Fast Rate Constants Research Articles

INVESTIGATION OF DYE-REGENERATION KINETICS AT DYE-SENSITIZED p-TYPE CuCrO2 FILM/ELECTROLYTES INTERFACE WITH SCANNING ELECTROCHEMICAL MICROSCOPY

The power conversion efficiency of p-type dye-sensitized solar cells (DSSC) is determined by the kinetics of hole injection and dye-regeneration reaction at the dye/electrolyte interface. In this work, the photochemical regeneration kinetics of dye adsorbed on CuCrO 2 mesoporous film was investigated by using scanning electrochemical microscopy with feedback mode. Organic P1 and C343 sensitizers in combination with iodide-based and thiolate-based electrolytes were selected to understand the effect of sensitizers and redox shuttles on dye-regeneration process. A fast regeneration kinetic rate constant was confirmed in thiolate-based sample compared with iodide-based electrolyte, indicating that the organic redox shuttle was an efficient mediator to optimize the performance of p-type DSSC.

Direct Electrochemistry and Electrocatalysis of Horseradish Peroxidase Immobilized in a DNA/Chitosan-Fe3O4 Magnetic Nanoparticle Bio-Complex Film

A DNA/chitosan-Fe3O4 magnetic nanoparticle bio-complex film was constructed for the immobilization of horseradish peroxidase (HRP) on a glassy carbon electrode. HRP was simply mixed with DNA, chitosan and Fe3O4 nanoparticles, and then applied to the electrode surface to form an enzyme-incorporated polyion complex film. Scanning electron microscopy (SEM) was used to study the surface features of DNA/chitosan/Fe3O4/HRP layer. The results of electrochemical impedance spectroscopy (EIS) show that Fe3O4 and enzyme were successfully immobilized on the electrode surface by the DNA/chitosan bio-polyion complex membrane. Direct electron transfer (DET) and bioelectrocatalysis of HRP in the DNA/chitosan/Fe3O4 film were investigated by cyclic voltammetry (CV) and constant potential amperometry. The HRP-immobilized electrode was found to undergo DET and exhibited a fast electron transfer rate constant of 3.7 s−1. The CV results showed that the modified electrode gave rise to well-defined peaks in phosphate buffer, corresponding to the electrochemical redox reaction between HRP(Fe(III)) and HRP(Fe(II)). The obtained electrode also displayed an electrocatalytic reduction behavior towards H2O2. The resulting DNA/chitosan/Fe3O4/HRP/glassy carbon electrode (GCE) shows a high sensitivity (20.8 A·cm−2·M−1) toward H2O2. A linear response to H2O2 measurement was obtained over the range from 2 μM to 100 μM (R2 = 0.99) and an amperometric detection limit of 1 μM (S/N = 3). The apparent Michaelis-Menten constant of HRP immobilized on the electrode was 0.28 mM. Furthermore, the electrode exhibits both good operational stability and storage stability.

Rate constant of the reaction between CH3O2 and OH radicals

The rate constant of the reaction(R1)OH+CH3O2→productshas been measured at 294K by simultaneous coupling of Laser Induced Fluorescence (LIF) and cw-Cavity Ring Down Spectroscopy (cw-CDRS) to laser photolysis. OH radicals were generated by 248nm photolysis of either H2O2 or O3 in the presence of H2O, CH3O2 radicals were generated simultaneously by photolysis of CH3I and their absolute concentrations were obtained by cw-CRDS. OH decays were measured under excess CH3O2 concentrations and a very fast rate constant of k1=(2.8±1.4)×10−10cm3s−1 was found independent of pressure at 50 and 100Torr helium.

A mediator-free glucose biosensor based on glucose oxidase/chitosan/α-zirconium phosphate ternary biocomposite

A novel glucose oxidase/chitosan/α-zirconium phosphate (GOD/chitosan/α-ZrP) ternary biocomposite was prepared by co-intercalating glucose oxidase (GOD) and chitosan into the interlayers of α-zirconium phosphate (α-ZrP) via a delamination–reassembly procedure. The results of X-ray diffraction, infrared spectroscopy, circular dichroism, and ultraviolet spectrum characterizations indicated not only the layered and hybrid structure of the GOD/chitosan/α-ZrP ternary biocomposite but also the recovered activity of the intercalated GOD improved by the co-intercalated chitosan. By depositing the GOD/chitosan/α-ZrP biocomposite film onto a glassy carbon electrode, the direct electrochemistry of the intercalated GOD was achieved with a fast electron transfer rate constant, ks, of 7.48±3.52s−1. Moreover, this GOD/chitosan/α-ZrP biocomposite modified electrode exhibited a sensitive response to glucose in the linear range of 0.25–8.0mM (R=0.9994, n=14), with a determination limit of 0.076mM.

Kinetic Mechanism of DNA Polymerization Catalyzed by Human DNA Polymerase ε

Eukaryotes require highly accurate and processive DNA polymerases to ensure faithful and efficient replication of their genomes. DNA polymerase ε (Polε) has been shown to catalyze leading-strand DNA synthesis during replication in vivo, but little is known about the kinetic mechanism of polymerization catalyzed by this replicative enzyme. To elucidate this mechanism, we have generated a truncated, exonuclease-deficient mutant of the catalytic subunit of human Polε (Polε exo-) and carried out pre-steady-state kinetic analysis of this enzyme. Our results show that Polε exo-, as other DNA polymerases, follows an induced-fit mechanism when catalyzing correct nucleotide incorporation. Polε exo- binds DNA with a Kd(DNA) of 79 nM and dissociates from the E·DNA binary complex with a rate constant of 0.021 s(-1). Although Polε exo- binds a correct incoming nucleotide weakly with a Kd(dTTP) of 31 μM, it catalyzes correct nucleotide incorporation at a fast rate constant of 248 s(-1) at 20 °C. Both a large reaction amplitude difference (42%) between pulse-chase and pulse-quench assays and a small elemental effect (0.9) for correct dTTP incorporation suggest that a slow conformational change preceding the chemistry step limits the rate of correct nucleotide incorporation. In addition, our kinetic analysis shows that Polε exo- exhibits low processivity during polymerization. To catalyze leading-strand synthesis in vivo, Polε likely interacts with its three smaller subunits and additional replication factors in order to assemble a replication complex and significantly enhance its polymerization processivity.

Modeling the performance of an ideal NaBH4–H2O2 direct borohydride fuel cell

A 2D direct borohydride fuel cell (DBFC) model has been developed to explore the prospective performance of this technology, for a cell with fast selective electrocatalysts and a selective membrane. In the modeled DBFC, a Nafion membrane in the Na+ form separates flow channels with aqueous fuel (0.1–0.5 M NaBH4/4 M NaOH) and oxidizer (4 M H2O2/4 M H2SO4). Electrochemical reactions occur on catalyst-coated channel walls. The electrocatalysts are selective for complete BH4− oxidation and H2O2 reduction, the reactions have fast forward rate constants, and only Na+ and H2O cross the membrane. The model captures interfacial charge transfer reactions and complex transport in the flow channels and membrane. Results show that current density and voltage efficiency vary by >50% from inlet to outlet due to concentration boundary layer development. The BH4− concentration boundary layer limits peak power density, despite migration and fuel utilizations below 10%. Power density increases with BH4− inlet concentration and fuel flow rate, but at the expense of lower fuel utilization. Water crosses the membrane up to 14 times its production rate at the anode. Low fuel utilization and water imbalance suggest the importance of system designs with reactant recirculation and water recovery.

Simulated single-cycle kinetics improves the design of surface plasmon resonance assays

Instruments based on the surface plasmon resonance (SPR) principle are widely used to monitor in real time molecular interactions between a partner, immobilized on a sensor chip surface and another one injected in a continuous flow of buffer. In a classical SPR experiment, several cycles of binding and regeneration of the surface are performed in order to determine the rate and the equilibrium constants of the reaction. In 2006, Karlsson and co-workers introduced a new method named single-cycle kinetics (SCK) to perform SPR assays. The method consists in injecting sequentially increasing concentrations of the partner in solution, with only one regeneration step performed at the end of the complete binding cycle. A 10 base-pair DNA duplex was characterized kinetically to show how simulated sensorgrams generated by the BiaEvaluation software provided by Biacore™ could really improve the design of SPR assays performed with the SCK method. The DNA duplex was investigated at three temperatures, 10, 20 and 30°C, to analyze fast and slow rate constants. The results show that after a short obligatory preliminary experiment, simulations provide users with the best experimental conditions to be used, in particular, the maximum concentration used to reach saturation, the dilution factor for the serial dilutions of the sample injected and the duration of the dissociation and association phases. The use of simulated single-cycle kinetics saves time and reduces sample consumption. Simulations can also be used to design SPR experiments with ternary complexes.

Kinetics, equilibrium, and mechanisms of sorption and desorption of 17α-ethinyl estradiol in two natural soils and their organic fractions

A study was conducted on the kinetics, equilibrium, and mechanisms of sorption and desorption of 17α-ethinyl estradiol (EE2) in six sorbents, which were two natural soils (Bulk1 and Bulk2) and their fractions obtained by alkaline extraction, namely, humic acids (HA1 and HA2), and mineral-bond humins (MHU1 and MHU2). These sorbents, characterized by total organic carbon (TOC), black carbon (BC), gas adsorption and Fourier transform infrared spectra, were shown to be porous solids containing aromatic (hard carbon) and aliphatic carbon (soft carbon). The two-compartment first-order model fitted the kinetics of sorption very well (R2>0.990). The fast and slow sorption rate constants ranged from 1.110h−1 and 0.026h−1 to 2.063h−1 and 0.067h−1, respectively. The slow sorption was attributed to the diffusion of EE2 in micropores rather than organic matter. The Freundlich model fitted the equilibrium of sorption and desorption very well. The nonlinearity of sorption took the order MHU>bulk soil>HA and was positively related to BC/TOC (p<0.01). The hysteresis in MHU2 with higher BC/TOC was stronger than that in Bulk2 with lower BC/TOC, but a contrary observation was found in MHU1 and Bulk1. This contradictory phenomenon could be attributed to the location difference of hard carbon which greatly affected the desorption process. These findings could give an insight into the sorption mechanisms and promote an accurate model for the transport, fate and risk assessment of EE2 in the environment.

Formation of Guanine-6-sulfonate from 6-Thioguanine and Singlet Oxygen: A Combined Theoretical and Experimental Study

As an end metabolism product of the widely used thiopurine drugs, 6-thioguanine (6-TG) absorbs UVA and produces (1)O2 by photosensitization. This unusual photochemical property triggers a variety of DNA damage, among which the oxidation of 6-TG itself by (1)O2 to the promutagenic product guanine-6-sulfonate (G(SO3)) represents one of the major forms. It has been suspected that there exists an initial intermediate, G(SO), prior to its further oxidation to G(SO2) and G(SO3), but G(SO) has never been observed. Using density functional theory, we have explored the energetics and intermediates of 6-TG and (1)O2. A new mechanism via G(SOOH) → G(SO2) → G(SO4) → G(SO3) has been discovered to be the most feasible energetically, whereas the anticipated G(SO) mechanism is found to encounter an inaccessibly high barrier and thus is prevented. The mechanism through the G(SOOH) and G(SO4) intermediates can be validated further by joint experimental measurements, where the fast rate constant of 4.9 × 10(9) M(-1) s(-1) and the reaction stoichiometry of 0.58 supports this low-barrier new mechanism. In addition to the dominant pathway of G(SOOH) → G(SO2) → G(SO4) → G(SO3), a side pathway with higher barrier, G(SOOH) → G, has also been located, providing a rationalization for the observed product distributions of G(SO2) and G(SO3) as major products and G as minor product. From mechanistic and kinetics points of view, the present findings provide new chemical insights to understand the high phototoxicity of 6-TG in DNA and point to methods of using 6-TG as a sensitive fluorescence probe for the quantitative detection of (1)O2, which holds particular promise for detecting (1)O2 in DNA-related biological surroundings.

The rate of adsorption of nanoparticles on microelectrode surfaces

Theory is developed for the rate of irreversible adsorption of nanoparticles from solution onto an electrode surface, including the effects of hindered diffusion of large nanoparticles. The effect of nanoparticle size on adsorption processes is studied, and found to be significant for large particles, where the nanoparticle radius to electrode radius ratio is larger than 1×10−3. The extent of adsorption in a typical electrochemical nanoparticle experiment at a 5μm radius hemispherical electrode is studied for different adsorption rate constants, along with the effect this has on concentration of nanoparticles in the vicinity of the electrode and the frequency of impacts of nanoparticles on the electrode. For fast adsorption rate constants, significant and long lasting (in extreme cases greater than 4h) concentration gradients can form, necessitating careful experimental practice.

Use of Partial AUC (PAUC) to Evaluate Bioequivalence—A Case Study with Complex Absorption: Methylphenidate

Methylphenidate modified-release products produce early and late peak concentrations critical for treatment of morning and afternoon symptoms of attention deficit hyperactivity disorder (ADHD). Standard bioequivalence (BE) criteria cannot be applied to these products. The performance of partial area under the drug concentration-time curve (PAUC), Cmax and AUCINF to assess BE were independently evaluated for two products. A two-stage analysis was performed on plasma data for two methylphenidate modified-release products (Product 1 and 2). Simulations using the fitted parameters determined how changes in fast absorption rate constant (K0Fast) and fraction available (F1) affected curve shape and BE determination using Cmax, AUCINF and PAUC. The sensitivity of the mean PAUC(test)/PAUC(reference) ratios to changes in K0Fast(test) are product dependent. Product 1 mean PAUC(test)/PAUC(reference) ratios for PAUC0-4h are more responsive to both decreases and increases in K0Fast(test) than Product 2. Product 2 showed a greater response in the mean PAUC(test)/PAUC(reference) ratio for PAUC0-4h when the K0Fast(test) is decreased and less response as the value is increased. PAUC estimated curve shape is sensitive to changes in absorption and are product specific, and may require a new PAUC metric for each drug. A non-product specific metric to assess curve shape is warranted.

Properties of a Model Aryl Boronic Acid and Its Boroxine

Many boronic acid-containing molecules are currently under investigation as possible therapeutics. An increase in the knowledge of the physical and chemical properties of these compounds will lead to their improved formulation into usable dosage forms. The current study describes the formation and characterization of a boronic acid anhydride, called a boroxine. The model boronic acid, 4-methoxybenzeneboronic acid is used. The current study demonstrates the utility of thermal (differential scanning calorimetry and thermogravimetric analysis) and spectral (solid-state nuclear magnetic resonance and ultraviolet spectroscopy) methods to quantitate and characterize the boronic acid and its boroxine, validated against definitive structures solved by single-crystal X-ray diffraction. The present work also demonstrates that the hydrolysis of the boroxine in the presence of water is very rapid in a time scale relative to drug substance manufacture and product formulation.

Fabrication of aluminum-doped α-Ni(OH)2 with hierarchical architecture and its largely enhanced electrocatalytic performance

Aluminum-doped α-Ni(OH)2 microspheres with flowerlike hierarchical structure (H-Al-α-Ni(OH)2) were successfully synthesized via a facile hydrothermal method with the assistance of ionic liquid (1-butyl-3-methyl imidazolium tetrafluoroborate, [BMIM]BF4). The XRD pattern and elemental analysis confirm that aluminum species incorporates into the lattice of α-Ni(OH)2; SEM and TEM images reveal that the as-prepared microspheres are composed of numerous frizzy nanoflakes shell attaching vertically to the core. The resulting H-Al-α-Ni(OH)2 sample exhibits a specific surface area of 91.2m2/g and a mesopore distribution (2–20nm) based on the BET measurements. Furthermore, the hierarchical H-Al-α-Ni(OH)2 modified electrode displays a couple of well-defined reversible redox peaks (ΔEp=67mV and Ia/Ic=0.91) and a fast direct electron transfer rate constant (ks=3.32s−1), owing to the high dispersion of active species as well as abundant mass transfer channels which facilitate the mass/electron transfer. In addition, the modified electrode presents a significant electrocatalytic performance towards the oxidation of hydrazine with a linear response range (5.0×10−6–1.0×10−4M), high sensitivity (144μA/μM cm2), low detection limit (0.8μM) as well as good stability. The hierarchical α-Ni(OH)2 with largely enhanced electrochemical behavior demonstrated in this work can be used in electrochemical sensor and electroanalysis.

Single-Molecule Analysis of the Recognition Forces Underlying Nucleo-Cytoplasmic Transport

Macromolecular exchange between the nucleus and cytoplasm of cells is gated at nuclear pores by a family of intrinsically-disordered nucleoporins (nups). These feature phenylalanine-glycine repeats in ‘cohesive’ domains (FG domains) that interact to form a physical barrier. Through unknown mechanisms, karyopherins (importins, exportins, transportins, NTRs) penetrate this barrier to facilitate the movement of large proteins and RNPs across without paying an external energetic cost, simply by interacting with FG domains. To address the molecular binding and dissociation mechanisms involved in this coupled gating-translocation process, single molecule force spectroscopy was used here to measure the interaction force between nup FG repeats, and between importin beta and nup FG repeats. As predicted, cohesive FG domains bound each other through multiple FG repeat interactions. In contrast importin bound only relaxed coil multiple FG repeats simultaneously, whereas just one FG binding site was assessed in collapsed coil multiple FG domains. Most importantly, the interaction forces and fast dissociation rate constants measured between two FG repeats, and between importin and one FG repeat, were almost identical. This suggests that the force needed to separate interactions between FG repeats of nups at the NPC (i.e. for kaps to penetrate the gate and translocate across) could be provided in full by the enthalpy gained through the formation of karyopherin-FG repeat interactions.

Zero-Valent Iron: Impact of Anions Present during Synthesis on Subsequent Nanoparticle Reactivity

Zero-valent iron particles are an effective remediation technology for ground water contaminated with halogenated organic compounds. In particular, nanoscale zero-valent iron is a promising material for remediation because of its high specific surface area, which results in faster rate constants and more effective use of the iron. An aspect of iron nanoparticle reactivity that has not been explored is the impact of anions present during iron metal nanoparticle synthesis. Solutions containing chloride, phosphate, sulfate, and nitrate anions and ferric ions were used to generate iron oxide nanoparticles. The resulting materials were dialyzed to remove dissolved by-products and then dried and reduced by hydrogen gas at high temperature. The reactivity of the resulting zero-valent iron nanoparticles was quantified by monitoring the kinetics as well as products of carbon tetrachloride reduction, and significant differences in reactivity and chloroform yield were observed. The reactivity of nanoparticles prepared in the presence of sulfate and phosphate demonstrated the highest reactivity and chloroform yield. Furthermore, substantial variations in the solid-state products of oxidation (magnetite, iron sulfide, goethite, etc.) were also observed.

Contribution of major lipophilic antioxidants to the antioxidant activity of basil extracts: an EPR study

The present research analyses the contribution of some lipid antioxidants to the antioxidant activity of lipophilic extracts from basil by an electron paramagnetic resonance (EPR) study using the stable free radical 1,1-diphenyl-2-picrylhydrazyl (DPPH). DPPH assay is considered an easy and accurate method with regard to measuring the antioxidant activity of plant extracts and EPR has already been employed to determine antioxidant activities of lipophilic plant extracts. Lipid extracts were obtained from basil grown hydroponically for 20 or 35 days from sowing and in soil for 35 days from sowing. Fast and slow rate constants were distinguishable in the decay kinetics of DPPH mixture added with lipid extract. Antioxidants with kinetics characterized by a fast decay rate were tocopherols and chlorophylls, whereas those characterized by a slow decay rate were carotenoids, among which were β-carotene, lutein, β-apo-8'-carotenal and zeaxanthin. The 20-day hydroponically grown sample, which showed higher contents of tocopherol, chlorophyll and carotenoid molecules, was the sample endowed with the higher content of fast lipophilic antioxidants (FLA) and slow lipophilic antioxidants (SLA). The three samples showed different compositions of FLA and SLA, giving rise to different decay kinetics. Despite the differences, in all samples tocopherol contributed about 0.3% to the bulk of FLA, whereas the figure for chlorophyll was about 40%, evidencing the relevant but little-studied role of chlorophyll as an antioxidant.

Kinetics of sorption‐desorption of benfuracarb insecticide in mollisols

Sorption-desorption processes govern the movement of pesticides in soil. These processes determine the potential hazard of the pesticide in a given environment for groundwater contamination and need to be investigated. In the present study, sorption-desorption processes of benfuracarb were investigated using a batch method in two mollisols. The kinetics of benfuracarb sorption in mollisols conformed to two-compartment (1 + 1) first-order kinetics. The fast sorption rate constant was about 3 times higher for silt loam than for loam soil. However, the slow sorption rate constants were statistically similar for both soils. The concentration-dependent sorption-desorption isotherms of benfuracarb could not closely conform to the Freundlich isotherm in mollisols of high organic C content. The computed values of both the sorption (log K) and desorption (log K') capacities were higher for silt loam than for loam soil. The desorption index (n'/n) values in the range 30.0-41.3 indicated poor reversibility of sorbed benfuracarb in mollisols. In view of the strong sorption of benfuracarb in mollisols with only partial desorption, the possibility of the leaching of soil-applied benfuracarb to contaminate groundwaters appears to be low.

Force relaxation and thin filament protein phosphorylation during acute myocardial ischemia

Ischemia impairs myocardial function and may contribute to the progression of heart failure. In this study, rats subjected to acute ischemia demonstrated reduced Ca(2+) -activated force as well as a decrease in myosin-binding protein-C, titin, and Ser23/24 phosphorylation of troponin I (TnI). All three proteins have been demonstrated to be downstream targets of β-adrenergic receptor activation (β-AR), leading to the hypothesis that decreased β-AR signaling during ischemia leads to reduced protein phosphorylation and reduced rate constants of force relaxation. To test this hypothesis, force relaxation transients were recorded from permeabilized perfused and ischemic rat heart fibers following photolysis of the caged chelator diazo-2. Relaxation transients were best fit by double exponential functions whereby the majority (>70%) of the force decline was described by the fast rate constant, which was ∼5 times faster than the slow rate constant. However, rate constants of relaxation between perfused and ischemic fibers were not different, despite significant decreases in sarcomeric protein phosphorylation in ischemic fibers. Treatment of perfused fibers with a cAMP analog increased Ser23/24 phosphorylation of TnI, yet the rate constants of relaxation remained unchanged. Interestingly, similar treatment of ischemic fibers did not impact TnI phosphorylation or force relaxation transients. Therefore, acute ischemia does not influence the rate constants of relaxation of permeabilized fibers. These results also suggest that the physiological level of sarcomeric protein phosphorylation is unlikely to be the primary driver of relaxation kinetics in permeabilized cardiac muscle fibers.

Direct electrochemistry of horseradish peroxidase on graphene-modified electrode for electrocatalytic reduction towards H 2O 2

Graphene was synthesized by a chemical method to reduce graphite oxide and well characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), powder X-ray diffraction (PXRD) and Fourier transform infrared (FTIR) spectra. Horseradish peroxidase (HRP) immobilized on a graphene film glassy carbon electrode was found to undergo direct electron transfer and exhibited a fast electron transfer rate constant of 4.63 s −1. The HRP-immobilized electrode was investigated by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The CV results showed that the modified electrode gave rise to well-defined peaks in phosphate buffer, corresponding to the electrochemical redox reaction between HRP–Fe(III) and HRP–Fe(II). The obtained electrode also displayed an electrocatalytic reduction behavior towards H 2O 2. The new H 2O 2 sensor shows a linear range of 0.33–14.0 μM ( R 2 = 0.9987) with a calculated detection limit of 0.11 μM (S/N = 3). Furthermore, the biosensor exhibits both good operational storage and storage stability.

ChemInform Abstract: Picosecond Radical Kinetics. Benzeneselenol as a Fast Radical Trapping Agent and Rate Constants for Ring Opening of the trans-(2- Phenylcyclopropyl)carbinyl Radical.

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