Left-handed Helical Structure Research Articles

Surfactant-mediated gelation by 12-hydroxyoctadecanoic acid in a nonionic surfactant system

In this study, we present a hydrogel fabrication utilizing a water-insoluble, low-molecular-weight organogelator by the surfactant-mediated gelation (SMG). Specifically, we employed a nonionic surfactant (poly(oxyethylene) sorbitan monooleate, Tween 80) and an organogelator (12-hydroxyoctadecanoic acid, 12-HOA) to produce hydrogels. Gelation experiments conducted at varying concentrations of surfactant and gelator demonstrated successful hydrogel formation in the water/Tween 80/12-HOA system. Moreover, we observed a significant dependence of surfactant concentration on gelation ability. The sol-gel transition temperature was found to be influenced by both the gelator and surfactant concentrations. Optical and electron microscopy analyses revealed that the SMG hydrogels comprised an entangled network of fibers with micrometer-scale widths, formed as bundles of submicron-wide fibers, and further composed of fine fibers measuring several tens of nanometers in width. These fine fibers exhibited a left-handed helical structure. Small- and wide-angle X-ray scattering corroborated the presence of a lamellar structure within the fine fibers, displaying a triclinic subcell morphology. The coexistence of micelles with the fiber network was confirmed through small-angle neutron scattering and UV–vis spectroscopy. Furthermore, dynamic viscoelasticity tests demonstrated that the SMG hydrogels exhibited typical solid-like properties indicative of gel behavior.

Nonreciprocity and chirality hosted by ferromagnetic helical chains: Heat generation vs spin filtering

Motivated by the booming development of spintronics based on chiral helical microstructures, we employed the standard nonequilibrium Green’s function theory to study nonreciprocity and chirality of the heat generation and spin filtering in ferromagnetic helical chains. Our results demonstrate that magnetization, spin–orbit interaction, and nonstep electrostatic potential distribution by bias jointly determine nonreciprocity of the heat generation, and only spin–orbit interaction determines nonreciprocity of the spin-polarized current. Chirality of the heat generation and spin-polarized current is determined by both magnetization and spin–orbit interaction, and some quantitative relationships related to chirality were discovered. However, a transverse field can break these relations and suppress heat generation significantly and modulate nonreciprocity and chirality of the spin-polarized current effectively. By further simulating the critical electrostatic potential distribution, we found with the transverse field applied, compared to the case with zero temperature, that the finite temperature less than one characteristic phonon energy can suppress nonreciprocity of the heat generation while enhancing that of the spin filtering. In terms of chirality, compared to the left-handed helical structure, the right-handed one is more advantageous for designing spin filtering diodes.

Preparation of magneto-electro-optically active polymer using Fe ionic liquid as electro-magnetic dopant

In this research, we report the synthesis of conjugated polymers with magnetism. Electrochemical polymerization in liquid crystal was conducted with 1-butyl-3-methylimidazolium tetrachloroferrate (BMITF), which is a paramagnetic character having a large magnetic susceptibility, as a supporting salt. The polymer films thus obtained had magnetism because BMITF remains in the films as a dopant. Poly(2,2′-bithiophene) and poly(bis-(3,4-ethylenedioxythiophene)) were prepared in nematic or cholesteric liquid crystal with BMITF by electrochemical polymerization. Transcription of the liquid crystal structure was succeeded with a small amount of BMITF. Blush or fingerprint structures were confirmed by polarizing optical microscopy observation. The addition of the excess amount of BMITF broke the structure of the liquid crystal. Poly(2,2′-bithiophene) transcribed the cholesteric liquid crystal structure showed a negative Cotton effect, indicating with left-handed helical structure. Poly(bis-(3,4-ethylenedioxythiophene)) transcribed the cholesteric liquid crystal structure showed a positive Cotton effect, indicating the polymer forms a right-handed helical structure. The X-ray photoelectron spectroscopy measurements, confirming the existence of Fe element in the polymers thus obtained. From the electron spin resonance measurements, the polymers thus obtained showed magnetic activity. This method affords facile synthesis of conjugated polymers with magnetism.

Integrating Low-Temperature-Resistant Two-Dimensional Elastic-Bending and Reconfigurable Plastic-Twisting Deformations into an Organic Crystal.

Integrating plasticity and elasticity in anisotropic molecular crystals is theoretically possible and is beneficial in enabling rich and complex deformations; however, it is much harder to implement in practice. Herein, we report a centimeter-long organic crystal that is two-dimensionally (2D) elastically bendable not only at room temperature but also at ultralow temperatures (-196 °C). The straight crystal can also be manually twisted and reconfigured to form arbitrary right-handed or left-handed helical structures. The integration of low-temperature-resistant (LTR) 2D elastic-bending and reconfigurable plastic-twisting deformations into one organic crystal expands the perspectives of the emerging crystal flexibility. Taking advantage of the unique multiple flexibility characteristics, spatial controllability of optical transmission for cryogenic applications and reusability of light-polarization rotations have been implemented simultaneously in an organic crystal.

Complexation with pre-formed “empty” V-type starch for encapsulation of aroma compounds

Aroma compounds are low-molecular-weight organic volatile molecules and are broadly utilized in the food industry. However, due to their high volatility and evaporative losses during processing and storage, the stabilization of these volatile ingredients using encapsulation is a commonly investigated practice. Complexation of aroma compounds using starch inclusion complex could be a potential approach due to the hydrophobicity of the left-handed single helical structure. In the present study, we used starch of three different V-type structures, namely V6h, V7, and V8, to encapsulate six different aroma compounds, including 1-decanol (DN), cis-3-hexen-1-ol (HN), 4-allylanisole (AN), γ-decalactone (DA), trans-cinnamaldehyde (CA), and citral (CT). The formed inclusion complexes samples were characterized using complementary techniques, including X-ray diffraction (XRD) and differential scanning calorimetry (DSC). The results showed that upon complexation with aroma compounds, all V-subtypes retained their original crystalline structures. However, different trends of crystallinity were observed for each type of the prepared inclusion complexes. Additionally, among three V-type starches, V6h-type starch formed inclusion complexes with aroma compounds most efficiently and promoted the formation of Form II complex. This study suggested that the structure of aroma compounds and the type of V starch could both affect the complexation properties.

Revealing the nature of localized and delocalized excitations of DNA

Unmatched opportunities for novel nanoscale technologies and applications are provided by deoxyribonucleic acid (DNA). In this paper, we propose a quantum mechanical investigation into the optical excitations of DNA using calculations based on time-dependent density functional theory. Our findings demonstrate that DNA exhibits photoabsorption in the ultraviolet region of the electromagnetic spectrum, and transition contribution maps demonstrate that the optical transitions of DNA contain both localized and delocalized excitations. Additionally, we simulated and contrasted the electronic circular dichroism (ECD) spectra of B-DNA (a right-handed double helical structure) and Z-DNA (a left-handed double helical structure). We discovered significant variations in the ECD spectra. The design of DNA-based nano-optical devices should benefit from the theoretical findings in this work.

Enantioseparation on helical poly(diphenylacetylene)s bearing optically-active pendants: Effects of differences in higher-order structures of kinetically-trapped and thermodynamically-stable states on chiral recognition ability

An optically-active poly(diphenylacetylene) (PDPA) bearing carboxy pendant groups with left-handed helicity memory (M-h-poly-1), synthesized using the noncovalent helicity-induction-and-memory strategy, was converted into a PDPA bearing optically-active pendant groups through an amide bonding (M-hKT-poly-2S), while maintaining the left-handed helicity memory, by reaction with (S)-1-phenylethylamine ((S)-2) using a condensing reagent at room temperature. Its chiral recognition ability was investigated as a chiral stationary phase (CSP) for high-performance liquid chromatography (HPLC). M-hKT-poly-2S exhibited significantly different chiral recognition ability towards racemates compared to the previously reported corresponding helical PDPA bearing the same optically-active pendant groups (M-hTS-poly-2S) (prepared by the reaction of an optically-inactive PDPA bearing carboxy pendants with (S)-2, followed by thermal annealing, to induce a left-handed helical structure in the polymer main chain). Although the main chains of both M-hKT-poly-2S and M-hTS-poly-2S formed almost completely left-handed helical structures, their higher-order structures varied slightly, as confirmed by various spectroscopic methods (UV-Vis, circular dichroism (CD), IR, and vibrational CD). M-hKT-TS-poly-2S, the PDPA formed on the thermal annealing of M-hKT-poly-2S, exhibited the same higher-order structure and chiral discrimination ability as M-hTS-poly-2S. Therefore, slight differences in the higher-order structures of the kinetically-trapped metastable state (M-hKT-poly-2S) and the thermodynamically-stable state (M-hTS-poly-2S), due to differences in synthetic procedures, significantly impact their chiral recognition abilities as CSPs, even with identical primary structures and helix-sense of the polymer main chain.

X-ray diffraction and in vivo studies reveal the quinary structure of Trypanosoma cruzi nucleoside diphosphate kinase 1: a novel helical oligomer structure.

Trypanosoma cruzi is a flagellated protozoan parasite that causes Chagas disease, which represents a serious health problem in the Americas. Nucleoside diphosphate kinases (NDPKs) are key enzymes that are implicated in cellular energy management. TcNDPK1 is the canonical isoform in the T. cruzi parasite. TcNDPK1 has a cytosolic, perinuclear and nuclear distribution. It is also found in non-membrane-bound filaments adjacent to the nucleus. In the present work, X-ray diffraction and in vivo studies of TcNDPK1 are described. The structure reveals a novel, multi-hexameric, left-handed helical oligomer structure. The results of directed mutagenesis studies led to the conclusion that the microscopic TcNDPK1 granules observed in vivo in T. cruzi parasites are made up by the association of TcNDPK1 oligomers. In the absence of experimental data, analysis of the interactions in the X-ray structure of the TcNDPK1 oligomer suggests the probable assembly and disassembly steps: dimerization, assembly of the hexamer as a trimer of dimers, hexamer association to generate the left-handed helical oligomer structure and finally oligomer association in a parallel manner to form the microscopic TcNDPK1 filaments that are observed in vivo in T. cruzi parasites. Oligomer disassembly takes place on the binding of substrate in the active site of TcNDPK1, leading to dissociation of the hexamers. This study constitutes the first report of such a protein arrangement, which has never previously been seen for any protein or NDPK. Further studies are needed to determine its physiological role. However, it may suggest a paradigm for protein storage reflecting the complex mechanism of action of TcNDPK1.

A thermodynamic understanding of the salt-induced B-to-Z transition of DNA containing BZ junctions

Z-DNA has attracted interest due to its distinctive left-handed helical structure. This non-canonical DNA structure is able to form transiently and plays an important role in cellular processes such as transcriptional regulation and DNA recombination. Alternating purine–pyrimidine sequences are well known to form Z-DNA under high-salt conditions, but the detailed mechanism of B-to-Z transition of DNA containing BZ junctions under these conditions is not well understood. Here, using single-molecule FRET and circular dichroism experiments, we studied the effect of BZ junctions on Z-DNA formation under high-salt conditions. Further thermodynamic analysis revealed that a discrepancy of different DNA substrates in the presence and absence of BZ junctions in Z-DNA formation can be attributed mainly to the competition between enthalpy and entropy. Salt-induced B-to-Z transition is entropically favored in the presence of BZ junctions and is enthalpically favored in their absence. This thermodynamic information provides a deeper understanding of Z-DNA formation of DNA containing BZ junctions.

Studying the helical conformations of aspereline peptides.

Asperelines are short-sequence peptaibol molecules, and these peptides composed of 10 residues were isolated from the Trichoderma asperellum. In our study, a detailed structural characterization was performed on the asperelines by means of molecular dynamics methods. For the aspereline peptides, the occurrence of various secondary structural elements (i.e. β-turns and helical structures) was investigated along their entire sequences. The results derived from the simulated annealing calculations led to the observations that in the case of asperelines, the types I, III and III' β-turn structures, as well as their stabilizing i←i+3 H-bonds appeared. However, beside the different β-turns, shorter or longer helical structures were also detected. Based on the results obtained by the molecular dynamics simulations, it was concluded that the three-dimensional structure of aspereline peptides could be characterized by helical conformations (i.e. 310 - and α-helix). Nevertheless, on the basis of individual molecular dynamics trajectories, it was observed that the asperelines could adopt not only the right-handed, but also the left-handed helical structures.

Dinuclear Triple-Stranded Helicates Comprising Al(III), Ga(III), or In(III) and a Hydrazine-Linked Bisiminopyrrolyl Ligand: Synthesis, Structure, Optical Resolution, and Chiroptical Properties

Abstract The synthesis of helical complexes is attracting increased attention because their chiral properties lead to a variety of functional applications. In this work, a series of neutral, dinuclear M(III) (M = Al, Ga, or In) triple-stranded helicates were prepared using a tetradentate bisiminopyrrole ligand (H2L). An X-ray crystallographic analysis revealed that both right- (P) and left-handed (M) helical structures exist in the solid state for Al2L3, Ga2L3, and In2L3. The enantiomers were successfully resolved by chiral column chromatography, and the chiroptical properties of the complexes were characterized by circular dichroism, circularly polarized emission spectroscopy, and time-dependent density functional theory calculations.

Atomic structure of potato virus X, the prototype of the Alphaflexiviridae family.

Potato virus X (PVX) is a positive-sense single-stranded RNA (ssRNA) filamentous plant virus belonging to the Alphaflexiviridae family, considered in recent years as a tool for nanotechnology applications. We present the cryo-electron microscopy structure of the PVX particle at a resolution of 2.2 Å. The well-defined density of the coat proteins and of the genomic RNA allowed a detailed analysis of protein-RNA interactions, including those mediated by solvent molecules. The particle is formed by repeated segments made of 8.8 coat proteins, forming a left-handed helical structure. The RNA runs in an internal crevice along the virion, packaged in 5-nucleotide repeats in which the first four bases are stacked in the classical way, while the fifth is rotated and nearly perpendicular. The resolution of the structure described here suggests a mechanism for the virion assembly and potentially provides a platform for the rational design of antiviral compounds and for the use of PVX in nanotechnology.

Flexible and Structural Coloured Composite Films from Cellulose Nanocrystals/Hydroxypropyl Cellulose Lyotropic Suspensions

Lyotropic colloidal aqueous suspensions of cellulose nanocrystals (CNCs) can, after solvent evaporation, retain their chiral nematic arrangement. As water is removed the pitch value of the suspension decreases and structural colour-generating films, which are mechanically brittle in nature, can be obtained. Increasing their flexibility while keeping the chiral nematic structure and biocompatible nature is a challenging task. However, if achievable, this will promote their use in new and interesting applications. In this study, we report on the addition of different amounts of hydroxypropyl cellulose (HPC) to CNCs suspension within the coexistence of the isotropic-anisotropic phases and infer the influence of this cellulosic derivative on the properties of the obtained solid films. It was possible to add 50 wt.% of HPC to a CNCs aqueous suspension (to obtain a 50/50 solids ratio) without disrupting the LC phase of CNCs and maintaining a left-handed helical structure in the obtained films. When 30 wt.% of HPC was added to the suspension of CNCs, a strong colouration in the film was still observed. This colour shifts to the near-infrared region as the HPC content in the colloidal suspension increases to 40 wt.% or 50 wt.% The all-cellulosic composite films present an increase in the maximum strain as the concentration of HPC increases, as shown by the bending experiments and an improvement in their thermal properties.

Novel triorganotin complexes based on phosphonic acid ligands: Syntheses, structures and in vitro cytostatic activity

Six novel organotin phosphonate complexes, [(Me3Sn)4(HL1)4]n1, [(Me3Sn)2(HL2)2]n2, [(Me3Sn)2L3(H2O)]n3, [(Ph3Sn)(HL1)]64, [(Ph3Sn)2L2]n5 and [(Ph3Sn)2L3]66, derived from phosphonic acid ligands [NaHL1 = 1-C10H7OPO2(OH)Na, H2L2 = 1-C10H7PO(OH)2, H2L3 = 2-C10H7PO(OH)2], have been synthesized and characterized by elemental analysis, FT-IR, NMR (1H, 13C, 31P and 119Sn) spectroscopy and X-ray crystallography. The structural analysis reveals that complexes 1 and 5 display 1D infinite zig-zag chain structures, and complex 2 shows 1D right-handed helical chain structure, while complex 3 displays 1D left-handed helical chain structure. Complexes 4 and 6 are 24-membered macrocyclic rings interconnected by P, O and Sn atoms. Additionally, the molecules of complexes 1 and 3 are further linked through intermolecular π···π and O-H···O interaction into supramolecular structures, respectively. Furthermore, we preliminarily estimated in vitro cytostatic activity of complexes 1–6 against the human cervix tumor cells (HeLa), human hepatocellular carcinoma cells (HepG-2) and human normal breast cells (HBL-100). Importantly, the anti-proliferative properties and possible pathway of complex 6 are investigated, and the results demonstrate that complex 6 could induce apoptotic cell death via an overload of intracellular reactive oxygen species (ROS) levels and the dysfunctional depolarization of mitochondrial membranes.

Circularly polarized luminescence from semiconductor quantum rods templated by self-assembled cellulose nanocrystals

We demonstrate a significant right-handed circularly polarized luminescence of CdSe/CdS quantum rods by doping them into a self-assembled left-handed helical structure of cellulose nanocrystals.

Unique Bora[1]ferrocenophanes with Sterically Protected Boron: A Potential Gateway to Helical Polyferrocenes.

Silicon-bridged [1]ferrocenophanes are a versatile class of monomers to obtain well-defined metallopolymers, however, their boron-bridged analogues are far less utilized despite being significantly higher strained. We assumed that the reactivity of known bora[1]ferrocenophanes towards ring-opening polymerization is hampered by π-donating R2 N groups at the bridging boron atom and therefore prepared the first bora[1]ferrocenophanes lacking such electronic stabilization. The new, isolated ferrocenophane with a 2,4,6-triisopropylphenyl group attached to the bridging boron atom exhibits the most tilted Cp rings among all isolated strained sandwich compounds [α(DFT)=33.3°] with a measured record value of the bathochromic shift (λmax =516 nm). Attempts to purify the mesityl analogue by vacuum sublimation transformed this monomer to a purple-colored polymer that resulted in Cotton effects in circular dichroism spectroscopy. DFT calculations revealed a left-handed helical structure for this polymer. This is the first evidence for a polyferrocene with a chiral secondary structure.

Fundamental helical geometry consolidates the plant photosynthetic membrane.

Plant photosynthetic (thylakoid) membranes are organized into complex networks that are differentiated into 2 distinct morphological and functional domains called grana and stroma lamellae. How the 2 domains join to form a continuous lamellar system has been the subject of numerous studies since the mid-1950s. Using different electron tomography techniques, we found that the grana and stroma lamellae are connected by an array of pitch-balanced right- and left-handed helical membrane surfaces of different radii and pitch. Consistent with theoretical predictions, this arrangement is shown to minimize the surface and bending energies of the membranes. Related configurations were proposed to be present in the rough endoplasmic reticulum and in dense nuclear matter phases theorized to exist in neutron star crusts, where the right- and left-handed helical elements differ only in their handedness. Pitch-balanced helical elements of alternating handedness may thus constitute a fundamental geometry for the efficient packing of connected layers or sheets.

Co-Assembled Supramolecular Nanostructure of Platinum(II) Complex through Helical Ribbon to Helical Tubes with Helical Inversion.

We demonstrated the morphology transformation of co-assemblies based on terpyridine-based ligands (1R and 1S) possessing R- or S-alanine analogues and their platinum(II) complex (2R-Pt and 2S-Pt). The right-handed helical ribbon of the co-assembly formed with 0.5 equivalents of 2R-Pt to 1R was converted into the left-handed helical ribbon with 0.6 equivalents of 2R-Pt. The left-handed helical ribbon structure of the co-assembly became a tubular structure in the presence of 0.8-1.0 equivalents of 2R-Pt. The morphology transformation via helical inversion at the supramolecular level was due to an orientation change of the amide groups caused by non-covalent Pt⋅⋅⋅Pt interactions between the terpyridine of 2R-Pt and that of 2R-Pt. This study provides insights into controlling the morphology of the transformation of helical ribbons into tubular structures through helicity inversion in co-assembled supramolecular nanostructures based on platinum(II) complexes.

Crystal structure and Hirshfeld surface analysis of 1,2-bis-(2',6'-diisoprop-oxy-[2,3'-bipyridin]-6-yl)benzene.

The title mol-ecule, C38H42N4O4, displays a helical structure induced by the combination of the C-C-C-C torsion angle [-10.8 (2)°] between two 2,3'-bipyridyl units attached to the 1,2-positions of the central benzene ring and consecutive connections between five aromatic rings through the meta- and ortho-positions. Intra-molecular C-H⋯π inter-actions between an H atom of a pyridine ring and the centroid of a another pyridine ring contributes to the stabilization of the helical structure. In the crystal, weak C-H⋯π inter-actions link the title mol-ecules into a two-dimensional supra-molecular network extending parallel to the ac plane, in which the mol-ecules with right- and left-handed helical structures are alternately arranged. Hirshfeld surface analysis and two-dimensional fingerprint plots indicate that the mol-ecular packing is dominated by van der Waals inter-actions between neighbouring H atoms, as well as by C-H⋯π inter-actions. One isopropoxyl group is disordered over two sets of sites [occupancy ratio 0.715 (5):0.285 (5)].

Comprehensive analysis of damage associated SNPs of MMP9 gene: A computational approach

Extracellular matrix is a dynamic meshwork of macromolecules that plays an important role in biological processes such as tissue remodeling and various developmental processes. Collagen is the chief component of ECM. Upon hydrolysis, it forms an irreversible left-handed helical structure which is further hydrolyzed by a specialized group of MMP family i.e. Gelatinases (MMP2 and MMP9). Present study was carried to figure out deleterious SNPs associated with MMP9 gene. Our results showed that two nsSNP (rs8125581 and rs41529445) that are present in catalytic domain are highly conserved and affect the protein structure and function.7 SNPs located in UTRs were found to alter miRNA seed region 13 SNPs of splice site were predicted to affect splice signals thereby affecting the post translational expression of MMP9. Most of the SNPs are still uncharacterized thereby present study provides a direction that can help to validate the relation between the altered expressions and functions of MMP9 protein in terms of disease susceptibility.