Distribution of organic and reduced sulfur forms in marsh soils of coastal Louisiana

Soil samples from a Louisiana Barataria Basin brackish marshes were fractionated into acid-volatile sulfides (AVS), HCl-soluble sulfur, elemental sulfur, pyrite sulfur, ester-sulfate sulfur, and carbon-bonded sulfur. Inorganic sulfur composed 13% of total sulfur in brackish marsh soil with HCl-soluble sulfur representing 63–92% of the inorganic sulfur fraction. AVS represented less than 1% of the total sulfur pool. Pyrite sulfur and elemental sulfur together accounted for 8–33% of the inorganic sulfur pool. Organic sulfur, in the forms of ester-sulfate sulfur and carbon-bonded sulfur, was the most dominant pool representing the majority of total sulfur in brackish marsh. Results were compared to values reported for fresh and salt marshes. Reported inorganic sulfur fractions were greater in adjacent marshes, constituting 24% of total sulfur in salt marsh, and 22% in freshwater marshes. Along a salinity gradient, HCl-soluble sulfur represented 78–86% of the inorganic sulfur fraction in fresh, brackish, and salt marsh. Organic sulfur in the forms of ester-sulfate sulfur and carbon-bonded sulfur was the major constituent (76–87%) of total sulfur in all marshes. Reduced sulfur species, except elemental sulfur, increased seaward along the salinity gradient. Accumulation of reduced sulfur forms through sedimentation processes was significant in marsh energy flow in fresh, brackish and salt marshes.

Spatial distribution of soil heavy metal pollution estimated by different interpolation methods: Accuracy and uncertainty analysis

Mapping the spatial distribution of contaminants in soils is the basis of pollution evaluation and risk control. Interpolation methods are extensively applied in the mapping processes to estimate the heavy metal concentrations at unsampled sites. The performances of interpolation methods (inverse distance weighting, local polynomial, ordinary kriging and radial basis functions) were assessed and compared using the root mean square error for cross validation. The results indicated that all interpolation methods provided a high prediction accuracy of the mean concentration of soil heavy metals. However, the classic method based on percentages of polluted samples, gave a pollution area 23.54-41.92% larger than that estimated by interpolation methods. The difference in contaminated area estimation among the four methods reached 6.14%. According to the interpolation results, the spatial uncertainty of polluted areas was mainly located in three types of region: (a) the local maxima concentration region surrounded by low concentration (clean) sites, (b) the local minima concentration region surrounded with highly polluted samples; and (c) the boundaries of the contaminated areas. (C) 2010 Elsevier Ltd. All rights reserved.

Effects of soil pH and organic matter on distribution of thorium fractions in soil contaminated by rare-earth industries

The labilities of thorium fractions including mobility and bioavailability vary significantly with soil properties. The effects of soil pH and soil organic matter on the distribution and transfer of thorium fractions defined by a sequential extraction procedure were investigated. Decrease of soil pH could enhance the phytoavailability and the potential availability of thorium in soil. Increase of organic matter reduced the phytoavailability of thorium, but enhanced the potential availability of it.

Poly(oligothiophene-alt-benzothiadiazole)s: Tuning the Structures of Oligothlophene Units toward High-Mobility "Black" Conjugated Polymers

A series of donor-acceptor low-bandgap conjugated polymers, i.e., PTnBT (n = 2-6), composed of alternating oligothiophene (OTh) and 2,1,3-benzothiadiazole (BT) units were synthesized by Stille cross-coupling polymerization. The number of thiophene rings in OTh units, that is n, was tuned from 2 to 6. All these polymers display two absorption bands in both solutions and films with absorption maxima depending on n. From solution to film, absorption spectra of the polymers exhibit a noticeable red shift. Both high- and low-energy absorption bands or P'F5BT and PT6BT films locate in the visible region, which are at 468 and 662 nm for PT5BT and 494 and 657 nm for PT6BT.

Investigation on internal electric field distribution of organic light-emitting diodes (OLEDs) with Eu2O3 buffer layer

We have found that organic light-emitting diode (OLED) performance was highly improved by using europium oxide (Eu2O3) as a buffer layer on indium tin oxide (ITO) in OLEDs based on tris-(8-hydroxyquinoline) aluminium (Alq(3)), which showed low turn-on voltage, high luminance, and high electroluminescent (EL) efficiency. The thickness of Eu2O3 generally was 0.5-1.5 nm. We investigated the effects of Eu2O3 on internal electric field distributions in the device through the analysis of current-voltage characteristics, and found that the introduction of the buffer layer balanced the internal electric field distributions in hole transport layer (HTL) and electron transport layer (ETL), which should fully explain the role of the buffer layer in improving device performance. Our investigation demonstrates that the hole injection is Fowler-Nordheim (FN) tunnelling and the electron injection is Richardson-Schottky (RS) thermionic emission, which are very significant in understanding the operational mechanism and improving the performance, of OLEDs.

Diffusion dynamics, moments, and distribution of first-passage time on the protein-folding energy landscape, with applications to single molecules

We study the dynamics of protein folding via statistical energy-landscape theory. In particular, we concentrate on the local-connectivity case with the folding progress described by the fraction of native conformations. We found that the first passage-time (FPT) distribution undergoes a dynamic transition at a temperature below which the FPT distribution develops a power-law tail, a signature of the intermittent nonexponential kinetic phenomena for the folding dynamics. Possible applications to single-molecule dynamics experiments are discussed.

Temperature dependence of the distribution of the first passage time: Results from discontinuous molecular dynamics simulations of an all-atom model of the second beta-hairpin fragment of protein G

More than 22 000 folding kinetic simulations were performed to study the temperature dependence of the distribution of first passage time (FPT) for the folding of an all-atom Go-like model of the second beta-hairpin fragment of protein G. We find that the mean FPT (MFPT) for folding has a U (or V)-shaped dependence on the temperature with a minimum at a characteristic optimal folding temperature T-opt*. The optimal folding temperature T-opt* is located between the thermodynamic folding transition temperature and the solidification temperature based on the Lindemann criterion for the solid. Both the T-opt* and the MFPT decrease when the energy bias gap against nonnative contacts increases. The high-order moments are nearly constant when the temperature is higher than T-opt* and start to diverge when the temperature is lower than T-opt*. The distribution of FPT is close to a log-normal-like distribution at T* greater than or equal to T-opt*. At even lower temperatures, the distribution starts to develop long power-law-like tails, indicating the non-self-averaging intermittent behavior of the folding dynamics. It is demonstrated that the distribution of FPT can also be calculated reliably from the derivative of the fraction not folded (or fraction folded), a measurable quantity by routine ensemble-averaged experimental techniques at dilute protein concentrations.

Phase identification in a series of liquid crystalline TPP polyethers and copolyethers having highly ordered mesophase structures. 7. Phase structures in a series of copolyethers containing odd and even numbers of methylene units of different compositions

A series of liquid crystalline copolyethers have been synthesized from 1-(4-hydroxy-4'-biphenyl)-2-(4-hydroxyphenyl)propane with 1,7-dibromoheptane and 1,12-dibromododecene [coTPPs(7/12)], which represents copolyethers containing both odd and even numbers of methylene units. The molar ratio of odd to even methylene units in this series ranges from 1/9 to 9/1. The coTPPs(7/12) exhibit multiple phase transitions during cooling and heating in differential scanning calorimetry experiments. For all these thermal transitions, a small undercooling and superheating dependence is observed upon cooling and heating at different rates. Three types of phase behaviors can be classified in coTPPs(7/12) on the basis of the structural analyses by wide-angle X-ray diffraction on powder and fiber samples and by electron diffraction experiments in transmission electron microscopy. At room temperature, highly ordered smectic and smectic crystal (SC) phases are identified in coTPPs(7/12: 1/9 and 2/8), which is similar to the homopolymer TPP(m = 12). The coTPPs(7/12: 3/7, 4/6, and 5/5) possess a hexagonal columnar (Phi(H)) phase in which the molecular and columnar axes are parallel to the fiber direction and perpendicular to the hexagonal lateral packing. The coTPPs(7/12: 6/4, 7/3, and 8/2) possess a tilted hexagonal columnar (Phi(TH)) phase with a single tilt angle which increases with the increasing composition of the seven-numbered methylene units. However, in coTPP(7/12: 9/1), a Phi(TH) phase with multiple tilt angles is found. Upon heating, phase structures in most coTPPs(7/12) involving the columnar phases enter directly into the nematic (N) phase, while the coTPP(7/12: 1/9) exhibits a highly ordered smectic F (S-F) phase before it reaches the N phase. One exception is found in coTPP(7/12: 2/8), wherein the transformation from the S-F to Phi(H) occurs prior to the N phase. Combining the copolymer phase behaviors observed with the corresponding homopolymers TPP(n = 7) and TPP(m = 12), a phase diagram describing transition temperatures with respect to the composition can be constructed.

Phase identification in a series of liquid crystalline TPP polyethers and copolyethers having highly ordered mesophase structures. 6. Structure changes from smectic to columnar phases in a series of copolyethers containing odd and even numbers of methylene units in equal molar composition

A series of liquid crystalline copolyethers has been synthesized from 1-(4-hydroxy-4'-biphenyl)-2-(4-hydroxyphenyl)propane and different alpha,omega-dibromoalkanes [coTPP(n/m)]. In this report, coTPPs having n = 5, 7, 9, 11 and m = 12 are studied, which represent copolyethers having both varying odd number and a fixed even number of methylene units. The compositions were fixed at an equal molar ratio (50/50). These coTPPs(nlm) show multiple phase transitions during cooling and heating in differential scanning calorimetry experiments. The undercooling dependence of these transitions is found to be small, indicating that these transitions are close to equilibrium, Although the coTPPs possess a high-temperature nematic (N) phase, the periodicity order along the chain direction is increasingly disturbed when the length of the odd-numbered methylene units decreases from n 11 to 5. in the coTPPs(5/12, 7/12, and 9/12), wide-angle X-ray diffraction experiments at different temperatures show that, shortly after the N phase formation during cooling, the lateral molecular packing improves toward a hexagonal lattice, as evidenced by a gradual narrowing of the scattering halo. This process represents the possible existence of an exotic N phase, which serves as a precursor to the columnar (Phi(H)) phase. A further decrease in temperature leads to a (PH phase having a long-range ordered, two-dimensional hexagonal lattice. In coTPP(11/12), the phase structures are categorized as highly ordered and tilted, smectic and smectic crystal phases, similar to homoTPPs, such as the smectic F (S-F) and smectic crystal G (SCG) phases. An interesting observation is found for coTPP(9/12), wherein a structural change from the high-temperature Phi(H) phase to the low-temperature S-F phase occurs. It can be proven that, upon heating, the well-defined layer structure disappears and the lateral packing remains hexagonal. The overall structural differences in this series of coTPPs between those of the columnar and highly ordered smectic phases are related to the disorders introduced into the layer structure by the dissimilarity of the methylene unit lengths in the comonomers.

Biological effect of rare earth (I) - Content and distribution of rare earth in normal human plasma

The content and distribution of rare earth(RE) in normal human plasma have been investigated by ultrafiltration, FPLC and ICP-MS methods, The results showed that there are trace RE in normal human plasma, and their contents are in accordance with their abundance, The RE can bond with immunoglobulin G(IgG), transferrin(Tf) and albumin(Alb) species, but mostly bond with Tf.

Probability distribution of the four-phase structure invariants of isomorphously related structure factors and its applications

The probability distribution of the four-phase structure invariants (4PSIs) involving four pairs of structure factors is derived by integrating the direct methods with isomorphous replacement (IR). A simple expression of the reliability parameter for 16 types of invariant is given in the case of a native protein and a heavy-atom derivative. Test calculations on a protein and its heavy-atom derivative using experimental diffraction data show that the reliability for 4PSI estimates is comparable with that for the three-phase structure invariants (3PSIs), and that a large-modulus invariants method can be used to improve the accuracy.

Laser light scattering of the molecular weight distribution of unfractionated phenolphthalein poly(aryl ether sulfone)

Two unfractionated samples of phenolphthalein poly( aryl ether sulfone) (PES-C) were characterized in CHCl3 at 25 degrees C by applying a recently developed laser light-scattering (LLS) procedure. The Laplace inversion of precisely measured intensity-intensity time correlation function lead us first to an estimate of the characteristic line-width distribution G(Gamma) and then to the translational diffusion coefficient distribution G(D). A combination of static and dynamic LLS results enabled us to determine D = (2.69 x 10(-4))M(-0.553), which agrees with the calibration of D = (2.45 x 10(-4))M(-0.55) previously established by a set of narrowly distributed PES-C samples. Using this newly obtained scaling between D and M, we were able to convert G(D) into a differential weight distribution f(w)(M) for the two PES-C samples. The weight-average molecular weights calculated from f(w)(M) are comparable to that obtained directly from static LLS. Our results showed that using two broadly distributed samples instead of a set of narrowly distributed samples have provided not only similar final results, but also a more practical method for the PES-C characterization. (C) 1997 John Wiley & Sons, Inc.

Dynamic light-scattering characterization of the molecular weight distribution of a broadly distributed phenolphthalein poly(aryl ether ketone)

Using a recently developed laser light-scattering (LLS) procedure, we accomplished the characterization of a broadly distributed unfractionated phenolphthalein poly(aryl ether ketone) (PEK-C) in CHCl3 at 25 degrees C. The laplace inversion of precisely measured intensity-intensity time correlation function from dynamic LLS leads us first to an estimate of the characteristic line-width distribution G(Gamma) and then to the translational diffusion coefficient distribution G(D). By using a previously established calibration of D (cm(2)/s) = 2.37 X 10(-4)M(-0.57), were able to convert G(D) into a differential weight distribution f(w)(M). The weight-average molecular weight M(w) calculated from f(w)(M) agrees well with that directly measured in static LLS. Our results indicate that both the calibration and LLS procedure used in this study are ready to be applied as a routine method for the characterization of the molecular weight distribution of PEK-C. (C) 1996 John Wiley & Sons, Inc.