Synergy between Brønsted acid sites and Lewis acid sites

Synergy between Br?nsted acid sites and Lewis acid sites in mesoporous Al-Zr-TUD-1 was demonstrated to exist in Br?nsted acid catalysed reactions, but not in Lewis acid catalysed reactions.     

Effect of ionic liquid on dielectric, mechanical and dynamic mechanical properties of multi-walled carbon nanotubes/polychloroprene rubber composites

This paper focuses on the influence of ionic liquid on carbon nanotube based elastomeric composites. Multi-walled carbon nanotubes (MWCNTs) are modified using an ionic liquid at room temperature, 1-butyl 3-methyl imidazolium bis (trifluoromethylsulphonyl) imide (BMI) and modified MWCNTs exhibit physical (cation–π/π–π) interaction with BMI. The polychloroprene rubber (CR) composites are prepared using unmodified and BMI modified MWCNTs. The presence of BMI not only increases the alternating current (AC) electrical conductivity and polarisability of the composites but also improves the state of dispersion of the tubes as observed from dielectric spectroscopy and transmission electron microscopy respectively. In addition to the hydrodynamic reinforcement, the formation of improved filler–filler networks is reflected in the dynamic storage modulus (E′) for modified MWCNTs/CR composites in amplitude sweep measurement upon increasing the proportion of BMI. Hardness and mechanical properties are also studied for the composites as a function of BMI.     

Performance of a 80 W copper vapor laser with “alignment free” unstable CAT-EYE resonator and other configurations using intra-cavity apertures

Performance of a kinetically enhanced copper vapor laser (KE-CVL) with various stable/unstable “alignment free” CAT-EYE resonator configurations are presented here in this paper. The laser used in the experiment was a 45 mm bore (∼2 l discharge volume) kinetically enhanced copper vapor laser developed in our laboratory and capable of generating maximum power of ∼80 W (at ∼9.8 kHz). The efficiency of the laser was ∼1.4% and beam divergence of ∼3.5 mrad in a plane-plane standard multimode cavity. For the first time performance of unstable CAT-EYE resonator is demonstrated with a CVL/KE-CVL. On using unstable CAT-EYE resonator the divergence of the laser beam reduced to ∼0.22 mrad (∼20-fold reduction as compared to conventional plane-plane cavity), ∼40 W output power and with excellent misalignment tolerance. The laser output power was found to be within ∼5% drift/decline with misalignment angle of about 4 mrad between the mirrors. This is a significant improvement in comparison to standard conventional unstable resonator (M ∼ 50) CVL where ∼0.5 mrad divergence is achieved with power drift/decline of about 45% at ∼4 mrad misalignment angle.Off-axis unstable CAT-EYE unstable resonator was also demonstrated for the first time with further reduction in beam divergence to ∼0.13 mrad and with output power of ∼28 W. The misalignment tolerance was found to be highest in case of off-axis unstable CAT-EYE resonator with decline/drift in laser power of only ∼10% for misalignment angle as high as ∼8 mrad. Performance with intra-cavity apertures in plane-plane type CAT-EYE resonator for transverse mode control is also presented for the first time in CVLs. It is observed that the laser beam divergence reduces significantly to 1.25 mrad (a factor of 2) on using an aperture of ∼3.5 mm at the CAT-EYE reflector as compared to its normal (R = F = d) configuration without aperture. In case of stable CAT-EYE resonator the average beam divergence reduces from 8 mrad to 4 mrad (factor of 2) on using intra-cavity aperture of about 3 mm. It was also observed that high misalignment tolerance was retained on using intra-cavity apertures in almost all the CAT-EYE resonators. Use of intra-cavity mesh was also demonstrated for the first time with stable CAT-EYE resonator for improving the beam focus-ability. Average beam divergence was reduced by a factor of 2.5 (from 8 mrad to 3 mrad) on using intra-cavity mesh. These new configurations in CAT-EYE resonators in KE-CVLs are found to be effective in improving and controlling the laser beam divergence significantly with additional characteristic of high misalignment tolerance.     

A density functional theory study on the water aggregation behaviour of fatty acid-based anionic surface active ionic liquids

Structural Chemistry - The hydrogen bond interactions between methyl-imidazolium cation (MIM+) and fatty acid anions (CmHnCOO–, where m?=?1–6; n-3–13) of ionic liquids...     

Influence of the Thiophene Ring on the Molecular Order of Structurally Simple π-Conjugated Smectogens: 13C NMR Study

Structurally simple rod-like π-conjugated mesogens with thiophene directly connected to phenyl, biphenyl, and fluorenone rings with terminal chains are synthesized respectively. The occurrence of smectic A/smectic C phases is concurred by a hot-stage optical polarising microscope (HOPM), differential scanning calorimetry (DSC), and X-ray diffraction (XRD). The static 1D and 2D ¹³C nuclear magnetic resonance (NMR) studies in the liquid crystalline phase are carried out to find the alignment-induced chemical shifts (AIS) and ¹³C−¹H dipolar couplings. The orientational order parameters of the mesogens determined from ¹³C−¹H dipolar couplings disclose that the long axis is not only collinear to the C3−C4 bond of the thiophene ring but also for the local axes of phenyl and biphenyl rings. For fluorenone-based mesogen, the molecular biaxiality is found to be high owing to the increased breadth of the molecule. The study unveils that the orientation of thiophene and the phenyl rings is similar in the current mesogens in stark contrast to mesogens, where thiophene is connected to phenyl rings through linking groups.     

Optimal estimation in random coefficient regression models

In linear regression models with random coefficients, the score function usually involves unknown nuisance parameters in the form of weights. Conditioning with respect to the sufficient statistics for the nuisance parameter, when the parameter of interest is held fixed, eliminates the nuisance parameters and is expected to give reasonably good estimating functions. The present paper adopts this approach to the problem of estimation of average slope in random coefficient regression models. Four sampling situations are discussed. Some asymptotic results are also obtained for a model where neither the regressors nor the random regression coefficients replicate. Simulation studies for normal as well as non-normal models show that the performance of the suggested estimating functions is quite satisfactory.     

13C NMR investigations of molecular order of rod-like,bent-core,and thiophene mesogens

In this review, methods to obtain the orientational order of topologically variant molecular mesogens using by one- and two-dimensional (2D) solid-state ¹³C nuclear magnetic resonance (NMR) spectroscopy are described. Besides ¹³C chemical shifts, the ¹³C─¹H dipolar couplings measured from 2D-separated local field (SLF) technique are used for computing the order parameters of a variety of mesogens. The investigated molecules are composed of a variable number of rings in the core, that is, core ranging from simply one ring to five rings. Among the mesogens investigated, a special focus has been placed on mesogens with thiophene rings, which are gaining popularity as liquid crystalline organic semiconductors. The replacement of a phenyl ring by thiophene in the core has a dramatic influence on molecular topology, as observed from the measured order parameters. The review highlights the advantages of the 2D SLF method for understanding the local dynamics and for mapping the topology of mesogens through the measured order parameters. SLF NMR studies of as many as 24 molecular mesogens that vary in terms of the molecular structure as well as topology are covered in the review. Order parameters of the rings have been estimated from the ¹³C─¹H dipolar couplings in the nematic, smectic A, smectic C, and tilted hexatic phases as well as in B₁ and B₂ mesophases of various mesogens. It is anticipated that, in the years to come, the 2D SLF method would provide advanced molecular information on structurally complex mesogens that are emerging in liquid crystal science through the incessant efforts of synthetic chemists. The mini review covers the orientational order of topologically variant molecular mesogens determined by 1D and 2D solid-state ¹³C NMR spectroscopy. Accordingly, rod-like, bent-core, and thiophene mesogens were subjected to 2D SLF measurements to get the order parameters from which the topology was established. The replacement of phenyl ring by thiophene and its influence on order parameters as well as on molecular topology is also discussed.     

An Ultra-Microporous Metal–Organic Framework with Exceptional Xe Capacity

Molecular confinement plays a significant effect on trapped gas and solvent molecules. A fundamental understanding of gas adsorption within the porous confinement provides information necessary to design a material with improved selectivity. In this regard, metal–organic framework (MOF) adsorbents are ideal candidate materials to study confinement effects for weakly interacting gas molecules, such as noble gases. Among the noble gases, xenon (Xe) has practical applications in the medical, automotive and aerospace industries. In this Communication, we report an ultra-microporous nickel-isonicotinate MOF with exceptional Xe uptake and selectivity compared to all benchmark MOF and porous organic cage materials. The selectivity arises because of the near perfect fit of the atomic Xe inside the porous confinement. Notably, at low partial pressure, the Ni–MOF interacts very strongly with Xe compared to the closely related Krypton gas (Kr) and more polarizable CO₂. Further ¹²⁹Xe NMR suggests a broad isotropic chemical shift due to the reduced motion as a result of confinement.     

An Yb(OTf)3‐catalyzed,convergent synthesis of new pyranyl‐ and chromenyl‐substituted quinolines through an eco‐friendly approach

A one‐pot, multicomponent, convergent microwave synthesis of some new pyranyl‐ and chromenyl‐substituted quinolines has been reported. Twenty compounds were prepared by the reaction of 2‐methoxy‐3‐formyl quinoline ( 1a‐d ), malononitrile ( 2 ), and kojic acid ( 4a‐d )/1,3‐cyclohexadione or dimedone ( 6a ‐ h )/α‐ or β‐naphthol ( 8a ‐ d , 8e ‐ h ). The structures were confirmed by infrared (IR), ¹H nuclear magnetic resonance (NMR), ¹³C NMR, mass, and single‐crystal X‐ray analyses. On comparison with the use of conventional Lewis acid catalysts and various metal triflates under microwave conditions, the latter contributed to good yields, in specific use of the recyclable Yb(OTf)₃ catalyst attributed to high yields of the desired product. The protocol reported herein is solvent free, cost effective, and eco‐friendly.     

Is the glass transition in some super-cooled polyphenyls preceded by molecular cluster formation?

A recently reported anomalous behaviour of the positronium annihilation rate with temperature in certain super-cooled organic liquids is explained in terms of a simple free-volume model modified in the presence of molecular cluster formation. This model apart from showing the entropic origin of the phenomenon accounts for the existence of the transition temperature “T_r” much above the glass-transition temperature T_g. It also predicts for the threshold temperature “T_r” fo clusters to commence formation a value of 310_-7.0^+8.0 K as against the experimental value of 304 K for ortho-terphenyl.