Benzopyrano-Fused Phenanthridine-Based Columnar Mesogens: Synthesis, Self-organization and Charge-Transport Properties.

Columnar mesogens constitute a fascinating class of supramolecular nano-architectures owing to the exceptional properties induced by their self-assembling behavior. Extending the π-conjugated core in such systems by incorporating heteroatoms extensively influences their mesomorphic, photophysical properties, etc., presenting them as potential candidates for optoelectronic applications. In the present work, a series of novel nitrogen and oxygen-incorporated chromenonaphthophenanthridine-based elliptical dimers have been synthesized through tandem Pictet-Spengler cyclization followed by ipso-aromatic substitution in one-pot. Mesophase characterization has been carried out by employing POM, DSC, and X-ray diffraction studies. Photophysical properties were investigated using UV-vis and emission spectroscopy. Furthermore, the charge transport properties were analyzed by time-of-flight measurements, and the observed ambipolar mobilities were found to be of the order of 10-3  cm2 V-1 s-1 . The high solubility, excellent thermal stability, self-organizing properties, and ambipolar charge transport characteristics make them promising candidates for applications in organic electronics.

13C Nuclear Magnetic Resonance Investigations of Molecular Mesogens with a Terminal Phenyl Ring Linked via a Spacer: Odd-Even Effect.

A set of mesogens considered as model molecules to the technologically important twist-bend (NTB) nematogens are investigated. They consist of a three-ring core connected to a phenyl ring via a flexible spacer and displayed enantiotropic nematic and smectic C mesophases. In such systems, odd or even number of atoms present in the spacer could influence the orientation of the terminal phenyl ring and thus have a bearing on designing the NTB phase, considered as intermediate between the nematic and the cholesteric phases. One-dimensional (1D) and two-dimensional (2D) 13C NMR spectra have been recorded in the liquid crystalline phases and the alignment-induced chemical shifts (AIS) and the 13C-1H dipolar couplings obtained. The order parameters of the phenyl rings reveal features relatable to the odd/even number of atoms of the flexible spacer and the type of linkage. The AIS plots of the phenyl rings of the even spacer-based mesogen showed the usual behavior for all of the phenyl rings with a decrease in AIS with increasing temperature. However, for the odd-spacer mesogens, unusual behaviors are noted for the terminal phenyl ring. Thus, two of the mesogens showed an increase of AIS in the smectic C phase that continued till the middle of the nematic phase temperature range, followed by a decrease. The other two odd-spacer mesogens also showed different behaviors. These observations indicate that the terminal phenyl ring is oriented at an angle with respect to the long molecular axis for the odd-spacer mesogens that changes as a function of temperature. The angles have been found to depend on the nature of the atom/group connecting the spacer to the terminal ring and the spacer length. Thus, the present study provides critical information on the design of the odd dimers that are recognized to generate fascinating NTB mesophases.

Direct method to grasp molecular topology of mesogens through 13C-1H dipolar couplings.

A prime factor in determining liquid crystalline phase formation is the overall molecular shape since molecules undergo rotational motion about the long axis. Molecular topology deals with the connectivity of atomic centers in a given molecular architecture, ultimately giving rise to the gross molecular shape. 13C NMR has emerged as the most important technique in establishing the molecular topology of mesogens in the liquid crystalline phase. In this work, we demonstrate the utility of 13C-1H dipolar couplings determined from 2D separated local field NMR for finding the topology of three different mesogens in the liquid crystalline phase. The core unit of the investigated mesogens fundamentally differs, which may be categorized as rod-like, laterally substituted, and bent-core shapes. 1D and 2D 13C NMR measurements in the liquid crystalline phase revealed fascinating information. The 13C-1H dipolar couplings extracted from 2D NMR are found to be sensitive to topologically variant core units. This permitted us to establish the molecular topology just by looking at the 13C-1H dipolar couplings of the protonated carbons of the constituent phenyl rings. By considering the dipolar couplings of rod-like mesogens as a reference, the large variation in the magnitude of 13C-1H dipolar couplings of the laterally substituted and bent-core mesogens is attributed to changes in the topology of their core units. The order parameters estimated from 13C-1H dipolar couplings enabled visualization of the ordering array of phenyl rings of the mesogens. Interestingly large 13C-1H dipolar couplings are observed for mesogens in which (a) laterally located phenyl ring and (b) central phenyl ring of bent-core mesogens exhibited different trends as revealed by the orientational order parameters.

Leaning induced layer undulated tilted smectic phase of asymmetric bent-core liquid crystals.

We report the synthesis and experimental studies on the liquid crystalline phase of a homologous series of compounds comprised of strongly asymmetric bent-core banana shaped molecules. Our x-ray diffraction studies clearly indicate that the compounds exhibit a frustrated tilted smectic phase with layer undulated structure. The low value of the dielectric constant as well as switching current measurements indicate the absence of polarization in this layer undulated phase. In spite of the absence of polarization, a planar aligned sample can be transformed irreversibly to a higher birefringent texture on the application of a high electric field. The zero field texture can only be retrieved by heating the sample to the isotropic phase and cooling it subsequently to the mesophase. We propose a double tilted smectic structure having layer undulation to account for the experimental observations with the layer undulation arising due to the leaning of the molecules in the layer.

Eosinophilic Meningitis and Intraocular Infection Caused by Dirofilaria sp. Genotype Hongkong.

Eosinophilic meningitis caused by human diroflarial infection is rare. We report a case of eosinophilic meningitis and concomitant intraocular dirofilarial infection in India. Sequencing of the mitochondrial genome identified the worm as Dirofilaria sp. genotype Hongkong, a close relative of D. repens nematodes.

Strikingly different molecular organization and molecular order of tetracatenar mesogens in columnar mesophases revealed by XRD and 13C NMR.

For a successful design of functional mesogens, it is paramount to understand factors that contribute to molecular organisation such as molecular shape, the non-covalent interactions of the constituent moieties as well as nanosegregation of incompatible molecular parts. In this study on four tetracatenar mesogens, we show that by a slight change in the length of the terminal chain, the molecular organization changes from lamellar to columnar phase and that the orientational order experiences profound change between the lamellar, the center rectangular columnar and the hexagonal columnar mesophases. We consider here, mesogens that exhibit lamellar and columnar mesophases with five phenyl rings in the central rod-like core which are subjected to XRD and high resolution solid state 13C NMR investigations in their mesophases. The XRD studies indicate that the lower homologs exhibit a lamellar mesophase while the higher homologs show either a centre rectangular columnar phase or a 2D hexagonal columnar mesophase. 13C NMR investigations reveal interesting and strikingly different molecular orientations in each of these phases. For example, values of order parameters of one of the phenyl rings in the core region of the mesogens vary from 0.75 and 0.77 for the lamellar mesogens to 0.45 and 0.17 for the centre rectangular columnar and the hexagonal columnar mesogens respectively. While these values indicate that the mesogenic molecules are oriented along the magnetic field as expected in the lamellar phases, the very low order parameter in the hexagonal columnar phase arises due to molecules distributed azimuthally in layers and undergoing motion about the columnar axis which itself is oriented orthogonal to the magnetic field. Such cutting edge information extracted from the combined use of XRD and 13C NMR studies on tetracatenar mesogens is expected to be of significant use for the study of π-conjugated polycatenar systems where functional properties depend on the molecular orientation and order.

Pseudo-polar tilted smectic phases exhibited by bent-core hockey stick shaped molecules.

We report experimental and theoretical studies on two new achiral fluid lamellar phases exhibited by bent-core hockey stick shaped molecules. The packing of these bent-core hockey stick shaped molecules in the layers leads to a pseudo-polar order in these tilted smectic phases. An anticlinic SmCA type stacking of the pseudo-polar layers is observed in the higher temperature smectic phase, while in the lower temperature phase the difference in the azimuthal angles of the tilt directions in successive layers is between zero and π with a randomized tilt organization between the successive layers. The randomness arises due to the sign degeneracy of the azimuthal angle difference of the tilt directions in successive layers. Both of these smectic phases show a strong electro-optic response which can be exploited for potential applications.

Monolayer to interdigitated partial bilayer smectic C transition in thiophene-based spacer mesogens: X-ray diffraction and (13)C nuclear magnetic resonance studies.

Mesophase organization of molecules built with thiophene at the center and linked via flexible spacers to rigid side arm core units and terminal alkoxy chains has been investigated. Thirty homologues realized by varying the span of the spacers as well as the length of the terminal chains have been studied. In addition to the enantiotropic nematic phase observed for all the mesogens, the increase of the spacer as well as the terminal chain lengths resulted in the smectic C phase. The molecular organization in the smectic phase as investigated by temperature dependent X-ray diffraction measurements revealed an interesting behavior that depended on the length of the spacer vis-a-vis the length of the terminal chain. Thus, a tilted interdigitated partial bilayer organization was observed for molecules with a shorter spacer length, while a tilted monolayer arrangement was observed for those with a longer spacer length. High-resolution solid state (13)C NMR studies carried out for representative mesogens indicated a U-shape for all the molecules, indicating that intermolecular interactions and molecular dynamics rather than molecular shape are responsible for the observed behavior. Models for the mesophase organization have been considered and the results understood in terms of segregation of incompatible parts of the mesogens combined with steric frustration leading to the observed lamellar order.

Structural investigation of resorcinol based symmetrical banana mesogens by XRD, NMR and polarization measurements.

Synthesis and structural characterization of two novel symmetrical banana mesogens built from resorcinol with seven phenyl rings linked by ester and imine with a terminal dodecyl/dodecyloxy chain has been carried out. Density functional theory (DFT) has been employed for obtaining the geometry optimized structures, the dipole moments and (13)C NMR chemical shifts. The HOPM and DSC studies revealed enantiotropic B2 and B7 phases for the dodecyl and dodecyloxy homologs respectively. The powder X-ray studies of both the mesogens indicate the presence of layer ordering. The polarization measurements reveal an anti-ferroelectric switching for the B2 phase of the dodecyl homolog whose structure has been identified as SmCSPA. The B7 phase of the dodecyloxy homolog was found to be non-switchable. High resolution (13)C NMR study of the dodecyl homolog in its mesophase has been carried out. (13)C-(1)H dipolar couplings obtained from the 2-dimensional separated local field spectroscopy experiment were used to obtain the orientational order parameters of the different segments of the mesogen. Very large (13)C-(1)H dipolar couplings observed for the carbons of the central phenyl ring (9.7-12.3 kHz) in comparison to the dipolar couplings of those of the side arm phenyl rings (less than 3 kHz) are a direct consequence of the ordering in the banana phase and the shape of the molecule. From the ratio of the local order parameter values, the bent-angle of the mesogen could be determined in a straight forward manner to be 120.5°.

Effect of smectic short-range order on the discontinuous anchoring transition in nematic liquid crystals.

We report studies on the temperature dependent alignment behavior of a homologous series of trans, trans- 4, 4'-dialkyl-(1α,1' α-bicyclohexyl)-4ß-carbonitrile (CCNs) on a perfluoropolymer coated cells. Among six compounds in the series, one (CCN-35) has only nematic phase and the remaining five have either smectic-A or smectic-B in addition to the nematic phase. We simultaneously performed temperature dependent dielectric measurements and optical polarising microscope observation. It is found that except for CCN-35 and CCN-73, the remaining four compounds exhibit discontinuous anchoring transition from planar to homeotropic and vice versa with increasing thermal hysteresis. We developed a simple theory taking into account the effect of smectic short-range order at the substrates to explain the experimental observations.

Glassy relaxation in a de Vries smectic liquid crystal consisting of bent-core molecules.

We report experimental investigations of a liquid crystal comprising thiophene-based achiral bent-core banana shaped molecules. The compound exhibits the following phase sequence on cooling: Isotropic (517.4 K), N (514.9 K), de Vries SmA (402 K), SmC. Practically no layer contraction was observed across the SmA to SmC transition, confirming the "de Vries" nature of the SmA phase. Interestingly, the crystallization does not occur on cooling the sample, unlike most other liquid crystals. Instead, the SmC phase undergoes a glass transition at 271 K even at a slow cooling rate. The dielectric spectroscopy studies carried out on the sample reveal the presence of a dielectric mode whose relaxation process is of the Cole-Cole type. The relaxation frequency of the mode was found to drop rapidly with decreasing temperature, confirming the glassy behavior. The variation of relaxation frequency with temperature follows the Vogel-Fulcher-Tammann equation, indicating the fragile glassy nature of the sample. This report identifies a bent-core liquid crystal exhibiting a "de Vries" SmA phase and glassy behavior at lower temperatures.

Novel Self-assembling Supramolecular Phenanthro[9,10-a]phenazine Discotic Liquid Crystals: Synthesis, Characterization and Charge Transport Studies.

The incorporation of heteroatoms in the chemical structure of organic molecules has been identified as analogous to the doping process adopted in silicon semiconductors to influence the nature of charge carriers. This strategy has been an eye-opener for material chemists in synthesizing new materials for optoelectronic applications. Phenanthro[9,10-a]phenazine-based mesogens have been synthesized via a cyclo-condensation pathway involving triphenylene-based diketones and o-phenyl diamines. The incorporation of phenazine moiety as discussed in this paper, alters the symmetric nature of the triphenylene. The phenanthro[9,10-a]phenazine-based mesogens exhibited hole mobility in the order of 10-4 cm2/Vs as measured by the space-charge limited current (SCLC) technique. The current density in SCLC device increases with increasing temperature which indicates that the charge transport is associated with the thermally activated hopping process. This report attempts to elucidate the self-organization of asymmetric phenanthro[9,10-a] phenazine in the supramolecular liquid crystalline state and their potential for the fabrication of high-temperature optoelectronic devices. However, the low charge carrier mobility can be one of the challenges for device performance.

Idiopathic intracranial hypertension in pediatric population: case series from India.

BACKGROUND: Idiopathic intracranial hypertension (IIH) is a well described entity in adults. In pediatric age group the presentation of disease can vary depending on the age of patients and is less frequently reported. AIM: The aim of this study is to describe the clinical features, investigations, treatment and outcome of IIH in pediatric population (age <18 years). MATERIALS AND METHODS: This retrospective hospital based study was carried out on 25 children with diagnosis of IIH based on modified Dandys criteria. Their clinical, investigation, treatment, outcome and follow-up for 2 year period were analyzed. RESULTS: Out of the 25 children, the youngest child was 4-month-old infant. The commonest symptom was headache (76%) followed by vomiting and papilledema (72%). The mean cerebrospinal fluid (CSF) pressure was 330 mm of H 2 O. In Infants irritability and bulging anterior fontanelle was seen. A total of 24 patients showed a complete resolution of symptom. None of patient had recurrence over a period of 2 years follow-up. CONCLUSION: IIH can present at any age group. This is the largest series of IIH reported in pediatric population in India. The clinical features are similar to adult patients except in infants. Absence of papilledema does not exclude the diagnosis of IIH. CSF pressure monitoring is needed in suspected cases of IIH. Early and prompt treatment can prevent deficits.

Spontaneous breaking of chiral symmetry in achiral bent-core liquid crystals: Excluded volume effect.

Bent-Core banana-shaped molecules exhibit tilted polar smectic phases with macroscopically chiral layer order even though the constituent molecules are achiral in nature. Here, we show that the excluded volume interactions between the bent-core molecules account for this spontaneous breaking of chiral symmetry in the layer. We have numerically computed excluded volume between two rigid bent-core molecules in a layer using two types of model structures of them and explored the different possible symmetries of the layer that are favored by the excluded volume effect. For both model structures of the molecule, the C_{2} symmetric layer structure is favored for most values of tilt and bending angle. However, the C_{s} and C_{1} point symmetries of the layer are also possible for one of the model structures of the molecules. We have also developed a coupled XY-Ising model and performed Monte Carlo simulation to explain the statistical origin of spontaneous chiral symmetry breaking in this system. The coupled XY-Ising model accounts for the experimentally observed phase transitions as a function of temperature and electric field.

Optical Anisotropy and Dimple Formation on Films Formed after Drying of Gelatinized Starch Solution Droplets.

We study the microstructures in the drying droplets of gelatinized starch solutions on a flat substrate. Cryogenic scanning electron microscopy studies on the vertical cross-section of these drying droplets for the first time reveal a relatively thinner solid elastic crust of uniform thickness at the free surface, an intermediate mesh region below the crust, and an inner core of a cellular network structure made of starch nanoparticles. We find that the deposited circular films formed after drying are birefringent and azimuthally symmetric with a dimple at their center. We propose that the dimple formation in our sample occurs due to the evaporation-induced stress on the gel network structure in the drying droplet. The polarizing optical microscopic studies show that these films are optically uniaxial at their center and increasingly biaxial away from the center.

Simple model for self-propulsion of microdroplets in surfactant solution.

We propose a simple active hydrodynamic model for the self-propulsion of a liquid droplet suspended in micellar solutions. The self-propulsion of the droplet occurs by spontaneous breaking of isotropic symmetry and is studied using both analytical and numerical methods. The emergence of self-propulsion arises from the slow dissolution of the inner fluid into the outer micellar solution as filled micelles. We propose that the surface generation of filled micelles is the dominant reason for the self-propulsion of the droplet. The flow instability is due to the Marangoni stress generated by the nonuniform distribution of the surfactant molecules on the droplet interface. In our model, the driving parameter of the instability is the excess surfactant concentration above the critical micellar concentration, which directly correlates with the experimental observations. We consider various low-order modes of flow instability and show that the first mode becomes unstable through a supercritical bifurcation and is the only mode contributing to the swimming of the droplet. The flow fields around the droplet for these modes and their combined effects are also discussed.

Clinical Characteristics and Treatment Outcome of Eosinophilic Meningoencephalitis in South Indian Children: Experience From a Prospective Registry.

BACKGROUND: To describe the clinical features and therapeutic outcomes of a prospective cohort of children with eosinophilic meningoencephalitis. METHODS: Children admitted with clinical features suggestive of meningitis along with cerebrospinal fluid (CSF) eosinophilia during the period of 14 years (2008 to 2021) were included. Their baseline characteristics, epidemiologic associations, and treatment outcomes were analyzed and compared with the previous studies. RESULTS: We identified 25 children (13 males) satisfying the inclusion criteria. The median age at presentation was 3.9 years (range 0.8 to 17 years); 68% were aged less than two years. Fourteen (56%) children had a history of exposure to snails. Most of them presented with fever, headache, irritability, lateral rectus palsy, and early papilledema. Symptoms started three to 42 days (median duration: 14 days) before admission to our center. All children had peripheral eosinophilia, which ranged from 9% to 41%. The mean CSF white blood cell count was 416/mm3 (range 50 to 1245 cells/mm3) with CSF eosinophilia ranging from 11% to 80%. Brain magnetic resonance imaging was done in 24 children and was normal in 15 (62.5%). Leptomeningeal enhancement was seen in two (8.3%) children, and other nonspecific changes were noted in seven (29.1%) children. All children recovered without any neurological deficits with a standard treatment regimen of albendazole and oral steroids. All were asymptomatic at the last follow-up. None of them had any recurrence during the follow-up period. CONCLUSION: We report one of the largest clinical series of children with eosinophilic meningoencephalitis from an endemic area of South India.

Age-related changes in the gut melatonin levels and its possible role in the regulation of feeding and digestibility, with the development of the gut from fingerling to adult stages of carp, Catla catla.

The present study aims to understand the feeding-related age-bound changes in gut histoarchitecture and its response to gut melatonin (GM) titer regulating major digestive enzymes in carp, Catla catla. Therefore, gut samples were collected from different growth stages of carp, viz. (i) fingerling (FL), body weight (BW) ≥ 3 g to ≤ 20 g; (ii) advanced fingerling (AFL), BW > 20 g to ≤ 40 g; (iii) early juvenile (EJv), BW > 40 g to ≤ 70 g; (iv) juvenile (Jv), BW > 70 g to ≤ 200 g; (v) late juvenile (LJv), BW > 200 g to ≤ 300 g; (vi) preadult (PA), BW > 300 g to ≤ 500 g; (vii) subadult (SA), BW > 500 g to ≤ 1.00 kg; and (viii) adult (AD), BW > 1 kg to ≤ 2.5 kg. Data analysis revealed that the highest titer of GM was noted in FL, moderate in AFL, Jv, and PA, lower in EJv, SA, and AD, and lowest in LJv. Results depicted a negative correlation between the development of the gut and its melatonin content. Moreover, GM was positively associated with feeding intensity and gastro-somatic index (GaSI) and negatively related to ovarian onset and development. Following correlation and principal component analysis, several pieces of evidence were recorded on the role of gut melatonin in regulating digestive physiology. Finally, it indicates that gut melatonin has a progressively influential role in improving digestion, particularly protein and microbial digestion, with the development of an adult gut from the fingerling stage.

Novel biallelic variants expand the SLC5A6-related phenotypic spectrum.

The sodium (Na+):multivitamin transporter (SMVT), encoded by SLC5A6, belongs to the sodium:solute symporter family and is required for the Na+-dependent uptake of biotin (vitamin B7), pantothenic acid (vitamin B5), the vitamin-like substance α-lipoic acid, and iodide. Compound heterozygous SLC5A6 variants have been reported in individuals with variable multisystemic disorder, including failure to thrive, developmental delay, seizures, cerebral palsy, brain atrophy, gastrointestinal problems, immunodeficiency, and/or osteopenia. We expand the phenotypic spectrum associated with biallelic SLC5A6 variants affecting function by reporting five individuals from three families with motor neuropathies. We identified the homozygous variant c.1285 A > G [p.(Ser429Gly)] in three affected siblings and a simplex patient and the maternally inherited c.280 C > T [p.(Arg94*)] variant and the paternally inherited c.485 A > G [p.(Tyr162Cys)] variant in the simplex patient of the third family. Both missense variants were predicted to affect function by in silico tools. 3D homology modeling of the human SMVT revealed 13 transmembrane helices (TMs) and Tyr162 and Ser429 to be located at the cytoplasmic facing region of TM4 and within TM11, respectively. The SLC5A6 missense variants p.(Tyr162Cys) and p.(Ser429Gly) did not affect plasma membrane localization of the ectopically expressed multivitamin transporter suggesting reduced but not abolished function, such as lower catalytic activity. Targeted therapeutic intervention yielded clinical improvement in four of the five patients. Early molecular diagnosis by exome sequencing is essential for timely replacement therapy in affected individuals.