Modeling Pb(II) adsorption onto sandy loam soil

The adsorption of Pb(II) onto hydrous sandy loam soil was investigated with batch equilibrium adsorption experiments. Results show that the amount of Pb(II) adsorbed increases with increasing pH and surface loading. It was demonstrated that the surface acidity of the soil could be determined using electrophoretic mobility measurements. The surface acidity constants, pK(a1)(int) and pK(a2)(int), were 1.57 and 3.43, respectively. A surface complex formation model (SCFM) was employed to describe the adsorption. The intrinsic stability constants, pK(i)(s), for the surface reaction between the Pb species and the ionized soil surface hydroxyl groups were determined from SCFM fitting. The adsorption free energy of Pb2+ and Pb(OH)+ ions ranges from -5.74 to -6.48 kcal/mol and from -9.68 to -10.00 kcal/mol, respectively, for surface loadings between 1.21 x 10(-5) and 2.41 x 10(-4) mol/g. The adsorption binding calculation indicated that the specific chemical interaction is the major mechanism responsible for the adsorption process.     

A New Octadecanuclear Copper(II)‐Lanthanide(III) Cluster Complex: Synthesis and Structural Characterization of [Cu12Nd6(OH)24(betaine)16(NO3)3(H2O)10](NO3)[PF6]14·5H2O

The new octadecanuclear Cu‐Ln complex, [Cu₁₂Nd₆(OH)₂₄(betaine)₁₆(NO₃)₃(H₂O)₁₀](NO₃)[PF₆]₁₄·5H₂O, was synthesized, which crystallizes in triclinic P1¯ space group, a = 18.649(6)Å, b = 20.363(7)Å, c = 19.865(7)Å, α = 116.61(2)°, β = 91.99(2)°, γ = 117.93(2)°, V = 5666(3)ų. Its crystal structure features a [Cu₁₂Nd₆(OH)₂₄(betaine)₁₆(NO₃)₃(H₂O)₁₀]¹⁵⁺ core of pseudocubic O_h symmetry, with the six Nd ions positioned at the vertices of a regular octahedron and the twelve Cu ions located at the midpoints of the twelve octahedral edges. The Cu‐Nd metal framework may be viewed as a cuboctahedron, which is interconnected by twenty‐four μ₃‐OH bridges that are each linked to one Nd ion and two Cu ions. In the centre of metal polyhedron, there is an encapsulated NO₃^— anion that exhibits a multi‐ coordinating mode.     

Investigating the chain conformations of spin‐coated polymer thin films by ToF‐SIMS depth profiling

Thin films of bromine‐terminated poly(bisphenol A octane ether) (BA‐C10) were prepared using 1,2‐dichlorobenzene (ODCB) as the solvent. The organization of the chains in these amorphous polymer films was evaluated using time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) depth profiling. For the thin films, the bifunctional polymer chains were folded and anchored to the substrate via their two Br end groups and a polymer brush of chain loops was formed on the substrate. As the film thickness increased, polymer chains in a random coil conformation were found to reside on the top of the polymer brush. Depth profiling revealed that the polymer chains were densely packed at the interface. Moreover, the polymer films showed thermal stability, implying strong interactions between the end groups and the substrate. Copyright © 2015 John Wiley & Sons, Ltd.     

Microcalorimetric Investigation on the lower critical solution temperature behavior of N-isopropycrylamide-co-acrylic acid copolymer in aqueous solution

The lower critical solution temperature (LCST) behaviors of random and segmented copolymers of N-isopropylacrylamide (NIPAM) and acrylic acid (AA) prepared in dioxane and water have been investigated by using ultrasensitive microcalorimetry (US-DSC). The introduction of AA increases the LCST of the former but slightly affects that of the latter. When the molar fraction of AA is low (approximately 2 mol %), the LCST of the segmented copolymer shifts to a higher temperature with increasing pH, while the LCST of the corresponding random copolymer slightly changes. Below the boiling point of water, the random copolymer and segmented copolymer with the molar fraction of AA about 15 mol % no longer exhibit an LCST at pH > 5. The addition of calcium ions leads the LCST of both the segmented copolymer and random copolymer to decrease. Our results suggest that the LCST behavior of the copolymers is determined by the clustering of poly(N-isopropylacrylamide) segments.     

Liquid chromatographic-electrospray tandem mass spectrometric determination of clarithromycin in human plasma

A rapid, sensitive and specific LC-MS-MS method has been developed for the determination of clarithromycin (CLA) in human plasma using roxithromycin (ROX) as the internal standard. Samples were prepared via liquid-liquid extraction with methyl tert-butyl ether (MTBE) and chromatographed on a Supelco RP(18) (4.6 x 50 mm, 3 microm particle size) column with a mobile phase consisting of acetonitrile:methanol:60 mM (pH 3.5) ammonium acetate buffer (32.5:32.5:35) at a constant flow rate of 0.8 mL/min. The run time was 3 min with retention times of approximately 1.65 and 1.70 min for CLA and ROX, respectively. Detection was performed on a PE Sciex API 365 mass spectrometer equipped with a turboionspray ionization source in multiple reaction monitoring (MRM) mode. The MRM pairs were m/z 748.5 --> m/z 158.2 for CLA and m/z 837.7 --> m/z 679.3 for ROX, respectively, with dwell times of 200 ms for each transition. The validated calibration curve range was 5.00-5000 ng/mL, based on 0.100 mL plasma sample volume with signal-to-noise ratio (S/N) greater than 60 for CLA at the lower limit of quantification level (5.00 ng/mL). The correlation coefficients (r(2)) of the calibration curves were better than or equal to 0.996. The inter-day (n = 18) precision and accuracy of the quality control (QC) samples were less than 3.58% RSD (relative standard deviation) and -10.8% bias, respectively. The intra-day (n = 6) precision and accuracy of the quality control samples were less than 5.0 and 12.6%, respectively. There was no significant deviation from the nominal values after a 10-fold dilution of high concentration QC samples using blank matrix. The QC samples were stable when left on the bench for 24 h or after three freeze-thaw cycles. The processed samples were also stable in HPLC autosampler at 10C for over 72 h. No matrix ionization suppression was observed when extracted blank matrix or reconstitution solvent was injected onto the system with post-column infusion of clarithromycin and roxithromycin. No carryover was observed when an extracted blank plasma sample was injected immediately after a 5000 ng/mL ULOQ (the upper limit of quantification) standard. The mean recovery was 81.5 and 78.3%, respectively, for clarithromycin and internal standard.     

Porphyrin-carborane organometallic assemblies based on 1, 2-dicarba-closo-dodecaborane (12) ligands

The assembly of soluble, air-stable, supramolecular structures {(Zn-TPyP)[Cp*Ir{S2C2(B10H10)}]4(THF)2}(2), {(Cu-TPyP)[Cp*Ir{S2C2(B10H10)}]4(THF)2}(3) and {(Zn-TPyP)[Cp*Ir{S2C2(B10H10)}]2.6(CHCl3)}n (4), based on metal-containing moieties [Cp*Ir{S2C2(B10H10)}] (1) bridged by nitrogen-based organic spacers, are described.     

Biodegradation behavior of poly(butylene adipate-co-terephthalate) (PBAT), poly(lactic acid) (PLA), and their blend under soil conditions

Poly(lactic acid) (PLA) and poly(butylene adipate-co-terephthalate) (PBAT) were mixed at a ratio of 40:60, extruded to form granules and cast into film; then, the PLA, PBAT, and PBAT/PLA film samples were buried in real soil environments. The residual degraded samples were taken regularly from the soil and analyzed by SEM, DSC, TGA, IR spectroscopy and elemental analysis. The analyses showed that PBAT and PLA had different biodegradation mechanisms. Further, the melting temperature and the melting point change of the various components in the PBAT/PLA blend before and after the biodegradation essentially followed the process of the changes in the respective single polymers. After biodegradation, the carbon atom content in the molecular structure of the PBAT, PLA, and PBAT/PLA samples decreased, while the oxygen atom content increased, indicating that the samples indeed degraded. The biodegradation rates of PBAT and PLA in the PBAT/PLA blend were not the same as those for the single materials.     

Synthesis,Crystal Structure,and Fungicidal Activity of a Novel 1,2,3-Thiadiazole Compound

Abstract

A new 1,2,3-thiadiazole compound, C₁₈H₁₈Cl₂N₄O₂S, has been synthesized and the crystal structure was determined by single crystal X-ray diffraction study. The fungicidal activity of the title compound was determined and the results showed that it displays moderate fungicidal activity.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Identification of a nanomolar affinity α-synuclein fibril imaging probe by ultra-high throughput in silico screening

Small molecules that bind with high affinity and specificity to fibrils of the α-synuclein (αS) protein have the potential to serve as positron emission tomography (PET) imaging probes to aid in the diagnosis of Parkinson''s disease and related synucleinopathies. To identify such molecules, we employed an ultra-high throughput in silico screening strategy using idealized pseudo-ligands termed exemplars to identify compounds for experimental binding studies. For the top hit from this screen, we used photo-crosslinking to confirm its binding site and studied the structure–activity relationship of its analogs to develop multiple molecules with nanomolar affinity for αS fibrils and moderate specificity for αS over Aβ fibrils. Lastly, we demonstrated the potential of the lead analog as an imaging probe by measuring binding to αS-enriched homogenates from mouse brain tissue using a radiolabeled analog of the identified molecule. This study demonstrates the validity of our powerful new approach to the discovery of PET probes for challenging molecular targets.