Time-resolved keto-enol tautomerization of the medicinal pigment curcumin.

Curcumin is a medicinal agent that exhibits anti-cancer and anti-Alzheimer's disease properties. It has a keto-enol moiety that gives rise to many of its chemical properties including metal complexation and acid-base equilibria. A previous study has shown that keto-enol tautomerization at this moiety is implicated in the anti-Alzheimer's disease effect of curcumin, highlighting the importance of this process.

Preparation of a poly(acrylic acid) based hydrogel with fast adsorption rate and high adsorption capacity for the removal of cationic dyes.

A biocompatible Dex-MA/PAA hydrogel was prepared through copolymerization of glycidyl methacrylate substituted dextran (Dex-MA) with acrylic acid (AA), which was applied as the adsorbent to remove cationic dyes from aqueous solutions. Dex-MA/PAA hydrogel presented a fast adsorption rate and the removal efficiency of Methylene Blue (MB) and Crystal Violet (CV) reached 93.9% and 86.

Molecular tweezers with a rotationally restricted linker and freely rotating porphyrin moieties.

The effect of the degree of conformational rigidity and/or flexibility on preorganisation in artificial molecular receptors continues to be actively explored by supramolecular chemists. This work describes a bis-porphyrin architecture, linked via a rigid polycyclic backbone, in which a sterically bulky 2,3,5,6-tetramethylphenyl diimide core restricts rotation to afford two non-interconvertible tweezer conformations; syn- and anti-. After separation, the host-guest chemistry of each conformation was studied independently.

β-Cyclodextrin- and adamantyl-substituted poly(acrylate) self-assembling aqueous networks designed for controlled complexation and release of small molecules.

Three aqueous self-assembling poly(acrylate) networks have been designed to gain insight into the factors controlling the complexation and release of small molecules within them. These networks are formed between 8.8% 6-(2-aminoethyl)amino-6-deoxy-6-β-cyclodextrin, β-CDen, randomly substituted poly(acrylate), PAAβ-CDen, and one of the 3.

Excited-state dynamics of the medicinal pigment curcumin in a hydrogel.

Curcumin is a yellow polyphenol with multiple medicinal effects. These effects, however, are limited due to its poor aqueous stability and solubility. A hydrogel of 3% octadecyl randomly substituted polyacrylate (PAAC18) has been shown to provide high aqueous stability for curcumin under physiological conditions, offering a route for photodynamic therapy.

Supramolecular polymer assembly in aqueous solution arising from cyclodextrin host-guest complexation.

The employment of cyclodextrin host-guest complexation to construct supramolecular assemblies with an emphasis on polymer networks is reviewed. The main driving force for this supramolecular assembly is host-guest complexation between cyclodextrin hosts and guest groups either of which may be discrete molecular species or substituents on a polymer backbone. The effects of such complexation on properties at the molecular and macroscopic levels are discussed.

A Cyclodextrin-Based Photoresponsive Molecular Gate that Functions Independently of Either Solvent or Potentially Competitive Guests.

The photoinduced interconversion between cinnamido-substituted cyclodextrins constitutes a gating switch through which the substituent moves to open or block access to the cyclodextrin cavity. Most unusually for a cyclodextrin-based device, the operation of this gate is solvent-independent and unaffected by potentially competitive guests. It occurs in MeOH and DMSO, as well as in water.

Femtosecond transient absorption spectroscopy of the medicinal agent curcumin in diamide linked γ-cyclodextrin dimers.

Curcumin is a biologically active polyphenol and a yellow pigment extracted from turmeric. Our previous study has shown effective encapsulation of curcumin using diamide linked γ-cyclodextrin dimers, namely 66γCD2su and 66γCD2ur, through cooperative 1:1 host-guest complexation. In this study, the excited-state dynamics of curcumin complexed with either 66γCD2su or 66γCD2ur in water are investigated using femtosecond transient absorption spectroscopy.

The capture and stabilization of curcumin using hydrophobically modified polyacrylate aggregates and hydrogels.

Hydrophobically modified polyacrylates are shown to suppress the degradation of the medicinal pigment curcumin under physiological conditions. In aqueous solution, the 3% octadecyl randomly substituted polyacrylate, PAAC18, forms micelle-like aggregates at a concentration of <1 wt % and a hydrogel at >1 wt %. Under both conditions, PAAC18 shows a remarkable ability to suppress the degradation of curcumin at pH 7.

Diamide linked γ-cyclodextrin dimers as molecular-scale delivery systems for the medicinal pigment curcumin to prostate cancer cells.

Diamide linked γ-cyclodextrin (γ-CD) dimers are proposed as molecular-scale delivery agents for the anticancer agent curcumin. N,N'-Bis(6(A)-deoxy-γ-cyclodextrin-6(A)-yl)succinamide (66γCD2su) and N,N'-bis(6(A)-deoxy-γ-cyclodextrin-6(A)-yl)urea (66γCD2ur) markedly suppress the degradation of curcumin by forming a strong 1:1 cooperative binding complexes. The results presented in this study describe the potential efficacy of 66γCD2su and 66γCD2ur for intracellular curcumin delivery to cancer cells.

Femtosecond transient absorption spectroscopy of copper(II)-curcumin complexes.

Ligand-metal interaction between curcumin and Cu(II) in methanol and sodium dodecyl sulfate (SDS) micelles was investigated using fluorescence spectroscopy and transient absorption spectroscopy. The Cu(II) ion exhibits a high efficiency in quenching the fluorescence of curcumin. By quantifying fluorescence quenching as a function of Cu(II) concentration, the complexation constants, K(1) and K(2), for the formation of the 1 : 1 and 1 : 2 Cu(II)-curcumin complexes, [Cu(II)-Cur](+) and [Cu(II)-Cur(2)], have been determined.

Options for change in the Australian energy profile.

Climate change is occurring largely as a result of increasing CO(2) emissions whose reduction requires greater efficiency in energy production and use and diversification of energy sources away from fossil fuels. These issues were central to the United Nation climate change discussions in Durban in December 2011 where it was agreed that a legally binding agreement to decrease greenhouse gas emissions should be reached by 2015. In the interim, nations were left with the agreement reached at the analogous 2009 Copenhagen and 2010 Cancun meetings that atmospheric CO(2) levels should be constrained to limit the global temperature rise to 2 °C.

Cooperative binding and stabilization of the medicinal pigment curcumin by diamide linked γ-cyclodextrin dimers: a spectroscopic characterization.

Diamide linked γ-cyclodextrin (γ-CD) dimers are used to capture curcumin and suppress its decomposition in water. In this study, succinamide and urea linked γ-CD dimers joined through the C6(A) carbon on each γ-CD are used. The γ-CD dimers, 66γCD(2)su and 66γCD(2)ur, show a remarkable ability to suppress the decomposition of curcumin and extend its half-life from less than 30 min to greater than 16 h.

Tailoring Polymeric Hydrogels through Cyclodextrin Host-Guest Complexation.

A close correllation between molecular-level interactions and macroscopic characteristics of polymer networks exists. The characteristics of the polymeric hydrogels assembled from β-cyclodextrin (β-CD) and adamantyl (AD) substituted poly(acrylate)s can be tailored through selective host-guest complexation between β-CD and AD substituents and their tethers. Dominantly, steric effects and competitive intra- and intermolecular host-guest complexation are found to control poly(acrylate) isomeric inter-strand linkage in polymer network formation.

The foundation of a light driven molecular muscle based on stilbene and alpha-cyclodextrin.

The rotaxane 3(E,E) serves as the basis of a light driven molecular muscle, where reversible photoisomerisation of the stilbene units causes the cyclodextrins to move off and on the stilbene units, contracting and extending the distance between the blocking groups.

Complexation behavior of alpha-, beta-, and gamma-cyclodextrin in modulating and constructing polymer networks.

A systematic study of the host-guest complexation by alpha-, beta-, and gamma-cyclodextrin (CD) in either the free state or as substituents of poly(acrylic acid) (PAA) with the hydrophobic n-octadecyl groups, C18, substituted onto PAA (HMPAA) and its effect on polymer aggregation and network formation is reported. Free alpha-CD, beta-CD, and gamma-CD mask hydrophobic associations between the C18 substituent of HMPAA in aqueous solution and form host-guest complexes with a 1:1 or CD:C18 substituent stoichiometry at 0.5 wt % polymer concentration.

Synthesis of alpha-cyclodextrin [2]-rotaxanes using chlorotriazine capping reagents.

Ten alpha-cyclodextrin [2]-rotaxanes have been prepared with alkane-, stilbene- and azobenzene-based axles, capped through nucleophilic substitution of either 2-chloro-4,6-dimethoxy-1,3,5-triazine or 2,4-dichloro-6-methoxy-1,3,5-triazine in aqueous solution, followed by further substitution of the remaining triazinyl chlorine in some cases when the latter capping reagent was used. In one case the rotaxane is a [c(2)]-daisy chain obtained by double-capping the corresponding hermaphroditic cyclic dimer. One of the rotaxane azobenzene derivatives was shown to undergo photochemically-induced reversible interconversion between its trans- and cis-isomers, causing the cyclodextrin to move back and forth along the axle, and therefore behave as a molecular shuttle.

Molecular fibers and wires in solid-state and solution self-assemblies of cyclodextrin [2]rotaxanes.

Cyclodextrin [2]rotaxanes have been prepared by coupling dimethylanilines with dicarboxylic acids using DMT-MM, in aqueous solutions of alpha-cyclodextrin, and the example illustrated shows unusual fluorescence emission and other spectroscopic behavior characteristic of the formation of molecular wires in solution, similar to the fibers observed in the solid state.

Synthesis and characterization of water-operative cationic and anionic metal-ion activated molecular receptors for aromatic anions.

Two new, octadentate, water-soluble, macrocyclic ligands, 1,4,7,10-tetrakis((2S)-(-)-2-hydroxy-3-[3'-(N,N,N-trimethylammonium)-phenoxy]-propyl)-1,4,7,10-tetraazacyclododecane tetratriflate, ((S)-tmappc12 triflate, L1 triflate) and 1,4,7,10-tetrakis((2S)-(-)-2-hydroxy-3-[2'-sulfo-4'-methylphenoxy]-propyl)-1,4,7,10-tetraazacyclododecane, ((S)-sthmppc12, L2H4) have been prepared with a view to using them to study anion sequestration in aqueous solution. Their pKa and metal-ion binding constant values with a range of alkaline earth, transition, and post-transition metals are reported. The eight-coordinate, water-soluble Cd(II) complexes of (L1)4+ and (L2)4-, [CdL1](CF3SO3)6 and (NH4)2-[CdL2], the former cationic and the latter anionic, have both been shown to be capable of acting as anion receptors in aqueous solution.

Harnessing the energy of molecular recognition in a nanomachine having a photochemical on/off switch.

6A-Deoxy-6A-(N-methyl-3-phenylpropionamido)-beta-cyclodextrin operates as a molecular machine, where the amide group serves as a torsion bar to harness the work output resulting from extraction of 1-adamantanol and consequent complexation of the aryl substituent by the cyclodextrin, when the latter behave as the piston and cylinder, respectively, of a molecular pump. At 25 degrees C, the complexation changes the ratio of the amide (Z)- and (E)-isomers from 2.4:1 to 25:1, on which basis the work performed on the amide bond is calculated to be 1.

Reversal of regioselectivity and enhancement of rates of nitrile oxide cycloadditions through transient attachment of dipolarophiles to cyclodextrins.

The reactions of nitrile oxides with monosubstituted dipolarophiles, such as propiolamide, typically afford proportionally 80 % or more of the 3,5-disubstituted cycloadducts. By contrast, the reactions of 6(A)-deoxy-6(A)-propynamido-beta-cyclodextrin with 4-tert-butylbenzonitrile oxide and 4-phenylbenzonitrile oxide afford >90 % and approximately 85 % of the corresponding 3,4-disubstituted isoxazoles, respectively. As well as reversing the regioselectivity, the cyclodextrin increases the rates of these cycloadditions.

Fossil fuels in the 21st century.

An overview of the importance of fossil fuels in supplying the energy requirements of the 21st century, their future supply, and the impact of their use on global climate is presented. Current and potential alternative energy sources are considered. It is concluded that even with substantial increases in energy derived from other sources, fossil fuels will remain a major energy source for much of the 21st century and the sequestration of CO2 will be an increasingly important requirement.

Aminocyclodextrins to facilitate the deprotonation of 4-tert-butyl-alpha-nitrotoluene.

6A-Amino-6A-deoxy-beta-cyclodextrin enhances the rate of the deprotonation of 4-tert-butyl-alpha-nitrotoluene. The rate constants for reaction of the cyclodextrin-bound species, kinc = 4 x 10(-3), 9 x 10(-3) and 19 x 10(-3) s(-1), at pH 6.0, 6.

Cyclodextrin and modified cyclodextrin complexes of E-4-tert-butylphenyl-4'-oxyazobenzene: UV-visible, 1H NMR and ab initio studies.

alpha-Cyclodextrin, beta-cyclodextrin, N-(6(A)-deoxy-alpha-cyclodextrin-6(A)-yl)-N'6(A)-deoxy-beta-cyclodextrin-6(A)-yl)urea and N,N-bis(6(A)-deoxy-beta-cyclodextrin-6(A)-yl)urea (alphaCD, betaCD, 1 and 2) form inclusion complexes with E-4-tert-butylphenyl-4'-oxyazobenzene, E-3(-). In aqueous solution at pH 10.0, 298.

Aminoacid N-substituted 1,4,7-triazacyclononane and 1,4,7,10-tetraazacyclododecane Zn2+, Cd2+ and Cu2+ complexes. A preparative, potentiometric titration and NMR spectroscopic study.

The pK(a)s and Zn2+, Cd2+ and Cu2+ complexation constants (K) for 1,4,7-tris[(2''S)-acetamido-2''-(methyl-3''-phenylpropionate)]-1,4,7-triazacyclononane, 1, 1,4,7-tris[(2''S)-acetamido-2''-(1''-carboxy-3''-phenylpropane)]-1,4,7-triazacyclononane, H(3)2, 1,4,7-tris[(2''S)-acetamido-2''-(methyl-3''-(1H-3-indolyl)propionate)]-1,4,7-triazacyclononane, 3, and 1,4,7,10-tetrakis[(2''S)-acetamido-2''-(methyl-3''-phenylpropionate)]-1,4,7,10-tetraazacyclododecane, 4, 1,4,7,10-tetrakis[(2''S)-acetamido-2''-(1''-carboxy-3''-phenylpropane)]-1,4,7,10-tetraazacyclododecane, H(4)5, in 20 : 80 v/v water-methanol solution are reported. The pK(a)s within the potentiometric detection range for H(3)1(3+) = 8.69 and 3.