Optical and static dielectric study of a terminally fluorinated liquid crystalline compound

Optical and static dielectric studies on a terminally fluorinated liquid crystalline compound have been carried out. Measurements of temperature variation of refractive indices of the compound are done by using thin prism method. A four-parameter model is validated by fitting the experimentally measured values of refractive indices, birefringence and average refractive indices of the compound with the theoretical ones. Refractive index and density data are utilized for determination of orientational order parameter. The temperature variation of dielectric permittivities of the compound are measured by a LCR meter.     

“Grafting through” polymerization involving surface-bound monomers

“Grafting through” polymerization represents copolymerization of free monomers in solution and polymerizable units bound to a substrate. Free polymer chains are formed initially in solution and can incorporate the surface-bound monomers, and thereby, get covalently bonded to the surface during the polymerization process. As more growing chains attach to the surface-bound monomers, an immobilized polymer layer is formed on the surface. We use a combination of computer simulation and experiments to comprehend this process for monomers bound to a flat impenetrable substrate. We concentrate specifically on addressing the effect of spatial density of the surface-bound monomers on the formation of the surface-attached polymers. We employ a lattice-based Monte Carlo model utilizing the bond fluctuation model scheme to provide molecular-level insight into the grafting process. For experimental validation, we create gradients of density of bound methacrylate units on flat silicon wafers using organosilane chemistry and carry out “grafting through” free radical polymerization initiated in bulk. We report that the proximity of the surface-bound polymerizable units promotes the “grafting through” process but prevents more free growing chains to “graft through'' the polymerizable units. The “grafting through” process is self-limiting in nature and does not affect the overall density of the surface-bound polymer layer, except in case of the highest theoretical packing density of surface-bound monomers. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 263–274     

Gold-Catalyzed Cross-Coupling Reactions: An Overview of Design Strategies,Mechanistic Studies,and Applications

Transition-metal-catalyzed cross-coupling reactions are central to many organic synthesis methodologies. Traditionally, Pd, Ni, Cu, and Fe catalysts are used to promote these reactions. Recently, many studies have showed that both homogeneous and heterogeneous Au catalysts can be used for activating selective cross-coupling reactions. Here, an overview of the past studies, current trends, and future directions in the field of gold-catalyzed coupling reactions is presented. Design strategies to accomplish selective homocoupling and cross-coupling reactions under both homogeneous and heterogeneous conditions, computational and experimental mechanistic studies, and their applications in diverse fields are critically reviewed. Specific topics covered are: oxidant-assisted and oxidant-free reactions; strain-assisted reactions; dual Au and photoredox catalysis; bimetallic synergistic reactions; mechanisms of reductive elimination processes; enzyme-mimicking Au chemistry; cluster and surface reactions; and plasmonic catalysis. In the relevant sections, theoretical and computational studies of Au^I/Au^III chemistry are discussed and the predictions from the calculations are compared with the experimental observations to derive useful design strategies.     

Electrocatalytic Reduction of Nitrogen to Ammonia Using Tiara-like Phenylethanethiolated Nickel Cluster

The fixing of N₂ to NH₃ is challenging due to the inertness of the N≡N bond. Commercially, ammonia production depends on the energy-consuming Haber-Bosch (H−B) process, which emits CO₂ while using fossil fuels as the sources of hydrogen and energy. An alternative method for NH₃ production is the electrochemical nitrogen reduction reaction (NRR) process as it is powered by renewable energy sources. Here, we report a tiara-like nickel-thiolate cluster, [Ni₆(PET)₁₂] (where, PET=2-phenylethanethiol)] as an efficient electro-catalyst for the electrochemical NRR at ambient conditions. Ammonia (NH₃: 16.2±0.8 μg h⁻¹ cm⁻²) was the only nitrogenous product over the potential of −2.3 V vs. F_c⁺/F_c with a Faradaic efficiency of 25%±1.7. Based on theoretical calculations, NRR by [Ni₆(PET)₁₂] proceeds through both the distal and alternating pathways with an onset potential of −1.84 V vs. RHE (i.e., −2.46 V vs. F_c⁺/F_c) which corroborates with the experimental findings.     

Topochemical Transformations of CaX2 (X=C,Si, Ge) to Form Free‐Standing Two‐Dimensional Materials

Topochemical transformations of layered materials CaX₂ (X=Si, Ge) are the method of choice for the high‐yield synthesis of pristine, defect‐free two‐dimensional systems silicane and germanane, which have advanced electronic properties. Based on solid‐state dispersion‐corrected calculations, mechanisms for such transformations are elucidated that provide an in‐depth understanding of phase transition in these layered materials. While formation of such layered materials is highly favorable for silicane and germanane, a barrier of 1.2 eV in the case of graphane precludes its synthesis from CaC₂ topochemically. The energy penalty required for distorting linear acetylene into a trans‐bent geometry accounts for this barrier. In contrast it is highly favorable in the heavier analogues, resulting in barrierless topochemical generation of silicane and germanane. Photochemical generation of the trans‐bent structure of acetylene in its first excited state (S₁) can directly generate graphane through a barrierless condensation. Unlike the buckled structure of silicene, the phase‐h of CaSi₂ with perfectly planar silicene layers exhibits the Dirac cones at the high symmetry points K and H. Interestingly, topochemical acidification of the cubic phase of calcium carbide is predicted to generate the previously elusive platonic hydrocarbon, tetrahedrane.     

Role of Solvent in Electron-Phonon Relaxation Dynamics in Core-Shell Au−SiO2 Nanoparticles

Relaxation dynamics of plasmons in Au−SiO₂ core-shell nanoparticles have been followed by femtosecond pump-probe technique. The effect of excitation pump energy and surrounding medium on the time constants associated with the hot electron relaxation has been elucidated. A gradual increase in the electron-phonon relaxation time with pump energy is observed and can be attributed to the higher perturbation of the electron distribution in AuNPs at higher pump energy. Variation in time constants for the electron-phonon relaxation in different solvents is rationalized on the basis of their thermal conductivities, which govern the rate of dissipation of heat of photoexcited electrons in the nanoparticles. On the other hand, phonon-phonon relaxation is found to be much less effective than electron-phonon relaxation for the dissipation of energy of the excited electron and the time constants associated with it remain unaffected by thermal conductivity of the solvent.     

Die langsame Strömung einer einfachen viskoelastischen Flüssigkeit durch einen endlich breiten Spalt

Zusammenfassung Es wird die zweidimensionale schleichende Strömung einer einfachen viskoelastischen Flüssigkeit durch einen endlich breiten Spalt mit Hilfe einer Störungsrechnung untersucht. Dabei wird vorausgesetzt, daß die Relaxationslänge klein gegen die Spaltbreite ist.Für einige Werte der Strömungsparameter werden Ergebnisse für die Geschwindigkeitsverteilung im Spalt, den Stromlinienverlauf und die Reibungsspannungen graphisch dargestellt und diskutiert. Obwohl wegen der Beschränkung der Lösungsmethode die bei Experimenten beobachteten Zirkulationsströmungen nicht beschrieben werden können, zeigen die Ergebnisse, daß die Tendenz der Abweichung vom newtonschen Verhalten in die gleiche Richtung geht.

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Summary The two-dimensional creeping flow of a simple viscoelastic fluid through a finite gap located in an infinitely wide plate is analysed by using a perturbation method.Solutions for the streamline pattern, the velocity distribution in the gap and the stress components are derived and discussed. Because of the restrictions of the perturbation method no circular flow, as observed in some experiments, is predicted, but the results indicate at least some tendencies into this direction.

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