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Novel platinum(II)-based anticancer complexes and molecular hosts as their drug delivery vehicles

Platinum(ii)-based DNA intercalators where the intercalating ligand is 1,10-phenanthroline or a phenanthroline derivative and where the ancillary ligand is either achiral (e.g. ethylenediamine) or chiral (e.g. diaminocyclohexane) show a range of cytotoxicities with a defined structure-activity relationship. The most cytotoxic are those that contain methylated-phenanthroline ligands and 1S,2S-diaminocyclohexane (S,S-dach) as the ancillary ligand. We have developed a new purification method using Sep-Pak C-18 reverse phase columns, which means these metal complexes can be made faster and cheaper compared to published methods. Platinum(ii)-based complexes containing imidazole, pyrrole and beta-alanine subunits, that are capable of recognising specific DNA base-pair sequences have also been synthesised. These include linear or hairpin polyamide ligands that can recognise DNA sequences up to seven base-pairs in length and contain single platinum centres capable of forming monofunctional adducts with DNA. We have now synthesised and characterised, by 1H and 195Pt NMR, ESI-MS and elemental analysis, the first dinuclear platinum(ii) DNA sequence selective agent. Finally, using 1H NMR we have examined the encapsulation of our platinum(ii)-based DNA intercalators by cucurbit[6]uril (CB[6]). Encapsulation by CB[6] was found to not significantly change the cytotoxicity of five platinum(ii)-based DNA intercalators, indicating it may have utility as a molecular carrier for improved drug delivery. This journal is The Royal Society of Chemistry.

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A novel water-soluble highly selective ?switch-on? ionic liquid-based fluorescent chemi-sensor for Ca(II)

A novel chemi-sensor involve new bis-ionic Schiff base sensor (BISBS), N,N?-bis-[5-((2,4-lutidiniumchloride)methylene)-3-methoxysalicylidene]-R,R-1,2-cyclohexanediimine, has been synthesized and characterized. BISBS chemi-sensor was designed based on internal charge transfer (ICT) fluorescence mechanism. This new water soluble chemi-sensor provides great selectivity fluorescence detection for Ca(II) ions in an important physiological pH range. Moreover, the interaction of Ca(II) with the deprotonated BISBS to produce a metal-ligand complex with a ratio of (1: 1) accompanying with an enhancement in the intensity of emission band located at 502?nm. Fluorescence switching-on during the chemical interaction between BISBS and Ca(II) ions is very easily noticed with naked eye, but other metal cations such as alkali, alkaline earth and transition metal don’t give any fluorescence changes. The novel developed BISBS sensor successively offers low limit of detection (LOD) 1.5?nM and fast tracing of Ca(II) in the physiological pH?7.6. Thus BISBS may provide a novel auspicious methodology for detection calcium cations in the environmental and biological samples.

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Enzymatic sulfation of phenolic hydroxy groups of various plant metabolites by an arylsulfotransferase

The bacterial arylsulfate sulfotransferase (AST) from Desulfitobacterium hafniense was used as a catalytic tool to derivatize poorly soluble aromatic compounds (polyphenols). As examples, we sulfated the natural occurring compounds p-coumaric acid, 6-hydroxyflavone, resveratrol, phloretin, and quercetin, using p-nitrophenylsulfate as the sulfate donor. The water-soluble sulfate esters were purified and characterized. Depending on the nature of the compound, one or more sulfate groups could be introduced in a stepwise order. The sulfation of resveratrol resulted in two different monosulfates (4′- and 3-sulfates), the 3,4′-disulfate, and the 3,5,4′-trisulfate. Sulfation of phloretin resulted in a monosulfate (4′-sulfate) and a disulfate (4,4′-disulfate). Although quercetin has five hydroxy groups that could be sulfated, surprisingly this enzyme system primarily catalyses the sulfation only at the 4′ position. This simple enzymatic one-step sulfation method is easy to use, and it allows a convenient and simple production of sulfated compounds with improved solubility.

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Acridinium compound having a plurality of luminescent groups and binding groups, and conjugate thereof

Acridinium compounds and their conjugates exhibiting high chemiluminescence yield are provided. Such compounds may be used to enable a highly sensitive specific binding assay. The acridinium compounds are represented by formula (I): STR1 wherein A is a linker; Z is a binding group; Y is a counter ion; R1 and R2 are independently a substituent; p and m are independently an integer of from 0 to 4; n is an integer of from 2 to 5; and X is an organic intervening moiety with a functionality of at least n, having an aryloxy group or an arylsulfonamide group through which X binds to carbonyl carbon bonded to 9-position of the acridinium ring.

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Rhodium-Catalyzed, Remote Terminal Hydroarylation of Activated Olefins through a Long-Range Deconjugative Isomerization

The Rh-catalyzed, remote terminal hydroarylation of active olefins at the C7-position of indoles and the ortho-position of indolines and anilines with the appropriate choice of a N-PtBu2 directing group through long-range deconjugative isomerization has been reported. This transformation not only overcomes the conjugate rule of Michael acceptors but also controls the positional selectivity of indoles, representing a significant advancement in both alkene isomerization and the C-H alkylation of indoles.

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On the Nature of “Soluble” Hypericin in Hypericum Species

The two red and two violet “soluble” pigments of Hypericum species were isolated by means of extraction, chromatography, and counter-current droplet chromatography.In contrast to authentic hypericin, they are soluble in common organic solvents and even in water.Using NMR experiments it was deduced that hypericin, pseudohypericin, protohypericin, and protopseudohypericin are present in the plant as their rapidly interconverting 3- and 4-phenolate ions.From AAS the main counter-ion of these phenolates was derived to be potassium.The potassium and N-ethyl-N,N-diisopropylammonium salts of hypericin was synthesized for comparison.A preparative procedure to isolate hypericin and pseudohypericin from plant material was developed.Keywords. “Soluble” Hypericin; Hypericin-, Pseudohypericin-, Protohypericin-, Protospeudohypericin-, Potassium salts; 1H-NMR; 13C-NMR; Droplet counter-current chromatography; Hypericum perforatum L.

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Formation and reaction of O=MnV species in the oxidation of phenolic substrates with H2O2 catalysed by the dinuclear manganese(IV) 1,4,7-trimethyl-1,4,7-triazacyclononane complex [Mn IV2(mu-O)3(TMTACN)2](PF 6)2

The oxidation of phenolic substrates with H2O2 catalysed by [MnIV2(mu-O)3(TMTACN) 2](PF6)21, (TMTACN, 1,4,7-trimethyl-1,4,7- triazacyclononane) has been investigated by use of ESI mass spectrometry. The role of the phenols as one-electron reductants and as co-ligands in the stabilisation and reaction of an intermediate O=MnV species has been analysed and the presence of a variety of manganese species in solution has been explained. Our results lead to a proposed mechanism for the catalytic oxidation of phenols in this system.

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New Macrocyclic Polyethers with Remote Binding Sites

The synthesis and binding properties of new macrocyclic polyethers are described.These systems incorporate 2,2′-bipyridyl functions in such a fashion that binding of metal nuclei can occur at either the macrocycle or the bipyridyl function.Evidence is presented that binding of alkali metals occurs at the crown ether cavity while binding of transition metals occurs at the bipyridyl function.Simultaneous binding of two different metals is interpreted in terms of electronic and allosteric effects.

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SYNTHESIS OF MAGNOLOL AND ITS ANALOGUE COMPOUNDS

A method is described for producing magnolol, or a derivative or analogue thereof. The method includes obtaining MOM ether of 5,5′-diallylbiphenyl-2,2′-diol or a derivative or analogue thereof and subsequently converting the MOM ether of 5,5′-diallylbiphenyl-2,2′-diol into magnolol or a derivative or analogue thereof.

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Electric Literature of 1436-59-5, Catalysts are substances that increase the reaction rate of a chemical reaction without being consumed in the process. 1436-59-5, Name is cis-Cyclohexane-1,2-diamine, molecular formula is C6H14N2. In a Article£¬once mentioned of 1436-59-5

Supramolecular assemblies from ditopic ligands and transition metal salts

Tetradentate salicylaldimine ligands of the H2salen-type bearing ort/io-A’-morpholinomethyl substituents function as ditopic ligands, bonding to Ni” or Cu” with the [N2O2]2″ donor set of the salen unit and a sulfate or two nitrate anions with the protonated morpholine units. The binding of the metal salt by the zwitterionic form of the ligand provides a novel approach to the transport of metal sulfates in metal recovery processes. A comparison of the solid state structures of a “free” ligand with a series of nickel(n) complexes demonstrates that the metal ion templates the ligand system, orientating the pendant morpholinium groups to form electrostatic and bifurcated hydrogen bonds in the sulfate complex to the dianion creating a neutral 1:1:1 [LMZ+X2] complex suitable for extraction into water immiscible solvents. Other binding modes involving bridging of metal complex units by anion binding to the pendant morpholine groups suggest that these ditopic ligands could also be used to assemble unusual three-dimensional arrays of metal complexes in the solid state. The Royal Society of Chemistry 2000.

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