From understanding structures in antiferro-ferri and ferroelelectric liquid crystals to an unusual electro-optic effect in a bent-core nematic; a celebration of innovative materials

ABSTRACT

The field of liquid crystals is truly multidisciplinary with numerous examples of virtuous circles of interaction between chemistry, physics, theory and engineering resulting in breakthroughs in both fundamental understanding and novel applications. This paper, written to mark John Goodby’s 65th birthday, offers a personal perspective of the synergy between chemistry and physics from a collaboration that has spanned three decades. The first part of the paper reviews some of the physics insights that resulted from chiral liquid crystals fundamental to understanding structures in ferroelectric, ferrielectric and antiferroelectric systems. The second part of the paper describes some of the remarkable consequences of the anomalous elasticity and flexoelectricity found in the nematic phases of bent-core materials. In particular, we present unusual bowing of disclination lines in the nematic phase of a bent-core material in the presence of a field. Finally, the paper summarises some future prospects relating for bent-core materials. The paper by no means captures the amazing breadth of contribution that John’s chemistry has made to the subject, but aims to exemplify how his generous collaborative approach coupled with innovative chemistry and physical insight has led to paradigm changes in our subject.     

Stereoselective synthesis of 1,8- and 1,5-diketo-trans-syn-trans-perhydroanthracenes

A stereOselective conversion of 1,8- and 1,5-diethoxy-9,10-anthraquinone to 1,8- and 1,5-diketo-$\text{trans}$-$\text{syn}$-$\text{trans}$-perhydroanthracenes by successive sodium borohydride, metal-ammonia, and catalytic reductions is described.     

Erratum to: A Nonlinear Generalization of Singular Value Decomposition and Its Applications to Mathematical Modeling and Chaotic Cryptanalysis

Singular Value Decomposition (SVD) is a powerful tool in linear algebra and has been extensively applied to Signal Processing, Statistical Analysis and Mathematical Modeling. We propose an extension of SVD for both the qualitative detection and quantitative determination of nonlinearity in a time series. The method is to augment the embedding matrix with additional nonlinear columns derived from the initial embedding vectors and extract the nonlinear relationship using SVD. The paper demonstrates an application of nonlinear SVD to identify parameters when the signal is generated by a nonlinear transformation. Examples of maps (Logistic map and Henon map) and flows (Van der Pol oscillator and Duffing oscillator) are used to illustrate the method of nonlinear SVD to identify parameters. The paper presents the recovery of parameters in the following scenarios: (i) data generated by maps and flows, (ii) comparison of the method for both noisy and noise-free data, (iii) surrogate data analysis for both the noisy and noise-free cases. The paper includes two applications of the method: (i) Mathematical Modeling and (ii) Chaotic Cryptanalysis.     

Preparation of Paclitaxel-Encapsulated Bio-Functionalized Selenium Nanoparticles and Evaluation of Their Efficacy against Cervical Cancer

The potentiality of nanomedicine in the cancer treatment being widely recognized in the recent years. In the present investigation, the synergistic effects of chitosan-modified selenium nanoparticles loaded with paclitaxel (PTX-chit-SeNPs) were studied. These selenium nanoparticles were tested for drug release analysis at a pH of 7.4 and 5.5, and further characterized using FTIR, DLS, zeta potential, and TEM to confirm their morphology, and the encapsulation of the drug was carried out using UPLC analysis. Quantitative evaluation of anti-cancer properties was performed via MTT analysis, apoptosis, gene expression analysis, cell cycle arrest, and over-production of ROS. The unique combination of phytochemicals from the seed extract, chitosan, paclitaxel, and selenium nanoparticles can be effectively utilized to combat cancerous cells. The production of the nanosystem has been demonstrated to be cost-effective and have unique characteristics, and can be utilized for improving future diagnostic approaches.     

Racemization at proline residues during peptide bond formation : A study of diastereomeric mixtures of synthetic alamethicin fragments by 270 MHz 1H NMR

The stepwise synthesis of amino terminal pentapeptide of alamethicin, Z-Aib-Pro-Aib-Ala-Aib-OMe, by the dicyclohexylcarbodiimide mediated couplings leads to extensive racemization at the Ala and Pro residues. Racemization is largely suppressed by the use of additives like N-hydroxysuccinimide and 1-hydroxybenzotriazole. The presence of diastereomeric peptides may be detected by the observation of additional methyl ester and benzylic methylene signals in the 270 MHz ¹H NMR spectra. Unambiguous spectral assignment of the signals to the diastereomers has been carried out by the synthesis and NMR studies of the D-Ala tetra and pentapeptides. The racemization at Pro is of particular relevance in view of the reported lack of inversion at C-terminal Pro on carboxyl activation.     

Role of the hydrophobic region of signal sequences in the targeting of proteins to membranes and translocation across the hydrophobic membrane barrier

Proteins destined for regions other than the cytoplasm in cells have to cross at least one membrane barrier before reaching their proper destination. Almost all such proteins are initially biosynthesized as precursors with signal sequences at the amino terminus. Signal sequences are essential and also sufficient for proteins to be targeted to membranes and also for translocation across membranes. One striking feature that is clearly evident amongst signal sequences of secretory proteins is a positively charged amino terminus followed by a region comprising 10–12 very hydrophobic amino acids. The structural and physico-chemical properties of signal sequences have been analysed. On the basis of the analyses it is proposed that the structural feature of a positively charged amino terminal region followed by a hydrophobic stretch of amino acids, rather than a conformational one, is recognised by components of the cells export machinery. It is also postulated that signal sequences insert in the lipid bilayer of the translocation competent membrane after targeting. The presence of the signal sequence results in the formation of local ‘defects’ in the bilayer which have a role in translocation of proteins across membranes.