Rate Equations Research Articles

Application of improved glomerular filtration rate estimation by a neural network model in patients with neurogenic lower urinary tract dysfunction.

Previous studies have indicated that creatinine (Cr)-based glomerular filtration rate (GFR) estimating equations - including the new Chronic Kidney Disease Epidemiology creatinine (CKD-EPIcr) equation without race and the estimated glomerular filtration rate (eGFR) equation developed for the Chinese population - displayed suboptimal performance in patients with neurogenic lower urinary tract dysfunction (NLUTD), which limited their clinical application for detecting changes in GFR levels in all cohorts. To develop a neural network model based on multilayer perceptron (MLP) for evaluating GFR in Chinese NLUTD patients, and compare the diagnostic performance with Cr-based multiple linear regression equations for Chinese and the CKD-EPIcr equation without race. Single-center, cross-sectional study of GFR estimation from serum Cr, demographic data, and clinical characteristics in Chinese patients with NLUTD. A total of 204 NLUTD patients, from 27 different geographic regions of China, were selected. A random sample of 141 of these subjects was included in the training sample set, and the remaining 63 patients were included in the testing sample set. The reference GFR (rGFR) was assessed by the technetium-99m-labeled diethylenetriaminepentaacetic acid (99mTc-DTPA) double plasma sample method. A neural network model based on MLP was developed to evaluate GFR in the training sample set, which was then validated in the testing sample set and compared with Cr-based GFR equations. The MLP-based model showed significant performance improvement in evaluating the difference, absolute difference, precision, and accuracy of GFR estimation compared with the Cr-based GFR equations. Additionally, compared with the rGFR, we found that the MLP-based model provided an acceptable level of accuracy (greater than 85%, which was within a 30% deviation from the rGFR). The MLP-based model offered significant advantages in estimating GFR in Chinese NLUTD patients, and its application could be suggested in clinical practice.

Representative rupture stress-based parameter for characterizing the intensity of creep fracture constraint effect on creep crack growth rate

The introduction of creep fracture constraint parameter offers the possibility of accurately obtaining the CCG rate for specimens/structures subject to different constraint levels through the establishment of constraint-dependent CCG rate equation. However, experimental evidence indicates that the existing constraint-dependent CCG rate equation is generally material- and stress regime-dependent. It is noted that the dependencies may be attributed to the intrinsic difference in creep failure mechanisms of materials, which has not been fully considered by previous constraint parameters. To cope with the dependencies, a parameter, Kz, for characterizing the intensity of constraint effect is proposed in this work based on the representative rupture stress, which could better reflect the operative creep failure mechanism sustained by the material. To justify the parameter, finite element analysis is carried out for five different materials based on experimental data available in the literature. Results show that, compared to the existing constraint parameters, R* and Ac, the Kz is capable of characterizing the crack-tip constraint level under the influence of creep failure mechanism. Furthermore, a generalized constraint-dependent CCG rate equation is established based on the Kz, which overcomes the material and stress regime dependencies of the existing equation. Finally, to clarify the advantage of the Kz, further comparison between the new parameter and the existing parameters is made.

Design and simulation implementation of bismuth-doped fiber laser

Rare-earth doped fibers are an important means of expanding the wavelength band of optical fibers. Currently, researchers aim to broaden the working wavelength band of optical fibers by doping with different rare-earth elements, thereby increasing the amount of information that can be transmitted. In this paper, a bismuth-doped fiber laser operating around 1300nm was designed. A basic physical model for implementing a bismuth-doped fiber laser was proposed based on the energy levels and transition processes of bismuth, rate, and power propagation equations. It was possible to determine the link between pump power and laser power at a wavelength of 1300 nm by modeling tests using the physical model. Additionally, the relationship between pump light and laser power in bismuth-doped fiber at different positions and propagation directions was analyzed. Suggestions for the future large-scale application of bismuth-doped fiber lasers around the 1300nm wavelength band were provided.

A Kinetic and Mechanistic Study of Ir (III)-Catalyzed Oxidation of Methionine by HCF (III) in an Aqueous Alkaline Medium

Introduction: The kinetic study of Ir (III) chloride-catalyzed oxidation of methionine by hexacyanoferrate (abbreviated as HCF) III ions in aqueous alkaline medium was performed spectrophotometrically at constant ionic strength of 0.5 moldm-3 and temperature of 35±0.10C. Method: The progress of the reaction was found to be first-order rate dependence kinetics with respect to [HCF (III)], [OH-], and [IrCl3]. The rate of reaction was found to decrease with an increased concentration of methionine. The ionic strength of the reaction mixture showed a positive salt effect on the reaction rate. Different activation parameters were also evaluated by studying the reaction at four different temperatures. The stoichiometry of the reaction showed Methionine: HCF (III) = 1:4. Result: The oxidation product of the reaction was found to be methionine sulphone, which was identified by an organic solvent method and IR Spectroscopy. Further, a suitable mechanism was proposed to explain all the experimental results. Conclusion: It is assumed that the reaction proceeded through complex formation between substrate (abbreviated) and iridium trichloride. A rate law was derived, which verified the results. CH3-S-(CH2)2-CH (NH2)-COO- + 4HCF (III) Ir (III), H2O CH3-SO2-(CH2)2-CH- (NH2)-COO- + 4HCF (II) result: 1.Methionine sulphone was found to be the main product of oxidation was identified using an organic solvent method and IR Spectroscopy. A suitable mechanism has been proposed to explain all the experimental results. It is assumed that reaction proceeds through complex formation between substrate (abbreviated) and iridium trichloride. A rate law has been derived which verifies the results. CH3 –S-(CH2)2-CH (NH2) – COO- + 4HCF (III) □(→┴(Ir(III),H2O) ) CH3-SO2-(CH2)2-CH (NH2)-COO- + 4HCF (II) 2. Degradation kinetic is anticipated to follow the first order kinetics at lower concentration. 3. The catalytic system can be recycled and reused without loss of activity. 4. The anticipated easy recovery of catalyst from the reaction mixture shows another positive signigficance.

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.

#717 Recipient/donor characteristics and immunosuppression impact eGFR creatinine and creatinine-cystatin c equations in kidney transplant recipients

Abstract Background and Aims Previous studies have shown substantial heterogeneity in the performance of estimated glomerular filtration rate (eGFR) equations when applied to kidney transplant recipients (KTRs). The impact of transplantation-related characteristics on eGFR equations based on creatinine (eGFRcr) compared with creatinine and cystatin C (eGFRcr-cys), however, remains insufficiently studied. Method We analyzed 596 KTRs transplanted at the University Hospital Zurich. The accuracies of four eGFRcr equations (CKD-EPI 2009 and 2021, EKFC 2021, KRS-GFR 2023) were compared with three eGFRcr-cys (CKD-EPI 2012 and 2021, EKFC 2023), and evaluated across a detailed range of transplantation-related variables. Performances were assessed using bias, P30, P20 and correct classification (CC). Multivariate analysis identified transplantation-related characteristics independently associated with a smaller or greater difference between eGFRcr and eGFRcr-cys equations. Results Based on eGFRcr-cys CKD-EPI 2012 as the reference, CKD-EPI 2021 (P30: 77.0%, P20: 56.4%, CC: 56.4%) and KRS-GFR 2023 (P30: 80.2%, P20: 64.9%, CC: 60.1%) had lower performance, while EKFC 2021 (P30: 88.6%, P20: 75.8%, CC: 66.8%), and CKD-EPI 2009 (P30: 87.1%, P20: 70.3%, CC: 64.6%) showed higher performance. Belatacept use was associated with a smaller difference between eGFRcr CKD-EPI 2009 and eGFRcr-cys CKD-EPI 2012 (OR 3.295, 1.605-6.764, p = 0.001), while a higher donor BMI was associated with a greater difference between eGFRcr KRS-GFR 2023 and eGFRcr-cys CKD-EPI 2012 (OR 1.077, 1.001-1.158, p = 0.046). Conclusion More recent eGFRcr equations do not overcome the limitations of non-GFR determinants of creatinine in KTRs, however European equations seem to be equally feasible in transplanted patients. Transplantation-related characteristics of the recipient, donor, and immunosuppressive medication affect the differences between eGFRcr and eGFRcr-cys, which needs attention in clinical practice.

Removal of reactive black 5 in water using adsorption and electrochemical oxidation technology: kinetics, isotherms and mechanisms

AbstractIn this work, a novel graphite intercalation compound (GIC) particle electrode was used to investigate the adsorption of Reactive Black 5 (RB5) and the electrochemical regeneration in a three-dimensional (3D) electrochemical reactor to recover its adsorptive capacity. Various adsorption kinetics and isotherm models were used to characterise the adsorption behaviour of GIC. Several adsorption kinetics were modelled using linearised and non-linearised rate laws to evaluate the viability of the sorption process. Studies on the selective removal of RB5 dyes from binary mixture in solution were evaluated. RSM optimisation studies were integrated with ANOVA analysis to provide insight into the significance of selectivity reversal from the salting effect of textile dye solution on GIC adsorbent. A unique range of adsorption kinetics and isotherms were used to evaluate the adsorption process. Non-linear models best simulated the kinetic data in the order: Elovich > Bangham > Pseudo-second-order > Pseudo-first-order. The Redlich–Peterson isotherm was calculated to have a dye loading capacity of 0.7316 mg/g by non-linear regression analysis. An error function analysis with ERRSQ/SSE of 0.1390 confirmed the accuracy of dye loading capacity predicted by Redlich–Peterson isotherm using non-linear regression analysis. The results showed that Redlich–Peterson and SIPS isotherm models yielded better fitness to experimental data than the Langmuir type. The best dye removal efficiency achieved was ~ 93% using a current density of 45.14 mA/cm2, whereas the highest TOC removal efficiency achieved was 67%.

Facile Access to Organostibines via Selective Organic Superbase Catalyzed Antimony‐Carbon Protonolysis

The selective formation of antimony‐carbon bonds via organic superbase catalysis under metal‐ and salt‐free conditions is reported. This novel approach utilizes electron‐deficient stibine, Sb(C6F5)3, to give upon base‐catalyzed reactions with weakly acidic aromatic and heteroaromatic hydrocarbons access to a range of new aromatic and heteroaromatic stibines, respectively, with loss of C6HF5. Also, the significantly less electron‐deficient stibines, Ph2SbC6F5 and PhSb(C6F5)2 smoothly underwent base‐catalyzed exchange reactions with a range of terminal alkynes to generate the stibines of formulae PhSb(C≡CPh)2, and Ph2SbC≡CR [R = C6H5, C6H4‐NO2, COOEt, CH2Cl, CH2NEt2, CH2OSiMe3, Sb(C6H5)2], respectively. These formal substitution reactions proceed with high selectivity as only the C6F5 groups serve as a leaving group to be liberated as C6HF5 upon formal proton transfer from the alkyne. Kinetic studies of the base‐catalyzed reaction of Ph2SbC6F5 with phenyl acetylene to form Ph2SbC≡CPh and C6HF5 suggested the empirical rate law to exhibit a first‐order dependence with respect to the base catalyst, alkyne and stibine. DFT calculations support a pathway proceeding via a concerted σ‐bond metathesis transition state, where the base catalyst activates the Sb‐C6F5 bond sequence through secondary bond interactions.

Facile Access to Organostibines via Selective Organic Superbase Catalyzed Antimony-Carbon Protonolysis.

The selective formation of antimony-carbon bonds via organic superbase catalysis under metal- and salt-free conditions is reported. This novel approach utilizes electron-deficient stibine, Sb(C6F5)3, to give upon base-catalyzed reactions with weakly acidic aromatic and heteroaromatic hydrocarbons access to a range of new aromatic and heteroaromatic stibines, respectively, with loss of C6HF5. Also, the significantly less electron-deficient stibines, Ph2SbC6F5 and PhSb(C6F5)2 smoothly underwent base-catalyzed exchange reactions with a range of terminal alkynes to generate the stibines of formulae PhSb(C≡CPh)2, and Ph2SbC≡CR [R = C6H5, C6H4-NO2, COOEt, CH2Cl, CH2NEt2, CH2OSiMe3, Sb(C6H5)2], respectively. These formal substitution reactions proceed with high selectivity as only the C6F5 groups serve as a leaving group to be liberated as C6HF5 upon formal proton transfer from the alkyne. Kinetic studies of the base-catalyzed reaction of Ph2SbC6F5 with phenyl acetylene to form Ph2SbC≡CPh and C6HF5 suggested the empirical rate law to exhibit a first-order dependence with respect to the base catalyst, alkyne and stibine. DFT calculations support a pathway proceeding via a concerted σ-bond metathesis transition state, where the base catalyst activates the Sb-C6F5 bond sequence through secondary bond interactions.

An encompassed representation of timescale hierarchies in first-order reaction network

Complex networks are pervasive in various fields such as chemistry, biology, and sociology. In chemistry, first-order reaction networks are represented by a set of first-order differential equations, which can be constructed from the underlying energy landscape. However, as the number of nodes increases, it becomes more challenging to understand complex kinetics across different timescales. Hence, how to construct an interpretable, coarse-graining scheme that preserves the underlying timescales of overall reactions is of crucial importance. Here, we develop a scheme to capture the underlying hierarchical subsets of nodes, and a series of coarse-grained (reduced-dimensional) rate equations between the subsets as a function of time resolution from the original reaction network. Each of the coarse-grained representations guarantees to preserve the underlying slow characteristic timescales in the original network. The crux is the construction of a lumping scheme incorporating a similarity measure in deciphering the underlying timescale hierarchy, which does not rely on the assumption of equilibrium. As an illustrative example, we apply the scheme to four-state Markovian models and Claisen rearrangement of allyl vinyl ether (AVE), and demonstrate that the reduced-dimensional representation accurately reproduces not only the slowest but also the faster timescales of overall reactions although other reduction schemes based on equilibrium assumption well reproduce the slowest timescale but fail to reproduce the second-to-fourth slowest timescales with the same accuracy. Our scheme can be applied not only to the reaction networks but also to networks in other fields, which helps us encompass their hierarchical structures of the complex kinetics over timescales.

Theoretical study on the mechanism of alcohol photooxidation on Nb2O5 surface.

Theoretical modeling of the solid-state photocatalysis is one of the important issues as various useful photocatalysts have been developed to date. In this work, we investigated the mechanism of the alcohol photooxidation on niobium oxide (Nb2O5) which was experimentally developed, using the density functional theory (DFT)/time-dependent (TD)DFT calculations based on the cluster model. The alcohol adsorption and the first hydrogen transfer from hydroxy group to surface occur in the ground state, while the second hydrogen transfer from CH proceeds in the excited states during the photoirradiation of UV or visible light. The spin crossing was identified and the low-lying triplet states were solved for the reaction pathway. The photoabsorption in the visible light region was characterized as the charge transfer transition from O 2p of alcohol to Nb 4d of the Nb2O5 surface. The spin density and the natural population analysis indicated the generation of spin density in the moiety of carbonyl compound and its dissipation to the interface of the surface, which partly explains the electron paramagnetic resonance measurement. It was confirmed that the rate determining step is the desorption of carbonyl compound and water molecule in agreement with the experimental rate equation analysis. The present findings with the theoretical modeling will provide useful information for the further studies of the solid-state photocatalysis.

Deep bed filtration and formation damage by particles with distributed properties

Current models for deep bed filtration describe particles with uniform properties. Yet, the sizes, densities, and mineral composition of particles vary significantly in the same injection well. The aim of this work is to provide an effective mathematical model for water injection of particles with distributed properties and formation damage prediction. We average the set of traditional population balance equations for single-property particles and obtain one upscaled equation. The upscaled equation for particle retention rate contains a non-linear function of suspended concentration, which we call the 'suspension function'. We derive analytical solutions for the upscaled equation for linear (coreflood) and radial (well injectivity) flows. Then we treat lab coreflood data to determine the model suspension function and provide a model for well injectivity prediction. The retention profile for the flow of uniform particles has an exponential form. Frequently reported in the literature, hyper-exponential forms have been hypothetically explained by multiple particle properties. The inverse solution allows revealing the individual filtration coefficients for binary mixtures from total breakthrough concentrations during coreflood. Treatment of the data from lab experiments reveals individual filtration coefficients that belong to common intervals. For the first time, deep bed filtration of particles with distributed properties is upscaled and presented using a single equation that reflects the particle property distribution. This equation provides an effective mathematical model for tuning lab coreflood data, determines the model function, and uses it for injectivity decline prediction.

Mechanism of Peroxynitrite Interaction with Ferric M. tuberculosis Nitrobindin: A Computational Study.

Nitrobindins (Nbs) are all-β-barrel heme proteins present along the evolutionary ladder. They display a highly solvent-exposed ferric heme group with the iron atom being coordinated by the proximal His residue and a water molecule at the distal position. Ferric nitrobindins (Nb(III)) play a role in the conversion of toxic peroxynitrite (ONOO-) to harmless nitrate, with the value of the second-order rate constant being similar to those of most heme proteins. The value of the second-order rate constant of Nbs increases as the pH decreases; this suggests that Nb(III) preferentially reacts with peroxynitrous acid (ONOOH), although ONOO- is more nucleophilic. In this work, we shed light on the molecular basis of the ONOO- and ONOOH reactivity of ferric Mycobacterium tuberculosis Nb (Mt-Nb(III)) by dissecting the ligand migration toward the active site, the water molecule release, and the ligand binding process by computer simulations. Classical molecular dynamics simulations were performed by employing a steered molecular dynamics approach and the Jarzynski equality to obtain ligand migration free energy profiles for both ONOO- and ONOOH. Our results indicate that ONOO- and ONOOH migration is almost unhindered, consistent with the exposed metal center of Mt-Nb(III). To further analyze the ligand binding process, we computed potential energy profiles for the displacement of the Fe(III)-coordinated water molecule using a hybrid QM/MM scheme at the DFT level and a nudged elastic band approach. These results indicate that ONOO- exhibits a much larger barrier for ligand displacement than ONOOH, suggesting that water displacement is assisted by protonation of the leaving group by the incoming ONOOH.

Macrocyclic Azapeptide Nitriles: Structure-Based Discovery of Potent SARS-CoV-2 Main Protease Inhibitors as Antiviral Drugs.

Given the crucial role of the main protease (Mpro) in the replication cycle of SARS-CoV-2, this viral cysteine protease constitutes a high-profile drug target. We investigated peptidomimetic azapeptide nitriles as auspicious, irreversibly acting inhibitors of Mpro. Our systematic approach combined an Mpro active-site scanning by combinatorially assembled azanitriles with structure-based design. Encouraged by the bioactive conformation of open-chain inhibitors, we conceptualized the novel chemotype of macrocyclic azanitriles whose binding mode was elucidated by cocrystallization. This strategy provided a favorable entropic contribution to target binding and resulted in the development of the extraordinarily potent Mpro inhibitor 84 with an IC50 value of 3.23 nM and a second-order rate constant of inactivation, kinac/Ki, of 448,000 M-1s-1. The open-chain Mpro inhibitor 58, along with the macrocyclic compounds 83 and 84, a broad-spectrum anticoronaviral agent, demonstrated the highest antiviral activity with EC50 values in the single-digit micromolar range. Our findings are expected to promote the future development of peptidomimetic Mpro inhibitors as anti-SARS-CoV-2 agents.

Kinetics and mechanism of the gas-phase reaction of the hydroxyl radical with meta-aminotoluene compound.

An ab initio investigation into the potential energy landscape of the meta-aminotoluene + •OHreaction has been conducted in this study. The calculated results reveal that the reaction channel leading to the product (NHC6H4CH3 + H2O) prevails under the 300-1700K temperature range, while the reaction path forming the product (NH2C6H4CH2 + H2O) dominates in the higher-temperature region (T ≥ 1800K). Within the specified temperature range, the product branching ratio for the former declines from 48 to 30%, while the latter shows an increase, reaching 29%. The overall second-order rate constants of the titled reaction obtained at the pressure 760Torr (N2) can be illustrated by the modified Arrhenius expression of ktotal = 1.46 × 10-13 T0.58 exp[(-0.759kcal.mol-1)/RT] cm3 molecule-1s-1 and ktotal = 1.86 × 10-22 T3.24 exp[(-5.086kcal.mol-1)/RT] cm3 molecule-1s-1, covering the temperature range of T = 300-600K and T > 600K, respectively. The total rate constant at the ambient conditions in this work, 1.43 × 10-11 cm3 molecule-1s-1, has been found to be roughly one order of magnitude lower than the available experimental data, ~ 1.2 × 10-10 cm3 molecule-1s-1, measured by Atkinson et al., Rinke et al., and Witte et al., or the theoretical value, 4.4 × 10-10 cm3 molecule-1s-1, and calculated by Abdel-Rahman and co-workers for the aniline + •OH reaction. The structures of reactants, transition states, intermediate states, and products of the meta-aminotoluene + •OHreaction are calculated with the aug-cc-pVTZ basis set and the methods DFT/B3LYP and CCSD(T). The rate constants and branching ratios in the 300-2000K temperature range are calculated with the statistical theoretical TST and RRKM master equation computations including tunneling corrections, with potential energy surface constructed by the CCSD(T)//B3LYP/aug-cc-pVTZ approach.

Restriction on molecular fluxionality by substitution: A case study for the 1,10-dicyanobullvalene.

We show herein that 1,10-dicyano substitution restricts the paragon fluxionality of bullvalene to just 14 isomers which isomerize along a single cycle. The restricted fluxionality of 1,10-dicyanobullvalene (DCB) is investigated by means of: (i) Bonding analyses of the isomer structures using the adaptive natural density partitioning (AdNDP). (ii) Quantum dynamical simulations of the isomerizations along the cyclic intrinsic reaction coordinate of the potential energy surface (PES). The PES possesses 14 equivalent potential wells supporting 14 isomers which are separated by 14 equivalent potential barriers supporting 14 transition states. Accordingly, at low temperatures, DCB appears as a hindered molecular rotor, without any delocalization of the wavefunction in the 14 potential wells, without any nuclear spin isomers, and with completely negligible tunneling. These results are compared and found to differ from those for molecular boron rotors. (iii) Born-Oppenheimer molecular dynamics (BOMD) simulations of thermally activated isomerizations. (iv) Calculations of the rate constants in the frame of transition state theory (TST) with reasonable agreement achieved with the BOMD results. (v) Simulations of the equilibration dynamics using rate equations for the isomerizations with TST rate coefficients. Accordingly, in the long-time limit, isomerizations of the 14 isomers, each with Cs symmetry, approach the "14 Cs → C7v" thermally averaged structure. This is a superposition of the 14 equally populated isomer structures with an overall C7v symmetry. By extrapolation, the results for DCB yield working hypotheses for so far un-explored properties e.g. for the equilibration dynamics of C10H10.

Modeling of heat conduction through rate equations

AbstractStarting from a classical thermodynamic approach, we derive rate-type equations to describe the behavior of heat flow in deformable media. Constitutive equations are defined in the material (Lagrangian) description where the standard time derivative satisfies the principle of objectivity. The statement of the Second Law is formulated in the classical form and the thermodynamic restrictions are then developed following a variant of the Coleman-Noll procedure where the entropy production too is given by a non-negative constitutive equation. Both the free energy and the entropy production are assumed to depend on a common set of independent variables involving, in addition to temperature, both temperature gradient and heat-flux vector together with their time derivatives. This approach results in rate-type constitutive function for the heat flux that are intrinsically consistent with the Second Law and easily amenable to analysis. In addition to providing already known models (e.g., Maxwell-Cattaneo-Vernotte’s and Jeffreys-like heat conductors), this scheme allows the formulation of new models of heat transport that are likely to apply also in nanosystems. This is consistent with the fact that higher-order time derivatives of the heat flux are in order when high-rate regimes occur.

Bioorthogonal Cycloadditions of C3-Trifluoromethylated 1,2,4-Triazines with trans-Cyclooctenes.

1,2,4-triazines are a valuable class of heterodienes that can be employed in inverse electron-demand Diels-Alder reactions. However, their broader application in bioorthogonal chemistry is limited due to their low reactivity. This article focuses on 3-(trifluoromethyl)-1,2,4-triazines, which can be efficiently prepared in a one-pot reaction from NH-1,2,3-triazoles. These triazines are highly reactive in reactions with strained cyclooctenes, giving second-order rate constants as high as 230 M-1 s-1. Despite their high reactivity, the compounds remain sufficiently stable under biologically relevant conditions. We show that some of the compounds are fluorogenic, a property of potential use in bioimaging. In addition, we demonstrate the successful application of the triazines in labeling model biomolecules. Our work shows that the reactivity of 1,2,4-triazines can be enhanced by the 3-CF3-substitution, which we consider an important step toward the wider use of this promising class of reagents.

Magnetic nanoparticles in square-wave fields for breakthrough performance in hyperthermia and magnetic particle imaging

Driving immobilized, single-domain magnetic nanoparticles at high frequency by square wave fields instead of sinusoidal waveforms leads to qualitative and quantitative improvements in their performance both as point-like heat sources for magnetic hyperthermia and as sensing elements in frequency-resolved techniques such as magnetic particle imaging and magnetic particle spectroscopy. The time evolution and the frequency spectrum of the cyclic magnetization of magnetite nanoparticles with random easy axes are obtained by means of a rate-equation method able to describe time-dependent effects for the particle sizes and frequencies of interest in most applications to biomedicine. In the presence of a high-frequency square-wave field, the rate equations are shown to admit an analytical solution and the periodic magnetization can be therefore described with accuracy, allowing one to single out effects which take place on different timescales. Magnetic hysteresis effects arising from the specific features of the square-wave driving field results in a breakthrough improvement of both the magnetic power released as heat to an environment in magnetic hyperthermia treatments and the magnitude of the third harmonic of the frequency spectrum of the magnetization, which plays a central role in magnetic particle imaging.

HYSTERESIS OF IMPLICIT EQUATIONS IN HYPOPLASTICITY FOR SOIL MATERIALS WITH GRANULAR HARDNESS DEGRADATION

AbstractWe study a hypoplastic model for soil and granular materials stemming from geomechanical engineering which further incorporates effects of degradation of the granular hardness, therefore allowing for the description of environmental weathering. The governing system is described by a nonlinear system of transcendental-differential equations for stress and strain rate, which is investigated with respect to its long-time dynamic. Under deviatoric stress control, two different solutions of the underlying, implicit differential equations are constructed analytically. The spherical components of stress and strain rate converge asymptotically to an attractor and lead to the sparsification of material states. Whereas under cyclic loading-unloading carried out in a numerical simulation, finite ratcheting of the deviatoric strain rate is observed in the form of a square spiral.