Virtual isotropic‐nematic transitions in alkyl cyanobiphenyls

Pretransitional fluctuations in the isotropic phase of liquid crystalline and non‐liquid crystalline alkyl cyanobiphenyls have been investigated using light scattering and magnetic birefringence measurements. We find evidence for a virtual isotropic‐nematic phase transition in short‐chain alkyl cyanobiphenyls with no observable nematic phase. The measured temperature dependence of fluctuations is well‐described by mean‐field theory. Virtual phase transition temperatures extrapolated from separate light scattering and magnetic birefringence experiments are in good agreement. Landau–de Gennes model parameters for the compounds investigated are calculated from the experimental results.     

Supramolecular main-chain liquid crystalline polymers and networks with competitive hydrogen bonding

A series of supramolecular polymers and networks with variable liquid crystalline characteristics have been created. These species are formed though the benzoic acid/pyridine associations of a flexible bisacid and a mixture of a rigid bispyridyl and a non-mesogenic tetrapyridyl. The networked systems displayed liquid crystalline characteristics up to and including 22.5% netpoint inclusion. Above this concentration, only crystalline and melting behaviours were observed. This observed phenomenon would seem to be linked to the statistical correlation of hydrogen bond acceptors and donors. There was also no observed phase segregation of the species after multiple heat/cool cycles and extended periods of time in the isotropic state. This would indicate that the thermodynamically more stable mesogenic phase cannot out-compete the non-liquid crystalline network. Computational analysis indicates no significant difference in hydrogen bond strength between the two different hydrogen bond acceptors.     

Thermotropic liquid crystal behaviour of gemini imidazolium-based ionic amphiphiles

Thermotropic ionic liquid crystals (LCs) are useful for a number of applications such as anisotropic ion transport and as organised reaction media/solvents because of their ordered fluid properties and intrinsic charge units. A large number of different ionic LC architectures are known, but only a handful of examples of gemini (i.e. paired or dimeric) ionic LCs have been prepared and studied. In this work, a series of 20 new symmetric, imidazolium-based, gemini cationic LCs containing two bridged imidazolium cations and two pendant alkyl chains was synthesised, and the thermotropic LC behaviours were characterised. The imidazolium unit provides a highly tunable and modular platform for the design and synthesis of gemini cationic LCs which offers excellent structure control. As expected, the thermotropic LC properties of these new amphilphilic, gemini ionic LCs were found to be strongly influenced by the length of the spacer between the imidazolium units, the length of the pendant alkyl tails, and the nature of the anion. Smectic A (SmA) thermotropic LC phases were observed in more than half of the gemini imidazolium LC systems studied.     

Active Sites of Dermatan Sulfate for Heparin Cofactor II. Isolation of a Nonasaccharide Fragment Containing Four Disaccharide Sequences [α-l-Iduronic Acid 2-O-Sulfate (1,3)-β-d-N-Acetylgalactosamine 4-Sulfate]

Abstract

The active site of dermatan sulfate (DS) for heparin cofactor II (HCII) was isolated in a fragment obtained by periodate oxidation, borohydride reduction, mild acid hydrolysis, and SE- and SAX-chromatography of beef mucosal and pig skin DS preparations. Characterization by mass spectrometry, one- and two-dimensional NMR spectroscopy, and HPLC analysis of disaccharides, obtained by exhaustive digestion with chondroitinase-ABC, indicates that the fragment has the prevalent structure 1, GalNAc-4SO₃-[IdoA-2SO₃-GalNAc-4SO₃]₄-R, where R is CH(CH₂OH)CH(COO^?)-OH. 1, is the largest DS fragment thus far isolated containing IdoA2SO₃ as the only uronic acid. Its lower activity (30%) with respect to the parent polymeric DS is explainable by Tollefsen model, requiring longer polyanionic chains for formation of ternary complex with thrombin.     

Spatial updating, spatial transients, and regularities of a complex automaton with nonperiodic architecture

We study the dynamics of patterns exhibited by rule 52, a totalistic cellular automaton displaying intricate behaviors and wide regions of active/inactive synchronization patches. Systematic computer simulations involving 2(30) initial configurations reveal that all complexity in this automaton originates from random juxtaposition of a very small number of interfaces delimiting active/inactive patches. Such interfaces are studied with a sidewise spatial updating algorithm. This novel tool allows us to prove that the interfaces found empirically are the only interfaces possible for these periods, independently of the size of the automata. The spatial updating algorithm provides an alternative way to determine the dynamics of automata of arbitrary size, a way of taking into account the complexity of the connections in the lattice.     

Spectral editing in solid-state MAS NMR of quadrupolar nuclei using selective satellite inversion

A sensitivity enhancement method based on selective adiabatic inversion of a satellite transition has been employed in a (pi/2)CT-(pi)ST1-(pi/2)CT spectral editing sequence to both enhance and resolve multisite NMR spectra of quadrupolar nuclei. In addition to a total enhancement of 2.5 times for spin 3/2 nuclei, enhancements up to 2.0 times is reported for the edited sites in a mixture of rubidium salts.     

Perturbation of Spin Crossover Behavior by Covalent Post‐Synthetic Modification of a Porous Metal–Organic Framework

Covalent post‐synthetic modification is a versatile method for gaining high‐level synthetic control over functionality within porous metal–organic frameworks and for generating new materials not accessible through one‐step framework syntheses. Here we apply this topotactic synthetic approach to a porous spin crossover framework and show through detailed comparison of the structures and properties of the as‐synthesised and covalently modified phases that the modification reaction proceeds quantitatively by a thermally activated single‐crystal‐to‐single‐crystal transformation to yield a material with lowered spin‐switching temperature, decreased lattice cooperativity, and altered color. Structure–function relationships to emerge from this comparison show that the approach provides a new route for tuning spin crossover through control over both outer‐sphere and steric interactions.     

Ultraviolet radiation as a limiting factor in leaf expansion and development

Reductions in leaf growth are a commonly observed response to ultraviolet radiation, but the underlying mechanisms remain poorly defined. This study examined the response of leaves exposed to a UV environment across a range of organizational scales, including leaf expansion rate, epidermal cell size and number, biomechanical properties, leaf–water relations and activity of cell-wall peroxidases. Two experimental approaches were used; Lettuce ( Lactuca sativa L.) plants were propagated under (a) supplementary UV-B (9 kJ m⁻² day⁻¹) in controlled environment (CE) conditions, and (b) field conditions, where plants were placed under three horticultural films with differing UV transmissions. In both experiments, UV-B caused the greatest reductions in leaf expansion and final leaf size, with some reductions attributable to UV-A wavelengths. In supplementary UV-B conditions, adaxial cell size was reduced, while in field plants, both cell size and cell number were lower in an increased UV environment, as was the case with abaxial cells in CE plants. Although leaf turgor and leaf extensibility were not affected by UV wavelengths, breaking strain of leaf tissue was decreased under supplementary UV-B. Cell-wall peroxidase activity was increased in both supplementary UV conditions and in the field, where only a zero UV environment showed no upregulation of cell-wall peroxidase.     

Fluctuations for the Ginzburg-Landau $${\nabla \phi}$$ Interface Model on a Bounded Domain

We study the massless field on \({D_n = D \cap \tfrac{1}{n} \mathbf{Z}^2}\), where \({D \subseteq \mathbf{R}^2}\) is a bounded domain with smooth boundary, with Hamiltonian \({\mathcal {H}(h) = \sum_{x \sim y} \mathcal {V}(h(x) - h(y))}\). The interaction \({\mathcal {V}}\) is assumed to be symmetric and uniformly convex. This is a general model for a (2 + 1)-dimensional effective interface where h represents the height. We take our boundary conditions to be a continuous perturbation of a macroscopic tilt: h(x) = n x · u + f(x) for \({x \in \partial D_n,\,u \in \mathbf{R}^2}\), and f : R ² → R continuous. We prove that the fluctuations of linear functionals of h(x) about the tilt converge in the limit to a Gaussian free field on D, the standard Gaussian with respect to the weighted Dirichlet inner product \({(f,g)_\nabla^\beta = \int_D \sum_i \beta_i \partial_i f_i \partial_i g_i}\) for some explicit β = β(u). In a subsequent article, we will employ the tools developed here to resolve a conjecture of Sheffield that the zero contour lines of h are asymptotically described by SLE(4), a conformally invariant random curve.