Evaluating phytochemical and microbial contributions to atrazine degradation.

The inclusion of warm-season grasses, such as switchgrass (Panicum virgatum) and eastern gamagrass (EG) (Tripsacum dactyloides), in vegetated buffer strips has been shown to mitigate herbicide contamination in runoff and increase herbicide degradation in soil. The mode of action by which buffer strip rhizospheres enhance herbicide degradation remains unclear, but microorganisms and phytochemicals are believed to facilitate degradation processes. The objectives of this study were to: 1) screen root extracts from seven switchgrass cultivars for the ability to degrade the herbicide atrazine (ATZ) in solution; 2) determine sorption coefficients (Kd) of the ATZ-degrading phytochemical 2-ß-D-glucopyranosyloxy-4-hydroxy-1,4-benzoxazin-3-one (DBG) to soil and Ca-montmorillonite, and investigate if DBG or ATZ sorption alters degradation processes; and 3) quantify ATZ degradation rates and soil microbial response to ATZ application in mesocosms containing soil and select warm-season grasses. Phytochemicals extracted from the roots of switchgrass cultivars degraded 44-85% of ATZ in 16-h laboratory assays, demonstrating that some switchgrass cultivars could rapidly degrade ATZ under laboratory conditions. However, attempts to isolate ATZ-degrading phytochemicals from plant roots were unsuccessful. Sorption studies revealed that DBG was strongly sorbed to soil (Kd = 87.2 L kg-1) and Ca-montmorillonite (Kd = 31.7 L kg-1), and DBG driven hydrolysis of ATZ was entirely inhibited when either ATZ or DBG were sorbed to Ca-montmorillonite. Atrazine degradation rates in mesocosm soils were rapid (t0.5 = 8.2-11.2 d), but not significantly different between soils collected from the two switchgrass cultivar mesocosms, the eastern gamagrass cultivar mesocosm, and the unvegetated mesocosm (control). Significant changes in three phospholipid fatty acid biomarkers were observed among the treatments. These changes indicated that different ATZ-degrading microbial consortia resulted in equivalent ATZ degradation rates between treatments. Results demonstrated that soil microbial response was the dominant mechanism controlling ATZ degradation in the soil studied, rather than root phytochemicals.

Single-particle and collective excitations of polar water molecules confined in nano-pores within a cordierite crystal lattice.

Recently, the low-temperature phase of water molecules confined within nanocages formed by the crystalline lattice of water-containing cordierite crystals has been reported to comprise domains with ferroelectrically ordered dipoles within the a, b-planes which are antiferroelectrically alternating along the c-axis. In the present work, comprehensive broad-band dielectric spectroscopy is combined with specific heat studies and molecular dynamics and Monte Carlo simulations in order to investigate in more detail the collective modes and single-particle excitations of nanoconfined water molecules. From DFT-MD simulations we reconstruct the potential-energy landscape experienced by the H2O molecules. A rich set of anisotropic temperature-dependent excitations is observed in the terahertz frequency range. Their origin is associated with the complex rotational/translational vibrations of confined H2O molecules. A strongly temperature dependent relaxational excitation, observed at radio-microwave frequencies for the electric field parallel to the crystallographic a-axis, E||a is analyzed in detail. The temperature dependences of loss-peak frequency and dielectric strength of the excitation together with specific heat data confirm a ferroelectric order-disorder phase transition at T0 ≈ 3 K in the network of H2O dipoles. Additional dielectric data are also provided for polarization E||b, too. Overall, these combined experimental investigations enable detailed conclusions concerning the dynamics of the confined water molecules that develop within their microscopic energy landscapes.

Histomorphometric and microarchitectural analysis of bone in metastatic breast cancer patients.

BACKGROUND: Despite widespread use of repeated doses of potent bone-targeting agents (BTA) in oncology patients, relatively little is known about their in vivo effects on bone homeostasis, bone quality, and bone architecture. Traditionally bone quality has been assessed using a trans-iliac bone biopsy with a 7 mm "Bordier" core needle. We examined the feasibility of using a 2 mm "Jamshidi™" core needle as a more practical and less invasive technique. METHODS: Patients with metastatic breast cancer on BTAs were divided according to the extent of bone metastases. They were given 2 courses of tetracycline labeling and then underwent a posterior trans-iliac trephine biopsy and bone marrow aspirate. Samples were analyzed for the extent of tumor invasion and parameters of bone turnover and bone formation by histomorphometry. RESULTS: Twelve patients were accrued, 1 had no bone metastases, 3 had limited bone metastases (LSM) (<3 lesions) and 7 had extensive bone metastases (ESM) (>3 lesions). Most of the primary tumors were estrogen receptor (ER)/progesterone receptor (PR) positive. The procedure was well tolerated. The sample quality was sufficient to analyze bone trabecular structure and bone turnover by histomorphometry in 11 out of 12 patients. There was a good correlation between imaging data and morphometric analysis of tumor invasion. Patients with no evidence or minimal bone metastases had no evidence of tumor invasion. Most had suppressed bone turnover and no detectable bone formation when treated with BTA. In contrast, 6 out of 7 patients with extensive bone invasion by imaging and evidence of tumor cells in the marrow had intense osteoclastic activity as measured by the number of osteoclasts. Of these 7 patients with ESM, 6 were treated with BTA with 5 showing resistance to BTA as demonstrated by the high number of osteoclasts present. 3 of these 6 patients had active bone formation. Based on osteoblast activity and bone formation, 3 out of 6 patients with ESM responded to BTA compared to all 3 with LSM. Compared to untreated patients, all patients treated with BTA showed a trend towards suppression of bone formation, as measured by tetracycline labelling. There was also a trend towards a significant difference between ESM and LSM treated with BTA, highly suggestive of resistance although limited by the small sample size. DISCUSSION: Our results indicate that trans-iliac bone biopsy using a 2 mm trephine shows excellent correlation between imaging assessment of tumor invasion and tumor burden by morphometric analysis of bone tissues. In addition, our approach provides additional mechanistic information on therapeutic response to BTA supporting the current clinical understanding that the majority of patients with extensive bone involvement eventually fail to suppress bone turnover (Petrut B, et al. 2008). This suggests that antiresorptive therapies become less effective as disease progresses.

Intercostal chest drain fixation strength: comparison of techniques and sutures.

OBJECTIVE: The accidental removal of an intercostal chest drain (ICD) is common and may result in serious complications. A number of fixation techniques and suture material are in use, and the selection is often based on personal preferences and equipment availability. This study is designed to determine which of the common techniques provides the strongest ICD fixation. METHODS: This study compared the mechanical strength of eight different ICD fixation techniques (purse string, 'Roman sandal', 'Jo'burg' (JO) technique, a suture through the tube, one and two passes through a locking plastic tie, tape fixation and a commercial disposable drainage tube holder) and two silk suture sizes using porcine cadavers and a digital push-pull dynamometer to simulate accidental removal of an ICD. A total of 14 different experimental set-ups produced 280 measurements. RESULTS: Significant differences in ICD fixation strength were observed. A modified JO technique using a size 1 silk suture was nearly three times stronger than a purse-string fixation using a size 0 silk and 10 times stronger from a commercial, adhesive-based device (180, 70 and 22, respectively). CONCLUSION: In situations where the mechanical strength of ICD fixation is important, using a size 1 silk and a modified JO technique may provide the strongest fixation.

Dielectric ordering of water molecules arranged in a dipolar lattice.

Intermolecular hydrogen bonds impede long-range (anti-)ferroelectric order of water. We confine H2O molecules in nanosized cages formed by ions of a dielectric crystal. Arranging them in channels at a distance of ~5 Å with an interchannel separation of ~10 Å prevents the formation of hydrogen networks while electric dipole-dipole interactions remain effective. Here, we present measurements of the temperature-dependent dielectric permittivity, pyrocurrent, electric polarization and specific heat that indicate an order-disorder ferroelectric phase transition at T0 ≈ 3 K in the water dipolar lattice. Ab initio molecular dynamics and classical Monte Carlo simulations reveal that at low temperatures the water molecules form ferroelectric domains in the ab-plane that order antiferroelectrically along the channel direction. This way we achieve the long-standing goal of arranging water molecules in polar order. This is not only of high relevance in various natural systems but might open an avenue towards future applications in biocompatible nanoelectronics.

First-principles comparative study of perfect and defective CsPbX3 (X = Br, I) crystals.

First principles Density Functional Theory (DFT) hybrid functional PBESOL0 calculations of the atomic and electronic structure of perfect CsPbI3, CsPbBr3 and CsPbCl3 crystals, as well as defective CsPbI3 and CsPbBr3 crystals are performed and discussed. For the perfect structure, decomposition energy into binary compounds (CsX and PbX2) is calculated, and a stability trend of the form CsPbBr3 > CsPbI3 > CsPbCl3 is found. In addition, calculations of the temperature-dependent heat capacity are performed and shown to be in good agreement with experimental data. As far as the defect structure is considered, it is shown that interstitial halide atoms in CsPbBr3 do not tend to form di-halide dumbbells Br2- while such dimers are energetically favoured in CsPbI3, analogous to the well-known H-centers in alkali halides. In the case of CsPbBr3, a loose trimer configuration (Br32-) seems to be energetically preferred. The effects of crystalline symmetry and covalency are discussed, alongside the role of defects in recombination processes.

Frustration-driven C 4 symmetric order in a naturally-heterostructured superconductor Sr2VO3FeAs.

A subtle balance between competing interactions in iron-based superconductors (FeSCs) can be tipped by additional interfacial interactions in a heterostructure, often inducing exotic phases with unprecedented properties. Particularly when the proximity-coupled layer is magnetically active, rich phase diagrams are expected in FeSCs, but this has not been explored yet. Here, using high-accuracy 75As and 51V nuclear magnetic resonance measurements, we investigate an electronic phase that emerges in the FeAs layer below T 0 ~ 155 K of Sr2VO3FeAs, a naturally assembled heterostructure of an FeSC and a Mott-insulating vanadium oxide. We find that frustration of the otherwise dominant Fe stripe and V Neel fluctuations via interfacial coupling induces a charge/orbital order in the FeAs layers, without either static magnetism or broken C 4 symmetry, while suppressing the Neel antiferromagnetism in the SrVO3 layers. These findings demonstrate that the magnetic proximity coupling stabilizes a hidden order in FeSCs, which may also apply to other strongly correlated heterostructures.

Nuclear Magnetic Resonance Signature of the Spin-Nematic Phase in LiCuVO_{4} at High Magnetic Fields.

We report a ^{51}V nuclear magnetic resonance investigation of the frustrated spin-1/2 chain compound LiCuVO_{4}, performed in pulsed magnetic fields and focused on high-field phases up to 56 T. For the crystal orientations H∥c and H∥b, we find a narrow field region just below the magnetic saturation where the local magnetization remains uniform and homogeneous, while its value is field dependent. This behavior is the first microscopic signature of the spin-nematic state, breaking spin-rotation symmetry without generating any transverse dipolar order, and is consistent with theoretical predictions for the LiCuVO_{4} compound.

Incipient ferroelectricity of water molecules confined to nano-channels of beryl.

Water is characterized by large molecular electric dipole moments and strong interactions between molecules; however, hydrogen bonds screen the dipole-dipole coupling and suppress the ferroelectric order. The situation changes drastically when water is confined: in this case ordering of the molecular dipoles has been predicted, but never unambiguously detected experimentally. In the present study we place separate H2O molecules in the structural channels of a beryl single crystal so that they are located far enough to prevent hydrogen bonding, but close enough to keep the dipole-dipole interaction, resulting in incipient ferroelectricity in the water molecular subsystem. We observe a ferroelectric soft mode that causes Curie-Weiss behaviour of the static permittivity, which saturates below 10 K due to quantum fluctuations. The ferroelectricity of water molecules may play a key role in the functioning of biological systems and find applications in fuel and memory cells, light emitters and other nanoscale electronic devices.

Fermi-Surface Topological Phase Transition and Horizontal Order-Parameter Nodes in CaFe2As2 Under Pressure.

Iron-based compounds (IBS) display a surprising variety of superconducting properties that seems to arise from the strong sensitivity of these systems to tiny details of the lattice structure. In this respect, systems that become superconducting under pressure, like CaFe2As2, are of particular interest. Here we report on the first directional point-contact Andreev-reflection spectroscopy (PCARS) measurements on CaFe2As2 crystals under quasi-hydrostatic pressure, and on the interpretation of the results using a 3D model for Andreev reflection combined with ab-initio calculations of the Fermi surface (within the density functional theory) and of the order parameter symmetry (within a random-phase-approximation approach in a ten-orbital model). The almost perfect agreement between PCARS results at different pressures and theoretical predictions highlights the intimate connection between the changes in the lattice structure, a topological transition in the holelike Fermi surface sheet, and the emergence on the same sheet of an order parameter with a horizontal node line.

Genetic parameters of objectionable fibers and of their associations with fleece traits in Corriedale sheep.

The aim of this research was to assess the variability and genetic relationships among binary traits denoting the presence or absence of objectionable fibers, namely pigmented (BINPPF), medullated (BINPMED), and kemp fibers (BINPK), and of fleece traits (fiber diameter [FD] and clean fleece weight [CFW]) in Corriedale sheep. Additionally, the total response to selection against objectionable fibers and indirect responses when selecting for fleece traits were evaluated. Fiber records from 679 animals and fleece records from 795 animals obtained from 2 experimental flocks (from 2005 to 2007) were used; the pedigree file included a total of 3,792 animals. Heritability and genetic correlations among the traits were estimated with a multivariate animal model under a Bayesian setting. Heritability estimates (posterior SD) for BINPPF, BINPMED, and BINPK were 0.35 (0.08), 0.37 (0.10), and 0.63 (0.09), respectively; for CFW and FD, estimates were 0.42 (0.09) and 0.43 (0.08), respectively. The genetic correlations between CFW and the 3 types of objectionable fibers were very low (i.e., <0.2). Thus selection for CFW is not expected to affect the number of such fibers in any direction. The same occurred for the genetic correlation between BINPK and FD. Genetic correlations between FD and BINPMED and FD and BINPPF were positive and favorable (0.50 and 0.56, respectively). Selecting for lower FD would decrease the numbers of objectionable fibers. The expected correlated responses in BINPPF, BINPMED, and BINPK when selecting for CFW were -0.03 (0.11), 0.03 (0.11), and -0.05 (0.18), respectively; when selecting for FD, the correlated responses were -0.26 (0.11), -0.26 (0.11), and -0.14 (0.16). Overall, this study reports novel information on genetic parameters for the presence of objectionable fibers and their associations with fleece traits in sheep. Our findings suggest that it could be possible to improve FD while at the same time reducing the content of BINPMED and BINPPF in wool; however, improvements in CFW are likely to have no effect on the numbers of objectionable fibers.

Long-term agroecosystem research in the central Mississippi river basin: goodwater creek experimental watershed and regional herbicide water quality data.

Goodwater Creek Experimental Watershed (GCEW) has been the focus area of a long-term effort to document the extent of and to understand the factors controlling herbicide transport. We document the datasets generated in the 20-yr-long research effort to study the transport of herbicides to surface and groundwater in the GCEW. This long-term effort was augmented with a spatially broad effort within the Central Mississippi River Basin encompassing 12 related claypan watersheds in the Salt River Basin, two cave streams on the fringe of the Central Claypan Areas in the Bonne Femme watershed, and 95 streams in northern Missouri and southern Iowa. Details of the analytical methods, periods of record, number of samples, study locations, and means of accessing these data are provided. In addition, a brief overview of significant findings is presented. A key finding was that near-surface restrictive soil layers, such as argillic horizons of smectitic mineralogy, result in greater herbicide transport than soils with high percolation and low clay content. Because of this, streams in the claypan soil watersheds of northeastern Missouri have exceptionally high herbicide concentrations and relative loads compared with other areas of the Corn Belt.

A broad spectrum of genomic changes in latinamerican patients with EXT1/EXT2-CDG.

Multiple osteochondromatosis (MO), or EXT1/EXT2-CDG, is an autosomal dominant O-linked glycosylation disorder characterized by the formation of multiple cartilage-capped tumors (osteochondromas). In contrast, solitary osteochondroma (SO) is a non-hereditary condition. EXT1 and EXT2, are tumor suppressor genes that encode glycosyltransferases involved in heparan sulfate elongation. We present the clinical and molecular analysis of 33 unrelated Latin American patients (27 MO and 6 SO). Sixty-three percent of all MO cases presented severe phenotype and two malignant transformations to chondrosarcoma (7%). We found the mutant allele in 78% of MO patients. Ten mutations were novel. The disease-causing mutations remained unknown in 22% of the MO patients and in all SO patients. No second mutational hit was detected in the DNA of the secondary chondrosarcoma from a patient who carried a nonsense EXT1 mutation. Neither EXT1 nor EXT2 protein could be detected in this sample. This is the first Latin American research program on EXT1/EXT2-CDG.

Lattice and polarizability mediated spin activity in EuTiO3.

EuTiO3 is shown to exhibit novel strong spin-charge-lattice coupling deep in the paramagnetic phase. Its existence is evidenced by an, until now, unknown response of the paramagnetic susceptibility at temperatures exceeding the structural phase transition temperature T(S) = 282 K. The 'extra' features in the susceptibility follow the rotational soft zone boundary mode temperature dependence above and below TS. The theoretical modeling consistently reproduces this behavior and provides reasoning for the stabilization of the soft optic mode other than quantum fluctuations.

Structure and bonding of superconducting LaC2.

We have synthesized polycrystalline samples of superconducting LaC2 and investigated them by x-ray and neutron powder diffraction, magnetic susceptibility and heat capacity measurements. Depending on the preparation conditions we find superconductivity below ~1.8 K. A comparison of the superconducting anomaly in the heat capacity with theoretical predictions indicates LaC2 to be a weak-coupling BCS-type superconductor. Evidence for a structural phase transition has not been found from the neutron powder diffraction experiments carried out down to 4 K. A negative thermal expansion of the c lattice parameter was observed below ~50 K. The electronic structure of LaC2 has been calculated ab initio and it is compared with that of YC2. The carbon-carbon distance of LaC2 has been determined from the neutron powder diffraction experiments and it is compared and discussed with respect to those observed in other superconducting binary and ternary La and Y carbides and carbide halides.

Nonlinear pressure dependence of TN in almost multiferroic EuTiO3.

The antiferromagnetic (AFM) phase transition temperature TN of EuTiO3 has been studied as a function of pressure p. The data reveal a nonlinear dependence of TN on p with TN increasing with increasing pressure. The exchange interactions exhibit an analogous dependence on p as TN (if the absolute value of the nearest neighbor interaction is considered) and there is evidence that the AFM transition is robust with increasing pressure. The corresponding Weiss temperature ΘW remains anomalous since it always exhibits positive values. The data are analyzed within the Bloch power law model and provide excellent agreement with experiment.

Antiferromagnetic Ordering of Magnetic Clusters Units in Nb(6)F(15).

We have studied the magnetic cluster compound Nb(6)F(15) which has an odd number of 15 valence electrons per (Nb(6)F(12))(3+) cluster core, as a function of temperature using nuclear magnetic resonance, magnetic susceptibility, electron magnetic resonance and neutron powder diffraction. Nuclear magnetic resonance of the (19)F nuclei shows two lines corresponding to the apical F(a-a) nucleus, and to the inner F(i) nuclei. The temperature dependence of the signal from the F(i) nuclei reveals an antiferromagnetic ordering at T < 5 K, with a hyperfine field of ~2 mT. Magnetic susceptibility exhibits a Curie-Weiss behavior with T(N) ~5 K, and µ(eff) ~1.57 µ(B) close to the expected theoretical value for one unpaired electron (1.73 µ(B)). Electron magnetic resonance linewidth shows a transition at 5 K. Upon cooling from 10 to 1.4 K, the neutron diffraction shows a decrease in the intensity of the low-angle diffuse scattering below Q ~0.27 Å(-1). This decrease is consistent with emergence of magnetic order of large magnetic objects (clusters). This study shows that Nb(6)F(15) is paramagnetic at RT and undergoes a transition to antiferromagnetic order at 5 K. This unique antiferromagnetic ordering results from the interaction between magnetic spins delocalized over each entire (Nb(6)F(12) (i))(3+) cluster core, rather than the common magnetic ordering.

Padé approximations for the magnetic susceptibilities of Heisenberg antiferromagnetic spin chains for various spin values.

The temperature dependence of the spin susceptibilities of S = 1, 3/2, 2, 5/2 and 7/2 Heisenberg antiferromagnetic 1D spins chains with nearest-neighbor coupling was simulated via quantum Monte Carlo calculations, within the reduced temperature range of 0.005 ≤ T* ≤ 100, and fitted to a Padé approximation with deviations between the simulated and fitted data of the same order of magnitude as or smaller than the quantum Monte Carlo simulation error. To demonstrate the practicality of our theoretical findings, we compare these results with the susceptibility of the well known 1D chain compound TMMC ([(CH(3))(4)N[MnCl(3)]], d(5), S = 5/2) and find that different intra-chain spin-exchange parameters result if we consider the data above and below the structural phase transition reported for TMMC at ~126 K. The structural phase transition, which gives rise to an anomaly in the magnetic susceptibility, is independent of the magnetic field up to magnetic fields of 7 T. Additionally, we show that the S = 1 system NiTa(2)O(6) with tri-rutile crystal structure can be very well described as a Heisenberg S = 1 spin chain.

EuFe2(As(1-x)P(x))2: reentrant spin glass and superconductivity.

By systematic investigations of the magnetic, transport, and thermodynamic properties of single crystals of EuFe(2)(As(1-x)P(x))(2) (0≤x≤1), we explore the complex interplay of superconductivity and Eu(2+) magnetism. Below 30 K, two magnetic transitions are observed for all P substituted crystals, suggesting a revision of the phase diagram. In addition to the canted A-type antiferromagnetic order of Eu(2+) at ∼20 K, a spin glass transition is discovered at lower temperatures. Most remarkably, the reentrant spin glass state of EuFe(2)(As(1-x)P(x))(2) coexists with superconductivity around x≈0.2.

Far-IR excitations in Cd2Re2O7 in the normal and superconducting states.

Cd(2)Re(2)O(7) is a pyrochlore superconductor with a transition temperature T(c) near 1 K. We report on the far-infrared optical properties of Cd(2)Re(2)O(7) at temperatures above and below T(c) with a particular emphasis on changes in the spectrum below T(c). Seventeen phonon modes are observed in the normal state optical conductivity spectrum of Cd(2)Re(2)O(7) at low temperatures in good agreement with a factor group analysis. In the superconducting state, a softening (~1 cm(-1)) of the phonon modes at 35 and 61 cm(-1) occurs and thermal reflectance spectra show the development of two additional strong absorption features, near 9.6 and 19.3 cm(-1). The dominant presence of lattice vibrational modes in the optical spectrum suggests that electron-phonon interaction plays an important role in the normal and superconducting state properties of Cd(2)Re(2)O(7).