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Synthesis of micro- and nanoparticles of pre-designed shape and surface properties is an integral part of soft and synthetic active matter. We report synthesis of matchstick-shaped (MS) magnetodielectric particles and demonstrate their potential as active agents with field-controllable trajectories in a nematic liquid crystal (NLC). The MS particles with homeotropic anchoring in NLCs align either parallel or perpendicular to the director depending on the dipolar or quadrupolar director distortions. When subjected to transverse electric and magnetic fields, the particles experience electric and magnetic torques trying to align them in the respective field directions. At equilibrium, the long axis is tilted at an angle with respect to the director. The change in orientation alters the surrounding elastic distortion, which results in unbalanced electroosmotic flows. These flows provide the necessary impetus for propelling the particles in various directions with different velocities depending on their orientations.
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We study the electrophoresis of metal-dielectric Janus particles with dipolar director symmetry in two nematic liquid crystals (LCs) having the same sign of conductivity anisotropy (Δσ) but opposite signs of dielectric anisotropy (Δε). The applied ac electric field is parallel and perpendicular to the director for positive and negative dielectric anisotropy LCs, respectively. We show that the Janus dipolar particles propel faster than the non-Janus dipolar particles in both LCs. The propelling speed of the Janus dipolar particles is also significantly higher compared to the quadrupolar Janus particles studied previously. We map the electroosmotic flow fields surrounding a Janus dipolar particle using microparticle image velocimetry (µ-PIV) and show that the flow on a metal hemisphere is stronger than that on a dielectric hemisphere. Altogether, Janus dipolar particles demonstrate efficient electrophoresis compared to both Janus and non-Janus quadrupolar particles. These findings may be useful for applications in active matter, microrobotic and microfluidic devices.
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We study DC and AC electrophoresis of silica nano and microrods in a thin film of a nematic liquid crystal. These particles induce virtual topological defects and demonstrate nontrivial electrophoresis. We measure several electrophoretic mobility coefficients and compare with those calculated theoretically. We demonstrate a competing effect of elastic and electrostatic torques that arises due to tilting of the rods in the liquid crystal. A simple theory describing this effect allows us to measure the effective polarisability of the rods. Our approach is simple and applicable to a wide variety of asymmetric and polarisable particles.
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Recently, an unprecedented observation of polar order, thermochromic behavior, and exotic mesophases in new chiral, bent-shaped systems with a -CH3 moiety placed at the transverse position of the central core was reported. Herein, a homologous series of compounds with even-numbered carbon chains from n=4 to 18 were synthesized, in which -Cl was substituted for -CH3 at the kink position and a drastic modification in the phase structure of the bent-shaped molecule was observed. An unusual stabilization of the cubic blue phase (BP) over a wide range of 16.4 °C has been witnessed. Two homologues in this series (1-12 and 1-14) exhibit an interesting phase sequence consisting of BPI/II, chiral nematic, twist grain boundary, smecticâ A, and smecticâ X (SmX) phases. The higher homologues (1-16 and 1-18) stabilize the SmX phase enantiotropically over the entire temperature range. Crystal structure analysis confirmed the bent molecular architecture, with a bent angle of 148°, and revealed the presence of two different molecular conformations in an asymmetric unit of compound 1-4. A DFT study corroborated that the -Cl moiety at the central core of the molecule led to an increase in the dipole moment along the transverse direction, which, in turn, facilitated the unusual stabilization of frustrated structures. Crystal polymorphism has been evidenced in three homologues (1-10, 1-12, and 1-14) of the series. On the application of mechanical pressure through grinding, compound 1-10 transformed from a bright yellow crystalline solid to a dark orange-green amorphous solid, which reversed upon dropwise addition of dichloromethane, indicating reversible mechanochromism in this class of compounds. In addition, excellent thermochromic behavior has been observed for compound 1-10 with a controlled temperature-color combination.
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Many bent-core nematic liquid crystals exhibit unusual physical properties due to the presence of smectic clusters, known as "cybotactic" clusters, in the nematic phase. Here, we investigate the effect of these clusters on the complex shear modulus (G*(ω)) of two asymmetric bent-core liquid crystals using a microrheological technique. The compound with a shorter hydrocarbon chain (8OCH3) exhibits only a nematic (N) phase whereas the compound with a longer chain (16OCH3) exhibits both nematic (N) and smectic-A (SmA) phases. The rheological results are correlated with the measurements of curvature elastic constants. Our results show that the directional shear modulus of 16OCH3, just above the SmA to N phase transition temperature, is strikingly different than that of 8OCH3, owing to the smectic clusters. An approximate size of the clusters is estimated using a simple model. Therefore, microrheological studies on bent-core nematic liquid crystals are very useful in extracting information about underlying smectic clusters.
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In recent years, investigation on the non-display applications of liquid crystals has increased considerably. One of the emerging applications is whispering gallery mode (WGM) lasing. Here, we report experimental studies on the morphology and WGM lasing in nematic (N), smectic-A (SmA) and smectic-C (SmC) microdroplets dispersed in a highly transparent and low refractive index perfluopolymer. The mesomorphic microdroplets, obtained by varying the temperature, exhibit radial director configuration. The SmA microdroplets are found to be highly stable and robust against mechanical stress compared to the N and SmC microdroplets. We study lasing properties such as intensity, threshold pump energy and linewidth, and show that overall the SmA microdroplets are superior to the N and SmC microdroplets. The experimental results are discussed based on the orientation of the dye molecules, director fluctuations and tilting at the interface.
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We report magnetic field tuning of the structure and Whispering Gallery Mode lasing from ferromagnetic nematic liquid crystal micro-droplets. Microlasers were prepared by dispersing a nematic liquid crystal, containing magnetic nanoparticles and fluorescent dye, in a glycerol-lecithin matrix. The droplets exhibit radial director structure, which shows elastic distortion at a very low external magnetic field. The fluorescent dye doped ferromagnetic nematic droplets show Whispering Gallery Mode lasing, which is tunable by the external magnetic field. The tuning of the WGM lasing modes is linear in magnetic field with a wavelength-shift of the order of 1 nm/100 mT. Depending on the lasing geometry, the WGMs are red- or blue-shifted.
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The design and synthesis of three room-temperature discotic nematic (ND ) liquid crystals (LCs) is presented. The LC consists of an azobenzene core attached to which are four pentaalkynylbenzene (PA) units through flexible alkyl spacers. The presence of a short azo linking group provides more disorder in the system, thereby reducing the packing efficiency among the PA units and resulting into the formation of a room-temperature ND phase over a wide temperature range. Dielectric constant and birefringence studies were performed to gain further insights into the physical properties of the mesophase.
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We report experimental studies on 2D colloidal crystals of dimers stabilized by vortex-like defects in planar nematic and π/2 twisted nematic cells. The dimers are prepared and self-assembled using a laser tweezer. We study the effect of temperature and electric field on the lattice parameters of the colloidal crystals. The lattice parameters vary with the temperature in the nematic phase and a discontinuous structural change is observed at the nematic to smectic-A phase transition. In the nematic phase, we observed a large change in the lattice parameters (≃30%) by applying an external electric field perpendicular to the plane of the 2D crystals. The idea and the active control of the lattice parameters could be useful for designing tunable colloidal crystals.
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Correction for 'Experimental studies on the rheology of cubic blue phases' by Rasmita Sahoo et al., Soft Matter, 2016, DOI: .
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We report detailed experimental studies on the rheology of cubic blue phases. We observe several flow regimes within each blue phase from rheomicroscopy and small angle light scattering experiments. Both the cubic blue phases exhibit solid-like response while the cholesteric phase shows gel-like behavior. The elastic modulus of BP-I is larger than that of BP-II. The shear induced yield transition occurs at a higher strain in BP-II than BP-I. Both the blue phases show stress relaxation through periodic modulation in step-strain experiments. Our results show that the rheological responses of these two phases are significantly different owing to the distinct networks of defect-disclinations.
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We report the first experimental studies on the temperature dependence of viscoelastic properties of a room temperature discotic nematic liquid crystal. The splay elastic constant is greater than the bend elastic constant and both show unusual temperature and order parameter dependence. The rotational viscosity is remarkably larger than conventional calamitic liquid crystals. We provide a simple physical explanation based on the columnar short-range order to account for the the unusual temperature dependence of the elastic constants.
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Colloidal self-assembly has been one of the major driving themes in material science to obtain functional and advanced optical materials with complex architecture. Most of the nematic colloids reported so far are based on the optically isotropic spherical microparticles. We study organic single crystal micro-sheets and investigate their orientation, interaction and directed assembly in a nematic liquid crystal. The micro-sheets induce planar surface anchoring of the liquid crystal. The elasticity mediated pair interaction of micro-sheets shows quadrupolar characteristics. The average orientation angle of the micro-sheets in a planar cell and the angle between two micro-sheets in a homeotropic cell are supported by the Landau-de Gennes Q-tensor modeling. The self-assembly of the micro-sheets is assisted by a laser tweezer to form larger two-dimensional structures which have the potential for application of colloids in photonics.
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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.
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Twist-bend (N_{tb}) and ferroelectric (N_{F}) nematic liquid crystals exhibit several novel effects and new physical properties. Here, we report experimental studies on the phase diagram and some physical properties of binary mixtures of CB9CB and RM734 mesogens. Both N-N_{tb} and N-N_{F} phase transition temperatures and the corresponding enthalpies decrease significantly and, eventually, these transitions disappear at some intermediate compositions, stabilizing wide nematic phase (N). Temperature-dependent birefringence several degrees above the N-N_{tb} phase transition shows strong director tilt fluctuations. The critical range of the fluctuations increases with the nematic range and the critical exponent is consistent with the mean field. The spontaneous polarization of RM734 decreases drastically with the addition of CB9CB mesogen. The temperature dependence of the splay elastic constant of the mixtures' high-temperature nematic (N) phase strikingly differs from that of the pristine CB9CB and RM734 mesogens. The study shows that a small inclusion of either compound has a substantial effect on the phase diagram and physical properties.
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Pancreatic ductal adenocarcinoma (PDAC) is a highly lethal malignancy that harbors mutations in homologous recombination-repair (HR-repair) proteins in 20%-25% of cases. Defects in HR impart a specific vulnerability to poly ADP ribose polymerase inhibitors and platinum-containing chemotherapy in tumor cells. However, not all patients who receive these therapies respond, and many who initially respond ultimately develop resistance. Inactivation of the HR pathway is associated with the overexpression of polymerase theta (Polθ, or POLQ). This key enzyme regulates the microhomology-mediated end-joining (MMEJ) pathway of double-strand break (DSB) repair. Using human and murine HR-deficient PDAC models, we found that POLQ knockdown is synthetically lethal in combination with mutations in HR genes such as BRCA1 and BRCA2 and the DNA damage repair gene ATM. Further, POLQ knockdown enhances cytosolic micronuclei formation and activates signaling of cyclic GMP-AMP synthase-stimulator of interferon genes (cGAS-STING), leading to enhanced infiltration of activated CD8+ T cells in BRCA2-deficient PDAC tumors in vivo. Overall, POLQ, a key mediator in the MMEJ pathway, is critical for DSB repair in BRCA2-deficient PDAC. Its inhibition represents a synthetic lethal approach to blocking tumor growth while concurrently activating the cGAS-STING signaling pathway to enhance tumor immune infiltration, highlighting what we believe to be a new role for POLQ in the tumor immune environment.
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Adenocarcinoma , Neoplasias Pancreáticas , Humanos , Animais , Camundongos , Adenocarcinoma/tratamento farmacológico , Adenocarcinoma/genética , Quebras de DNA de Cadeia Dupla , Linhagem Celular Tumoral , Neoplasias Pancreáticas/tratamento farmacológico , Neoplasias Pancreáticas/genética , Nucleotidiltransferases/genética , Nucleotidiltransferases/metabolismo , Recombinação Homóloga , Transdução de Sinais , Imunidade , Neoplasias PancreáticasRESUMO
The tumor microenvironment (TME) in pancreatic ductal adenocarcinoma (PDAC) is a complex ecosystem that drives tumor progression; however, in-depth single cell characterization of the PDAC TME and its role in response to therapy is lacking. Here, we perform single-cell RNA sequencing on freshly collected human PDAC samples either before or after chemotherapy. Overall, we find a heterogeneous mixture of basal and classical cancer cell subtypes, along with distinct cancer-associated fibroblast and macrophage subpopulations. Strikingly, classical and basal-like cancer cells exhibit similar transcriptional responses to chemotherapy and do not demonstrate a shift towards a basal-like transcriptional program among treated samples. We observe decreased ligand-receptor interactions in treated samples, particularly between TIGIT on CD8 + T cells and its receptor on cancer cells, and identify TIGIT as the major inhibitory checkpoint molecule of CD8 + T cells. Our results suggest that chemotherapy profoundly impacts the PDAC TME and may promote resistance to immunotherapy.
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Adenocarcinoma , Carcinoma Ductal Pancreático , Neoplasias Pancreáticas , Humanos , Neoplasias Pancreáticas/tratamento farmacológico , Neoplasias Pancreáticas/genética , Neoplasias Pancreáticas/patologia , Adenocarcinoma/tratamento farmacológico , Adenocarcinoma/genética , Adenocarcinoma/patologia , Microambiente Tumoral/genética , Ecossistema , Carcinoma Ductal Pancreático/tratamento farmacológico , Carcinoma Ductal Pancreático/genética , Carcinoma Ductal Pancreático/patologia , Análise de Sequência de RNA , Neoplasias PancreáticasRESUMO
"de Vries" liquid crystals, defined by a maximum layer shrinkage of ≤1% from the smectic A to C phase transition, are an integral component of ferroelectric liquid crystal (FLC) displays. Bona fide de Vries materials described in the literature are primarily perfluorinated, polysiloxane and polysilane-terminated rod-like (or calamitic) LCs. Herein, for the first time, we report a series of newly designed achiral unsymmetrical bent-core molecules with terminal alkoxy chains exhibiting similar properties to "de Vries" LCs. The new molecular structure is based on the systematic distribution of four phenyl rings attached via ester and imine linkers having 3-amino-2-methylbenzoic acid as the central core with a bent angle of 147°. Detailed microscopic investigations in differently aligned (planar as well as homeotropic) cells along with SAXS/WAXS studies revealed that the materials exhibited a SmA-SmC phase sequence along with the appearance of the nematic phase at higher temperatures. SAXS measurements divulged the layer spacings (d-spacings) and hence, the layer shrinkage was calculated ranging from 0.19% to 0.68% just below the SmA-SmC transition. The variation of the calculated molecular tilt angle (α) derived from the temperature-dependent SAXS data, followed the power law with exponent values 0.29 ± 0.01 and 0.25 ± 0.01 for compounds 1/10 and 1/12, respectively. The experimental values obtained were very close to the theoretically predicted values for the materials with de Vries-like properties. The analysis of temperature-dependent birefringence studies based on the prediction of the Landau theory, showed a dip across the SmA-SmC phase transition typical of compounds exhibiting the de Vries characteristics. The collective results obtained suggest "de Vries" SmA as a probable model for this bent-core system which may find applications in displays.
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Spin-lattice relaxation rates (R(1H) and R(1F)) of two nuclear species ((1)H and (19)F) are measured at different temperatures in the isotropic phase of a liquid crystal (4(')-butoxy-3(')-fluoro-4-isothiocyanatotolane-4OFTOL), over a wide range of Larmor frequency (10 kHz-50 MHz). Their dispersion profiles are found to be qualitatively very different, and the R(1F) in particular shows significant dispersion (varying over two orders of magnitude) in the entire isotropic range, unlike R(1H). The proton spin-lattice relaxation, as has been established, is mediated by time modulation of magnetic dipolar interactions with other protons (case of like spins), and the discernable dispersion in the mid-frequency range, observed as the isotropic to nematic transition is approached on cooling, is indicative of the critical slowing of the time fluctuations of the nematic order. Significant dispersion seen in the R(1F) extending to very low frequencies suggests a distinctly different relaxation path which is exclusively sensitive to the ultra slow modes apparently present in the system. We find that under the conditions of our experiment at low Zeeman fields, spin-rotation coupling of the fluorine with the molecular angular momentum is the dominant mechanism, and the observed dispersion is thus attributed to the presence of slow torques experienced by the molecules, arising clearly from collective modes. Following the arguments advanced to explain similar slow processes inferred from earlier detailed ESR measurements in liquid crystals, we propose that slowly relaxing local structures representing such dynamic processes could be the likely underlying mechanism providing the necessary slow molecular angular momentum correlations to manifest as the observed low frequency dispersion. We also find that the effects of the onset of cross-relaxation between the two nuclear species when their resonance lines start overlapping at very low Larmor frequencies (below ~400 kHz), provide an additional relaxation contribution.
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We study the pair interaction of charged silica microrods in chiral nematic liquid crystals and show that the microrods with homeotropic surface anchoring form a bound state due to the competing effect of electrostatic (Coulomb) and elastic interactions. The robustness of the bound state is demonstrated by applying external electrical and mechanical forces that perturbs their equilibrium position as well as orientation. In the bound state we have measured the correlated thermal fluctuations of the position, using two-particle cross-correlation spectroscopy that uncovers their hydrodynamic interaction. These findings reveal unexplored aspects of liquid-crystal dispersions which are important for understanding the assembly and dynamics of nano- and microparticles in chiral nematic liquid crystals.