The interaction of CO,N2 and NO with Cu cations in ZSM-5: quantum chemical description and IR study

In this paper we study the properties of Cu ions and their interactions with diatomic molecules in Cu-exchanged ZSM-5. We present DFT quantum chemical calculations for models composed of the Cu site and a diatomic molecule accompanied by IR investigations for various forms of CuZSM-5. Two series of calculations with density functional theory have been undertaken in order to investigate the influence of zeolitic framework on properties of exchanged cations: (i) for small models built of free mono- and divalent copper cation interacting with CO, N₂ and NO and (ii) 5- or 6-member ring models of ZSM-5 hosting the cation and a diatomic molecule. Comparison of calculated and experimental IR X–Y frequencies supports our model and brings some insight into the activation mechanism.

     

Platinum and palladium ions adsorption at the trace amounts by radiation crosslinked carboxymethylchitin and carboxymethylchitosan hydrogels

Adsorption of palladium and platinum ions at the trace amounts onto radiation crosslinked carboxymethylchitin (CMCht) and carboxymethylchitosan (CMChts) has been investigated. Maximum adsorption capacities for palladium were 2.679 and 1.053 mg/g dry gel, whereas for platinum they were 2.513 and 1.155 mg/dry gel for CMCht and CMChts, respectively. Retention capacity values for palladium were 0.45 and 0.06; for platinum 0.25 and 0.11 mEquiv./g for CMCht and CMChts, correspondingly. It has been shown that adsorption of Pd and Pt ions onto both hydrogels were dependent on the chloric and nitric ions concentration. Desorption experiments in HCl and HNO₃ solutions proved that adsorption is governed by chelating mechanism rather than ion‐exchange one. SEM‐EDX spectroscopy showed that palladium and platinum ions were homogeneously distributed in all sections of hydrogel matrix. DSC experiments demonstrated decreasing in the decomposition temperature of polymers after inclusion of palladium and platinum ions, suggesting that metals are causing lowering of stability in polymer structural integrity. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 4015–4023, 2007     

Diazepinoporphyrazines Containing Peripheral Styryl Substituents and Their Promising Nanomolar Photodynamic Activity against Oral Cancer Cells in Liposomal Formulations

The photochemical properties and photodynamic activity of three porphyrazines (Pzs) containing annulated diazepine rings, including novel demetalated porphyrazine‐possessing bis(styryl)diazepine moieties were investigated. The porphyrazines were evaluated in terms of their electronic absorption and emission properties, their tendency to undergo aggregation and photodegradation, as well as their singlet oxygen generation efficiency. The in vitro photodynamic activity of the porphyrazines and their liposomal formulations were examined by using two oral squamous cell carcinoma cell lines. Magnesium(II) tribenzodiazepinoporphyrazine ( 1 ) revealed the highest phototoxic effect in both cell lines used, H413 and HSC‐3. Encapsulation of Pz 1 into L ‐α‐phosphatidyl‐d,l ‐glycerol:1‐palmitoyl‐2‐oleoyl‐sn‐glycero‐3‐phosphocholine liposomes resulted in a nearly threefold increase in photocytotoxicity relative to that of the solution of Pz 1 (IC₅₀ values of 45 and 129 nM , respectively).     

Distinct Solid‐Electrolyte‐Interphases on Sn (100) and (001) Electrodes Studied by Soft X‐Ray Spectroscopy

Soft X‐ray absorption spectroscopy with different probe depth was employed to characterize the solid electrolyte interphases (SEIs) formed on β‐Sn single crystals with two different surface orientations. Based on comparative studies of C‐K, O‐K, and F‐K absorption spectra between the SEIs and reference samples, SEI on Sn (100) mainly consists of porous Li₂CO₃ species with electrolyte uptake, while SEI on Sn (001) essentially consists of LiF and organic molecules, with a small amount of –CO₃ and electrolyte buried inside. Theoretical calculation suggests that Sn (001) surface is more reactive than (100), especially after air exposure. The reactive (001) surface facilitates the decomposition of LiPF₆ to form a LiF layer. In contrast, SEI on (100) surface is predominately from the typical decomposition of carbonate‐based electrolyte. While the LiF passivates Sn (001) electrode after one cycle, the porous carbonate layer on (100) surface does not prevent further decomposition of electrolyte after many cycles. This leads to drastically different electrochemical behavior and morphology of the two SEIs. The result is a direct proof that surface properties of active materials could strongly impact the SEI formation on electrodes even with the same electrolyte. Such effect could lead to distinct SEI formation and electrochemical performance.     

Penalized solutions to functional regression problems

Recent technological advances in continuous biological monitoring and personal exposure assessment have led to the collection of subject-specific functional data. A primary goal in such studies is to assess the relationship between the functional predictors and the functional responses. The historical functional linear model (HFLM) can be used to model such dependencies of the response on the history of the predictor values. An estimation procedure for the regression coefficients that uses a variety of regularization techniques is proposed. An approximation of the regression surface relating the predictor to the outcome by a finite-dimensional basis expansion is used, followed by penalization of the coefficients of the neighboring basis functions by restricting the size of the coefficient differences to be small. Penalties based on the absolute values of the basis function coefficient differences (corresponding to the LASSO) and the squares of these differences (corresponding to the penalized spline methodology) are studied. The fits are compared using an extension of the Akaike Information Criterion that combines the error variance estimate, degrees of freedom of the fit and the norm of the basis function coefficients. The performance of the proposed methods is evaluated via simulations. The LASSO penalty applied to the linearly transformed coefficients yields sparser representations of the estimated regression surface, while the quadratic penalty provides solutions with the smallest L₂-norm of the basis function coefficients. Finally, the new estimation procedure is applied to the analysis of the effects of occupational particulate matter (PM) exposure on heart rate variability (HRV) in a cohort of boilermaker workers. Results suggest that the strongest association between PM exposure and HRV in these workers occurs as a result of point exposures to the increased levels of PM corresponding to smoking breaks.     

Computational spectroscopy and DFT investigations into nitrogen and oxygen bond breaking and bond making processes in model deNOx and deN2O reactions

Molecular DFT modeling combined with computational spectroscopy (EPR and IR) were applied for analysis of the NO bond breaking and NN and OO bond making in the context of deNO_x and deN₂O reactions. Interaction of NO, N₂O and NO₂ with cationic (transition metals) and anionic (surface O²⁻ ions) centers was explored at the molecular level. The elementary events such as reactant coordination, charge and spin redistributions, which are principal molecular constraints for efficient decomposition of the nitrogen oxides (N₂O and NO) were discussed. Particular attention was paid to dynamics of the NO bond cleavage in N₂O molecule through electron and oxygen atom transfer routes, evaluation of preferable coordination modes of NO, discrimination between inner- and outer-sphere mechanism of NN bond formation, and the influence of spin and electronic redistribution on the reaction course (spin catalysis). Owing to their simplicity and well known surface chemistry, model systems selected for studies of such processes include MoO_x/SiO₂, MgO and ZSM-5 zeolite exchanged with various transition metal ions (TMI) of different electron configuration and spin multiplicity: Mo⁵⁺ (d¹, ²D) Fe³⁺, Mn²⁺, Cr⁺ (d⁵, ⁶S), Fe²⁺ (d⁶, ⁵D), Co²⁺ (d⁷, ⁴F), Ni²⁺ (d⁸, ³F), Cu²⁺ (d⁹, ²D) and Cu⁺, Zn²⁺ (d¹⁰, ¹S).     

Electron spin resonance studies on silver atoms in imogolite fibers

The formation and stabilization of reduced silver species in imogolite have been studied by electron spin resonance (ESR) spectroscopy. Ag-loaded imogolite samples after degassing and dehydration were γ-irradiated at 77 K and monitored by ESR as the temperature increased. Some samples were exposed to methanol vapour after dehydration. It was found that imogolite shows exceptional ability to stabilize silver atoms. In dehydrated Ag-imogolite silver atoms generated at low temperature remain stable at room temperature. Silver atoms are also formed in imogolite samples exposed to methanol. However, in contrast to silver agglomeration in molecular sieves and smectites exposed to methanol there is no indication of the formation of cationic silver clusters in Ag-imogolite. It is postulated that there are special trapping sites in imogolite structure which effectively stabilize silver atoms.     

Modeling of Flow System Dynamics

This paper presents non-linear and linear models of flow system of laboratory stand (semi-industrial scale) with pressurized fluidized bed boiler. The non-linear model belongs to the class of lumped parameter models. The linear model was obtained experimentally using a novel method for design of control systems in industrial plants - MIKOZ. This study has connection with comparison of various methods of mathematical modeling of flow systems frequently encountered in power equipment.     

Hydrodenitrogenation of indole over Mo2C catalyst: Insights into mechanistic events through DFT modeling

The molecular reaction mechanism of hydrodenitrogenation of indole was studied using density-functional theory calculations of the adsorbed o-ethylaniline surrounded by mobile hydrogen atoms. It was found that the hydrogenation of o-ethylaniline occurs through two steps: consisting in redistribution of the π electron density to form multiple partial MoC(ring) bonds with the surface upon adsorption, and a subsequent hydrogen attack directed on the aromatic ring or the amine group. The direction of the hydrogen attack and the associated energy barriers determine the rate constants of the early (DDN, direct denitrogenation) and late (HYD, hydrogenation) nitrogen removal steps, and thus rules the selectivity of indole hydrodenitrogenation to ethylcyclohexane or ethylbenzene.     

High temperature electrolysis using Molten Carbonate Electrolyzer

Molten Carbonate Fuel Cells (MCFC) are a well-developed and commercial technology that can operate also as an electrolyzer producing hydrogen from steam. In this study, a system for the production of hydrogen based on Molten Carbonate Electrolyzer (MCE) is presented. The system receives, as an external input, water and recovers internally the additional gas streams required as input to the electrolyzer. The system products are, separately, pure oxygen and hydrogen. A calculation sheet was implemented to analyze the energy equilibrium and gas mix compositions. The system can produce 0.074 Nl h^?1 cm^?2 of hydrogen with an inlet power density of 0.213 W cm^?2 for an energy consumption of 3.40 kWh Nm_H2^?3. Sensitivity studies on current density, utilization factors of both steam and CO₂ were analyzed considering energy equilibrium of the stack unit and the post processing processes. Results show how current density has higher impact on system equilibrium compared to the other parameters.