High-Valent Iron-Oxo and -Nitrido Complexes: Bonding and Reactivity

Multiple-bonded iron-oxo and -nitrido species have been identified or proposed as key intermediates in a range of important chemical transformations. The reported model complexes feature various coordination geometries and distinct electronic structures, and therefore exhibit diverse reactivity. The present contribution highlights the synergy from both experimental and theoretical standpoints to elucidate their different bonding situations and delineate their common mechanistic features in hydrogen-atom abstraction processes. Our analysis reveals that a radical centered on the abstracting atom E (E=O, N), which is generated via homolysis of covalent Fe−E bonds upon approaching the transition state, is an intrinsic C−H cleaving agent. The iron-oxo species is predicted to be more reactive than its nitride congener, in general, because the O−H bond formed in the H-atom transfer process is often stronger than the corresponding N−H bond.     

Efficient Host-Guest Complexation of a Bisporphyrin Host with Electron Deficient Guests: Synthesis,Structure, and Photoinduced Electron Transfer

The encapsulation of 1,8-naphthalic anhydride (NAN), 9-dicyanomethylenefluorene (9-DCF), acenaphthenequinone (ANQ), and 4-chloro-7-nitrobenzofurazan (NBD-Cl) by diethylpyrrole-bridged bisporphyrin (H₄DEP) and its dizinc(II) analogue (Zn₂DEP) are employed to investigate the structural and spectroscopic changes within the bisporphyrin cavity upon substrate binding. Synthesis and X-ray structures of all four encapsulated host-guest complexes (H₄DEP⋅NAN, H₄DEP⋅9-DCF, Zn₂DEP⋅ANQ, and Zn₂DEP⋅NBD-Cl) are reported here. The binding constant calculations show strong 1 : 1 binding between the hosts (H₄DEP and Zn₂DEP) and the guests (NAN/9-DCF/ANQ/NBD-Cl). ¹H-NMR spectra also support the retention of the host-guest assemblies in solution. Negative and positive shifts of the reduction and oxidation potentials, respectively, indicate that it is difficult to reduce/oxidize the encapsulated complexes. The emission intensities of the bisporphyrins (H₄DEP and Zn₂DEP) are substantially quenched in all the complexes, owing to photoinduced electron transfer from the excited state of the bisporphyrins to guest molecules. All the experimental evidence is further substantiated by DFT calculations. Such an efficient electron transfer is only possible when the donor and the acceptor moieties are in close propinquity to each other, which eventually lowers the reorganization energy.     

Synthesis of flexible polymeric shielding materials for soft gamma rays: Physicomechanical and attenuation characteristics of radiation crosslinked polydimethylsiloxane/Bi2O3 composites

Flexible lead‐free high energy radiation shielding material was developed through internal compounding. Polymer‐filler interaction, crosslinking density, specific gravity, physicomechanical characteristics, percentage attenuation, and thermal stability of the crosslinked composites were estimated. It was found that even at very high filler loading composites can be crosslinked; however, the crosslinking density was composition dependent and was highest in 10–50 wt% loading range at 100 kGy and 200 kGy. The Nielsen model was applied to understand the micromechanics of the system. Attenuation of gamma radiation from Am241 was not affected by the crosslinking density. Thermal stability of the composites was found to be significantly affected with bismuth oxide loading. POLYM. COMPOS., 37:756–762, 2016. © 2014 Society of Plastics Engineers     

Segmentation of breast lesion in DCE-MRI by multi-level thresholding using sine cosine algorithm with quasi opposition-based learning

Pattern Analysis and Applications - In recent times, the high prevalence of breast cancer in women has increased significantly. Breast cancer diagnosis and detection employing computerized...     

An EPQ model with promotional demand in random planning horizon: population varying genetic algorithm approach

One of the economic production quantity problems that have been of interest to researchers is the production with reworking of the imperfect items including waste most disposal form and vending the units. The available models in the literature assumed that the decay rate of the items is satisfied from three different points of view: (i) minimum demands of the customer’s requirement, (ii) demands to be enhanced for lower selling price and (iii) demands of the customers who are motivated by the advertisement. The model is developed over a finite random planning horizon, which is assumed to follow the exponential distribution with known parameters. The model has been illustrated with a numerical example, whose parametric inputs are estimated from market survey. Here the model is optimized by using a population varying genetic algorithm.     

A survey of stochastic ω-regular games

We summarize classical and recent results about two-player games played on graphs with ω-regular objectives. These games have applications in the verification and synthesis of reactive systems. Important distinctions are whether a graph game is turn-based or concurrent; deterministic or stochastic; zero-sum or not. We cluster known results and open problems according to these classifications.     

Security analysis of GTRBAC and its variants using model checking

Security analysis is a formal verification technique to ascertain certain desirable guarantees on the access control policy specification. Given a set of access control policies, a general safety requirement in such a system is to determine whether a desirable property is satisfied in all the reachable states. Such an analysis calls for the use of formal verification techniques. While formal analysis on traditional Role Based Access Control (RBAC) has been done to some extent, recent extensions to RBAC lack such an analysis. In this paper, we consider the temporal RBAC extensions and propose a formal technique using timed automata to perform security analysis by analyzing both safety and liveness properties. Using safety properties one ensures that something bad never happens while liveness properties show that some good state is also achieved. GTRBAC is a well accepted generalized temporal RBAC model which can handle a wide range of temporal constraints while specifying different access control policies. Analysis of such a model involves a process of mapping a GTRBAC based system into a state transition system. Different reduction rules are proposed to simplify the modeling process depending upon the constraints supported by the system. The effect of different constraints on the modeling process is also studied.     

Technical note The effect of rate of decay of rain path profile on microwave communication

The attenuation of radio waves due to rain can be predicted with a good degree of accuracy, provided the rain rate characteristics over the entire path of propagation are known. The attenuation due to rain is usually deduced on the basis of point rain rate, which can lead to inaccuracy in the estimation of attenuation. We use the concept of rate of decay of rain path profile to estimate the attenuation due to rain. The attenuation has been deduced at 11GHz and 13.4 GHz for 56 elevation angle by using the theory of decay rate of rain path profile, its controlling factor, gamma, and rain rate distribution over Delhi, a tropical station in India. The theoretically-estimated attenuation is compared with observed values, as well as with values obtained using the International Radio Consultative Committee (CCIR) method. The CCIR model is found to overestimate the attenuation.     

Interdiffusion in the Fe-Pt System

Diffusion-couple experiments are conducted in the Fe-Pt system. The phase boundary compositions of the phases measured in this study are found to be different than the compositions published previously. In the γ-FePt solid solution, the interdiffusion coefficient increases with the Pt content up to 25 at. pct Pt. Fe is the faster diffusing species in this phase. The trend in the interdiffusion coefficient is explained with the help of calculated driving force for diffusion. To reduce errors, the average interdiffusion coefficients are calculated in the FePt and FePt₃ compounds.