Twist-bend nematics,liquid crystal dimers,structure–property relations

ABSTRACT

One of the current challenges in liquid crystal science is to understand the molecular factors leading to the formation of the intriguing twist-bend nematic phase (N_TB) and determine its properties. During our earlier hunt for the N_TB phase created on cooling directly from the isotropic phase and not the nematic phase, we had prepared 30 symmetric liquid crystal dimers. These had odd spacers and methylene links to the two mesogenic groups; desirable but clearly not essential features for the formation of the N_TB. Here, we report the phases that the dimers exhibit and their transition temperatures as functions of both the lengths of the spacer and the terminal chains. In addition we describe the transitional entropies, their optical textures, the X-ray scattering patterns and the ²H NMR spectra employed in characterising the phases. All of which may lead to important properties of the twist-bend nematic phase.     

Metamorphosis of images in reproducing kernel Hilbert spaces

Metamorphosis is a method for diffeomorphic matching of shapes, with many potential applications for anatomical shape comparison in medical imagery, a problem which is central to the field of computational anatomy. An important tool for the practical application of metamorphosis is a numerical method based on shooting from the initial momentum, as this would enable the use of statistical methods based on this momentum, as well as the estimation of templates from hyper-templates using morphing. In this paper we introduce a shooting method, in the particular case of morphing images that lie in a reproducing kernel Hilbert space (RKHS). We derive the relevant shooting equations from a Lagrangian frame of reference, present the details of the numerical approach, and illustrate the method through morphing of some simple images.     

Self‐Assembled PAA‐Based Nanoparticles as Potential Gene and Protein Delivery Systems

A series of nanoparticles is prepared via layer‐by‐layer assembly of oppositely charged, synthetic biocompatible polyamidoamine polymers as potential carriers. Particle size, surface charge and internal chain mobility are quantified as a function of the polymer type and number of layers. The effect of addition of surfactant is examined to simulate the effects of nanoparticle dissolution. The cyctotoxicity of these particles (in epithelia and murine cell lines) are orders of magnitude lower than polyethyleneimine controls. Stable nanoparticles may be prepared from mixtures of strongly, oppositely charged polymers, but less successfully from weakly charged polymers, and, given their acceptable toxicity characteristics, such modularly designed constructs show promise for drug and gene delivery.

     

Synthesis of Substituted Trans-1,6-Dimethylbicyclo[4.3.0]-non-2-enes Using A Claisen Rearrangement of α-(Thioalkoxy) Esters

The Claisen rearrangement of α-(thioalkoxy)-esters provided access to substituted trans-1, 6-dimethylbicyclo[4.3.0]non-2-enes characteristic of the CD rings of the cucurbitanes.     

Expanding the Toolbox of Metal–Phenolic Networks via Enzyme‐Mediated Assembly

Functional coatings are of considerable interest because of their fundamental implications for interfacial assembly and promise for numerous applications. Universally adherent materials have recently emerged as versatile functional coatings; however, such coatings are generally limited to catechol, (ortho‐diphenol)‐containing molecules, as building blocks. Here, we report a facile, biofriendly enzyme‐mediated strategy for assembling a wide range of molecules (e.g., 14 representative molecules in this study) that do not natively have catechol moieties, including small molecules, peptides, and proteins, on various surfaces, while preserving the molecule's inherent function, such as catalysis (≈80 % retention of enzymatic activity for trypsin). Assembly is achieved by in situ conversion of monophenols into catechols via tyrosinase, where films form on surfaces via covalent and coordination cross‐linking. The resulting coatings are robust, functional (e.g., in protective coatings, biological imaging, and enzymatic catalysis), and versatile for diverse secondary surface‐confined reactions (e.g., biomineralization, metal ion chelation, and N‐hydroxysuccinimide conjugation).     

Polyphenol‐Mediated Assembly of Proteins for Engineering Functional Materials

Functional materials composed of proteins have attracted much interest owing to the inherent and diverse functionality of proteins. However, establishing general techniques for assembling proteins into nanomaterials is challenging owing to the complex physicochemical nature and potential denaturation of proteins. Here, a simple, versatile strategy is introduced to fabricate functional protein assemblies through the interfacial assembly of proteins and polyphenols (e.g., tannic acid) on various substrates (organic, inorganic, and biological). The dominant interactions (hydrogen‐bonding, hydrophobic, and ionic) between the proteins and tannic acid were elucidated; most proteins undergo multiple noncovalent stabilizing interactions with polyphenols, which can be used to engineer responsiveness into the assemblies. The proteins retain their structure and function within the assemblies, thereby enabling their use in various applications (e.g., catalysis, fluorescence imaging, and cell targeting).     

A Theoretical Study of ãA2 CH2

The potential energy surface and dipole moment surfaces of the ã⁴A₂ electronic state of CH₂⁺ are calculated ab initio using an augmented correlation-consistent polarized valence quadruple-ζ (aug-cc-pVQZ) basis set, with the incorporation of dynamical correlation using the coupled cluster method with single and double excitations and perturbatively connected triple excitations [CCSD(T)]. We use these surfaces in the MORBID program system to calculate rotation and rotation-vibration term values for ã-state CH₂⁺, CD⁺₂, and CHD⁺ and to simulate the rotation and rotation-vibration absorption spectrum of CH₂⁺ in the ã⁴A₂ electronic state. Our work is motivated by studies of CH₂⁺ that use the Coulomb explosion imaging technique and by the goal of predicting spectra that may be obtained from discharge sources. Although the ã state is the lowest-lying excited state above the X?/Ã ground state pair, it turns out to be relatively high-lying, and we determine that T_e(ã)=30447.5 cm⁻¹. The equilibrium bond angle for ã-state CH₂⁺ is only 77.1°; as a result the asymmetric top κ value is close to 0, and the molecule is equally far from the oblate and prolate symmetric top limits in this electronic state.