Bindings of NO, CO, and O2 to multifunctional globin type dehaloperoxidase follow the ‘sliding scale rule’

2017 ◽  
Vol 474 (20) ◽  
pp. 3485-3498 ◽  
Author(s):  
Gang Wu ◽  
Jing Zhao ◽  
Stefan Franzen ◽  
Ah-Lim Tsai
Keyword(s):  
Oxygen Carrier ◽  
Sperm Whale ◽  
Dissociation Rate ◽  
Heme Iron ◽  
Binding Affinities ◽  
Ligand Selectivity ◽  
Sliding Scale ◽  
One Step ◽  
Sensor Proteins ◽  
Kinetics Of

Dehaloperoxidase–hemoglobin (DHP), a multifunctional globin protein, not only functions as an oxygen carrier as typical globins such as myoglobin and hemoglobin, but also as a peroxidase, a mono- and dioxygenase, peroxygenase, and an oxidase. Kinetics of DHP binding to NO, CO, and O2 were characterized for wild-type DHP A and B and the H55D and H55V DHP A mutants using stopped-flow methods. All three gaseous ligands bind to DHP significantly more weakly than sperm whale myoglobin (SWMb). Both CO and NO bind to DHP in a one-step process to form a stable six-coordinate complex. Multiple-step NO binding is not observed in DHP, which is similar to observations in SWMb, but in contrast with many heme sensor proteins. The weak affinity of DHP for O2 is mainly due to a fast O2 dissociation rate, in accordance with a longer εN–Fe distance between the heme iron and distal histidine in DHP than that in Mb, and an open-distal pocket that permits ligand escape. Binding affinities in DHP show the same 3–4 orders separation between the pairs NO/CO and CO/O2, consistent with the ‘sliding scale rule’ hypothesis. Strong gaseous ligand discrimination by DHP is very different from that observed in typical peroxidases, which show poor gaseous ligand selectivity, correlating with a neutral proximal imidazole ligand rather than an imidazolate. The present study provides useful insights into the rationale for DHP to function both as mono-oxygenase and oxidase, and is the first example of a globin peroxidase shown to follow the ‘sliding scale rule’ hypothesis in gaseous ligand discrimination.

scholarly journals The proximal and distal pockets of the H93G myoglobin cavity mutant bind identical ligands with different affinities: Quantitative analysis of imidazole and pyridine binding

2008 ◽  
Vol 22 (2-3) ◽  
pp. 123-141 ◽  
Author(s):  
Jing Du ◽  
Masanori Sono ◽  
John H. Dawson
Keyword(s):  
Ligand Binding ◽  
Magnetic Circular Dichroism ◽  
Sperm Whale ◽  
Heme Iron ◽  
Model Systems ◽  
Binding Affinities ◽  
Quantitative Evidence ◽  
High Affinity Binding Site ◽  
Free Heme ◽  
Exogenous Ligand

His93Gly sperm whale myoglobin (H93G Mb) has the proximal histidine ligand removed to create a cavity for exogenous ligand binding, making it a versatile template for the preparation of model heme complexes. In this study, we have measured the first and second ligand binding affinities of imidazole and pyridine to form mono- and bis-ligated ferric and ferrous H93G Mb complexes. Electronic absorption spectroscopy has been utilized to determine the binding affinities for the proximal (Kd1, first ligand) and distal (Kd2, second ligand) pockets of H93G Mb. Magnetic circular dichroism spectroscopy has been used to confirm the identity of the complexes. The binding affinities for the first ligand are one hundred- to one thousand-fold higher than those for the second ligand (Kd1«Kd2) for the same exogenous ligand. This is entirely opposite to what is seen with free heme in organic solvents whereKd1»Kd2. Thus, the proximal pocket is the high affinity binding site. The lower affinity for the distal pocket can be attributed to steric hindrance from the distal histidine. This report provides quantitative evidence for differential ligand binding affinities of the proximal and distal pockets of H93G Mb, a unique property that facilitates generation of heme iron derivatives not easily prepared with other heme model systems.

scholarly journals Recognition of hydrogen isotopomers by an open-cage fullerene

2013 ◽  
Vol 371 (1998) ◽  
pp. 20110629 ◽  
Author(s):  
Yasujiro Murata ◽  
Shih-Ching Chuang ◽  
Fumiyuki Tanabe ◽  
Michihisa Murata ◽  
Koichi Komatsu
Keyword(s):  
Equilibrium Constants ◽  
Equilibrium Mixture ◽  
Size Difference ◽  
Binding Affinities ◽  
Kinetic Isotope ◽  
Molecular Sizes ◽  
Lower Temperature ◽  
Kinetics Of ◽  
Pressure Hydrogen

We present our study on the recognition of hydrogen isotopes by an open-cage fullerene through determination of binding affinity of isotopes H 2 /HD/D 2 with the open-cage fullerene and comparison of their relative molecular sizes through kinetic-isotope-release experiments. We took advantage of isotope H 2 /D 2 exchange that generated an equilibrium mixture of H 2 /HD/D 2 in a stainless steel autoclave to conduct high-pressure hydrogen insertion into an open-cage fullerene. The equilibrium constants of three isotopes with the open-cage fullerene were determined at various pressures and temperatures. Our results show a higher equilibrium constant for HD into open-cage fullerene than the other two isotopomers, which is consistent with its dipolar nature. D 2 molecule generally binds stronger than H 2 because of its heavier mass; however, the affinity for H 2 becomes larger than D 2 at lower temperature, when size effect becomes dominant. We further investigated the kinetics of H 2 /HD/D 2 release from open-cage fullerene, proving their relative escaping rates. D 2 was found to be the smallest and H 2 the largest molecule. This notion has not only supported the observed inversion of relative binding affinities between H 2 and D 2 , but also demonstrated that comparison of size difference of single molecules through non-convalent kinetic-isotope effect was applicable.

scholarly journals Solid-State Redox Kinetics of CeO2 in Two-Step Solar CH4 Partial Oxidation and Thermochemical CO2 Conversion

Catalysts ◽  
2021 ◽  
Vol 11 (6) ◽  
pp. 723
Author(s):  
Mahesh Muraleedharan Nair ◽  
Stéphane Abanades
Keyword(s):  
Solid State ◽  
Solar Energy ◽  
Kinetic Models ◽  
Oxygen Carrier ◽  
Co2 Conversion ◽  
Oxidation Reactions ◽  
Redox Kinetics ◽  
Concentrated Solar Energy ◽  
Ceria Reduction ◽  
Kinetics Of

The CeO2/CeO2−δ redox system occupies a unique position as an oxygen carrier in chemical looping processes for producing solar fuels, using concentrated solar energy. The two-step thermochemical ceria-based cycle for the production of synthesis gas from methane and solar energy, followed by CO2 splitting, was considered in this work. This topic concerns one of the emerging and most promising processes for the recycling and valorization of anthropogenic greenhouse gas emissions. The development of redox-active catalysts with enhanced efficiency for solar thermochemical fuel production and CO2 conversion is a highly demanding and challenging topic. The determination of redox reaction kinetics is crucial for process design and optimization. In this study, the solid-state redox kinetics of CeO2 in the two-step process with CH4 as the reducing agent and CO2 as the oxidizing agent was investigated in an original prototype solar thermogravimetric reactor equipped with a parabolic dish solar concentrator. In particular, the ceria reduction and re-oxidation reactions were carried out under isothermal conditions. Several solid-state kinetic models based on reaction order, nucleation, shrinking core, and diffusion were utilized for deducing the reaction mechanisms. It was observed that both ceria reduction with CH4 and re-oxidation with CO2 were best represented by a 2D nucleation and nuclei growth model under the applied conditions. The kinetic models exhibiting the best agreement with the experimental reaction data were used to estimate the kinetic parameters. The values of apparent activation energies (~80 kJ·mol−1 for reduction and ~10 kJ·mol−1 for re-oxidation) and pre-exponential factors (~2–9 s−1 for reduction and ~123–253 s−1 for re-oxidation) were obtained from the Arrhenius plots.

scholarly journals Desensitization Contributes to the Synaptic Response of Gain-of-Function Mutants of the Muscle Nicotinic Receptor

2006 ◽  
Vol 128 (5) ◽  
pp. 615-627 ◽  
Author(s):  
Sergio Elenes ◽  
Ying Ni ◽  
Gisela D. Cymes ◽  
Claudio Grosman
Keyword(s):  
Nicotinic Receptor ◽  
Dissociation Rate ◽  
Gain Of Function ◽  
Naturally Occurring ◽  
Channel Opening ◽  
Speed Up ◽  
High Concentrations ◽  
Dissociation Rate Constants ◽  
Kinetics Of ◽  
Peak Value

Although the muscle nicotinic receptor (AChR) desensitizes almost completely in the steady presence of high concentrations of acetylcholine (ACh), it is well established that AChRs do not accumulate in desensitized states under normal physiological conditions of neurotransmitter release and clearance. Quantitative considerations in the framework of plausible kinetic schemes, however, lead us to predict that mutations that speed up channel opening, slow down channel closure, and/or slow down the dissociation of neurotransmitter (i.e., gain-of-function mutations) increase the extent to which AChRs desensitize upon ACh removal. In this paper, we confirm this prediction by applying high-frequency trains of brief (∼1 ms) ACh pulses to outside-out membrane patches expressing either lab-engineered or naturally occurring (disease-causing) gain-of-function mutants. Entry into desensitization was evident in our experiments as a frequency-dependent depression in the peak value of succesive macroscopic current responses, in a manner that is remarkably consistent with the theoretical expectation. We conclude that the comparatively small depression of the macroscopic currents observed upon repetitive stimulation of the wild-type AChR is due, not to desensitization being exceedingly slow but, rather, to the particular balance between gating, entry into desensitization, and ACh dissociation rate constants. Disruption of this fine balance by, for example, mutations can lead to enhanced desensitization even if the kinetics of entry into, and recovery from, desensitization themselves are not affected. It follows that accounting for the (usually overlooked) desensitization phenomenon is essential for the correct interpretation of mutagenesis-driven structure–function relationships and for the understanding of pathological synaptic transmission at the vertebrate neuromuscular junction.

scholarly journals Determination of Dental Adhesive Composition throughout Solvent Drying and Polymerization Using ATR–FTIR Spectroscopy

Polymers ◽  
2021 ◽  
Vol 13 (22) ◽  
pp. 3886
Author(s):  
Arwa Almusa ◽  
António H.S. Delgado ◽  
Paul Ashley ◽  
Anne M. Young
Keyword(s):  
Light Exposure ◽  
Light Emitting Diode ◽  
Attenuated Total Reflectance ◽  
Drying Time ◽  
Light Emitting ◽  
Spectral Changes ◽  
One Step ◽  
Urethane Dimethacrylate ◽  
Kinetics Of

The of this study aim was to develop a rapid method to determine the chemical composition, solvent evaporation rates, and polymerization kinetics of dental adhesives. Single-component, acetone-containing adhesives One-Step (OS; Bisco, USA), Optibond Universal (OU; Kerr, USA), and G-Bond (GB; GC, Japan) were studied. Filler levels were determined gravimetrically. Monomers and solvents were quantified by comparing their pure Attenuated Total Reflectance-Fourier Transform Infra-Red (ATR–FTIR) spectra, summed in different ratios, with those of the adhesives. Spectral changes at 37 °C, throughout passive evaporation for 5 min, then polymerisation initiated by 20 s, and blue light emitting diode (LED) (600 mW/cm2) exposure (n = 3) were determined. Evaporation and polymerisation extent versus time and final changes were calculated using acetone (1360 cm−1) and methacrylate (1320 cm−1) peaks. OS, OU, and GB filler contents were 0, 9.6, and 5.3%. FTIR suggested OS and OU were Bis-GMA based, GB was urethane dimethacrylate (UDMA) based, and that each had a different diluent and acidic monomers and possible UDMA/acetone interactions. Furthermore, initial acetone percentages were all 40−50%. After 5 min drying, they were 0% for OS and OU but 10% for GB. Whilst OS had no water, that in OU declined from 18 to 10% and in GB from 25 to 20% upon drying. Evaporation extents were 50% of final levels at 23, 25, and 113 s for OS, OU, and GB, respectively. Polymerisation extents were all 50 and 80% of final levels before 10 and at 20 s of light exposure, respectively. Final monomer polymerisation levels were 68, 69, and 88% for OS, OU, and GB, respectively. An appreciation of initial and final adhesive chemistry is important for understanding the properties. The rates of evaporation and polymerisation provide indications of relative required drying and light cure times. UDMA/acetone interactions might explain the considerably greater drying time of GB.

One‐step synthesis of amino‐functionalised magnetic mesoporous silica and synergistic adsorption kinetics of tetracycline and copper

2018 ◽  
Vol 13 (8) ◽  
pp. 1219-1223 ◽  
Author(s):  
Mancheng Zhang ◽  
Wei Wang ◽  
Zengyin Zhu ◽  
Changsheng Qu ◽  
Qing Zhou ◽  
...  
Keyword(s):  
Mesoporous Silica ◽  
Adsorption Kinetics ◽  
One Step ◽  
Kinetics Of ◽  
Magnetic Mesoporous Silica
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