Helical Alignment Research Articles

A molecular synergy of non-covalent interactions facilitated via theobromine modifying the self-assembly process of type I collagen

Type I Collagen is a multifunctional fibrous protein present significantly in the connective tissues. Generally, fibril formation process of an interstitial collagen begins with a triple helix alignment to form a pentafibril, which sequentially self-assembles into a microfibril. Typically, this sequential formation can be achieved under an in vitro condition as well by maintaining certain specific physiological parameters to mimic the interstitial microenvironment of collagen. The necessity to study such a kinetically driven process is due to its implications in template fabrication particularly as a scaffold to enhance the growth of specific stem cells or accelerating nanoparticle synthesis. Drawing inspiration from this, theobromine, a methylxanthine that contributes towards the hydrogen bond network via dimerization and stacking interaction was used as a small molecule in modifying the molecular level interactions of a self-assembled collagen. Initially, rheological studies revealed certain variations in the viscous properties of collagen on addition of theobromine. Turbidity assay showed an increase in the rate of fibril formation and its topographical changes were observed through the high-resolution scanning electron microscope. The stability and probable physico-chemical interactions between collagen and theobromine were comprehended from the vibrational frequency changes recorded using (FT-IR) (ATR) and conformational changes using Circular Dichroism (CD) studies. Our results show possible multibinding sites on theobromine, which would compete to bind with the polar and non-polar residues exposed over the monomeric surfaces of triple helix causing a local conformational fluctuation modifying protein-protein interaction.

The Nanoscale Ordering of Cellulose in a Hierarchically Structured Hybrid Material Revealed Using Scanning Electron Diffraction.

Cellulose, being a renewable and abundant biopolymer, has garnered significant attention for its unique properties and potential applications in hybrid materials. Understanding the hierarchical arrangement of cellulose nanofibers is crucial for developing cellulose-based materials with enhanced mechanical properties. In this study, the use of Scanning Electron Diffraction (SED) is presented to map the nanoscale orientation of cellulose fibers in a bio-composite material with a preserved wood cell structure. The SED data provides detailed insights into the ordering of cellulose with an extraordinary resolution of ≈15nm. It enables a quantitative analysis of the fiber orientation over regions as large as entire cells. A highly organized arrangement of cellulose fibers within the secondary cell wall is observed, with a gradient of orientations toward the outer part of the wall. The in-plane fiber rotation is quantified, revealing a uniform orientation close to the middle lamella. Transversely sectioned material exhibits similar trends, suggesting a layered cell wall structure. Based on the SED data, a 3D model depicting the complex helical alignment of fibers throughout the cell wall is constructed. This study demonstrates the unique opportunities SED provides for characterizing the nanoscale hierarchical arrangement of cellulose nanofibers, empowering further research on a range of hybrid materials.

Formation of helical spin alignment in the AFM/FM/AFM trilayers by spin–orbit torque controlled exchange bias

Non-collinear spin structures can exhibit unusual magnetic properties that cannot be expected in an ordinary collinear ferromagnet (FM) due to the chiral alignment of magnetic moments, offering new opportunities for applications in the field of spintronics. In the present study, we demonstrate that exchange bias pinning can be applied to a single FM layer in two different directions simultaneously, resulting in modified magnetic behaviors due to the formation of non-collinear helical spin structures in the multilayers of Co0.7Ni0.3O (antiferromagnet, AFM)/Co0.7Ni0.3 (FM)/Co0.7Ni0.3O (AFM)/Pt (heavy metal, HM). The pinning of spins at one interface between FM and AFM/HM was controlled by spin Hall current originating from the electrical current through the HM layer at room temperature, while the spins at the other interface between FM and AFM were pinned in a fixed direction, hence allowing for the formation of a helical spin structure along the FM layer thickness with controllable chirality at room temperature. Modified magnetic behaviors of a helical spin structure were confirmed from measurements of magnetic hysteresis and magnetoresistance, as well as direct observation of magnetic domains.

Structural, functional and mechanistic insights uncover the role of starch in foxtail millet cultivars with different congee-making quality

Ten foxtail millet cultivars with different congee-making quality were investigated for relationships between starch structures, functional properties and congee-making qualities. Swelling power, pasting peak viscosity (PV) and setback (SB), gel hardness and resilience, and gelatinization onset (To), peak (Tp) and range (R) temperature were correlated with congee-making performance significantly. Good eating-quality cultivars with these parameters were in the range of 15.41–18.58 %, 3095–3279 cp, 1540–1745 cp, 430–491 g, 0.47–0.57, 64.43–65.28 °C, 69.97–70.32 °C and 23.38–24.52 °C, respectively. Correlation analysis showed that amylose, amylopectin B2 chains and A21 were essential parameters controlling the functional properties. Amylose molecules with linear molecular morphology would cause crystal defects and a wide range of molecular weight distribution. Additionally, they were more prone to re-association, which influenced the PV, SB, To, Tp and gel hardness. B2 chains impacted the gelatinization temperature range (R), gel resilience and swelling behavior by affecting the alignment of double helices and the size of starch particles and pores. Starch with more binding sites of bound water (A21) tended to leach from the swelling granules easily and contributed to higher values of PV. The content of amylose, B2 chains and A21 of good eating-quality cultivars were 16.19–18.46 %, 11.60–11.69 % and 96.50–97.02 %, respectively.

Massive, soft, and tunable chiral photonic crystals for optical polarization manipulation and pulse modulation

Photonic crystals enable modulation of light waves in space, time, and frequency domains; in particular, chiral photonic crystals are uniquely suitable for polarization rotation and switching of complex vector fields. Current development of chiral photonic crystals, nevertheless, are still confronted with limitations of one form or the other such as large optical losses, limited or absence of tunability, narrow operation bandwidth, and/or insufficient optical thickness for practical implementation. In this work, we show that cholesteric liquid crystals as 1D tunable chiral photonic crystals are promising alternatives to not only address all these issues and deficiencies but also enable new photonic applications in wider temporal and spectral realms. Our work entails a detailed study of the dynamical evolution of cholesteric helical self-assembly and defect formation in the bulk of thick cholesteric liquid crystals under various applied electric field conditions and a thorough exploration of how applying fields of vastly different frequencies can eliminate and/or prevent the formation of unremovable defects and to control the alignment of cholesteric helices in the entire bulk. We have developed a dual-frequency field assembly technique that enables robust room-temperature fabrication of stable well-aligned cholesteric liquid crystals to unprecedented thickness (containing thousands of grating periods) demanded by many photonic applications. The resulting chiral photonic crystals exhibit useful much-sought-after capabilities impossible with other existing or developing chiral photonic crystals—compactness (single, flat, millimeter-thick optical element), high transmission, dynamic tunability, large polarization rotation, and various switching/modulation possibilities for ultrafast and continuous-wave lasers in the visible, near- and mid-infrared regimes.

Hierarchical nano-helix as a new reinforcing unit for simultaneously ultra-strong and super-tough alginate fibers

Fabricating alginate fibers of high strength and toughness remains a great challenge because of the difficulty in improving both strength and toughness simultaneously. Herein, this work reported the hierarchical assembly of sodium alginate nano-helix and its potential application as a new reinforcing unit for alginate fibers. Contributed from the hierarchical structures of α-helix, β-sheet and tertiary helical alignment of nanofibrils, nano-helix improved the tensile strength of fibers with enhanced modulus, and prolonged elongation through unravelling the tertiary structures. Thus, the strength, elongation and toughness of alginate fibers were all enhanced by >200 %, solving the tradeoff of strength and toughness. The mechanical performance of nano-helix engineered alginate fibers is superior to present alginate fibers and even some other biomass-based fibers. The assembly of nano-helix provides a feasible reinforcing strategy for polysaccharide based materials, achieving simultaneous improvement of strength and toughness.

Liquid-crystalline ordering in bacterial cellulose produced by Gluconacetobaсter hansenii on glucose-containing media

This research is dedicated to the studies of the microscale morphology of bacterial cellulose (BC) obtained by means of static cultivation of Gluconacetobacter hansenii GH-1/2008. We found that the microscale morphology depended on the BC production rate that was varied by using different glucose concentrations in the cultivation medium. It was revealed that at higher production rates, BC fibrils were aligned in a liquid-crystalline-like (LC-like) order. The observed helical alignment was always left-handed. The half-periods of the helix varied from 50 μm to 150 μm depending on the cultivation conditions. The mechanical and water absorption properties of the obtained BC pellicles were measured. The former correlated mainly with the density of the samples; the latter were the best for films with layered structure, where the BC had segregated into fleece sheets separated by gaps with low density of fibrils.

Biophysical studies on latarcins: antimicrobial peptides from spider venom

The ant spider Lachesena tarabaevi produces one of the most potent venom that is largely composed of membrane active peptides. A group of seven linear antimicrobial peptides isolated from the venom of this spider which belong to the latarcin family are reported to be cytolytic and highly membrane active[1]. However, there is no single study where the secondary structure, membrane alignment of all peptides have been systematically addressed. Here, using circular dichroism(CD) spectroscopy, oriented CD, solid-state 15N-NMR and fluorescence spectroscopy, we have characterized the secondary structure and helix alignment of all seven peptides in their membrane-bound state [2].

Helically aligned fused carbon hollow nanospheres with chiral discrimination ability.

While the functions of carbon materials with precisely controlled nanostructures have been reported in many studies, their chiral discriminating abilities have not been reported yet. Herein, chiral discrimination is achieved using helical carbon materials devoid of chiral attachments. A Fe3O4 nanoparticle template with ethyl cellulose (carbon source) is self-assembled on dispersed multiwalled carbon nanotubes (MWCNTs) fixed in a lamellar structure, with helical nanoparticle alignment induced by the addition of a binaphthyl derivative. Carbonization followed by template removal produces helically aligned fused carbon hollow nanospheres (CHNSs) with no chiral molecules left. Helicity is confirmed using vacuum-ultraviolet circular dichroism spectroscopy. Chiral discrimination, as revealed by the electrochemical reactions of binaphthol and a chiral ferrocene derivative in aqueous and nonaqueous electrolytes, respectively, is attributable to the chiral space formed between the CHNS and MWCNT surfaces.

Membrane Interactions of Latarcins: Antimicrobial Peptides from Spider Venom.

A group of seven peptides from spider venom with diverse sequences constitute the latarcin family. They have been described as membrane-active antibiotics, but their lipid interactions have not yet been addressed. Using circular dichroism and solid-state 15N-NMR, we systematically characterized and compared the conformation and helix alignment of all seven peptides in their membrane-bound state. These structural results could be correlated with activity assays (antimicrobial, hemolysis, fluorescence vesicle leakage). Functional synergy was not observed amongst any of the latarcins. In the presence of lipids, all peptides fold into amphiphilic α-helices as expected, the helices being either surface-bound or tilted in the bilayer. The most tilted peptide, Ltc2a, possesses a novel kind of amphiphilic profile with a coiled-coil-like hydrophobic strip and is the most aggressive of all. It indiscriminately permeabilizes natural membranes (antimicrobial, hemolysis) as well as artificial lipid bilayers through the segregation of anionic lipids and possibly enhanced motional averaging. Ltc1, Ltc3a, Ltc4a, and Ltc5a are efficient and selective in killing bacteria but without causing significant bilayer disturbance. They act rather slowly or may even translocate towards intracellular targets, suggesting more subtle lipid interactions. Ltc6a and Ltc7, finally, do not show much antimicrobial action but can nonetheless perturb model bilayers.

Microstructural heterogeneity of the collagenous network in the loaded and unloaded periodontal ligament and its biomechanical implications

The periodontal ligament (PDL) is a highly heterogeneous fibrous connective tissue and plays a critical role in distributing occlusal forces and regulating tissue remodeling. Its mechanical properties are largely determined by the extracellular matrix, comprising a collagenous fiber network interacting with the capillary system as well as interstitial fluid containing proteoglycans. While the phase-contrast micro-CT technique has portrayed the 3D microscopic heterogeneity of PDL, the topological parameters of its network, which is crucial to understanding the multiscale constitutive behavior of this tissue, has not been characterized quantitatively. This study aimed to provide new understanding of such microscopic heterogeneity of the PDL with quantifications at both tissue and collagen network levels in a spatial manner, by combining phase-contrast micro-CT imaging and a purpose-built image processing algorithm for fiber analysis. Both variations within a PDL and among the PDL with different shapes, i.e. round-shaped and kidney-shaped PDLs, are described in terms of tissue thickness, fiber distribution, local fiber densities, and fiber orientation (namely azimuthal and elevation angles). Furthermore, the tissue and collagen fiber network responses to mechanical loading were evaluated in a similar manner. A 3D helical alignment pattern was observed in the fiber network, which appears to regulate and adapt a screw-like tooth motion under occlusion. The microstructural heterogeneity quantified here allows development of sample-specific constitutive models to characterize the PDL’s functional and pathological loading responses, thereby providing a new multiscale framework for advancing our knowledge of this complex limited mobility soft-hard tissue interface.

A 3D supramolecular framework assembled via π⋅⋅⋅π interactions and CH⋅⋅⋅Cl hydrogen-bonds with second-harmonic generation response

A three-dimensional (3D) supramolecular framework [CuII2Cl3(tpen)]2⋅[CuIICl4] (1) (tpen = N,N,N',N'-tetra(2-pyridylmethyl) ethylenediamine) assembled from [CuII2Cl3(tpen)]+ and [CuIICl4]2– via π⋅⋅⋅π interactions and CH⋅⋅⋅Cl hydrogen-bonds has been obtained by solvothermal synthesis. The π-stacked supramolecular layers of the [CuII2Cl3(tpen)]+ ions are connected by the [CuIICl4]2– anions in a distorted tetrahedral geometry to form a 3D architecture via CH⋅⋅⋅Cl hydrogen-bonds. Due to the helical alignment of the [CuII2Cl3(tpen)]+ and the oriented [CuIICl4]2–, compound 1 crystallizes in the tetragonal non-centrosymmetric (NCS) space group P–421/c. The compound shows a moderate band-gap of 2.48 eV and a UV cutoff edge of 420 nm. For the NCS structure of compound 1, a phase-matchable second harmonic generation (SHG) response of ~0.009 times that of KH2PO4 (KDP) was observed.

A supertetrahedral T2 [Mn4Ce6] cluster showing second-harmonic generation response

The self-assembly reaction of MnCl2·4H2O, Ce(acac)3·xH2O (acac = deprotonated acetylacetone), and acenaphthenequinone dioxime (acndH2) in a mixture of methanol and dimethyl formamide (DMF) has led to a [MnIII4CeIV6] cluster MnIII4CeIV6(μ-O)8(acnd)4(OAc)4(acac)4(CH3O)4(DMF)4 (1) with a supertehedral T2 metal topology. Owing to the helical alignment of the supertetrahedral clusters, compound 1 shows a weak second-harmonic generation (SHG) response. Magnetic studies reveal very weak antiferromagnetic couplings between the paramagnetic MnIII ions.

Vibrational circular dichroism studies of exceptionally strong chirality inducers in liquid crystals.

7,7'-Disubstituted 2,2'-methylenedioxy-1,1'-binaphthyls are highly efficient chirality inducers in nematic liquid crystals. The absolute configuration of these compounds is, however, hard to determine as they only crystallize as racemic mixtures. In this work a Vibrational Circular Dichroism (VCD) study is reported that provides an unambiguous determination of the absolute configuration of these compounds. An in-depth General Coupled Oscillator (GCO) analysis of the source of the VCD signal reveals that the unusual structure of these binaphthyl compounds inherently leads to strong and robust VCD bands. Combined with linear transit calculations, our VCD studies allow for the determination of key structural parameters.

Stereochemical Relay through a Cationic Intermediate: Helical Preorganization Dictates Direction of Conrotation in the halo-Nazarov Cyclization.

A stereocontrolled halo-Prins/halo-Nazarov cyclization protocol is reported, where chiral information from a secondary alcohol is relayed through several intermediates yielding halocyclopentene products diastereoselectively. An enantiopure product is obtained when a nonracemic secondary alcohol is used. Experimental and computational studies are described, enabling the design and synthesis of systems that ionize and cyclize with >95% chirality transfer through a mechanism involving the creation and preservation of transient helical chirality in a pentadienyl cation intermediate. First, a diastereoselective alkynyl Prins cyclization is executed to synthesize a conformationally distorted dihydropyran intermediate with a curved backbone and high reactivity. This chiral precursor adopts a specific helical alignment early in the subsequent cationic ionization/halo-Nazarov cyclization process, dictating the direction of conrotation in the electrocyclization. Notably, despite the ablation of an sp3 stereogenic center during ionization, the low halo-Nazarov barrier enables efficient capture of a cationic intermediate with dynamic conformational chirality. The ionization and electrocyclization thus occur with "memory of chirality".

Helical Pore Alignment on Cylindrical Carbon.

Interest in chiral substances has mainly focused on the substances themselves, but not on the accompanying space, especially regarding the pore alignment. As a method to form both the chiral substance and the accompanying space, cylindrical self-assembly of uniform polystyrene nanoparticles with fructose is carried out in the presence of both carbon and sodium alginate, which is followed by heat treatment in an inert atmosphere. The carbonization generates fructose-derived honeycomb-like carbon walls with helically aligned nanopores left after the polystyrene decomposition. The diffuse reflectance circular dichroism measurements give peaks with opposite signs for the d- and l-fructose-derived cylindrical carbons. Circularly polarized light sensitivity in transient photoconductivity is confirmed apparently in the carbon-based helical structures. This sensitivity as well as straightforward formation of composites with another component to give helicity shows potential applications of the helically aligned pores.

Assembly of carbon nanodots in graphene-based composite for flexible electro-thermal heater with ultrahigh efficiency

A high-efficiency electro-thermal heater requires simultaneously high electrical and thermal conductivities to generate and dissipate Joule heat efficiently. A low input voltage is essential to ensure the heater’s safe applications. However, the low voltage generally leads to low saturated temperature and heating rate and hence a low thermal efficiency. How to reduce the input voltage while maintaining a high electro-thermal efficiency is still a challenge. Herein, a highly electrical and thermal conductive film was constructed using a graphene-based composite which has an internal three-dimensional (3D) conductive network. In the 3D framework, cellulose nanocrystalline (CNC) phase with chiral liquid crystal manner presents in the form of aligned helix between the graphene oxide (GO) layers. Carbon nanodots (CDs) are assembled inside the composite as conductive nanofillers. Subsequent annealing and compression results in the formation of the assembled GO-CNC-CDs film. The carbonized CNC nanorods (CNR) with the helical alignment act as in-plane and through-plane connections of neighboring reduced GO (rGO) nanosheets, forming a conductive network in the composite film. The CDs with ultrafast electrons transfer rates provide additional electrons and phonons transport paths for the composite. As a result, the obtained graphene-based composite film (rGO-CNR-CDs) exhibited a high thermal conductivity of 1,978.6 W·m−1·K−1 and electrical conductivity of 2,053.4 S·cm−1, respectively. The composite film showed an outstanding electro-thermal heating efficiency with the saturated temperature of 315 °C and maximum heating rate of 44.9 °C·s−1 at a very low input voltage of 10 V. The freestanding graphene composite film with the delicate nanostructure design has a great potential to be integrated into electro-thermal devices.

Supramolecular structure and pasting/digestion behaviors of rice starches following concurrent microwave and heat moisture treatment

From a supramolecular structure viewpoint, we concern how concurrent microwave and heat moisture treatment (M/HMT) tailors the pasting and digestion features of indica rice starch (IRS) and waxy rice starch (WRS), using combined analytical methods such as scanning electron microscopy and small-angle X-ray scattering. The results confirm that, for the starches (especially IRS), M/HMT led to a concave granule surface, weakened alignment of helices in lamellae, loosened packing of chains in amorphous regions, and somewhat disrupted crystallites. Consequently, the susceptibility of starch structures to hydrothermal effects was insignificantly altered, as reflected by unchanged pasting temperature; the enzyme absorption/hydrolysis could be properly accelerated, as affirmed by a modestly increased digestion rate and slightly reduced enzymatic resistance. Also, compared to WRS, IRS had more amylose with relatively long branches, which probably contributed to starch chain interactions during M/HMT. This tended to reduce the paste viscosity related to the swelling degree of starch granules, and increase the paste stabilities during heating and cooling related to the robustness of swelled granules and the reorganization of glucan chains.

Electro-Thermal Formation of Uniform Lying Helix Alignment in a Cholesteric Liquid Crystal Cell

We demonstrated previously that the temperature of a sandwich-type liquid crystal cell with unignorable electrode resistivity could be electrically increased as a result of dielectric heating. In this study, we take advantage of such an electro-thermal effect and report on a unique electric-field approach to the formation of uniform lying helix (ULH) texture in a cholesteric liquid crystal (CLC) cell. The technique entails a hybrid voltage pulse at frequencies f1 and, subsequently, f2, which are higher and lower than the onset frequency for the induction of dielectric heating, respectively. When the cell is electrically sustained in the isotropic phase by the voltage pulse of V = 35 Vrms at f1 = 55 kHz or in the homeotropic state with the enhanced ionic effect at V = 30 Vrms and f1 = 55 kHz, our results indicate that switching of the voltage frequency from f1 to f2 enables the succeeding formation of well-aligned ULH during either the isotropic-to-CLC phase transition at f2 = 1 kHz or by the electrohydrodynamic effect at f2 = 30 Hz. For practical use, the aligning technique proposed for the first time in this study is more applicable than existing alternatives in that the obtained ULH is adoptable to CLCs with positive dielectric anisotropy in a simple cell geometry where complicated surface pretreatment is not required. Moreover, it is electrically switchable to other CLC textures such as Grandjean planar and focal conic states without the need of a temperature controller for the phase transition, the use of ion-rich LC materials, or mechanical shearing for textural transition.

External Field Assisted Freeze Casting

Freeze casting under external fields (magnetic, electric, or acoustic) produces porous materials having local, regional, and global microstructural order in specific directions. In freeze casting, porosity is typically formed by the directional solidification of a liquid colloidal suspension. Adding external fields to the process allows for structured nucleation of ice and manipulation of particles during solidification. External control over the distribution of particles is governed by a competition of forces between constitutional supercooling and electromagnetism or acoustic radiation. Here, we review studies that apply external fields to create porous ceramics with different microstructural patterns, gradients, and anisotropic alignments. The resulting materials possess distinct gradient, core–shell, ring, helical, or long-range alignment and enhanced anisotropic mechanical properties.