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The development of advanced methods for the synthesis of nano- and microparticles in the field of biomedicine is of high interest due to a range of reasons. The current synthesis methods may have limitations in terms of efficiency, scalability, and uniformity of the particles. Here, we investigate the synthesis of submicron calcium carbonate using a microfluidic chip with a T-shaped oil supply for droplet-based synthesis to facilitate control over the formation of submicron calcium carbonate particles. The design of the chip allowed for the precise manipulation of reaction parameters, resulting in improved porosity while maintaining an efficient synthesis rate. The pore size distribution within calcium carbonate particles was estimated via small-angle X-ray scattering. This study showed that the high porosity and reduced size of the particles facilitated the higher loading of a model peptide: 16 vs. 9 mass.% for the particles synthesized in a microfluidic device and in bulk, correspondingly. The biosafety of the developed particles in the concentration range of 0.08-0.8 mg per plate was established by the results of the cytotoxicity study using mouse fibroblasts. This innovative approach of microfluidically assisted synthesis provides a promising avenue for future research in the field of particle synthesis and drug delivery systems.

Poly(diphenylene phthalide) (PDP) belongs to the class of carbocyclic organic electroactive polymers, which exhibits electric conductive properties when an external electric field and/or mechanical stress is applied. In this work, the transport properties of thin-film layered lead-PDP-lead structures were experimentally studied in a wide temperature range. At sufficiently high temperatures, the current voltage characteristics are satisfactorily described in terms of the injection model of currents limited by the space charge. At temperatures below ≈8 K, a number of samples exhibit features that can be explained by the effect of induced superconductivity in a thin film of conducting polymer enclosed between two massive superconductors (lead)., (Copyright © 2022, Arutyunov et al.)

An experimental quasi-equilibrium phase diagram of the polyvinylidene fluoride (PVDF)-camphor mixture is constructed using an original optical method. For the first time, it contains a boundary curve that describes the dependence of camphor solubility in the amorphous regions of PVDF on temperature. It is argued that this diagram cannot be considered a full analogue of the eutectic phase diagrams of two low-molar-mass crystalline substances. The phase diagram is used to interpret the polarized light hot-stage microscopy data on cooling the above mixtures from a homogeneous state to room temperature and scanning electron microscopy data on the morphology of capillary-porous bodies formed upon camphor removal. Based on our calorimetry and X-ray studies, we put in doubt the possibility of incongruent crystalline complex formation between PVDF and camphor previously suggested by Dasgupta et al. (Macromolecules 2005, 38, 5602-5608). We also describe and discuss the high-temperature crystalline structure of racemic camphor, which is not available in the modern literature.

Liquid crystals self-assemble on nanopatterned alignment layers into purely soft matter metasurfaces sensitive to external stimuli and imparting tailored spatial modulations to transmitted light wavefronts. Upon fine optimization, they are capable of efficient light deflection by virtue of anomalous refraction into a dominating transmission diffraction order. To expand the spectral range and acquire additional functionality, we put forward the double-sided metasurface design based on the liquid crystal alignment by a pair of complementing patterned substrates. We numerically optimize, fabricate, and experimentally characterize metasurfaces refracting red light with an efficiency of up to 70% and sustaining the efficiency above 50% in a broad range of visible wavelengths exceeding 500 nm. We verify that the refraction is reversibly switched in less than 10 ms by voltages of a few volts. We also report on a remarkable mechanical reconfigurability, as micrometer-scale relative substrate shift flips the refraction direction., (© 2022 the author(s), published by De Gruyter, Berlin/Boston.)

Neodymium iron borate NdFe 3 (BO 3 ) 4 is an intensively studied multiferroic with high electric polarization values controlled by a magnetic field. It is characterized by a large quadratic magnetoelectric effect, rigidity in the base plane and a rather strong piezoelectric effect. In this work, the atomic structure of (Nd 0.91 Bi 0.09 )Fe 3 (BO 3 ) 4 was studied by single-crystal X-ray diffraction in the temperature range 20-500 K (space group R32, Z = 3). The Bi atoms found in the composition partially substitute the Nd atoms in the 3a position; they entered the structure due to the growth conditions in the presence of Bi 2 Mo 3 O 12 . It was shown that in the temperature range 20-500 K there is no structural phase transition R32→P3 1 21, which occurs in rare-earth iron borates (RE = Eu-Er, Y) with an effective rare-earth cation radius smaller than that of Nd. The temperature dependence of the unit-cell c parameter reveals a slight increase on cooling below 90 K, which is similar to the results obtained previously for iron borates of Gd, Y and Ho. The atomic distances (Nd,Bi)-O, (Nd,Bi)-B, (Nd,Bi)-Fe, Fe-O, Fe-B and Fe-Fe in the iron chains and between chains decrease steadily with decreasing temperature from 500 to 90 K, whereas the B1(3b)-O distance does not change and the average B2(9e)-O distance increases slightly. There is a uniform decrease in the atomic displacement parameters with decreasing temperature, with a more pronounced decrease for the Nd(3a) and O2(9e) atoms. The O2(9e) atoms are characterized by the maximum atomic displacement parameters and the most elongated atomic displacement ellipsoids. The characteristic Debye and Einstein temperatures, and the static component in the atomic displacements were determined for cations using multi-temperature diffraction data. It was shown that the Nd cations have the weakest bonds with the surrounding atoms and the B cations have the strongest.

Nanosystems for targeted delivery and remote-controlled release of therapeutic agents has become a top priority in pharmaceutical science and drug development in recent decades. Application of a low frequency magnetic field (LFMF) as an external stimulus opens up opportunities to trigger release of the encapsulated bioactive substances with high locality and penetration ability without heating of biological tissue in vivo. Therefore, the development of novel microencapsulated drug formulations sensitive to LFMF is of paramount importance. Here, we report the result of LFMF-triggered release of the fluorescently labeled dextran from polyelectrolyte microcapsules modified with magnetic iron oxide nanoparticles. Polyelectrolyte microcapsules were obtained by a method of sequential deposition of oppositely charged poly(allylamine hydrochloride) (PAH) and poly(sodium 4-styrenesulfonate) (PSS) on the surface of colloidal vaterite particles. The synthesized single domain maghemite nanoparticles integrated into the polymer multilayers serve as magneto-mechanical actuators. We report the first systematic study of the effect of magnetic field with different frequencies on the permeability of the microcapsules. The in situ measurements of the optical density curves upon the 100 mT LFMF treatment were carried out for a range of frequencies from 30 to 150 Hz. Such fields do not cause any considerable heating of the magnetic nanoparticles but promote their rotating-oscillating mechanical motion that produces mechanical forces and deformations of the adjacent materials. We observed the changes in release of the encapsulated TRITC-dextran molecules from the PAH/PSS microcapsules upon application of the 50 Hz alternating magnetic field. The obtained results open new horizons for the design of polymer systems for triggered drug release without dangerous heating and overheating of tissues.

Morphological transition between hexagonal and lamellar patterns in thin polystyrene- block -poly(4-vinyl pyridine) films simultaneously exposed to a strong in-plane electric field and saturated solvent vapor is studied with atomic force and scanning electron microscopy. In these conditions, standing cylinders made of 4-vinyl pyridine blocks arrange into threads up to tens of microns long along the field direction and then partially merge into standing lamellas. In the course of rearrangement, the copolymer remains strongly segregated, with the minor component domains keeping connectivity between the film surfaces. The ordering tendency becomes more pronounced if the cylinders are doped with Au nanorods, which can increase their dielectric permittivity. Non-selective chloroform vapor works particularly well, though it causes partial etching of the indium tin oxide cathode. On the contrary, 1,4-dioxane vapor selective to polystyrene matrix does not allow for any morphological changes.

We report the formation of high optical power microlenses in the near-surface region of the liquid crystal layer. Such microlenses, possessing a very small focal length f at a rather large aperture A ( f / A ∼2), are able to focus the light into spots of a characteristic size comparable with the wavelength. Using numerical modeling, a specific patterning profile of a liquid crystal (LC) alignment surface by an ion beam is proposed to provide the aligning properties necessary for the formation of an array of microlenses with a focal length comparable to the LC cell thickness. The proposed microlens arrays are produced, and their optical properties are discussed.

High-quality Fe 1-x Ga x BO 3 single crystals (0.0 ≤ x ≤ 1.0) in the form of basal plates were synthesized by the flux technique. The exact content of Fe and Ga and homogeneity of their distribution in the crystal structure were determined by energy-dispersive X-ray spectroscopy. The crystal structure was refined using single-crystal X-ray diffraction data. The electronic and magnetic properties were studied using Mössbauer spectroscopy. It is shown that even a small content of diamagnetic gallium leads to a rearrangement of the crystal structure and essentially changes the magnetic hyperfine parameters of the crystals.

We report on experimental investigations of the lasing effect in novel chiral liquid crystal (CLC) systems with a deformed lying helix (DLH). The lasing is studied for both odd- and even-order field-induced stop-bands, which are characteristic exclusively of the DLH state. The DLH state is achieved in special CLC cells with periodic boundary conditions, when the surface alignment is flipped between planar and vertical states. The alignment surfaces are prepared using focused ion-beam lithography. In an electric field, such CLC systems undergo an orientational transition, when the initial Grandjean-plane texture with the helix axis perpendicular to the CLC layer is transformed into the DLH state with the helix axis oriented in the plane of the layer. Due to field-induced strong deformation, the DLH system is characterized by a set of photonic stop-bands with a fine spectral structure; namely, on these fine-structured sub-bands, we have observed and studied the low-threshold lasing effect.

Self-assembling of liquid-crystal metasurfaces on polymer layers patterned by a focused ion beam manifests itself in distinctly colored optical transmission, as light from certain spectral bands is efficiently diffracted by the periodic liquid crystal modulations. We explore the metasurface electro-optics by applying voltage across the liquid crystal to straighten its director distribution and reroute the diffracted light into the direct transmission. We show that the characteristic times of switching from the diffracting to the transmitting state can be decreased down to a millisecond by increasing the driving voltage up to 6-8 V, while the main part of the relaxation back into the periodically deformed diffracting state occurs within about a few milliseconds, i.e., by an order of magnitude faster than the relaxation of the analogous homogeneous electro-optical liquid crystal cell. We explain the profound dynamics in terms of superimposed exponential modes governed by an interplay of the metasurface geometric parameters, the liquid crystal viscosity, and elasticity.

An experimental phase diagram of the isotactic polypropylene-camphor system is constructed using an original optical method. It considerably deviates from the dynamic diagram, which can be obtained using conventional differential scanning calorimetry (DSC), and contains an additional boundary line that describes camphor solubility in the polymer. An accurate phase diagram makes it possible to perform a detailed and consistent thermodynamic analysis of the DSC, optical, and scanning electron microscopy data on the cooling of prehomogenized mixtures of different compositions, which leads to the formation of capillary-porous bodies via thermally induced phase separation. The removal of camphor results in the formation of polypropylene membranes, the morphology and functional properties of which, such as the total pore volume, mean pore size, permeability coefficient, and breaking stress, appear to be highly dependent on the composition of the initial binary system. It is shown that thermally induced phase separation induces the formation of microscopic cracks in the studied membranes. The crack density decreases with the polymer content in the initial system, but at 53 wt % of polypropylene, the membrane becomes completely impermeable to isopropanol despite the presence of large ∼4 μm pores, thus questioning the perspectives of its practical use. In general, the study makes it possible to achieve a deeper understanding of the membrane formation process via thermally induced phase separation in the mixtures of semicrystalline polymers with low molar mass substances.

Background: The alignment of liquid crystals by surfaces is crucial for applications. It determines the director configuration in the bulk, its stability against defects and electro-optical switching scenarios. The conventional planar alignment of rubbed polymer layers can be locally flipped to vertical by irradiation with a focused ion beam on a scale of tens of nanometers. Results: We propose a digital method to precisely steer the liquid crystal director tilt at polymer surfaces by combining micrometer-size areas treated with focused ion beam and pristine areas. The liquid crystal tends to average the competing vertical and planar alignment actions and is stabilized with an intermediate pretilt angle determined by the local pattern duty factor. In particular, we create micrometer-sized periodic stripe patterns with this factor gradually varying from 0 to 1. Our optical studies confirm a predictable alignment of a nematic liquid crystal with the pretilt angle continuously changing from 0° to 90°. A one-constant model neglecting the difference between the elastic moduli reproduces the results quantitatively correctly. Conclusion: The possibility of nanofabrication of polymer substrates supporting an arbitrary (from planar to vertical) spatially inhomogeneous liquid crystal alignment opens up prospects of "imprinting" electrically tunable versatile metasurfaces constituting lenses, prisms and q-plates.

Formation of photonic liquid crystal metasurfaces on rubbed polyimide substrates patterned by focused ion beam is demonstrated. Modulation of the surface anchoring conditions with periods from 1 to 6 micrometers gives rise to periodic deformation of the nematic liquid crystal director field. The exact periodicity is confirmed by the light diffraction measurements. Distinct colors originating from the specific zero-order diffraction spectra are observed and qualitatively explained in terms of an analytical model within the one-constant approximation. Quantitatively accurate optical spectra are obtained by the full scale numerical simulations taking into account all relevant material parameters. The results pave the way for hybrid liquid-crystal-based metasurfaces with tunable optical transmission, diffraction, and lasing.

High refractive index makes silicon the optimal platform for dielectric metasurfaces capable of versatile control of light. Among various silicon modifications, its monocrystalline form has the weakest visible light absorption but requires a careful choice of the fabrication technique to avoid damage, contamination or amorphization. Presently prevailing chemical etching can shape thin silicon layers into two-dimensional patterns consisting of strips and posts with vertical walls and equal height. Here, the possibility to create silicon nanostructure of truly tree-dimensional shape by means of the focused ion beam lithography is explored, and a 300 nm thin film of monocrystalline epitaxial silicon on sapphire is patterned with a chiral nanoscale relief. It is demonstrated that exposing silicon to the ion beam causes a substantial drop of the visible transparency, which, however, is completely restored by annealing with oxidation of the damaged surface layer. As a result, the fabricated chiral metasurface combines high (50-80%) transmittance with the circular dichroism of up to 0.5 and the optical activity of up to 20° in the visible range. Being also remarkably durable, it possesses crystal-grade hardness, heat resistance up to 1000 °C and the inertness of glass.

An accurate X-ray diffraction study of (Y 0.95 Bi 0.05 )Fe 3 (BO 3 ) 4 single crystals in the temperature range 90-500 K was performed on a laboratory diffractometer and used synchrotron radiation. It was established that the crystal undergoes a diffuse structural phase transition in the temperature range 350-380 K. The complexity of localization of such a transition over temperature was overcome by means of special analysis of systematic extinction reflections by symmetry. The transition temperature can be considered to be T str ≃ 370 K. The crystal has a trigonal structure in the space group P3 1 21 at temperatures of 90-370 K, and it has a trigonal structure in the space group R32 at 375-500 K. There is one type of chain formed by the FeO 6 octahedra along the c axis in the R32 phase. When going into the P3 1 21 phase, two types of nonequivalent chains arise, in which Fe atoms are separated from the Y atoms by a different distance. Upon lowering the temperature from 500 to 90 K, a distortion of the Y(Bi)O 6 , FeO 6 , B(2,3)O 3 coordination polyhedra is observed. The distances between atoms in helical Fe chains and Fe-O-Fe angles change non-uniformly. A sharp jump in the equivalent isotropic displacement parameters of O1 and O2 atoms within the Fe-Fe chains and fluctuations of the equivalent isotropic displacement parameters of B2 and B3 atoms were observed in the region of structural transition as well as noticeable elongation of O1, O2, B2, B3, Fe1, Fe2 atomic displacement ellipsoids. It was established that the helices of electron density formed by Fe, O1 and O2 atoms may be structural elements determining chirality, optical activity and multiferroicity of rare-earth iron borates. Compression and stretching of these helices account for the symmetry change and for the manifestation of a number of properties, whose geometry is controlled by an indirect exchange interaction between iron cations that compete with the thermal motion of atoms in the structure. Structural analysis detected these changes as variations of a number of structural characteristics in the c unit-cell direction, that is, the direction of the helices. Structural results for the local surrounding of the atoms in (Y 0.95 Bi 0.05 )Fe 3 (BO 3 ) 4 were confirmed by EXAFS and Mössbauer spectroscopies.

We have studied the alignment of a nematic liquid crystal (LC) material on aluminum subwavelength nanogratings as a function of the period, p , and the slit width to period ratio, w/p . A method, based on Fourier analysis of the transmittance spectra of the LC grating system, has been applied. We show that the gratings provide stable planar alignment only for shorter periods and narrower slits ( p < 400 nm, w / p < 2/3). As these parameters increase, the homogeneous surface alignment changes to domains with different tilt angles or to spatially modulated alignment. We have also obtained a 90° twisted LC director distribution, implying sufficiently strong azimuthal LC anchoring at the grating surface.

Technologies capable of fabricating complex shaped silicon metasurfaces attract increasing attention. The focused ion beam fabrication technique is considered traditionally as causing thick damaged layers in silicon resulting in a significant rise of the optical absorption loss. We examine the structure of the FIB-fabricated nanostructures on the silicon-on-sapphire (SOS) platform and its optical characteristics before and after thermal oxidation. We show that being thermally oxidised the FIB-patterned silicon subwavelength nanostructure tends to regain its chiral optical features. The impact of the oxidation process on the silicon nanostructure optical behaviour is discussed., (© 2017 The Authors Journal of Microscopy © 2017 Royal Microscopical Society.)

Chiral metamaterials - artificial subwavelength structures with broken mirror symmetry - demonstrate outstanding degree of optical chirality that exhibits sophisticated spectral behavior and can eventually reach extreme values. Based on the fundamental causality principle we show how one can unambiguously relate the metamaterial circular dichroism and optical activity by the generalized Kramers-Kronig relations. Contrary to the conventional relations, the generalized ones provide a unique opportunity of extracting information on material-dependent zeroes of transmission coefficient in the upper half plane of complex frequency. We illustrate the merit of the formulated relations by applying them to the observed ultra chiral optical transmission spectra of subwavelength arrays of chiral holes in silver films. Apart from the possibility of precise verification of experimental data, the relations enable resolving complex eigenfrequencies of metamaterial intrinsic modes and resonances.

Studies of DNA condensation have opened new perspectives in biotechnology and medicine. DNA condensation induced by polyamines or trivalent metal ions in vitro at room temperature has been investigated in detail. Our recent studies have demonstrated Mg(2+)-mediated formation of DNA condensates during the PCR. In this study, we report the unique morphology and fine structure of PCR-generated condensed DNA particles using electron and atomic force microscopy. The principal morphologies of studied DNA condensates are 3D particles of micrometer dimensions, oval microdisks of nanometer thickness, filaments, and compact nano-sized particles. SEM examinations have revealed a new structural type of spherical and elliptical 3D microparticles formed by numerous definitely oriented microdisks and their segments. AFM revealed a granular structure of the microdisk surface and the smallest nano-sized disks and thinnest nanofibrils - that appear to be the primary products of DNA condensation during the PCR. We suggest that the formation of DNA nanofibrils and nanodisks in PCR occurs due to Mg(2+) - mediated intermolecular (lateral) and intramolecular condensation of ssDNA. Aggregation of elementary nanodisks in the course of thermal PCR cycles, occurring both by magnesium cations and via complementary interactions, give a rise to large nano-sized aggregates and more complex microparticles.