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We present results concerning the formation of Langmuir−Blodgett (LB) films of a class I hydrophobin from Pleurotus ostreatusat the air−water interface, and their structure as Langmuir−Blodgett (LB) films when deposited on silicon substrates. LB films of the hydrophobin were investigated by atomic force microscopy (AFM). We observed that the compressed film at the air−water interface exhibits a molecular depletion even at low surface pressure. In order to estimate the surface molecular concentration, we fit the experimental isotherm with Volmerʼs equation describing the equation of state for molecular monolayers. We found that about 1/ 10of the molecules contribute to the surface film formation. When transferred on silicon substrates, compact and uniform monomolecular layers about 2.5 nm thick, comparable to a typical molecular size, were observed. The monolayers coexist with protein aggregates, under the typical rodlet form with a uniform thickness of about 5.0 nm. The observed rodlets appear to be a hydrophilic bilayer and can then be responsible for the surface molecular depletion. [ABSTRACT FROM AUTHOR]

The interaction between chiral drugs and biomimetic membranes is of interest in biophysical research and biotechnological applications. There is a belief that the membrane composition, particularly the presence of cholesterol, could play a pivotal role in determining enantiospecific effects of pharmaceuticals. Our study explores this topic focusing on the interaction of ibuprofen enantiomers (S- and R-IBP) with cholesterol-containing model membranes. The effects of S- and R-IBP at 20 mol% on bilayer mixtures of dipalmitoylphosphatidylcholine (DPPC) with 0, 10, 20 and 50 mol% cholesterol were investigated using circular dichroism and spin-label electron spin resonance. Morphological changes due to IBP enantiomers were studied with atomic force microscopy on supported cholesterol-containing DPPC monolayers. The results reveal that IBP isoforms significantly and equally interact with pure DPPC lipid assemblies. Cholesterol content, besides modifying the structure and the morphology of the membranes, triggers the drug enantioselectivity at 10 and 20 mol%, with the enantiomers differently adsorbing on membranes and perturbing them. The spectroscopic and the microscopic data indicate that IBP stereospecificity is markedly reduced at equimolar content of Chol mixed with DPPC. This study provides new insights into the role of cholesterol in modulating enantiospecific effects of IBP in lipid membranes., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Bent-core liquid crystals, a class of mesogenic compounds with non-linear molecular structures, are well known for their unconventional mesophases, characterized by complex molecular (and supramolecular) ordering and often featuring biaxial and polar properties. In the nematic phase, their unique behavior is manifested in the formation of nano-sized biaxial clusters of layered molecules (cybotactic groups). While this prompted their consideration in the quest for nematic biaxiality, experimental evidence indicates that the cybotactic order is only short-ranged and that the nematic phase is macroscopically uniaxial. By combining atomic force microscopy, neutron reflectivity and wide-angle grazing-incidence X-ray scattering, here, we demonstrate that multilayer films of a bent-core nematic, deposited on silicon by a combined Langmuir-Blodgett and Langmuir-Schaefer approach, exhibit macroscopic in-plane ordering, with the long molecular axis tilted with respect to the sample surface and the short molecular axis (i.e., the apex bisector) aligned along the film compression direction. We thus propose the use of Langmuir films as an effective way to study and control the complex anchoring properties of bent-core liquid crystals.

Curcumin, a plant polyphenol extracted from the Chinese herb turmeric, has gained widespread attention in recent years because of its multifunctional properties as antioxidant, antinflammatory, antimicrobial, and anticancer agent. Effects of the molecule on mitochondrial membranes properties have also been evidenced. In this work, the interaction of curcumin with models of mitochondrial membranes composed of dimyristoylphosphatidylcholine (DMPC) or mixtures of DMPC and 4 mol% tetramyristoylcardiolipin (TMCL) has been investigated by using biophysical techniques. Spectrophotometry and fluorescence allowed to determine the association constant and the binding energy of curcumin with pure DMPC and mixed DMPC/TMCL aqueous bilayers. The molecular organization of pure DMPC and cardiolipin-containing Langmuir monolayers at the air-water interface were investigated and the morphology of the monolayers transferred into mica substrates were characterized through atomic force microscopy (AFM). It is found that curcumin associates at the polar/apolar interface of the lipid bilayers and the binding is favored in the presence of cardiolipin. At 2 mol%, curcumin is well miscible with lipid monolayers, particularly with mixed DMPC/TMCL ones, where compact terraces formation characterized by a reduction of the surface roughness is observed in the AFM topographic images. At 10 mol%, curcumin perturbs the stability of DMPC monolayers and morphologically are evident terraces surrounded by cur aggregates. In the presence of TMCL, very few curcumin aggregates and larger compact terraces are observed. The overall results indicate that cardiolipin augments the incorporation of curcumin in model membranes highlighting the mutual interplay cardiolipin-curcumin in mitochondrial membranes., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier B.V.)

The behavior of lyotropic chromonic liquid crystals (LCLCs) in confined environments is an interesting research field that still awaits exploration, with multiple key variables to be uncovered and understood. Microfluidics is a highly versatile technique that allows us to confine LCLCs in micrometric spheres. As microscale networks offer distinct interplays between the surface effects, geometric confinement, and viscosity parameters, rich and unique interactions emerging at the LCLC-microfluidic channel interfaces are expected. Here, we report on the behavior of pure and chiral doped nematic Sunset Yellow (SSY) chromonic microdroplets produced through a microfluidic flow-focusing device. The continuous production of SSY microdroplets with controllable size gives the possibility to systematically study their topological textures as the function of their diameters. Indeed, doped SSY microdroplets produced via microfluidics, show topologies that are typical of common chiral thermotropic liquid crystals. Furthermore, few droplets exhibit a peculiar texture never observed for chiral chromonic liquid crystals. Finally, the achieved precise control of the produced LCLC microdroplets is a crucial step for technological applications in biosensing and anticounterfeiting.

Bent-core mesogens (BCMs) are a class of thermotropic liquid crystals featuring several unconventional properties. However, the interpretation and technological exploitation of their unique behavior have been hampered by the difficulty of controlling their anchoring at surfaces. To tackle this issue, we report the nanoscale structural characterization of BCM films prepared using the Langmuir-Blodgett technique. Even though BCMs are quite different from typical amphiphilic molecules, we demonstrate that stable molecular films form over water, which can then be transferred onto silicon substrates. The combination of Brewster angle microscopy, atomic force microscopy, and X-ray reflectivity measurements shows that the molecules, once transferred onto a solid substrate, form a bilayer structure with a bottom layer of flat molecules and an upper layer of upright molecules. These results suggest that Langmuir-Blodgett films of BCMs can provide a useful means to control the alignment of this class of liquid crystals.

Induced or spontaneous chirality in natural systems is an intriguing issue. In recent years, a lot of attention has been focused on chirality of chromonic liquid crystals, a class of materials that is able to self-assemble in columnar structures. However, the mechanism involved in the arising of chirality in these materials, that starts at the molecular level and controls the supramolecular structure, is poorly understood; however, it is certainly affected by ionic strength. In this work we present the results obtained doping Cromolyn, a chromonic material, with a strong helical-twisting-power peptide, and confining it in a spherical geometry. We demonstrate, by means of optical polarized microscopy and structural analysis, that both the geometrical constraint and the presence of the chiral dopant enhance the chiral effect; we also demonstrate that they favor the rise of a highly ordered helical superstructure, that may be optimized upon adding an ionic dye to the system. Finally, we report a procedure for the preparation of free-standing polymeric films, embedding and preserving the microspheres, and paving the way for the creation of biocompatible and eco-friendly optical devices to be used in the sensor and anticounterfeiting fields.

In this paper, the role of solvent characteristics on the rheological and physicochemical properties of organogels was investigated using different techniques. Vegetable oils, such as rice, sunflower and castor oil were used as solvents, for producing organogels with monoglycerides of fatty acids or a mixture of fatty alcohols (policosanol) as gelators. Moreover, two non-edible oils (silicon and paraffin oil) were also used for analysing the properties of solvents completely different in nature with respect to the edible ones, for a better interpretation of the given results. Organogels were investigated from a rheological point of view and through a microscopic analysis, given by polarised light (POM) and atomic force (AFM) microscopy, and X-rays to study the crystallinity of the system. The IR technique was used to analyse the intermolecular interactions, resulting in interesting information about the effect of oil polarity on the driving forces promoting structuration. This investigation showed that when solvents of a similar chemical nature are used, their physical properties, mainly oil polarity, are strictly related to the properties of the organogel, such as the onset of crystallisation temperature, the stiffness of the final material and its crystallinity. Anyway, these physical parameters seem insufficient to describe properly the role of solvents when oils of a different chemical nature are compared., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

In this study, we argue that ion motion in electrolytic cells containing Milli-Q water, weak electrolytes, or liquid crystals may exhibit unusual diffusive regimes that deviate from the expected behavior, leading the system to present an anomalous diffusion. Our arguments lie on the investigation of the electrical conductivity and its relationship with the mean square displacement, which may be used to characterize the ionic motion. In our analysis, the Poisson-Nernst-Planck diffusional model is used with extended boundary conditions to simulate the charge transfer, accumulation, and/or adsorption-desorption at the electrode surfaces.

Resveratrol is a natural polyphenol found in various plants with potential therapeutic activity as anti-oxidant, anti-inflammatory, cardioprotective and anti-tumoral. Lipid membranes are among cellular components that are targets of its action. In this work ESR of chain labeled lipids, calorimetry, X-ray diffraction and molecular docking are used to study the interaction of resveratrol with membrane model systems of dipalmitoylphosphatidylcholine (DPPC) as a function of resveratrol concentration (0-30 mol% of the lipid) and temperature (10-50°C). Resveratrol incorporated in DPPC bilayers induces considerable motional restriction at the lipid tail termini, removing the gradient of increasing mobility along the chain found in DPPC bilayers in the gel phase. In contrast, it leaves unperturbed the DPPC chain flexibility profile in the liquid-crystalline phase. At low concentration, resveratrol progressively reduces the pre-transition temperature and eliminates the pre-transition for content ≥5mol%. A reduced cooperativity and a downshift of the main transition temperature are observed, especially at high content. The typical diffraction pattern of DPPC multibilayers in the L β' phase is converted to a lamellar pattern with reduced d-spacing of untilted lipid chain in a hexagonal packing at 30 mol% of resveratrol. Molecular docking indicates that the energetically favoured anchoring site is the polar headgroup region, where resveratrol acts as a spacer. The overall results are consistent with the formation in DPPC of an interdigitated L βi gel phase induced by 30 mol% resveratrol., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Molecular recognition is among the most important chemical events in living systems and has been emulated in supramolecular chemistry, driven by chemical and biochemical sensing potential. Identifying host-guest association in situ at the interface, between the substrate-bound receptors and the analyte-containing media, is essential to predict complexation performances in term of the receptor conformation, orientation and organization. Herein, we report the first sum-frequency vibrational spectroscopy study of molecular recognition at the solid-gas interface. The binding capability of tetraquinoxaline cavitands toward volatile aromatic and aliphatic compounds, namely benzonitrile and acetonitrile, is investigated as test system. We prove the selective complexation of the receptors, organized in a solid-supported hybrid bilayer, toward aromatic compounds. Quantitative analysis allows to correlate the average orientations of the guest molecules and the host binding pockets, establishing "on-axis" complexation of benzonitrile within the cavitand cavity. The study is readily applicable to other receptors, molecular architectures, interfaces and analytes.

A collection of more than 1800 carbonized papyri, discovered in the Roman 'Villa dei Papiri' at Herculaneum is the unique classical library survived from antiquity. These papyri were charred during 79 A.D. Vesuvius eruption, a circumstance which providentially preserved them until now. This magnificent collection contains an impressive amount of treatises by Greek philosophers and, especially, Philodemus of Gadara, an Epicurean thinker of 1st century BC. We read many portions of text hidden inside carbonized Herculaneum papyri using enhanced X-ray phase-contrast tomography non-destructive technique and a new set of numerical algorithms for 'virtual-unrolling'. Our success lies in revealing the largest portion of Greek text ever detected so far inside unopened scrolls, with unprecedented spatial resolution and contrast, all without damaging these precious historical manuscripts. Parts of text have been decoded and the 'voice' of the Epicurean philosopher Philodemus is brought back again after 2000 years from Herculaneum papyri.

Quinoxaline cavitands (QxCav) are transferred by Langmuir-Schaefer method on self-assembled monolayers (SAMs) of octadecyltrichlorosilane (OTS) and N,N-dimethyl-N-octadecyl-3-aminopropyltrimethoxysilyl chloride (DMOAP) on fused silica substrates. The molecular architectures of both the hydrophobic SAMs templates and the hybrid cavitand-organosilanes bilayers at the solid-air interface are investigated and correlated by sum-frequency vibrational spectroscopy. The results show that QxCav are always in the closed vase configuration and orient with their principal axis normal to the substrates. The role of the alkyl chains density in the SAM templates on the QxCav transfer ratio is pointed out.

In this paper we report how the confining surfaces and the ionic effects of different concentration of guanosine solution can be used to vary the alignment of liquid crystal phases of guanosine nucleotides. Liquid crystal phases of guanosine 5'-monophosphate ammonium salt and guanosine 5'-monophosphate free acid in pure water, with and without silver sulphate, were studied by polarized optical microscope. A periodic modulation of the texture was observed. This modulation depends on both on the concentration and on the presence of silver ions in the liquid crystal phase. We demonstrate that, according to the surface energy of the alignment layers, it is possible to homeotropically align the guanosine chromonic phase without applying any external magnetic field. Finally, we report the formation of spherical, vesicle-like guanosine 5'-monophosphate aggregates, when the solution was confined between two hydrophobic surfaces containing exposed Si groups., (Copyright © 2014 Elsevier B.V. All rights reserved.)

A new type of flexible cholesteric liquid crystal mirror is presented. The simple and effective method for the deposition of a cholesteric mixture on a paper substrate and the particular design of the device give a homogeneous alignment of the cholesteric texture providing mirrors with an intense and uniform light reflectance. A desired polarization state for the reflected light, linear or circular, can be easily obtained varying the thickness and optical anisotropy of the polymer cover film. By using non-azobenzene based photosensitive materials a permanent array of RGB mirrors with high reflectivity can be obtained on the same device. Paper like reflective mirrors are versatile and they can find applications in reflective displays, adaptive optics, UV detectors and dosimeters, information recording, medicine and IR converters.

We demonstrate theoretically that the presence of ions in insulating materials such as nematic liquid crystals may be responsible for the dielectric spectroscopy behavior observed experimentally. It is shown that, at low frequencies, an essentially non-Debye relaxation process takes place due to surface effects. This is accomplished by investigating the effects of the adsorption-desorption process on the electrical response of an electrolytic cell when the generation and recombination of ions is present. The adsorption-desorption is governed by a non-usual kinetic equation in order to incorporate memory effects related to a non-Debye relaxation and the roughness of the surface. The analysis is carried out by searching for solutions to the drift-diffusion equation that satisfy the Poisson equation relating the effective electric field to the net charge density. We also discuss the effect of the mobility of the ions, i.e., situations with equal and different diffusion coefficients for positive and negative ions, on the impedance and obtain an exact expression for the admittance. The model is compared with experimental results measured for the impedance of a nematic liquid crystal sample and a very good agreement is obtained.

The spontaneous formation of dendritic aggregates is observed in a two-dimensional confined layered system consisting of a film composed of liquid crystal, dye and solvent cast above a polymer substrate. The observed aggregates are promoted by phase separation processes induced by dye diffusion and solvent evaporation. The growth properties of the aggregates are studied through the temporal evolution of their topological properties (surface, perimeter, fractal dimension). The fractal dimension of the completely formed structures, when they are coexistent with different types of structures, is consistent with theoretical and experimental values obtained for Diffusion-Limited Aggregates. Under different experimental conditions (temperature and local dye concentration) the structure forms without interactions with other kinds of structures, and its equilibrium fractal dimension is smaller. The fractal dimension is thus not a universal property of the observed structures, but rather depends on the experimental conditions.

A two-dimensional model within the Q-tensor description of liquid crystals is used to describe the inhomogeneous order reconstruction in a nematic cell driven by tony modulation in the anchoring conditions. Homogeneous and inhomogeneous reconstruction are contrasted: the former is defectless, the latter is defect mediated. While the transition thresholds are comparable in both cases and in good agreement with experimental data, the biaxial wall breaking is considerably slower in the inhomogeneous transition than in the homogeneous one. The shape of the signal given by the electric current flowing through the cell allows us to distinguish the actual path followed by the transition.

We present the time resolved experimental characterization of the biaxial switching between two topologically distinct textures of a nematic liquid crystal cell submitted to a strong electric field. This fast electro-optical effect is governed by the electric induced order reconstruction in the nematic bulk, which is an actual challenge for a complete theoretical description of the nematodynamics. The electric measurements across the cell are suitable to this purpose since they well discriminate among the dielectric, the ionic, and the order reconstruction contributions. A phenomenological model describes the experimental data, allowing the measurements of the order reconstruction characteristic time.

We have experimentally observed the biaxial switching between two topologically distinct textures of a nematic liquid crystal cell submitted to a strong electric field. The effect is deduced from optical and electrical measurements across the cell. Above a static threshold, a bulk order reconstruction is observed, where the final nematic orientation in the centre becomes perpendicular to its initial one, inducing a total pi change of orientation across the cell. Using short electric field pulses, a higher dynamical threshold is observed. These experiments are explained by a Landau-de Gennes-Khalatnikov model. The threshold implies the local exchange of two eigenvalues of the nematic order tensor through intermediate biaxial states. The onset of the effect in a thin splay-bend wall decreases the static threshold by almost an order of magnitude. The model explains reasonably well the static and dynamic measurements within the present description of nematic biaxiality.

We present an optical study of the influence of both the flexoelectric effect and surface polarization on a hybrid-aligned nematic cell using the half-leaky guided mode technique. Tilt angle profiles, obtained from fits of experimental data (reflectivity curves) taken under applied voltages, are compared with the ones derived by a complete theoretical model. Measurements with an applied alternating voltage allow the evaluation of the anchoring energy by solving the torque balance equation at the planar surface. From measurements with static fields, the sum of flexoelectric coefficients and the surface polarization are determined by numerical solution of Euler-Lagrange equations.

Deoxyguanosine-5'-monophosphate in water self-associates into stable structures, which include liquid-crystalline hexagonal and cholesteric phases. The structural unit is a four-stranded helix, composed of stacked Hoogsteen-bonded guanosine quartets. By using the osmotic stress method, we recently measured the force between helices in KCl solutions up to 2 M. In addition to the long-range electrostatic force, a short-range hydration repulsive contribution was recognized. The hydration repulsion is exponential, and shows a decay length independent from the ionic strength of the solution. Here, we report that more concentrated KCl solutions cause condensation of the guanosine helix in a hexagonal phase with constant equilibrium separation of approximately 7 A between helix surfaces. Long-range attraction, which induces the self-assembly, and short-range repulsion, which prevents the contact between the helices, are implied. By using osmotic stress, the force needed to push helices closer from the spontaneously assumed position has been measured. The attractive force was then estimated as a difference between the net force and the repulsive contribution, revealing an exponential decay length about two times larger than that of the short-range repulsion. The agreement with the helix interaction theory introduced recently by Kornyshev and Leikin (Kornyshev, A. A., and S. Leikin, 1997. Theory of interaction between helical molecules. J. Phys. Chem. 107:3656-3674) suggests that the repulsive and attractive forces originate from helix-specific interactions.