Ab initio dynamics of cellulose pyrolysis: nascent decomposition pathways at 327 and 600 °c

We modeled nascent decomposition processes in cellulose pyrolysis at 327 and 600 °C using Car-Parrinello molecular dynamics (CPMD) simulations with rare events accelerated with the metadynamics method. We used a simulation cell comprised of two unit cells of cellulose Iβ periodically repeated in three dimensions to mimic the solid cellulose. To obtain initial conditions at reasonable densities, we extracted coordinates from larger classical NPT simulations at the target temperatures. CPMD-metadynamics implemented with various sets of collective variables, such as coordination numbers of the glycosidic oxygen, yielded a variety of chemical reactions such as depolymerization, fragmentation, ring opening, and ring contraction. These reactions yielded precursors to levoglucosan (LGA)-the major product of pyrolysis-and also to minor products such as 5-hydroxy-methylfurfural (HMF) and formic acid. At 327 °C, we found that depolymerization via ring contraction of the glucopyranose ring to the glucofuranose ring occurs with the lowest free-energy barrier (20 kcal/mol). We suggest that this process is key for formation of liquid intermediate cellulose, observed experimentally above 260 °C. At 600 °C, we found that a precursor to LGA (pre-LGA) forms with a free-energy barrier of 36 kcal/mol via an intermediate/transition state stabilized by anchimeric assistance and hydrogen bonding. Conformational freedom provided by expansion of the cellulose matrix at 600 °C was found to be crucial for formation of pre-LGA. We performed several comparison calculations to gauge the accuracy of CPMD-metadynamics barriers with respect to basis set and level of theory. We found that free-energy barriers at 600 °C are in the order pre-LGA < pre-HMF < formic acid, explaining why LGA is the kinetically favored product of fast cellulose pyrolysis.     

Application of homotopy analysis method for fractional Swift Hohenberg equation – Revisited

In this article, the homotopy analysis method is used to obtain the approximate analytical solutions of the non-linear Swift Hohenberg equation with fractional time derivative. The fractional derivative is described in Caputo sense. Numerical results reveal that the method is easy to implement, reliable and accurate when applied to time fractional nonlinear partial differential equations. Effects of parameters of physical importance on the probability density function and the convergence of the approximate series solution using residual error formula with the proper choices of auxiliary parameter for various fractional Brownian motions and standard motion are depicted through graphs and tables for different particular cases.     

Viscosity and excess molar volume of binary mixtures of methanol with n-butylamine and di-n-butylamine at 303.15, 313.15 and 323.15 K. Characterization in terms of ERAS model

The excess molar volume V_m^E, viscosity deviation Δη, and excess Gibbs energy of activation ΔG^?E of viscous flow have been investigated from the density ρ and viscosity η measurements of binary mixtures of methanol with n-butylamine and di-n-butylamine over the entire range of mole fractions at 303.15, 313.15, and 323.15 K. The systems studied exhibit very strong cross association through strong O–H…N bonding between –OH and –NH– groups. As a consequence of this strong intermolecular association, both the systems have very large negative V_m^E and positive Δη and ΔG^?E over entire range of composition and at all the temperatures of investigation. V_m^E of the studied mixtures is consistently described by the ERAS model. The values of cross association constants K_AB illustrate that cross-associates are more pronounced in primary amine mixtures than that in secondary amine.     

Effect of pulse slippage on density transition-based resonant third-harmonic generation of short-pulse laser in plasma

The resonant third-harmonic generation of a self-focusing laser in plasma with a density transition was investigated. Because of self-focusing of the fundamental laser pulse, a transverse intensity gradient was created, which generated a plasma wave at the fundamental wave frequency. Phase matching was satisfied by using a Wiggler magnetic field, which provided additional angular momentum to the third-harmonic photon to make the process resonant. An enhancement was observed in the resonant third-harmonic generation of an intense short-pulse laser in plasma embedded with a magnetic Wiggler with a density transition. A plasma density ramp played an important role in the self-focusing, enhancing the third-harmonic generation in plasma. We also examined the effect of the Wiggler magnetic field on the pulse slippage of the third-harmonic pulse in plasma. The pulse slippage was due to the group-velocity mismatch between the fundamental and third-harmonic pulses.     

Simulative investigation of the impact of EDFA and SOA over BER of a single-tone RoF system

In this paper, we investigate the impact of EDFA and SOA amplifiers over BER and Q-parameter of a Radio-over-Fiber (Rof) system consisting of two different system set-ups using direct- and external-laser modulation techniques. In this work, we also measured and compared the electric Rf power at receiver at different modulating Rf frequencies up to 20 GHz using two different optical amplifiers, i.e. EDFA and SOA. Further, we also compared the received electric Rf power at different optical powers without and with different optical amplifiers. An improvement of −11 dB (approx.) of received Rf power was observed using EDFA with the external modulation technique, on comparing with direct modulation.     

Role of the gouy phase in the coherent phase control of the photoionization and photodissociation of vinyl chloride

We demonstrate theoretically and experimentally that the Gouy phase of a focused laser beam may be used to control the photoinduced reactions of a polyatomic molecule. Quantum mechanical interference between one- and three-photon excitation of vinyl chloride produces a small phase lag between the dissociation and ionization channels on the axis of the molecular beam. Away from the axis, the Gouy phase introduces a much larger phase lag that agrees quantitatively with theory without any adjustable parameters.     

Pulse Slippage of Resonant Third Harmonic Generation in Electron-Hole Plasma

Effect of pulse slippage on resonant third harmonic generation of a short pulse laser in electron-hole plasma in the presence of wiggler magnetic field has been investigated. The group velocity mismatch of the third harmonic pulse and the fundamental pulse is significant in electron hole plasma. As the third harmonic pulse has higher group velocity than that of fundamental pulse, therefore, it moves faster than the fundamental pulse. It gets slipped out of the domain of fundamental pulse and its amplitude saturates. Phase matching condition is satisfied by applying wiggler magnetic field,which provides additional angular momentum to the third harmonic photon to make the process resonant. Enhancement in the efficiency of third harmonic generation of an intense short pulse laser in electron-hole plasma embedded with a magnetic wiggler is seen.     

Structural insights of dipeptidyl peptidase-IV inhibitors through molecular dynamics-guided receptor-dependent 4D-QSAR studies

Dipeptidyl peptidase-IV (DPP-IV) inhibitors are promising antidiabetic agents. Currently, several DPP-IV inhibitors have been approved for therapeutic use in diabetes mellitus. Receptor-dependent 4D-QSAR is comparatively a new approach which uses molecular dynamics simulations to generate conformational ensemble profiles of compounds representing a dynamic state of compounds at a target’s binding site. This work describes a receptor-dependent 4D-QSAR study on triazolopiperazine derivatives. QSARINS multiple linear regression method was adopted to generate 4D-QSAR models. A model with 9 variables was found to have better predictive accuracy with \({R}^{2}=0.692\), \({Q}^{2}\) (leave-one-out) = 0.592 and \({R}^{2}\) predicted = 0.597. The location of these 9 variables at the binding site of DPP-IV revealed the importance of the residues Val711, Tyr662, Tyr666, Val202, Asp200 and Thr199 in making critical interactions with DPP-IV inhibitors. The study of these critical interactions revealed the structural features required in DPP-IV inhibitors. Thus, in this study the importance of a halogen substituent on a phenyl ring, the extent of substitution on the triazolopiperazine ring, the presence of an ionizable amino group and the presence of a hydrophobic substituent that can bind deeper in binding pocket of DPP-IV were revealed.     

Performance Analysis for Downstream Next Generation Converged WSN-PON ODN Network Incorporating Diverse Phase Delay

In this article, a cluster-based WSN convergence with passive optical network (PON) as optical distributed network (ODN) has been proposed, where sensed information of WSN is transferred over fiber cable to enhance the transmission range. The proposed integrated WSN-PON network has been investigated at different fiber lengths incorporating diverse phase delays to WSN data. The performance of the proposed scheme is reported in terms of optical spectrum, SNR, and BER. The outcomes prove fruitful convergence of WSN-PON ODN and serve as a guideline to develop such a converged network.