Dioxygen activation at monovalent nickel

The monovalent oxidation state of nickel has received a growing amount of attention in recent years, in part due to its suggested catalytic role in a number of metalloprotein-mediated transformations. In coordination chemistry, nickel(I) is suitable for reductive activation of dioxygen, provided ligands are used that stabilize this less common oxidation state against disproportionation reactions. Two distinct molecular systems have been explored, which have provided access to new nickel-dioxygen structure types, namely, monomeric side-on and end-on superoxo and trans-micro-1,2-peroxo-dinickel complexes. The geometric and electronic structures of the complexes have been established by advanced spectroscopic methods, including resonance Raman and X-ray absorption spectroscopies, and augmented by density functional theory analyses.     

Finding intermediates in the O2 activation pathways of non-heme iron oxygenases

Intermediates in the reaction cycle of an oxygenase are usually very informative with respect to the chemical mechanism of O 2 activation and insertion. However, detection of these intermediates is often complicated by their short lifetime and the regulatory mechanism of the enzyme designed to ensure specificity. Here, the methods used to detect the intermediates in an extradiol dioxygenase, a Rieske cis-dihydrodiol dioxygenase, and soluble methane monooxygenase are discussed. The methods include the use of alternative, chromophoric substrates, mutagenesis of active site catalytic residues, forced changes in substrate binding order, control of reaction rates using regulatory proteins, and initialization of catalysis in crystallo.     

Laser flash photolysis generation of high-valent transition metal-oxo species: insights from kinetic studies in real time

High-valenttransition metal-oxo species are active oxidizing species in many metal-catalyzed oxidation reactions in both Nature and the laboratory. In homogeneous catalytic oxidations, a transition metal catalyst is oxidized to a metal-oxo species by a sacrificial oxidant, and the activated transition metal-oxo intermediate oxidizes substrates. Mechanistic studies of these oxidizing species can provide insights for understanding commercially important catalytic oxidations and the oxidants in cytochrome P450 enzymes. In many cases, however, the transition metal oxidants are so reactive that they do not accumulate to detectable levels in mixing experiments, which have millisecond mixing times, and successful generation and direct spectroscopic characterization of these highly reactive transients remain a considerable challenge. Our strategy for understanding homogeneous catalysis intermediates employs photochemical generation of the transients with spectroscopic detection on time scales as short as nanoseconds and direct kinetic studies of their reactions with substrates by laser flash photolysis (LFP) methods. This Account describes studies of high-valent manganese- and iron-oxo intermediates. Irradiation of porphyrin-manganese(III) nitrates and chlorates or corrole-manganese(IV) chlorates resulted in homolytic cleavage of the O-X bonds in the ligands, whereas irradiation of porphyrin-manganese(III) perchlorates resulted in heterolytic cleavage of O-Cl bonds to give porphyrin-manganese(V)-oxo cations. Similar reactions of corrole- and porphyrin-iron(IV) complexes gave highly reactive transients that were tentatively identified as macrocyclic ligand-iron(V)-oxo species. Kinetic studies demonstrated high reactivity of the manganese(V)-oxo species, and even higher reactivities of the putative iron(V)-oxo transients. For example, second-order rate constants for oxidations of cis-cyclooctene at room temperature were 6 x 10(3) M(-1) s(-1) for a corrole-iron(V)-oxo species and 1.6 x 10(6) M(-1) s(-1) for the putative tetramesitylporphyrin-iron(V)-oxo perchlorate species. The latter rate constant is 25,000 times larger than that for oxidation of cis-cyclooctene by iron(IV)-oxo perchlorate tetramesitylporphyrin radical cation, which is the thermodynamically favored electronic isomer of the putative iron(V)-oxo species. The LFP-determined rate constants can be used to implicate the transient oxidants in catalytic reactions under turnover conditions where high-valent species are not observable. Similarly, the observed reactivities of the putative porphyrin-iron(V)-oxo species might explain the unusually high reactivity of oxidants produced in the cytochrome P450 enzymes, heme-thiolate enzymes that are capable of oxidizing unactivated carbon-hydrogen bonds in substrates so rapidly that iron-oxo intermediates have not been detected under physiological conditions.     

Biodiesel production via transesterification: Process safety insights from kinetic modeling

Biodiesel is an alternative non-petroleum based fuel, consisting of alkyl esters obtained either by esterification of free fatty acids with low molecular weight alcohols, or by transesterification of triglycerides. The realization of a biodiesel unit can pose several safety issues and inherent safety application opportunities as the production involves the transport, use and storage of hazardous materials, either flammable or toxic. In the experimental phase, we studied, at laboratory scale, different alkali catalysts and the relevant reaction parameters, considering inherent safety opportunities. An accurate kinetic model of the transesterification process was developed and validated, allowing to provide possible minimization and simplification plant options.     

Substituent effects of iron porphyrins: Structural, kinetic, and theoretical studies

Substituent effects of iron porphyrin complexes on the structures and kinetic processes have been examined for the first time. Basing on the premise that iron porphyrin is functional analogous to heme, a series of iron porphyrin derivatives bearing different substituents at the meso positions of the corrole ring are investigated as to their electrochemistry, the relationships among the electron transfer (ET) processes, their structures, and orbital energies. The good coherence between the experiment and theory indicates that the ET rate can be accelerated when electron-donating substituents are introduced to the iron porphyrin ring. Finally, the implications of the results are discussed in the influence of stability of iron porphyrin complexes on the ability to carry molecular oxygen, which may suggest it possible to dominate the biological activity of heme by selecting the appropriate substituents to iron porphyrin ring.     

Mass transfer studies at iron felts

Mass transfer has been studied at flow-through iron felts using the reduction of ferricyanide or copper cementation on iron as test reactions. Empirical correlations between a modified Sherwood number and the Reynolds number are proposed. Comparisons of the mass-transfer performance of iron felts with other three-dimensional structures are made.List of symbols a ₃ specific surface area per unit felt volume (m^–1) - A empty cross-section of the reactor (m²) - C concentration (mol m^–3) - C ₀ inlet concentration (mol m^–3) - d _h hydraulic diameter (m) - e fibre thickness (m) - E electrode potential (V) - D diffusion coefficient (m²s^–1) - F Faraday constant (A s mol^–1) - i current density (A m^–2) - I total current (A) - I _L limiting current (A) - J _m mass transfer j-factor=(k/v)Sc ^2/3 - K mass transfer coefficient (m s^–1) - l fibre width (m) - L electrode thickness (m) - Re Reynolds number - vd _h/ - Re modified Reynolds number - vl/ - Sc Schmidt number = /D - Sh modified sherwood number = ka _e l ²/D - t time (s) - T Temperature (K) - superficial liquid flow velocity (m s^–1) Greek characters void fraction - dynamic viscosity (kg m^–1 s^–1) - kinematic viscosity (m² s^–1) - ₃ charge number of the electrode reaction - iron density (kg m^—) - _a apparent density of the felt (kg m^–3) - _m residence time of the reservoir (s)     

Reductive removal of hexavalent chromium from aqueous solution using sepiolite-stabilized zero-valent iron nanoparticles: Process optimization and kinetic studies

We studied the optimization of hexavalent chromium (Cr(VI)) removal from aqueous solution using the synthesized zero-valent iron nanoparticles stabilized with sepiolite clay (S-ZVIN), under various parameters such as reaction time (min), initial solution pH and concentration of S-ZVIN (g·L^?1) using response surface methodology (RSM). The kinetic study of Cr(VI) was conducted using three types of the most commonly used kinetic models including pseudo zero-order, pseudo first-order, and pseudo second-order models. The rate of reduction reaction showed the best fit with the pseudo first-order kinetic model. The process optimization results revealed a high agreement between the experimental and the predicted data (R²=0.945, Adj-R²=0.890). The results of statistical analyses showed that reaction time was the most impressive factor influencing the efficiency of removal process. The optimum conditions for maximum response (98.15%) were achieved at the initial pH of 4.7, S-ZVIN concentration of 1.3 g·L^?1 and the reaction time of 75 min.     

Microbial detoxification of superoxide: the non-heme iron reductive paradigm for combating oxidative stress

A reductive paradigm has emerged in recent years for detoxification of superoxide and other redox active diatomic molecules in air-sensitive bacteria and archaea. Adventitiously generated superoxide in many anaerobic or microaerophilic bacteria and archaea is scavenged by superoxide reductase (SOR) rather than the classical superoxide dismutases characteristic of aerobic microbes. SORs contain a novel five-coordinate, square-pyramidal [Fe(His)4(Cys)] ferrous active site, which adds a sixth glutamate ligand upon oxidation. This Account summarizes the recently elucidated structural and mechanistic features of SORs. The non-heme iron reductive scavenging paradigm in these air-sensitive microbes also extends to recently characterized enzymes that scavenge hydrogen peroxide and nitric oxide and to oxygen sensing proteins.     

A UV-LEDs based photomicroreactor for mechanistic insights and kinetic studies in the norbornadiene photoisomerization

In this work, we report a simple and inexpensive UV-LEDs based photomicroreactor assembly constructed by commercially available components. The photoisomerization of norbornadiene to quadricyclane was selected to validate this novel photomicroreactor design. Mass transport limitation was eliminated and indicated by dimensionless numbers Fo and Da _II, and photons loss was evaluated considering the absorption and reflection of the microreactor walls. The solvents, photosensitizers, and light sources selections were optimized for achieving better photochemical performance and mechanistic insights. The detailed comparison between the high-pressure mercury arc lamp and the UV-LEDs strip revealed great potential of UV-LEDs as appealing light source for photochemical transformations. Moreover, the reaction mechanism was thoroughly discussed and illustrated by the Jablonski diagram indicating electronic states transitions. According to possible intermediate steps, a kinetic model was proposed with the reaction rate constant being correlated with the photon flux, which is valuable for process optimization and further understanding reaction mechanisms.     

Comparative kinetic studies of polypyrrole electrogeneration from acetonitrile solutions

The formation and growth of polypyrrole films on platinum electrodes from acetonitrile media has been followed by microgravimetricex situ determination of the polymer grafted on the electrode. Kinetic parameters were also obtained from the charge consumed during polymerization. The electrogenerated polymer films were checked in the background electrolyte by voltammetry and chronoamperometry. Assuming a constant oxidation or reduction charge per unit of polymer weight, these charges were used to obtain the reaction order during the polymerization processes. The kinetics were found to be dependent on [pyrrole]^0.5 [LiClO₄]^0.5 from gravimetric determination; [pyrrole]^0.4 [LiClO₄]^0.5 from the polymerization charge; [pyrrole]^0.4 [LiClO₄]^0.5 from the anodic charge of the control voltammograms and [pyrrole]^0.4 [LiClO₄]^0.4 from the anodic and cathodic charge of the control chronoamperograms. Good agreement was found between the different methods. The good agreement between order dependence was due to the low water content.     

A polyacrylonitrile-based gelled electrolyte: electrochemical kinetic studies

The bulk and interfacial properties of thin films of a polyacrylonitrile-based (PAN-based) gelled electrolyte, which was tested in conjunction with lithium electrodes, were evaluated at room temperature. The typical composition of the gelled electrolyte (GE) studied was PAN (9.13 wt %); propylene carbonate, or PC (84.87 wt %); and LiBF₄ (6 wt %). A.c. and d.c. measurements were used to determine the bulk conductivity and the interfacial apparent charge-transfer resistance (R _act) of the GE. While the bulk conductivity remains stable at around 10^–3 S cm^–1, the R _act varies initially before reaching a steady value. The steady R _act value obtained from the electrochemical measurements is near 1000 cm². The plating/stripping efficiency of lithium, from potentiostatic and galvanostatic measurements, is 70 to 80%.     

Removal of iron from drinking water by electrocoagulation: Adsorption and kinetics studies

The present study provides an electrocoagulation process for the removal of iron from drinking water with aluminum alloy as the anode and stainless steel as the cathode. The studies were carried out as a function of pH, temperature and current density. The adsorption capacity was evaluated with both the Langmuir and the Freundlich isotherm models. The results showed that the maximum removal efficiency of 98.8% was achieved at a current density of 0.06 A dm⁻², at a pH of 6.5. The adsorption of iron preferably fitting the Langmuir adsorption isotherm suggests monolayer coverage of adsorbed molecules. The adsorption process follows second-order kinetics. Temperature studies showed that adsorption was endothermic and spontaneous in nature.     

Natural colorant from the bark of Macaranga peltata: kinetic and adsorption studies on silk

The colour component from the bark of Macaranga peltata has been extracted and, using spectral techniques, the main colouring ingredient has been identified as ellagic acid. The dyeing properties of the extract on silk have been studied. The colour coordinates of the dyed samples were found to be in the yellow–red quadrant of the colour space diagram and the dyed samples exhibited acceptable fastness properties. The effect of temperature and dye concentration on the rate of dyeing has been studied. Adsorption studies revealed that the process fits well with the Langmuir isotherm model. The thermodynamic parameters of the dyeing process have been evaluated using an Arrhenius plot. The experimental results revealed that the adsorption was exothermic and spontaneous in nature, and exhibited first‐order kinetics. Further, the effect of electrolyte on rate of dyeing has also been recorded. The rate of adsorption increases as the disrupting effect of the added electrolyte cation increases and follows the order: Al³⁺ > Ca²⁺ > Na⁺.     

Biosorption from aqueous solutions by eggshell membranes and Rhizopus oryzae: equilibrium and kinetic studies

This study assesses the use of eggshell membranes and Rhizopus oryzae as media for the biosorption of p‐chlorophenol (p‐CP), 2,4‐dichlorophenol (2,4‐DCP), 3,5‐dichlorophenol (3,5‐DCP), reactive dye and cadmium from aqueous solutions. The performance of the adsorbents was quantified by measuring the equilibrium uptake and the batch rate kinetics from solutions. The constants in the Freundlich, Langmuir and Redlich–Peterson isotherm models were calculated through the linearization of the equations and linear regression. The kinetics of the adsorption systems for cadmium and a reactive dye have been assessed in a batch stirred adsorber. The effect of the process parameters such as pH, adsorbate concentration, adsorbent dosage, adsorbent particle size, temperature and agitation speed are reported. The external mass transfer coefficients are reported for some different system conditions. Both materials are determined to be effective adsorbents and could find application in the treatment of contaminated wastestreams. © 2002 Society of Chemical Industry     

Kinetics of epoxy cure: a rapid technique for kinetic parameter estimation

A rapid estimation technique is proposed for the determination of the kinetic parameters describing the autocatalytic reaction of epoxy cure. The method utilizes information from a single characteristic point, namely, the point of maximum rate of cure. The proposed method yields results which are in very close agreement with more rigorous regression techniques.     

Quantum chemistry behind bioimaging: insights from ab initio studies of fluorescent proteins and their chromophores

The unique properties of green fluorescent protein (GFP) have been harnessed in a variety of bioimaging techniques, revolutionizing many areas of the life sciences. Molecular-level understanding of the underlying photophysics provides an advantage in the design of new fluorescent proteins (FPs) with improved properties; however, because of its complexity, many aspects of the GFP photocycle remain unknown. In this Account, we discuss computational studies of FPs and their chromophores that provide qualitative insights into mechanistic details of their photocycle and the structural basis for their optical properties. In a reductionist framework, studies of well-defined model systems (such as isolated chromophores) help to understand their intrinsic properties, while calculations including protein matrix and/or solvent demonstrate, on the atomic level, how these properties are modulated by the environment. An interesting feature of several anionic FP chromophores in the gas phase is their low electron detachment energy. For example, the bright excited ππ* state of the model GFP chromophore (2.6 eV) lies above the electron detachment continuum (2.5 eV). Thus, the excited state is metastable with respect to electron detachment. This autoionizing character needs to be taken into account in interpreting gas-phase measurements and is very difficult to describe computationally. Solvation (and even microsolvation by a single water molecule) stabilizes the anionic states enough such that the resonance excited state becomes bound. However, even in stabilizing environments (such as protein or solution), the anionic chromophores have relatively low oxidation potentials and can act as light-induced electron donors. Protein appears to affect excitation energies very little (<0.1 eV), but alters ionization or electron detachment energies by several electron volts. Solvents (especially polar ones) have a pronounced effect on the chromophore's electronic states; for example, the absorption wavelength changes considerably, the ground-state barrier for cis-trans isomerization is reduced, and fluorescence quantum yield drops dramatically. Calculations reveal that these effects can be explained in terms of electrostatic interactions and polarization, as well as specific interactions such as hydrogen bonding. The availability of efficient computer implementations of predictive electronic structure methods is essential. Important challenges include developing faster codes (to enable better equilibrium sampling and excited-state dynamics modeling), creating algorithms for properties calculations (such as nonlinear optical properties), extending standard excited-state methods to autoionizing (resonance) states, and developing accurate QM/MM schemes. The results of sophisticated first-principle calculations can be interpreted in terms of simpler, qualitative molecular orbital models to explain general trends. In particular, an essential feature of the anionic GFP chromophore is an almost perfect resonance (mesomeric) interaction between two Lewis structures, giving rise to charge delocalization, bond-order scrambling, and, most importantly, allylic frontier molecular orbitals spanning the methine bridge. We demonstrate that a three-center Hückel-like model provides a useful framework for understanding properties of FPs. It can explain changes in absorption wavelength upon protonation or other structural modifications of the chromophore, the magnitude of transition dipole moment, barriers to isomerization, and even non-Condon effects in one- and two-photon absorption.     

Design and characterisation of a close-concentric annular reactor for kinetic studies at high temperatures

A novel annular reactor for kinetic studies at high temperature and flow conditions has been designed to keep eccentricity tolerances below 10%. In a previous work, we have shown that it is very important to keep such low eccentricity values in order to collect reliable kinetic data from this type of reactors. As proposed in this study, a modified reactor with the use of a spacer could guarantee an annular duct with low levels of eccentricity. Manufacturing tolerances or deformation effects giving rise to eccentricity can be significantly minimised when using this apparatus. The reactor has been both experimentally and theoretically characterised. Carbon monoxide oxidation was used as a model reaction under mass-transfer limited conditions revealing an eccentricity of ∼5%. With such small eccentricity levels, a concentric annular form can be assumed in the reactor analysis. Simple 1D or 2D models can therefore be inexpensively used in the evaluation of the kinetic data. Also, prior to the design of the annular reactor, a numerical investigation was carried out to clarify the effects of eccentricity, physical properties of the carrier gas and the annular aspect ratio on mass-transfer limitations. Contrary to expectations, a considerable increase in the fuel mass-diffusivity by carrier gas substitution did not change the mass-transfer rates for cases when eccentricity and aspect ratios were high.     

Removal of strontium from aqueous solutions by adsorption onto activated carbon: kinetic and thermodynamic studies

This work reports the adsorption of strontium from aqueous solutions onto activated carbon. Various factors such as pH, initial concentration of strontium, particle size and temperature were considered. The optimum conditions obtained were: pH value = 4.0, contact time = 8 h, initial concentration of Sr(II) = 100 mg/l, particle size = 270 μm and temperature of 293.15 K. The adsorption of strontium(II) on activated carbon follows pseudo-first order kinetics and the energy of activation E_a calculated using the Arrehenius equation was found to be 3.042 kJ/mol.The adsorption isotherms could be fitted by the Langmuir model with the maximum adsorption capacity Q_o being 5.07×10^–4 mol/g at 293.15 K. A dimensionless separation factor R_L was used to judge the favourable adsorption. The values of the mass transfer coefficient β_L (cm/s) at different temperatures indicated that the velocity of mass transfer of Sr(II) ions onto activated carbon was slow. The intraparticle diffusion mechanism is of great importance in determining the overall rate of removal and the negative entropy of activation ΔS^# value 145.13 J/mol K, reflects that no significant change occurs in the internal structure of activated carbon during adsorption of strontium(II). The Gibbs free energy ΔG°_ads values range from –36.61 kJ/mol to –41.75 kJ/mol at 293.15–333.15 K, which show the physical adsorption properties of activated carbon and indicate the feasibility of the process.