Sharif Digital Repository

The gas-phase kinetics of diallyl sulfide pyrolysis were studied experimentally and theoretically in a static system over the temperature range 433-463 K and a total pressure of 80 Torr in a glass vessel with the free radical inhibitor cyclohexene. The experimental results show that this reaction is homogeneous, unimolecular and follows a first-order rate law. Theoretical studies at the B3LYP/6-31G* computational level indicate that the elimination reaction proceeds through a six-centered cyclic transition state and the reaction mechanism is concerted and non-synchronous. Copyright © 2003 John Wiley & Sons, Ltd  

A combined theoretical and experimental kinetic and mechanism of diallyl disulfide pyrolysis reaction in the gas phase was studied in a static system over the temperature range of 586.7-621.2 K and a total pressure of 72 Torr in the presence of cyclohexene as radicals inhibitor. The experimental results show that the reaction is homogeneous, unimolecular and proceeds through a radical mechanism. Theoretical calculations at the B3LYP level using the 6-31G*, 6-31++G* and 6-311++G* basis sets confirm the radical mechanism for the diallyl disulfide pyrolysis. The calculated kinetic and activation parameters especially at the B3LYP/6-31G* level are in good agreement with the experimental data. ©... 

Structural and kinetic aspects of the retro-cheletropic ene reactions of 2,2-dimethyl but-3-enal, 1-methyl-6-methylenecyclohexa-2,4-diene-1-carbaldehyde and their deuterated derivatives were investigated using a variety of computational methods. Theoretical calculations were carried out with ab initio and DFT methods at the RHF, MP2 and B3LYP levels of the theory, using the 6-31G* basis set. Vibrational frequency analysis confirmed the stationary states including the transition state (TSs) structures. Intrinsic reaction coordinate calculations show the localized TSs connect with the corresponding minima associated with the reactants and the products. The mechanistic studies on the... 

This paper presents a new architecture for a DLL based frequency synthesizer for wireless transceivers. Owing to its DLL based nature, the synthesizer generates the target frequencies with minimum phase noise and jitter. To cover the desired frequency proposed architecture consists of mixer and divider. As an example, VHF frequency band of IRAN is covered. The circuit level design guidelines and power consumption trade-offs are presented. It was shown that for the mentioned standard a 40 delay cell and 9 switches for switching channels is sufficient. Simulation results confirm the analytical predictions  

This paper presents a new architecture for a DLL based frequency synthesizer. Occupying low area, lower power consumption and phase noise are the advantages of this novel architecture. DLLs are first ordered systems, so good stability can be obtained in this design. This structure also can be used for generating fractional multiple of reference frequencies. The proposed circuit can operate at a substantially low supply voltage. A case in point, the synthesizer is adopted to create the channel frequencies of French DVB-H/T standard. The circuit is designed based on 0.13um CMOS Technology. Also power consumption trade-offs are introduced. It was shown that 27 delay cells are sufficient to... 

A low power 10 bit, 40 MS/s pipeline analog to digital converter is presented. A number of low-power techniques are proposed in various levels of abstraction. In circuit level, a low power class A/AB opamp with direct common-mode-feedback circuit (CMFB) is proposed which significantly reduces power in the opamps. In backend design, optimal series capacitors are layed out to break the deadlock between the mismatch and loading effect of the first stage capacitors. A customized software tool is developed based on the proposed opamp and architecture which provides optimum stage scaling factors, tail current and opamp transistor sizes. Simulations in 0.13um CMOS technology show that the ADC... 

Ab initio, DFT, Monte Carlo statistical mechanics and atom in molecule methods have been applied to investigate the hydrogen bonding effect of protic solvents, apart from the bulk properties, on the reaction of cyclopentadiene and vinyl acetate. The results show that methanol accelerates the rate of the reaction more than water. DFT calculations demonstrate that the interaction of the carbonyl group oxygen atom with solvent molecules in transition state is stronger and more effective than the ether-type oxygen atom. Also, when the solvent molecule is near the oxygen of the carbonyl group the rate of reaction is larger than when it is near the ether-type oxygen. In addition, methanol... 

Ag2O particles were loaded on the surface of ZnCr-LDH via an anion-exchange precipitation approach by using privilege of the memory trace feature of the LDH-type materials. The structural properties of the resulted photocatalyst were explored by different spectroscopic and microscopic methods. The photocatalytic studies on acid black degradation ascertained that the prepared Ag2O/ZnCr-LDH nanocomposite represented an observably increased degradation performance of organic pollutants compared with pure Ag2O and ZnCr-LDH. This improved photocatalytic performance can be ascribed to the enhanced surface area, good order distributing of particles and effective charge carrier transfer and... 

Metal Organic Frameworks (MOFs) have received enormous attention in catalysis field due to their special structures and various promising applications. One of the intriguing applications of MOFs is utilization of them as precursors for synthesis of metal oxide nanomaterials. Base on this strategy, in this work, we have applied Cu-MOF to prepare a series of noble metal nanoparticles (Ag and Au) decorated CuO (M/CuO) as efficient catalyst. As-prepared nanocomposites were characterized by various analytical techniques and their catalytic performances appraised by using of the catalytic reduction of p-nitrophenol to p-aminophenol as a reliable model reaction. Experimental results suggest that... 

Ab initio quantum mechanics and ONIOM calculations were used to study solvent and substituent effects on the reactions of 1,4-benzoquinone with cyclopentadiene and cyclohexadiene derivatives in tetrahydrofuran and greater water solvents. These calculations revealed (i) that increasing the number of electron donating methyl group substituents and (ii) the proximity of substituents to the reacting carbons (carbon atoms which contribute to the forming C-C bonds) on the diene, promote charge transfer from the diene to the dienophile in the transition state. © 2008 Science Reviews 2000 Ltd. These effects increase the negative charge on the oxygen atoms, destabilize the transition state in the... 

The kinetics and mechanism of the reactions of hydroxylamine and aminoxide anion with methyl iodide were studied with ab initio calculations, Monte-Carlo and QM/MM simulations in gas and aqueous phases. Geometrical parameters and charge calculations show that these reactions proceed through the SN2 (bimolecular nucleophilic displacement) mechanism only. The solvent effects on these reactions were studied by inserting water molecules in reaction media, Onsager model, Monte-Carlo and QM/MM simulations. Activation parameters indicate the expected variation in activation energy and rate coefficient in aqueous phase in comparison to the gas phase. The shift of potential energy barrier through the... 

In this paper, a tolerance allocation approach is proposed which attempts to select tolerances for individual dimensional variables of a product in a way that minimizes the cost while maintaining critical design requirements. The algorithm uses a reciprocal power cost-tolerance function which incorporates variable sensitivities computed in a DLM-based tolerance analysis technique. The process capabilities are applied as constraints and the genetic algorithm is used to find the optimum solution. The method is applied to a heavy duty brake problem and its results are presented. Copyright © 2005 SAE International  

Ab initio molecular orbital calculations have been used to investigate the structures and the transition states of 1,3-dipolar cycloadditions between benzonitrile oxide with ethylene, cyclopentene, acrylonitrile and tetracyanoethylene in heptane and water: calculations reveal enhanced hydrogen bonding of a water molecule to the transition states for the cycloaddition 1,3-dipolar of reaction of benzonitrile oxide with cyclopentene, the optimal interaction energies being 0.7 kcal/mol more favourable for hydrogen bonding to the oxygen atom in the transition states than for the reactants  

TiO2-based photocatalysts are seen as the most common agents for the photodegradation of bacteria. In this study, AgCl/TiO2, hydroxyapatite(Hp)/AgCl/TiO2, AgI/TiO2, and Hp/AgI/TiO2 were prepared by the deposition-precipitation method on P25 TiO2 nanoparticles and were characterized by XRD, SEM, FT-IR, EDX and BET methods. The prepared composites showed high efficiency for the inactivation of Escherichia coli (E. coli) bacteria under visible light and in dark media with different catalyst amounts of 12 and 24 mg, respectively. In less than 30 min, AgI/TiO2, prepared by the combination of cationic surfactant and PVPI2, disinfected 1 × 107 colony-forming units of E. coli completely. However,... 

This paper presents a new architecture for a DLL based frequency synthesizer for wireless transceivers. Owing to its DLL based nature, the synthesizer generates the target frequencies with minimum phase noise. The proposed architecture takes the advantage of a combination of a frequency divider and an edge combiner to create the desired frequencies. As an example, the synthesizer is adopted to create the channel frequencies of French DVB-H/T standard. The circuit level design guidelines and power consumption trade-offs are presented. It was shown that for the mentioned standard a mere 6 stage delay line is sufficient. Simulation results confirm the analytical predictions  

We demonstrate theoretically by density functional non-equilibrium Green's function method that a much simplest two-terminal wire can exhibit switching, and we present a realistic theory of its behavior. We consider a C20-bowl molecular wire sandwiched between an Au (1 0 0) substrate and a monatomic Au scanning tunneling microscope (STM) tip. Lateral motion of the tip over the pentagon ring causes it to change from one conformation class to the other and to switch between a strongly and a weakly conducting state. Thus, surprisingly, despite their apparent simplicity, these Au/C20/Au nanowires are shown to be a convenient switch, the simplest two-terminal molecular switches to date.... 

In this paper, the evolution of elastic–plastic damage in the composite laminates under fatigue conditions is modeled. Continuum damage mechanics (CDM) has been coupled with the bridge micromechanics model to estimate the fatigue damage and life for laminated composite structures. Based on the elastic–plastic bridging model, three damage variables are defined. These variables estimate the fiber, matrix, and fiber/matrix damage response at the ply scale. To model the beginning of plastic deformation, a yield function is utilized, and evolution equations of the damage variables are obtained. Then the developed deformation plastic model is calculated. The model parameters are calibrated by... 

The purpose of this study is to define a piecewise fatigue damage model (PFDM) for the prediction of damage in composite laminates under cyclic loading based on the continuum damage mechanics (CDM) model. Assuming that damage in fiber-reinforced plastic structures accumulates nonlinearly, a piecewise degradation growth function is defined and coupled with CDM and micromechanics approaches. The model divides the damage behavior of fiber, matrix, and fiber/matrix debonding at the ply scale, into three different stages. For generality, a fully multi-stage damage formulation on a single-ply level is employed. The unknown parameters of the PFDM are estimated according to obtained experimental... 

The heterogeneous environmentally friendly catalyst and photocatalyst based on Ag, Pt, Ag–Pt nanoparticles (NPs) loading on the γ-Fe2O3/CuO nanocomposite which was derived from Fe-metal organic framework (Fe-MIL-88B) and Cu-metal organic framework (Cu (tpa)) was introduced. The catalytic and photocatalytic activities of Ag–Pt loading on the γ-Fe2O3/CuO nanocomposite were performed for a reduction process (4-nitrophenol (4-Nip) to 4-aminophenol (4-Amp)), and decomposition organic dyes (AB92, MB) in the LED light. Metal-organic framework (MOFs) composed with inorganic and organic linker which used as suitable precursors to obtain different type of nanostructures for environmental applications.... 

In this work, the synthesis, characterization, and kinetic investigation of the free-radical polymerization of 4-acetylaminobenzene propenoic ester (ABPE) and 4-methylbenzene propenoic ester (MBPE) were studied. The kinetic behaviors of ABPE and MBPE in the polymerization initiated by azobisisobutyronitrile in dimethylformamide solutions at temperatures between 50 and 120°C were investigated, and experimental and theoretical conversion-time curves were compared. Both monomers showed a polymerization ceiling temperature (T c ). Tc was calculated with experimental values of k pk1/2 with a constant concentration of 0.7 mol/L for monomers. Tc was about 141 and 131 °C for ABPE and MBPE,...