Bulk photovoltaic effect in ferroelectric nematic liquid crystals.

The bulk photovoltaic (BPV) effect in ferroelectric liquid crystals is of increasing scientific interest owing to its great potential for light-energy conversion. The ferroelectric nematic phase exhibits a huge spontaneous polarization that can be aligned to a preferred direction. In this Letter, we investigate the tensorial properties of the BPV effect in the planarly aligned ferroelectric nematic phase of the liquid crystalline material RM734. A steady-state short-circuit photocurrent of ~160 pA and an open-circuit photovoltage of ~50 mV were observed in a cell with a thickness of 5.5 µm under the illumination of ultraviolet light without any bias voltage. Based on the photocurrent measurements in different electrode configurations, the non-zero elements of the BPV tensor were obtained. The BPV effect is attributed to the combination of the spontaneous polarization and the asymmetric distribution of photoinduced charge carriers. This study not only provides an understanding of the bulk PV mechanism in soft ferroelectrics but also promises a wide range of unprecedented, to the best of our knowledge, benefits for light harvesting to engineer marketable photovoltaic devices.

Dynamically tunable lamellar surface structures from magnetoactive elastomers driven by a uniform magnetic field.

Stimuli responsive materials are key ingredients for any application that requires dynamically tunable or on-demand responses. In this work we report experimental and theoretical investigation of magnetic-field driven modifications of soft-magnetic elastomers whose surface was processed by laser ablation into lamellar microstructures that can be manipulated by a uniform magnetic field. We present a minimal hybrid model that elucidates the associated deflection process of the lamellae and explains the lamellar structure frustration in terms of dipolar magnetic forces arising from the neighbouring lamellae. We experimentally determine the magnitude of the deflection as a function of magnetic flux density and explore the dynamic response of lamellae to fast changes in a magnetic field. A relationship between the deflection of lamellae and modifications of the optical reflectance of the lamellar structures is resolved.

GC ends control topology of DNA G-quadruplexes and their cation-dependent assembly.

GCn and GCnCG, where n = (G2AG4AG2), fold into well-defined, dimeric G-quadruplexes with unprecedented folding topologies in the presence of Na+ ions as revealed by nuclear magnetic resonance spectroscopy. Both G-quadruplexes exhibit unique combination of structural elements among which are two G-quartets, A(GGGG)A hexad and GCGC-quartet. Detailed structural characterization uncovered the crucial role of 5'-GC ends in formation of GCn and GCnCG G-quadruplexes. Folding in the presence of 15NH4+ and K+ ions leads to 3'-3' stacking of terminal G-quartets of GCn G-quadruplexes, while 3'-GC overhangs in GCnCG prevent dimerization. Results of the present study expand repertoire of possible G-quadruplex structures. This knowledge will be useful in DNA sequence design for nanotechnological applications that may require specific folding topology and multimerization properties.

Supramolecular Polymorphism of (G4C2)n Repeats Associated with ALS and FTD.

Guanine-rich DNA sequences self-assemble into highly stable fourfold structures known as DNA-quadruplexes (or G-quadruplexes). G-quadruplexes have furthermore the tendency to associate into one-dimensional supramolecular aggregates termed G-wires. We studied the formation of G-wires in solutions of the sequences d(G4C2)n with n = 1, 2, and 4. The d(G4C2)n repeats, which are associated with some fatal neurological disorders, especially amyotrophic lateral sclerosis (ALS) and frontotemporal dementia (FTD), represent a challenging research topic due to their extensive structural polymorphism. We used dynamic light scattering (DLS) to measure translational diffusion coefficients and consequently resolve the length of the larger aggregates formed in solution. We found that all three sequences assemble into longer structures than previously reported. The d(G4C2) formed extremely long G-wires with lengths beyond 80 nm. The d(G4C2)2 formed a relatively short stacked dimeric quadruplex, while d(G4C2)4 formed multimers corresponding to seven stacked intramolecular quadruplexes. Profound differences between the multimerization properties of the investigated sequences were also confirmed by the AFM imaging of surface films. We propose that π-π stacking of the basic G-quadruplex units plays a vital role in the multimerization mechanism, which might be relevant for transformation from the regular medium-length to disease-related long d(G4C2)n repeats.

Intercellular Bridge Mediates Ca2+ Signals between Micropatterned Cells via IP3 and Ca2+ Diffusion.

Intercellular bridges are plasma continuities formed at the end of the cytokinesis process that facilitate intercellular mass transport between the two daughter cells. However, it remains largely unknown how the intercellular bridge mediates Ca2+ communication between postmitotic cells. In this work, we utilize BV-2 microglial cells planted on dumbbell-shaped micropatterned assemblies to resolve spatiotemporal characteristics of Ca2+ signal transfer over the intercellular bridges. With the use of such micropatterns, considerably longer and more regular intercellular bridges can be obtained than in conventional cell cultures. The initial Ca2+ signal is evoked by mechanical stimulation of one of the daughter cells. A considerable time delay is observed between the arrivals of passive Ca2+ diffusion and endogenous Ca2+ response in the intercellular-bridge-connected cell, indicating two different pathways of the Ca2+ communication. Extracellular Ca2+ and the paracrine pathway have practically no effect on the endogenous Ca2+ response, demonstrated by application of Ca2+-free medium, exogenous ATP, and P2Y13 receptor antagonist. In contrast, the endoplasmic reticulum Ca2+-ATPase inhibitor thapsigargin and inositol trisphosphate (IP3) receptor blocker 2-aminoethyl diphenylborate significantly inhibit the endogenous Ca2+ increase, which signifies involvement of IP3-sensitive calcium store release. Notably, passive Ca2+ diffusion into the connected cell can clearly be detected when IP3-sensitive calcium store release is abolished by 2-aminoethyl diphenylborate. Those observations prove that both passive Ca2+ diffusion and IP3-mediated endogenous Ca2+ response contribute to the Ca2+ increase in intercellular-bridge-connected cells. Moreover, a simulation model agreed well with the experimental observations.

Multifunctional and tunable trigate graphene metamaterial with "Lakes of Wada" topology.

Many plasmon-induced transparency (PIT) metamaterials previously reported had limited functions. Their tunabilities were realized by complex discrete structures, which greatly increased the difficulty and cost of device fabrication and adversely affected their resonance characteristics. It is an open question to adjust the Fermi levels of many graphene patterns with only a few in-plane electrodes. We propose and numerically study a novel electrically tunable and multifunctional trigate graphene metamaterial (TGGM) based on the concept of "Lakes of Wada". Benefiting from the trigate regulation, our proposed TGGM turns out to exhibit excellent characteristics, that can not only be used for terahertz band-stop filter, terahertz refractive index sensor, near-field optical switch, slow-light device, but also for double PIT window metamaterial with broad transparency windows and large tunable frequency range.

Ferroelectric-Ferroelastic Phase Transition in a Nematic Liquid Crystal.

Ferroelectric ordering in liquids is a fundamental question of physics. Here, we show that ferroelectric ordering of the molecules causes the formation of recently reported splay nematic liquid-crystalline phase. As shown by dielectric spectroscopy, the transition between the uniaxial and the splay nematic phase has the characteristics of a ferroelectric phase transition, which drives an orientational ferroelastic transition via flexoelectric coupling. The polarity of the splay phase was proven by second harmonic generation imaging, which additionally allowed for determination of the splay modulation period to be of the order of 5-10 microns, also confirmed by polarized optical microscopy. The observations can be quantitatively described by a Landau-de Gennes type of macroscopic theory.

Microfluidic assemblies designed for assessment of drug effects on deformability of human erythrocytes.

Extreme deformability of human erythrocytes is a prerequisite for their ability to squeeze through narrow capillaries of the blood microcirculation system. Various drugs can modify this deformability and consequently provoke circulation problems. We demonstrate that microfluidic assemblies are very convenient platforms for in vitro study of the associated processes. Two types of microfluidic channels were designed to quantitatively investigate modifications of erythrocyte deformability induced by hydrogen peroxide, ethanol and pentoxifylline based on transit velocity measurements. With a high sensitivity our microfluidic assemblies show that hydrogen peroxide decreases erythrocyte deformability in a dose-dependent manner. Then, results on ethanol resolve a biphasic nature of this reactant on the deformability of single erythrocyte cells. Results on pentoxifylline provide evidence that, similar to ethanol, also this medical drug has a double-sided effect on the erythrocyte deformability, i.e. increasing the deformability at low concentrations, while decreasing it at higher ones. Taken together, our microfluidic designs propose a potent measurement method for the erythrocyte deformability, as well as providing a perspective to evaluate effects of drugs on it.

Optical second harmonic generation in a ferromagnetic liquid crystal.

A comparative experimental investigation of the dependence of second harmonic generation (SHG) on an applied external voltage between a standard nematic liquid crystalline material and an analogue ferromagnetic nematic liquid crystalline material was performed by using a fundamental optical beam at an 800 nm wavelength. For the ferromagnetic material, the dependence of SHG on an applied magnetic field was also examined. Three different polarization combinations of the fundamental and the second harmonic radiation were analysed. The SHG signal observed in the former material is attributed to a combination of electric field-induced SHG (EFISHG) and flexoelectric deformation-induced SHG, while the SHG signal observed in the latter material is attributed solely to flexoelectric deformation-induced SHG. The obtained dependences of the SHG signal on the associated optical retardation show that, in the most favourable polarization combination, the two contributions generate about the same effective nonlinear optical susceptibility.

Molecular recognition of a lipophilic guanosine derivative in Langmuir films at the air-water interface.

Molecular recognition of a lipophilic deoxyguanosine derivative at the air-water interface was investigated by film balance experiments and Brewster Angle Microscopy. Results showed that guanosine, despite strong tendency towards self-assembly, interacts with both complementary and noncomplementary liponucleosides (lipophilic derivatives of deoxycytidine and deoxythymidine). At surface pressures below 17mN/m, attractive and repulsive interactions were present in case of both mixed monolayers and were the strongest at guanosine molar fractions of 0.5 and 0.75. At higher values of surface pressure, deoxyguanosine-deoxycytidine interactions were strictly attractive and were present only for monolayers with guanosine molar fraction of 0.75. On the contrary, attractive and repulsive interactions remained present in case of deoxyguanosine-deoxythymidine mixed monolayers. This indicates that interactions between guanosine and cytidine are much stronger than guanosine-thymidine interactions. Interactions for none of the nucleoside pairs, however, are specific and π-stacking interactions between the aromatic planes of liponucleoside derivatives probably dominate over hydrogen bonding interactions. This article is part of a Special Issue entitled "G-quadruplex" Guest Editor: Dr. Concetta Giancola and Dr. Daniela Montesarchio.

Compartmentalized liquid crystal alignment induced by sparse polymer ribbons with surface relief gratings.

We report on the liquid crystal (LC) alignment induced by sparse polymer ribbons fabricated by the two-photon polymerization-based direct laser writing method. Each ribbon is fabricated by a single scan of the laser through the photoresist and possesses surface relief gratings on both sides. The relief gratings are caused by the optical interference between the incident and reflected laser beams. With the aid of these relief gratings, LC molecules can be well aligned along the selected direction of the ribbons. LC cells with the Z-shaped and checkerboard-type microstructures are constructed based on the sparse out-of-plane polymeric ribbons. Our results show that with such polymer ribbons a compartmentalized LC alignment in the arbitrary microstructures can be realized.

Surface-Adsorbed Long G-Quadruplex Nanowires Formed by G:C Linkages.

G-quadruplexes connected into long, continuous nanostructures termed G-wires show properties superior to dsDNA when applied in nanotechnology. Using AFM imaging, we systematically studied surface adsorption of a set of G-rich oligonucleotides with GC-termini for their ability to form long G-wires through G:C pairing. We investigated the effects of increasing sequence length, the type of nucleotide in the side loops, and removal of the CG-3' terminus. We found that sequences with adenine in the side loops most readily form G-wires. The role of magnesium as an efficient surface-anchoring ion was also confirmed. Conversely, as resolved from dynamic light scattering measurements, magnesium had no ability to promote G-quadruplex formation in solution. These insights may help in selecting prosperous candidates for construction of G-quadruplex based nanowires and to explore them for their electronic properties.

Ion-specific self-assembly of a lipophilic guanosine derivative in thin surface films.

We investigated the effect of various ions on the surface assembly of a guanosine derivative with one hexadecanoyl chain at the air-water interface. The ions were added to the water subphase prior to spreading of the surface film. Like in bulk water, also at the air-water interface, K(+) ions exhibit the strongest influence on the assembly features as they induce structural transformation from lamellar to mosaic-like assembly. In contrast, Li(+) and Na(+) ions only slightly modify the properties of the assembled film with respect to those observed on pure water. The nature of anions plays an important role in the surface self-assembly as well. We found that (Pic(-)) is 2 orders of magnitude more effective for assembly regulation than Cl(-). All surface assemblies observed in our study are very stable and robust, and consequently they remain practically unperturbed after Langmuir-Blodgett transfer onto a solid support.

Temperature-induced labelling of Fluo-3 AM selectively yields brighter nucleus in adherent cells.

Fluo-3 is widely used to study cell calcium. Two traditional approaches: (1) direct injection and (2) Fluo-3 acetoxymethyl ester (AM) loading, often bring conflicting results in cytoplasmic calcium ([Ca(2+)]c) and nuclear calcium ([Ca(2+)]n) imaging. AM loading usually yields a darker nucleus than in cytoplasm, while direct injection always induces a brighter nucleus which is more responsive to [Ca(2+)]n detection. In this work, we detailedly investigated the effects of loading and de-esterification temperatures on the fluorescence intensity of Fluo-3 in response to [Ca(2+)]n and [Ca(2+)]c in adherent cells, including osteoblast, HeLa and BV2 cells. Interestingly, it showed that fluorescence intensity of nucleus in osteoblast cells was about two times larger than that of cytoplasm when cells were loaded with Fluo-3 AM at 4 °C and allowed a subsequent step for de-esterification at 20 °C. Brighter nuclei were also acquired in HeLa and BV2 cells using the same experimental condition. Furthermore, loading time and adhesion quality of cells had effect on fluorescence intensity. Taken together, cold loading and room temperature de-esterification treatment of Fluo-3 AM selectively yielded brighter nucleus in adherent cells.

Generation and erasure of femtosecond laser-induced periodic surface structures on nanoparticle-covered silicon by a single laser pulse.

We experimentally show that the generation and erasure of femtosecond laser-induced periodic surface structures on nanoparticle-covered silicon inducted by irradiation with a single laser pulse (800 nm, 120 fs, linear polarization) depend on the pulse fluence. We propose that this is due to competition between periodic surface structuring originating from the interference of incident light with surface plasmon polaritons and surface smoothing associated with surface melting. Experimental results are supported by theoretical analysis of transient surface modifications based on combining the two-temperature model and the Drude model.

Programmed self-assembly of a quadruplex DNA nanowire.

The ability to produce, reproducibly and systematically, well-defined quadruplex DNA nanowires through controlled rational design is poorly understood despite potential utility in structural nanotechnology. The programmed hierarchical self-assembly of a long four-stranded DNA nanowire through cohesive self-assembly of GpC and CpG "sticky" ends is reported. The encoding of bases within the quadruplex stem allows for an uninterrupted π-stacking system with rectilinear propagation for hundreds of nanometers in length. The wire is mechanically stable and features superior nuclease resistance to double-stranded DNA. The study indicates the feasibility for programmed assembly of uninterrupted quadruplex DNA nanowires. This is fundamental to the systematic investigation of well-defined DNA nanostructures for uses in optoelectronic and electronic devices as well as other structural nanotechnology applications.

Surface Modification of Magnetoactive Elastomers by Laser Micromachining.

It has been recently demonstrated that laser micromachining of magnetoactive elastomers is a very convenient method for fabricating dynamic surface microstructures with magnetically tunable properties, such as wettability and surface reflectivity. In this study, we investigate the impact of the micromachining process on the fabricated material's structural properties and its chemical composition. By employing scanning electron microscopy, we investigate changes in size distribution and spatial arrangement of carbonyl iron microparticles dispersed in the polydimethylsiloxane (PDMS) matrix as a function of laser irradiation. Based on the images obtained by a low vacuum secondary electron detector, we analyze modifications of the surface topography. The results show that most profound modifications occur during the low-exposure (8 J/cm2) treatment of the surface with the laser beam. Our findings provide important insights for developing theoretical models of functional properties of laser-sculptured microstructures from magnetoactive elastomers.

Electro-Optic Response of Polymer-Stabilized Cholesteric Liquid Crystals with Different Polymer Concentrations.

Polymer-stabilized cholesteric liquid crystals (PSCLCs) have emerged as promising candidates for one-dimensional photonic lattices that enable precise tuning of the photonic band gap (PBG). This work systematically investigates the effect of polymer concentrations on the AC electric field-induced tuning of the PBG in PSCLCs, in so doing it explores a range of concentrations and provides new insights into how polymer concentration affects both the stabilization of cholesteric textures and the electro-optic response. We demonstrate that low polymer concentrations (≈3 wt. %) cause a blue shift in the short wavelength band edge, while high concentrations (≈10 wt. %) lead to a contraction and deterioration of the reflection band. Polarization optical microscopy was conducted to confirm the phase transition induced by the application of an electric field. The observations confirm that increased polymer concentration stabilizes the cholesteric texture. Particularly, the highly desired fingerprint texture was stabilized in a sample with 10 wt. % of the polymer, whereas it was unstable for lower polymer concentrations. Additionally, higher polymer concentrations also improved the dissymmetry factor and stability of the lasing emission, with the dissymmetry factor reaching the value of around 2 for samples with 10 wt. % of polymer additive. Our results provide valuable comprehension into the design of advanced PSCLC structures with tunable optical properties, enhancing device performance and paving the way for innovative photonic applications.

Cell-cell communication induces random spikes of spontaneous calcium oscillations in multi-BV-2 microglial cells.

As the first and main form of active immune defense in the central nervous system, microglial cells usually exhibit complicated intracellular calcium (Ca²âº) activity that can regulate the downstream components of signaling cascades. In the present work, spontaneous oscillations of the cytosolic calcium concentration ([Ca²âº]c) in multi-BV-2 microglial cells were observed by video microscopy. These cells exhibited random spikes of Ca²âº oscillations. Cross-correlation analysis of the temporal dependence of the oscillations indicated the existence of cell-cell communication mediated by extracellular messengers. Numerical simulations based on a simple mathematical model suggested that these communications could induce random spikes of spontaneous Ca oscillations in the multi-cell system. Short-time imaging analysis of random spikes in different regions of a single cell showed that spontaneous Ca²âº oscillations resulted from Ca²âº wave generated by other cells as well as from calcium elevation inside the cell. Taken together, our data demonstrate that cell-cell communication existed between the BV-2 microglial cells in vitro and further resulted in the random spikes of spontaneous Ca²âº oscillations.

Polarization patterning in ferroelectric nematic liquids via flexoelectric coupling.

The recently discovered ferroelectric nematic liquids incorporate to the functional combination of fluidity, processability and anisotropic optical properties of nematic liquids, an astonishing range of physical properties derived from the phase polarity. Among them, the remarkably large values of second order optical susceptibility encourage to exploit these new materials for non-linear photonic applications. Here we show that photopatterning of the alignment layer can be used to structure polarization patterns. To do so, we take advantage of the flexoelectric effect and design splay structures that geometrically define the polarization direction. We demonstrate the creation of periodic polarization structures and the possibility of guiding polarization by embedding splay structures in uniform backgrounds. The demonstrated capabilities of polarization patterning, open a promising new route for the design of ferroelectric nematic based photonic structures and their exploitation.