Reversible Supracolloidal Self-Assembly of Cobalt Nanoparticles to Hollow Capsids and Their Superstructures

The synthesis and spontaneous, reversible supracolloidal hydrogen bond-driven self-assembly of cobalt nanoparticles (CoNPs) into hollow shell-like capsids and their directed assembly to higher order superstructures is presented. CoNPs and capsids form in one step upon mixing dicobalt octacarbonyl (Co₂CO₈) and p-aminobenzoic acid (pABA) in 1,2-dichlorobenzene using heating-up synthesis without additional catalysts or stabilizers. This leads to pABA capped CoNPs (core ca. 5 nm) with a narrow size distribution. They spontaneously assemble into tunable spherical capsids (d≈50–200 nm) with a few-layered shells, as driven by inter-nanoparticle hydrogen bonds thus warranting supracolloidal self-assembly. The capsids can be reversibly disassembled and reassembled by controlling the hydrogen bonds upon heating or solvent exchanges. The superparamagnetic nature of CoNPs allows magnetic-field-directed self-assembly of capsids to capsid chains due to an interplay of induced dipoles and inter-capsid hydrogen bonds. Finally, self-assembly on air–water interface furnishes lightweight colloidal framework films.     

Loop states in lattice gauge theory

We reformulate d-dimensional SU(2) lattice gauge theory in terms of gauge invariant loop state variables by solving the SU(2) Gauss law as well as the corresponding Mandelstam constraints. The loop states satisfying the Gauss law and the Mandelstam constraints in d dimension are explicitly constructed in terms of the SU(2) harmonic oscillator prepotential operators. We show that these mutually independent (orthonormal) loop states carry certain non-negative integer Abelian fluxes over the lattice links and are characterized by 3(d−1) gauge invariant angular momentum quantum numbers per lattice site. Thus, they provide a complete orthonormal loop basis in the physical Hilbert space of the gauge theory. Further, we derive the loop Hamiltonian and show that it counts, creates and annihilates the Abelian fluxes over the plaquettes. The generalization to SU(N) gauge group is discussed.     

Development and validation of reversed phase liquid chromatographic method utilizing ultraviolet detection for quantification of irinotecan (CPT-11) and its active metabolite, SN-38, in rat plasma and bile samples: application to pharmacokinetic studies

A new, simple, sensitive and specific reversed-phase high performance liquid chromatographic (HPLC) method using ultraviolet detection was developed and validated for the analysis of CPT-11 (lambda(max)=254 nm, 365 nm) and its major active metabolite, SN-38 (lambda(max)=380 nm) in rat plasma and bile. The sample pre-treatment from plasma involved a single protein precipitation step with cold acetonitrile. In case of bile, liquid-liquid extraction with dichloromethane: tert-butyl methyl ether (3:7) was carried out. Topotecan, a structurally related camptothecin, was used as an internal standard. An aliquot of 50 microL was injected onto a C-18 column. The chromatographic separation was achieved by gradient elution consisting of acetonitrile and water (pH 3.0 adjusted with 20% o-phosphoric acid) at a flow rate of 1.0 ml/min. Total run time for each sample was 30 min. All the analytes viz. topotecan, CPT-11, SN-38 were well separated with retention times of 11.4, 13.4 and 15.5 min, respectively. Method was found to be selective, linear (R(2) approximately 0.999), accurate (recovery+/-15%) and precise (<5% C.V.) in the selected concentration ranges for both the analytes. The quantification limit for CPT-11 was 40 ngml(-1) and for SN-38 was 25 ngml(-1). The percent extraction efficiency was approximately 97% for CPT-11 and SN-38 from plasma while extraction recovery of CPT-11 and SN-38 from bile was approximately 70% and approximately 60%, respectively. The method was successfully used to determine plasma and biliary excretion time profiles of CPT-11 and SN-38, following oral and intravenous CPT-11 administration in rats. In the present study, irinotecan showed an absolute bioavailability of 30% as calculated from the pharmacokinetic data.     

Structural, thermoanalytical and molecular modeling studies on N-(3-hydroxypropyl) 3 alpha,12 alpha-dihydroxy-5 beta-cholan-24-amide and its monohydrates

The synthetic method for preparing N-(3-hydroxypropyl) 3 alpha,12 alpha-dihydroxy-5 beta-cholan-24-amide can lead to formation of at least three different crystal forms - an anhydrous compound and two monohydrates. The structural and thermal properties of these forms have been characterized by 13C-CP/MAS-NMR and IR spectroscopy, thermo- gravimetry, differential scanning calorimetry and by powder and single crystal x-ray crystallography. In addition, theoretical 13C-NMR chemical shift calculations were also performed for the anhydrous compound and for the first monohydrate, starting from single crystal structures and the structures of these species have now been verified. The first monohydrate, C27H47NO4 x H2O, crystallizes in orthorhombic space group P2(1)2(1)2(1) with cell parameters: a = 7.1148(2), b = 18.1775(5), c = 20.1813(6), Z = 4.     

Structural studies on lithocholyl-N-(2-aminoethyl)amide in the solid state

The synthetic procedure of lithocholyl-N-(2-aminoethyl)amide yielded a mixture of several forms detected by solid state ¹³C CP/MAS NMR although the solution state NMR unambiguously ascertained that the compound was pure. By recrystallization from various solvents one pure polymorph alongside with four solvates were isolated. The structures of the pure polymorph and the solvates were characterized by ¹³C and ¹⁵N CP/MAS NMR and powder X-ray diffraction (PXRD) methods. Variable contact time and dipolar dephasing experiments were employed to obtain optimized CP parameters and to distinguish various CH _n (n = 0–3) resonances. CSA analyses of spinning side bands at different spinning rates showed small variations in the shielding tensor values of the carbonyl group between the pure polymorph (recrystallized from acetonitrile, tetrahydrofuran and 1,4-dioxane) and p-xylene solvate.     

Chemical activation of egg shell membrane for covalent immobilization of enzymes and its evaluation as inert support in urinary oxalate determination

Egg shell membrane is a novel, robust, microporous, cost effective, easily available organic support material. In recent studies egg shell membranes were utilized as organic support for enzyme immobilization. But low conjugation yield limits its application as good support for biotechnological industries. In present study egg shell membrane was chemically treated to introduce free functional groups for covalent linkage of proteins to increase its conjugation yield and stability of conjugate complex. Many enzymes were tested for immobilization on modified egg shell membrane like oxalate oxidase, glucose oxidase, peroxidase and lipase. A fifteen to sixteen fold increase in conjugation yield was observed when immobilization was performed after chemical treatment in comparison to immobilization on native membrane with slight change in specific activity of immobilized enzyme which ranges from 5% to 15%. Egg shell membrane bound enzymes showed slight changes in their kinetic properties after immobilization. Egg shell membrane bound oxalate oxidase shows detection limit of 1.5 μM when used for urinary oxalate determination. Egg shell membrane support shows no interference to enzyme activity and a good correlation of 0.99 was observed with the values estimated using commercially available Sigma kit. The immobilized oxalate oxidase, glucose oxidase, peroxidase and lipase were stable up to duration of 180 days and there is respective loss of 10%, 13%, 24%, and 33% of initial activity. Overall result strengthens our view of using chemically modified egg shell membrane as solid support for better immobilization of enzymes and can be used in various biotechnological applications.     

Acyclic Edge Coloring of Triangle‐Free Planar Graphs

An acyclic edge coloring of a graph is a proper edge coloring such that there are no bichromatic cycles. The acyclic chromatic index of a graph is the minimum number k such that there is an acyclic edge coloring using k colors and is denoted by a′(G). It was conjectured by Alon, Sudakov and Zaks (and much earlier by Fiamcik) that a′(G) ? Δ + 2, where Δ = Δ(G) denotes the maximum degree of the graph. If every induced subgraph H of G satisfies the condition |E(H)| ? 2|V(H)|?1, we say that the graph G satisfies Property A. In this article, we prove that if G satisfies Property A, then a′(G) ? Δ + 3. Triangle‐free planar graphs satisfy Property A. We infer that a′(G) ? Δ + 3, if G is a triangle‐free planar graph. Another class of graph which satisfies Property A is 2‐fold graphs (union of two forests). © 2011 Wiley Periodicals, Inc. J Graph Theory     

Interplay between size, composition, and phase transition of nanocrystalline Cr(3+)-doped BaTiO3 as a path to multiferroism in perovskite-type oxides

Multiferroics, materials that exhibit coupling between spontaneous magnetic and electric dipole ordering, have significant potential for high-density memory storage and the design of complex multistate memory elements. In this work, we have demonstrated the solvent-controlled synthesis of Cr(3+)-doped BaTiO(3) nanocrystals and investigated the effects of size and doping concentration on their structure and phase transformation using X-ray diffraction and Raman spectroscopy. The magnetic properties of these nanocrystals were studied by magnetic susceptibility, magnetic circular dichroism (MCD), and X-ray magnetic circular dichroism (XMCD) measurements. We observed that a decrease in nanocrystal size and an increase in doping concentration favor the stabilization of the paraelectric cubic phase, although the ferroelectric tetragonal phase is partly retained even in ca. 7 nm nanocrystals having the doping concentration of ca. 5%. The chromium(III) doping was determined to be a dominant factor for destabilization of the tetragonal phase. A combination of magnetic and magneto-optical measurements revealed that nanocrystalline films prepared from as-synthesized paramagnetic Cr(3+)-doped BaTiO(3) nanocrystals exhibit robust ferromagnetic ordering (up to ca. 2 μ(B)/Cr(3+)), similarly to magnetically doped transparent conducting oxides. The observed ferromagnetism increases with decreasing constituent nanocrystal size because of an enhancement in the interfacial defect concentration with increasing surface-to-volume ratio. Element-specific XMCD spectra measured by scanning transmission X-ray microscopy (STXM) confirmed with high spatial resolution that magnetic ordering arises from Cr(3+) dopant exchange interactions. The results of this work suggest an approach to the design and preparation of multiferroic perovskite materials that retain the ferroelectric phase and exhibit long-range magnetic ordering by using doped colloidal nanocrystals with optimized composition and size as functional building blocks.