Network Dynamics in Elemental Assimilation and Metabolism

Metabolism and physiology frequently follow non-linear rhythmic patterns which are reflected in concepts of homeostasis and circadian rhythms, yet few biomarkers are studied as dynamical systems. For instance, healthy human development depends on the assimilation and metabolism of essential elements, often accompanied by exposures to non-essential elements which may be toxic. In this study, we applied laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) to reconstruct longitudinal exposure profiles of essential and non-essential elements throughout prenatal and early post-natal development. We applied cross-recurrence quantification analysis (CRQA) to characterize dynamics involved in elemental integration, and to construct a graph-theory based analysis of elemental metabolism. Our findings show how exposure to lead, a well-characterized toxicant, perturbs the metabolism of essential elements. In particular, our findings indicate that high levels of lead exposure dysregulate global aspects of metabolic network connectivity. For example, the magnitude of each element’s degree was increased in children exposed to high lead levels. Similarly, high lead exposure yielded discrete effects on specific essential elements, particularly zinc and magnesium, which showed reduced network metrics compared to other elements. In sum, this approach presents a new, systems-based perspective on the dynamics involved in elemental metabolism during critical periods of human development.     

Phonon confinement and substitutional disorder in Cd1−xZnxS nanocrystals

1‐longitudinal optical (LO) phonons in free‐standing mixed Cd_1−xZn_xS nanocrystals, synthesized using chemical precipitation, are investigated using Raman spectroscopy. As expected for the nanocrystals, the 1‐LO modes are found to appear at slightly lower wavenumbers than those in the bulk mixed crystals and exhibit one‐mode behavior. On the other hand, the line broadening is found to be much more than that can be accounted on the basis of phonon confinement. From the detailed line‐shape analysis it turns out that the substitutional disorder in the mixed crystals contributes much more to the line broadening than the phonon confinement. The linewidth arising from these mechanisms are also extracted from the analysis. Copyright © 2009 John Wiley & Sons, Ltd.     

Nano-graphitic clustering and break down of phonon selection rule in diamond-like carbon films

Diamond-like carbon films are deposited on silicon substrates at different substrate bias using ECR-CVD technique. Raman spectroscopic studies show the presence of broad G and D peaks. In contrast to the position of D peak, the G peak shows a systematic red-shift with increase in the bias voltage. From the analysis it is found that an increase in bias voltage decreases the sp² cluster diameter. Furthermore, two additional Raman peaks at around 690 and 880 cm^?1 are also observed. These peaks, forbidden in the first order Raman scattering, arise due to the breakdown of phonon selection rule in graphitic nanoclusters.     

Study of Optical Properties of <Emphasis Type="Italic">Macrophomina phaseolina</Emphasis> Impregnated Sol-gel Derived Silica Matrices

In the present frame of work, Macrophomina phaseolina is encapsulated in silica matrices at various concentrations by low temperature sol-gel technique using tetraethylorthosilicate (TEOS) as precursor. The optical and photophysical properties of these samples have been studied by second harmonics of Nd:YAG laser at 532 nm. UV-visible absorption spectra of samples have been recorded and it is found that the absorption increases with increase in concentration of fungus. Further, a decrease in output transmission intensity of the laser has been observed with increase in fungus concentration. The temporal response of these samples has also been examined. The results show that the fungus concentration can be measured within ∼15–20 min. This method of optical sensing of fungus in test sample is faster than other techniques, such as the conventional colorimetric method which takes about 1 h.     

Fabrication of dissolved O2 metric uric acid biosensor using uricase epoxy resin biocomposite membrane

Uricase purified from 20-day-old leaves of cowpea was immobilized on to epoxy resin membrane with 80% retention of initial activity of free enzyme and a conjugation yield of 0.056 mg/cm². The uricase epoxy resin bioconjugate membrane was mounted over the sensing part of the combined electrode of ‘Aqualytic’ dissolved O₂ (DO) meter to construct a uric acid biosensor. The biosensor measures the depletion of dissolved O₂ during the oxidation of uric acid by immobilized uricase, which is directly proportional to uric acid concentration. The biosensor showed optimum response within 10-12 s at a pH 8.5 and 35 °C. A linear relationship was found between uric acid concentration from 0.025 to 0.1 mM and O₂ (mg/l) consumed. The biosensor was employed for measurement of uric acid in serum. The mean value of uric acid in serum was 4.92 mg/dl in apparently healthy males and 3.11 mg/dl in apparently healthy females. The mean analytic recoveries of added uric acid in reaction mixture (8.9 and 9.8 mg/dl) were 93.6 ± 2.34 and 87.18 ± 3.17% respectively. The within and between batch CVs were <6.5 and <5.0%, respectively. The serum uric acid values obtained by present method and standard enzymic colorimetric method, showed a good correlation (r = 0.996) and regression equation being y = 0.984x + 0.0674. Among the various metabolites tested only, glucose (11%), urea (38%), NaCl (25%) and cholesterol (13%) and ascorbic acid (56%) caused decrease, while, MgSO₄ and CaCl₂ had no effect on immobilized enzyme. The enzyme electrode showed only 32% decrease during its use for 100 times over a period of 60 days at 4 °C.     

Glutinane triterpenes from the stem bark of <Emphasis Type="Italic">Euonymus hamiltonianus</Emphasis>

Three new glutinane-type triterpenes, 19α-glutin-5-en-19-ol (1), 2β,15α,21β-glutin-11-ene-2,15,21-triol (2), and 2β,19α-glutin-7,21-diene-2,19-diol (3), were isolated from the stem bark of Euonymus hamiltonianus. Their structures were determined by 1D and 2D NMR along with MS and IR. Published in Khimiya Prirodnykh Soedinenii, No. 3, pp. 321–323, May–June, 2009.     

Preparation and characterization of bis[4-dimethylamino-2-pyrimidyl] dichalcogenides (S, Se, Te): X-ray crystal structure of bis[4-dimethylamino-2-pyrimidyl] diselenide and its physicochemical behavior in microemulsion media

Novel and synthetically important bis[4-dimethylamino-2-pyrimidyl] dichalcogenides (S, Se, Te) have been prepared and characterized with the help of elemental analysis and various spectroscopic techniques. The methodology employs hydrazine hydrate in dimethylformamide to reduce elemental chalcogen to generate the dichalcogenide anions, E₂²⁻ (E=S, Se, Te), followed by reaction with 2,4-dichloropyrimidine to afford bis[4-dimethylamino-2-pyrimidyl] dichalcogenides in good yield. It further exploits the additional compositional degree of freedom available in mixed surfactant solution to allow solubilization and stabilization of bis[4-dimethylamino-2-pyrimidyl] diselenide in microemulsion media.     

Preparation of chitosan–polyethylene glycol coated cotton membranes for wound dressings: preparation and characterization

Cotton fabric was coated with chitosan (CS) and polyethylene glycol (PEG) followed by freeze‐drying. The influence of PEG on the physical characteristics and the surface morphology was investigated. The scanning electron microscopy of the coated fabric revealed a porous structure. The porosity of the material was 54–70% and the pore size was in the range of 75–120µm. The increase in the PEG content in the blend composition led to an enhanced destabilization of pores, leading to an increase in the pore size with elongated morphology. There seems to be phase separation between the two components which is an important factor for the observed behavior of the porous structure. The Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC) showed that the CS and PEG have limited interaction. DSC suggested that addition of PEG to CS does not interfere with the crystallization behavior due to limited interaction with CS. The thermogravimetric analysis (TGA) showed that the membranes are thermally stable and PEG enhances the thermal stability of the CS coated membranes. The air and water permeability of the membranes tended to decrease with the increase in the PEG content. Copyright © 2008 John Wiley & Sons, Ltd.     

EPR and optical absorption studies on VO2+ ions in L-asparagine monohydrate single crystals

X-Band electron paramagnetic resonance (EPR) studies of VO(2+) ions in l-asparagine monohydrate single crystals have been done at room temperature. Detailed EPR analysis indicates the presence of two magnetically inequivalent VO(2+) sites. Both the vanadyl complexes are found to take up interstitial position. The angular variation of the EPR spectra in three planes ab, bc and ca are used to determine principal g and A tensors. For the two sites the spin Hamiltonian parameters are, site I: g(x)=1.9633, g(y)=2.0274, g(z)=1.9797, A(x)=88, A(y)=61, A(z)=161x10(-4)cm(-1); site II: g(x)=1.9627, g(y)=1.9880, g(z)=1.9425, A(x)=90, A(y)=66, A(z)=167x10(-4)cm(-1). The optical absorption study is also carried out at room temperature and absorption bands are assigned to various transitions. The theoretical band positions are obtained using energy expressions and a good agreement is found with the experimental values. By correlating EPR and optical data different molecular orbital coefficients are evaluated and the nature of bonding in the crystal is discussed.     

Block Copolymer Directed Nanoporous Metal Thin Films

Porous metal thin films have high potential for use in applications such as catalysis, electrical contacts, plasmonics, as well as energy storage and conversion. Structuring metal thin films on the nanoscale to generate high surface areas poses an interesting challenge as metals have high surface energy. In this communication, we demonstrate direct access to nanostructured metal nanoparticle hybrid thin films with high nanoparticle loadings through spin coating of a mixture of block copolymer and ligand stabilized platinum and palladium nanoparticles. Plasma cleaning to remove the organics results in a conductive metal thin film. We expect that the methods described here can be generalized to other metals, mixtures of metal nanoparticles, and intermetallics.