Doublet Chirality Transfer and Reversible Helical Transition in Poly(3,5‐disubstituted phenylacetylene)s with Pyrene as a Probe Unit†

A novel doublet chirality transfer (DCT) model was demonstrated in cis poly(3,5‐disubstituted phenylacetylene)s, i.e., S‐I , R‐I , and S‐I‐NMe . The chiral message from the stereocenter of alkylamide substituent at 3‐position induced the polyene backbone to take cis‐transoid helical conformation with a predominant screw sense. And in turn the helical backbone acted as a scaffold to orient the pyrene probes, which was linked to phenyl rings through 5‐position, to array in an asymmetric manner. A combinatory analyses of ¹H NMR, Raman, FTIR, UV‐vis absorption, CD, and computer simulation suggested that the main‐chain stereostructure, solvent nature, and intramolecular hydrogen bonds played important and complex roles on DCT. High cis‐structure content and intramolecular hydrogen bonds were beneficial for the realization of DCT. Reversible helix‐helix transition was observed in S‐I by changing the nature of solvents. In DMF, S‐I adopted a relatively contracted helix, where the main chain exhibited strong optical activity, but that of pyrene was weak. In contrast, a relatively stretched helix formed in CHCl₃, in which the optical activity of pyrene was much larger, whereas that of the polyene backbone was the weakest. This helix‐helix transition was attributed to the intramolecular hydrogen bonds, which was confirmed by solution‐state FTIR spectra and computer calculations.     

Parallel Homochiral and Anti‐Parallel Heterochiral Hydrogen‐Bonding Interfaces in Multi‐Helical Abiotic Foldamers

A hydrogen‐bonding interface between helical aromatic oligoamide foldamers has been designed to promote the folding of a helix‐turn‐helix motif with a head‐to‐tail arrangement of two helices of opposite handedness. This design complements an earlier helix‐turn‐helix motif with a head‐to‐head arrangement of two helices of identical handedness interface. The two motifs were shown to have comparable stability and were combined in a unimolecular tetra‐helix fold constituting the largest abiotic tertiary structure to date.     

Conformational Transformation Exhibited by the Peptide Extracted from Crystalline Region of Bombyx mori Silk Fibroin in Solid and Solution States

The conformational transformation of a 30-residue peptide H（Ala-Gly-Ser-Gly-AIa-Gly）5OH, i.e., （AGSGAG）5, extracted from highly crystalline region of Bombyx mori （B. mori） silk fibroin was described by using the high resolution solid state 13^C NMR, and CD spectroscopies. Based on the conformation-dependent 13^C NMR chemical shifts of the Ala, Gly and Ser residues and the line-shape analysis of the conformation sensitive Ala Cβ resonance, the peptide revealed a strong preference for silk Ⅱ structural form, i,e,, an antiparallel fl-sheet structure （φ= - 140±20°and ψ= 135±20°） in solid state. On the contrary, the CD spectra of this peptide in the two non-native hexafluorinated fibre spinning solvents, hexafluoroisopropanol （HFIP） and hexafluoroacetone （HFA）, exhibited the existence of an unusual tightly-folded conformation resembling 310-helix （φ=- 60±20° and ψ=-30±20°）, as judged from the R ratio of [θ]222/[θ]203 in HFIP solution, whereas a dynamically averaged unordered structure in HFA, Taken together, the information inclined to hypothesis that the primary structure of the highly crystalline regions of B. mori silk fibroin may be easily accessible to the large conformational changes, which in turn may be critical for facilitating the structural transformation from unprocessed silk fibroin （silk I form） to processed silk fiber （silk Ⅱform）.     

Formation of double helix self-assembled monolayers of ethynylhelicene oligomer disulfides on gold surfaces

Optically active ethynylhelicene pentamers and hexamers linked by disulfide bonds were synthesized. They formed self-assembled monolayers (SAMs) with double helix structure on gold surfaces, which were analyzed by infrared reflection-absorption spectroscopy (IR-RAS), quartz crystal microbalance (QCM), surface plasmon resonance (SPR), and circular dichroism (CD). Double helix SAMs could be formed on gold surfaces either from double helices or random coils in solution. The double helices on the surface were more stable than in solution. This result suggested the presence of strong intercomplex interactions between double helix complexes on the surface.     

Ordered long‐helical conformation of isotactic polypropylene obtained in constrained environment of nanoclay

Special crystallization event of isotactic polypropylene (iPP) in a constrained environment, a layered clay network, was followed by in situ Fourier transform infrared (FTIR) spectroscopy during the cooling process. Before occurrence of nucleation/crystallization, a conformationally ordered phase, which consists of significant amounts of long 3₁ helices with 14 monomeric units, has been identified for the first time. More importantly, it was found that the long‐ordering helices could play a more important role than short ones for the confined crystallization. It could be tentatively explained as due to the existence of constrained regions in the proximity of the nanoclay platelets or tactoids and the heterogeneous nucleation capability of the surface of nanoclay. Copyright © 2011 John Wiley & Sons, Ltd.     

On the “Tertiary Structure” of Poly‐Carbenes; Self‐Assembly of sp3‐Carbon‐Based Polymers into Liquid‐Crystalline Aggregates

The self‐assembly of poly(ethylidene acetate) (st‐PEA) into van der Waals‐stabilized liquid‐crystalline (LC) aggregates is reported. The LC behavior of these materials is unexpected, and unusual for flexible sp³‐carbon backbone polymers. Although the dense packing of polar ester functionalities along the carbon backbone of st‐PEA could perhaps be expected to lead directly to rigid‐rod behavior, molecular modeling reveals that individual st‐PEA chains are actually highly flexible and should not reveal rigid‐rod induced LC behavior. Nonetheless, st‐PEA clearly reveals LC behavior, both in solution and in the melt over a broad elevated temperature range. A combined set of experimental measurements, supported by MM/MD studies, suggests that the observed LC behavior is due to self‐aggregation of st‐PEA into higher‐order aggregates. According to MM/MD modeling st‐PEA single helices adopt a flexible helical structure with a preferred trans‐gauche syn‐syn‐anti‐anti orientation. Unexpectedly, similar modeling experiments suggest that three of these helices can self‐assemble into triple‐helical aggregates. Higher‐order assemblies were not observed in the MM/MD simulations, suggesting that the triple helix is the most stable aggregate configuration. DLS data confirmed the aggregation of st‐PEA into higher‐order structures, and suggest the formation of rod‐like particles. The dimensions derived from these light‐scattering experiments correspond with st‐PEA triple‐helix formation. Langmuir–Blodgett surface pressure–area isotherms also point to the formation of rod‐like st‐PEA aggregates with similar dimensions as st‐PEA triple helixes. Upon increasing the st‐PEA concentration, the viscosity of the polymer solution increases strongly, and at concentrations above 20 wt % st‐PEA forms an organogel. STM on this gel reveals the formation of helical aggregates on the graphite surface–solution interface with shapes and dimensions matching st‐PEA triple helices, in good agreement with the structures proposed by molecular modeling. X‐ray diffraction, WAXS, SAXS and solid state NMR spectroscopy studies suggest that st‐PEA triple helices are also present in the solid state, up to temperatures well above the melting point of st‐PEA. Formation of higher‐order aggregates explains the observed LC behavior of st‐PEA, emphasizing the importance of the “tertiary structure” of synthetic polymers on their material properties.     

Determining the chromophore in the amylopectin–iodine complex by theoretical and experimental studies

A partial hydrolysis of amylose followed by the addition of iodine provides a spectrum almost identical to that of the amylopectin–iodine (API) complex suggesting the involvement of smaller “amylose-like” units in the API complex. Our theoretical studies on different polyiodine and polyiodide species suggest that a nearly linear I₄ unit stabilized within the cavity of a small “amylose-like” helix is responsible for the characteristic API spectrum. Since there are 2.75 anhydroglucose residues (AGU) for every iodine atom in the amylose–iodine (AI) complex and a structural similarity exists between the API and the AI (amylose–iodine) complexes, we identify (C₆H₁₀O₅)₁₁I₄ to be the chromophore in the API complex. © 1994 John Wiley & Sons, Inc.     

Phase modulation using different orientations of a chiral nematic in liquid crystal over silicon devices

Modulation of the intensity of light by high quality reflective micro-displays is predominantly carried out by liquid crystal over silicon (LCoS) spatial light modulator (SLM) technology for applications such as pico-projectors. Wider use of these devices, in applications such as computer-generated holography and optical correlation, is limited by their phase modulation ability and illumination polarisation state dependence. These devices rely on planar or twisted nematic liquid crystals to modulate the light, but due to their viscoelastic properties they are inherently slow. Research into the use of the polymer stabilised blue phase has already shown that it can offer high speed phase modulation. However, other chiral nematic orientations are yet to be compared in LCoS devices. In this article, we demonstrate that polymer-stabilised chiral nematic liquid crystal electro-optical effects can offer phase modulation in silicon backplane devices. The uniform standing helix and focal conic textures are shown to be independent of the input light polarisation state and the uniform lying helix is shown to be polarisation dependent. These optical responses are then compared with that of the blue phase to identify a suitable orientation for further development in LCoS technology in order to find a high-speed, full phase modulating material.     

A Chiral Helical Compound Based on Achiral Components

The title compound, [Cu(dpa)(2,2'-bipy)(H2O)2]n 1 (H2dpa = diphenic acid and 2,2'- bipy = 2,2'-bipyridine), has been synthesized and its structure was determined by single-crystal X-ray diffraction. The crystal is of orthorhombic, space group P212121 with a = 10.597(4), b = 11.317(4), c = 17.630(7) , V = 2114.3(14) 3, C24H20CuN2O6, Mr = 495.97, Z = 4, Dc = 1.558 g/cm3, μ = 1.079 mm-1, F(000) = 1020, Flack value = 0.052(18), R = 0.0430 and wR = 0.1016 for 3381 observed reflections (I > 2σ(I)). In compound 1, the dpa ligands link metal ions into helical structures in the same direction.