scholarly journals A Labile Metallo-Porphyrin as Tool to Control J-Aggregates Chiroptical Properties

2020 ◽  
Author(s):  
Luigi Monsù Scolaro ◽  
Ilaria Occhiuto ◽  
Mariachiara Trapani ◽  
ROBERTO ZAGAMI ◽  
Andrea Romeo ◽  
...  
Keyword(s):  
Dipolar Coupling ◽  
Initial Conditions ◽  
Coupling Mechanism ◽  
Precise Control ◽  
Rate Determining Step ◽  
Initial Nucleus ◽  
Acidic Conditions ◽  
J Aggregates ◽  
Kinetics Of ◽  
Autocatalytic Growth

The zinc(II) metal derivative of 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (TPPS4) is quite labile and readily demetallates under acidic conditions, affording the parent diacid porphyrin in a monomeric form. The rate of this process is first order on [ZnTPPS4] and second order on [H+], allowing a precise control of the monomer release in solution. Under high ionic strength, this latter species is able to self-assemble into J-aggregates, whose kinetics of growth are largely modulated by pH. The aggregation kinetics have been treated according to a well-established model, in which the formation of an initial nucleus is the rate determining step preceding the autocatalytic growth of the whole assembly. The extinction spectra of the aggregates suggest the occurrence of a dipolar coupling mechanism very similar to that operating in metal nanoparticles. Spontaneous symmetry breaking takes place in these aggregates as evidenced by unusual circular dichroism spectra. The intensity and sign of the effect is controlled by the aggregation rate and therefore can be tuned through a proper choice of initial conditions.

scholarly journals Role of Cobalt(III) Cationic Complexes in the Self-Assembling Process of a Water Soluble Porphyrin

2020 ◽  
Vol 22 (1) ◽  
pp. 39
Author(s):  
Nadia Manganaro ◽  
Roberto Zagami ◽  
Mariachiara Trapani ◽  
Maria Angela Castriciano ◽  
Andrea Romeo ◽  
...  
Keyword(s):  
Dipolar Coupling ◽  
Water Soluble ◽  
The Self ◽  
Rate Determining Step ◽  
Self Assembling ◽  
Acidic Conditions ◽  
J Aggregates ◽  
Water Soluble Porphyrin ◽  
Amino Complex

Under moderate acidic conditions, the cationic (+3) complexes ions tris(1,10-phenanthroline)cobalt(III), [Co(phen)3]3+, and hexamminecobalt(III), [Co(NH3)6]3+, efficiently promote the self-assembling process of the diacid 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (H2TPPS4) into J-aggregates. The growth kinetics have been analyzed according to a well-established autocatalytic model, in which the rate determining step is the initial formation of a nucleus containing m porphyrin units (in the range 2–3), followed by a stage whose rate constant kc evolves as a power of time. The observed catalytic rate constants and the extent of J-aggregation increase on increasing the metal complex concentration, with the phen complex being the less active. The UV/Vis extinction spectra display quite broad envelops at the J-band, especially for the amino-complex, suggesting that electronic dipolar coupling between chromophores is operative in these species. The occurrence of spontaneous symmetry breaking has been revealed by circular dichroism and the measured dissymmetry g-factor decreases on increasing the aggregation rates. The role of these metal complexes on the growth and stabilization of porphyrin nano-assemblies is discussed in terms of the different degree of hydrophilicity and hydrogen bonding ability of the ligands present in the coordination sphere around the metal center.

scholarly journals Effects of the Mixing Protocol on the Self-Assembling Process of Water Soluble Porphyrins

2021 ◽  
Vol 22 (2) ◽  
pp. 797
Author(s):  
Maria Angela Castriciano ◽  
Sergio Cardillo ◽  
Roberto Zagami ◽  
Mariachiara Trapani ◽  
Andrea Romeo ◽  
...  
Keyword(s):  
Alternative Pathway ◽  
Ion Pairs ◽  
Resonance Light Scattering ◽  
Water Soluble ◽  
Self Assembling ◽  
Vis Spectroscopy ◽  
Acidic Conditions ◽  
J Aggregates ◽  
Kinetics Of ◽  
Tartrate Anion

The hierarchical self-assembling kinetics of the porphyrin 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (H2TPPS44−) into J-aggregates at high ionic strength under acidic conditions and eventually in the presence of an added chiral templating agent (tartrate) were investigated through UV/Vis spectroscopy, resonance light scattering, and circular dichroism (CD). The effect of changing the mixing order of the various components in the solution on the kinetic parameters and the expression of chirality on the final J-aggregates was evaluated. In this latter case, only when the chiral tartrate anion is premixed with the porphyrin, the resulting nano-architectures exhibit CD spectra that reflect the handedness of the chiral inducer. We discuss a general mechanistic scheme, with the involvement of ion pairs or dimers that offer an alternative pathway to the aggregation process.

Spectroscopic and kinetic investigations on porphyrin J-aggregates induced by polyamines

2010 ◽  
Vol 14 (08) ◽  
pp. 713-721 ◽  
Author(s):  
Andrea Romeo ◽  
Maria Angela Castriciano ◽  
Luigi Monsù Scolaro
Keyword(s):  
Early Stage ◽  
Model System ◽  
Kinetic Investigation ◽  
Aggregation Process ◽  
Kinetic Behavior ◽  
Rate Determining Step ◽  
Mesoscopic Structure ◽  
Acidic Conditions ◽  
J Aggregates ◽  
Kinetic Investigations

A non-covalent supramolecular approach to build up mesoscopic fractal J-aggregates of meso-tetrakis(4-sulfonatophenyl)porphyrin by using different polyamines under mild acidic conditions is reported. Spermine-induced J-aggregates have been treated as a model system for a kinetic investigation. The kinetic analysis has been performed through two non-conventional approaches as function of a different reagent mixing protocol. In particular, an autocatalytic pathway in which the formation of aggregation nuclei is the rate-determining step is found when porphyrin is added to the reaction mixture as first reagent. In order to gain information on this early stage, a kinetic investigation has been carried out as function of different parameters, such as pH, and both spermine and porphyrin concentration. The nucleation becomes particularly evident when polyamines with fewer than three protonable nitrogen atoms are used. In these cases, a sort of "YES/NO" effect for the aggregation process has been found as a function of the reagent mixing order protocol. Most importantly, the observed kinetic behavior strongly affects the mesoscopic structure of the final aggregates.

Kinetics of carbon monoxide methanation on a Ni/SiO2 catalyst

1990 ◽  
Vol 55 (7) ◽  
pp. 1678-1685
Author(s):  
Vladimír Stuchlý ◽  
Karel Klusáček
Keyword(s):  
Carbon Monoxide ◽  
Reaction Rate ◽  
Catalyst Activity ◽  
Adsorbed Hydrogen ◽  
Reaction Products ◽  
Co Methanation ◽  
Molar Ratios ◽  
Rate Determining Step ◽  
Higher Temperature ◽  
Kinetics Of

Kinetics of CO methanation on a commercial Ni/SiO2 catalyst was evaluated at atmospheric pressure, between 528 and 550 K and for hydrogen to carbon monoxide molar ratios ranging from 3 : 1 to 200 : 1. The effect of reaction products on the reaction rate was also examined. Below 550 K, only methane was selectively formed. Above this temperature, the formation of carbon dioxide was also observed. The experimental data could be described by two modified Langmuir-Hinshelwood kinetic models, based on hydrogenation of surface CO by molecularly or by dissociatively adsorbed hydrogen in the rate-determining step. Water reversibly lowered catalyst activity and its effect was more pronounced at higher temperature.

scholarly journals Single entity electrochemistry and the electron transfer kinetics of hydrazine oxidation

Nano Research ◽  
2021 ◽  
Author(s):  
Ruiyang Miao ◽  
Lidong Shao ◽  
Richard G. Compton
Keyword(s):  
Electron Transfer ◽  
Bulk Solution ◽  
Relative Contribution ◽  
Rate Determining Step ◽  
Multistep Process ◽  
Ph Range ◽  
Electro Catalytic Oxidation ◽  
Single Particle Impact ◽  
The Impact ◽  
Kinetics Of

AbstractThe mechanism and kinetics of the electro-catalytic oxidation of hydrazine by graphene oxide platelets randomly decorated with palladium nanoparticles are deduced using single particle impact electrochemical measurements in buffered aqueous solutions across the pH range 2–11. Both hydrazine, N2H4, and protonated hydrazine N2H5+ are shown to be electroactive following Butler-Volmer kinetics, of which the relative contribution is strongly pH-dependent. The negligible interconversion between N2H4 and N2H5+ due to the sufficiently short timescale of the impact voltammetry, allows the analysis of the two electron transfer rates from impact signals thus reflecting the composition of the bulk solution at the pH in question. In this way the rate determining step in the oxidation of each specie is deduced to be a one electron step in which no protons are released and so likely corresponds to the initial formation of a very short-lived radical cation either in solution or adsorbed on the platelet. Overall the work establishes a generic method for the elucidation of the rate determining electron transfer in a multistep process free from any complexity imposed by preceding or following chemical reactions which occur on the timescale of conventional voltammetry.

Nanostructured Doped Silica Films Application as Sensitive Layers for Chemical Sensors

2013 ◽  
Vol 684 ◽  
pp. 7-11
Author(s):  
Sergey Krutovertsev ◽  
Alla Tarasova ◽  
Olga Ivanova ◽  
Larisa Krutovertseva
Keyword(s):  
Initial Conditions ◽  
Sol Gel ◽  
Silica Films ◽  
Adsorption Activity ◽  
Developed Surface ◽  
Sol Gel Process ◽  
Sensitive Characteristics ◽  
The Right ◽  
Kinetics Of ◽  
Matrix Factors

The sensor behavior of nanostructured doped silica films produced by sol-gel way were examined. Hygroscopic substances and polyoxometalates were used as additives to make more significant sensitive characteristics of initial matrix. Factors that have effect on sol preparation and films forming were investigated. Adsorption activity of the sensitive films was studied and it was shown that the films had a highly developed surface with nano-size pores. Change of initial conditions of sol-gel process gives opportunity to influence on kinetics of gel formation and consequently, on structure and properties of final materials. The study showed that the conditions of the environment affected the sensors characteristics markedly, which can be improved by choosing of the right procedure of forming and treatment. Influence of type and additive substances quantity into doped films was discussed in the paper

Kinetics of chromate reduction by pyrite and biotite under acidic conditions

2006 ◽  
Vol 21 (9) ◽  
pp. 1469-1481 ◽  
Author(s):  
Chul-Min Chon ◽  
Jae Gon Kim ◽  
Hi-Soo Moon
Keyword(s):  
Chromate Reduction ◽  
Acidic Conditions ◽  
Kinetics Of

scholarly journals The kinetics of the hydrogen chloride oxidation

2013 ◽  
Vol 78 (12) ◽  
pp. 2115-2130 ◽  
Author(s):  
Martinez Gonzalez ◽  
Tanja Vidakovic-Koch ◽  
Rafael Kuwertz ◽  
Ulrich Kunz ◽  
Thomas Turek ◽  
...  
Keyword(s):  
Kinetic Parameters ◽  
Gas Phase ◽  
Hydrogen Chloride ◽  
Reaction Order ◽  
Membrane Electrode ◽  
Polarization Data ◽  
Rate Determining Step ◽  
Electrode Assemblies ◽  
Apparent Kinetic Parameters ◽  
Kinetics Of

Hydrogen chloride (HCl) oxidation has been investigated on technical membrane electrode assemblies in a cyclone flow cell. Influence of Nafion loading, temperature and hydrogen chloride mole fraction in the gas phase has been studied. The apparent kinetic parameters like reaction order with respect to HCl, Tafel slope and activation energy have been determined from polarization data. The apparent kinetic parameters suggest that the recombination of adsorbed Cl intermediate is the rate determining step.

scholarly journals Dye removal abilities of the mesophilic and thermophilic biomass: a kinetics study

2018 ◽  
Vol 20 (2) ◽  
pp. 408-416
Keyword(s):  
Intraparticle Diffusion ◽  
Second Order ◽  
Intraparticle Diffusion Model ◽  
First Order Kinetics ◽  
Different Types ◽  
Pseudo Second Order ◽  
Acidic Conditions ◽  
Red Dye ◽  
Experimental Kinetics ◽  
Kinetics Of

Mesophilic biomass and thermophilic biomass samples were isolated and used to remove Dorasyn Red dye from aqueous solutions. The biosorption kinetics of dye uptake by four different types of biomass at three temperatures (20, 30, and 40 °C) were investigated using pseudo-first order kinetics, pseudo-second order kinetics, intraparticle diffusion, Elovich, and Bangham models. The pseudo-second-order kinetics model and the first stage of the intraparticle diffusion model were effective in describing the experimental kinetics data. The biosorption results showed that the mesophilic biomass samples could be useful for removing dye under acidic conditions.

scholarly journals Effect of Thermophysical Properties on Coupled Heat and Mass Transfer in Porous Material during Forced Convective Drying

2014 ◽  
Vol 6 ◽  
pp. 830387 ◽  
Author(s):  
Wei Cai ◽  
Lexian Zhu ◽  
Shilin Dong ◽  
Guozhen Xie ◽  
Junming Li
Keyword(s):  
Porous Medium ◽  
Diffusion Coefficient ◽  
Temperature Distribution ◽  
Moisture Content ◽  
Initial Conditions ◽  
Positive Impact ◽  
Soret Effect ◽  
Convective Drying ◽  
Large Temperature ◽  
Kinetics Of

The convective drying kinetics of porous medium was investigated numerically. A mathematical model for forced convective drying was established to estimate the evolution of moisture content and temperature inside multilayered porous medium. The set of coupled partial differential equations with the specified boundary and initial conditions were solved numerically using a MATLAB code. An experimental setup of convective drying had been constructed and validated the theoretical model. The temperature and moisture content of the potato samples were dynamically measured and recorded during the drying process. Results indicate that thermal diffusion coefficient has significant positive impact on temperature distribution and mass diffusion coefficient might directly affect the moisture content distribution. Soret effect has a significant impact on heat flux and temperature distribution in the presence of large temperature gradient.

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