Thermogravimetric analysis of plant water content in relation with heavy metal stress

We have used simultaneous thermogravimetry & differential scanning calorimetry (TG/DSC) to estimate water content of wheat plants exposed to toxic concentration of copper and cadmium. Our study revealed that water content tends to decrease along with the increase of the exogenous heavy metal supply. These data suggested a different status of water: on the one hand, form an organ to another, and on the other hand, in stressed plants compared with control plants. The observed differences could be correlated with reshaping processes induced by heavy metal stress, especially at cell wall level. Accumulation of fibrous constituents having important properties like ion binding and water-holding capacity, may affect water distribution and interactions. TG/DSC appears as a promising technique for revealing certain aspects of stress biochemistry and physiology in plants.     

Chemisorption of Exchange‐Coupled [Ni2L(dppba)]+ Complexes on Gold by Using Ambidentate 4‐(Diphenylphosphino)benzoate Co‐Ligands

A new strategy for the fixation of redox‐active dinickel(II) complexes with high‐spin ground states to gold surfaces was developed. The dinickel(II) complex [Ni₂L(Cl)]ClO₄ ( 1 ClO₄), in which L^2? represents a 24‐membered macrocyclic hexaaza‐dithiophenolate ligand, reacts with ambidentate 4‐(diphenylphosphino)benzoate (dppba) to form the carboxylato‐bridged complex [Ni₂L(dppba)]⁺, which can be isolated as an air‐stable perchlorate [Ni₂L(dppba)]ClO₄ ( 2 ClO₄) or tetraphenylborate [Ni₂L(dppba)]BPh₄ ( 2 BPh₄) salt. The auration of 2 ClO₄ was probed on a molecular level, by reaction with AuCl, which leads to the monoaurated Ni^II₂Au^I complex [Ni^II₂L(dppba)Au^ICl]ClO₄ ( 3 ClO₄). Metathesis of 3 ClO₄ with NaBPh₄ produces [Ni^II₂L(dppba)Au^IPh]BPh₄ ( 4 BPh₄), in which the Cl^? is replaced by a Ph^? group. The complexes were fully characterized by ESI mass spectrometry, IR and UV/Vis spectroscopy, X‐ray crystallography ( 2 BPh₄ and 4 BPh₄), cyclic voltammetry, SQUID magnetometry and HF‐ESR spectroscopy. Temperature‐dependent magnetic susceptibility measurements reveal a ferromagnetic coupling J=+15.9 and +17.9 cm^?1 between the two Ni^II ions in 2 ClO₄ and 4 BPh₄ (H=?2 JS₁S₂). HF‐ESR measurements yield a negative axial magnetic anisotropy (D<0), which implies a bistable (easy axis) magnetic ground state. The binding of the [Ni₂L(dppba)]ClO₄ complex to gold was ascertained by four complementary surface analytical methods: contact angle measurements, atomic‐force microscopy, X‐ray photoelectron spectroscopy, and spectroscopic ellipsometry. The results indicate that the complexes are attached to the Au surface through coordinative Au? P bonds in a monolayer.     

Quantum dot–NBD–liposome luminescent probes for monitoring phospholipase A2 activity

In this paper we describe the fabrication and characterization of new liposome encapsulated quantum dot–fluorescence resonance energy transfer (FRET)-based probes for monitoring the enzymatic activity of phospholipase A_2. To fabricate the probes, luminescent CdSe/ZnS quantum dots capped with trioctylphosphine oxide (TOPO) ligands were incorporated into the lipid bilayer of unilamellar liposomes with an average diameter of approximately 100 nm. Incorporating TOPO capped quantum dots in liposomes enabled their use in aqueous solution while maintaining their hydrophobicity and excellent photophysical properties. The phospholipid bilayer was labeled with the fluorophore NBD C₆-HPC (2-(6-(7-nitrobenz-2-oxa-1,3-diazol-4-yl)amino)hexanoyl-1-hexa decanoyl-sn-glycero-3-phosphocholine). The luminescent quantum dots acted as FRET donors and the NBD dye molecules acted as FRET acceptors. The probe response was based on FRET interactions between the quantum dots and the NBD dye molecules. The NBD dye molecules were cleaved and released to the solution in the presence of the enzyme phospholipase A_2. This led to an increase of the luminescence of the quantum dots and to a corresponding decrease in the fluorescence of the NBD molecules, because of a decrease in FRET efficiency between the quantum dots and the NBD dye molecules. Because the quantum dots were not attached covalently to the phospholipids, they did not hinder the enzyme activity as a result of steric effects. The probes were able to detect amounts of phospholipase A₂ as low as 0.0075 U mL^?1 and to monitor enzyme activity in real time. The probes were also used to screen phospholipase A₂ inhibitors. For example, we found that the inhibition efficiency of MJ33 (1-hexadecyl-3-(trifluoroethyl)-sn-glycero-2-phosphomethanol) was higher than that of OBAA (3-(4-octadecyl)benzoylacrylic acid).     

The influence of titanium dioxides,alumina and calcium carbonate on the thermal stability of barium carbonate

Using static oxygen-bomb calorimetry, the standard enthalpies of combustion of the 2,4-and 2,6-isomers of dinitrophenol have been determined as ?2697.22 and ?2723.08 ± 3.18 kJ mole^?1, respectively. Standard enthalpies of formation have been calculated as ?235.50 and ?209.64 ± 3.27 kJ mole^?1, respectively.     

Amperometric Detection of 4‐Chlorophenol on Two Types of Expanded Graphite Based Composite Electrodes

The assessment of an expanded graphite‐Ag‐zeolite‐epoxy composite (EG‐Z‐Ag‐Epoxy) electrode for the determination of 4‐chlorophenol (4‐CP) is described and compared to the corresponding expanded graphite‐epoxy composite (EG‐Epoxy) electrode. Cyclic voltammetry was used to characterize the electrochemical behavior and determination of 4‐CP at both electrodes in 0.1 M Na₂SO₄ and 0.1 M NaOH supporting electrolytes. A substantial enhancement of sensitivity for the determination of 4‐CP at the EG‐Z‐Ag‐Epoxy electrode was reached by applying a chemical preconcentration step prior to voltammetric quantification. Also, under these last conditions the lowest limit of detection of 1 μM illustrates the analytical versatility of this electrode in a concentration range where aquatic 4‐chlorophenol pollution is known to occur.     

Liquid crystalline phases and their dispersions in aqueous mixtures of glycerol monooleate and glyceryl monooleyl ether

The aqueous phase behavior of mixtures of 1-glycerol monooleate (GMO) and its ether analogue, 1-glyceryl monooleyl ether (GME) has been investigated by a combination of polarized microscopy, X-ray diffraction, and NMR techniques. Three phase diagrams of the ternary GMO/GME/water system have been constructed at 25, 40, and 55 degrees C. The results demonstrate that the increasing amount of GME favors the formation of the reversed phases, evidenced by the transformation of the lamellar and bicontinuous cubic liquid crystalline phases of the binary GMO/water system into reversed micellar or reversed hexagonal phases. For a particular liquid crystalline phase, increasing the GME content has no effect on the structural characteristics and hydration properties, thus suggesting ideal mixing with GMO. Investigations of dispersed nanoparticle samples using shear and a polymeric stabilizer, Pluronic F127, show the possibility of forming two different kinds of bicontinuous cubic phase nanoparticles by simply changing the GMO/GME ratio. Also NMR self-diffusion measurements confirm that the block copolymer, Pluronic F127, used to facilitate dispersion formation, is associated with nanoparticles and provides steric stabilization.     

Living photolytic ring-opening polymerization of amino-functionalized [1]ferrocenophanes: synthesis and layer-by-layer self-assembly of well-defined water-soluble polyferrocenylsilane polyelectrolytes

Facile synthetic routes have been developed that provide access to cationic and anionic water-soluble polyferrocenylsilane (PFS) polyelectrolytes with controlled molecular weight and narrow polydispersity. Living photolytic ring-opening polymerization of amino-functionalized [1]ferrocenophane (fc) monomers [fcSiMe{C[triple chemical bond]CCH(2)N(SiMe(2)CH(2))(2)}] (3), [fcSi{C[triple chemical bond]CCH(2)N(SiMe(2)CH(2))(2)}(2)] (10), [fcSiMe(C[triple chemical bond]CCH(2)NMe(2))] (14), and [fcSiMe(p-C(6)H(4)CH(2)NMe(2))] (20) yielded the corresponding polyferrocenylsilanes [(fcSiMe{C[triple chemical bond]CCH(2)N(SiMe(2)CH(2))(2)})(n)](5), [(fcSi{C[triple chemical bond]CCH(2)N(SiMe(2)CH(2))(2)}(2))(n)] (11), [{fcSiMe(C[triple chemical bond]CCH(2)NMe(2))}(n)] (15), and [{fcSiMe(p-C(6)H(4)CH(2)NMe(2))}(n)] (21) with controlled architectures. Further derivatization of 5, 15, and 21 generated water-soluble polyelectrolytes [(fcSiMe{C[triple chemical bond]CCH(2)N(CH(2)CH(2)CH(2)SO(3)Na)(2)})(n)] (6), [{fcSiMe(C[triple chemical bond]CCH(2)NMe(3)OSO(3)Me)}(n)] (7), and [{fcSiMe(p-C(6)H(4)CH(2)NMe(3)OSO(3)Me)}(n)] (22), respectively. The polyelectrolytes were readily soluble in water and NaCl aqueous solutions, with 6 and 22 exhibiting long-term stability in aqueous media. The PFS materials 6 and 22, have been utilized in the layer-by-layer (LbL) self-assembly of electrostatic superlattices. Our preliminary studies have indicated that films made from controlled low molecular-weight PFSs possess a considerably thinner bilayer thickness and higher refractive index than those made from PFSs that have an uncontrolled high molecular-weight. These results suggest that the structure and optical properties of LbL ultra-thin films can be tuned by varying polyelectrolyte chain length. The water-soluble low molecular weight PFSs are also useful materials for a range of applications including LbL self-assembly in highly confined spaces.     

Improved in vivo human carotid artery wall T2 estimation

T₂^? quantification has been shown to noninvasively and accurately estimate tissue iron content in the liver and heart; applying this to thin-walled carotid arteries introduces a new challenge to the estimation process. With most imaging voxels in a vessel being along its boundaries, errors in parameter estimation may result from partial volume mixing and misregistration due to motion in addition to noise and other common error sources. To minimize these errors, we propose a novel technique to reliably estimate T₂^? in thin regions of vessel wall. The technique weights data points to reduce the influence of expected error sources. It uses neighborhoods of data to increase the number of points for fitting and to assess lack of fit for automated outlier detection and deletion. The performance of this method was observed in simulations, phantom and in vivo patient studies and compared to results obtained using a pixelwise linear least squares estimation of T₂^?. The new proposed method showed a closer match to the expected results, and a 4.2-fold decrease in interobserver variability for in vivo studies. This increased confidence in estimation should improve the ability to reliably quantify iron noninvasively in the arterial wall.     

Hepatic sarcoidosis: MR appearances in patients with chronic liver disease

Purpose

To describe the MR appearances of hepatic sarcoidosis in patients with chronic liver disease and correlate the results with clinical stage of disease as measured with the Mayo end-stage liver disease (MELD) score.

Materials and methods

Twenty patients with chronic liver disease and histopathological diagnosis of hepatic sarcoidosis who underwent MR imaging were included in this study. Two abdominal radiologists retrospectively reviewed all images for the presence of cirrhosis, imaging pattern of the liver, intrahepatic biliary dilatation, presence of areas of parenchymal atrophy, presence of splenic nodules and lymphadenopathy. Imaging findings were correlated with the MELD score.

Results

Of the patients, 14/20 had imaging findings of cirrhosis, 9/20 had a large macronodular pattern of liver cirrhosis and 5/20 had a diffuse pattern of liver cirrhosis. Peripheral wedge-shaped areas of parenchymal atrophy were observed in 10 patients. The combination of a central macronodular pattern and peripheral atrophy was observed in 9/20 patients. The pattern of cirrhosis had statistically significant correlation with the presence of wedge-shaped areas of parenchymal atrophy (p < 0.005). No statistically significant difference was revealed between the clinical score of patients who had imaging findings consistent with cirrhosis and those who did not.

Conclusion

MR imaging appearances of chronic sarcoid liver disease are diverse and do not appear to correlate with severity of clinical disease. Large central regenerative nodules and wedge-shaped areas of peripheral parenchymal atrophy are frequent findings and may help to suggest the diagnosis.