Terminal Chain Length Research Articles

Biphenyl Based Non-symmetrical Bent-Core Mesogens Containing a Chiral Moiety and an Olefinic End Group

New nonsymmetrical bent-core compounds consisting of a biphenyl-3,4′-diol central unit, a chiral terminal chain and an olefinic end group at the other terminus have been synthesized and characterized to study the influence of a chiral moiety, the length of terminal alkenyl chain, and the number of aromatic rings in the rod-like wings which are substituted at the 3- and 4-position of central biphenyl core on mesophase properties of bent-core mesogens. The liquid crystalline properties of the compounds were investigated by differential scanning calorimetry, optical polarizing microscopy, and electro-optic methods. Depending on the length of the olefinic chain and the number of aromatic rings in the rod-like wings, the bent-core compounds with a chiral moiety show B1 type mesophase, polar smectic C phase (SmCP) or nonmesomorphic behavior.

Effects of terminal group and chain length on temperature-responsive chromatography utilizing poly(N-isopropylacrylamide) synthesized via RAFT polymerization

Even using the same homo poly(N-isopropylacrylamide) immobilized silica beads as stationary phases, terminal functional group and chain length significantly affected temperature-dependent elution behavior of steroids.

Effects of terminal chain length in hydrogen-bonded chiral switches on phototunable behavior of chiral nematic liquid crystals: helicity inversion and phase transition.

A novel series of photoresponsive chiral switches are fabricated by a facile hydrogen-bonded (H-bonded) assembly method, in which the binaphthyl azobenzene molecule is used as the proton acceptor, and binaphthyl acids with opposite chiral configuration are proton donors. We find that the helical twisted power of H-bonded chiral switches and the helical handedness of induced chiral nematic liquid crystals (N*-LCs) are mainly determined by the terminal flexible chain length in proton donors of binaphthyl acids. Controlling the lengths of the terminal flexible chain leads to different photoswitching behaviors by light irradiation, such as a helical inversion in the N*-LCs and a phase transition from N*-LCs to nematic LCs. This is mainly because of chiral counteraction and intensity attenuation of opposite chiral configurations between the proton acceptor and proton donor during UV-vis irradiation. Additionally, the thermal switching behavior of N*-LCs doped with H-bonded chiral switches is also demonstrated, and the related tuning mechanism may be attributed to the H-bonded effect and the changes in a dihedral angle of the binaphthyl rings. This facile assembly approach provides a new way for the fabrication of functional chiral switches for photonic applications.

The Gelation Ability and Morphology Study of Organogel System Based on Calamitic Hydrazide Derivatives

The gelation property of a series of LMOG bearing hydrazide and azobenzene groups, namely, N‐4‐(alkoxyphenyl)‐N′‐4‐[(4‐methoxyphenyl)azophenyl] benzohydrazide (BNBC‐n, n = 8,12,14), has been systematically studied in this work. The obtained results demonstrate that the gelling ability in organic solvents is significantly influenced by the length of terminal alkoxy chain. In different organic solvents, it is hard to observe the organogel formation for BNBC‐8 molecule. On the contrary, the organogelators BNBC‐12 and BNBC‐14 bearing longer terminal chains have shown great ability to gel organic solvents to form stable organogels. The critical gelation concentration for BNBC‐12 reaches as low as 5.3 × 10−3 M, which can be considered as a supergelator. It has been manifested that the aggregation morphology of organogel strongly depends on the nature of the gelling solvents and the length of the terminal alkoxy chain. The gelation of BNBC‐n provides an easy method for the preparation of multidimensional structure and manipulation of morphology from ribbons, hollow tube fiber to 3D net‐like structure in different solvents. The cooperation of hydrogen bonding, π‐π interaction, and Van der Waals force is suggested to be the main contribution to this self‐assembled structure.

Structure–property relationship in charge transporting behaviour of room temperature liquid crystalline perylenebisimides

A homologous series of pentadecyl phenol functionalized perylenebisimide (PBI) terminated with trialkoxy gallate esters was synthesized, where the terminal alkyl chain length was varied from n = 4 to 12 (PBI-En). The thermotropic liquid crystalline (LC) characteristics of the molecules were analyzed using differential scanning calorimetry (DSC), polarized light microscopy (PLM) combined with variable temperature wide angle X-ray diffraction (WXRD) techniques. A clear odd–even oscillation was observed in the melting as well as isotropization enthalpies as a function of alkyl spacer length in the terminal gallate unit, with the even spacers exhibiting higher values. The higher members of the series with n > 8 exhibited thermotropic liquid crystalline textures in the PLM, which remained stable until room temperature. The nature of the LC phase was identified to be columnar rectangular and columnar hexagonal based on detailed analysis of the WXRD pattern recorded in the LC phase. The WXRD pattern of the room temperature LC frozen samples indicated a nearly constant intra columnar stack distance of ∼3.7 A for all the members. The space-charge-limited current (SCLC) values of the LC frozen sample films were analyzed for dependence of the bulk mobility estimate on the nature of the LC phase. The columnar hexagonal phase exhibited a mobility value one order (10−3 cm2 V−1 s−1) higher than that of crystalline (10−4 cm2 V−1 s−1) and two orders higher than that of columnar rectangular phase (10−5 cm2 V−1 s−1), indicating a strong dependence of packing on bulk mobility.

Thermotropic Liquid Crystalline Dimers with Varying Alkoxy Terminal Chain Length

We have design and synthesized of homologous Series I dimers and to study the effect of molecular structure variation and change in alkoxy terminal chain length (n = 6, 7, 8) on mesomorphic properties of liquid crystals. Explore further understanding of the structure-property relationship of liquid crystal homologous Seriesl dimers having varying alkoxy terminal chain length. It was found that the decrease in crystalline phase, smectic C and nematic phase transition temperatures with increasing terminal alkoxy chain length. The molecular structures of the Seriesl dimer were characterized by Fourier transform infrared spectroscopy (FT-IR) and proton nuclear magnetic resonance (1H NMR) spectroscopy. Their mesomorphic properties were investigated by differential scannning calorimetry (DSC) and on the hot-stage of a polarizing microscope (POM).

Effect of alkoxy terminal chain length on mesomorphism of 1,6-disubstituted pyrene-based hexacatenar liquid crystals: columnar phase control

Synthesis and mesophase-transition behaviors of six 1,6-disubstituted pyrene-based hexacatenar liquid crystals 1n (n=8–18) are reported here. They were synthesized by the Sonogashira coupling between 1,6-diethynylpyrene and 2-bromothiophene bearing a trialkoxybenzoyl group. The phase-transition behavior was studied by differential scanning calorimetry and polarized optical microscopy; a few mesophase progressions, I–Col/I–X–Col and Col–Sm, were observed, where X was an optically isotropic but unidentified phase. The structures of Colr, Colh, and Sm phases were analyzed by the X-ray crystallography, and the effect of the terminal alkoxy chain length on the mesomorphism was evaluated.

Synthesis, mesomorphic, photophysical and computational studies of new achiral four-ring unsymmetrical bent-core mesogens and their Copper(II) complexes

New achiral four-ring unsymmetrical bent-core mesogens derived from 2,5-dihydroxybenzaldehyde and their copper(II) complexes have been synthesised as a new design with an imine and ester linkage. These new bent-core molecules resemble hockey-stick shape, which possesses 4-n-alkyloxy chain (4-n-hexyloxy and 4-n-decyloxy) at one end and methyl or methoxy group at the other end of the molecule. The synthesis, spectroscopic characterisation, phase transition temperature and characterisation of phase behaviour are reported. The bent-core molecules exhibited monotropic nematic and smectic A phase depending on the terminal chain length. Interestingly, copper(II) complexes of bent-core molecules displayed monotropic nematic phase. This is the first report on copper(II) complexes of bent-core molecules that exhibited nematic phase. The four-ring bent-core molecule exhibited fluorescence with large stoke shift. The density functional theory calculations of bent-core molecules and their copper(II) complexes are carried out using Gaussian 09 program at B3LYP level to obtain the stable molecular conformation, dipole moment, highest occupied molecular orbital (HOMO), lowest unoccupied molecular orbital (LUMO) energies and bending angle of the compounds. The natural atomic charges and electronic configurations of the atoms of free ligands as well as the complexes have been evaluated.

The effect of the alkyl chain length on the mesomorphic properties of new lactic acid derivatives

New series of lactic acid derivatives with alkyl terminal chain have been synthesised and their mesomorphic properties studied. We have varied the length of chiral and non-chiral terminal alkyl chains and found that prolonging both chains has a strong effect on the SmA*–SmC* phase transition. Most of the new materials exhibit only paraelectric SmA* phase; for homologues with a longer non-chiral chain (m ≥ 10), the ferroelectric (SmC*) phase appears below the SmA* on cooling and persists down to a room temperature. The role of the chiral terminal chain in the molecule is quite opposite – only its short length supports the existence of ferroelectric phase. Additionally, a hexatic phase appeared below the SmA*–SmC* phase sequence for several homologues at low temperatures. All materials have been studied using standard experimental techniques (differential scanning calorimetry (DSC), texture observations, polarisation and tilt angle measurements, etc.). Liquid crystalline properties of new materials have been compared with the previously prepared and studied lactic acid derivatives.

New features of a smectic-A-crystal-B phase transition in a homologous series of liquid crystals

The components Lj of the Lorentz tensor and the polarizability density of molecules G in the smectic-A and crystalline-B phases have been determined for homologues of the series of alkyl-p-(4-alkoxybenzylideneamino-)cinnamates. The quantity Lj (G) in both phases is a linear (quadratic) function of the orientational order parameter of molecules S, which is invariant (noninvariant) with respect to the A-B transition, which is manifested in the form of jumps δLj and δG and enhancement of the G(S) dependence. An increase in the length of terminal molecular chains and weakening of interlayer correlation of molecules are accompanied by strengthening of the A-B transition of the first order and G(S) dependences in both phases together with an increase in δLj and δG. Change δG and dependence G(S) in the B phase are related to change in the conformation (flattening) of aromatic molecular cores.

Side‐on main‐chain liquid crystalline polymers prepared by acyclic diene metathesis polymerization and thiol‐ene click step‐growth polymerization

ABSTRACTIn this manuscript, we design and synthesize a series of X‐shaped mesogenic monomers, bearing two terminal‐alkene tails. Starting from these X‐shaped monomers, acyclic diene metathesis polymerization and thiol‐ene polyaddition are applied for the first time to prepare two series of side‐on main‐chain liquid crystalline polymers (LCPs), respectively. The mesomorphic behaviors and structure‐property relationships of these new polymers are studied in detail by a combination of 1H NMR, GPC, TGA, DSC, POM, and XRD experiments. It turns out that the length of alkoxy terminal chains of the embedded mesogens and the length of the spacer connecting two adjacent mesogens on the polymer backbones markedly influence the mesomorphic properties. Furthermore, a side‐on main‐chain liquid crystalline elastomer fiber is prepared by crosslinking the LCP using a UV‐sensitive bifunctional benzophenone crosslinker. In comparison with the pure polymer fiber's monodomain alignment, the crosslinked elastomer fiber however shows nonaligned polydomain structure, probably due to the order competitions between the mixed crosslinkers, mesogens, and polymer backbones. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 1086–1098

A structure–property relationship study of bent-core mesogens with pyridine as the central unit

The synthesis and characterization of pyridine bent-core liquid crystals are reported. Some compounds exhibit B1 and B7 mesophases. Lower and wider mesophase ranges are obtained by decreasing the polarity of linkers between the pyridine ring and the inner aromatic rings, and increasing the length of terminal chains.

Toxicity and biodegradability of dicationic ionic liquids

Ionic liquids (ILs) formed by multivalent cations are generally of higher thermal and electrochemical stability, which makes them attractive for use in high-temperature applications. Whereas the influence of structural elements on the physicochemical properties of dicationic ILs (DILs) is well established, such systematic investigations on their ecotoxicity and biodegradablility are still lacking. The present study investigates the influence of the dicationic structural elements on these characteristics and addresses the question whether already established structure–activity relationships of common ILs can be applied to DILs. Therefore, a set of 10 DILs with different linkage chain length, terminal alkyl side chain length, linkage chain polarity and head groups were synthesized and studied in several biodegradation and toxicity tests. The results showed that the acute toxicity was in many cases below the levels observed for monocationic ILs. However, none of the DILs could be degraded within the performed biodegradation experiments. Hence, DILs are a potential less toxic alternative to monocationic ILs, but further work on their design is necessary.

Synthesis and Characterization of Two Phenyl Ring Core-Based Thiophene Mesogens

Novel thiophene mesogens built with two phenyl ring core and alkoxy terminal chains are synthesized by multistep route. The phenyl ring core is connected to thiophene by ester unit at (a) 2-position and (b) 3-position to yield 2-series of mesogens. The structural characterization of them is accomplished by using spectroscopy tools and the mesophase characteristics are evaluated by HOPM and DSC. The 13C chemical shifts of representative mesogens calculated from DFT by quantum chemical calculations are compared with experimental 13C chemical shifts and further utilized for structural assignment of core unit carbons. A good agreement between calculated and experimental values is noticed. An enantiotropic nematic phase is confirmed for all the mesogens and accordingly threaded nematic texture in HOPM is observed and is supported by DSC transition enthalpy values. The mesophase as well as thermal stabilities of the mesogens are discussed with reference to terminal chain length and position of the linking unit on thiophene.

Three armed star mesogens based on 1,3,5-benzenetricarboxylic acid: Synthesis and mesophase characterization

A series of star mesogens based on 1,3,5-benzenetricarboxylic acid central core, side arms containing two phenyl rings, linked through azomethine groups and hexamethylene spacers, which connect the central core and side arms were synthesised via divergent approach. The mesogens synthesised and their intermediates were structurally well characterized, using FT-IR, 1H NMR, 13C NMR spectroscopy and elemental analysis techniques. The mesophase characterization was carried out using a hot stage-polarizing optical microscopy (POM), differential scanning calorimetry (DSC) and X-ray diffraction (XRD) techniques. Enantiotropic mesophases were observed for all the mesogens synthesised. An increase in the terminal chain length stabilized the smectic phase. Nematic phase was observed for the mesogens with short terminal chain length, whereas smectic polymorphism was observed on increasing the terminal chain length. XRD results suggested a tripod-like assembly of molecules in the mesophase.

Glycosylation and functionality of recombinant β-glucocerebrosidase from various production systems

The glycosylation of recombinant β-glucocerebrosidase, and in particular the exposure of mannose residues, has been shown to be a key factor in the success of ERT (enzyme replacement therapy) for the treatment of GD (Gaucher disease). Macrophages, the target cells in GD, internalize β-glucocerebrosidase through MRs (mannose receptors). Three enzymes are commercially available for the treatment of GD by ERT. Taliglucerase alfa, imiglucerase and velaglucerase alfa are each produced in different cell systems and undergo various post-translational or post-production glycosylation modifications to expose their mannose residues. This is the first study in which the glycosylation profiles of the three enzymes are compared, using the same methodology and the effect on functionality and cellular uptake is evaluated. While the major differences in glycosylation profiles reside in the variation of terminal residues and mannose chain length, the enzymatic activity and stability are not affected by these differences. Furthermore, the cellular uptake and in-cell stability in rat and human macrophages are similar. Finally, in vivo studies to evaluate the uptake into target organs also show similar results for all three enzymes. These results indicate that the variations of glycosylation between the three regulatory-approved β-glucocerebrosidase enzymes have no effect on their function or distribution.

Apolar novel mesogenic symmetric dimers composed of five-ring bent-core monomeric units

The synthesis and mesomorphic properties of parts of six different series of symmetric dimers composed of five-ring bent-core monomeric units have been investigated. By design, all the dimers are apolar as all the dipoles of the monomers cancel with each other. The mesomorphic properties have been investigated (1) as a function of the length of the terminal chain for a fixed spacer unit, and (2) as a function of the length of the spacer unit for a fixed terminal chain length. Interestingly, two orthogonal lamellar phases have been observed in many of these dimers which differ from one another only in the layer spacing. The chemical structure of the dimers has been determined using a combination of spectroscopic techniques and elemental analysis. The mesophases are characterised using complementary methods such as polarising optical microscopy, differential scanning calorimetry, X-ray diffraction and electro-optical measurements.

Synthesis, mesomorphic properties and structural studies on 1,3,5-trisubstituted benzene-based star-shaped derivatives containing Schiff base ester as the peripheral arm

Six new symmetrical three-armed star-shaped liquid crystals comprising phloroglucinol (1,3,5-trihydroxybenzene) as a core center and three Schiff base ester as the mesogenic arms have been synthesized. Their molecular structures were supported by spectroscopic techniques (FT-IR, 1H NMR, 13C NMR and two dimensional COSY, HMQC and HMBC). Each of the member differs in the length of the terminal alkyl chain (RCOO where R=C8H17, C10H21, C12H25, C14H29, C16H33, C18H37). All the star-shaped mesogens are found to be monotropic smectogens with the short chain derivative (R=C8H17) exhibits only smectic A phase. While both the smectic A and smectic C phases are common for the derivatives with C10H21C16H33 alkyl chain, the member with C18H37 shows only smectic C phase. Further investigation by X-ray diffraction confirms the smectic phase of the materials whereby two sharp reflections at 28.8Å and 57.3Å recorded via small angle in a ratio of 1:2 indicate unambiguously the presence of layered structure and a diffused scattering via the wide angle (4.5Å) indicates a liquid-like order within the smectic layer. Increasing the length of terminal flexible chain has influenced remarkably the thermal and phase stability of the titled compounds. Besides, the liquid crystalline properties of all intermediary ω-brominated Schiff base ester prior joining to the benzene core were also evaluated.

Dissipative Particle Dynamics Simulation of the Phase Behavior of T-Shaped Ternary Amphiphiles Possessing Rodlike Mesogens

We employed dissipative particle dynamics simulations to explore the phase behavior of T-shaped ternary amphiphiles composed of rodlike cores connected by two incompatible end chains and side grafted segments. By fine-tuning the number of terminal and lateral beads, three phase diagrams for the model systems with different terminal chain lengths are constructed in terms of temperature and lateral chain length, which have some common features and mostly compare favorably with experimental studies with the exception a couple of new phases. It is worthwhile to highlight that the mixed cylindrical phase and the perforated layer phase, as the experimentally observed mesophases exclusive for facial amphiphilies, are found in simulations for the first time. Also, a novel gyroid structure is observed in series of T-shaped ternary amphiphiles for the first time. Furthermore, by evaluating the effective volume fraction of lateral chains, the phase sequence spanning from conventional smectic layer phase via perforated layer structures and polygonal cylindrical arrays to novel lamellar mesophase is established, which is not just qualitatively consistent with the related experimental findings but even the stability windows of some mesophases quantitatively correspond well to experimental results. The success of reproducing the in-plane ordering of rods in the lamellar phase as well as the generic phase diagram of such T-shaped ternary amphiphiles in great detail implies that our genetic model qualitatively captures many of the characteristics of the phase behavior of real T-shaped molecules and could serve as a satisfactory basis for further exploration of self-organization in other related soft matter systems.

Star mesogens — Synthesis and structural characterization using 1D and 2D solution NMR techniques and mesophase characterization

Novel star mesogens based on trimesic acid and symmetrical side arm cores with terminal alkoxy groups were synthesized via a divergent approach. The central core and side arms were connected through alkyl spacers. All the synthesized mesogens and their intermediates were characterized thoroughly using Fourier transform infrared (FT-IR), 1H nuclear magnetic resonance (NMR), 13C NMR, and mass spectrometers. One representative mesogen was subjected to the two-dimensional (2D) NMR experiments to ascertain the structure of the mesogens. The mesophase characterization was carried out using hot-stage optical polarizing microscopy (HOPM), differential scanning calorimetry (DSC), and X-ray diffraction (XRD) techniques. Many of the molecules with an ethyloxy spacer were found to be nonmesogenic, whereas all the molecules with a butyloxy spacer showed liquid crystalline phases. The increase of terminal chain length decreased the transition temperatures. The nematic phase was observed for the mesogens with short terminal chain length, whereas smectic polymorphism was observed on increasing the terminal chain length. The results of a variable temperature powder X-ray diffraction of the representative sample support the smectic layer ordering.