Phytoestrogens decorated nanocapsules for therapeutic methionine γ-lyase targeted delivery.

The main task of targeted therapy is the selective destruction of cancer cells without affecting normal ones. For these purposes, small molecules and antibodies are used that target specific receptors and proteins or block signaling pathways in tumor cells. The natural phytoestrogens daidzein (Dz) and genistein (Gn) possess binding capacity to estrogen receptors (ER). Methionine γ-lyase (MGL) is promising in two strategies of antitumor therapy: for the elimination of l-methionine, which is necessary for the proliferation of tumor cells, and for the production of cytotoxic dialkyl thiosulfinates in situ. For delivery of MGL-loaded nanocapsules (nanoreactors) to the surface of cancer cells a technique for Dz or Gn incorporation into the shell of polyionic vesicles (PICsomes) was developed. The nanoreactors were characterized by dynamic light scattering and transmission electron microscopy. The enzyme retained its catalytic efficiency inside the decorated PICsomes. The binding of Dz/Gn-nanoreactors to the surface of ER + MCF7 breast adenocarcinoma cells was demonstrated. For the first time an influence of enzyme-loaded PICsomes and their individual components on embryos development was evaluated. The high rate of blastocysts formation (>80%) was observed for all tested components and nanoreactors themselves. A strong inhibitory effect on the early embryonic development of MGL-loaded PICsomes in the presence of S-alkyl-l-cysteine sulfoxide substrates was showed. This proves that the substrates can freely penetrate through the polymer shell of the polyionic vesicle and are cleaved by MGL to form cytotoxic thiosulfinates. The data obtained for phytoestrogens decorated PICsomes may be applied in enzyme therapy of malignant tumors.

Amorphization and nanocrystal formation in a Pd-Ni-Cu-P alloy after cooling under different conditions.

Structure formation during solidification of a Pd-Ni-Cu-P melt is studied. It is demonstrated that changes in the heat transfer conditions lead to a nonlinear change in the characteristics of the structure. The article presents the regimes of cooling the samples and the results of their structure and composition studies. It is found that a decrease in the cooling rate of the alloy leads to an increase in the size, proportion and composition of nanoinclusions in an amorphous matrix. X-ray diffraction method, electron probe microanalysis, transmission microscopy and scanning calorimetry are used for samples characterization. This article is part of the theme issue 'Transport phenomena in complex systems (part 2)'.

Formation of wurtzite sections in self-catalyzed GaP nanowires by droplet consumption.

Wurtzite GaP nanowires are interesting for the direct bandgap engineering and can be used as templates for further growth of hexagonal Si shells. Most wurtzite GaP nanowires have previously been obtained with Au catalysts. Here, we show that long (∼500 nm) wurtzite sections are formed in the top parts of self-catalyzed GaP nanowires grown by molecular beam epitaxy on Si(111) substrates in the droplet consumption stage, which is achieved by abruptly increasing the atomic V/III flux ratio from 2 to 3. We investigate the temperature dependence of the length of wurtzite sections and show that the longest sections are obtained at 610 °C. A supporting model explains the observed trends using a phase diagram of GaP nanowires, where the wurtzite phase is formed within a certain range of the droplet contact angles. The optimal growth temperature for growing wurtzite nanowires corresponds to the largest diffusion length of Ga adatoms, which helps to maintain the required contact angle for the longest time.

Localization and transient emission properties in InGaN/GaN quantum wells of different polarities within core-shell nanorods.

Transient photoluminescence (PL) characteristics and localization phenomena in InGaN/GaN core-shell nanorods (NRs) were investigated from 6 K up to 285 K. The NRs exhibit three well-defined PL bands in the near-UV, blue, and green range ascribed to the emission of quantum well (QW) areas situated at the (1.00) sidewalls, (10.1) top facets, and (00.1) tip, respectively. At low temperature, time-resolved PL shows a fast decay time of about 0.5 ns for the semi- and non-polar QWs, while the polar QWs exhibit at least a twice-longer time. Rapid delocalization of carriers above 50 K indicates shallow potential fluctuations in the QWs. At room temperature, the characteristic fast PL decay time of the three QW bands stabilizes around 300 ps. The slow decaying PL components have different characteristic decay times that are explained by additional localization at basal stacking faults (BSFs), taking into account the quantum confined Stark effect. In addition, narrow excitonic luminescence lines are observed in the BSF-enriched polar QWs, providing direct evidence of the impact of the BSF/QW crossings on the optical properties of the NRs. A PL rise time of about 100 ps does not show any deviation between bands. These findings are suggestive of similar transport mechanisms in temperature equilibrium without inter-facet transport between different QWs. We believe that predictable transient characteristics can play a key role in creating uniform NR ensembles for device applications.

Insight into the performance of multi-color InGaN/GaN nanorod light emitting diodes.

We report on the thorough investigation of light emitting diodes (LEDs) made of core-shell nanorods (NRs) with InGaN/GaN quantum wells (QWs) in the outer shell, which are grown on patterned substrates by metal-organic vapor phase epitaxy. The multi-bands emission of the LEDs covers nearly the whole visible region, including UV, blue, green, and orange ranges. The intensity of each emission is strongly dependent on the current density, however the LEDs demonstrate a rather low color saturation. Based on transmission electron microscopy data and comparing them with electroluminescence and photoluminescence spectra measured at different excitation powers and temperatures, we could identify the spatial origination of each of the emission bands. We show that their wavelengths and intensities are governed by different thicknesses of the QWs grown on different crystal facets of the NRs as well as corresponding polarization-induced electric fields. Also the InGaN incorporation strongly varies along the NRs, increasing at their tips and corners, which provides the red shift of emission. With increasing the current, the different QW regions are activated successively from the NR tips to the side-walls, resulting in different LED colors. Our findings can be used as a guideline to design effectively emitting multi-color NR-LEDs.

InAs/AlGaAs quantum dots for single-photon emission in a red spectral range.

We report on comparative optical studies of InAs/Al0.44Ga0.56As quantum dots (QDs) grown by molecular beam epitaxy either with or without a thin GaAs interlayer inserted between the AlGaAs barrier and InAs QDs. Emission properties of individual QDs are investigated by micro-photoluminescence spectroscopy using 500-nm-size etched cylindric mesa structures. The single-photon statistics of the QDs of both types, emitting in the red spectral range between 636 and 750 nm, is confirmed by the measurements of the second-order correlation function. A negligibly small exciton fine structure splitting is detected in the majority of the QDs grown with the GaAs interlayer that implies the possibility of generating pairs of entangled photons with high entanglement fidelity.

New method for MBE growth of GaAs nanowires on silicon using colloidal Au nanoparticles.

We present a new method for the deposition of colloidal Au nanoparticles on the surface of silicon substrates based on short-time Ar plasma treatment without the use of any polymeric layers. The elaborated method is compatible with molecular beam epitaxy, which allowed us to carry out the detailed study of GaAs nanowire synthesis on Si(111) substrates using colloidal Au nanoparticles as seeds for their growth. The results obtained elucidated the causes of the difference between the initial nanoparticle sizes and the diameters of the grown nanowires.

Measuring the height-to-height correlation function of corrugation in suspended graphene.

Nanocorrugation of 2D crystals is an important phenomenon since it affects their electronic and mechanical properties. The corrugation may have various sources; one of them is flexural phonons that, in particular, are responsible for the thermal conductivity of graphene. A study of corrugation of just the suspended graphene can reveal much of valuable information on the physics of this complicated phenomenon. At the same time, the suspended crystal nanorelief can hardly be measured directly because of high flexibility of the 2D crystal. Moreover, the relief portion related to rapid out-of-plane oscillations (flexural phonons) is also inaccessible by such measurements. Here we present a technique for measuring the Fourier components of the height-height correlation function H(q) of suspended graphene which includes the effect of flexural phonons. The technique is based on the analysis of electron diffraction patterns. The H(q) is measured in the range of wavevectors q≈0.4-4.5nm(-1). At the upper limit of this range H(q) does follow the T/κq(4) law. So, we measured the value of suspended graphene bending rigidity κ=1.2±0.4eV at ambient temperature T≈300K. At intermediate wave vectors, H(q) follows a slightly weaker exponent than theoretically predicted q(-3.15) but is closer to the results of the molecular dynamics simulation. At low wave vectors, the dependence becomes even weaker, which may be a sign of influence of charge carriers on the dynamics of undulations longer than 10nm. The technique presented can be used for studying physics of flexural phonons in other 2D materials.

One-step synthesis of a suspended ultrathin graphene oxide film: application in transmission electron microscopy.

Ultrathin graphene films find their use as advantageous support for nano- and biomaterials investigations. Thin film causes a very slight deterioration to measured signals, thus providing more details of the object's structure at nanoscale. The ultimate thinness of graphene works in the best way for this purpose. However, obtaining suspended thin film of a large-area, which is convenient for applications, is often a relatively complicated and time-consuming task. Here we present a one-step 1-min technique for synthesis of an extremely thin (about 1-2 nm) continuous film suspended over cells of a conventional copper grid (50-400 µm mesh). This technique enables us to acquire a large-area film which is water-resistant, stable in organic solvents and can act as a support when studying nanoparticles or biomaterials. Moreover, the very mechanism of the film formation can be interesting from the point of view of other applications of ultrathin graphene oxide papers.

Monodisperse spherical mesoporous silica particles: fast synthesis procedure and fabrication of photonic-crystal films.

A procedure for the synthesis of monodisperse spherical mesoporous silica particles (MSMSPs) via the controlled coagulation of silica/surfactant clusters into spherical aggregates with mean diameters of 250-1500 nm has been developed. The synthesis is fast (taking less than 1 h) because identical clusters are simultaneously formed in the reaction mixture. The results of microscopic, x-ray diffraction, adsorption and optical measurements allowed us to conclude that the clusters are ∼15 nm in size and have hexagonally packed cylindrical pore channels. The channel diameters in MSMSPs obtained with cethyltrimethylammonium bromide and decyltrimethylammonium bromide as structure-directing agents were 3.1 ± 0.15 and 2.3 ± 0.12 nm, respectively. The specific surface area and the pore volume of MSMSP were, depending on synthesis conditions, 480-1095 m(2) g(-1) and 0.50-0.65 cm(3) g(-1). The MSMSP were used to grow opal-like photonic-crystal films possessing a hierarchical macro-mesoporous structure, with pores within and between the particles. A selective filling of mesopore channels with glycerol, based on the difference between the capillary pressures in macro- and mesopores, was demonstrated. It is shown that this approach makes it possible to control the photonic bandgap position in mesoporous opal films by varying the degree of mesopore filling with glycerol.

Quantum cutting in Li (770 nm) and Yb (1000 nm) co-dopant emission bands by energy transfer from the ZnO nano-crystalline host.

Li-Yb co-doped nano-crystalline ZnO has been synthesized by a method of thermal growth from the salt mixtures. X-ray diffraction, transmission electron microscopy, atomic absorption spectroscopy and optical spectroscopy confirm the doping and indicate that the dopants may form Li-Li and Yb(3+)-Li based nanoclusters. When pumped into the conduction and exciton absorption bands of ZnO between 250 to 425 nm, broad emission bands of about 100 nm half-height-width are excited around 770 and 1000 nm, due to Li and Yb dopants, respectively. These emission bands are activated by energy transfer from the ZnO host mostly by quantum cutting processes, which generate pairs of quanta in Li (770 nm) and Yb (1000 nm) emission bands, respectively, out of one quantum absorbed by the ZnO host. These quantum cutting phenomena have great potential for application in the down-conversion layers coupled to the Si solar cells.

Preparation and luminescence of bulk oxyfluoride glasses doped with Ag nanoclusters.

Bulk oxyfluoride glasses doped with Ag nanoclusters have been prepared using the melt quenching technique. When pumped in the absorption band of Ag nanoclusters between 300 to 500 nm, these glasses emit a very broad luminescence band covering all the visible range with a weak tail extending into the near infrared. The maximum of the luminescence band and its color shifts to the blue with a shortening of the excitation wavelength and an increasing ratio of oxide to fluoride components, resulting in white color luminescence at a particular ratio of oxide to fluoride; with a quantum yield above 20%.

[Maps of preferential conformation of dipeptides in the structural regions of globular proteins]. / Karty preimushchestvennogo konformatsionnogo sostoianiia dipeptidov v strukturirovannykh uchastkakh globuliarnykh belkov.

According to X-ray crystallographic analysis of 46 globular proteins the probability of dipeptides frequency in alpha-helical beta-sheet and random coil conformations has been studied on the basis of which the maps of preferentially conformational state of dipeptide in different elements of secondary structure of proteins have been obtained.