Dynamic combinatorial libraries constructed on polymer scaffolds

Functionalized polymers were prepared by grafting acylhydrazides onto a polyvinylbenzaldehyde scaffold through reversible hydrazone linkages. The dynamic nature of these linkages allows the functionalized polymers to exchange and reshuffle their appendages, and the resultant mixture of polymers can be considered as a dynamic combinatorial library constructed upon a polymer scaffold. The dynamic nature of these functionalized polymers was demonstrated.     

Dynamic combinatorial libraries of disulfide cages in water

[structure: see text] Dynamic combinatorial libraries (DCLs) containing water-soluble disulfide-linked cages (alongside macrocyclic structures) have been generated and characterized. Unlike most other strategies for generating molecular cages, the structures are held together by covalent bonds, which are formed under thermodynamic control. The diversity of the cages generated opens new possibilities for a generalized combinatorial strategy toward molecular encapsulation.     

Dynamic combinatorial libraries based on hydrogen-bonded molecular boxes

This article describes two different types of dynamic combinatorial libraries of host and guest molecules. The first part of this article describes the encapsulation of alizarin trimer 2a3 by dynamic mixtures of up to twenty different self-assembled molecular receptors together with the amplification and selection of the best binder. Receptors (1a-d)3.(DEB)6 are formed by the self-assembly of six diethyl barbiturate (DEB) and calix[4]arene dimelamine derivatives 1a-d by using hydrogen bonds. The largest amplification factor (2.8) for a host assembly (1a3.(DEB)6) was observed after the addition of 2a to four-component library 1a(n).1b(3-n).(DEB)6 (n=0-3). Addition of 2a to twenty-component library 1a(n).1b(m).1c(o).1d(3-(n+m+o)).(DEB)6 (n, m, o=0-3; (n+m+o)相似文献   

Macrolactone-based dynamic combinatorial libraries of cholate monomers bearing recognition functionality

Dynamic combinatorial libraries were generated incorporating new pyridine and dimethylaniline containing monomers. These libraries were analyzed using ¹H NMR and HPLC–UV–MS.     

Optical sensors for determination of heavy metal ions

A review is given on optical means for single shot testing (probing) as well as continuous monitoring (sensing) of heavy metal ions (HMs). Following an introduction into indicator based approaches, we discuss the types of indicator dyes and polymeric supports used, as well as existing sensing schemes for HMs. The wealth of information is compiled in the form of tables and critically reviewed. Notwithstanding the tremendous work performed so far, it is obvious that still severe limitations do exist in terms of selectivity, limits of detection, dynamic ranges, applicability to specific problems, and reversibility. On the other hand, such sensors have found — and will find — their application whenever rapid and cost-effective testing is required, where personnel is scarce or unskilled, and in field tests. Despite their limitations, the number of such sensors (and of irreversible probes) for HMs is likely to increase in future.     

Dynamic combinatorial libraries: new opportunities in systems chemistry

Combinatorial chemistry is a tool for selecting molecules with special properties. Dynamic combinatorial chemistry started off aiming to be just that. However, unlike ordinary combinatorial chemistry, the interconnectedness of dynamic libraries gives them an extra dimension. An understanding of these molecular networks at systems level is essential for their use as a selection tool and creates exciting new opportunities in systems chemistry. In this feature article we discuss selected examples and considerations related to the advanced exploitation of dynamic combinatorial libraries for their originally conceived purpose of identifying strong binding interactions. Also reviewed are examples illustrating a trend towards increasing complexity in terms of network behaviour and reversible chemistry. Finally, new applications of dynamic combinatorial chemistry in self-assembly, transport and self-replication are discussed.     

Solid-phase extraction for combinatorial libraries

Solid-phase extraction (SPE) has during the last three years emerged as a convenient method for the purification of compound libraries prepared by solution synthesis. The widespread use of SPE in combinatorial chemistry can be explained by straightforward SPE method development facilitated by the availability of numerous commercial SPE resins. High-speed automated SPE is readily accomplished by taking advantage of commercial laboratory robot systems. The present review summarizes and discusses advancements made in the use of different SPE resins and molecule tagging techniques for optimization of ion-exchange, reversed-phase, normal-phase and fluorous-phase SPE in combinatorial chemistry.     

Two-dimensional nanomaterial based sensors for heavy metal ions

Two-dimensional (2D) nanomaterials are promising building blocks for sensors due to their unique physical, chemical, electronic, and optical properties. This review (with 253 references) first summarizes the historical developments of 2D nanomaterials and discusses the advantages of 2D nanomaterials when applied for constructing sensors. Next, their properties are discussed, with subsections on electronic, optical, mechanical and chemical properties. This is followed by an overview on methods for syntheses and the effects of positive and/or negative charges on the properties and in sensing applications. Then, recent advances in 2D nanomaterial-based electrochemical, fluorometric, colorimetric, electrochemiluminescent, photoelectrochemical, and field-effect transistor sensors are discussed. The discussion also includes the preparation of sensing elements, the roles of such nanomaterials, and assay strategies. Finally, on the basis of the current achievements in the field of 2D nanomaterials, the perspectives on the challenges and opportunities for the exploration of 2D nanomaterial-based sensors are put forward.

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Pore-functionalized polymer membranes for preconcentration of heavy metal ions

Functionalized membranes containing carboxylate, phosphate and sulfonate groups were prepared by UV-initiator induced graft polymerization of the functional monomer (acrylic acid, ethylene glycol methacrylate phosphate (EGMP) and 2-acrylamido-2-methyl-1-propane sulfonic acid) with a crosslinker (methylenebisacrylamide) in the pores of poly(propylene) host membranes. The functionalized membranes thus obtained were characterized by gravimetry, FTIR spectroscopy, radiotracers and scanning electron microscopy for the degree of grafting and water uptake, presence of functional groups, ion-exchange capacity, and physical structure of the membranes, respectively. The uptakes of Cs⁺, Ag⁺, Sr²⁺, Cd²⁺, Hg²⁺, Zn²⁺, Eu³⁺, Am³⁺, Hf⁴⁺ and Pu⁴⁺ ions in the functionalized membranes were studied as a function of acidity of the equilibrating aqueous solution. Among the functionalized membranes prepared in the present work, the EGMP-grafted membrane (with phosphate groups) showed acid concentration dependent selectivity towards multivalent metal ions like Eu³⁺, Am³⁺, Hf⁴⁺ and Pu⁴⁺. The solvent extraction studies of EGMP monomer in methyl isobutyl ketone (MIBK) solvent indicated that divalent and trivalent metal ions form complexes with EGMP in 1:2 proportion, but the distribution coefficients of trivalent metal ions were significantly higher that for the divalent ions. The uptakes of Eu³⁺ ions in monomeric EGMP (dissolved in MIBK) and polymeric EGMP (in the forms of crosslinked gel and membrane) were studied as a function of concentration of H⁺ ions in the equilibrating solution. This study indicated that polymeric EGMP has better binding ability towards Eu³⁺ as compared to monomeric EGMP. The variation of distribution coefficients of Eu³⁺/Am³⁺ in gel and membrane as a function of H⁺ ion concentration in the equilibrating aqueous solution indicated that ionic species held in the membrane and gel were not same. These results indicated that proximity of functional groups (phosphate) plays an important role in metal ion binding with polymeric EGMP.     

New synthesized ligands for detection of heavy metal ions

Some new chemo-sensors (4,4'-((1E,1′E)-(2,2′-dichloro-[1,1′-biphenyl]-4,4′-diyl)bis(diazene-2,1-diyl))bis(3,5-dihydroxybenzoic acid), 4-((E)-(4-(N-(4-((E)-(4-carboxy-2,6-dihydroxyphenyl)diazenyl)phenyl)sulfamoyl)phenyl)diazenyl)-3,5-dihydroxybenzoic acid, 4-((E)-(4-((4-((E)-(4-carboxy-2,6-dihydroxyphenyl)diazenyl)-2-sulfophenyl)amino)phenyl)diazenyl)-3,5-dihydroxybenzoic acid) were synthesized. These synthesized sensors were then characterized by FTIR, TLC, UV–Visible spectrophotometry, and NMR techniques. The sensors showed the best results for detection of all type of heavy metal ions simply by changing the colour of metal ion solution and by shifting in the λ_max values of sensors due to interactions.     

Dynamic combinatorial libraries of metalloporphyrins: templated amplification of disulfide-linked oligomers

Disulfide-linked cyclic porphyrin oligomers from dimer to tetramer can be selected and amplified virtually quantitatively from a dynamic combinatorial library using bis-thiol substituted zinc(II) porphyrin units with appropriate amine donor templates.     

Lariat-crown ether based fluorescence sensors for heavy metal ions

Exploratory investigations were conducted to probe several aspects of a new strategy for the design of metal ion fluorescence sensors. The results of the investigation show that lariat-crown ethers that contain amine and thioether side chains, and a naphthalene chromophore can be efficiently prepared by using sequences that rely on key single electron transfer promoted photocyclization reactions. Members of this novel family of lariat-crown ethers serve as selective fluorescence sensors for the divalent metal cation of Mg, Hg, and Pb. The response of the sensors to the divalent metal ion is modulated by the nature of the heteroatom(s) incorporated into the side chains. Specifically, lariat-crown ethers that contain tertiary amine groups in their side chains display an off-on type response to Mg(II), Hg(II), and Pb(II). In contrast, thioether side chain containing lariat-crown ethers behave differently in that their fluorescence intensities decrease in the presence of increasing concentrations of these divalent metal cations. These responses can be understood on the basis of selective divalent metal ion induced disruption of intramolecular single electron transfer (SET)-quenching (for side chain amine containing lariat-crown ethers) and the enhancement of intersystem crossing (for side chain thioether containing lariat-crown ethers) of the singlet excited state of the naphthalene fluorophore.     

Dye-ligand immobilized IPNs membrane for removal heavy metal ions

We have developed a novel approach to obtain high metal sorption capacity utilizing a membrane containing chitosan and an immobilized reactive dye (i.e. Reactive Yellow-2). The composite membrane was characterized by SEM, FT-IR, swelling test, and elemental analysis. The membrane has uniform small pores distribution and the pore dimensions are between 5 and 10 μm, and the HEMA:chitosan ratio was 50:1. The reactive dye immobilized composite membrane was used in the removal of heavy metal ions [i.e., Pb(II), Hg(II) and Cd(II)] from aqueous medium containing different amounts of these ions (5-600 mg l⁻¹) and at different pH values (2.0-7.0). The maximum adsorption capacities of heavy metal ions onto the composite membrane under non-competitive conditions were 64.3 mmol m⁻² for Pb(II), 52.7 mmol m⁻² for Hg(II), 39.6 mmol m⁻² for Cd(II) and the affinity order was Pb(II) > Hg(II)>Cd(II).     

Use of membrane electrolysis for recovery of heavy metal ions

Use of membrane electrolysis for recovery of heavy metal ions from cyanide electrolytes at a zinc-and cadmium-plating shop, with subsequent processing of zinc-or cadmium-plated articles in solutions containing Cr(VI) compounds, was studied.     

Dynamic combinatorial carbohydrate libraries: probing the binding site of the concanavalin A lectin

Dynamic combinatorial chemistry (DCC) has emerged as an efficient approach to receptor/ligand identification based on the generation of combinatorial libraries by reversible interconversion of the library constituents. In this study, the implementation of such libraries on carbohydrate-lectin interactions was examined with the plant lectin Concanavalin A as a target species. Dynamic carbohydrate libraries were generated from a pool of carbohydrate aldehydes and hydrazide linker/scaffold components through reversible acylhydrazone exchange, resulting in libraries containing up to 474 constituents. Dynamic deconvolution allowed the efficient identification of the structural features required for binding to Concanavalin A and the selection of a strong binder, a tritopic mannoside, showing an IC(50)-value of 22 microM.     

Silicas with thiourea grafted groups for the concentration of heavy metal ions

Two methods for the chemical bonding of thiourea and its derivatives on dispersed silica have been developed as a result of a detailed study of the process of the thiourea chemisorption on silica surface. Obtained S-containing silicas possess a high extraction efficiency for heavy metal ions.     

Dynamic adsorption and desorption of heavy metal ions on poly(acrylaminophosphonic-carboxyl-hydrazide) chelating fiber

The dynamic adsorption and desorption properties, including the effect of pH value and flow rate on the adsorption, eluent acidity and volume, eluting velocity and re-use, of Cu(II), Pb(II), Zn(II), Cd(II), Mn(II), Ni(II), Co(II) and Hg(II) ions on the column loaded with poly(acrylaminophosphonic-carboxyl-hydrazide) chelating fiber were investigated. The recovery of Mn(II), Co(II), Cd(II), Ni(II) and Zn(II) ions in the presence of Na, K, Ca and Mg ions was examined. The preconcentration of trace amounts of Mn(II), Co(II), Cd(II), Ni(II) and Zn(II) ions from model solution samples was carried out with satisfactory results. The amount of the metal ions detected after preconcentration and recovery by this technique was basically in agreement with the added amount. The method is rapid, precise and simple. Received: 15 October 1997 / Revised: 17 March 1998 / Accepted: 20 March 1998     

Dynamic adsorption and desorption of heavy metal ions on poly(acrylaminophosphonic-carboxyl-hydrazide) chelating fiber

The dynamic adsorption and desorption properties, including the effect of pH value and flow rate on the adsorption, eluent acidity and volume, eluting velocity and re-use, of Cu(II), Pb(II), Zn(II), Cd(II), Mn(II), Ni(II), Co(II) and Hg(II) ions on the column loaded with poly(acrylaminophosphonic-carboxyl-hydrazide) chelating fiber were investigated. The recovery of Mn(II), Co(II), Cd(II), Ni(II) and Zn(II) ions in the presence of Na, K, Ca and Mg ions was examined. The preconcentration of trace amounts of Mn(II), Co(II), Cd(II), Ni(II) and Zn(II) ions from model solution samples was carried out with satisfactory results. The amount of the metal ions detected after preconcentration and recovery by this technique was basically in agreement with the added amount. The method is rapid, precise and simple. Received: 15 October 1997 / Revised: 17 March 1998 / Accepted: 20 March 1998