Enhancing the photocytotoxic potential of curcumin on terpyridyl lanthanide(III) complex formation

Lanthanide(III) complexes Ln(R-tpy)(cur)(NO3)(2)] (Ln = La(III) in 1, 2; Gd(III) in 5, 6) and Ln(R-tpy)(scur)(NO3)(2)] (Ln = La(III) in 3, 4; Gd(III) in 7, 8), where R-tpy is 4'-phenyl-2,2':6',2 `'-terpyridine (ph-tpy in 1, 3, 5, 7), 4'-(1-pyrenyl)-2,2':6',2 `'-terpyridine (py-tpy in 2, 4, 6, 8), Hcur is curcumin (in 1, 2, 5, 6) and Hscur is diglucosylcurcumin (in 3, 4, 7, 8), were prepared and their DNA photocleavage activity and photocytotoxicity studied. Complexes La(ph-tpy)(cur)(NO3)(2)] (1) and Gd(ph-tpy)(cur)(NO3)(2)] (5) were structurally characterized. The complexes in aqueous-DMF showed an absorption band near 430 nm and an emission band near 515 nm when excited at 420 nm. The complexes are moderate binders to calf-thymus DNA. They cleave plasmid supercoiled DNA to its nicked circular form in UV-A (365 nm) and visible light (454 nm) via O-1(2) and (OH)-O-center dot pathways. The complexes are remarkably photocytotoxic in HeLa cells in visible light (lambda = 400-700 nm) and are non-toxic in the dark. FACScan analysis of the HeLa cells treated with 2 and 4 showed cell death via an apoptotic pathway. Nuclear localization of 1-4 is evidenced from confocal imaging on HeLa cells. The hydrolytic instability of curcumin gets significantly reduced upon binding to the lanthanide ions while retaining its photocytotoxic potential.

Electrochemical capacitors: Technical challenges and prognosis for future markets

Electrochemical capacitors are potential devices that could help bringing about major advances in future energy storage. They are lightweight and their manufacture and disposal has no detrimental effects on the environment. A comprehensive description of fundamental science of electrochemical capacitors is presented. Similarities and differences between electrochemical capacitors and secondary batteries for electrical energy storage are highlighted and various types of electrochemical capacitors are discussed with special reference to lead-carbon hybrid ultracapacitors. Some envisaged applications of electrochemical capacitors are described along with the technical challenges and prognosis for future markets. (C) 2012 Published by Elsevier Ltd.

Thermodynamics of TmRhO3, Phase Equilibria, and Chemical Potentials in the System Tm-Rh-O

Phase equilibria in the system Tm-Rh-O at 1200 K is established by isothermal equilibration of selected compositions and phase identification after quenching to room temperature. Six intermetallic phases (Tm3Rh, Tm7Rh3, Tm5Rh3, Tm3Rh2, TmRh, TmRh2 +/-delta) and a ternary oxide TmRhO3 are identified. Based on experimentally determined phase relations, a solid-state electrochemical cell is devised to measure the standard free energy of formation of orthorhombic perovskite TmRhO3 from cubic Tm2O3 and beta-Rh2O3 in the temperature range from (900 to 1300) K. The results can be summarized as: Delta G(f,ox)(o) +/- 104/J.mol(-1) = -46474 + 3.925(T/K). Invoking the Neumann-Kopp rule, the standard enthalpy of formation of TmRhO3 from its constituent elements at 298.15 K is estimated as -1193.89 (+/- 2.86) kJ.mol(-1). The standard entropy of TmRhO3 at 298.15 K is evaluated as 103.8 (+/- 1.6) J.mol(-1).K-1. The oxygen potential-composition diagram and three-dimensional chemical potential diagram at 1200 K and temperature-composition diagrams at constant partial pressures of oxygen are computed from thermodynamic data. The compound TmRhO3 decomposes at 1688 (+/- 2) K in pure oxygen and at 1583 (+/- 2) K in air at standard pressure.

Molecular Marriage through Partner Preferences in Covalent Cage Formation and Cage-to-Cage Transformation

Unprecedented self-sorting of three-dimensional purely organic cages driven by dynamic covalent bonds is described. Four different cages were first synthesized by condensation of two triamines and two dialdehydes separately. When a mixture of all the components was allowed to react, only two cages were formed, which suggests a high-fidelity self-recognition. The issue of the preference of one triamine for a particular dialdehyde was further probed by transforming a non-preferred combination to either of the two preferred combinations by reacting it with the appropriate triamine or dialdehyde.

Self-Adapting Peripherally Heterofunctionalized Hyperbranched Polymers: Formation of Janus and Tripodal Structures

A peripherally clickable hyperbranched polyester carrying numerous propargyl terminal groups was prepared by a simple melt transesterification polycondensation of a suitably designed AB(2) monomer; this clickable hyperscaffold was then transformed into a variety of different derivatives by using the Cu-catalyzed azide-yne click reaction. Functionalization of the periphery with equimolar quantities of mutually immiscible segments, such as hydrocarbon, fluorocarbon, and PEG, yielded frustrated molecular systems that readapt and form structures wherein the immiscible segments appear to self-segregate to generate either Janus structures (when two immiscible segments are present) or tripodal structures (when three immiscible segments are present). Evidence for such self-segregation was obtained from a variety of studies, such as differential scanning calorimetry, Langmuir isotherms, AFM imaging, and small-angle X-ray scattering measurements. Crystallization of one or more of the peripheral segments reinforced this self-segregation; the weight-fraction-normalized enthalpies of melting associated with the different domains revealed a competition between the segments to optimize their crystalline organization. When one or more of the segments are amorphous, the remaining segments crystallize more effectively and consequently exhibit a higher melting enthalpy. AFM images of monolayers, transferred from the Langmuir trough, revealed that the thickness matches the expected values; furthermore, contact angle measurements clearly demonstrated that the monolayer films are fairly hydrophobic, and in the case of the tripodal hybramers, the presence of domains of hydrocarbon and fluorocarbon appears to impart nanoscale chemical heterogeneity that is reflected in the strong hysteresis in the advancing and receding contact angles.

Study of the Formation of Nano-Networks in Colloidal Particles

The authors studied the formation of a wafer-scale network of connected colloidal beads by reactive ion etching. The dimensions of the connections have been studied as a function of etching time for colloidal beads of different sizes, and could be well controlled. The authors have found that the nano-network forms and disappears for the same time of etching independent of the diameter of the polystyrene beads. With recent interest of connected colloidal networks in various optical sensing applications, such as photonic crystals, as surface-enhanced Raman scattering substrates, the studies have potential uses in the development of wafer-scale nanophotonic sensors.

System Gd-Rh-O: Thermodynamics and phase relations

Thermodynamic properties of GdRhO3 are investigated in the temperature range from 900 to 1300 K by employing a solid-state electrochemical cell, incorporating calcia-stabilized zirconia as the electrolyte. The standard Gibbs free energy of formation of GdRhO3 from component binary oxide Gd2O3 with C-rare earth structure and Rh2O3 with orthorhombic structure can be expressed as; Delta G(f(ox))(o)(+/- 60)/J mol(-1) = -56603 + 3.78(T/K) Based on the thermodynamic information on GdRhO3 from experiment and auxiliary data for binary oxides from the literature and estimated properties of Gd-Rh alloys, phase relations are computed for the system Gd-Rh-O at 1273 K. Gibbs free energies for intermetallic phases in the binary Gd-Rh are evaluated using calorimetric data available in the literature for two compositions and Miedema's model, consistent with the binary phase diagram. Isothermal section of the ternary phase diagram, oxygen potential-composition diagram and a 3-D chemical potential diagram for the system Gd-Rh-O at 1273 K are developed. Phase relations in the ternary Gd-Rh-O are also computed as a function of temperature at constant oxygen partial pressures. The ternary oxide, GdRhO3 decomposes to Gd2O3 with B-rare earth structure, metallic Rh and O-2 at 1759(+/- 2) K in pure O-2 and 1649(+/- 2) K in air at a total pressure P-0 -0.1 MPa. (c) 2012 Elsevier B.V. All rights reserved.

Regulation of lipid biosynthesis, sliding motility, and biofilm formation by a membrane-anchored nucleoid-associated protein of mycobacterium tuberculosis

Bacteria use a number of small basic proteins for organization and compaction of their genomes. By their interaction with DNA, these nucleoid-associated proteins (NAPs) also influence gene expression. Rv3852, a NAP of Mycobacterium tuberculosis, is conserved among the pathogenic and slow-growing species of mycobacteria. Here, we show that the protein predominantly localizes in the cell membrane and that the carboxy-terminal region with the propensity to form a transmembrane helix is necessary for its membrane localization. The protein is involved in genome organization, and its ectopic expression in Mycobacterium smegmatis resulted in altered nucleoid morphology, defects in biofilm formation, sliding motility, and change in apolar lipid profile. We demonstrate its crucial role in regulating the expression of KasA, KasB, and GroEL1 proteins, which are in turn involved in controlling the surface phenotypes in mycobacteria.

Towards the understanding of formation of micro/nano holes of Ge/GeO2 through phase mapping

Here, we report for the first time a simple thermal oxidation strategy for the large area synthesis of Ge/GeO2 nanoholes from Ge and studied the luminescence of Ge/GeO2 and hole formation mechanism through phase and luminescence mapping. Photoluminescence mapping reveals that the emission in the visible range is only from the hole region, which provokes the necessity of the nanoholes. Such materials can also be used to convert ultraviolet to visible radiation for detection by conventional phototubes and to coat blue or ultraviolet diodes to obtain white light.

EQCM investigation of electrochemical deposition and stability of Co-Pi oxygen evolution catalyst of solar energy storage

Photoassisted electrolysis of water is considered as an effective way of storing solar energy in the form of hydrogen fuel. This overall reaction involves the oxidation of water to oxygen at the anode and the reduction of protons to hydrogen at the cathode. Cobalt-phosphate-based catalyst (Co-Pi) is a potentially useful material for oxygen evolution reaction. In the present study, electrochemical deposition of Co-Pi catalyst is carried out on Au-coated quartz crystal from 0.1 M phosphate buffer (pH 7) containing 0.5 mM Co2+ ion, along with the simultaneous measurement of mass changes at the electrode surface. Cyclic voltammograms and mass variations are recorded during the course of deposition. A current peak is observed at 0.92 V vs Ag/AgCl, 3 M KCl corresponding to oxidation of Co2+ ion. The mass of the electrode starts increasing at this potential, suggesting the deposition of a Co(III)-based insoluble product on the electrode surface. The stability of the catalyst is also studied at several potentials in both buffered and nonbuffered electrolyte by monitoring the real-time mass variations.

Spontaneous formation of branched nanochains from room temperature molten amides: visible and near-IR active, SERS substrates for non-fluorescent and fluorescent analytes

Highly stable, branched gold nanoworms are formed spontaneously in an acetamide-based room temperature molten solvent without any additional external stabilizing or aggregating agent. The nanoworms can be anchored onto solid substrates such as indium tin oxide (ITO) without any change in morphology. The anchored nanoworms are explored as substrates for surface enhanced Raman scattering (SERS) studies using non-fluorescent 4-mercaptobenzoic acid (4-MBA) and fluorescent rhodamine 6G (R6G) as probe molecules. The anchored nanostructured particles respond to near IR (1064 nm) as well as visible (785, 632.8 and 514 nm) excitation lasers and yield good surface enhancement in Raman signals. Enhancement factors of the order 10(6)-10(7) are determined for the analytes using a 1064 nm excitation source. Minimum detection limits based on adsorption from ethanolic solutions of 1028 M 4-MBA and aqueous solutions of 1027 M R6G are achieved. Experimental Raman frequencies and frequencies estimated by DFT calculations are in fairly good agreement. SERS imaging of the nanostructures suggests that the substrates comprising of three dimensional, highly interlinked particles are more suited than particles fused in one dimension. The high SERS activity of the branched nanoworms may be attributed to both electromagnetic and charge transfer effects.

Probing hemoglobin confinement inside submicron silica tubes using synchrotron SAXS and electrochemical response

The configuration of hemoglobin in solution and confined inside silica nanotubes has been studied using synchrotron small angle X-ray scattering and electrochemical activity. Confinement inside submicron tubes of silica aid in preventing protein aggregation, which is vividly observed for unconfined protein in solution. The radius of gyration (R-g) and size polydispersity (p) of confined hemoglobin was found to be lower than that in solution. This was also recently demonstrated in case of confined hemoglobin inside layered polymer capsules. The confined hemoglobin displayed a higher thermal stability with Rg and p showing negligible changes in the temperature range 25-75 degrees C. The differences in configuration between the confined and unconfined protein were reflected in their electrochemical activity. Reversible electrochemical response (from cyclic voltammograms) obtained in case of the confined hemoglobin, in contrary to the observance of only a cathodic response for the unconfined protein, gave direct indication of the differences between the residences of the electroactive heme center in a different orientation compared to that in solution state. The confined Hb showed loss of reversibility only at higher temperatures. The electron transfer coefficient (alpha) and electron transfer rate constant (k(s)) were also different, providing additional evidence regarding structural differences between the unconfined and confined states of hemoglobin. Thus, absence of any adverse effects due to confinement of proteins inside the inorganic matrices such as silica nanotubes opens up new prospects for utilizing inorganic matrices as protein ``encapsulators'', as well as sensors at varying temperatures.

Determination of favorable inter-particle interactions for formation of substitutionally ordered solid phases from a binary mixture of oppositely charged colloidal suspensions

The solid phase formed by a binary mixture of oppositely charged colloidal particles can be either substitutionally ordered or substitutionally disordered depending on the nature and strength of interactions among the particles. In this work, we use Monte Carlo molecular simulations along with the Gibbs-Duhem integration technique to map out the favorable inter-particle interactions for the formation of substitutionally ordered crystalline phases from a fluid phase. The inter-particle interactions are modeled using the hard core Yukawa potential but the method can be easily extended to other systems of interest. The study obtains a map of interactions depicting regions indicating the type of the crystalline aggregate that forms upon phase transition.

Employing denaturation for rapid electrochemical detection of myoglobin using TiO2 nanotubes

An alternative antibody-free strategy for the rapid electrochemical detection of cardiac myoglobin has been demonstrated here using hydrothermally synthesized TiO2 nanotubes (Ti-NT). The denaturant induced unfolding of myoglobin led to easy access of the deeply buried electroactive heme center and thus the efficient reversible electron transfer from protein to electrode surface. The sensing performance of the Ti-NT modified electrodes were compared vis a vis commercially available titania and GCEs. The tubular morphology of the Ti-NT led to facile transfer of electrons to the electrode surface, which eventually provided a linear current response (obtained from cyclic voltammetry) over a wide range of Mb concentration. The sensitivity of the Ti-NT based sensor was remarkable and was equal to 18 mu A mg(-1) ml (detection limit = 50 nM). This coupled with the rapid analysis time of a few tens of minutes (compared to a few days for ELISA) demonstrates its potential usefulness for the early detection of acute myocardial infarction (AMI).