Synthesis of a novel cis-proline-derived cyclic type VI beta-turn mimic via ring-closing metathesis

A cis-proline derived cyclic mimic of a type VI beta-turn is synthesized via a ring-closing metathesis reaction. The solution NMR conformational study indicates that the major conformer of the cyclic peptide adopts a type VIa beta-turn in CDCl(3) and a type VIb beta-turn in DMSO-d(6).     

Phase behavior of mixtures of polyoxyethylene(10) stearyl ether (Brij-76), 1-butanol, isooctane, and mixed polar solvents I. Water and formamide (or N,N-dimethyl formamide)

The isothermal phase diagram of the quaternary system polyoxyethylene(10) stearyl ether (Brij-76)/1-butanol/isooctane/water has been constructed at 30 degrees C with equal amounts of oil and water. A regular fishtail diagram was obtained, confirming the establishment of hydrophile-lipophile balance (HLB) in the system. Mixing of formamide (FA) [or N,N-dimethyl formamide (DMF)] with water as a cosolvent altered the HLB and decreased the solubilization capacity of the quaternary system. No three-phase body appeared at high FA or DMF content. Similar observations were noted for temperature-induced phase diagrams. The effect of DMF was more pronounced than that of FA in reducing the maximum solubilization capacity. The results have been summarized on the basis of HLB and mutual solubility of the components.     

Carbohydrate assisted fluorescence turn-on gluco-imino-anthracenyl conjugate as a Hg(II) sensor in milk and blood serum milieu

A new anthracenyl-imino-glucosyl conjugate (L) selectively senses Hg(2+) by turn-on fluorescence with a 13 ± 1 fold enhancement by forming a 2?:?1 complex in pH 5 to 10 even in the presence of several biologically and ecologically relevant metal ions, with a 25 ± 2% fluorescence enhancement at the EPA limit of 2 ppb. L is equally sensitive towards Hg(2+) in the presence of albumin proteins and in blood serum and milk.     

Novel ascorbic acid based ionic liquids for the in situ synthesis of quasi-spherical and anisotropic gold nanostructures in aqueous medium

A series of newly designed ascorbic acid based room temperature ionic liquids were successfully used to prepare quasi-spherical and anisotropic gold nanostructures in an aqueous medium at ambient temperature. The synthesis of these room temperature ionic liquids involves, first, the preparation of a 1-alkyl (such as methyl, ethyl, butyl, hexyl, octyl, and decyl) derivative of 3-methylimidazolium hydroxide followed by the neutralization of the derivatised product with ascorbic acid. These ionic liquids show significantly better thermal stability and their glass transition temperature (Tg) decreases with increasing alkyl chain length. The ascorbate counter anion of these ionic liquids acts as a reducing agent for HAuCl4 to produce metallic gold and the alkylated imidazolium counter cation acts as a capping/shape-directing agent. It has been found that the nature of the ionic liquids and the mole ratio of ionic liquid to HAuCl4 has a significant effect on the morphology of the formed gold nanostructures. If an equimolar mixture of ionic liquid and HAuCl4 is used, predominantly anisotropic gold nanostructures are formed and by varying the alkyl chain length attached to imidazolium cation of the ionic liquids, various particle morphologies can formed, such as quasispherical, raspberry-like, flakes or dendritic. A probable formation mechanism for such anisotropic gold nanostructures has been proposed, which is based on the results of some control experiments.     

Linear {NiII–LnIII–NiII} Complexes Containing Twisted Planar Ni(μ‐phenolate)2Ln Fragments: Synthesis,Structure, and Magnetothermal Properties

Sequential reaction of a multisite LH₄ ligand {2‐[2‐hydroxy‐3‐(hydroxymethyl)‐5‐methylbenzylideneamino]‐2‐methylpropane‐1,3‐diol} with appropriate lanthanide salts followed by the addition of Ni(NO₃)₂ ? 6 H₂O in a 4:1:2 stoichiometric ratio in the presence of triethylamine afforded four heterobimetallic trinuclear complexes [Ni₂Gd(LH₃)₄] ? 3 NO₃ ? 3 MeOH ? H₂O ? CH₃CN ( 1 ), [Ni₂Tb(LH₃)₄] ? 3 NO₃ ? 3 MeOH ? CH₃CN ( 2 ), [Ni₂Dy(LH₃)₄] ? 3 NO₃ ? 3 MeOH ? H₂O ? CH₃CN ( 3 ), and [Ni₂Ho(LH₃)₄] ? 3 NO₃ ? 3 MeOH ? H₂O ? CH₃CN ( 4 ). Complexes 1 – 4 possess linear trimetallic cores with a central lanthanide ion. Magnetic studies revealed a predominant ferromagnetic interaction between the Ni and Ln centers. Alternating current susceptibility measurements of complex 3 showed a small frequency dependence of the out‐of‐phase signal, χ′′_M , under zero direct current field, but without achieving a net maximum above 2 K. Magnetic studies on 1 revealed that it has a significant magnetocaloric effect.     

ROLE OF MEROCYANINE DYE AS A PROTON PUMP IN PHOTOVOLTAGE GENERATION

A novel photoelectrochemical cell using a proton pump mechanism in the aggregated planar structure of oxidised cholesterol incorporating merocyanine dyes is reported. Lipid dye binding, as verified from spectral studies and photoisomerisation of the dye, is responsible for this photovoltage generation whose magnitude and storage duration are related to the equilibrium constant of dye-lipid binding through an empirical formula.     

Biocompatibility of gold nanoparticles and their endocytotic fate inside the cellular compartment: a microscopic overview

Macrophages are one of the principal immune effector cells that play essential roles as secretory, phagocytic, and antigen-presenting cells in the immune system. In this study, we address the issue of cytotoxicity and immunogenic effects of gold nanoparticles on RAW264.7 macrophage cells. The cytotoxicity of gold nanoparticles has been correlated with a detailed study of their endocytotic uptake using various microscopy tools such as atomic force microscopy (AFM), confocal-laser-scanning microscopy (CFLSM), and transmission electron microscopy (TEM). Our findings suggest that Au(0) nanoparticles are not cytotoxic, reduce the production of reactive oxygen and nitrite species, and do not elicit secretion of proinflammatory cytokines TNF-alpha and IL1-beta, making them suitable candidates for nanomedicine. AFM measurements suggest that gold nanoparticles are internalized inside the cell via a mechanism involving pinocytosis, while CFLSM and TEM studies indicate their internalization in lysosomal bodies arranged in perinuclear fashion. Our studies thus underline the noncytotoxic, nonimmunogenic, and biocompatible properties of gold nanoparticles with the potential for application in nanoimmunology, nanomedicine, and nanobiotechnology.     

Analytical model for the magnetophoretic capture of magnetic microspheres in microfluidic devices

Magnetic microspheres are used as mobile substrates in micro-total-analysis systems (μTAS), since the particles can be selectively functionalized to attach different bioconjugates and can be precisely manipulated using external magnetic field gradients. A large number of MEMS-based bio-analytical devices employ magnetophoretic separation as an important step during their operation. An analytical technique is proposed in this paper that describes the magnetophoretic transport of magnetic microspheres under an imposed magnetic field when there is a pressure-driven or electroosmotic flow through a microchannel. Successful magnetophoretic capture occurs if the strength of the field-inducing magnetic dipole exceeds a critical value, or if the particles are larger than a critical size. The magnetophoretic separator performance is characterized in terms of capture efficiency. The analysis shows that the capture efficiency is a function of two independent non-dimensional parameters, λ and γ that in turn involve all the physical design and operating parameters of the microfluidic separator, e.g., the dipole strength, particle size and susceptibility, fluid viscosity and velocity, channel height, and the separation of the dipole. Parametric plots of capture efficiency as function of λ and γ helps in choosing the right design and operation parameter of a practical microfluidic separator for a target level of performance.     

Separation of Palladium by Extraction Chromatographic Technique Using Cyanex 471X (Tri Isobutyl Phosphine Sulfide) on Chromosorb-102

In a preliminary study performed with the waste rocks from the future uranium mine to be explored in Brazil, 106 samples were taken from the eight main lithologies found in the massif and analysed by instrumental neutron activation analysis (INAA) for 20 elements. For samples from the same lithology, a high variability in the concentration of most of the elements was found (coefficient of variation larger than 20%), which might be attributed to either insufficient homogenisation of minerals or to local variation within lithology. The hypothesis that the variability within the lithology does not have an influence to the total variability was tested by analysing 5 replicates of the 5 most contrasting samples from the predominant lithology (plagioclase-microcline-gneiss), chosen after applying statistical evaluation (principal components and cluster analyses). Results indicated that homogenisation of samples was adequate due to low variation among replicates. The hypothesis tested was rejected with a confidence level higher than 99% for all the elements, corroborating the large intra-lithology variability.     

Use of EM algorithm for data reduction under sparsity assumption

Recent scientific applications produce data that are too large for storing or rendering for further statistical analysis. This motivates the construction of an optimum mechanism to choose only a subset of the available information and drawing inferences about the parent population using only the stored subset. This paper addresses the issue of estimation of parameter from such filtered data. Instead of all the observations we observe only a few chosen linear combinations of them and treat the remaining information as missing. From the observed linear combinations we try to estimate the parameter using EM based technique under the assumption that the parameter is sparse. In this paper we propose two related methods called ASREM and ESREM. The methods developed here are also used for hypothesis testing and construction of confidence interval. Similar data filtering approach already exists in signal sampling paradigm, for example, Compressive Sampling introduced by Candes et al. (Commun Pure Appl Math 59(8):1207–1223, 2006) and Donoho (IEEE Trans Inf Theory 52: 1289–1306, 2006). The methods proposed in this paper are not claimed to outperform all the available techniques of signal recovery, rather our methods are suggested as an alternative way of data compression using EM algorithm. However, we shall compare our methods to one standard algorithm, viz., robust signal recovery from noisy data using min-\(\ell _{1}\) with quadratic constraints. Finally we shall apply one of our methods to a real life dataset.