A rapid method for determining low concentrations of 210Pb in drinking water using MnO2 fibers.

A rapid method for determining low activity concentrations of 210Pb in drinking water was developed and tested. The method consists of a few stages for sample preparation that involve passing 12 L of water through a column with acrylic fibers implanted with MnO2 (used to adsorb 210Pb). The MnO2 fibers are oven-dried, compressed and measured by a broad-energy germanium detector used to quantify 210Pb via its characteristic 46.5 keV γ-ray. The time taken for sample preparation is approximately 4 h and recovery factors for lead in tap water of 87 ± 3% were achieved. After a measurement duration of 4 h, the minimum detectable activity concentration reaches 0.02 Bq/L for 210Pb, being well below the respective limit for drinking water in Israel (0.2 Bq/L) as well as the value recommended by the World Health Organization (0.1 Bq/L). Furthermore, a measurement duration of 48 h provides a minimum detectable activity concentration of ∼0.006 Bq/L, which is similar in magnitude to other, well-established methods that rely on lengthy and rather complex procedures. Thus, the combination of MnO2 fibers and gamma-ray spectrometry may be attractive for routine use by analytical laboratories that monitor radioactivity in drinking water.

Competing Magnetic Interactions in the Antiferromagnetic Topological Insulator MnBi_{2}Te_{4}.

The antiferromagnetic (AFM) compound MnBi_{2}Te_{4} is suggested to be the first realization of an AFM topological insulator. We report on inelastic neutron scattering studies of the magnetic interactions in MnBi_{2}Te_{4} that possess ferromagnetic triangular layers with AFM interlayer coupling. The spin waves display a large spin gap and pairwise exchange interactions within the triangular layer are long ranged and frustrated by large next-nearest neighbor AFM exchange. The degree of frustration suggests proximity to a variety of magnetic phases, potentially including skyrmion phases, which could be accessed in chemically tuned compounds or upon the application of symmetry-breaking fields.

Liquid-like thermal conduction in intercalated layered crystalline solids.

As a generic property, all substances transfer heat through microscopic collisions of constituent particles 1 . A solid conducts heat through both transverse and longitudinal acoustic phonons, but a liquid employs only longitudinal vibrations2,3. As a result, a solid is usually thermally more conductive than a liquid. In canonical viewpoints, such a difference also serves as the dynamic signature distinguishing a solid from a liquid. Here, we report liquid-like thermal conduction observed in the crystalline AgCrSe2. The transverse acoustic phonons are completely suppressed by the ultrafast dynamic disorder while the longitudinal acoustic phonons are strongly scattered but survive, and are thus responsible for the intrinsically ultralow thermal conductivity. This scenario is applicable to a wide variety of layered compounds with heavy intercalants in the van der Waals gaps, manifesting a broad implication on suppressing thermal conduction. These microscopic insights might reshape the fundamental understanding on thermal transport properties of matter and open up a general opportunity to optimize performances of thermoelectrics.

Oriented polyvinylidene fluoride-trifluoroethylene (P(VDF-TrFE)) films by Langmuir-Blodgett deposition: a synchrotron X-ray diffraction study.

Langmuir-Blodgett films of polyvinylidene fluoride trifluoroethylene - P(VDF-TrFE)-copolymers possess substantially improved electrocaloric and pyroelectric properties, when compared with conventionally spin-cast films. In order to rationalize this, we prepared single-layered films of P(VDF-TrFE) (70 : 30) using both deposition techniques. Grazing incidence wide-angle X-ray scattering (GIWAXS), reveals that Langmuir-Blodgett deposited films have a higher concentration of the ferroelectric ß-phase crystals, and that these films are highly oriented with respect to the substrate. Based on these observations, we suggest alternative means of deposition, which may substantially enhance the electrocaloric effect in P(VDF-TrFE) films. This development has significant implications for the potential use of P(VDF-TrFE) in solid-state refrigeration.

Stripe antiferromagnetic spin fluctuations in SrCo2As2.

Inelastic neutron scattering measurements of paramagnetic SrCo2As2 at T=5 K reveal antiferromagnetic (AFM) spin fluctuations that are peaked at a wave vector of Q(AFM)=(1/2,1/2,1) and possess a large energy scale. These stripe spin fluctuations are similar to those found in AFe2As2 compounds, where spin-density wave AFM is driven by Fermi surface nesting between electron and hole pockets separated by Q(AFM). SrCo2As2 has a more complex Fermi surface and band-structure calculations indicate a potential instability toward either a ferromagnetic or stripe AFM ground state. The results suggest that stripe AFM magnetism is a general feature of both iron and cobalt-based arsenides and the search for spin fluctuation-induced unconventional superconductivity should be expanded to include cobalt-based compounds.

Level crossings and zero-field splitting in the {Cr8}-cubane spin cluster studied using inelastic neutron scattering and magnetization.

Inelastic neutron scattering (INS) in variable magnetic field and high-field magnetization measurements in the millikelvin temperature range were performed to gain insight into the low-energy magnetic excitation spectrum and the field-induced level crossings in the molecular spin cluster {Cr(8)}-cubane. These complementary techniques provide consistent estimates of the lowest level-crossing field. The overall features of the experimental data are explained using an isotropic Heisenberg model, based on three distinct exchange interactions linking the eight Cr(III) paramagnetic centers (spins s = 3/2), that is supplemented with a relatively large molecular magnetic anisotropy term for the lowest S = 1 multiplet. It is noted that the existence of the anisotropy is clearly evident from the magnetic field dependence of the excitations in the INS measurements, while the magnetization measurements are not sensitive to its effects.

Charge inversion at minute electrolyte concentrations.

Anionic dimyristoylphosphatidic acid monolayers spread on LaCl3 solutions reveal strong cation adsorption and a sharp transition to surface overcharging at unexpectedly low bulk salt concentrations. We determine the surface accumulation of La3+ with anomalous x-ray reflectivity and find that La3+ compensates the lipid surface charge by forming a Stern layer with approximately 1 La3+ ion per 3 lipids below a critical bulk concentration, ct approximately 500 nM. Above ct, the surface concentration of La3+ increases to a saturation level with approximately 1 La3+ per lipid, thus implying that the total electric charge of the La3+ exceeds the surface charge. This overcharge is observed at approximately 4 orders of magnitude lower concentration than predicted in ion-ion correlation theories. We suggest that transverse electrostatic correlations between mobile ions and surface charges (interfacial Bjerrum pairing) may contribute to the charge inversion.

Induced crystallization of polyelectrolyte-surfactant complexes at the gas-water interface.

Synchrotron x-ray and surface-tension studies of a strong polyelectrolyte (PE) in the semidilute regime (approximately 0.1 M monomer charges) with varying surfactant concentrations show that minute surfactant concentrations induce the formation of a PE-surfactant complex at the gas-solution interface. X-ray reflectivity and grazing angle x-ray diffraction show the complex PE-surfactant resides at the interface and the alkyl chains of the surfactant form a two-dimensional liquidlike monolayer. With the addition of salt (NaCl), columnar crystals with distorted-hexagonal symmetry are formed.

Commensurate-incommensurate magnetic phase transition in magnetoelectric single crystal LiNiPO(4).

Neutron scattering studies of single crystal LiNiPO4 reveal a spontaneous first-order commensurate-incommensurate magnetic phase transition. Short- and long-range incommensurate phases are intermediate between the high temperature paramagnetic and the low temperature antiferromagnetic phases. The modulated structure has a predominant antiferromagnetic component, giving rise to satellite peaks in the vicinity of the fundamental antiferromagnetic Bragg reflection, and a ferromagnetic component, giving rise to peaks at small momentum transfers around the origin at (0,+/-Q,0). The wavelength of the modulated magnetic structure varies continuously with temperature. It is argued that the incommensurate short- and long-range phases are due to spin-dimensionality crossover from a continuous to the discrete Ising state.

The structure of D-erythro-C18 ceramide at the air-water interface.

X-ray reflectivity (XR) and diffraction at grazing angles of incidence (GID) were conducted to determine the structure of synthetic D-erythro C18-ceramide films at the air-water interface at various surface pressures (pi). Analysis of the GID reveals that the monomolecular film, at the crystalline phase (pi > 0 mN/m), is predominantly hexagonal. In this crystalline phase, the analysis of the reflectivity yields an electron density profile that consists of three distinct homogeneous slabs, one associated with the headgroup region and the other two with the hydrocarbon chains. At large molecular areas (pi approximately 0), isolated crystalline domains coexist with two-dimensional gas phase. Within the crystalline domains, we find an orthorhombic arrangement of the chains that coexists with the hexagonal symmetry. It is argued that the two-dimensional orthorhombic crystals are induced by hydrogen bonding between headgroups even at very low surface pressures. Although their structure is incommensurate with the simple hexagonal arrangement, they act as nucleation centers for the conventional hexagonal phase which dominates at high pi.

Polarization-modulated infrared spectroscopy and x-ray reflectivity of photosystem II core complex at the gas-water interface.

The state of photosystem II core complex (PS II CC) in monolayer at the gas-water interface was investigated using in situ polarization-modulated infrared reflection absorption spectroscopy and x-ray reflectivity techniques. Two approaches for preparing and manipulating the monolayers were examined and compared. In the first, PS II CC was compressed immediately after spreading at an initial surface pressure of 5.7 mN/m, whereas in the second, the monolayer was incubated for 30 min at an initial surface pressure of 0.6 mN/m before compression. In the first approach, the protein complex maintained its native alpha-helical conformation upon compression, and the secondary structure of PS II CC was found to be stable for 2 h. The second approach resulted in films showing stable surface pressure below 30 mN/m and the presence of large amounts of beta-sheets, which indicated denaturation of PS II CC. Above 30 mN/m, those films suffered surface pressure instability, which had to be compensated by continuous compression. This instability was correlated with the formation of new alpha-helices in the film. Measurements at 4 degreesC strongly reduced denaturation of PS II CC. The x-ray reflectivity studies indicated that the spread film consists of a single protein layer at the gas-water interface. Altogether, this study provides direct structural and molecular information on membrane proteins when spread in monolayers at the gas-water interface.

Antiferromagnetic Ordering and Paramagnetic Behavior of Ferromagnetic Cu6 and Cu18 Clusters in BaCuO2+x.

Magnetization and neutron diffraction measurements on polycrystalline BaCuO2+x revealed a combination of magnetic behaviors. The Cu(6) ring clusters and Cu(18) sphere clusters in this compound had ferromagnetic ground states with large spins 3 and 9, respectively. The Cu(6) rings ordered antiferromagnetically below the Néel temperature T(N) = 15 +/- 0.5 kelvin, whereas the Cu(18) spheres remained paramagnetic down to 2 kelvin. The ordered moment below T(N) was 0.89(5) Bohr magnetons per Cu in the Cu(6) rings, demonstrating that quantum fluctuation effects are small in these atomic clusters. The Cu(18) clusters are predicted to exhibit ferromagnetic intercluster order below about 1 kelvin.

Influence of surface chemistry on the structural organization of monomolecular protein layers adsorbed to functionalized aqueous interfaces.

The molecular organization of streptavidin (SA) bound to aqueous surface monolayers of biotin-functionalized lipids and binary lipid mixtures has been investigated with neutron reflectivity and electron and fluorescence microscopy. The substitution of deuterons (2H) for protons (1H), both in subphase water molecules and in the alkyl chains of the lipid surface monolayer, was utilized to determine the interface structure on the molecular length scale. In all cases studied, the protein forms monomolecular layers underneath the interface with thickness values of approximately 40 A. A systematic dependence of the structural properties of such self-assembled SA monolayers on the surface chemistry was observed: the lateral protein density depends on the length of the spacer connecting the biotin moiety and its hydrophobic anchor. The hydration of the lipid head groups in the protein-bound state depends on the dipole moment density at the interface.

Recognition processes at a functionalized lipid surface observed with molecular resolution.

The specific binding of proteins to functionalized lipid monolayers on aqueous subphases was characterized by neutron reflectivity and fluorescence microscopy measurements. Due to the high affinity and high specificity of their noncovalent interaction, streptavidin (SA) and biotin (vitamin H) were chosen as a model system to investigate the structural characteristics of a recognition process on a molecular length scale. Changes in the neutron reflection from the surfaces of NaCl aqueous (H2O or D2O) protein solutions (10(-8) M SA) were used to monitor the interaction of the protein with a monolayer of a biotinylated lipid in situ. Refinement of the reflectivity data and independent fluorescence microscopic observation of the interface using FITC-labeled SA showed that the protein forms macroscopically homogeneous (and presumably crystalline) domains covering a large portion of the surface. Moreover, the neutron reflection experiments clearly showed the formation of a monomolecular protein layer with an effective thickness, dp = 43.7 +/- 2 A. The area per protein molecule occupied in the film was A0 = 2860 +/- 200 A2 and nw = 260 +/- 100 water molecules were associated with each protein molecule. Quantitative binding was found to occur at biotin surface concentrations as low as 1 molecule/1,250 A2 (compared with approximately 1 molecule/40 A2 for dense packing). This study demonstrates the application of a promising new tool for the systematic investigation of molecular recognition processes in protein/lipid model systems.

Structural properties of phosphatidylcholine in a monolayer at the air/water interface: Neutron reflection study and reexamination of x-ray reflection measurements.

Neutron reflectivities of phosphatidylcholine monolayers in the liquid condensed (LC) phase on ultrapure H(2)O and D(2)O subphases have been measured on a Langmuir film balance. Using a dedicated liquid surface reflectometer, reflectivities down to R = 10(-6) in the momentum transfer range Q(z) = 0-0.4 A(-1) were accessed.In a new approach, by refining neutron reflectivity data from chain-perdeuterated DPPC-d(62) in combination with x-ray measurements on the same monolayer under similar conditions it is shown that the two techniques mutually complement one another. This analysis leads to a detailed conception of the interface structure. It is found that in the LC phase (which is analogous to the L(beta), phase in vesicle dispersions) the head group is interpenetrated with subphase water (4 +/- 2.5 molecules per lipid) and the average tilt angle of the hydrophobic chains from the surface normal is 33 +/- 3 degrees.