Controlling the contents of microdroplets by exploiting the permeability of PDMS

A microfluidic device capable of exploiting the permeability of small molecules through polydimethylsiloxane (PDMS) has been fabricated in order to control the contents of microdroplets stored in storage wells. We demonstrate that protein precipitation and crystallization can be triggered by delivery of ethanol from a reservoir channel, thus controlling the protein solubility in microdroplets. Likewise quorum sensing in bacteria was triggered by delivery of the auto-inducer N-(3-oxododecanoyl)-l-homoserine lactone (OdDHL) through the PDMS membrane of the device.     

Low Charge Density Cationic Polymers for Gene Delivery: Exploring the Influence of Structural Elements on in vitro Transfection

A series of end‐functionalized poly(trimethylene carbonate) DNA carriers, characterized by low cationic charge density and pronounced hydrophobicity, is used to study structural effects on in vitro gene delivery. As the DNA‐binding moieties are identical in all polymer structures, the differences observed between the different polymers are directly related to the functionality and length of the polymer backbone. The transfection efficiency and cytotoxicity of the polymer/DNA complexes are thus found to be dependent on a combination of polymer charge density and functionality, highlighting the importance of such structural considerations in the development of materials for efficient gene delivery.

     

Synthesis of Comb Tri‐ and Tetrablock Copolymers Catalyzed by the Grubbs First Generation Catalyst

High molecular weight tri‐ and tetrablock copolymers were synthesized from the commercially available Grubbs first generation catalyst for the first time. These polymers had degrees of polymerization from 430 to 1 100, molecular weights up to 419 000 g · mol⁻¹, and narrow polydispersities. Oxanorbornene monomers were chosen due to their fast rates of polymerization and slow rates of cross metathesis. Polystyrene arms were grown from selected blocks by atom transfer radical polymerization to yield architecturally complex comb tri‐ and tetrablock copolymers. These polymers self‐assembled in the solid state into ordered morphologies that were characterized by scanning electron microscopy.

     

A57Fe Mössbauer study of Nd(Fe0.5Co0.5)9Si2

A⁵⁷Fe Mössbauer study of Nd(Fe_0.5Co_0.5)₉Si₂ has been carried out over the temperature range 4.2–295 K. The analysis of the Mössbauer spectra, combined with X-ray diffraction on a magnetically aligned powder sample, shows that the easy-magnetization direction lies in the basal plane of this tetragonal BaCd₁₁ structure at 295 K, but is canted at an angle of 29(5) above the basal plane at 4.2 K. AC susceptibility measurements performed in the temperature range 77–295 K reveal a peak spanning the range 87–106 K, with the maximum occurring at 96 K. From these data, we conclude that there is a spin-reorientation from basal c-plane to a canted magnetic structure in this compound, with an onset at 96 K as the temperature decreases.     

One-way optoelectronic switching of photochromic molecules on gold

We investigate photochromic molecular switches that are self-assembled on gold. We use two experimental techniques; namely, the mechanically controllable break-junction technique to measure electronic transport, and UV/Vis spectroscopy to measure absorption. We observe switching of the molecules from the conducting to the insulating state when illuminated with visible light (lambda=546 nm), in spite of the gold surface plasmon absorption present around this wavelength. However, we fail to observe the reverse process which should occur upon illumination with UV light (lambda=313 nm). We attribute this to quenching of the excited state of the molecule in the open form by the presence of gold.     

Magnetic properties of Nd3+ in Nd−Ba−Cu−O-compounds

Neutron diffraction, neutron spectroscopy and magnetization measurements have been employed to study the structural, electronic, and magnetic behavior of eleven compounds with the general formula Nd_1+y Ca _v Ba_2–y–v Cu₃O _x (0y0.5; 0v0.25; 6x7). The structure turned out to react to oxygen reduction similar as other 123-compounds, yielding discontinuities close to the metal-insulator-transition and the well-known relations of bond lengths as a function ofT _c. The crystalline electric field (CEF) interaction, splitting the 10-fold degenerate ground-state J-multiplet of the Nd³⁺-ions into five doublet states, was investigated by neutron spectroscopy. The derived CEF parameters have been used to determine changes in the electronic surroundings of the Nd³⁺ ions. In addition, with the help of the CEF parameters the thermodynamic magnetic properties of these compounds were calculated which turn out to be in good agreement with the experimental data.     

Single-phase Bi2+x(Ca,Sr) n+1 Cu n O2n+4+δ, n = 0, 1, 2, 3 AND ∞, and some substitutional DERIVATIVES

The preparation, structure and properties of five members of the homologous series Bi_2+x(Ca,Sr) _n+1 Cu _n O_2n+4+δ are discussed, namely for n = 0, 1, 2, 3 and ∞. The two end members are insulating phases with a fixed oxygen stoichiometry but the members n = 1, 2 and 3 are superconducting phases with T_c depending on the calcium to strontium ratio and on oxygen stoichiometry as determined by annealing temperature and oxygen partial pressure. Maximum zero resistance T_c 's obtained are n = 1: 76 K, n = 2: 91 K and n = 3: 106 K. The effects of Pb-substitution in n = 2 and n = 3 are discussed with particular reference to the stabilisation of the latter phase. Rare-earth substitution is shown to raise T_c for n = 2 to at least 101 K without the introduction of the n = 3 phase.     

High precision54Mn NMRON in antiferromagnetic MnCl2.4H2O,using a new method of nuclear spin cooling in the mK region

A practical method of nuclear spin cooling in the mK region, based on dramatic reduction in the spin-lattice relaxation time T₁ at the antiferromagnetic-spin flop and spin flopparamagnetic phase transitions, is described. Far lower temperatures (down to 13 mK) than have been obtained to date (～ 90 mK) are achieved in reasonable times, greatly increasing the sensitivity of NMRON. Following resonance, active isotope spins can be rapidly reset (in times ～ 1 second) to thermal equilibrium. For⁵⁴Mn in MnCl₂.4H₂O, hyperfine parameters A=?203.75 MHz, P=0.155 MHz and the exchange/ crystal field parameter combination B_ex + 4¦D¦/gμ_B=1.355 T have been determined from good agreement between perturbation theory to second order and detailed NMRON results in applied fields parallel to the easy axis in the range 0-0.7 T. Splitting of observed lines in zero applied field (? 3.05 MHz) is mainly due to the pseudo-quadrupole (second order magnetic) interaction. Small third order effects (～0.05 MHz) have been resolved.     

Irreducible tensor operators and selective/hard single and double resonance experiments in insulators: Applications to NMRON and MQ-NMR

Recently, pulsed NMRON experiments have been carried out on trace amounts of radioactive⁵⁴Mn in the antiferromagnet MnCl₂4H₂O at 500 MHz (Le Gros et al. [1]). In this compound, the quadrupole splitting between the two lowest NMR transitions is ≈3 MHz, which precludes the use of non-selective (hard) rf pulses. Yet within the restricted 2*2 manifold, associated with a given transition, the nuclear rotation is “hard”. In this paper, the theory of “selective-hard” NMRON and MQ-NMR experiments is developed within the framework of irreducible tensor operators. In essence, the theory extends the early work of Jaynes [4] to deal with the higher-order multipolar states created during the course of a given NMR experiment. Several new pulsed NMRON and MQ-NMR experiments are proposed. For example, it is demonstrated how “ouble resonance”, “selective-hard” experiments on the pseudo spin-1 manifold spanned by |±1> and |0> Zeeman states of any integer spinI could be used to extract small chemical shifts in the face of very large quadrupole splittings.