Slow light in bacteriorhodopsin solution using coherent population oscillations

Slow light is demonstrated in liquid phase in an aqueous bacteriorhodopsin (bR) solution at room temperature. Group velocity as low as 3 m/s (all the way to c) is achieved by exploiting the photoisomerization property of bR for coherent population oscillations. Slow light in the liquid phase offers several advantages over solids or vapors for a variety of applications: (i) shorter lifetimes of the M state facilitate slow light at higher modulation frequencies, (ii) convection makes it possible to obtain large signal delays even at high input powers, and (iii) solution concentration is another convenient parameter to vary the signal delay over a wide range.     

Electrochemical characterization of composite membranes based on crown-ethers intercalated into montmorillonite

Oxyethylene macrocyclic compounds (crown-ethers) act as ligands of intracrystalline cations of certain layered silicates as montmorillonites. Stable intercalation materials are formed which are used to prepare organic-inorganic membranes by encapsulating these intercalation compounds with a poly-butadiene thin coating. Electrochemical Impedance Spectroscopy (EIS) is used to study the resulting composite membranes in contact with aqueous electrolytes. From the impedance plots, the ionic resistance of the membranes is obtained. The thickness of the polybutadiene coating is an important factor determining the ability of ions to pass across the membrane. Marked differences in the ionic resistance are observed as a function of the nature of the interlayer macrocyclic compound. For non-intercalated montmorillonite membranes, the ionic resistance is strongly reduced, whereas for some crown-ether intercalated materials such as 18-crown-6 and dibenzo 24-crown-8, iono-selective membranes are obtained. Concerning the nature of the electrolyte, cations exhibiting greater hydration energies show higher difficulties to pass through the membrane and, consequently, the ionic resistance increases.     

Coordination Chemistry Dictates the Structural Defects in Lead Halide Perovskites

We show the influence of species present in precursor solution during formation of lead halide perovskite materials on the structural defects of the films. The coordination of lead by competing solvent molecules and iodide ions dictate the type of complexes present in the films. Depending on the processing conditions all PbIS₅⁺, PbI₂S_4, PbI₃S₃^?, PbI₄S₂^2?, PbI₅S₂^3?, PbI₆^4?and 1D (Pb₂I₄)_n chains are observed by absorption measurements. Different parameters are studied such as polarity of the solvent, concentration of iodide ions, concentration of solvent molecules and temperature. It is concluded that strongly coordinating solvents will preferentially form species with a low number of iodide ions and less coordinative solvents generate high concentration of PbI₆^?. We furthermore propose that all these plumbate ions may act as structural defects determining electronic properties of the photovoltaic films.     

Complexes formed between nitrilotris(methylenephosphonic acid) and M(2+) transition metals: isostructural organic-inorganic hybrids

Nitrilotris(methylenephosphonic acid) (NTP, [N(CH(2)PO(3)H(2))(3)]) recently has been found to form three-dimensional porous structures with encapsulation of templates as well as layered and linear structures with template intercalation. It was, therefore, of interest to examine the type of organic-inorganic hybrids that would form with metal cations. Mn(II) was found to replace two of the six acid protons, while a third proton bonds to the nitrilo nitrogen, forming a zwitter ion. Two types of compounds were obtained. When the ratio of acid to Mn(II) was less than 10, a trihydrate, Mn[HN(CH(2)PO(3)H)(3)(H(2)O)(3)] (2) formed. Compound 2 is monoclinic P2(1)/c, with a = 9.283(2) A, b = 16.027(3) A, c = 9.7742(2) A, beta = 115.209(3) degrees, V = 1315.0(5) A(3), and Z = 4. The Mn atoms form zigzag chains bridged by two of the three phosphonate groups. The third phosphonate group is only involved in hydrogen bonding. The metal atoms are octahedrally coordinated with three of the sites occupied by water molecules. Adjacent chains are hydrogen-bonded to each other through POH and HN donors, and the additional participation of all the water hydrogens in H-bonding results in a corrugated sheet-like structure. Use of excess NTP at a ratio to metal of 10 to 1 yields an anhydrous compound Mn[HN(CH(2)PO(3)H)(3)] (1), P2(1)/n, a = 9.129(1) A, b = 8.408(1) A, c = 13.453(1) A, beta = 97.830(2) degrees, V = 1023.0(2) A(3), and Z = 4. Manganese is five coordinate forming a distorted square pyramid with oxygens from five different phosphonate groups. The sixth oxygen is 2.85 A from an adjacent Mn, preventing octahedral coordination. All the protonated atoms, three phosphonate oxygens and N, form moderately strong hydrogen bonds in a compact three-dimensional structure. The open-structured trihydrate forms a series of isostructural compounds with other divalent transition metal ions as well as with mixed-metal compositions. This is indicative that the hydrogen bonding controls the type of structure formed irrespective of the cation.     

Synthesis, Structures, and Thermal Expansion of the La2W2−xMoxO9 Series

The La₂W_2−xMo_xO₉ series has been synthesized by the ceramic method. An alternative synthesis using microwave radiation is also reported. La₂W₂O₉ has two polymorphs and the low-temperature phase (α) transforms to the high-temperature form (β) at 1077°C. The influence of the W/Mo substitution in this phase transition has been investigated by DTA. The β structure for x≥0.7 compositions can be prepared as single phase at any cooling rate. The β phase for 0.3≤x≤0.7 compounds can be prepared as single phase by quenching, whereas a mixture of α and β phases is obtained by slow cooling. The W/Mo ratio in both coexisting phases is different with the β-phase having a higher Mo content. The x=0.1 and 0.2 compounds have been prepared as mixtures of phases. The room temperature structure of β-La₂W_1.7Mo_0.3O₉ has been analyzed by the Rietveld method in P2₁3 space group. The final R-factors were R_WP=9.0% and R_F=5.6% with a structure similar to that of β-La₂Mo₂O₉. Finally, the thermal expansion of both types of structures has been determined from a thermodiffractometric study. The thermal expansion coefficients were 2.9×10⁻⁶ and 9.7×10⁻⁶°C⁻¹ for α-La₂W₂O₉ and β-La₂W_1.2Mo_0.8O₉, respectively.     

DNA purification using dynamic solid-phase extraction on a rotationally-driven polyethylene-terephthalate microdevice

We report the development of a disposable polyester toner centrifugal device for semi-automated, dynamic solid phase DNA extraction (dSPE) from whole blood samples. The integration of a novel adhesive and hydrophobic valving with a simple and low cost microfabrication method allowed for sequential addition of reagents without the need for external equipment for fluid flow control. The spin-dSPE method yielded an average extraction efficiency of ∼45% from 0.6 μL of whole blood. The device performed single sample extractions or accommodate up to four samples for simultaneous DNA extraction, with PCR-readiness DNA confirmed by effective amplification of a β-globin gene. The purity of the DNA was challenged by a multiplex amplification with 16 targeted amplification sites. Successful multiplexed amplification could routinely be obtained using the purified DNA collected post an on-chip extraction, with the results comparable to those obtained with commercial DNA extraction methods. This proof-of-principle work represents a significant step towards a fully-automated low cost DNA extraction device.     

Permeabilization of biological and artificial membranes by a bacterial dirhamnolipid produced by Pseudomonas aeruginosa

Pseudomonas aeruginosa, when cultured under the appropriate conditions, secretes rhamnolipids to the external medium. These glycolipids constitute one of the most interesting classes of biosurfactants so far. A dirhamnolipid fraction was isolated and purified from the crude biosurfactant, and its action on model and biological membranes was studied. Dirhamnolipid induced leakage of internal contents, as measured by the release of carboxyfluorescein, in phosphatidylcholine unilamellar vesicles, at concentrations below its CMC. Membrane solubilization was not observed within this concentration range. The presence of inverted cone-shaped lipids in the membrane, namely lysophosphatidylcholine, accelerated leakage, whereas cone-shaped lipids, like phosphatidylethanolamine, decreased leakage rate. Increasing concentrations of cholesterol protected the membrane against dirhamnolipid-induced leakage, which was totally abolished by the presence of 50 mol% of the sterol. Dirhamnolipid caused hemolysis of human erythrocytes through a lytic mechanism, as shown by the similar rates of K⁺ and hemoglobin leakage, and by the absence of effect of osmotic protectants. Scanning electron microscopy showed that the addition of the biosurfactant changed the usual disc shape of erythrocytes into that of spheroechinocytes. The results are discussed within the frame of the biological actions of dirhamnolipid, and the possible future applications of this biosurfactant.     

High proton conductivity in a flexible, cross-linked, ultramicroporous magnesium tetraphosphonate hybrid framework

Multifunctional materials, especially those combining two or more properties of interest, are attracting immense attention due to their potential applications. MOFs, metal organic frameworks, can be regarded as multifunctional materials if they show another useful property in addition to the adsorption behavior. Here, we report a new multifunctional light hybrid, MgH(6)ODTMP·2H(2)O(DMF)(0.5) (1), which has been synthesized using the tetraphosphonic acid H(8)ODTMP, octamethylenediamine-N,N,N',N'-tetrakis(methylenephosphonic acid), by high-throughput methodology. Its crystal structure, solved by Patterson-function direct methods from synchrotron powder X-ray diffraction, was characterized by a 3D pillared open framework containing cross-linked 1D channels filled with water and DMF. Upon H(2)O and DMF removal and subsequent rehydration, MgH(6)ODTMP·2H(2)O (2) and MgH(6)ODTMP·6H(2)O (3) can be formed. These processes take place through crystalline-quasi-amorphous-crystalline transformations, during which the integrity of the framework is maintained. A water adsorption study, at constant temperature, showed that this magnesium tetraphosphonate hybrid reversibly equilibrates its lattice water content as a function of the water partial pressure. Combination of the structural study and gas adsorption characterization (N(2), CO(2), and CH(4)) indicates an ultramicroporous framework. High-pressure CO(2) adsorption data are also reported. Finally, impedance data indicates that 3 has high proton conductivity σ = 1.6 × 10(-3) S cm(-1) at T = 292 K at ~100% relative humidity with an activation energy of 0.31 eV.     

A new family of oxide ion conductors based on tricalcium oxy-silicate

Tricalcium oxy-silicates, Ca3(SiO4)O and Ca2.93Mg0.07(Si0.98Al0.02O4)O0.99 [square]0.01, have been prepared as crystalline single phases. Ca3(SiO4)O and Ca2.93Mg0.07(Si0.98Al0.02O4)O0.99 [square]0.01 have triclinic and monoclinic structures, respectively. The samples show oxide anion conductivity with a small p-type electronic contribution under oxidizing conditions. At 1023 K, the oxide transport numbers range between 0.97 and 0.85 from reducing (dry 5%-H2-Ar/air gradient) to oxidizing (O2/air gradient) conditions in the 1023-1173 K interval. The thermal analyses showed a large weight loss on heating due to the presence of water in the materials. The monoclinic compound has ionic conductivities higher than those of the triclinic stoichiometric oxy-silicate, as expected due to the introduction of oxide vacancies. Typical total conductivities for these un-optimised solids are 10(-5)-10(-4) S cm(-1) at 1100 K. These compounds may contain a small amount of water, approximately 0.05 H2O moles per chemical formula, and they display an important proton contribution under a humidified atmosphere.