Template‐Free Supracolloidal Self‐Assembly of Atomically Precise Gold Nanoclusters: From 2D Colloidal Crystals to Spherical Capsids

We report supracolloidal self‐assembly of atomically precise and strictly monodisperse gold nanoclusters involving p‐mercaptobenzoic acid ligands (Au₁₀₂‐pMBA₄₄) under aqueous conditions into hexagonally packed monolayer‐thick two‐dimensional facetted colloidal crystals (thickness 2.7 nm) and their bending to closed shells leading to spherical capsids (d ca. 200 nm), as controlled by solvent conditions. The 2D colloidal assembly is driven in template‐free manner by the spontaneous patchiness of the pMBA ligands around the Au₁₀₂‐pMBA₄₄ nanoclusters preferably towards equatorial plane, thus promoting inter‐nanocluster hydrogen bonds and high packing to planar sheets. More generally, the findings encourage to explore atomically precise nanoclusters towards highly controlled colloidal self‐assemblies.     

Local concentration of gel phase domains in supported lipid bilayers under light irradiation in binary mixture of phospholipids doped with dyes for photoinduced activation

Recently, lipid bilayers supported on solid substrates are considered to offer potential as biological devices utilizing biological membranes and membrane proteins. In particular, artificially patterned supported bilayers hold great promise for the development of biological devices. In this study, we show control of the formation and location of phase-separated domain structures by light irradiation for gel phase and liquid-crystalline phase separation structures in a DMPC-DOPC binary lipid bilayer tagged with dye molecules on SiO2/Si substrates. Upon light irradiation, the gel phase domain structures disappeared from the phase-separated bilayers. This disappearance indicates that the light irradiation causes a local increase in the temperature of the lipid bilayer. In this disappearance phenomenon, the photoinduced activation of dye lipids, e.g. fluorescent lipids, is considered to play an important role, since the same phenomenon does not occur in lipid bilayers that have a low concentration of dye lipids. Thus, the local increase in temperature is propagated by light absorption of the dye lipid and subsequent photoinduced activation of nonradiative molecular vibrations. Subsequent interruption of the photoinduced activation for molecular motion allowed the gel phase domain structures to precipitate and grow again. Moreover, the domain area fraction remaining after the photoinduced activation was higher than that before the photoinduced activation. This result indicates that the local increase in temperature propagated by dye-excitation enhances formation of the gel phase domains. By utilizing this phenomenon, we could preferentially induce formation of domain structures within the light-irradiated regions. This technique could be the basis for a new patterning technique based on domain structures. Moreover, these domain structure patterns can be eliminated by increasing the temperature, allowing rewritable patterning.     

Comparison of infrared-excited up-converting phosphors and europium nanoparticles as labels in a two-site immunoassay

Research in the field of immunoassays and labels used in the detection has been recently focused on particulate reporters, which possess very high specific activity that excludes the label as a sensitivity limiting factor. However, the large size and shape of the particulate labels may produce additional problems to immunoassay performance. The aim of this work was to study with two identical non-competitive two-site immunoassays whether up-converting phosphor (UCP) particles are comparable in performance with europium(III) chelate-dyed nanoparticles as particulate labels. In addition we strived to verify the common assumption of the photostability of up-converting phosphor particles supporting their potential applicability in imaging. Detection limits in two-site immunoassay for free prostate-specific antigen (free-PSA) were 0.53 ng L⁻¹ and 1.3 ng L⁻¹ using two different up-converting phosphors and 0.16 ng L⁻¹ using europium(III) nanoparticle. Large size distribution and non-specific binding of up-converting phosphor particles caused assay variation in low analyte concentrations and limited the analytical detection limit. The non-specific binding was the major factor limiting the analytical sensitivity of the immunoassay. The results suggests the need for nanoscaled and uniformely sized UCP-particles to increace the sensitivity and applicability of up-converting phosphor particles. Anti-Stokes photoluminescence of up-converting phosphor particles did not photobleach when measured repeatedly, on the contrary, the time-resolved fluorescence of europium nanoparticles photobleached relatively rapidly.     

Antibody-free lanthanide-based fluorescent probe for determination of protein tyrosine kinase and phosphatase activities

A single-labeled peptide probe for measuring peptide phosphorylation status was developed by using a phosphate sensitive terbium chelate. The activity of Abl protein tyrosine kinase and T-cell protein Tyrosine phosphatase (TC PTP) was monitored in real time. To study the probe design in detail, variable substrate peptide sequences, where the enzyme target site was located from two to five amino acids apart from the nearest tyrosine residue, were synthesized. The maximum change observed in fluorescence intensity after phosphorylation was up to 320%, when the phosphorylated tyrosine was located two amino acids from the lysine coupled to the phosphate sensitive terbium chelate, demonstrating an excellent performance for a homogeneous assay. Also the longer distance of five amino acids between the phosphorylated tyrosine residue and terbium chelate resulted up to 260% change in fluorescence intensity.

Lipase-catalyzed acylation in a continuous down-flow fixed-bed reactor

The kinetic resolution of racemic 1-phenylethanol with ethyl acetate was investigated in a down-flow fixed-bed reactor operated in a continuous mode mainly at the molar ratio of 1: 3 in 400 mL toluene at 70°C. The catalytic activity of the immobilized lipase was studied by: (i) changing the flow rates, (ii) utilizing different substrate concentrations, (iii) applying step changes using ethyl acetate, ethyl benzene, acetic acid, acetophenone etc., (iv) investigating the inhibitory effect of either the desired or the stoichiometric products (R)-1-phenylethyl acetate and ethanol, respectively), (v) elucidating the effect of water on the activity and stability of the immobilized lipase. The residence time distribution and the reactor hydrodynamics were also discussed along with kinetic modelling. The results were linked to the one-pot reactions.     

Formation of a missing row reconstruction on a Cu(100) surface: An atom scale density functional theory based study

The oxygen-induced reconstruction of Cu(100) surfaces has been studied in great detail. Experimentally, missing row reconstruction occurs with an O coverage of 0.5 monolayer (ML). Several DFT-based calculations of vacancy-surface Cu pairs were performed at O coverage between 0 and 0.5 ML. No structure was identified in these calculations as being energetically favoured over the ideal Cu(100) structure. When a Cu atom (0.125 ML) was added to the system, a new energetically favourable missing row and added Cu-O-Cu row structure was found. It has been suggested that this structure is an important intermediate step towards the missing row formation. The transition from the missing and added row structure to the (2√2 × √2)R45^o-O reconstruction has the energetic requirement of very good binding sites for the Cu atoms, which can be found on the step boundaries. These results are in excellent agreement with the step edge growth and the formation of strongly anisotropic islands observed by Lahtonen et al. (J. Chem. Phys. 129 (2008) 124703).     

Dynamic analysis for axially moving viscoelastic panels

In this study, stability and dynamic behaviour of axially moving viscoelastic panels are investigated with the help of the classical modal analysis. We use the flat panel theory combined with the Kelvin–Voigt viscoelastic constitutive model, and we include the material derivative in the viscoelastic relations. Complex eigenvalues for the moving viscoelastic panel are studied with respect to the panel velocity, and the corresponding eigenfunctions are found using central finite differences. The governing equation for the transverse displacement of the panel is of fifth order in space, and thus five boundary conditions are set for the problem. The fifth condition is derived and set at the in-flow end for clamped–clamped and clamped-simply supported panels. The numerical results suggest that the moving viscoelastic panel undergoes divergence instability for low values of viscosity. They also show that the critical panel velocity increases when viscosity is increased and that the viscoelastic panel does not experience instability with a sufficiently high viscosity coefficient. For the cases with low viscosity, the modes and velocities corresponding to divergence instability are found numerically. We also report that the value of bending rigidity (bending stiffness) affects the distance between the divergence velocity and the flutter velocity: the higher the bending rigidity, the larger the distance.     

Indoor Planning for High Speed Downlink Packet Access in WCDMA Cellular Network

The aim of this paper is to show the special characteristics of the indoor environment related to radio propagation and furthermore to radio network planning. The aspects of the radio network planning are highlighted especially for Wideband Code Division Multiple Access (WCDMA) radio access technology that is used widely in the third generation mobile networks. Moreover, the detailed planning parameters in indoor environment are studied for High Speed Downlink Packet Access (HSDPA) in order to support high throughput data applications in Universal Mobile Telecommunications System (UMTS). The final target of the paper is to compare pico cell, distributed antenna system (DAS), and radiating cable network configurations in indoor environment to provide the optimal radio conditions for the data applications, and thus to serve highest number of mobile users. Several measurement campaigns with different antenna configurations have been conducted in order to study the effect of multi path related parameters, as delay spread of the signal. Also other capacity related parameters as received signal levels, interference, throughput, and transmit power levels have been studied in order to find out the optimal solution for HSDPA in UMTS. The results clearly show that pico cells and distributed antenna system have outstanding performance in indoor propagation channel compared to radiating cable. In sense of signal quality, pico cell performance is slightly better compared to distributed antenna system. However, measurements with HSDPA indicate that practical capacity of DAS outperforms pico cells. The measurements also show that separation of the antennas is a key capacity related parameter when planning WCDMA based indoor systems.     

Environmental protection of inkjet-printed Ag conductors

Electrically conductive silver nanoparticle ink patterns were fabricated using the inkjet printing method. Two different polymer films were used as the substrate materials. The patterns were exposed to humidity and salt fog and the electrical performance (sheet resistance and RF performance) as well as mechanical endurance (adhesion) were measured before and after the environmental tests. The electrical properties of the printed structures remained good in all the measurable samples. The adhesion between the ink and a substrate material appeared to be a greater challenge in harsh environments. Protection capabilities of one dip coated and one hot laminated barrier materials were evaluated during the environmental tests. The results showed that there is a need for environmental protection in printed electronics. Especially the laminated barrier films can offer a potential solution for shielding printed electronics in harsh environments as they can provide good mechanical protection, and can easily be integrated in roll-to-roll process.