Whispering gallery modes in photoluminescence and Raman spectra of a spherical microcavity with CdTe quantum dots: anti-Stokes emission and interference effects

We have studied the photoluminescence and Raman spectra of a system consisting of a polystyrene latex microsphere coated by CdTe colloidal quantum dots. The cavity-induced enhancement of the Raman scattering allows the observation of Raman spectra from only a monolayer of CdTe quantum dots. Periodic structure with very narrow peaks in the photoluminescence spectra of a single microsphere was detected both in the Stokes and anti-Stokes spectral regions, arising from the coupling between the emission of quantum dots and spherical cavity modes.     

Theory of chromatography of complex cyclic polymers: eight-shaped and daisy-like macromolecules

A theory of chromatography of eight-shaped, trefoil-shaped and daisy-like polymers is developed. For a model of an ideal chain in a slit-like pore exact equations and a number of approximate formulae for the distribution coefficient K of these polymers are derived. All modes of chromatography of complex macrocycles of arbitrary molar mass in both narrow and wide pores are covered by the theory. It is shown that complex macrocycles always elute after linear polymers and rings of the same contour length. The effective chromatographic radius of eight-shaped and daisy-like macromolecules, which determines retention in size-exclusion chromatography are calculated. The increase in the retention with molar mass is predicted for all types of macrocycles at the critical interaction condition. Non-monotonous molar mass dependences of K are found at pre-critical interaction. We simulate separation of complex cyclic polymers from linear and ring precursors, discuss possibilities to separate symmetric and asymmetric eights, and speculates on the use of chromatography for separating knotted and unknotted polymer rings. According to the theory, the chromatography under the critical and pre-critical interaction conditions is expected to be especially efficient in these and similar problems. Boundary conditions for the theory and its applicability to real systems are discussed.     

Study of hemocompatibility and endothelial cell interaction of tecoflex-based electrospun vascular grafts

Abstract

Ensuring long-term functioning and efficient endothelialization of small diameter vascular grafts (VG) is an urgent task of tissue engineering. A solution may be to use electrospun VGs prepared from blends polyurethane with gelatin and/or bivalirudin. Here, properties of 3D matrices were explored by SEM, contact angle measurements and IR spectroscopy, and their interaction with blood and endothelial cells was studied. Introduction of gelatin into matrices enhanced adhesion and proliferation of endotheliocytes and enabled adhesion of platelets, whereas bivalirudin inhibited platelet adhesion while having no negative effect on the adhesion and proliferation of endothelial cells.     

Engineering of functional supramacromolecular complexes of proteins (enzymes) using reversed micelles as matrix microreactors

The size of the inner water cavity of reversed micelles formedin a triple system ‘water-surfactant-organic solvent’can be widely varied by changing the degree of surfactant hydration.This gives grounds to use reversed micelles as matrix microreactorsfor the design of supramolecular complexes of proteins. Usingultracentrifugation analysis, it has been demonstrated thatthe oligomeric composition of various enzymes (ketoglutaratedehydrogenase, alkaline phosphatase, lactic dehydrogenase, glyceraldehyde-3-phosphatedehydrogenase) solubilized in reversed micelles of Aerosol OT[sodium bis(2-ethylehexyl)sulfosuccinate] in octane changesupon variation of the degree of hydration. An oligomeric complexforms under conditions when the radius of the micelle innercavity is big enough to incorporate this complex as a whole.At lower degrees of hydration the micelles ‘uncouple’such complexes to their components. The catalytic propertiesof various oligomeric complexes have been studied. Possibilitiesof using reversed micelles for the separation of subunits ofoligomeric enzymes under non-denaturating conditions have beendemonstrated. In particular, the isolated subunits of alkalinephosphatase, lactic dehydrogenase and glyceralde-hyde-3-phosphatedehydrogenase have been found to be active in Aerosol OT reversedmicelles. The dependences of the catalytic activity of oligomericenzymes represent saw-like curves. The maxima of the catalyticactivity observed at these curves relate to the functioningof various oligomeric forms of an enzyme. The radii of the micelleinner cavity under conditions when these maxima are observedcorrelate with the linear dimensions of the enzyme oligomericforms. Correlation of the position of a maximum with the shapeof an oligomeric complex is discussed.     

Hydrothermal microwave-assisted synthesis of LaFeO3 catalyst for N2O decomposition

Lanthanum orthoferrite powders were synthesized via one-step hydrothermal reactions under mild conditions using microwave and conventional heating. The use of microwave irradiation during the synthesis allows one to obtain nanocrystalline LaFeO₃ with a higher yield and reduced crystallite and particle size within a 16 times shorter duration (3 hours) at a lower temperature of 220°C as compared to the conventional heating. The catalytic decomposition of nitrous oxide was performed over both samples, it was shown that the sample obtained under microwave conditions demonstrates enhanced activity as a catalyst: N₂O decomposes completely at 700°C over the catalyst formed at microwave conditions, while the comparative catalyst prepared by conventional heating reaches a lower conversion of only 60% at the same temperature and catalytic reaction conditions.     

The influence of poly(3,4-ethylenedioxythiophene) modification on the transport properties and fuel cell performance of Nafion-117 membranes

Nafion-117/PEDOT composite membranes were synthesized by in situ chemical polymerization of 3,4-ethylenedioxythiophene (EDOT) using ammonium persulfate as an oxidant. The polymerization of EDOT in Nafion membranes for various EDOT/oxidant treatment sequences was studied for the first time. PEDOT introduction leads to a slight decrease in both the ion-exchange capacity and water uptake of the composite membranes, as well as to an increase in cationic transport. Membranes initially treated with an oxidant exhibit better conductivity and lower hydrogen permeability. The effect of both modification of Nafion-117 membranes by PEDOT and hot-pressing of hydrogen-oxygen membrane-electrode assemblies (MEAs) on the performance of proton-exchange membrane fuel cells was studied. The maximum power density of the fabricated MEAs increases 1.5-fold: from 510 (for a pristine Nafion-117 membrane) to 810 mW cm⁻² (for a membrane modified by PEDOT). The current density at a voltage of 0.4 V reaches 1248 and 2246 mA cm⁻², respectively.     

Life under ice in the perennial ice‐covered Lake Glubokoe in Summer (East Antarctica)

This study focuses on hydrological and biotic variables in Lake Glubokoe, which is located in Thala Hills of Enderby Land (East Antarctica). Water and sediment samples and physical measurements were collected once a week in the austral summer (19 December 2010 – 6 February 2011). This lake exhibits perennial ice cover that reached a thickness of 2.5–2.7 m during the study period. A very low concentration of planktonic chlorophyll‐a (0.06–0.45 μg L^?1) was measured in the lake, indicating its ultra‐oligotrophic status. The water was poorly populated by algae and metazoans, especially in upper waters below ice cover to a depth of 2 m. Small planktonic organisms (2–5 μm) were observed throughout the study period, but larger organisms (>8 μm) such as the cyanobacteria Planktolyngbya limnetica occurred only during the warmest period (January). Only few individuals of metazoans (rotifers) were found in planktonic samples. Due to deep light penetration (10–15% of incoming active solar radiation reached the depth of 30 m), thick cyanobacterial mats (30 cm) cover all the bottom surface (grey silts) in the lake. Abundant benthic biota associated with these mats was found (up to 1000 ind. m^?2). Among the benthic metazoans, bdelloid rotifers and tardigrades were the dominating taxa. The results of this study suggest a typical ecological feature of most subglacial lakes in East Antarctica is that metazoans are very poor in the pelagic zone, preferring instead to occupy an area near the lake bottom because of a favourable constant temperature of 4 °C, good level of dissolved oxygen and available food resources as the bacterial detritus.     

Laser-Printed Plasmonic Metasurface Supporting Bound States in the Continuum Enhances and Shapes Infrared Spontaneous Emission of Coupled HgTe Quantum Dots

In order to advance the development of quantum emitter-based devices, it is essential to enhance light-matter interactions through coupling between semiconductor quantum dots with high quality factor resonators. Here, efficient tuning of the emission properties of HgTe quantum dots in the infrared spectral region is demonstrated by coupling them to a plasmonic metasurface that supports bound states in the continuum. The plasmonic metasurface, composed of an array of gold nanobumps, is fabricated using single-step direct laser printing, opening up new opportunities for creating exclusive 3D plasmonic nanostructures and advanced photonic devices in the infrared region. A 12-fold enhancement of the photoluminescence in the 900–1700 nm range is observed under optimal coupling conditions. By tuning the geometry of the plasmonic arrays, controllable shaping of the emission spectra is achieved, selectively enhancing specific wavelength ranges across the emission spectrum. The observed enhancement and shaping of the emission are attributed to the Purcell effect, as corroborated by systematic measurements of radiative lifetimes and optical simulations based on the numerical solution of Maxwell's equations. Moreover, coupling of the HgTe photoluminescence to high quality factor modes of the metasurface improves emission directivity, concentrating output within an ≈20° angle.     

A Novel Magnetic Hardening Mechanism for Nd-Fe-B Permanent Magnets Based on Solid-State Phase Transformation

Permanent magnets based on neodymium-iron-boron (Nd-Fe-B) alloys provide the highest performance and energy density, finding usage in many high-tech applications. Their magnetic performance relies on the intrinsic properties of the hard-magnetic Nd₂Fe₁₄B phase combined with control over the microstructure during production. In this study, a novel magnetic hardening mechanism is described in such materials based on a solid-state phase transformation. Using modified Nd-Fe-B alloys of the type Nd₁₆Fe_bal-x-y-zCo_xMo_yCu_zB₇ for the first time it is revealed how the microstructural transformation from the metastable Nd₂Fe₁₇B_x phase to the hard-magnetic Nd₂Fe₁₄B phase can be thermally controlled, leading to an astonishing increase in coercivity from ≈200 kAm⁻¹ to almost 700 kAm⁻¹. Furthermore, after thermally treating a quenched sample of Nd₁₆Fe₅₆Co₂₀Mo₂Cu₂B₇, the presence of Mo leads to the formation of fine FeMo₂B₂ precipitates, in the range from micrometers down to a few nanometers. These precipitates are responsible for the refinement of the Nd₂Fe₁₄B grains and so for the high coercivity. This mechanism can be incorporated into existing manufacturing processes and can prove to be applicable to novel fabrication routes for Nd-Fe-B magnets, such as additive manufacturing.