PEGylated inorganic nanoparticles

Application of inorganic nanoparticles in diagnosis and therapy has become a critical component in the targeted treatment of diseases. The surface modification of inorganic oxides is important for providing diversity in size, shape, solubility, long-term stability, and attachment of selective functional groups. This Minireview describes the role of polyethylene glycol (PEG) in the surface modification of oxides and focuses on their biomedical applications. Such a PEGylation of surfaces provides "stealth" characteristics to nanomaterials otherwise identified as foreign materials by human body. The role of PEG as structure-directing agent in synthesis of oxides is also presented.     

Effect of ambient pressure on the crystalline phase of nano TiO2 particles synthesized by a dc thermal plasma reactor

The synthesis of nanoparticles of titanium dioxide (TiO₂) with varying percentages of anatase and rutile phases is reported. This was achieved by controlling the operating pressure in a transferred-arc, direct current thermal plasma reactor in which titanium vapors are evaporated, and then exposed to ambient oxygen. The average particle size remained around 15 nm in each case. The crystalline structure of the as-synthesized nanoparticles of TiO₂ was studied with X-ray diffraction analysis; whereas the particle morphology was investigated with the help of transmission electron microscopy. The precursor species responsible for the growth of these nanoparticles was studied with the help of optical emission spectroscopy. As inferred from the X-ray diffraction analysis, the relative abundance of anatase TiO₂ was found to be dominant when synthesized at 760 Torr, and the same showed a decreasing trend with decreasing chamber pressure. The study also reveals that anatase TiO₂ is a more effective photocatalytic agent in degrading methylene blue by comparison to its rutile phase.     

Arc plasma synthesized LaB<Subscript>6</Subscript> nanocrystallite film on various substrates as a field emitter

Lanthanum hexaboride (LaB₆) nanocrystallites/nanowires have been successfully synthesized using gas phase condensation in arc plasma. Our results show that the LaB₆ nanowires have ~20 nm diameter and length of several micrometers. The as-synthesized LaB₆ nanocrystallites and nanowires are crystalline in nature. Field emission studies were carried out on as synthesized LaB₆ nano-powder deposited on W and Re tips and foils, and also on Si foil substrates under ultra high vacuum. The Fowler–Nordheim plots obtained from the current–voltage characteristics are found to be linear in accordance with the quantum mechanical tunneling phenomenon. High value of field enhancement factor (8177) is observed for LaB₆ on Re substrate, indicating that the electron emission is from the nanometric features of the LaB₆. Our results show that the arc plasma synthesized LaB₆ nanocrystalline film exhibits good emission stability as emitter without severe deviations from the initial set value and also a strong ability to withstand the ion bombardment, which is useful for low operation voltage vacuum micro/nano electronic devices.     

A generalization of sumset and its applications

Let A be a nonempty finite subset of an additive abelian group G and let r and h be positive integers. The generalized h-fold sumset of A, denoted by \(h^{(r)}A\), is the set of all sums of h elements of A, where each element appears in a sum at most r times. The direct problem for \(h^{(r)}A\) is to find a lower bound for \(|h^{(r)}A|\) in terms of |A|. The inverse problem for \(h^{(r)}A\) is to determine the structure of the finite set A for which \(|h^{(r)}A|\) is minimal with respect to some fixed value of |A|. If \(G = \mathbb {Z}\), the direct and inverse problems are well studied. In case of \(G = \mathbb {Z}/p\mathbb {Z}\), p a prime, the direct problem has been studied very recently by Monopoli (J. Number Theory, 157 (2015) 271–279). In this paper, we express the generalized sumset \(h^{(r)}A\) in terms of the regular and restricted sumsets. As an application of this result, we give a new proof of the theorem of Monopoli and as the second application, we present new proofs of direct and inverse theorems for the case \(G = \mathbb {Z}\).     

Solvent- and Substrate-Induced Chiroptical Inversion in Amphiphilic,Biocompatible Glycoconjugate Supramolecules: Shape-Persistent Gelation,Self-Healing,and Antibacterial Activity

We have shown solvent- and substrate-dependent chiral inversion of a few glycoconjugate supramolecules. (Z)-F-Gluco, in which d -glucosamine has been attached chemically to Cbz-protected l -phenylalanine at the C terminus, forms a self-healing hydrogel through intertwining of the nanofibers wherein the gelators undergo lamellar packing in the β-sheet secondary structures with a single chiral handedness. Dihybrid (Z)-F-gluco nanocomposite gel was prepared by in-situ formation of silver nanoparticles AgNPs in the gel; this enhances the mechanical properties of the composite gel through physical crosslinking without altering the packing pattern. In contrast, (Z)-L-gluco bearing an l -leucine moiety does not form a hydrogel but an organogel. Interestingly, the chiral handedness of the aggregates of (Z)-L-gluco can be reversed by choosing suitable solvents. In addition to self-healing behavior, (Z)-L-gluco gel revealed shape persistency. Further, (Z)-F-gluco hydrogel is benign, nontoxic, non-immunogenic, and non-allergenic in animal cells. AgNP-loaded (Z)-F-gluco hydrogel showed antibacterial activity against both Gram-positive and Gram-negative bacteria.     

Silanylidene and Germanylidene Anions: Valence‐Isoelectronic Species to the Well‐Studied Phosphinidene

The reduction of TipMCl₃ (Tip=2,4,6‐triisopropylphenyl) (M=Si, Ge) with KC₈ in the presence of cyclic alkyl(amino) carbene (cAAC) afforded the acyclic silanylidene and germanylidene anions in the form of potassium salt [K(cAAC)MTip]₂ (M=Si ( 1 ); Ge ( 2 )). The silanylidene and germanylidene anions are valence‐isoelectronic to the well‐studied phosphinidene and are a new class of acyclic anions of Group 14. Compounds 1 and 2 were isolated and well characterized by NMR and single‐crystal X‐ray structure analysis. Furthermore, the structure and bonding of compounds 1 and 2 was investigated by computational methods.     

The solution behavior of poly(vinylpyrrolidone): its clouding in salt solution, solvation by water and isopropanol, and interaction with sodium dodecyl sulfate

This article deals with the solution properties of poly(vinylpyrrolidone) (PVP) in salt and surfactant environment. The cloud point (CP) of PVP has been found to be induced by the salts NaCl, KCl, KBr, Na2SO4, MgSO4, and Na3PO4. On the basis of CP values for a salt at different [PVP], the energetics of the clouding process have been estimated. The effect of the surfactant, sodium dodecyl sulfate (SDS), on the salt-induced CP has also been studied, and reduction in CP at low [SDS] and increase in CP at high [SDS] have been observed. The water vapor adsorption of PVP has been determined by isopiestic method. The results display a BET Type III isotherm whose analysis has helped to obtain the monolayer capacity of PVP and formation of multilayer on it. The solvation of PVP in a solution of water and a water-isopropanol mixture has been determined by conductometry from which contribution of the individual components were estimated. The interaction of PVP with SDS in solution led to formation of a complex entity, which has been studied also by conductometry adopting a binding-equilibrium scheme. SDS has been found to undergo two types of binding as monomers in the pre- critical aggregation concentration (CAC) range and as small clusters in the post CAC region. The stoichiometries of binding and binding constant were evaluated.     

Synthesis of β-octabromocalix[4]pyrroles and conformational diversity in their acetone inclusion complexes

Two β-octabromocalix[4]pyrroles were synthesized using a modified strategy, which provides the advantage of large scale preparation with rapid purification. The acetone inclusion complexes of these compounds show different structural orientations featuring diverse types of novel hydrogen bonding owing to varied meso-substitution along with the presence of eight peripheral bromine atoms.     

Interaction with Al and Zn induces structure formation and aggregation in natively unfolded caseins

Caseins are phosphoproteins that form the principal protein component of milk, their chief function being the transport of inorganic calcium and phosphate to the neonates. The four major members of the casein family are alpha(s1)-, alpha(s2)- (together referred to as alpha(s)-casein), beta- and kappa-casein, each having a characteristic high negative net charge as well as high hydrophobicity and preferring extended conformational states in solution. We have investigated the influence of the polyvalent metal cations Zn(II) and Al(III) on the structure of bovine caseins, using fluorescence and circular dichroic (CD) spectroscopy and light scattering. Changes in Trp and ANS fluorescence parameters (blue shifts of the emission maxima and enhancement of fluorescence intensity) and in the far-UV CD spectra of the caseins caused by the presence of both metals suggest that conformational changes are induced in them by low concentrations (20-40 microM) of the metal cations. These changes lead to formation of solvent-accessible hydrophobic clusters or cavities that, in turn, cause self-association and precipitation of caseins at higher concentration of the metals. These conclusions are supported by increased binding of ThT to the caseins, as well as enhancement of light scattering intensity, observed in presence of Al(III). The chaperonic property of alpha(s)-casein, which enables it to inhibit thermal aggregation of alcohol dehydrogenase, is shown to be partially destroyed by Zn(II)-induced structural alterations, due possibly to loss of flexibility of the natively unfolded casein chains.