Spontaneous chiral symmetry breaking in polar fluid-heliconical ferroelectric nematic phase.

Spontaneous mirror symmetry breaking by formation of chiral structures from achiral building blocks and emergent polar order are phenomena rarely observed in fluids. Separately, they have both been found in certain nematic liquid crystalline phases; however, they have never been observed simultaneously. Here, we report a heliconical arrangement of achiral molecules in the ferroelectric nematic phase. The phase is thus spontaneously both polar and chiral. Notably, the pitch of the heliconical structure is comparable to the wavelength of visible light, giving selective reflection controllable by temperature or application of a weak electric field. Despite bearing resemblance to the heliconical twist-bend nematic phase, this chiral ferroelectric nematic phase arises from electrical interactions that induce a noncollinear orientation of electric dipoles.

Description of Naviculavanseea sp. nov. (Naviculales, Naviculaceae), a new species of diatom from the highly alkaline Lake Van (Republic of Türkiye) with complete characterisation of its organellar genomes and multigene phylogeny.

The current article describes Naviculavanseeasp. nov., a new species of diatom from Lake Van, a highly alkaline lake in Eastern Anatolia (Türkiye). The description is based on light and scanning electron microscopy performed on two monoclonal cultures. The complete nuclear rRNA clusters and plastid genomes have been sequenced for these two strains and the complete mitogenome for one of them. The plastome of both strains shows the probable loss of a functional ycf35 gene. They also exhibit two IB4 group I introns in their rrl, each encoding for a putative LAGLIDADG homing endonuclease, with the first L1917 IB4 intron reported amongst diatoms. The Maximum Likelihood phylogeny inferred from a concatenated alignment of 18S, rbcL and psbC distinguishes N.vanseea sp. nov. from the morphologically similar species Naviculacincta and Naviculamicrodigitoradiata.

Liquid Crystal Dimers and the Twist-Bend Phases: Non-Symmetric Dimers Consisting of Mesogenic Units of Differing Lengths.

The syntheses and characterisation of the 4-[{[4-({n-[4-(4-cyanophenyl)phenyl]-n-yl}oxy)phenyl]-methylidene}amino]phenyl-4-alkoxybenzoates (CBnOIBeOm) are reported with n=8 and 10 and m=1-10. The two series display fascinating liquid crystal polymorphism. All twenty reported homologues display an enantiotropic nematic (N) phase at high temperature. When the length of the spacer (n) is greater than that of the terminal chain (m), the twist-bend nematic (NTB) phase is observed at temperatures below the N phase. As the length of the terminal chain is increased and extends beyond the length of the spacer up to three smectic phases are observed on cooling the N phase. One of these smectic phases has been assigned as the rare twist-bend smectic C subphase, the SmCTB-α phase. In all the smectic phases, a monolayer packing arrangement is seen, and this is attributed to the anti-parallel associations of the like mesogenic units.

To Be or Not To Be Polar: The Ferroelectric and Antiferroelectric Nematic Phases.

We report two new series of compounds that show the ferroelectric nematic, NF, phase in which the terminal chain length is varied. The longer the terminal chain, the weaker the dipole-dipole interactions of the molecules are along the director and thus the lower the temperature at which the axially polar NF phase is formed. For homologues of intermediate chain lengths, between the non-polar and ferroelectric nematic phases, a wide temperature range nematic phase emerges with antiferroelectric character. The size of the antiparallel ferroelectric domains critically increases upon transition to the NF phase. In dielectric studies, both collective ("ferroelectric") and non-collective fluctuations are present, and the "ferroelectric" mode softens weakly at the N-NX phase transition because the polar order in this phase is weak. The transition to the NF phase is characterized by a much stronger lowering of the mode relaxation frequency and an increase in its strength, and a typical critical behavior is observed.

Ferroelectric Nematic-Isotropic Liquid Critical End Point.

A critical end point above which an isotropic phase continuously evolves into a polar (ferroelectric) nematic phase with an increasing electric field is found in a ferroelectric nematic liquid crystalline material. The critical end point is approximately 30 K above the zero-field transition temperature from the isotropic to nematic phase and at an electric field of the order of 10 V/µm. Such systems are interesting from the application point of view because a strong birefringence can be induced in a broad temperature range in an optically isotropic phase.

Light-Responsive Supramolecular Nanotubes-Based Chiral Plasmonic Assemblies.

We describe the fabrication of dual-responsive (thermo/light) chiral plasmonic films. The idea is based on using photoswitchable achiral liquid crystal (LCs) forming chiral nanotubes for templating helical assemblies of Au NPs. Circular dichroism spectroscopy (CD) confirms chiroptical properties coming from the arrangement of organic and inorganic components, with up to 0.2 dissymmetry factor (g-factor). Upon exposure to UV light, organic molecules isomerize, resulting in controlled melting of organic nanotubes and/or inorganic nanohelices. The process can be reversed using visible light and further modified by varying the temperature, offering a control of chiroptical response of the composite material. These properties can play a key role in the future development of chiral plasmonics, metamaterials, and optoelectronic devices.

Intrinsically Chiral Twist-Bend Nematogens: Interplay of Molecular and Structural Chirality in the NTB Phase.

The front cover artwork is provided by Dr Rebecca Walker of the Liquid Crystals Group at the University of Aberdeen. The image is a cartoon depiction of the formation of the heliconical chiral twist-bend nematic phase (N*TB ) from its constituent bent molecules. The presence of a single enantiomer of the chiral, lactate-based liquid crystal dimers biases the formation of helices with only one handedness, unlike in the conventional NTB phase, observed for achiral molecules, for which the left- and right-handed helices are doubly degenerate. Read the full text of the Research Article at 10.1002/cphc.202200807.

Molecular Shape, Electronic Factors, and the Ferroelectric Nematic Phase: Investigating the Impact of Structural Modifications.

The synthesis and characterisation of two series of low molar mass mesogens, the (4-nitrophenyl) 2-alkoxy-4-(4-methoxybenzoyl)oxybenzoates (NT3.m) and the (3-fluoro-4-nitrophenyl) 2-alkoxy-4-(4-methoxybenzoyl)oxybenzoates (NT3F.m), are reported in order to investigate the effect of changing the position of a lateral alkoxy chain from the methoxy-substituted terminal ring to the central phenyl ring in these two series of materials based on RM734. All members of the NT3.m series exhibited a conventional nematic phase, N, which preceded the ferroelectric nematic phase, NF , whereas all the members of the NT3F.m series exhibited direct NF -I transitions except for NT3F.1 which also exhibited an N phase. These materials cannot be described as wedge-shaped, yet their values of the ferroelectric nematic-nematic transition temperature, T N F N ${{_{{\rm N}{_{{\rm F}}}{\rm N}}}}$ , exceed those of the corresponding materials with the lateral alkoxy chain located on the methoxy-substituted terminal ring. In part, this may be attributed to the effect that changing the position of the lateral alkoxy chain has on the electronic properties of these materials, specifically on the electron density associated with the methoxy-substituted terminal aromatic ring. The value of TNI decreased with the addition of a fluorine atom ortho to the nitro group in NT3F.1, however, the opposite behaviour was found when the transition temperatures of the NF phase were compared which are higher for the NT3F.m series. This may reflect a change in the polarity and polarizability of the NT3F.m series compared to the NT3.m series. Therefore, it is suggested that, rather than simply promoting a tapered shape, the role of the lateral chain in inhibiting anti-parallel associations and its effect on the electronic properties of the molecules are the key factors in driving the formation of the NF phase.

Intrinsically Chiral Twist-Bend Nematogens: Interplay of Molecular and Structural Chirality in the NTB Phase.

Non-symmetric lactate-based chiral liquid crystal dimers containing an odd-membered spacer are shown to exhibit a chiral twist-bend nematic phase which is stable on cooling to room temperature. A comparison of racemic and optically pure materials reveals that the pitch length in the N*TB phase is not influenced by molecular chirality, whereas the nematic-twist-bend nematic transition temperature is increased.

Unmasking the structure of a chiral cubic thermotropic liquid crystal phase by a combination of soft and tender resonant X-ray scattering.

A resonant X-ray scattering response for two structural models of a chiral cubic phase with a giant unit cell, one composed of a continuous grid and micelles and the other with three continuous grids, is studied theoretically and compared to experimental measurements. For both structural models resonant enhancement of all the symmetry-allowed diffraction peaks is predicted, as well as the existance of several symmetry forbidden peaks (pure resonant peaks). Experimental measurements were performed at the carbon and sulphur absorption edge. Only one pure resonant peak was observed, which is predicted by both models. Two low-angle symmetry allowed peaks, not observed in non-resonant scattering, were resonantly enhanced and their intensity angular dependence can distinguish between the two structural models.

New patterns of twist-bend liquid crystal phase behaviour: the synthesis and characterisation of the 1-(4-cyanobiphenyl-4'-yl)-10-(4-alkylaniline-benzylidene-4'-oxy)decanes (CB10O·m).

The synthesis and characterisation of the 1-(4-cyanobiphenyl-4'-yl)-10-(4-alkylanilinebenzylidene-4'-oxy)decanes (CB10O·m) are reported. This series shows a rich liquid crystal polymorphism including twist-bend nematic and smectic phases. All the homologues reported exhibit an enantiotropic conventional nematic phase. For the homologues with m ≤ 10, the local packing in the nematic phases and the layer spacing in the smectic phases indicates an intercalated arrangement of the molecules. An intercalated smectic CA phase is observed if m/11 ≈ 0.5. Either side of this condition, the twist-bend nematic phase is observed, a novel pattern of behaviour for a series on increasing a terminal chain length. For longer chain lengths, m = 12, 14, 16 and 18, two twist-bend smectic C (SmCTB) phases are observed, and the packing of the molecules is now of a bilayer-type. The higher temperature variant is termed SmCTB-SH in which SH (single helix) refers to the presence of a short, distorted clock-type helix. In the lower temperature SmCTB-DH phase, an additional longer helix is superimposed on the short one, and DH denotes double helix.

Tuneable helices of plasmonic nanoparticles using liquid crystal templates: molecular dynamics investigation of an unusual odd-even effect in liquid crystalline dimers.

Liquid crystalline (LC) dimers formed helical nanofilaments depending on the parity of the alkyl linker, revealing an unusual odd-even effect. Molecular dynamics simulations were used to investigate the observed tendency. Elongation of the linker translates to an increase of the pitch of the helices, which allows achieving tuneable helical assemblies of Au nanoparticles doped to the LC matrix. The impact of the tuneable pitch of helices on the chiral optical properties of composites was investigated with full-wave simulations based on the T-matrix method.

Chiral columns forming a lattice with a giant unit cell.

Mesogenic materials, quinoxaline derivatives with semi-flexible cores, are reported to form a new type of 3D columnar phase with a large crystallographic unit cell and Fddd lattice below the columnar hexagonal phase. The 3D columnar structure is a result of frustration imposed by the arrangement of helical columns of opposite chiralities into a triangular lattice. The studied materials exhibit fluorescence properties that could be easily tuned by modification of the molecular structure; for compounds with the extended π electron conjugated systems the fluorescence is quenched. For molecules with a flexible structure the fluorescence quantum yield reaches 25%. On the other hand, compounds with a more rigid mesogenic core, for which the fluorescence is suppressed, show effective photogeneration of charge carriers. For some materials bi-polar hole and electron transport was observed.

Light-Driven Fabrication of a Chiral Photonic Lattice of the Helical Nanofilament Liquid Crystal Phase.

A photonic lattice is an efficient platform for optically exploring quantum phenomena. However, its fabrication requires high costs and complex procedures when conventional materials, such as silicon or metals, are used. Here, we demonstrate a simple and cost-effective fabrication method for a reconfigurable chiral photonic lattice of the helical nanofilament (HNF) liquid crystal (LC) phase and diffraction grating showing wavelength-dependent diffraction with a rotated polarization state. Furthermore, the UV-exposed areas of the HNF film having chiral characteristics act as optical building blocks that induce resonant intensity modulation in the reflectance and transmittance modes and the optical rotation of the linear polarization. Our photonic lattice of the HNF can be an efficient platform for a chirality-embedded photonic lattice at a low cost.

Nitzschia anatoliensis sp. nov., a cryptic diatom species from the highly alkaline Van Lake (Turkey).

In this article we describe Nitzschia anatoliensis Górecka, Gastineau & Solak sp. nov., an example of a diatom species inhabiting extreme habitats. The new species has been isolated and successfully grown from the highly alkaline Van Lake in East Turkey. The description is based on morphology (light and scanning electron microscopy), the sequencing of its organellar genomes and several molecular phylogenies. This species could easily be overlooked because of its extreme similarity to Nitzschia aurariae but molecular phylogenies indicate that they are only distantly related. Furthermore, molecular data suggest that N. anatoliensis may occur in several alkaline lakes of Asia Minor and Siberia, but was previously misidentified as Nitzschia communis. It also revealed the very close genetic proximity between N. anatoliensis and the endosymbiont of the dinotom Kryptoperidinium foliaceum, providing additional clues on what might have been the original species of diatoms to enter symbiosis.

Mitochondrial and Plastid Genomes of the Monoraphid Diatom Schizostauron trachyderma.

We provide for the first time the complete plastid and mitochondrial genomes of a monoraphid diatom: Schizostauron trachyderma. The mitogenome is 41,957 bp in size and displays two group II introns in the cox1 gene. The 187,029 bp plastid genome features the typical quadripartite architecture of diatom genomes. It contains a group II intron in the petB gene that overlaps the large single-copy and the inverted repeat region. There is also a group IB4 intron encoding a putative LAGLIDADG homing endonuclease in the rnl gene. The multigene phylogenies conducted provide more evidence of the proximity between S. trachyderma and fistula-bearing species of biraphid diatoms.

Multiple Polar and Non-polar Nematic Phases.

Liquid-crystal materials exhibiting up to three nematic phases are reported. Dielectric response measurements show that while the lower temperature nematic phase has ferroelectric order and the highest temperature nematic phase is apolar, the intermediate phase has local antiferroelectric order. The modification of the molecular structure by increasing the number of lateral fluorine substituents leads to one of the materials showing a direct isotropic-ferronematic phase transition.

Photonic Bandgap in Achiral Liquid Crystals-A Twist on a Twist.

Achiral mesogenic molecules are shown to be able to spontaneously assemble into liquid crystalline smectic phases having either simple or double-helical structures. At the transition between these phases, the double-helical structure unwinds. As a consequence, in some temperature range, the pitch of the helix becomes comparable to the wavelength of visible light and the selective reflection of light in the visible range is observed. The photonic bandgap phenomenon is reported for achiral liquid crystals.

Multigene phylogenetic data place monoraphid diatoms Schizostauron and Astartiella along with other fistula-bearing genera in the Stauroneidaceae1.

Presented here are new insights into the marine monoraphid diatom genera Schizostauron and Astartiella, based on molecular and morphological data, including descriptions of new species. Although no unambiguous morphological synapomorphies between the two genera are currently recognized, they are closely related by DNA sequence data. Heterovalvate frustules of Schizostauron are characterized by a bifid stauros on the raphe-bearing valve and intricate areolate occlusions on the sternum valve. In Astartiella, the raphe-bearing valve is characterized by a process resembling a fistula by morphology, while the sternum valve presents a particular striation pattern. Observations by light and electron microscopy were made, along with a molecular phylogenetic analysis using a three-gene (SSU, rbcL, and psbC) concatenated dataset. Three new Schizostauron species are described (S. kajotkei, S. rawaii, S. papilliareae), and two new combinations proposed (S. citronella and S. trachyderma) for species that were previously included either in Achnanthes and Cocconeis, respectively. Likewise, six new species of Astartiella (A. almalikii, A. bornmanii, A. chunlianlii, A. marksii, A. persica, and A. wangii) are described. Molecular results exclude Schizostauron and Astartiella from three clades of exclusively monoraphid diatoms, the Achnanthaceae, Cocconeidaceae, and Achnanthidiaceae, instead placing them in the Stauroneidaceae. Morphological features of Schizostauron and Astartiella, such as the stauros, fistula, and coaxial internal proximal raphe endings, are found in other genera in this clade, whereas the only common feature with monoraphid diatoms as whole group is the heterovalvy of frustules.

Understanding and Controlling the Crystallization Process in Reconfigurable Plasmonic Superlattices.

The crystallization of nanomaterials is a primary source of solid-state, photonic structures. Thus, a detailed understanding of this process is of paramount importance for the successful application of photonic nanomaterials in emerging optoelectronic technologies. While colloidal crystallization has been thoroughly studied, for example, with advanced in situ electron microscopy methods, the noncolloidal crystallization (freezing) of nanoparticles (NPs) remains so far unexplored. To fill this gap, in this work, we present proof-of-principle experiments decoding a crystallization of reconfigurable assemblies of NPs at a solid state. The chosen material corresponds to an excellent testing bed, as it enables both in situ and ex situ investigation using X-ray diffraction (XRD), transmission electron microscopy (TEM), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), atomic force microscopy (AFM), and optical spectroscopy in visible and ultraviolet range (UV-vis) techniques. In particular, ensemble measurements with small-angle XRD highlighted the dependence of the correlation length in the NPs assemblies on the number of heating/cooling cycles and the rate of cooling. Ex situ TEM imaging further supported these results by revealing a dependence of domain size and structure on the sample preparation route and by showing we can control the domain size over 2 orders of magnitude. The application of HAADF-STEM tomography, combined with in situ thermal control, provided three-dimensional single-particle level information on the positional order evolution within assemblies. This combination of real and reciprocal space provides insightful information on the anisotropic, reversibly reconfigurable assemblies of NPs. TEM measurements also highlighted the importance of interfaces in the polydomain structure of nanoparticle solids, allowing us to understand experimentally observed differences in UV-vis extinction spectra of the differently prepared crystallites. Overall, the obtained results show that the combination of in situ heating HAADF-STEM tomography with XRD and ex situ TEM techniques is a powerful approach to study nanoparticle freezing processes and to reveal the crucial impact of disorder in the solid-state aggregates of NPs on their plasmonic properties.