Water Permeation Through DMPC Lipid Bilayers using Polarizable Charge Equilibration Force Fields

We investigate permeation energetics of water entering a model dimyristoylphosphatidylcholine (DMPC) bilayer via molecular dynamics simulations using polarizable Charge Equilibration (CHEQ) models. Potentials of mean force show 4.5-5.5 kcal/mol barriers for water permeation into bilayers. Barriers are highest when water coordination within the bilayer is prevented, and also when using force fields that accurately reproduce experimental alkane hydration free energies. The magnitude of the average water dipole moment decreases from 2.6 Debye (in bulk) to 1.88 Debye (in membrane interior). This variation correlates with the change in a water molecule's coordination number.     

Spectrophotometric determination of ciprofloxacin by ion pair formation

Various aspects of application of derivative spectrophotometry to chemical analysis and investigations of equilibria and kinetics of reactions are scrutinised. In this work the viability of a spectrophotometric technique for the determination of ciprofloxacin has been deliberated. The method is based on the formation of ion-association complexes of ciprofloxacin with nickel(II) tetra thiocyanate, which are extracted into organic solvent (40% n-butanol in methylene chloride) having absorption maxima at 623 nm. The precision and accuracy of the method was checked by UV reference methods. The validation study indicated the parameters, which are in good agreement with the data obtained from standard methods. The proposed method was fruitfully applied to determine ciprofloxacin in their tablet formulations.     

Template–polymer commensurability and directed self‐assembly block copolymer lithography

Block copolymer directed self‐assembly (BCP) with chemical epitaxy is a promising lithographic solution for patterning features with critical dimensions under 20 nm. In this work, we study the extent to which lamellae‐forming poly(styrene‐b‐methyl methacrylate) can be directed with chemical contrast patterns when the pitch of the block copolymer is slightly compressed or stretched compared to the equilibrium pitch observed in unpatterned films. Critical dimension small angle X‐ray scattering complemented with SEM analysis was used to quantify the shape and roughness of the line/space features. It was found that the BCP was more lenient to pitch compression than to pitch stretching, tolerating at least 4.9% pitch compression, but only 2.5% pitch stretching before disrupting into dislocation or disclination defects. The more tolerant range of pitch compression is explained by considering the change in free energy with template mismatch, which suggests a larger penalty for pitch stretching than compressing. Additionally, the effect of width mismatch between chemical contrast pattern and BCP is considered for two different pattern transfer techniques. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 595–603     

Assessment of Fiber Chromatic Dispersion Based on Elimination of Second-Order Harmonics in Optical OFDM Single Sideband Modulation Using Mach Zehnder Modulator

This work addresses the analytical and numerical investigations of the transmission performance of an optical Single Sideband (SSB) modulation technique generated by a Mach Zehnder Modulator (MZM) with a 90° and 120° hybrid coupler. It takes into account the problem of chromatic dispersion in single mode fibers in Passive Optical Networks (PON), which severely degrades the performance of the system. Considering the transmission length of the fiber, the SSB modulation generated by maintaining a phase shift of π/2 between the two electrodes of the MZM provides better receiver sensitivity. However, the power of higher-order harmonics generated due to the nonlinearity of the MZM is directly proportional to the modulation index, making the SSB look like a quasi-double sideband (DSB) and causing power fading due to chromatic dispersion. To eliminate one of the second-order harmonics, the SSB signal based on an MZM with a 120° hybrid coupler is simulated. An analytical model of conventional SSB using 90° and 120° hybrid couplers is established. The latter suppresses unwanted (upper/lower) first-order and second-order (lower/upper) sidebands. For the analysis, a varying quadrature amplitude modulation (QAM) Orthogonal Frequency Division Multiplexing (OFDM) signal with a data rate of 5 Gb/s is upconverted using both of the SSB techniques and is transmitted over a distance of 75 km in Single Mode Fiber (SMF). The simulation results show that the SSB with 120° hybrid coupler proves to be more immune to chromatic dispersion as compared to the conventional SSB technique. This is in tandem with the theoretical analysis presented in the article.     

Electrochemical performance of multi-walled carbon nanotube composite electrodes is enhanced with larger diameters and reduced specific surface area

Multi-walled carbon nanotubes (MWCNT) have been widely used to fabricate composite electrodes due to their electrochemical properties. MWCNTs can be fabricated by various approaches and a range of MWCNT types and sizes has been developed. This study focuses on understanding the influence MWCNT diameter and specific surface area has on the electrochemical properties of a composite electrode. MWCNTs with fixed length range and diameters ranging from 10–20 to 50–80 nm were examined in this study. The amount of MWCNT utilised to fabricate the electrodes was identical and above the percolation threshold. MWCNT electrodes fabricated with larger diameters showed enhanced thermodynamic and kinetic properties towards common redox species which covered surface-insensitive, surface-sensitive and adsorption-based processes. Overall, these findings indicate that the number of strands of MWCNT alone is not essential for enhanced conductivity in composite materials but other geometric parameters play important roles.     

Stable Crystalline Forms of Na Polysulfides: Experiment versus Ab Initio Computational Prediction

For the design of light‐metal–sulfur batteries and for the understanding of their performance, knowledge on the stable crystalline polysulfides is very important. We confronted experimental and ab initio crystal structure prediction studies on the stability of Na polysulfides. The selected evolutionary‐based structure‐prediction algorithm was able to quickly and correctly predict the thermodynamically stable crystalline forms of Na polysulfides with small unit cells. For Na polysulfides with large unit cells, the algorithm correctly proposed short unbranched polysulfide chains to be energetically favorite structural motifs, but could not find proper three‐dimensional structures in the limited number of generations. Experimentally, the polysulfides were studied by X‐ray diffraction and ²³Na solid‐state NMR spectroscopy. Complemented by calculations of the isotropic chemical shifts and quadrupolar coupling constants, NMR spectroscopy proved to be an excellent tool for the examination of Na polysulfides, because it allowed easy distinction and quantification of components in the samples.     

Kamlet–Taft Solvation Parameters of Solvate Ionic Liquids

The Kamlet–Taft solvent parameters of solvate ionic liquids (SILs) prepared from lithium salts with glyme and glycol ligands are determined. The dipolarity/polarisibilities (π*) are high, similar to those found in conventional ionic liquids. The H‐bond basicities (β) depend strongly on the anion. The H‐bond acidities (α) are high in both glyme and glycol SILs, indicating that the lithium is acting as a H‐bond donor site. “Poor” SILs have glyme‐rich and salt‐rich regions. In these liquids the π* and β values are almost identical to the parent glyme or glycol, and the α values are determined by the salt alone.