Linking metal–organic cages pairwise as a design approach for assembling multivariate crystalline materials

Using metal–organic cages (MOCs) as preformed supermolecular building-blocks (SBBs) is a powerful strategy to design functional metal–organic frameworks (MOFs) with control over the pore architecture and connectivity. However, introducing chemical complexity into the network via this route is limited as most methodologies focus on only one type of MOC as the building-block. Herein we present the pairwise linking of MOCs as a design approach to introduce defined chemical complexity into porous materials. Our methodology exploits preferential Rh-aniline coordination and stoichiometric control to rationally link Cu₄L₄ and Rh₄L₄ MOCs into chemically complex, yet extremely well-defined crystalline solids. This strategy is expected to open up significant new possibilities to design bespoke multi-functional materials with atomistic control over the location and ordering of chemical functionalities.

A new strategy to design atomically precise multivariate metal–organic frameworks is presented. This is achieved by linking two preformed metal–organic cages via a precisely tuned Rh–aniline interaction.     

Drag reduction and solvation in polymer solutions

A model is described which explains drag reduction (DR) in dilute polymer solutions in terms of solvation of macromolecular chains and formation of relatively stable domains. The domains partly suppress the vortex formation, act as energy sinks, and also play a role in mechanical degradation in flow (MDF). We report ultrasonically determined solvation numbers for a series of copolymers with the same chemical structure but differing widely in their intrinsic viscosities. The solvation numbers confirm the model. Thus, we have a criterion for selection of DR agents with low MDF for: oil well operations; crude oil transport; fire fighting; high sewer throughput; irrigation; hydrotransport of solids; marine applications; and biomedical applications including the arteriosclerosis prevention.     

Analysis of polycyclic aromatic hydrocarbons by ion trap tandem mass spectrometry

An ion-trap mass spectrometer with a wave board and tandem mass spectrometry software was used to analyze gas chromatographically separated polycyclic aromatic hydrocarbons (PAHs) by using collision-induced dissociation (CID). The nonresonant (multiple collision) mode was used to determine the conditions for CID ionization of 18 PAHs. Unlike in electron impact (EI) analysis, the relative abundances of progeny ions of isomers were statistically different (using Student’s t-test) in CID analysis, thus making isomer identification by CID possible. For comparison, CID and EI were applied to the analysis of used motor oil. CID analysis was shown to be more sensitive than EI analysis of the used motor oil. Precision at the 10-ppb level for EI and CID showed relative standard deviations of 5. 2 and 7. 7%, respectively.     

Manufacturing of Volumetric Glass–Based Composites with Single‐ and Double‐QD Doping

Quantum dot (QD)‐based light‐emitting materials are gaining increased attention because of their easily tunable optical properties desired for various applications in biology, optoelectronics, and photonics. However, few methods can be used to manufacture volumetric materials doped with more than one type of QD other than QD‐polymer hybrids, and they often require complicated preparation processes and are prone to luminescence quenching by QD aggregation and separation from the matrix. Here, simultaneous doping of a volumetric glass‐based nanocomposite with two types of QDs is demonstrated for the first time in a single‐step process using the nanoparticle direct doping method. Glass rods doped with CdTe, CdSe/ZnS, or co‐doped with both QDs, are obtained. Photoluminescence and lifetime experiments confirm temperature‐dependent double emission with maxima at 596 and 720 nm with mean lifetimes up to 16 ns, as well as radiative energy transfer from the short wavelength–emitting QDs to the long wavelength–emitting QDs. This approach may enable the simple and cost‐efficient manufacturing of bulk materials that produce multicolor luminescence with cascade excitation pumping. Applications that could benefit from this include broadband optical fiber amplifiers, backlight systems in LCD screens, high‐power LEDs, or down‐converting solar concentrators used to increase the efficiency of solar panels.     

Solvothermal synthesis of nanocrystalline zinc oxide doped with Mn2+, Ni2+, Co2+ and Cr3+ ions

ZnO nanopowders doped with Mn²⁺, Ni²⁺, Co²⁺ and Cr³⁺ ions have been synthesised for the first time using a solvothermal reaction with microwave heating. The nanopowders were produced from a solution of zinc acetate and manganese (II), chromium (III), nickel (II) and cobalt (II) acetates, using ethylene glycol as a solvent. The content of Ni²⁺, Co²⁺ and Cr³⁺ ions in the solution and in the solid phase were close to each other up to 5 mol%. The doping level of Mn²⁺ ions in the solid is about 50% of that in the solution. No phases or compounds other than ZnO were detected by X-ray diffraction with Mn²⁺, Co²⁺ and Ni²⁺ doping. With Cr³⁺ ions a small amount of chromium oxide was found. None of the powders displayed any luminescence after doping. The Mn²⁺-doped powder displayed a paramagnetic behaviour. ESR and magnetisation investigations have revealed that no clustering of Mn²⁺ ions occurred up to a doping level of 3.9 mol%. The average grain size of powders doped with Ni²⁺, Cr³⁺, Co²⁺ and Mn²⁺ for a 10 mol% ion content in the solution was about 20 nm and the grain size dispersion 30%. With increasing dopant content the grain size decreased. It appears that the solvothermal process employed allows relatively high doping levels of the transition metal ions to be achieved without any dopant clustering or oxide precipitation.     

Study of free convective boundary layer of isothermal lateral surface of axisymmetrical horizontal body

Approximate analytical solution of simplified Navier–Stokes and Fourier–Kirchhoff equations describing free convective heat transfer from isothermal surface has been presented. It is supposed that the surface has the horizontal axis of symmetry and its axial cross-section lateral boundary is a concave function. The equation for the boundary layer thickness is derived for typical for natural convection assumptions. The most important are that the convective fluid flow is stationary and the normal to the surface component of velocity is negligibly small in comparison with the tangential one. The theoretical results are verified by two characteristic cases of the revolution surfaces namely for horizontal conic and vertical round plate. Both limits of presented solution coincide with known formulas.     

Crystal structure and vibrational properties of new luminescent hosts K3YF6 and K3GdF6

The luminescence hosts K₃YF₆ and K₃GdF₆ were obtained in a single-crystal form. Their crystal structure was determined from single-crystal X-ray diffraction data. Both crystals adopt monoclinic system with space group P2₁/n, Z=2. Lattice parameters for K₃YF₆ are refined to the following values , , , β=90.65(3) and for K₃GdF₆, , , β=90.80(3). The vibrational analysis, IR and Raman spectroscopy at room temperature, was applied to these compounds in order to study the site symmetry of Y³⁺ and Gd³⁺ ions.     

Application of thin-layer chromatography image analysis technique in quantitative determination of sphingomyelin

A sensitive and convenient method for sphingomyelin determination was developed based on thinlayer chromatography (TLC) and image-processing analysis. The mobile phase composition, detection and quantification conditions were systematically investigated through several trials. The molybdenum blue reaction allowed specific detection of the phospholipid with a high sensitivity and a wide linear range. Digital images of TLC plate chromatograms were captured with flatbed scanner and converted into peak chromatograms using TLSee® software and quantitative analysis was conducted. The linearity, sensitivity, accuracy and precision of the system were evaluated. The limits of detection and quantification were 0.5 and 1.7 μg/spot, respectively. Separation of the mixture consisting of sphingomyelin, phosphatidylcholine, and phosphatidylethanolamine was also carried out.     

Spin-label W-band EPR with Seven-Loop–Six-Gap Resonator: Application to Lens Membranes Derived from Eyes of a Single Donor

Spin-label W-band (94 GHz) electron paramagnetic resonance (EPR) with a five-loop–four-gap resonator (LGR) was successfully applied to study membrane properties (Mainali et al. J Magn Reson 226:35–44, 2013). In that study, samples were equilibrated with the selected gas mixture outside the resonator in a sample volume ~100 times larger than the sensitive volume of the LGR and transferred to the resonator in a quartz capillary. A seven-loop–six-gap W-band resonator has been developed. This resonator permits measurements on aqueous samples of 150 nL volume positioned in a polytetrafluoroethylene (PTFE) gas permeable sample tube. Samples can be promptly deoxygenated or equilibrated with an air/nitrogen mixture inside the resonator, which is significant in saturation-recovery measurements and in spin-label oximetry. This approach was tested for lens lipid membranes derived from lipids extracted from two porcine lenses (single donor). Profiles of membrane fluidity and the oxygen transport parameter were obtained from saturation-recovery EPR using phospholipid analog spin-labels. Cholesterol analog spin-labels allowed discrimination of the cholesterol bilayer domain and acquisition of oxygen transport parameter profiles across this domain. Results were compared with those obtained previously for membranes derived from a pool of 100 lenses. Results demonstrate that EPR at W-band can be successfully used to study aqueous biological samples of small volume under controlled oxygen concentration.