Kinetic Method Research Articles

Plasma ferritin, C-reactive protein, and adenosine deaminase levels in tuberculous lymphadenitis and pleuritis and their role in monitoring treatment response

BackgroundWe aimed to assess the plasma levels of ferritin, C-reactive protein (CRP), and adenosine deaminase (ADA) at baseline and their utility as biomarkers to monitor response to treatment in extrapulmonary tuberculosis (EPTB) patients.MethodsProspective measurements of ferritin, CRP, and ADA were done in unstimulated plasma samples of 92 EPTB (49 TB lymphadenitis and 43 TB pleuritis) patients registered for anti-TB treatment. Blood samples were taken at the start, 2, and 6 months of treatment, plasma levels of ferritin and CRP were measured by the enzyme-linked immunosorbent assay and ADA levels by kinetic chemistry method at each time point. Data was analyzed using SPSS version 22. Non-parametric tests were used for paired analysis and two groups’ comparison. Spearman’s rank test was used for correlation analysis. A Chi-square test was used for categorical variables. A p-value < 0.05 was considered statistically significant.ResultsBefore the start of treatment, plasma levels of ferritin were raised in 13% and 45%, CRP in 21% and 64%, and ADA in 70% and 60% of TB lymphadenitis and pleuritis cases respectively. Levels of all three biomarkers with raised values at baseline decreased significantly with treatment at both 2 and 6 months in all patients. [Ferritin (2 months p = 0.001, 6 months p < 0.001), CRP (2 months p < 0.001, 6 months p < 0.001), ADA (2 months p = 0.039, 6 months p < 0.004)]. Plasma levels of ferritin (median 300 ng/ml range = 145–758 ng/ml) and CRP (median 11.73 mg/L, range = 10.45–17.84 mg/L) were significantly higher in TB pleuritis patients, while the levels of ADA were not significantly different among the two groups. Biosignatures generated by different combinations showed that a combination of all three biomarkers could predict treatment response in 83% and 100% of all patients at 2 and 6 months of treatment respectively.ConclusionA combination of serum ferritin, CRP, and ADA shows a promising role in monitoring response to treatment in TB lymphadenitis and TB pleuritis patients. Similar studies in larger cohorts are needed to establish a definite role of these biomarkers in EPTB patients.

Study on the thermal hazards of anionic surfactant AES on lignite via experiments and calculations

Spray dust reduction is a commonly used dust reduction method in coal mines and has been widely adopted. However, the thermal stability of coal dust after being wetted by dust suppressants remains unknown. The work aimed to investigate the potential environmental hazards posed by the secondary dust dispersion resulting from the cracking of lump coal dust after being wetted by surfactants and subsequently air-dried. Lignite and AES were used as experimental samples. Use thermodynamic equations to analyze, calculate, and compare the changes in the average apparent activation energy of lignite before and after AES solution wetting. Compared with lignite before AES solution wetting, the combustion characteristic index of lignite decreased by 1.93 % after wetting, and before and after AES solution wetting, the average apparent activation energy of lignite calculated by reaction kinetics methods decreased by 7.6 %, 6.7 %, and 17.1 % respectively. FTIR analysis shows the proportion of aliphatic hydrocarbons in lignite after AES solution wetting has decreased compared with before wetting, and the proportion of oxygen-containing functional groups has shown an upward trend. The work elucidated the complex microscopic mechanisms underlying hazards caused by secondary dust dispersion, providing new scientific evidence for preventing and controlling coal dust explosion accidents.

Ultrafast degradation of Cu(II)-EDTA by peroxymonosulfate activated with polyoxometalate clusters intercalated layered double hydroxides: Simultaneous decomplexation and resourcelization

Technologies used to handle metal pollution are often ineffective for complexed metals, which have refractory biodegradability, high solubility, and strong mobility, posing significant threats to the ecological environment. This work proposed a novel catalytic system for the proper disposal of Cu(II)-EDTA pollution. Polyoxometalate cluster intercalated CaFe layered double hydroxide (LDH-CoPW) prepared through a mild and convenience method was applied to activate peroxymonosulfate (PMS) for the degradation of Cu(II)-EDTA and the simultaneous immobilization of the released Cu(II). Compared to direct waste or complex regeneration of catalysts, the application of used LDH-CoPW in clean energy production was proposed to further reduce carbon emissions. Under the combination of 0.1 g/L of LDH CoPW and 0.1 mM of PMS, nearly 100 % of Cu(II)-EDTA was removed within 3 min of reaction time, and 49.6 % of Cu(II) was adsorbed within 60 min of reaction time. The second-order reaction kinetic constants of Co(IV) = O with various probes were confirmed by competition kinetics method. Based on this, Co(IV) = O was identified as the dominant RSs using a scientific probe-based kinetic model. Furthermore, CaFe-LDH did not directly activate PMS but ensured the reactivity of the catalytic system by promoting the redox cycle of cobalt species. Finally, due to the regulation of Cu on the electronic structure of the catalyst, the electrochemical performance of the used LDH-CoPW surpassed that of fresh LDH-CoPW and CaFe-LDH, showing great potential in clean energy production.

Numerical simulation method for the assessment of the effect of molar activity on the pharmacokinetics of radioligands in small animals

BackgroundIt is well recognized that the molar activity of a radioligand is an important pharmacokinetic parameter, especially in positron emission tomography (PET) of small animals. Occupation of a significant number of binding sites by radioligand molecules results in low radioligand accumulation in a target region (mass effect). Nevertheless, small-animal PET studies have often been performed without consideration of the molar activity or molar dose of radioligands. A simulation study would therefore help to assess the importance of the mass effect in small-animal PET. Here, we introduce a new compartmental model-based numerical method, which runs on commonly used spreadsheet software, to simulate the effect of molar activity or molar dose on the pharmacokinetics of radioligands.ResultsAssuming a two-tissue compartmental model, time-concentration curves of a radioligand were generated using four simulation methods and the well-known Runge–Kutta numerical method. The values were compared with theoretical values obtained under an ultra-high molar activity condition (pseudo-first-order binding kinetics), a steady-state condition and an equilibrium condition (second-order binding kinetics). For all conditions, the simulation method using the simplest calculation yielded values closest to the theoretical values and comparable with those obtained using the Runge–Kutta method. To satisfy a maximum occupancy less than 5%, simulations showed that a molar activity greater than 150 GBq/μmol is required for a model radioligand when 20 MBq is administered to a 250 g rat and when the concentration of binding sites in target regions is greater than 1.25 nM.ConclusionsThe simulation method used in this study is based on a very simple calculation and runs on widely used spreadsheet software. Therefore, simulation of radioligand pharmacokinetics using this method can be performed on a personal computer and help to assess the importance of the mass effect in small-animal PET. This simulation method also enables the generation of a model time-activity curve for the evaluation of kinetic analysis methods.

Prevalence of chronic kidney disease and associated factors among adult diabetic patients: a hospital-based cross-sectional study.

Chronic kidney disease (CKD) has a significant impact on public health with a high morbidity and death rate. Most diabetic patients, in the course of their lives, develop diabetic kidney disease. In the least developed nations, its size is outstripping itself. This study aimed to determine the prevalence of chronic kidney disease and associated factors among adult diabetic patients. A hospital-based cross-sectional study was conducted on 328 adult diabetic patients from 1 December 2023 to 4 April 2024 at the Ayder Comprehensive Specialized Hospital, northern Ethiopia. A systematic random sampling method was utilized to select the study participants. Pretested structured questionnaires were used to collect sociodemographic, economic, and behavioral/lifestyle factors. Medical records were also reviewed to collect clinical data. Creatinine analysis was performed by kinetic alkaline picrate method and Chronic Kidney Disease Epidemiology Collaboration 2021 equation was used to calculate the glomerular filtration rate from the serum creatinine, age, and sex. Proteinuria was determined by using the dipstick semiquantitative method. Data were entered and analyzed using SPSS version 29. A variable with a p-value of <0.25 in bivariate logistic regression analyses was analyzed in multivariate logistic regression to identify the associated factors. In multivariable logistic regression, a variable was deemed statistically significant if it had a p-value <0.05. Associations were presented as odds ratio (OR) along with 95% confidence intervals (CIs). The prevalence of chronic kidney diseases in adult diabetic patients was 26.5% (95% CI, 21.8%-31.7%). About 5.2%, 12.5%, 7.3%, 0.9%, and 0.6% had stage 1-5 chronic kidney diseases, respectively. Hypertension [adjusted OR (AOR) = 2.390; 95% CI, 1.394-4.099, p = 0.002], >10-year duration of diabetes (AOR = 2.585; 95% CI, 2.321-5.807; p = 0.001), and family history of kidney diseases (AOR = 2.884; 95% CI, 1.338-6.218; p = 0.007) were associated factors of chronic kidney diseases. The study revealed that one in four diabetic patients had chronic kidney disease. Special attention should be given to patients with family history of CKD, long duration on diabetes, and concomitant hypertension.

Investigating the Impact of Nano‐Metal Oxides (Copper and Iron) on the Thermal Decomposition Behavior of Advanced Propellants with Nitrocellulose/Polyurethane Binders

AbstractThis research delves into the combined effects of green nano metal oxides (copper and iron) and polyurethane (PU) modification on the thermal degradation kinetics of propellant based on solid ammonium nitrate composite modified simple base (CMSB). Surface modification of ammonium nitrate particles was achieved through repeated spray coating, ensuring effective catalyst binding. The formulated compositions of propellants underwent thorough thermal characterization, including thermogravimetric (TG) and differential scanning calorimetry (DSC) analyses. TG analysis revealed a significant decrease in the propellant's thermal degradation temperature, attributed to AN modification with nano metal oxides (nMOs) and the use of PU/NC as a binder. Isoconversional kinetic methods (It‐KAS, It‐FWO, and VYA/CE) were employed for further analysis, allowing prediction of kinetic parameters. Additionally, kinetic analysis results allowed calculation of the critical ignition temperature. The thermokinetic results underscore the substantial impact of nMOs particles and PU modification regarding the reactivity and catalytic performance of propellant containing ammonium nitrate, leading to a noteworthy reduction in activation energy and critical ignition temperature. Furthermore, modifying the binder with nitrocellulose and incorporating nanoparticles significantly reduces ignition delay and combustion duration while increasing flame intensity in CMDB solid propellants, enhancing overall combustion efficiency.

Elucidating high-pressure chemistry in acetylene oxidation: Jet-stirred reactor experiments, pressure effects, and kinetic interpretation

Acetylene plays a crucial role as an intermediate in the combustion of complex hydrocarbons, such as, e.g., jet fuels. In this study, high-pressure acetylene oxidation has been investigated by a combination of kinetic and experimental methods using a jet-stirred reactor (JSR) in the range of 497–910 K at p = 24 atm. The study covered three fuel-equivalence ratios: φ = 0.5 (fuel-lean), φ = 1.0 (stoichiometric), and φ = 3.0 (fuel-rich). Mole fraction profiles of 10 species, including CO, CO2, CH4, C2H4, C2H6, C3H6, C3H8, CH3OH, CH3CHO, and C3H4O, were identified and quantified using gas chromatography (GC) and gas chromatography-mass spectrometry (GC–MS). A kinetic model for describing the high-pressure chemistry of acetylene oxidation is proposed, which well characterizes important experimental findings, such as the fuel oxidation reactivity and the speciation of crucial products. At high pressures (p = 24 atm), acetylene exhibits a higher fuel consumption than at lower pressures (p = 1 and 12 atm) because of the increased sensitivity of dehydrogenation reactions by OH radicals accelerating the oxidation of the fuel at low temperatures. Furthermore, fuel-specific intermediates are observed, including acetaldehyde, propanal, small alkanes, and alkenes. These species mainly result from H-abstraction reactions by OH following O2-addition reactions from triple carbon bond moieties in acetylene. The formation of further products, such as carbon monoxide and carbon dioxide, is closely related to the consumption of these fuel-specific species. In particular, the formation of aromatics, such as e.g., benzene and toluene, are detected at trace levels in the current experiments due to the rapid formation and decomposition process occurring at high pressures. By analyzing the distinct kinetic behavior, it was found that acetylene was almost completely depleted at higher system pressure (p = 24 atm). Some intermediates are rather active and can react with O2 and peroxides. Consequently, the high-pressure oxidation of acetylene mainly proceeds along the pathway of CC → CHCHOH → HOCHO/OCHCHO → CO → CO2 at the high-pressure chemistry (p = 24 atm). Overall, this study provides valuable insights into the pressure-dependent combustion behavior of acetylene and its implications for optimizing jet fuel combustion processes.

The homodimerization domain of the Stl repressor is crucial for efficient inhibition of mycobacterial dUTPase

The dUTPase is a key DNA repair enzyme in Mycobacterium tuberculosis, and it may serve as a novel promising anti-tuberculosis target. Stl repressor from Staphylococcus aureus was shown to bind to and inhibit dUTPases from various sources, and its expression in mycobacterial cells interfered with cell growth. To fine-tune and optimize Stl-induced inhibition of mycobacterial dUTPase, we aimed to decipher the molecular details of this interaction. Structural background of the complex between dUTPase and a truncated Stl lacking the repressor C-terminal homodimerization domain has been described, however, the effects of this truncation of Stl on enzyme binding and inhibition are still not known. Using several independent biophysical, structural and enzyme kinetic methods, here we show that lack of the repressor homodimerization domain strongly perturbs both enzyme binding and inhibition. We also investigated the role of a mycobacteria-specific loop in the Stl-interaction. Our results show that removal of this loop leads to a ten-fold increase in the apparent inhibition constant of Stl. We present a high-resolution three-dimensional structure of mycobacterial dUTPase lacking the genus-specific loop for structural insight. Our present data suggest that potent inhibition of mycobacterial dUTPase by Stl requires the wild-type full-length protein context.

Limitation of summer extreme high temperatures on radial growth relieve with increasing latitude in subtropics

Global warming has induced an increase in the intensity and frequency of summer extreme high temperature events in Chinese subtropical forest, which contributes to a large component of net primary ecological production among global forests. However, how summer extreme high temperature events would influence tree radial growth in these humid subtropical forest remains unclear. We investigated the non-linear response of tree radial growth to temperature, soil moisture and their mixed effect across broad latitude gradients in Chinese subtropical forests, using a method of modelling cambial growth kinetics of Schima superba. The results showed that radial growth was constrained by summer extreme high temperatures and this limiting effect relieved from south to north. However, we also found a growth constraint imposed by soil moisture during spring and autumn, which intensified toward northern sites. Coincidentally, the radial growth pattern showed a distinct transition from bimodal to unimodal from South to North sites, with no significant changes in cambium phenology over the time scale from 1986 to 2014 being observed. In general, we determined that limitation of extreme high temperatures on radial growth relieve with increasing latitude in subtropics. This study provides a theoretical basis for promoting the accurate assessment of carbon sink potential and for predicting future forest dynamics in subtropics.

Model-predictive kinetic control with data-driven models on EAST

Abstract In this work, model-predictive control (MPC) was combined for the first time with singular perturbation theory, and an original plasma kinetic control method based on extremely simple data-driven models and a two-time-scale MPC algorithm has been developed. A comprehensive review is presented in this paper. Slow and fast semi-empirical models are identified from data, by considering the fast kinetic plasma dynamics as a singular perturbation of a quasi-static equilibrium, which itself is governed, on the slow time scale, by the flux diffusion equation. This control technique takes advantage of the large ratio between the time scales involved in magnetic and kinetic plasma transport. It is applied here to the simultaneous control of the safety factor profile, q(x), and of several kinetic variables, such as the poloidal beta parameter, βp, and the internal inductance parameter, li, on the EAST tokamak. In the experiments, the available control actuators were lower hybrid current drive (LHCD) and co-current neutral beam injection (NBI) from different sources. Ion cyclotron resonant heating (ICRH) and electron cyclotron resonant heating (ECRH) are used as additional actuators in control simulations. In the controller design, an observer provides, in real time, an estimate of the system states and of the mismatch between measured and predicted outputs, which ensures robustness to model errors and offset-free control. A number of control applications are described in the paper, either in nonlinear simulations with EAST-like parameters or in real experiments on EAST. Various controller configurations were tested, with up to three controlled variables chosen among q0 = q(x=0), q1 = q(x=0.5), βp and li. Both the extensive nonlinear simulations and the experiments described in this paper have demonstrated the relevance of combining model-predictive control, data-driven models and singular perturbation methods for plasma kinetic control.

Kinetic Modeling of Brilliant Blue Discoloration by Ozonation

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

Kinetic Bacterial Endotoxin Testing Methods: Specifics of Analytical Conditions Exemplified by Medicinal Products from Different Classes

INTRODUCTION. Kinetic bacterial endotoxin (BE) testing methods based on amoebocyte lysate from the haemolymph of the horseshoe crab can quantify BEs in parenteral medicinal products across a broad range of concentrations. To develop a specific analytical procedure that is based on these methods and can be implemented into pharmaceutical quality control and standardisation, it is required to ascertain the conditions for its use, in particular, to determine the lowest product dilution that would neutralise interfering factors.AIM. This study aimed to develop an analytical procedure for the quantitative determination of BEs by the kinetic chromogenic method.MATERIALS AND METHODS. The study examined samples of medicinal products containing active substances from different classes, including a monoclonal antibody (mepolizumab) and a direct-acting anticoagulant (nadroparin). The BE limits for mepolizumab and nadroparin were ≤20 EU/mL and ≤95 EU/mL, respectively. The samples were tested at different dilutions, which did not exceed the maximum valid dilution. The measurements were performed using a BioТek EL×800 photocolourimeter and EndoScan-V software.RESULTS. The results for mepolizumab samples show that the kinetic chromogenic method can quantify BEs in mepolizumab medicinal products in the dilution range of 1:10 to 1:40. The study detected BEs in quantities of 0.0078–0.224 EU/mL within this dilution range. However, at a dilution ratio of 1:50 or higher, the method is suitable only for qualitative BE tests. For nadroparin medicinal products, the quantitative determination of BEs should start at a dilution of 1:1000 (the study demonstrated no influence of interfering factors at this dilution).CONCLUSIONS. The authors developed analytical procedures for the determination of BEs in mepolizumab and nadroparin medicinal products by the kinetic chromogenic method (method D). When developing analytical procedures for the quantification of BEs in individual medicinal products, the developer should determine the lowest sample dilution that would neutralise interfering factors. Subsequently, the dilution should be specified in the documentation for the analytical procedure. This approach can enhance assay accuracy and save time and resources in routine testing.

A practical guide for the assay-dependent characterisation of irreversible inhibitors.

Irreversible targeted covalent inhibitors, in the past regarded as inappropriately reactive and toxic, have seen a recent resurgence in clinical interest. This paradigm shift is attributed to the exploitation of the two-step mechanism, in which a high affinity and selectivity (i.e., low K I) scaffold binds the target and only then does a pendant low intrinsic reactivity warhead react with the target (moderate k inact). This highlights the importance of evaluating inhibitors by deriving both their K I and k inact values. The development of methods to evaluate these inhibitors by accounting for their time-dependent nature has been crucial to the discovery of promising clinical candidates. Herein, we report all the practical kinetic methods available to date to derive k inact and K I values. These methods include direct observation of covalent modification, continuous assay (Kitz & Wilson) evaluation, and discontinuous incubation and pre-incubation time-dependent IC50 assays. We also provide practical guidelines and examples for performing these assays, comparison of their utility, and perspectives for their extended applications. This review aims to provide clarity about the use of these methods for reporting complete inhibitor kinetic profiles, guiding irreversible drug development towards increased target affinity and selectivity, while modulating in vivo stability and on-target reactivity.

Dye-Decolorizing Peroxidases Maintain High Stability and Turnover on Kraft Lignin and Lignocellulose Substrates.

Fungal enzyme systems for the degradation of plant cell wall lignin, consisting of, among others, laccases and lignin-active peroxidases, are well characterized. Additionally, fungi and bacteria contain dye-decolorizing peroxidases (DyP), which are also capable of oxidizing and modifying lignin constituents. Studying DyP activity on lignocellulose poses challenges due to the heterogeneity of the substrate and the lack of continuous kinetic methods. In this study, we report the kinetic parameters of bacterial DyP from Amycolatopsis 75iv2 and fungal DyP from Auricularia auricula-judae on insoluble plant materials and kraft lignin by monitoring the depletion of the cosubstrate of the peroxidases with a H2O2 sensor. In the reactions with spruce, both enzymes showed similar kinetics. On kraft lignin, the catalytic rate of bacterial DyP reached 30 ± 2 s-1, whereas fungal DyP was nearly 3 times more active (81 ± 7 s-1). Importantly, the real-time measurement of H2O2 allowed the assessment of continuous activity for both enzymes, revealing a previously unreported exceptionally high stability under turnover conditions. Bacterial DyP performed 24,000 turnovers of H2O2, whereas the fungal DyP achieved 94,000 H2O2 turnovers in 1 h with a remaining activity of 40 and 80%, respectively. Using mass spectrometry, the depletion of the cosubstrate H2O2 was shown to correlate with product formation, validating the amperometric method.

Assessing Drug Product Shelf Life Using the Accelerated Stability Assessment Program: A Case Study of a GLPG4399 Capsule Formulation.

Objective: To evaluate and project the shelf life of GLPG4399, an early-phase clinical drug formulation by applying the Accelerated Stability Assessment Program (ASAP) approach. Methods: Forced degradation conditions were implemented to identify the stability-limiting degradation product. The drug and its degradation products were separated using a validated liquid chromatography method. Then, the selected clinical capsule formulation was placed in a glass vial and exposed to accelerated short-term conditions of combinations of high- and low-level heat and humidity in an open state for 5 weeks. The liquid chromatography results were evaluated using the ASAP, which is based on the moisture-modified Arrhenius principle. The resulting data were fitted using a suitable diffusion kinetics method. Results: The developed model was applied to predict the shelf life of the drug product when using clinically appropriate primary packaging (high-density polyethylene container). The derived stability parameters of the moisture-modified Arrhenius equation were the Arrhenius collision frequency, activation energy, and humidity sensitivity constant. The goodness of fit parameters R2 (>0.95) and goodness of prediction Q2 (>0.80) parameters for the selected model were acceptable. The results of the accelerated, short-term stability study were verified against real-time, long-term 12-month data. Conclusions: We demonstrated the application of the ASAP approach to evaluate the shelf life of a GLPG4399 solid capsule formulation. The studied ASAP approach can be extended to evaluate the stability and shelf-life estimations of other early-phase clinical formulations.

Kinetic, Spectral and Mechanistic Regularities of New Reaction Systems With Chromogenic SN2‐Type Reaction for Detection of Epoxy Compounds

ABSTRACTNew reaction systems “oxirane – nucleophile X– – proton‐donor reagent AH – solvent” have been proposed for the detection of epoxides in which nucleophilic opening of the oxirane ring occurs accompanied by the formation of a colored product. The kinetic and mechanistic regularities of reactions in the proposed systems were investigated. Reaction orders with respect to the components of the systems have been determined: close to 1 – for oxirane and X−, close to 0 – for AH. It was shown that the proposed chromogenic reactions represent nucleophilic substitution of SN2‐type and allow the detection of epoxides containing both a terminal and internal epoxy group, which can be used to monitor processes in systems where epoxides are either the initial compounds or the synthesis products. Based on the conducted studies, it is possible to develop methods for the quantitative determination of epoxides using kinetic methods of analysis and UV–visible spectroscopy.

A Nonlinear Approach in the Quantification of Numerical Uncertainty by High-Order Methods for Compressible Turbulence with Shocks

This is a comprehensive overview on our research work to link interdisciplinary modeling and simulation techniques to improve the predictability and reliability simulations (PARs) of compressible turbulence with shock waves for general audiences who are not familiar with our nonlinear approach. This focused nonlinear approach is to integrate our “nonlinear dynamical approach” with our “newly developed high order entropy-conserving, momentum-conserving and kinetic energy-preserving methods” in the quantification of numerical uncertainty in highly nonlinear flow simulations. The central issue is that the solution space of discrete genuinely nonlinear systems is much larger than that of the corresponding genuinely nonlinear continuous systems, thus obtaining numerical solutions that might not be solutions of the continuous systems. Traditional uncertainty quantification (UQ) approaches in numerical simulations commonly employ linearized analysis that might not provide the true behavior of genuinely nonlinear physical fluid flows. Due to the rapid development of high-performance computing, the last two decades have been an era when computation is ahead of analysis and when very large-scale practical computations are increasingly used in poorly understood multiscale data-limited complex nonlinear physical problems and non-traditional fields. This is compounded by the fact that the numerical schemes used in production computational fluid dynamics (CFD) computer codes often do not take into consideration the genuinely nonlinear behavior of numerical methods for more realistic modeling and simulations. Often, the numerical methods used might have been developed for weakly nonlinear flow or different flow types other than the flow being investigated. In addition, some of these methods are not discretely physics-preserving (structure-preserving); this includes but is not limited to entropy-conserving, momentum-conserving and kinetic energy-preserving methods. Employing theories of nonlinear dynamics to guide the construction of more appropriate, stable and accurate numerical methods could help, e.g., (a) delineate solutions of the discretized counterparts but not solutions of the governing equations; (b) prevent numerical chaos or numerical “turbulence” leading to FALSE predication of transition to turbulence; (c) provide more reliable numerical simulations of nonlinear fluid dynamical systems, especially by direct numerical simulations (DNS), large eddy simulations (LES) and implicit large eddy simulations (ILES) simulations; and (d) prevent incorrect computed shock speeds for problems containing stiff nonlinear source terms, if present. For computation intensive turbulent flows, the desirable methods should also be efficient and exhibit scalable parallelism for current high-performance computing. Selected numerical examples to illustrate the genuinely nonlinear behavior of numerical methods and our integrated approach to improve PARs are included.

BIOCHEMICAL PROFILE OF BLOOD IN HORSES DETECTED SUFFERING FROM SURRAIN EAST SUMBA, EAST NUSA TENGGARA, INDONESIA

The infectious animal disease known as surra, or trypanosomiasis in animals, is caused by Trypanosoma evansi.In Indonesia, surra has been recognized as a strategic infectious disease affecting animals. East Nusa Tenggara Province, identified as a center of livestock farming in Indonesia, is also known as an endemic area for surra and requires attention. Therefore, this study was aimed to determine the biochemical profile of blood in horses infected with T. evansi in East Sumba Regency. The parameters observed included blood glucose levels, total protein, creatinine, alanine transaminase (ALT), and aspartate transaminase (AST). Samples were collected from horses raised by the community in East Sumba Regency. The biochemicalexamination was performed using the Photometer 5010V5+ instrument.Blood glucose was examined usingGOD-PAP deproteinization method; totalprotein was determined using a photometry colorimetric test; creatinine was carried using the Jaffe-fixed time kinetic method; ALT and AST were performed using the kinetic method; and UV Test. The results showed that the average biochemical profile of blood in Sumba horses infected with T. evansi was glucose (68.17±5.11mg/dL); protein (5.417±1.82g/dL); creatinine (1.74±0.39mg/dL); urea (28.93±6.26mg/dL); AST (357.00±117.02U/L); and ALT (20.17±6.30U/L). Meanwhile, the average blood biochemical profile in Sumba horses not infected with T. evansi was glucose (99.00±14.96mg/dL); protein (7.20±1.72g/dL); creatinine (1.55±0.51mg/dL);urea (28.13±6.88mg/dL); AST (312.83±94.42U/L); and ALT (23.33±9.45U/L). Blood glucose levels in horsesinfected with T. evansiwere significantly lower (P&lt;0.01) compared to non-infected horses. Apart from blood glucose levels, all observed parameters were in normal ranges.

Gas phase proton affinities of proline-containing peptides. 1: ProGly, ProAla, ProVal, ProLeu, ProIle, and ProPro

The gas-phase proton affinities (PA) for a series of proline-containing dipeptides have been measured in an ESI triple quadrupole instrument using the extended kinetic method. Proton affinities for ProGly (1), ProAla (2), ProVal (3), ProLeu (4), ProIle (5), and ProPro (6) were determined to be 969.6 ± 7.8, 990.4 ± 7.7, 987.6 ± 7.9, 982.8 ± 8.0, 988.8 ± 10.1, and 996.5 ± 12.2 kJ/mol, respectively. Predictions for the proton affinities for 1–6 were also obtained through isodesmic calculations at the B3LYP/6-311++G(d,p)//B3LYP/6-31+G(d) level of theory. The predicted proton affinities for 1 and 6 of 966.9 and 991.0 kJ/mol are in agreement with the experimental values. However, the predicted proton affinities for 2–5 of 973.5, 975.9, 975.7, and 975.9 are between 8 and 15 kJ/mol lower than the experimental values. Additional calculations with a larger basis set (B3LYP/6-311++G(2df,2p), inclusion of dispersion (B3LYP-D3/6-311++G(d,p)), switching to second order perturbation theory (MP2/6-31++G(d,p) and MP2/6-311++G(2df,2p), or switching density functional (M06-2x/6-311++G(d,p) and M06-2x/6-311++G(2df,2p) show only modest changes in derived thermochemistry lending support to the original calculations. We recommend using the experimental proton affinities for ProGly and ProPro and using the calculated values for ProAla, ProVal, ProLeu, and ProIle with the experimental proton affinities as upper limits.

Enhanced organic aerosol formation induced by inorganic aerosol formed in laboratory photochemical experiments

Atmospheric inorganic gases such as NOx, SO2, and NH3 have diverse effects on the formation of secondary organic aerosol (SOA). A comprehensive investigation is necessary to fully understand the atmospheric processing of SOA. In this study, we examined the photooxidation of xylene isomers in the presence of inorganic gases using a combined facility comprising a smog chamber (SC) and an oxidation flow reactor (OFR). SC experiments at higher xylene concentrations and humid conditions revealed SOA yields of 37%, 39%, and 39% with NH3, compared to 15%, 11%, and 13% without NH3, for o-, m-, and p-xylene, respectively. This increase was primarily attributed to the enhanced formation of secondary inorganic aerosol (SIA) in the presence of NH3, consequently increasing aerosol surface area and aerosol water content (AWC). Vapor wall losses (VWL), estimated using a kinetic method, were substantial even with the elevated aerosol surface area provided by SIA. Additional photochemical reactions in the OFR showed a gradual increase in SOA mass and yield over an atmospheric equivalent aging time of 0.5–4.0 days. In the OFR, the SOA yield increased significantly when negligible xylene remained after SC reactions. Fresh SOA formation in the OFR might have decreased the oxygen-to-carbon ratio and oxidation state of carbon, which gradually increased with increasing OFR aging. High OH radical exposure in the OFR likely caused the photodegradation of SC-formed ON, as evidenced by an abrupt decrease in the NO+/NO2+ ratio measured. This study indicates that SOA formation potential of the aromatic hydrocarbon is highly underestimated without considering the combined effects of inorganic gases along with aging.