Sharif Digital Repository

An Iron(lV)-oxo heme(+·) complex (Compound I, Cpd I) is the proposed active species of heme enzymes such as the cytochromes P450 and Is elusive; therefore, biomimetic studies on active site mimics give valuable Insight Into the fundamental properties of heme active species. In this work we present density functional theory (DFT) calculations on substrate hydroxylatlon by a Compound I mimic [FeIV=O(Por+̇)Cl] and its one-electron reduced form [FeIV=O(Por)Cl]-. Thus, recent experimental studies showed that [FeIV =O(Por)Cl]- is able to react with substrates via hydride transfer reactions [Jeong, Y. J.; Kang, Y.; Han, A.-R.; Lee, Y.-M.; Kotani, H.; Fukuzumi, S.; Nam, W. Angew. Chem., Int. Ed.... 

We present the first density functional theory study on α-ketoglutarate dependent halogenase and focus on the mechanism starting from the iron(IV)-oxo species. The studies show that the high-valent iron(IV)-oxo species reacts with substrates via an initial and rate determining hydrogen abstraction that is characterized by a large kinetic isotope effect (KIE) of 26.7 leading to a radical intermediate. This KIE value is in good agreement with experimental data. The reaction proceeds via two-state reactivity patterns on competing quintet and septet spin state surfaces with close lying hydrogen abstraction barriers. However the septet spin radical intermediate gives very high barriers for... 

Combined experimental and theoretical studies on the reactivity of iodosylbenzene (PhIO) show that PhIO is capable of activating weak C-H bonds of hydrocarbons via a hydrogen abstraction mechanism. © 2009 The Royal Society of Chemistry  

Mononuclear nonheme iron containing systems are versatile and vital oxidants of substrate hydroxylation reactions in many biosystems, whereby the rate constant of hydroxylation correlates with the strength of the C-H bond that is broken in the process. The thermodynamic reason behind these correlations, however, has never been established. In this work results of a series of density functional theory calculations of substrate hydroxylation by a mononuclear nonheme iron(IV)-oxo oxidant with a 2 His/ 1Asp structural motif analogous to aketoglutarate dependent dioxygenases are presented. The calculations show that these oxidants are very efficient and able to hydroxylate strong C-H bonds,... 

In this work we present results of density functional theory (DFT) calculations on dicopper patellamides and their affinity for molecular oxygen and carbonate. Patellamides are cyclic octapeptides that are produced by a cyanobacterium, and may show promise as therapeutics. Thus, carbonate binding to a dicopper patellamide center gives a stable cyclic octapeptide with a twist of almost 90°. The system exists in close-lying open-shell singlet and triplet spin states with two unpaired electrons in orthogonal σ* orbitals on each metal center. Subsequently, we replaced carbonate with dioxygen and found a stable Cu2(μ-O)2 diamond shaped patellamide core. In this structure the original dioxygen... 

The catalytic activity of highvalent iron-oxo active species of heme enzymes is known to be dependent on the nature of the axial ligand trans to the iron-oxo group. In a similar fashion, experimental studies on iron-oxo porphyrin biomimetic systems have shown a significant axial ligand effect on ethylbenzene hydroxylation, with an axial acetonitrile ligand leading to phenyl hydroxylation products and an axial chloride anion giving predominantly benzyl hydroxylation products. To elucidate the fundamental factors that distinguish this regioselectivity reversal in iron-oxo porphyrin catalysis, we have performed a series of density functional theory calculations on the hydroxylation of... 

Distant, dusty and extremely luminous galaxies form a key component of the high redshift universe, tracing the period of intense cosmic activity that ultimately gave rise to the present-day universe. These highly luminous galaxies, first detected in the ground-based submillimeter region, are however optically very faint, which hampers identification of the optical counterpart and the measurement of a redshift. We are developing a new direct-detection submm spectrograph DESHIMA. By taking advantage of the rapidly advancing technology of superconducting microresonators, DESHIMA will revolutionize the appearance and capabilities of a submm spectrograph. There will no longer be large grating... 

In photoacoustic tomography (PAT) systems, the tangential resolution decreases due to the finite size of the transducer as the off-center distance increases. To address this problem, we propose a multi-angle detection approach in which the transducer used for data acquisition rotates around its center (with specific angles) as well as around the scanning center. The angles are calculated based on the central frequency and diameter of the transducer and the radius of the region-of-interest (ROI). Simulations with point-like absorbers (for point-spread-function evaluation) and a vasculature phantom (for quality assessment), and experiments with ten 0.5 mm-diameter pencil leads and a leaf... 

In this paper, we propose a novel method for academic assessment inspired by the decentralized applications made possible by blockchain technology. The proposed method applies to a wide range of academic material, including assignments, exams, academic papers, etc and tackles issues regarding potential personal bias and makes assessment possible without the need to rely on a few assessors. We examine the challenges and possibilities that arise with this method and further explore more general applications in areas such as education. In the experiments conducted for this research, poll results show generally positive views toward the fairness of this system compared to the traditional... 

The unpredictable nature and devastating impact of earthquakes enforce governments of disaster-prone regions to provide practical response plans to minimize damage and losses resulting from earthquakes. Logistics management is one of the key issues that should be considered for an appropriate response, in particular, the planning of the transport of commodities required during response and the evacuation of injured people. This paper develops a dynamic model for dispatching and routing vehicles in response to an earthquake. We focus on the transport of both commodity towards affected areas and injured people to hospitals. The proposed model is capable of receiving updated information at any... 

In this paper we developed a new mathematical model for the flow inside cascade impactors and via this simplified model, we determined the particle size distribution by a fast and low cost computational method. Using cascade impactors for determining the particle size distribution, one can use comprehensive CFD methods to fully simulate the particle traces. Although the results from those CFD analyses can be very accurate, usually that is not a time and cost efficient routine. In contrast, we showed that by using our proposed calculation we can estimate the particle size distribution very fast and yet with the slight error -comparing to the results from CFD method. Cascade impactors are... 

Humanitarian logistics is regarded as a key area for improved disaster management efficiency and effectiveness. In this study, a multi-objective integrated logistic model is proposed to locate disaster relief centers while taking into account network costs and responsiveness. Because this location problem is NP-hard, we present a genetic approach to solve the proposed model  

Computer-assisted collaborative peer grading is a developing growth area in academic evaluation. However, peer assessment often needs help with problems such as the lack of reliability, transparency, fairness, grading speed, and motivation to participate among students. The literature suggests several principles that each partly address the said issues. We propose a novel decentralized approach to academic peer assessment, using blockchain as an underlying technology, to address the principal problems in traditional peer assessment. We also derive design concepts for a modern courseware (CW) application consisting of our method and apply them to implement our approach in a CW called... 

Demand response (DR) is known as a key solution in modern power systems and electricity markets for mitigating wind power uncertainties. However, effective incorporation of DR into power system operation scheduling needs knowledge of the price–elastic demand curve that relies on several factors such as estimation of a customer’s elasticity as well as their participation level in DR programs. To overcome this challenge, this paper proposes a novel autonomous DR scheme without prediction of the price–elastic demand curve so that the DR providers apply their selected load profiles ranked in the high priority to the independent system operator (ISO). The energy and reserve markets clearing... 

An adaptive neural guidance and control system is proposed in this paper for a generic fixed-wing aerial robot. Unlike most of the existing low-level control systems, which utilize a non-adaptive guidance loop, in this work both the guidance and control loops are trained using an efficient adaptive neural algorithm. A feedforward neural network is employed in each loop to identify uncertain dynamics, while an adaptive disturbance observer allows to compensate for both the external disturbances and estimation error of the neural network. This would lead to a resilient flight control system, and thus, the asymptotic stability of both the guidance and control loops can be theoretically ensured... 

Here we study the effects of many-body interactions on rate and mechanism in protein folding by using the results of molecular dynamics simulations on numerous coarse-grained Cα-model single-domain proteins. After adding three-body interactions explicitly as a perturbation to a Gō-like Hamiltonian with native pairwise interactions only, we have found (i) a significantly increased correlation with experimental φ values and folding rates, (ii) a stronger correlation of folding rate with contact order, matching the experimental range in rates when the fraction of three-body energy in the native state is ≈20%, and (iii) a considerably larger amount of three-body energy present in chymotripsin... 

The fish freshness was evaluated using machine vision technique through color changes of eyes and gills of farmed and wild gilthead sea bream (Sparus aurata), being employed lightness (L*), redness (a *), yellowness (b*), chroma (c *), and total color difference (ΔE) parameters during fish ice storage. A digital color imaging system, calibrated to provide accurate CIELAB color measurements, was employed to record the visual characteristics of eyes and gills. The region of interest was automatically selected using a computer program developed in MATLAB software. L*, b *, and ΔE of eyes increased with storage time, while c* decreased. The a* parameter of fish eyes did not show clear a trend... 

Gift shopping can be challenging due to the limited prior knowledge of the recipient's preferences, leading to after-purchase regret. The effectiveness of Fashion Recommender Systems (FRS) in the context of gift purchases with limited preference data remains underexplored. We considered a gift-buying scenario and conducted an experiment with 192 pairs of participants to compare FRS versus humans in recommending fashion gifts to buyers.We find both FRS and humans score >50% correctness in recommending the right gift, even without direct interaction with gift-givers or recipients. Although the buyers know the gift receivers directly, they lead to less accuracy. Additionally, we identify... 

A new type of aggregation-induced emission (AIE) luminogen containing a dimeric metal fragment and two or three phthalazine ligands is described, which shows dynamic motions of ligands around the metal centers in solution. Based on the variable-temperature and EXSY NMR spectroscopy data, X-ray crystallography structures, and computational results, three different pathways (i.e., reversible exchange with haptotropic shifts, circulation of ligands around the dimeric metal fragment, and walking on the spot of ligands on the metal centers) were considered for this dynamic behavior. Restriction of these dynamic processes in the aggregate forms of the compounds (in H2O/CH3CN solvent mixtures)... 

The gas turbine (GT) is known to feature low capital cost to power ratio, high flexibility, high reliability without complexity, short delivery time, early commissioning and commercial operation and fast starting-accelerating. Hence, researchers all over the world are working to increase the output power and efficiency of gas turbine cycle. One of the important techniques to increase the output power of such cycles is the compressor inlet air cooling method. The objective of this paper is to analysis the gas turbine cycle from both energy and exergy point of view. Thus, two important methods for increasing the output power, i.e. fog and media inlet air cooling systems are discussed....