Determination Of Rate Constants Research Articles

Synthesis of the cis‐ and trans‐3‐Fluoro Analogues of Febrifugine and Halofuginone

AbstractThe novel synthesis of racemic cis‐ and trans‐3‐fluorofebrifugine and halofuginone is described. This straight‐forward seven‐step process relies on an electrophilic fluorination‐allylation sequence that generates a mixture of N‐Cbz protected, diastereomeric 2‐allyl‐3‐fluoropiperidines. On separation, a Wacker oxidation‐methyl functionalisation sequence enabled introduction of the required quinazolinone portion. Finally, removal of the N‐Cbz protecting group lead to isolation of the 3‐fluorofebrifugine dihydrobromide analogues that are of potentially pharmacological use. Analysis of the NMR spectra for each stereoisomer provides information concerning the preferred conformers of the different diastereomers. Evidence indicates that the cis‐diastereomer favours a conformation where the F‐atom occupies an axial orientation. In contrast, for its trans‐stereoisomeric counterpart, the 2‐substituent overrides any F‐atom effect and it preferentially occupies a conformer where both substituents occupy equatorial positions. Finally, interconversion between the cis‐ and trans‐diastereomers was studied. In DMSO‐d6 and as their free‐bases, isomerisation of each diastereomer gave a common 65 : 35 ratio of trans‐ to cis‐3‐fluorofebrifugine. Determination of the reaction rate constants for the isomerisation process at different temperatures enabled calculation of the activation energy barriers, for each process, using an Arrhenius plot. The activation energy barrier for the isomerisation of the trans‐isomer was 94.3±4.9 kJ mol−1, whereas for the cis‐isomer it was 84.5±3.9 kJ mol−1.

Transferable and Interpretable Prediction of Site-Specific Dehydrogenation Reaction Rate Constants with NMR Spectra.

Accurate and efficient determination of site-specific reaction rate constants over a wide temperature range remains challenging, both experimentally and theoretically. Taking the dehydrogenation reaction as an example, our study addresses this issue by an innovative combination of machine learning techniques and cost-effective NMR spectra. Through descriptor screening, we identified a minimal set of NMR chemical shifts that can effectively determine reaction rate constants. The constructed model performs exceptionally well on theoretical data sets and demonstrates impressive generalization capabilities, extending from small molecules to larger ones. Furthermore, this model shows outstanding performance when applied to limited experimental data sets, highlighting its robust applicability and transferability. Utilizing the Sure Independence Screening and Sparsifying Operator (SISSO) algorithm, we also present an interpretable rate constant-temperature-NMR (k-T-NMR) relationship with a mathematical formula. This study reveals the great potential of combining machine learning with easily accessible spectroscopic descriptors in the study of reaction kinetics, enabling the rapid determination of reaction rate constants and promoting our understanding of reactivity.

Computational Study on the Inhibition Mechanisms of the Ziegler-Natta Catalyst in the Propylene Polymerization Process: Part 1 Effects of Acetylene and Methylacetylene

Acetylene and methylacetylene are impurities commonly found in the raw materials used for the production of polymers such as polypropylene and polyethylene. Experimental evidence indicates that both acetylene and methylacetylene can decrease the productivity of the Ziegler-Natta catalyst and alter the properties of the resulting polymer. However, there is still a lack of understanding regarding the mechanisms through which these substances affect this process. Therefore, elucidating these mechanisms is crucial to develop effective solutions to this problem. In this study, the inhibition mechanisms of the Ziegler-Natta catalyst by acetylene and methylacetylene are presented and compared with the incorporation of the first propylene monomer (chain initiation) to elucidate experimental effects. The Density Functional Theory (DFT) method was used, along with the B3LYP-D3 functional and the 6-311++G(d,p) basis set. The recorded adsorption energies were −11.10, −13.99, and −0.31 kcal mol−1, while the activation energies were 1.53, 2.83, and 28.36 kcal mol−1 for acetylene, methylacetylene, and propylene, respectively. The determined rate constants were 4.68 × 1011, 5.29 × 1011, and 2.3 × 10−8 M−1 s−1 for acetylene, methylacetylene, and propylene, respectively. Based on these values, it is concluded that inhibition reactions are more feasible than propylene insertion only if an ethylene molecule has not been previously adsorbed, as such an event reinforces propylene adsorption.

Structure-Reactivity Relationships in a Small Library of Imine-Type Dynamic Covalent Materials: Determination of Rate and Equilibrium Constants Enables Model Prediction and Validation of a Unique Mechanical Softening in Dynamic Hydrogels.

The development of next generation soft and recyclable materials prominently features dynamic (reversible) chemistries such as host-guest, supramolecular, and dynamic covalent. Dynamic systems enable injectability, reprocessability, and time-dependent mechanical properties. These properties arise from the inherent relationship between the rate and equilibrium constants (RECs) of molecular junctions (cross-links) and the resulting macroscopic behavior of dynamic networks. However, few examples explicitly measure RECs while exploring this connection between molecular and material properties, particularly for polymeric hydrogel systems. Here we use dynamic covalent imine formation to study how single-point compositional changes in NH2-terminated nucleophiles affect binding constants and resulting hydrogel mechanical properties. We explored both model small molecule studies and model polymeric macromers, and found >3-decade change in RECs. Leveraging established relationships in the literature, we then developed a simple model to describe the cross-linking equilibrium and predict changes in hydrogel mechanical properties. Interestingly, we observed that a narrow ≈2-decade range of Keq's determine the bound fraction of imines. Our model allowed us to uncover a regime where adding cross-linker before saturation can decrease the cross-link density of a hydrogel. We then demonstrated the veracity of this predicted behavior experimentally. Notably this emergent behavior is not accounted for in covalent hydrogel theory. This study expands upon structure-reactivity relationships for imine formation, highlighting how quantitative determination of RECs facilitates predicting macroscopic behavior. Furthermore, while the present study focuses on dynamic covalent imine formation, the underlying principles of this work are applicable to the general bottom-up design of soft and recyclable dynamic materials.

Linear Free Energy Relationships Associated with Hydride Transfer From [(6,6'-R2-bpy)Re(CO)3H]: A Cautionary Tale in Identifying Hydrogen Bonding Effects in the Secondary Coordination Sphere.

Six rhenium hydride complexes, [(6,6'-R2-bpy)Re(CO)3H] (bpy = 2,2'-bipyridine, R = OEt, OMe, NHMe, Me, F, Br), were synthesized. These complexes insert CO2 to form rhenium formate complexes of the type [(6,6'-R2-bpy)Re(CO)3{OC(O)H}]. All the rhenium formate species were characterized using X-ray crystallography, which revealed that the bpy ligand is not coplanar with the metal coordination plane containing the two nitrogen donors of the bpy ligand but tilted. A solid-state structure of [(6,6'-Me2-bpy)Re(CO)3H] determined using MicroED also featured a tilted bpy ligand. The kinetics of CO2 insertion into complexes of the type [(6,6'-R2-bpy)Re(CO)3H] were measured experimentally and the thermodynamic hydricities of [(6,6'-R2-bpy)Re(CO)3H] species were determined using theoretical calculations. A Brønsted plot constructed using the experimentally determined rate constants for CO2 insertion and the calculated thermodynamic hydricities for [(6,6'-R2-bpy)Re(CO)3H] revealed a linear free energy relationship (LFER) between thermodynamic and kinetic hydricity. This LFER is different to the previously determined relationship for CO2 insertion into complexes of the type [(4,4'-R2-bpy)Re(CO)3H]. At a given thermodynamic hydricity, CO2 insertion is faster for complexes containing a 6,6'-substituted bpy ligand. This is likely in part due to the tilting observed for systems with 6,6'-substituted bpy ligands. Notably, the 6,6'-(NHMe)2-bpy ligand could in principle stabilize the transition state for CO2 insertion via hydrogen bonding. This work shows that if only the rate of CO2 insertion into [(6,6'-(NHMe)2-bpy)Re(CO)3H] is compared to [(4,4'-R2-bpy)Re(CO)3H] systems, the increase in rate could be easily attributed to hydrogen bonding, but in fact all 6,6'-substituted systems lead to faster than expected rates.

Thermodynamic and kinetic study of palladium(II) complexation with 1-methyl-2-mercaptoimidazole (methimazole) and their importance for structural design of metallodrugs

The acidobasic and complexing properties of 1-methyl-2-mercaptoimidazole (Methimazole, an anti-thyroid drug) were investigated. The pKa 11.49 ± 0.03 was estimated by molecular absorption spectroscopy (I = 0.10 M NaCl, t = 25.0 ± 0.1 °C). This value is in good agreement with the value 11.58 ± 0.05, obtained using the solvent-extraction technique. Theoretical (LFER and quantum chemical calculations) and experimental (1H/13C NMR spectroscopy) methods confirmed that the ligand prefers to be in the thion form, and the proton dissociation takes place on the nitrogen atom. Using glass electrode potentiometry, the complexation of the Pd(II) ion by the methimazole ligand occurs without the participation of protons. The best chemical model considers the [Pd(HL)]2+, [Pd(HL)2]2+ and [Pd(HL)3]2+ complex species, whose stability constants were also determined using spectroscopy and capillary zone electrophoretic (CZE) measurements. The metal complexes dissociate at –log [H+] > 7, where an uncharged palladium(II) hydroxide is formed. The formation kinetics of the palladium(II) complex with methimazole were studied in perchloric and hydrochloric acids (I = 1.00 M, t = 15–40 °C) and the determined rate constants and activation parameters are consistent with literature values determined for the reactions of the Pd(II) ion with thiourea derivatives. The rate constants decrease by two orders of magnitude in both media, which can be assigned to a lower tendency of the chloride ion to dissociate from the [PdCl4]2− complex species than the water molecule from the [Pd(H2O)4]2+ ion. The presented results can be utilized for the design of new Pd and Pt metallodrugs.

Homomolecular Triplet-Triplet Annihilation in Metalloporphyrin Photosensitizers.

Metalloporphyrins are ubiquitous in their applications as triplet photosensitizers, particularly for promoting sensitized photochemical upconversion processes. In this study, bimolecular excited state triplet-triplet quenching kinetics, termed homomolecular triplet-triplet annihilation (HTTA), exhibited by the traditional triplet photosensitizers-zinc(II) tetraphenylporphyrin (ZnTPP), palladium(II) octaethylporphyrin (PdOEP), platinum(II) octaethylporphyrin (PtOEP), and platinum(II) tetraphenyltetrabenzoporphyrin (PtTPBP)─were revealed using conventional transient absorption spectroscopy. Nickel(II) tetraphenylporphyrin was used as a control sample as it is known to be rapidly quenched intramolecularly through ligand-field state deactivation and, therefore, cannot result in triplet-triplet annihilation (TTA). The single wavelength transients associated with the metalloporphyrin triplet excited state decay─measured as a function of incident laser pulse energy in toluene─were well modeled using parallel first- and second-order kinetics, consistent with HTTA being operable. The combined transient kinetic data enabled the determination of the first-order rate constants (kT) for excited triplet decay in ZnTPP (4.0 × 103 s-1), PdOEP (3.6 × 103 s-1), PtOEP (1.2 × 104 s-1), and PtTPBP (2.1 × 104 s-1) as well as the second-order rate constant (kTT) for HTTA in ZnTPP (5.5 × 109 M-1 s-1), PdOEP (1.1 × 1010 M-1 s-1), PtOEP (7.1 × 109 M-1 s-1), and PtTPBP (1.6 × 1010 M-1 s-1). In most instances, triplet excited state extinction coefficients are either reported for the first time or have been revised using ultrafast transient absorption spectroscopy and singlet depletion: ZnTPP (78,000 M-1 cm-1) at 470 nm, PdOEP (67,000 M-1 cm-1) at 430 nm, PtOEP (51,000 M-1 cm-1) at 418 nm, and PtTPBP (100,000 M-1 cm-1) at 460 nm. The combined experimental results establish competitive time scales for homo- and heteromolecular TTA rate constants, implying the significance of considering HTTA processes in future research endeavors harnessing TTA photochemistry using common metalloporphyrin photosensitizers.

(Invited) Quantitative Prediction of Exciton Dynamics

Thermally activated delayed fluorescence (TADF) is now an established way to convert inhelently dark triplet excitons into light through reverse intersystem crossing (RISC).1-4 To realize the RISC process, minimizing the energy gap (ΔE ST) between S1 and T1 is considered to be effective theoretically, and this has been realized experimentally. At the beginning of the research, RISC had been the rate-limiting process in TADF, although RISC was possible. In such situation, we have shown that acceleration of RISC has now become possible through a variety of methods.5-7 Although excellent TADF materials and highly efficient TADF-based organic light-emitting diodes (OLEDs) have been realized as described above, the fundamental understanding is still insufficient. In the presentation, we first show our recently-proposed method for quantitatively predicting rate constants of all electronic transitions relevant to light emission.8-10 The method proposed here has successfully predicted all rate constants quantitatively and therefore can predict TADF performance precisely. The method also allows quantitative predictions of dynamics (time evolution) of experimentally-obtained rate constants for radiative, non-radiative, intersystem crossing, and RISC as well as exciton population dynamics.11 Such an approach will contribute significantly to the fundamental science of exciton dynamics.We express sincere thanks to my group members. This work was supported by JSPS KAKENHI Grant Numbers JP20H05840 (Grant-in-Aid for Transformative Research Areas, “Dynamic Exciton”). Computation time and NMR measurements were supported by the international Joint Usage/Research Centre at the Institute for Chemical Research, Kyoto University, Japan. Uoyama, H.; Goushi, K.; Shizu, K.; Nomura, H.; Adachi, C., Highly efficient organic light-emitting diodes from delayed fluorescence. Nature 2012, 492, 234. Kaji, H., et al., Purely organic electroluminescent material realizing 100% conversion from electricity to light. Nat. Commun. 2015, 6, 8476. Yang, Z., et al., Recent advances in organic thermally activated delayed fluorescence materials. Chem. Soc. Rev. 2017, 46, 915. Wong, M. Y.; Zysman-Colman, E., Purely organic thermally activated delayed fluorescence materials for organic light-emitting diodes. Adv. Mater. 2017, 29, 1605444. Wada, Y.; Nakagawa, H.; Matsumoto, S.; Wakisaka, Y.; Kaji, H., Organic light emitters exhibiting very fast reverse intersystem crossing. Nat. Photon. 2020, 14, 643. Ren, Y.; Wada, Y.; Suzuki, K.; Kusakabe, Y.; Geldsetzer, J.; Kaji, H., Efficient blue thermally activated delayed fluorescence emitters showingvery fast reverse intersystem crossing. Appl. Phys. Express 2021, 14, 071003. Wada, Y.; Wakisaka, Y.; Kaji, H., Efficient direct reverse intersystem crossing between charge transfer‐type singlet and triplet states in a purely organic molecule. ChemPhysChem 2021, 22, 625. Shizu, K.; Kaji, H., Theoretical determination of rate constants from excited states: Application to benzophenone. J. Phys. Chem. A 2021, 125, 9000. Shizu, K.; Kaji, H., Comprehensive understanding of multiple resonance thermally activated delayed fluorescence through quantum chemistry calculations. Commun. Chem. 2022, 5. Shizu, K.; Ren, Y. X.; Kaji, H., Promoting reverse intersystem crossing in thermally activated delayed fluorescence via the heavy-atom effect. J. Phys. Chem. A 2023, 127, 439.Shizu, K.; Kaji, H., submitted.

Unveiling the environmental significance of acetylperoxyl radical: Reactivity quantification and kinetic modeling.

Acetylperoxyl radical (CH3C(O)OO•) is among highly reactive organic radicals which are known to play crucial roles in atmospheric chemistry, aqueous chemistry and, most recently, peracetic acid (PAA)-based advanced oxidation processes. However, fundamental knowledge for its reactivity is scarce and severely hampers the understanding of relevant environmental processes. Herein, three independent experimental approaches were exploited for revelation and quantification of the reaction rates of acetylperoxyl radical. First, we developed and verified laser flash photolysis of biacetyl, ultraviolet (UV) photolysis of biacetyl, and pulse radiolysis of acetaldehyde, each as a clean source of CH3C(O)OO•. Then, using competition kinetics and selection of suitable probe and competitor compounds, the rate constants between CH3C(O)OO• and compounds of diverse structures were determined. The three experimental approaches complemented in reaction time scale and ease of operation, and provided cross-validation of the rate constants. Moreover, the formation of CH3C(O)OO• was verified by spin-trapped electron paramagnetic resonance, and potential influence of other reactive species in the systems was assessed. Overall, CH3C(O)OO• displays distinctively high reactivity and selectivity, reacting especially favorably with naphthyl and diene compounds (k ∼ 107-108 M-1 s-1) but sluggishly with N- and S-containing groups. Significantly, we demonstrated that incorporating acetylperoxyl radical-oxidation reactions significantly improved the accuracy in modeling the degradation of environmental micropollutants by UV/PAA treatment. This study is among the most comprehensive investigation for peroxyl radical reactivity to date, and establishes a robust methodology for investigating organic radical chemistry. The determined rate constants strengthen kinetic databases and improve modeling accuracy for natural and engineered systems.

Moment analysis method for determination of rate constants of solute permeation across interface of spherical molecular aggregates by means of high-performance liquid chromatography

A moment analysis method was developed for the study of solute permeation at the interface of spherical molecular aggregates. At first, new moment equations were developed for determining the partition equilibrium constant (Kp) and permeation rate constants (kin and kout) of solutes from the first absolute (μ1A) and second central (μ2C) moments of elution peaks measured by using high-performance liquid chromatography (HPLC). Then, the method was applied to the analysis of mass transfer phenomena of three solutes, i.e., hydroquinone, resorcinol, and catechol, at the interface of sodium dodecylsulfate (SDS) micelles. HPLC data were measured by using an ODS column and an aqueous phosphate buffer solution (pH = 7.0) as the mobile phase solvent. Pulse response experiments were conducted while changing SDS concentration (5 - 20 mmol dm−3) in the mobile phase under the conditions that the surface of ODS stationary phase was dynamically coated by SDS monomers. In order to demonstrate the effectiveness of the moment analysis method using HPLC, the values of Kp, kin, and kout were determined for the three solutes as 35 - 69, 2.4 × 10−8 - 1.4 × 10−6 m s−1, and 7.0 × 10−10 - 2.1 × 10−8 m s−1, respectively. Their values increase with an increase in the hydrophobicity of the solutes. The method has some advantages for the study of interfacial solute permeation of molecular aggregates. For example, neither immobilization nor chemical modification of both solute molecules and molecular aggregates is required when elution peaks are measured by using HPLC. Interfacial solute permeation takes place in the mobile phase without any chemical reaction or physical action on molecular aggregates. The values of Kp, kin, and kout were analytically determined from those of μ1A and μ2C by using the moment equations. The results of this study must contribute to the dissemination of an opportunity for studying the interfacial solute permeation of molecular aggregates to many researchers because of extremely high versatility of HPLC.

A consistent explanation of seemingly inconsistent experimental and theoretical data for N[formula omitted]O + O via MultiScale Informatics

The N2O + O reaction plays a critical role in NOx formation at high pressures and low peak temperatures, in the “dark zone” region of deflagration waves of organic energetic materials, and in N2O consumption in NH3 combustion. While the rate constant for N2O + O = NO + NO (R3) is considered reasonably well established, viewpoints regarding the rate constants for N2O + O = N2 + O2 (R2)—and even the main products of the N2O + O reaction—have not reached a consensus, with studies from the past few years continuing to reach drastically different conclusions. To date, no single model has been presented that can reproduce all key datasets on both sides of the debate. Using the MultiScale Informatics (MSI) approach, we identified a model consistent with a vast catalog of theoretical and experimental data previously used to determine rate constants for R2, R3, and other key reactions influencing experimental interpretations. Notably, this MSI model (presented herein) reproduces all experimental datasets previously used to anchor low-activation-energy k2 expressions that greatly favor R2 at intermediate temperatures. However, its kinetic parameters are also consistent with theoretical calculations that instead show high activation energy for R2 and k2 values many orders of magnitude lower—such that R3 is the main channel at essentially all temperatures. This model is also consistent with our new experimental data (presented in our companion paper) at optimally selected conditions that avoid the interpretation ambiguities that have hindered definitive conclusions from previous experimental data. The present analysis elucidates the role of secondary reactions that would have artificially inflated the apparent k2/k3 ratio previously deduced from experiments in a manner that may not have been detectable from even multi-species measurements at typical conditions—and may, therefore, explain the persistent historical difficulties in establishing the main products of N2O + O.Novelty and significance statementDespite decades of research, viewpoints regarding the rate constants for N2O + O = N2 + O2 (R2)—and even the main products of the N2O + O reaction—have not reached a consensus, with studies from the past few years still reaching drastically different conclusions. To date, no single model has been presented that can reproduce all key datasets on both sides of the debate. Here, we present a single model consistent with a vast catalog of theoretical and experimental data, including all experimental datasets previously used to anchor low-activation-energy expressions for k2 that greatly favor R2 as the main channel at intermediate temperatures—but with kinetic parameters consistent with theoretical calculations that instead show high activation energy for R2 and N2O + O = NO + NO (R3) as the main channel at essentially all temperatures.

Real-Time Metabolic Magnetic Resonance Spectroscopy of Pancreatic and Colon Cancer Tumor-Xenografts with Parahydrogen Hyperpolarized 1-13C Pyruvate-d3.

Parahydrogen-induced polarization (PHIP) is an emerging technique to enhance the signal of stable isotope metabolic contrast agents for Magnetic Resonance (MR). The objective of this study is to continue establishing 1-13C-pyruvate-d3, signal-enhanced via PHIP, as a hyperpolarized contrast agent, obtained in seconds, to monitor metabolism in human cancer. Our focus was on human pancreatic and colon tumor xenografts. 1-13C-vinylpyruvate-d6 was hydrogenated using parahydrogen. Thereafter, the polarization of the protons was transferred to 13C. Following a workup procedure, the free hyperpolarized 1-13C-pyruvate-d3 was obtained in clean aqueous solution. After injection into animals bearing either pancreatic or colon cancer xenografts, slice-selective MR spectra were acquired and analyzed to determine rate constants of metabolic conversion into lactate and alanine. 1-13C-pyruvate-d3 proved to follow the increased metabolic rate to lactate and alanine in the tumor xenografts.

Charge Transfer Kinetics in Halide Perovskites: On the Constraints of Time-Resolved Spectroscopy Measurements.

Understanding photophysical processes in lead halide perovskites is an important aspect of optimizing the performance of optoelectronic devices. The determination of exact charge carrier extraction rate constants remains elusive, as there is a large and persistent discrepancy in the reported absolute values. In this review, we concentrate on experimental procedures adopted in the literature to obtain kinetic estimates of charge transfer processes and limitations imposed by the spectroscopy technique employed. Time-resolved techniques (e.g., transient absorption-reflection and time-resolved photoluminescence spectroscopy) are commonly employed to probe charge transfer at perovskite/transport layer interfaces. The variation in sample preparation and measurement conditions can produce a wide dispersion of the measured kinetic parameters. The selected time window and the kinetic fitting model employed introduce additional uncertainty. We discuss here evaluation strategies that rely on multiexponential fitting protocols (regular or stretched) and show how the dispersion in the reported values for carrier transfer rate constants can be resolved.

Theoretical studies on the kinetics and mechanism of hydroxyl radical reaction with quinclorac and quinmerac herbicides in aqueous media

AbstractThe kinetic and mechanistic studies for the reaction of hydroxyl radical with two quinoline based herbicides, namely, quinclorac and quinmerac has been performed using various computational methods in aqueous media. Geometry optimizations were performed using Density Functional Theory (DFT) methods including water as the solvent. Local reactivity parameters of these herbicides towards the •OH radical are predicted using condensed Fukui function. Single point energies of various species were calculated using double hybrid method, namely, B2PLYP–D for better accuracy. The pKa values for these acid based herbicides allow them to exist in deprotonated form in aqueous condition. Hence, the calculations are also performed for the deprotonated or the anionic form apart from the neutral species. Individual rate coefficients for •OH radical addition reaction with each carbon atoms were evaluated using conventional transition state theory using one–dimensional tunneling corrections. The solvent effect on reaction is implemented through Collins–Kimball formulations. Both the approaches, namely, the Fukui index and individual rate constant determination confirms that the most reactive site for the •OH radical addition in these two herbicide is the carbon atom attached to the COOH group. The total rate constant for the •OH radical reaction with both neutral and anionic forms of these two herbicides are relatively high and equal to its diffusion‐limit value. Evaluation of the ecotoxicities of the parent herbicides and their OH adducts is estimated using the structure–activity relationship concept.

Hydrolysis rate constants of ATP up to 120 °C and 1.6 GPa: Implications for life at extreme conditions

Extreme environments are habitats for a diverse array of microorganisms, namely extremophiles, that have evolved unique biochemical adaptations to their geological setting. Some examples of extremophiles can be found in the subseafloor or near hydrothermal vents on the ocean floor. Cultivated strains of extremophiles have demonstrated the ability to tolerate temperatures (T) up to 122 °C and pressures (P) up to 125 MPa. Organisms depend on the stability of key metabolites, such as adenosine triphosphate (ATP), to survive and reproduce under these conditions. In order to maintain their intracellular ATP levels, living cells must compensate for the abiotic hydrolysis of ATP, which occurs at a particularly rapid rate at high temperatures. The role of high pressures and high temperatures in abiotic hydrolysis of ATP has been rarely investigated despite the potential for this phenomenon to contribute to limit the adaptation of microorganisms to simultaneous extreme temperatures and pressures. This study presents new data on the effect of pressure on the abiotic hydrolysis of ATP to adenosine diphosphate (ADP) at elevated temperatures. In situ Raman spectra were measured at high pressure and high temperature of the hydrolysis of aqueous disodium ATP solutions in two experimental systems: a hydrothermal diamond anvil cell (HDAC) and a gas-pressurized autoclave. These two systems permitted the determination of hydrolysis rate constants of ATP into ADP up to 1670 MPa at 80 °C, 100 °C, and 120 °C. The data exhibited Arrhenian behavior with a slight decrease in activation energy from 0.5 MPa to 140 MPa. The effect of pressure on ATP hydrolysis rate constants was found to be vanishingly low in the so far known vital range up to 125 MPa. Abiotic hydrolysis rates of ATP showed a pronounced increase at higher pressures. For example, at 100 °C, a rise in pressure from 365 MPa to approximately 1670 MPa results in a nearly tenfold increase in the ATP hydrolysis rate constant. When compared with the typical ATP turnover times reported in living cells, the abiotic ATP hydrolysis rates determined in this study provide insights into the pressure and temperature conditions that could be consistent with living microorganisms.

Ultrasonic monitoring of enzymatic hydrolysis of proteins. 2. relaxation effects

The paper investigates the occurrence of relaxation processes in enzymatic hydrolysis of whey proteins in phosphate buffer using high-resolution ultrasonic spectroscopy. The hydrolysis produces a frequency-dependent evolution of ultrasonic velocity and attenuation originated by the proton transfer between the phosphate ions and the terminal −NH2 group of protein hydrolysates. Such frequency dependence is absent in other systems, e.g., Tris buffer. Real-time profiles of ultrasonic velocity and attenuation measured during the hydrolysis of β–lactoglobulin, α–lactalbumin and bovine serum albumin by α–chymotrypsin were employed in quantitative analysis of the relaxation mechanisms, relaxation times, determination of the proton transfer rate constants and the reaction volume. The proton transfer is characterised by the rate constant 9.4 × 107 L mol−1 s−1 and the adiabatic reaction volume 24 × 10−6 m3 mol−1. The obtained reaction volume agrees well with thermodynamic data for ionisation volumes and enthalpies of the terminal amino group and phosphate. The described methodology for estimating the relaxation contribution to ultrasonic characteristics allows for precision real-time ultrasonic measurements of the concentration of peptide bonds cleaved during protein hydrolysis in a broad range of environmental conditions.

Performance evaluation of Bi/Zn‐impregnated commercial TiO2 nanoparticles for photocatalytic nitrobenzene decomposition

AbstractBACKGROUNDCommercial TiO2 nanoparticles were subjected to modification through Bi and Zn metal doping. The resulting catalysts were comprehensively characterized, and their performance was then reviewed for removal of model pollutant nitrobenzene in water.RESULTSAmidst the synthesized catalysts, the co‐doping of Bi/Zn (0.25:0.75 wt%) demonstrated the best photocatalytic degradation activity, achieving 95% degradation within 90 min of reaction time, with 2.99 × 10−2 min−1 rate constant value. The involvement of different radicals during the degradation process was elucidated by employing appropriate radical scavengers. Furthermore, the degradation results were investigated applying the first‐order kinetic model, leading to the determination of reaction rate constants and initial rates of the degradation process.CONCLUSIONAn improved photocatalytic activity was observed with metal doping due to the synergistic effect of doped metals with commercial TiO2 and profound charge transfer among them. It was observed that performance was increased with temperature rise in the practical range of application, that is, 5–20 °C. This behavior was due to high rate of movement of charge carriers. Further, involvement and functioning of various radical species such as h+, OH− and O2− in nitrobenzene degradation were successfully established using appropriate radical scavengers. © 2024 Society of Chemical Industry (SCI).

Millistructured Coiled Flow Inverter for Biphasic Continuous Flow 5‐Chloromethylfurfural Synthesis

AbstractSyntheses of alternative platform chemicals, such as 5‐chloromethylfurfural (CMF), from bio‐based starting materials are often associated with complicated kinetic schemes and mass transfer processes. Millistructured flow reactor concepts can help to elucidate kinetic schemes and determine rate constants which are of crucial importance for the design of respective technical processes. For the first time, the influence of proton concentration on the rate constants involved in the biphasic synthesis of CMF is systematically investigated. Results are discussed in terms of green chemistry metrics.

Machine Learning for Experimental Reactivity of a Set of Metal Clusters toward C-H Activation.

Understanding the mechanisms of C-H activation of alkanes is a very important research topic. The reactions of metal clusters with alkanes have been extensively studied to reveal the electronic features governing C-H activation, while the experimental cluster reactivity was qualitatively interpreted case by case in the literature. Herein, we prepared and mass-selected over 100 rhodium-based clusters (RhxVyOz- and RhxCoyOz-) to react with light alkanes, enabling the determination of reaction rate constants spanning six orders of magnitude. A satisfactory model being able to quantitatively describe the rate data in terms of multiple cluster electronic features (average electron occupancy of valence s orbitals, the minimum natural charge on the metal atom, cluster polarizability, and energy gap involved in the agostic interaction) has been constructed through a machine learning approach. This study demonstrates that the general mechanisms governing the very important process of C-H activation by diverse metal centers can be discovered by interpreting experimental data with artificial intelligence.

A DFT study of the antioxidant potency of α-tocopherol and its derivatives: PMHC, Trolox, and α-CEHC

In this research, antioxidant potency (in terms of peroxyl radical scavenging and catalytic iron ions sequestration) of α-tocopherol and its analogues, has been theoretically investigated. A DFT based kinetic estimation of HOO• radical scavenging potency of PMHC (lipophilic α-TOH derivative) and Trolox (hydrophilic α-TOH derivative) was performed in eight solvents of different polarity. Calculations employing M06-2X functional, accompanied by 6-311++G(d,p) basis set and SMD solvation model, were found as more accurate in reproducing experimentally determined rate constants than M05-2X functional. Rate constant of Trolox in pentyl ethanoate also was estimated by using Snelgrove−Ingold equation and Abraham’s β2H solvent parameter. Scavenging of CH3OO• and HOO• radicals, which is influenced by location, orientation, and dynamics of α-TOH and its derivatives in the membrane lipid bilayer, was estimated by using M06-2X functional. Position of α-TOH phenolic OH group is opposite to that of its metabolite α-CEHC: α-TOH’s OH group is located at the membrane-water interface, and α-CEHC’s OH group is deeply buried into the bilayer. In the aqueous phase both fHAT and SET were investigated, and inside the bilayer only fHAT was considered as feasible. The spontaneous disproportionation of HOO•/O2•− in aqueous solutions should be taken into account to predict potency of antioxidant in scavenging of HOO• radicals. Iron chelating ability of α-TOH and α-CEHC was also investigated. Obtained results indicate α-CEHC, α-tocopherol final catabolite, as more potent scavenger of CH3OO• and HOO• radicals and iron ions chelator than the parent molecule.