Anna Zep

Do the short helices exist in the nematic TB phase

Dimeric compounds forming twist-bend nematic, Ntb, phase show unusual optical textures related to the formation of arrays of focal conic defects (FCDs). Some of the focal conics exhibit submicron internal structure with 8 nm periodicity, which is very close to that found in the crystalline phase of the material, that might suggest surface freezing.

A Twist-Bend Nematic (NTB) Phase of Chiral Materials†

New chiral dimers consisting of a rod-like and cholesterol mesogenic units are reported to form a chiral twist-bend nematic phase (NTB *) with heliconical structure. The compressibility of the NTB phase made of bent dimers was found to be as large as in smectic phases, which is consistent with the nanoperiodic structure of the NTB phase. The atomic force microscopy observations in chiral bent dimers revealed a periodicity of about 50 nm, which is significantly larger than the one reported previously for non-chiral compounds (ca. 10 nm).

Physical gels made of liquid crystalline B4 phase

The achiral liquid crystalline materials showing two B4 (HN) phases have been found to exhibit strong gelation ability for various organic solvents with reversible sol-gel phase transition. The gel is formed by helical tubules, which build entangled 3D network, encapsulating the solvent. The equilibrium of left- and right-handed tubules is preserved in the gel, even if the chiral solvent is used.

Multiple nematic phases observed in chiral mesogenic dimers

A sequence of seven nematic phases has been observed in chiral mesogenic dimers, having odd number of carbon atoms in the spacer, thus a bent shape. The highest temperature phase is a chiral nematic (cholesteric) phase on heating or blue phases on cooling. The lowest temperature nematic phase expels the chiral twist and exhibits spontaneous bent–splay modulation.

Synthesis and Organic Surface Modification of Luminescent, Lanthanide-Doped Core/Shell Nanomaterials (LnF3@SiO2@NH2@Organic Acid) for Potential Bioapplications: Spectroscopic, Structural, and in Vitro Cytotoxicity Evaluation

A facile coprecipitation reaction between Ce(3+), Gd(3+), Tb(3+), and F(-) ions, in the presence of glycerine as a capping agent, led to the formation of ultrafine, nanocrystalline CeF3:Tb(3+) 5%, Gd(3+) 5% (LnF3). The as-prepared fluoride nanoparticles were successfully coated with an amine modified silica shell. Subsequently, the obtained LnF3@SiO2@NH2 nanostructures were conjugated with 4-ethoxybenzoic acid in order to prove the possibility of organic modification and obtain a new functional nanomaterial. All of the nanophosphors synthesized exhibited intense green luminescence under UV light irradiation. Based on TEM (transmission electron microscopy) measurements, the diameters of the cores (≈12 nm) and core/shell particles (≈50 nm) were determined. To evaluate the cytotoxic activity of the nanomaterials obtained, their effect on human erythrocytes was investigated. LnF3 nanoparticles were bound to the erythrocyte membrane, without inducing any cytotoxic effects. After coating with silica, the nanoparticles revealed significant cytotoxicity. However, further functionalization of the nanomaterial with -NH2 groups as well as conjugation with 4-ethoxybenzoic acid entailed a decrease in cytotoxicity of the core/shell nanoparticles.

Photoresponsive helical nanofilaments of B4 phase

New dimeric compounds forming a helical nanofilament phase (B4) are reported. It is shown that filaments can be aligned in the macro-scale when grown from aligned smectic phase. Due to the photosensitivity of the mesogenic material, the patterning of the sample is possible by selective UV irradiation, which reversibly melts the B4 phase and as a result locally changes the alignment of nanofilaments. Also, photosensitive composite materials are reported, in which nanofilaments encapsulate the smectic phase. In such composites, as the UV melting of filaments occurs, the layer spacing of the smectic matrix is shortened or lengthened depending on whether the cis or trans conformation of dimers enriches the matrix.

Eu3+ and Tb3+ doped LaPO4 nanorods, modified with a luminescent organic compound, exhibiting tunable multicolour emission

Co-precipitation reaction followed by hydrothermal treatment were used to synthesise Eu3+ or Tb3+ doped LaPO4 nanorods, of 5–10 nm in width and 50–100 nm in length. Surface modification of the as-prepared nanoparticles with a selected luminescent organic compound resulted in formation of hybrid inorganic–organic nanomaterials. The products obtained exhibited tunable multicolour luminescence, dependent on the surface modification and applied excitation wavelength. The colour of their emission can be altered from red-orange to yellow-green. Powder X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM) and scanning transmission electron microscopy (STEM) confirmed the structure and morphology of the products synthesized. Successful surface modification of the nanophosphors was evidenced by analytical and spectroscopic techniques such as dynamic light scattering (DLS) – providing size distribution histograms and zeta potentials of the nanoparticles; IR spectroscopy and elemental analysis which proved the presence of an organic phase in the structure; spectrofluorometry (excitation/emission spectra and luminescence decay curves) which confirmed the formation of hybrid, surface modified nanomaterials revealing tunable multicolour emission.

Stable electro-optic response in wide-temperature blue phases realized in chiral asymmetric bent dimers [Invited]

We report that an asymmetric bent dimer, consisting of a rod mesogen and a cholesterol mesogen linked by a flexible spacer with 9 carbon atoms, was found to form blue phases with a record-wide temperature range. Moreover, highly stable, fast electro-optic switching is possible. In addition to the stable Kerr effect, the electrostriction effect was also observed.

Phototunable Liquid‐Crystalline Phases Made of Nanoparticles

The properties of liquid-crystalline (LC) hybrid systems made of inorganic nanoparticles grafted with photosensitive azo compounds are presented. For materials with a large density of azo ligands at the surface, the LC structure can be reversibly melted by UV light, and the return to the LC state does not require the absorption of visible light. For systems with a lower density of azo ligands, UV light causes shortening of the distance between metal sublayers in the lamellar phase. Interestingly, the azo derivatives attached to the nanoparticle surface show very different kinetics of cis/trans conformational change as compared to the free molecules. The cis form of free ligands in solution is stable for days, whereas the isomerization of molecules attached to the nanoparticle surface to the trans form takes only a few minutes. Apparently, owing to the crowded environment, azo ligands immobilized at a metal surface behave as they would in the condensed state.

From Sponges to Nanotubes: A Change of Nanocrystal Morphology for Acute-Angle Bent-Core Molecules

The crystalline (B4 ) phase made of acute-angle bent-core molecules (1,7-naphthalene derivatives), which exhibits an unusual, highly porous sponge-like morphology, is presented. However, if grown in the presence of low-weight mesogenic molecules, the same crystal forms nanotubes with a very high aspect ratio. The nanotubes become unstable upon increasing the amount of dopant molecules, and the sponge-like morphology reappears. The phase is optically active, and the optical activity is an order of magnitude smaller than in the B4 phase made of conventional bent-core molecules. The optical activity is related to the spatial inhomogeneity of the layered structure and is reduced due to the low apex angle and low tilt of the molecules. The arrangement of molecules within the layers was deduced from the bathochromic absorption shift in the B4 phase.