Azo-hydrazo Tautomerism and Inclusion Complexation of 1-phenylazo-2-naphthols with Various Solvents and β-cyclodextrin

Spectral characteristics of sudan I (SDI), sudan II (SDII) and mordant violet-5 (MV5) have been studied in various solvents and β-cyclodextrin (β-CD). The inclusion complex of the above molecules with β-CD was analyzed by UV-visible, fluorometry, and DFT methods. The solvent study shows that azo-hydrazo tautomer is present in these molecules. The increase in the fluorescence intensity and a large bathochromic shift in the S₁ state indicate these molecules forms 1:1 inclusion complex with β-CD.     

On the static Lovelock black holes

We consider static spherically symmetric Lovelock black holes and generalize the dimensionally continued black holes in such a way that they asymptotically for large $r$ go over to the d-dimensional Schwarzschild black hole in dS/AdS spacetime. This means that the master algebraic polynomial is not degenerate but instead its derivative is degenerate. This family of solutions contains an interesting class of pure Lovelock black holes which are the $N$ th order Lovelock $\Lambda $ -vacuum solutions having the remarkable property that their thermodynamical parameters have the universal character in terms of the event horizon radius. This is in fact a characterizing property of pure Lovelock theories. We also demonstrate the universality of the asymptotic Einstein limit for the Lovelock black holes in general.     

Analytic approximations of queues with lightly- and heavily-correlated autoregressive service times

We consider a single-server queueing system. The arrival process is modelled as a Poisson process while the service times of the consecutive customers constitute a sequence of autoregressive random variables. Our interest into autoregressive service times comes from the need to capture temporal correlation of the channel conditions on wireless network links. If these fluctuations are slow in comparison with the transmission times of the packets, transmission times of consecutive packets are correlated. Such correlation needs to be taken into account for an accurate performance assessment. By means of a transform approach, we obtain a functional equation for the joint transform of the queue content and the current service time at departure epochs in steady state. To the best of our knowledge, this functional equation cannot be solved by exact mathematical techniques, despite its simplicity. However, by means of a Taylor series expansion in the parameter of the autoregressive process, a “light-correlation” approximation is obtained for performance measures such as moments of the queue content and packet delay. We illustrate our approach by some numerical examples, thereby assessing the accuracy of our approximations by simulation. For the heavy correlation case, we give differential equation approximations based on the time-scale separation technique, and present numerical examples in support of this approximation.     

Spin state selective coherence transfer: a method for discrimination and complete analyses of the overlapped and unresolved 1H NMR spectra of enantiomers

In general, the proton NMR spectra of chiral molecules aligned in the chiral liquid crystalline media are broad and featureless. The analyses of such intricate NMR spectra and their routine use for spectral discrimination of R and S optical enantiomers are hindered. A method is developed in the present study which involves spin state selective two dimensional correlation of higher quantum coherence to its single quantum coherence of a chemically isolated group of coupled protons. This enables the spin state selective detection of proton single quantum transitions based on the spin states of the passive nuclei. The technique provides the relative signs and magnitudes of the couplings by overcoming the problems of enantiomer discrimination, spectral complexity and poor resolution, permitting the complete analyses of the otherwise broad and featureless spectra. A non-selective 180 degrees pulse in the middle of MQ dimension retains all the remote passive couplings. This accompanied by spin selective MQ-SQ conversion leads to spin state selective coherence transfer. The removal of field inhomogeneity contributes to dramatically enhanced resolution. The difference in the cumulative additive values of chemical shift anisotropies and the passive couplings, between the enantiomers, achieved by detecting Nth quantum coherence of N magnetically equivalent spins provides enhanced separation of enantiomer peaks. The developed methodology has been demonstrated on four different chiral molecules with varied number of interacting spins, each having a chiral centre.     

Molecular Design Strategy for Orange Red Thermally Activated Delayed Fluorescence Emitters in Organic Light-Emitting Diodes (OLEDs)

Pure organic molecules based thermally activated delayed fluorescence (TADF) emitters have been successfully developed in recent years for their propitious application in highly efficient organic light emitting diodes (OLEDs). In the case of orange red emitters, the non-radiative process is known to be a serious issue due to its lower lying singlet energy level. However, recent studies indicate that there are tremendous efforts put to develop efficient orange red TADF emitters. In addition, the external quantum efficiency (EQE) of heteroaromatic based orange red TADF OLEDs surpassed 30 %. Such heteroaromatic type emitters showed wide emission spectra; therefore, more attention is being paid to develop highly efficient orange red TADF emitters along with good color purity. Herein, the recent progress of orange red TADF emitters based on molecular structures, such as cyanobenzene, heteroaromatic, naphthalimide, and boron-based acceptors, are reviewed. Further, our insight on these acceptors has been provided by their photophysical studies and device performances. Future perspectives of orange red TADF emitters for real practical applications are discussed.     

Electrochemical and photocatalytic investigation of nickel oxide for energy storage and wastewater treatment

Nickel oxide (NiO) was synthesized via a one-step facile method. X-ray diffraction analysis confirmed the face-centered cubic structure of NiO. The bonding nature and surface purity were confirmed via Fourier-transform infrared spectroscopy. NiO revealed partial spherical morphology with less particle aggregation. The optical bandgap of NiO was found to be 3.75 eV. Cyclic voltammetry revealed well-defined oxidation and reduction peaks for NiO. The charge–discharge curve exhibited specific capacitance of 184.6 F/g at current density of 0.3 A/g. NiO electrode exhibited longer cyclic stability of 93 % up to 1500 cycles. In addition, NiO + H₂O₂ revealed efficient photocatalytic degradation of methylene blue (organic pollutant) under visible-light irradiation with degradation efficiency of ~88 %. These results confirm that nanosized NiO is more suitable for dual application.

     

Enantiomeric discrimination by double quantum excited selective refocusing (DQ-SERF) experiment

The differences in chemical shift anisotropies, dipolar couplings, and quadrupolar couplings of two enantiomers in the chiral liquid crystalline media are employed to visualize enantiomers. In spite of the fact that proton has high magnetic moment and is abundantly present in all the chiral molecules, 1H NMR is not exploited to its full potential because of severe overlap of unresolved transitions arising from long- and short-distance couplings. Furthermore, the two spectra from R and S enantiomers result in doubling of the number of observable transitions. The present study demonstrates the application of the selectively excited homonuclear double quantum (DQ) coherence correlated to its single quantum coherence of an isolated methyl group in a chiral molecule. The DQ dimension retains only the passive couplings within the protons of the methyl group while the long-distance passive couplings are refocused, removing the overlap of central transitions, and each enantiomer displays a doublet instead of a triplet unlike in regular selective refocusing experiment. The doublet separation being different for each enantiomer results in their discrimination. The cross section taken along the single quantum dimension pertaining to each transition in the DQ dimension provides the one-dimensional spectra for each individual enantiomer with the complete removal of the overlapped transitions from the other enantiomer. The experiment is robust, the pulse sequence is easy to implement, and the methodology has been demonstrated on different chiral molecules.     

Review of non-reactive and reactive wetting of liquids on surfaces

Wettability is a tendency for a liquid to spread on a solid substrate and is generally measured in terms of the angle (contact angle) between the tangent drawn at the triple point between the three phases (solid, liquid and vapour) and the substrate surface. A liquid spreading on a substrate with no reaction/absorption of the liquid by substrate material is known as non-reactive or inert wetting whereas the wetting process influenced by reaction between the spreading liquid and substrate material is known as reactive wetting. Young's equation gives the equilibrium contact angle in terms of interfacial tensions existing at the three-phase interface. The derivation of Young's equation is made under the assumptions of spreading of non-reactive liquid on an ideal (physically and chemically inert, smooth, homogeneous and rigid) solid, a condition that is rarely met in practical situations. Nevertheless Young's equation is the most fundamental starting point for understanding of the complex field of wetting. Reliable and reproducible measurements of contact angle from the experiments are important in order to analyze the wetting behaviour. Various methods have been developed over the years to evaluate wettability of a solid by a liquid. Among these, sessile drop and wetting balance techniques are versatile, popular and provide reliable data. Wetting is affected by large number of factors including liquid properties, substrate properties and system conditions. The effect of these factors on wettability is discussed. Thermodynamic treatment of wetting in inert systems is simple and based on free energy minimization where as that in reactive systems is quite complex. Surface energetics has to be considered while determining the driving force for spreading. Similar is the case of spreading kinetics. Inert systems follow definite flow pattern and in most cases a single function is sufficient to describe the whole kinetics. Theoretical models successfully describe the spreading in inert systems. However, it is difficult to determine the exact mechanism that controls the kinetics since reactive wetting is affected by a number of factors like interfacial reactions, diffusion of constituents, dissolution of the substrate, etc. The quantification of the effect of these interrelated factors on wettability would be useful to build a predictive model of wetting kinetics for reactive systems.