Characterization of the 310-helix in model peptides by HRMAS NMR spectroscopy

A tetra- and a hepta-homopeptide from the C(alpha)-tetrasubstituted Aib (alpha-aminoisobutyric acid) residue were covalently linked to the POEPOP resin by the fragment-condensation approach. The conformational preferences of the two model peptides were determined for the first time on a solid support by means of high-resolution magic angle spinning NMR spectroscopy. The results obtained indicate that the Aib homopeptides adopt a regular 3(10)-helical structure even when they are covalently bound to a polymeric matrix, and thus confirm the remarkable conformational stability of the peptides rich in this amino acid. An ATR-FTIR spectroscopic investigation, performed in parallel, also confirmed that these polymer-bound peptides do indeed adopt a helical conformation. The results of this study open the possibility to exploit the peptide-resin conjugates based on C(alpha)-tetrasubstituted alpha-amino acids as helpful, structurally organized templates in molecular recognition studies or as catalysts in asymmetric synthesis.     

Thiophene and naphthalene-based double helix: Synthesis,structures and chirality

Both racemate and enantiomer of a novel double helix,binaphthylcyclooctaterthiophene(BN-COTh),which is a DNA-like molecule constructed by two single helices intertwined with each other via covalent bonds,have been synthesized with two building blocks,cycloocta-tetrathiophene(COTh) and cyclooctadinaphthyldithiophene(CONT) fused together via Negishi coupling reaction.Another homologue,dinaphthylcyclooctaterthiophene(DN-COTh) has been employed together as a model compound.Besides the synthetic work,BN-COTh and DN-COTh have been investigated by studying their crystal structures,spectroscopic behaviors,chiral resolution and chiral characteristics,including circular dichroism(CD) spectra and optical rotations.In addition,the novel crystal of enantiomer of(R,R,R)-BN-COTh has been explored.The enantiomer molecules packing along b-axis to form a larger and extended assembly packing due to intermolecular interactions between the enantiomer molecules and chloroform molecules in crystal.     

Two negative minima of the first normal stress difference in a cellulose‐based cholesteric liquid crystal: Helix uncoiling

The shear rate dependence of material functions such as shear viscosity (η) and the first normal stress difference (N₁) were given and interpreted earlier by Kiss and Porter. Their widely accepted work revealed the possibility of having a negative minimum of N₁ for polymeric liquid crystals. In this work, we disclose for the first time the evidence of two negative N₁ minima on a sheared cellulosic lyotropic system. The lower shear rate minimum is ascribed to the uncoiling of the cholesteric helix, as theoretically predicted earlier. Our findings contribute also to the understanding of the other minimum already reported in the literature and attributed to the nematic director tumbling mode. Moreover, the elastic change that the LC‐HPC sample undergoes during the helix unwinding of the cholesteric structure is also by means of oscillatory measurements. This study is a contribution for the understanding of the structure‐properties relationship linked with the complex rheological behavior of chiral nematic cellulose‐based systems and may help to improve their further processing. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 821–830     

Polymeric Tubular Aromatic Amide Helices

Conjugated polymers may be induced by intra‐ and/or intermolecular non‐covalent forces to fold into helical conformations. Helices formed by aromatic amide, hydrazide, and urea polymers possess a well‐organized cavity and depth, which is defined by their degree of polymerization. Driving forces may be intramolecular hydrogen bonding and/or solvophobicity, or guest induction. The resulting long helices represent a new class of unimacromolecular dynamic tubular architectures that exhibit unique properties or functions in, for example, molecular recognition, chirality transfer, and ion transporting. The recent advances are highlighted here.

     

Induced chiral helical effect on the main chain of aliphatic polyacetylenes

11‐Dodecyn‐1‐ol as an achiral, aliphatic, monosubstituted acetylene was copolymerized with cholesteryl 3‐butynyl carbonate as a chiral, aliphatic, monosubstituted acetylene with Rh(nbd)[B(C₆H₅)₄] (nbd = norbornadiene) in tetrahydrofuran. The main chain of the obtained copolymers seemed to be mainly composed of the cis‐type structure. The backbone π–π* transition of these copolymers showed significant circular dichroism (CD), indicating an excess of one‐handed helical conformation. These CD signals were varied with the contents of the cholesteryl units in the copolymers. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 913–917, 2001     

A new version of Bishop frame and an application to spherical images

In this work, we introduce a new version of Bishop frame using a common vector field as binormal vector field of a regular curve and call this frame as “Type-2 Bishop Frame”. Thereafter, by translating type-2 Bishop frame vectors to the center of unit sphere of three-dimensional Euclidean space, we introduce new spherical images and call them as type-2 Bishop spherical images. Frenet-Serret apparatus of these new spherical images are obtained in terms of base curve's type-2 Bishop invariants. Additionally, we express some interesting relations and illustrate two examples of our main results.     

On Darboux helices in Euclidean 4‐space

The notion of Darboux helix in Euclidean 3‐space was introduced and studied by Yayl? et al. 2012. They show that the class of Darboux helices coincide with the class of slant helices. In a special case, if the curvature functions satisfy the equality κ² + τ² = constant, then these curves are curve of the constant precession. In this paper, we study Darboux helices in Euclidean 4‐space, and we give a characterization for a curve to be a Darboux helix. We also prove that Darboux helices coincide with the general helices. In a special case, if the first and third curvatures of the curve are equal, then Darboux helix, general helix, and V₄‐slant helix are the same concepts.     

Geometric Hermite interpolation by spatial Pythagorean-hodograph cubics

It is shown that, depending upon the orientation of the end tangents t₀,t₁ relative to the end point displacement vector p=p₁–p₀, the problem of G¹ Hermite interpolation by PH cubic segments may admit zero, one, or two distinct solutions. For cases where two interpolants exist, the bending energy may be used to select among them. In cases where no solution exists, we determine the minimal adjustment of one end tangent that permits a spatial PH cubic Hermite interpolant. The problem of assigning tangents to a sequence of points p₀,...,p_n in R³, compatible with a G¹ piecewise-PH-cubic spline interpolating those points, is also briefly addressed. The performance of these methods, in terms of overall smoothness and shape-preservation properties of the resulting curves, is illustrated by a selection of computed examples.     

Raman spectroscopy of proteins: a review

In this work, 26 proteins of different structure, function and properties are investigated by Raman spectroscopy with 488, 532 and 1064 nm laser lines. The excitation lines were chosen in NIR and Vis range as the most common and to show the difference due to normal and resonance effect, sometimes accompanied by the fluorescence. The selected proteins were divided, according to the Structural Classification of Proteins, into four classes according to their secondary structure, i.e. α‐helical (α), β‐sheet (β), mixed structures (α/β, α + β, s) and others. For all compounds, FT‐Raman and two Vis spectra are presented along with the detailed band assignment. To the best of our knowledge, this is the first review showing the potential of Raman spectroscopy for the measurement and analysis of such a large collection of individual proteins. This work can serve as a comprehensive vibrational spectra library, based on our and previous Raman measurements. Copyright © 2013 John Wiley & Sons, Ltd.     

Laser emission at the second-order photonic band gap in an electric-field-distorted cholesteric liquid crystal

ABSTRACT

We study the optical properties of a cholesteric liquid crystal doped with a fluorescent dye in the regime of highly distorted helix without full helix unwinding. The distortion was achieved by applying a pulsed AC electric field, perpendicular to the helix axis. If the pulse is in the millisecond range, the helix is deformed but keeps its original pitch even for electric fields higher than the theoretical critical field for helix unwinding. In this field regime, very pronounced high-order photonic band gaps are observed, in agreement with our calculations. We theoretically explore the possibility of obtaining viable laser emission at the second-order photonic band gap, and experimentally find that lasing is not only possible but has a figure of merit similar to that of the usual laser at the main-gap region. Therefore, electric-field-induced high-order photonic band gaps are potentially useful for multiline laser applications.