probe its structure and function. To accomplish this, larger quantities of the molecule were synthesized in an efficient manner using a microwave method, in only 30 min. The structure of the inhibitor was determined by X-ray crystallography in its neutral and protonated form yielding useful structural information. The protonation site in the X-ray structure was found to be the trialkylamine basic site, but nuclear magnetic resonance (NMR) H/D exchange experiments shows that protonation at the triaminopyrimidine sp2 C is also accessible in solution. Density Functional Theory (DFT) calculations were performed and supported the experimental H/D exchange results. Docking studies with several protonated forms of the inhibitor with caspase-1 revealed the compound binds favorably in an allosteric site, with the strongest binding from the protonated form where the proton is bound to the sp2 C. Due to the involvement of caspase-1 in inflammatory cancers, CK-1–41 was screened against a panel of cancer cell lines displaying modest activity against some of the cell lines tested. These studies further clarify the structure and biological function of the representative member of the triaminopyrimidine inhibitors of caspase-1.

White light-emissive triphenylamine-based triazole derivatives: Fluorescence switching response to volatile acid

Two triphenylamine-based tris and bis-triazole molecules (TTA and BTA) were reported, exhibiting significant fluorescence in the solid and solution states. TTA and BTA were highly sensitive towards trifluoroacetic acid (TFA) vapor by visible color change as the triazole nitrogen can easily be protonated. Triazoles show extreme sensitivity because of the reliable intramolecular charge transfer (ICT) interactions; the protonation of triazole moieties resulted in a bathochromic shift in UV–visible and fluorescence spectra. These spectra alterations were reversible when the base triethylamine (TEA) was added. When protonated, the fluorescence changed from blue to cyan, returning to blue on TEA addition (deprotonation). TTA displayed an Aggregation-Induced Enhanced Emission (AIEE) effect in the water: acetonitrile (7:3) combination. Density Functional Theory (DFT) calculations were utilized to calculate the energy gap between the HOMO-LUMO of TTA and BTA and their protonated forms. Both the triazoles were highly stable in a di-protonated state. Aside from acid sensitivity, TTA and BTA emitted white light with a high Color Rendering Index (CRI) of 87 % and 98 %, respectively, in the solid and the polymer composite thin film because of their multiple emission bands.

Heavy Water Microdroplet Surface Enriches the Lighter Isotopologue Impurities.

Water microdroplets promote unusual chemical reactions at the air-water interface. However, the interfacial structure of water microdroplets and its potential influence on chemical processes are still enigmatic. Here, we present evidence of in-droplet fractionation of water isotopologues. Employing a sonic spray, we atomized the heavy water (D2O, 99.9 atom % D) solution of three classes of organic compounds (basic, acidic, and neutral). The analytes were predominantly desorbed from the resulting droplet surface in protonated form rather than deuterated form, as detected by mass spectrometry. This result remained unaltered upon adding formic acid-d2 (DCOOD) to the droplet. Monitoring Dakin oxidation of benzaldehyde at the surface of binary microdroplets composed of 1:1 (v/v) D2O/H218O revealed the preferred formation of phenolate-16O over phenolate-18O. Atmospheric pressure chemical ionization mass spectrometric analysis of the vapor composition in the sprayed aerosol revealed the preferential evaporation of lighter water isotopologue impurities from the surface of heavy water microdroplets. These results indicate the enrichment of lighter water isotopologue impurities (HOD/H2O) on the surface of heavy water microdroplets, implying possible future developments for water isotopologue fractionation using microdroplets.

Transpersulfidation or H2S Release? Understanding the Landscape of Persulfide Chemical Biology.

Persulfides (RSSH) are biologically important reactive sulfur species that are endogenously produced, protect key cysteine residues from irreversible oxidation, and are important intermediates during different enzymatic processes. Although persulfides are stronger nucleophiles than their thiol counterparts, persulfides can also act as electrophiles in their neutral, protonated form in specific environments. Moreover, persulfides are electrophilic at both sulfur atoms, and the reaction with a thiolate can lead to either H2S release with disulfide formation or alternatively result in transpersulfidation. Despite the broad acceptance of these reaction pathways, the specific properties that control whether persulfides react through the H2S-releasing or transpersulfidation pathway remain elusive. Herein, we use a combined computational and experimental approach to directly investigate the reactivity between persulfides and thiols to answer these questions. Using density functional theory (DFT) calculations, we demonstrate that increasing steric bulk or electron withdrawal near the persulfide can shunt persulfide reactivity through the transpersulfidation pathway. Building from these insights, we use a synthetic persulfide donor and an N-iodoacetyl l-tyrosine methyl ester (TME-IAM) trapping agent to experimentally monitor and measure transpersulfidation from a bulky penicillamine-based persulfide to a cysteine-based thiol, which, to the best of our knowledge, is the first direct observation of transpersulfidation between low-molecular-weight species. Taken together, these combined approaches highlight how the properties of persulfides are directly impacted by local environments, which has significant impacts in understanding the complex chemical biology of these reactive species.

DFT insights into the basicity of some cyclic allenes

ABSTRACT The proton affinity (PA) and gas phase basicity values of previously reported cyclic allene series are investigated using high-level quantum chemical calculations. Some of the studied structures possessed more than one protonation site. All protonation types were explored for each structure and the compounds with PA value more than ≈1030 kJ mol−1 were considered superbasic structures. Cyclic allene's basicity strength was affected by ring size, adjacent heteroatom's presence and resonance existence in protonated form.

Dose–response effects of two nicotine salt formulations on electronic cigarette appeal and sensory attributes

ObjectivesVarious organic acids are used to create nicotine salt formulations, which may improve the appeal and sensory experience of vaping electronic cigarettes (e-cigarettes). This clinical experiment examined the effects of...

Refined linkage analysis of the sulphated marine polysaccharide fucoidan of Cladosiphon okamuranus with a focus on fucose

Methylation followed by depolymerization and gas chromatography (GC) is an effective methodology for the linkage analysis of polysaccharides, including fucoidan, a sulphated algal polysaccharide. However, this sample material demands attention to experimental details to prevent aberrations in the analytical result. The use of deficient bases for methylation, the presence of water, analyte degradation during hydrolysis, and coelution of the target analytes during gas chromatography create doubts about published results. We therefore investigated critical parameters of the method and carefully optimized the steps of the protocol to ensure the integrity of the results for the fucose monomers.Fucoidan from Cladosiphon okamuranus was used as reference sample to determine the glycosidic bonds, and sulphate positions in the monomer. Fucoidan in protonated form was methylated in a strictly water-free environment using lithium dimsyl as base and methyl iodide for methylation. The methylated polymer was isolated by solid phase extraction, which was crucial to recover also the highly sulfated fraction. Hydrolysis was conducted with trifluoroacetic acid. To separate all target analytes in GC-FID/MS, a stationary phase with high cyanopropyl content (HP-88) was required, as the commonly employed phenyl siloxane phases result in co-elution, which distorts the result severely.

Phenothiazine Embedded Dithiasmaragdyrins.

Two different types of novel phenothiazine-embedded dithiasmaragdyrins containing one phenothiazine ring, two thiophene rings and two pyrrole rings connected via three meso carbons and two direct bonds in the macrocyclic framework were synthesized over the sequence of synthetic steps starting with phenothiazine. Three examples of phenothiazine-embedded dithiasmaragdyrins were synthesized by condensing appropriate phenothiazine-based pentapyrrane with pentafluorobenzaldehyde and two examples of phenothiazine sulfone embedded dithiasmaragdyrins were synthesized by condensing phenothiazine-based diol with appropriate meso-aryl dipyrromethane under mild acid-catalysed conditions. 1D&2D NMR studies revealed that the thiophene rings adopted inverted orientation in phenothiazine sulfone embedded dithiasmaragdyrins whereas in phenothiazine-embedded dithiasmaragdyrins, the thiophene rings were in normal orientation. Both types of macrocycles exhibit nonaromatic absorption features and showed panchochromic absorption features in its neutral and protonated forms. The electrochemical studies indicated that the phenothiazine-embedded dithiasmaragdyrins were more electron-rich compared to phenothiazine sulfone embedded dithiasmaragdyrins. DFT studies revealed that both types of dithiasmaragdyrins exhibit significantly distorted structures and TD-DFT studies support the experimental observations.

Polyaniline-Based Cationic Porous Organic Polymers for Fast and Efficient Anion-Exchange-Driven Capture of Cr2O7 2.

Efficient treatment of wastewater contaminated with carcinogenic Cr(VI) has been a long-term challenge for both academic and industrial research efforts. Removal of Cr(VI) species by ion exchange is a relatively simple and efficient method, and its combination with highly tailorable nanomaterials is promising for the treatment of such wastewater. Here, we report a type of cationic porous organic polymer (POP), namely, PTPA-PIP, which can be prepared simply by converting the corresponding aromatic polyamine PTPA to its protonated form, thereby significantly increasing its hydrophilicity and ability to disperse homogeneously in water, crucial for application in water treatment. In addition to detailed characterization of the physicochemical properties of PTPA-PIP (including using Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS), Brunauer-Emmett-Teller (BET), and solid-state NMR techniques), adsorption experiments demonstrate that PTPA-PIP removes low-concentration dichromate anions with very high performance, including excellent exchange capacity (maximum capacity of 230 mg Cr2O7 2-/g PTPA-PIP), ultrafast removal (initial adsorption rate of 83 mg g-1 min-1), excellent selectivity (∼10% loss of adsorption capacity in the presence of 40-fold concentration of competing anions), as well as superior reusability (reusable for at least 5 cycles without compromised performance). These results demonstrate that PTPA-PIP is an outstanding candidate for application in industrial settings for the effective removal of harmful Cr(VI) pollutants in wastewater.

An oxo‐acetato‐bridged trinuclear cobalt(III) cluster‐persuaded cobalt oxide active electrocatalyst for efficient hydrogen evolution activity

This study presents the synthesis and electrocatalytic performance of the cobalt(III) complex [Co3(μ1,1,1‐O)(μ1,3‐CH3CO2)(L)3]2(DMF)3 (Cotri), featuring a double deprotonated (N,O)‐donor ligand (L2‐), where the protonated form of it (H2L) is 2,2′‐(hydrazine‐1,2‐diylidenebis(ethan‐1‐yl‐1‐ylidene))diphenol. The X‐ray structure reveals a trinuclear cobalt cluster formed with three cobalt(III) centers interlinking through oxido (μ1,1,1‐O) and acetato (μ1,3‐O2CCH3) bridges in coupling with bis‐congregator‐type chelating ligands. Cotri adopts cobalt centers of octahedral and trigonal bipyramidal coordination geometries and bears a dominant Co(2)…H(DMF) agostic interactions appraised by lattice dimethyl formamide (DMF) molecules. Further, Cotri shows promising heterogeneous electrocatalytic hydrogen evolution activity in 1 M KOH, with an overpotential of 441 mV to achieve 10 mA/cm2 current density. Tafel slope analysis suggests the Volmer–Heyrovsky step as the rate‐determining step. The number of active sites and TOF for Cotri were estimated at 4.010 × 10−8 mol and 0.2467 s−1, respectively, ensuring its excellent hydrogen generation activity. Stability assessments through controlled potential electrolysis (CPE) and cyclic voltammetry (CV) for multiple cycles addressed the transformation of Cotri to Co2O3 nanoparticles, which turned out to be a more active Co2O3 electrocatalyst. The morphology and particle size of the in situ developed Co2O3 active catalyst under the electrochemical conditions attributes to the superior hydrogen evolution activity.

Photo-Oxidation of α-Pinene Oxidation Products in Atmospheric Waters - pH- and Temperature-Dependent Kinetic Studies.

The atmospheric α-pinene oxidation leads to three carboxylic acids: norpinonic acid (NPA), pinic acid (PA), and 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA). In this study, the OH radical kinetics in the aqueous phase of these carboxylic acids were investigated at different temperatures and pH values of solutions. Activation parameters and the corresponding atmospheric lifetimes of the acids in the troposphere were derived. The overall second-order rate constants for the individual speciation forms of the acids (AH and A- for NPA; AH2, AH- and A2- for PA; and AH3, AH2-, AH2- and A3- for MBTCA) were determined. At 298 K, the rate constants for reactions of protonated forms (AHx) of NPA, PA, and MBTCA with •OH, were (1.5 ± 0.2) × 109 L mol-1 s-1, (2.4 ± 0.1) × 109 L mol-1 s-1, and (4.1 ± 0.6) × 108 L mol-1 s-1, respectively. For the fully deprotonated forms (Ax-) of studied acids, the second-order rate constants were (2.2 ± 0.2) × 109 L mol-1 s-1, (2.8 ± 0.1) × 109 L mol-1 s-1, and (10.2 ± 0.7) × 108 L mol-1 s-1 at 298 K, respectively. It was found that the reactions of NPA and PA with OH radicals are faster than with MBTCA. For MBTCA, the reaction rate depends on pH more strongly at elevated temperatures (>298 K). The atmospheric lifetimes of the acids considered due to their reactivity with •OH were calculated for different model scenarios at a temperature of 283 K and pH = 2 in the aqueous phase. For this purpose, liquid water content (LWC) was used for aerosols and clouds under storm conditions and at various aqueous-phase concentrations of OH radicals. The lifetimes decreased with increasing LWC (from 10-12 m3 m-3 in aerosol to 10-5 m3 m-3 in storms), indicating that the acids undergo significant aqueous processing under realistic atmospheric conditions. Besides, the aerosol systems appeared less effective in removing PA and NPA, with lifetimes ranging from hundreds of days to tens and hundreds of hours, respectively. Clouds were more effective, with lifetimes ranging from tens of hours to a single second or less. MBTCA, which dissolves better in water, was effectively removed in all systems, with the longest lifetime of approximately 90 min.

Molecular Environment Modulates CO2 Liberation from Carboxy-Biotin.

Carboxy-biotin serves as a coenzyme in certain carboxylases, exhibiting the remarkable capability to transfer a carboxy group to specific substrates. This process is made possible by the presence of biotin, a unique molecule that consists of a sulfur-containing tetrahydrothiophene ring fused to a ureido group. It is covalently attached to the enzyme via a flexible linker, allowing for its functionality. Biotin-dependent carboxylases consist of two distinct domains. The first domain (BC) facilitates biotin carboxylation by utilizing ATP, while the second domain (CT) transfers CO2 to the substrate. The process of ATP-dependent carboxylation using bicarbonate in the biotin carboxylase domain (BC) is well-known. However, the precise mechanism by which CO2 is released in the carboxyltransferase domain (CT) is still not fully understood. We employed advanced computational chemistry methods to investigate the decarboxylation process of carboxy-biotin in various molecular environments and different protonation states. Regardless of the polarity of the molecular surroundings, decarboxylation only occurs spontaneously in the protonated form. To determine the protonation state of biotin in different environments, we established an accurate computational chemistry method for calculating the pKa value of carboxy-biotin, reaching sub-kcal/mol accuracy. Based on our findings, nonpolar environments, such as the active site of the carboxyltransferase domain, have the ability to cause the spontaneous release of CO2 from carboxy-biotin. The CO2 release takes place spontaneously from protonated carboxy-biotin, promoting the carboxylation of substrates.