Search Results (190)

Bent-shaped liquid crystal (LC) dimers, trimers, and oligomers are intriguing because of their unique liquid crystallinities, which have gained further impetus after the identification of the twist-bend nematic (N_TB) phase in these molecules. LC trimers exhibiting the N_TB phase still remain relatively rare compared to the predominant LC dimers. We report the first homologs of selenium-linked LC trimers, 4,4′-bis[ω-(4-cyanobiphenyl-4′-ylseleno)alkoxy]biphenyls (CBSenOBOnSeCB) with carbon numbers in the alkyl-chain spacers, n = 7 or 9). Polarizing optical microscopy, differential scanning calorimetry, and X-ray diffraction (XRD) measurements were performed to investigate the phase transition behavior and mesophase structures of the trimers. Both CBSenOBOnSeCB trimers exhibited nematic (N) and N_TB phases. The XRD measurements revealed the presence of smectic A-like cybotactic clusters with a triply intercalated structure in the N and N_TB phases. The LC phase transition temperatures of CBSenOBOnSeCB were lower than those of the already-known ether-linked CBOnOBOnOCB and thioether-linked CBSnOBOnSCB counterparts. This trend is ascribed to the enhanced molecular bending and molecular flexibility of CBSenOBOnSeCB, which are caused by the smaller bond angle and greater bond flexibility of C–Se–C compared to C–O–C and C–S–C. This study offers a new molecular design for multiply linked LC oligomers with heavier chalcogen atoms. Full article

This manuscript describes the development of a nano-sized synthetic smectic clay hydrogel (LAP) that enables controlled oxygen delivery, making it a promising candidate for treating skin wound infections and promoting healing. LAP is an ingredient in various dermatological products, including powders, creams and emulsions. We investigated the antibacterial effect of the LAP hydrogel by incorporating calcium peroxide (CPO), an oxygen-releasing agent, and measuring the size of the inhibitory halo. We found that CPO hydrogels in LAP showed a significant increase in oxygen release during the first five hours, especially at low CPO concentrations. For example, the hydrogel with 5% CPO showed a controlled release profile with a final percentage oxygen release of 2.47 ± 0.01% after 5 h. In contrast, the hydrogels with 10% and 20% CPO achieved lower final oxygen release values, 0.67 ± 0.01% and 0.75 ± 0.01%, respectively, suggesting that the encapsulation efficiency of LAP is higher at higher concentrations. LAP also proved to be an effective oxygen barrier and showed inherent antimicrobial activity. The research confirmed the antibacterial properties of the hydrogel, with inhibition sites observed against both E. coli and S. aureus. These results emphasize the potential of this hydrogel to serve as an effective tool for wound treatment by providing sustained oxygenation and fighting microbial infections. Full article

Photoluminescent liquid crystals with photoluminescence (PL) and liquid-crystalline (LC) properties have attracted attention as PL-switching materials owing to their thermally induced phase transitions, such as crystal → smectic A/nematic → isotropic phase transitions. Our group previously developed tetrafluorinated tolane mesogenic dimers linked by flexible alkylene-1,n-dioxy spacers, demonstrating that the position of the tetrafluorinated aromatic ring critically influences the LC behavior. However, these compounds exhibited very weak fluorescence owing to an insufficient D–π–A character of the π-conjugated mesogens, which facilitated internal conversion from emissive ππ* to non-emissive πσ* states. We designed and synthesized derivatives in which the mesogen–spacer linkage was modified from ether to ester, thereby enhancing the D–π–A character. Thermal and structural analyses revealed spacer-length parity effects: even-numbered spacers induced nematic phases, whereas odd-numbered spacers stabilized smectic A phases. Photophysical studies revealed multi-state PL across solution, crystal, and LC phases. Strong blue PL (Φ_PL = 0.39–0.48) was observed in solution, while crystals exhibited aggregation-induced emission enhancement (Φ_PL = 0.48–0.77) with spectral diversity. In LC states, Φ_PL values up to 0.36 were maintained, showing reversible intensity and spectral shifts with phase transitions. These findings establish design principles that correlate spacer parity, phase behavior, and PL properties, enabling potential applications in PL thermosensors and responsive optoelectronic devices. Full article

Among the recently developed ferroelectric nematic liquid crystals, FNLC-919, synthesized by Merck Electronics KGaA, stands out for its stable, room-temperature, ferroelectric nematic (N_F) phase. This renders it a promising candidate for both fundamental research and device-level applications. In this study, we present a comprehensive experimental investigation of FNLC-919, focusing on its structural, optical, dielectric, and elastic properties in the paraelectric nematic (N) and the intermediate antiferroelectric phase (dubbed N_X) that occur in a temperature range between the N and N_F phases. Key material parameters such as ferroelectric polarization, viscosity, and nanostructure are characterized as functions of temperature in all mesophases, while the orientational elastic constants are determined only in the N and N_X phases. Our findings are compared with prior results concerning the benchmark compound DIO that also exhibits the phase sequence N-N_X-N_F and reveals a smectic-like mass density wave coinciding with antiferroelectric ordering in the N_X phase. Full article

The synthesis, phase behavior and semiconductor properties of two novel organosilicon tetramers with dialkyl-substituted [1]benzothieno[3,2-b]benzothiophene (BTBT) moieties, D4-Und-BTBT-Hex and D4-Hex-BTBT-Oct, are described. The synthesis of these molecules was carried out by sequential modification of the BTBT core by carbonyl-containing functional alkyl substituents using the Friedel–Crafts reaction, followed by the reduction in the keto group. The target tetramers, D4-Und-BTBT-Hex and D4-Hex-BTBT-Oct, were obtained by the hydrosilylation reaction between tetraallylsilane and corresponding 1,1,3,3-tetramethyl-1-(ω-(7-alkyl[1]benzothieno[3,2-b]benzothiophen-2-yl)alkyl)disiloxanes. The chemical structure of the compounds obtained was confirmed by NMR ¹H-, ¹³C- and ²⁹Si-spectroscopy, gel permeation chromatography and elemental analysis. Their phase behavior was investigated by differential scanning calorimetry, polarization optical microscopy and X-ray diffraction analysis. It was found that D4-Und-BTBT-Hex shows higher crystallinity at room temperature as compared to D4-Hex-BTBT-Oct, while both molecules possess smectic ordering favorable for active layer formation in organic field-effect transistors (OFETs). The active layers were applied by spin-coating under conditions of a homogeneous thin layer formation with a low content of defects. The devices obtained from D4-Und-BTBT-Hex have demonstrated good semiconductor characteristics in OFETs with a hole mobility up to 3.5 × 10⁻² cm² V⁻¹ s⁻¹, a low threshold voltage and an on/off ratio up to 10⁷. Full article

The functional integration of chiral liquid crystals and π-conjugated compounds has great potential for creating novel exotic materials. A series of chiral donor–acceptor (D–A)-type fluorenone derivatives was synthesized to investigate the influence of molecular structure upon their liquid-crystalline phase-transition behavior, ferroelectricity, photophysical properties, and photoconductive properties. Polarizing optical microscopy (POM), differential scanning calorimetry (DSC), and X-ray diffraction (XRD) analyses revealed that several D–A-type fluorenone derivatives exhibited liquid crystal (LC) phases. These chiral LC fluorenone derivatives exhibited polarization hysteresis in the chiral smectic C (SmC*) phase. Among the four fluorenone-based ferroelectric liquid crystals (FLCs), (R,R)-2a exhibited the largest spontaneous polarization (over 3.0 × 10² nC cm⁻²). The formation of intramolecular charge-transfer (ICT) states in each compound was evidenced by the UV–vis absorption spectroscopy. Ambipolar carrier transport in the SmC* phases of the fluorenone-based FLCs was elucidated by the time-of-flight (TOF) method. The mobilities of holes and electrons in the SmC* phases were on the order of 10⁻⁵ cm² V⁻¹ s⁻¹, which is on par with the carrier mobilities of low-ordered smectic phases in conventional LC semiconductors. Full article

This study addresses the challenges of osteochondral tissue engineering by developing a hybrid scaffold with intercalated layers of poly(ε-caprolactone) (PCL) in combination with different concentrations of nanosized synthetic smectic clay (Lap) and a hydrogel of chitosan, collagen and demineralized bone powder (DBP). The scaffold design specifically targets the critical junction between subchondral bone and calcified cartilage and utilizes the mechanical strength of PCL/Lap nanocomposites and the bioactivity of the chitosan/collagen/DBP hydrogel to support tissue regeneration. The PCL/Lap nanocomposite, characterized by increased hydrophilicity, improved swelling behavior, and enhanced stiffness, provides a robust scaffold, while the hydrogel layers improve bioactivity and fluid retention. Three-dimensional printing technology was used to fabricate multi-layer scaffold, ensuring interfacial cohesion between the layers. Rheological, morphological, chemical, and mechanical characterizations confirmed the successful integration of the materials and the mechanical suitability for the subchondral environment. Biocompatibility assays demonstrated the non-hemolytic nature of the scaffolds and a favorable trend in cell viability with increasing Lap content. This study presents a novel scaffold design that effectively combines mechanical stability and biological functionality. It fulfills the complex requirements of osteochondral repair and offers a promising platform for future tissue engineering strategies. Full article

Using reactive atomistic molecular dynamics, we simulate the network formation and bulk properties of chemically identical liquid crystal elastomers (LCEs) and isotropic elastomers. The nematic elastomer is from a family of materials that have been shown to be auxetic at a molecular level. The network orientational order parameters and glass transition temperatures measured from our simulations are in strong agreement with experimental data. We reproduce, in silico, the magnitude and onset of strain-induced nematic order in isotropic simulations. Application of uniaxial strain to nematic LCE simulations causes biaxial order to emerge, as has been seen experimentally for these auxetic LCEs. At strains of ~1.0, the director reorients to be parallel to the applied strain, again as seen experimentally. The simulations shed light on the strain-induced order at a molecular level and allow insight into the individual contributions of the side-groups and crosslinker. Further, the agreement between our simulations and experimental data opens new possibilities in the computational design of high-molecular-weight liquid crystals, especially where an understanding of the properties under mechanical actuation is desired. Moreover, the simulation methodology we describe will be applicable to other combinations of orientational and/or positional order (e.g., smectics, cubics). Full article

Eleven novel asymmetric pyrimidine derivatives were synthesized. The pyrimidine core was functionalized with a coumarin chromophore and a pro-mesogenic fragment bearing either chiral or linear alkyl chains of variable length and substitution patterns. The thermal properties were investigated using polarized optical microscopy, differential scanning calorimetry, and small-angle X-ray scattering, revealing that only selected derivatives exhibited liquid crystalline phases with ordered columnar or smectic organizations. Linear and nonlinear optical properties were characterized by UV–Vis absorption, fluorescence spectroscopy, two-photon absorption, and second-harmonic generation. Optical responses were found to be highly sensitive to the substitution pattern: derivatives functionalized at the 4 and 3,4,5 positions exhibited enhanced 2PA cross-sections and pronounced SHG signals, whereas variations in alkyl chain length exerted only a minor influence. Notably, compounds forming highly ordered non-centrosymmetric mesophases produced robust SHG-active thin films. Importantly, strong SHG responses were obtained without the need for a chiral center, as the inherent asymmetry of the linear alkyl chain derivatives was sufficient to drive self-organization into non-centrosymmetric materials. These results demonstrate that asymmetric pyrimidine-based architectures combining π-conjugation and controlled supramolecular organization are promising candidates for nonlinear optical applications such as photonic devices, multiphoton imaging, and optical data storage. Full article

This study investigates the temperature-driven transmission switching behavior of our proposed smart glass, which utilizes a biphasic liquid crystal system under continuous application of a distinctive homeotropic (H) state voltage (V_H). By ascertaining V_H at temperatures near the phase transition point, the minimum voltage required to sustain the H state in the smectic A* (SmA*) phase is identified. Interestingly, this minimum V_H is unable to induce the H state in the chiral nematic (N*) phase, thereby maintaining a low-transmission scattering state; i.e., the focal conic (FC) state. This empowers passive, bidirectional optical switching between the transparent H state (in the SmA* phase) and the scattering FC state (in the N* phase) in an unaligned liquid crystal cell. This work employs two dissimilar chiral dopants, R811/S811 and CB7CB/R5011, both capable of inducing the SmA* phase. Neither resulting cell system underwent surface orientation treatment, and a black dye was incorporated to enhance the contrast ratio. The results indicate that the more efficacious CB7CB/R5011 system achieves a contrast ratio of 17 between the transparent and scattering states, with a corresponding haze level of 78%. To further reduce energy consumption, the experimental framework was transitioned from a continuous-voltage to a variable-voltage mode, giving rise to an increased haze level of 88%. The proposed switching scheme holds promise for diverse applications, notably in smart windows and light shutters. Full article

This study reports on the preparation and comprehensive characterisation of new brominated hydrogen-bonded liquid crystalline (HBLC) materials. Two distinct series of supramolecular complexes were prepared by hydrogen-bond formation between 3-bromo-4-pentyloxybenzoic acid as the proton donor and non-fluorinated and fluorinated azopyridines with variable terminal chains as proton acceptors. The successful formation of a hydrogen bond was confirmed by FTIR spectroscopy. The impact of alkyl chain length and fluorination on the mesomorphic properties of the HBLCs was systematically investigated. The molecular self-assembly was thoroughly examined using polarised optical microscopy (POM) and differential scanning calorimetry (DSC), revealing the presence of smectic C (SmC), smectic A (SmA), and nematic (N) phases, with thermal stability being highly dependent on the molecular architecture. Notably, the introduction of fluorine atoms significantly influenced the phase transition temperatures and the overall mesophase range. Using bromine as a lateral substituent induces the formation of SmC phases in these HBLCs, a feature absent in their non-brominated analogues. Further structural insights were obtained through X-ray diffraction (XRD) investigations, confirming the nature of the observed LC phases. Additionally, the photo-responsive characteristics of these HBLCs were explored via UV-Vis spectroscopy, demonstrating their ability to undergo reversible photoisomerisation upon light irradiation. These findings underscore the critical role of precise molecular design in tailoring the properties of HBLCs for potential applications such as optical storage devices. Full article

Two cholesterol-based liquid crystalline materials were synthesized by incorporating perfluorinated acyl chains of different lengths with the help of epichlorohydrin and copper(I)-mediated azide-alkyne 2+3 dipolar cycloaddition chemistries. These materials were characterized by differential scanning calorimetry, cross-polarized optical microscopy and powder X-ray diffraction. The compound with the longer perfluorinated chain exhibited a smectic A (SmA) phase as confirmed by XRD and POM, while the shorter-chain derivative exhibited diffraction peaks suggestive of both simple SmA* ordering as well as lamellar solid phase exhibiting multilayer ordering. Full article

Soft nanocomposites were prepared by dispersing lipophilic carbon quantum dots (CQDs) in the liquid crystal compound 8CB. The quality of the dispersion was evaluated using fluorescence microscopy, while the microstructure of the samples was examined via polarized optical microscopy. We investigated the influence of CQDs on the orientational order parameter S as a function of temperature and sample composition by measuring birefringence. Additionally, the Fréedericksz transition threshold, along with the characteristic response and relaxation times, was measured for each sample as a function of temperature and applied voltage amplitude. The extracted rotational viscosity ${\gamma }_1$ exhibits a pretransitional divergence upon cooling toward the smectic-A phase. Its temperature dependence was analyzed using established models from the literature, and the corresponding activation energy was determined. Notably, our analysis suggests that the presence of CQDs alters the power-law dependence of ${\gamma }_1$ on the orientational order parameter S. The influence of CQDs on the elastic constants has been investigated. Full article

Polypropylene (PP), with its good physical, thermal, and mechanical properties and excellent processing capabilities, has become one of the most used synthetic polymers. It is known that the overall properties of semicrystalline polymers, including PP, are governed by morphology, which is influenced by the crystallization behavior of the polymer under specific conditions. The most important industrial PP remains the isotactic one, and it has been studied extensively for its polymorphic characteristics and crystallization behavior for over half a century. Due to its regular chain structure, isotactic polypropylene (iPP) belongs to the group of polymers with a high tendency for crystallization. The rapid quenching of molten iPP fails to produce a completely amorphous polymer but leads to an intermediate crystalline order. On the other hand, slow cooling yields a material with high crystalline content. The processing conditions that occur in practice and industry are between these two extremes and, in some cases, are even very close. Therefore, the study of limits in processability and the impact of extreme preparation conditions on morphology, structure, thermal, and mechanical properties fills a gap in the current understanding of how the processing conditions of iPP can be used to design the desired properties for specific applications and is in the focus of this research. The first set of samples (Q samples) was obtained by rapid quenching, while the second was prepared by very slow cooling from the melt to room temperature (SC samples). Testing of samples was performed by optical microscopy (OM), scanning electron microscopy (SEM), wide-angle X-ray diffraction (WAXD), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), dynamic dielectric spectroscopy (DDS), and mechanical measurements. Characterization revealed that slowly cooled samples exhibited a significantly higher degree of crystallinity and larger crystallites (χ ≥ 55% and L₍₁₁₀₎ ≈ 20 nm), compared to quenched samples (χ < 30%, L₍₁₁₀₎ ≤ 3 nm). Mechanical testing showed a drastic contrast: quenched samples exhibited elongation at break > 500%, while slowly cooled samples broke below 15%, reflecting their brittle behavior. For the first time, DDS is applied to investigate molecular mobility differences between processing-dependent structural forms, specifically the mesomorphic (smectic) and α-monoclinic forms. In slowly cooled samples, α relaxation exhibited both enhanced intensity and an upward temperature shift, indicating stronger structural constraints due to a much higher crystalline phase content and significantly larger crystallite size, respectively. These findings provide novel insights into the structure–property–processing relationship, which is crucial for industrial applications. Full article

Three liquid crystalline mixtures were investigated, consisting of compounds abbreviated as MHPOBC and 3F5FPhF6 with molar ratios 0.9:0.1 (MIX5FF6-1), 0.75:0.25 (MIX5FF6-2), and 0.5:0.5 (MIX5FF6-3). The presence of the smectic A*, smectic C*, and smectic C_A* phases was observed in all mixtures. The hexatic smectic X_A* phase, present in pure MHPOBC, disappeared quickly with an increasing admixture of 3F5FPhF6. Vitrification of smectic C_A* was observed for the equimolar mixture, with the glass transition temperature and fragility index comparable to the pure glassforming 3F5FPhF6 component. Partial crystallization to conformationally or orientationally disordered crystal phases was observed on cooling in two mixtures with a smaller fraction of 3F5FPhF6. Broadband dielectric spectroscopy was applied to study the relaxation times in smectic and crystal phases. Vogel–Fulcher–Tammann, Mauro–Yue–Ellison–Gupta–Allan, and critical-like models were applied for analysis of the α-relaxation time in supercooled smectic X_A* and smectic C_A* phases. Full article