Demonstration of α-Helical Structure of Peptides Tethered to Gold Surfaces Using Surface Infrared and Circular Dichroic Spectroscopies

Langmuir ◽  
2012 ◽  
Vol 28 (7) ◽  
pp. 3510-3515 ◽  
Author(s):  
Ignacio F. Gallardo ◽  
Lauren J. Webb
1979 ◽  
Vol 44 (1) ◽  
pp. 167-173 ◽  
Author(s):  
Slavomír Bystrický ◽  
Rudolf Kohn ◽  
Tibor Sticzay

The CD spectra of aqueous solutions of homopolymeric sodium oligogalacturonates and D-galacturonans of polymerization degree n = 1-64, as well as lower calcium oligogalacturonates (n = 1-5) were measured. Chiroptic properties were correlated with the polymerization degree in terms of optical superposition of monomeric unit increments. Interpretation of obtained data, respecting further physicochemical properties entitles to conclude that the conformation of macromolecules of D-galacturonan in solution is close to helical structure.


In contrast to relatively well developed experimental and theoretical studies on polypeptides and proteins (see Gratzer 1967 and McLachlan 1967, this volume) the investigation of optical activity of polynucleotides and nucleic acids were very restricted. The optical rotatory dispersion curves of polynucleotides examined in the visible and near u. v. fit one-term Drude equation regardless of the conformation (Fresco 1961; Levedahl & James 1957; Ts’o, Helmkamp & Sander 1962). Recent circular dichroism (c. d.) measurements of several polynucleotides and nucleic acids (figure 1) indicated clearly the presence of dichroic bands in the u. v. region of base absorption which can be related to the dissymmetrical helical conformation (Brahms 1963). The intensity of circular dichroic bands decreases strongly under the conditions in which the helical structure is unstable and goes to random coil form (Brahms 1964; Brahms & Mommaerts 1964). Thus polyadenylic acid (poly A ) is known according to X-ray data to exist at acid pH in a helical two strand and right handed conformation (Rich, Davies, Crick & Watson 1961). In acid solution the same polyadenylic acid exhibits strong circular dichroic bands which disappear at high temperature (figure 2).


Biochemistry ◽  
1990 ◽  
Vol 29 (20) ◽  
pp. 4839-4843 ◽  
Author(s):  
Gabor Mocz ◽  
I. R. Gibbons

1988 ◽  
Vol 53 (11) ◽  
pp. 2833-2842 ◽  
Author(s):  
Slavomír Bystrický ◽  
Anna Malovíková ◽  
Tibor Sticzay ◽  
Karel Bláha

The selected model polypeptides poly(Lys-Ala) and poly(Lys-Ala-Ala-Ala) underwent a helix-forming interaction with potassium pectates and pectinates of various esterification degree (E) and with some potassium oligogalacturonates (n = 2-5, 9, 13). Formation of the complex quantitatively monitored by a circular dichroic measurement showed that the specific band distribution of charged side chains of lysine units at the surface of helical structure does not constitute grounds for the local mode of interaction. Potassium pectinate of esterification degree E 57%, corresponding to polypeptides by charge density, does not reveal enhanced complexation values. The complex-forming efficacy continuously decreases with the increase of the esterification degree of pectin. Saturation of charges of the polypeptide was achieved predominantly by the spatial action of the superhelical structure of D-galacturonate chains.


Author(s):  
George C. Ruben ◽  
William Krakow

Tobacco primary cell wall and normal bacterial Acetobacter xylinum cellulose formation produced a 36.8±3Å triple-stranded left-hand helical microfibril in freeze-dried Pt-C replicas and in negatively stained preparations for TEM. As three submicrofibril strands exit the wall of Axylinum , they twist together to form a left-hand helical microfibril. This process is driven by the left-hand helical structure of the submicrofibril and by cellulose synthesis. That is, as the submicrofibril is elongating at the wall, it is also being left-hand twisted and twisted together with two other submicrofibrils. The submicrofibril appears to have the dimensions of a nine (l-4)-ß-D-glucan parallel chain crystalline unit whose long, 23Å, and short, 19Å, diagonals form major and minor left-handed axial surface ridges every 36Å.The computer generated optical diffraction of this model and its corresponding image have been compared. The submicrofibril model was used to construct a microfibril model. This model and corresponding microfibril images have also been optically diffracted and comparedIn this paper we compare two less complex microfibril models. The first model (Fig. 1a) is constructed with cylindrical submicrofibrils. The second model (Fig. 2a) is also constructed with three submicrofibrils but with a single 23 Å diagonal, projecting from a rounded cross section and left-hand helically twisted, with a 36Å repeat, similar to the original model (45°±10° crossover angle). The submicrofibrils cross the microfibril axis at roughly a 45°±10° angle, the same crossover angle observed in microflbril TEM images. These models were constructed so that the maximum diameter of the submicrofibrils was 23Å and the overall microfibril diameters were similar to Pt-C coated image diameters of ∼50Å and not the actual diameter of 36.5Å. The methods for computing optical diffraction patterns have been published before.


2019 ◽  
Author(s):  
Adam Al-Janabi ◽  
Richard Mandle

<p>The nematic twist-bend (N<sub>TB</sub>) liquid crystal phase possesses a local helical structure with a pitch length of a few nanometres and is the first example of spontaneous symmetry breaking in a fluid system. All known examples of the N­<sub>TB­</sub> phase occur in materials whose constituent mesogenic units are aromatic hydrocarbons. It is not clear if this is due to synthetic convenience or a <i>bona fide</i> structural requirement for a material to exhibit this phase of matter. In this work we demonstrate that materials consisting largely of saturated hydrocarbons could also give rise to this mesophase. Furthermore, replacement of 1,4-disubstituted benzene with <i>trans</i> 1,4-cyclohexane or even 1,4-cubane does not especially alter the transition temperatures of the resulting material nor does it appear to impact upon the heliconical tilt angle, suggesting the local structure of the phase is unperturbed. Calculating the probability distribution of bend angles reveals that the choice of isosteric group has little impact on the overall molecular shape, demonstrating the shape-driven nature of the N<sub>TB</sub> phase. </p>


1988 ◽  
Vol 251 (3) ◽  
pp. 691-699 ◽  
Author(s):  
R W Olafson ◽  
W D McCubbin ◽  
C M Kay

Biochemical and physiological studies of Synechococcus cyanobacteria have indicated the presence of a low-Mr heavy-metal-binding protein with marked similarity to eukaryotic metallothioneins (MTs). We report here the characterization of a Synechococcus prokaryotic MT isolated by gel-permeation and reverse-phase chromatography. The large number of variants of this molecule found during chromatographic separation could not be attributed to the presence of major isoproteins as assessed by amino acid analysis and amino acid sequencing of isoforms. Two of the latter were shown to have identical primary structures that differed substantially from the well-described eukaryotic MTs. In addition to six long-chain aliphatic residues, two aromatic residues were found adjacent to one another near the centre of the molecule, making this the most hydrophobic MT to be described. Other unusual features included a pair of histidine residues located in repeating Gly-His-Thr-Gly sequences near the C-terminus and a complete lack of association of hydroxylated residues with cysteine residues, as is commonly found in eukaryotes. Similarly, aside from a single lysine residue, no basic amino acid residues were found adjacent to cysteine residues in the sequence. Most importantly, sequence alignment analyses with mammalian, invertebrate and fungal MT sequences showed no statistically significant homology aside from the presence of Cys-Xaa-Cys structures common to all MTs. On the other hand, like other MTs, the prokaryotic molecule appears to be free of alpha-helical structure but has a considerable amount of beta-structure, as predicted by both c.d. measurements and the Chou & Fasman empirical relations. Considered together, these data suggested that some similarity between the metal-thiolate clusters of the prokaryote and eukaryote MTs may exist.


ChemNanoMat ◽  
2021 ◽  
Author(s):  
Xiaojie Shi ◽  
Jinrun Liu ◽  
Ye Kong ◽  
Borui Xu ◽  
Tianlong Li ◽  
...  

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