Highly effective electrochemical anion sensing based on oxoporphyrinogen

The effect of anion binding on the oxidation potential of an anion receptor, N₂₁,N₂₃-dibenzyl-5,10,15,20-(3,5-di-t-butyl-4-oxo-cyclohexa-2,5-dienylidene)porphyrinogen, 1 in o-dichlorobenzene is reported. The anion binding site of 1, at its inner pyrrolic amine hydrogens, is an integral part of the highly conjugated macrocycle, thus predicting larger potential shifts upon anion binding. Accordingly, cathodic shifts up to 600 mV are observed upon anion binding and such potential shifts correlate well with the anion binding constants.     

Stable pseudotetrahedral supermolecules based on an oxoporphyrinogen

Topologically asymmetric compounds, important as chiral nanoscale building blocks, were synthesized using stepwise N-alkylation on tetrakis(3,5-di-t-butyl-4-oxocyclohexadien-2,5-yl) porphyrinogen as revealed by X-ray crystallographic studies on a porphyrinogen molecule bearing four different N-substituents.     

Chromogenic anion sensors

Chromogenic sensors for anions generally consist of two parts: anion receptors and chromophores. In this review, 6 types of chromogenic anion sensors are described, namely, NH-based hydrogen bonding, Lewis acid, metal-ion template, transition metal complexes, chromogenic guest displacement and chromoreactands. The first 4 types possess anion receptors attached directly to the chromophores while the guest displacement techniques employ indicators as the ones that were replaced by specific anions. The last type has emerged recently and uses specific reactions between chromogenic hosts or indicators and particular anions to cause dramatic colour changes.     

A new fluorescent chemosensor for anion based on an artificial cyclic tetrapeptide

A cyclic tetrapeptide composed of alternating glycine and 8-amino-4-iso-butoxyquinoline-2-carboxylic acid was designed and synthesized. Its complexation properties with anions were performed by fluorescence spectroscopy and ¹H NMR method.     

Microphase separated structures based on N-substituted polydiallylamines

The ionogenic polymers namely poly(N,N-diallyl-N-cetylammonium hydronitrate) (PDACA · HNO₃) and poly(N,N-diallyl-N,N-dimethylammonium chloride)-block-poly(cetyl acrylate) (PDADMACl-block-PA-16) were synthesized via activation of the terminal double bond of the PDADMACl precursor and initiation of the polymerization of the acrylic monomer in alcohol solution. The microphase separated structure of a blend of both homopolymers and of the block copolymer was proved by differential scanning calorimetry (DSC) and X-ray diffraction measurements. Side chain crystallization in PDA-CA · HNO₃ completely restricts the crystallization of the ionogenic backbones which, however, control the layered structure and the crystallization of the aliphatic chains. In PDADMACl-block-PA-16 crystalline polyacrylate blocks coexist with crystalline ionogenic blocks. The length of the polyacrylate block influences the ability of the ionogenic block to form the crystalline structure.     

Synthesis of an anion receptor for acetate based on the frame of ferrocene

An anion receptor was synthesized with ferrocene as binding frame. Anion recognition can be monitored by anion complexation-induced changes in UV-vis absorption spectra. Interaction between the receptor and acetate was described on the basis of ¹H NMR experiments.     

An electrolytic system based on the anion exchange reaction between KCl and an anion exchange resin

We have developed a novel electrolytic system based on the anion exchange reaction between KCl and Amberlyst A26. It was demonstrated by preparative electrolysis experiments as well as cyclic voltammetry that the anion exchange reaction offers a unique electrolytic system for electroreduction of organic compounds. On the basis of the electrolytic system, electroreduction of aromatic carbonyl compounds was successfully achieved by using an undivided cell to provide the corresponding coupling products as pinacols in good to high yields with high diastereoselectivity.     

Chromogenic and fluorogenic sensing of Cu based on coumarin

A new highly selective, reversible, chromogenic, and fluorogenic chemosensor (4) based on thiazole-coumarin moieties for quantification of copper ions in aqueous-DMSO was designed and synthesized. The mechanism of fluorescence was based on ICT, which was modified by the introduction of an electron-donating diethylamino group making it chromogenic and increasing the binding affinity. The selectivity toward copper ions was not affected by the presence of representative alkali metals, alkali earth metals, or other transition metals.     

Enhancement of singlet oxygen generation based on incorporation of oxoporphyrinogen (OxP) into microporous solids

Singlet oxygen, ¹O₂, generating compounds are highly useful for photodynamic therapy or organic oxidative transformations. In this work, the synthesis and photochemical performances for singlet oxygen generation of a range of oxoporphyrinogen-containing porous coordination polymers (OxP-PCPs) are reported. Oxoporphyrinogens, a previously unreported class of singlet oxygen generators derived from the oxidation of the antioxidant-substituted porphyrin tetrakis(3,5-di-tert-butyl-4-hydroxyphenyl)porphyrin, were converted to molecular tectons by the introduction of oligophenylene-carboxylate linkers and incorporated into porous coordination polymers using well-known oxo-Zr(IV)₆ cluster chemistry. Their structures and textural properties were analyzed revealing substantial surface areas up to 650 m² g^?1 for the optimum linker length (biphenylyl). The oxoporphyrinogen precursors exhibit good quantum yields of singlet oxygen generation (up to Φ = 0.37), and a high level of activity is maintained in the resulting coordination polymers, which appear to be superior for singlet oxygen generation to the precursors and to a reported reference material. These OxP-PCP materials were applied for the selective oxidation of sulfides to sulfoxides. This work demonstrates that the excellent singlet oxygen generator oxoporphyrinogens can be successfully incorporated as porous solids and conveniently applied in heterogeneous oxidative transformations.     

A selective colorimetric anion sensor based on an amide group containing macrocycle

A new colorimetric anion sensor 4 allows for selective 'naked-eye' differentiation of F-, AcO- and H2PO4- with similar basicity.     

Chromogenic radical based optical sensor membrane for screening of antioxidant activity

Solid-state optical sensor membranes based on immobilised chromogenic radicals for the assessment of antioxidant activity have been studied. Two stable lipophilic chromogenic radicals, DPPH (2,2-diphenyl-1-picrylhydrazyl radical) and galvinoxyl radical, GV, (2,6-di-tert-butyl-α-(3,5-di-tert-butyl-oxo-2,5-cyclohexadien-1-ylidene)-p-tolyloxy radical), were immobilised in plasticised PVC films and screened for suitability as indicators of antioxidative activity. The spectrophotometric characterisation of the polymer films containing immobilised free radicals was performed, and the response of the immobilised free radicals toward standard antioxidants was studied. It has been demonstrated that the immobilised radicals retain their reactivity towards antioxidants and the results suggest that the reactivity of immobilised radicals is comparable to standard solution-based DPPH assays. Polymer films containing immobilised DPPH radical respond to standard antioxidants in aqueous solutions by changing colour irreversibly from purple (absorption maximum at 520 nm) to yellow. The initial slopes of the response curves to the phenolic antioxidant gallic acid, obtained in the 1-50 mM concentration range, gave a linear calibration plot in a 1 min exposure cuvette test. The polymer films were used to screen antioxidative activity of beverage and food samples known to contain antioxidants, such as black and green tea, coffee, red wine, fruit juice, olive oil and sunflower oil. It has been demonstrated that a rapid and simple qualitative screening test of untreated samples is possible using a test strip based on immobilised DPPH radical.     

Fluorescent sensor for fluoride anion based on a sulfonamido-chromone scaffold

New scaffolds of sulfonamido-chromone derivatives recently synthesized were found to be effective fluorescent sensors for fluoride anion. This new class of fluorophore showed a blue shift in the emission spectra upon addition of various equivalents of fluoride. These compounds also exhibit excellent selectivity for the fluoride anion via a deprotonation process. They were also shown to have a detection limit of F^? down to 0.5?ppm.     

Synthesis and physical properties of N-substituted polyimides based on imidazole

AB-type monomers based on imidazole for the preparation of polyimides were synthesized by carrying out a substitution at the 1-position of 2-amino-4,5-dicyanoimidazole, followed by hydrolysis. Thus, pendant groups such as hexyl and 2,4-dinitrophenyl as an aliphatic long chain and an electron-withdrawing group, respectively, were introduced at the 1-position of the imidazole monomer. A solid-state polymerization was employed to prepare the poly(imidazoleimide)s in the form of a film from poly(imidazoleamic acid chloride)s by heating up to 180–200°C. The carbonyl stretching peaks of the imide ring appear at 1808 (sym) cm^?1 and 1756 (antisym) cm^?1. The effects of monomer structure on reactivity and the degree of imidization were investigated by comparing the viscosity of the resultant polymers and intensity of carbonyl peak at 1808 cm^?1. The difference in the hydrolysis rate between polyimides having short or long aliphatic pendant groups at the 1-position was observed using FT-IR. The inherent viscosity of the N-hexyl polyimide was 1.26 dL/g in N-methyl pyrrolidinone (NMP) and 0.22 dL/g in the case of N-2,4-dinitrophenyl poly(amic acid) in methanesulfonic acid at 30°C. The structural, physical, and material properties of the polyimides were characterized by infrared, nuclear magnetic resonance, luminescence, viscosimetric methods, differential scanning calorimetry, thermogravimetric analysis, optical microscopy, and wide angle x-ray scattering. Solution properties were also investigated by monitoring the viscosity as a function of time at 30°C. Luminescence spectroscopy of the poly(1-methyl imidazole imide) and poly(1-methyl imidazoleamic acid) films shows an emission band centered at 535 and 505 nm, respectively. Thermal properties are described comparing the weight loss and decomposition temperature as a function of the polymer structure and the degree of imidization. © 1993 John Wiley & Sons, Inc.     

Enantioselective fluorescent sensor for dibenzoyl tartrate anion based on chiral binaphthyl derivatives bearing an amino acid unit

The fluorescent photoinduced electron transfer (PET) chemosensors 1–3 based on (S)-1,1′-bi-2-naphthol were designed for their recognition of dibenzoyl tartrate anions. The binding properties for hydroxy acid anions were examined by the fluorescence and ¹H NMR spectra. The results indicated that receptor 1 exhibit excellent enantioselectivity toward the enantiomers of dibenzoyl tartrate anion.     

Chromogenic and fluorescent ‘‘turn-on' chemodosimeter for fluoride based on F~–-sensitive self-immolative linker

A new chromogenic and fluorescent ‘‘turn-on" chemodosimeter 3 was designed and synthesized by using a fluoride-sensitive self-immolative linker, in combination with the fluorescent dyes 7-hydroxy-4-trifluoromethyl coumarin. The chemodosimeter exhibited high selectivity and sensitivity toward fluoride anions through ‘‘turn-on" chromogenic and fluorogenic dual modes.     

硫脲类阴离子受体的设计合成与阴离子识别

硫脲类化合物具有生物活性,是优良的氢键供体,与阴离子特别是含氧阴离子形成氢键配合物。本文设计合成了系列二苯基硫脲衍生物,通过取代基效应调控硫脲衍生物分子内电转移过程,阴离子与硫脲基团结合后,增强了分子内供体的给电子能力,进一步促进电荷转移过程,据此识别不同的阴离子。由于主体分子与阴离子间形成氢键的能力及阴离子碱性的差异,可达到选择性结合的目的。     

A catenated anion receptor based on indolocarbazole

A catenated anion receptor 7 comprising two indolocarbazole units was prepared by olefin ring-closing metathesis using Grubbs’ catalyst. Receptor 7 possesses a cage-like cavity where anions are encapsulated by forming four hydrogen bonds in the order of Cl⁻ > AcO⁻ >  >  > Br⁻ >  > I⁻ ≈  in 1% H₂O/acetone.     

Ammonium based anion receptors

Selective anion recognition has been a tremendous challenge to chemists over the decades. However, with the advent of the concepts inherent in ‘supramolecular chemistry,’ the field now flourishes. Of the major types of receptors, polyamines have been studied widely as anion hosts by a number of researchers. Both electrostatic interactions and hydrogen bonds between protonated amines and the anion guests govern the binding in these systems. Exceptions to this rule are found in the quaternary ammonium systems, which utilize primarily electrostatic interactions and topological complementarity for binding purposes. This review focuses only on amine-based hosts, and is divided into acyclic and macrocyclic categories, the latter of which are based on cyclic dimension. The resulting four categories are: acyclic, monocyclic, bicyclic, and polycyclic. Within the major categories, binding is discussed according to the nature of the anion target, i.e. ‘simple’ inorganic anions, organic anions, and anionic metal complexes.     

Agglomerated carbon based phases for anion exchange chromatography

Carbon-clad zirconia particles have been converted into ion exchange media through addition of charged latexes after covalent modification of the carbon surface. A variety of methodologies were investigated to introduce a negative charge to the carbon surface in the form of either sulfonate or oxygen containing functionalities (e.g. hydroxyl or carboxylate). Short analytical sized columns (35 mm × 4 mm I.D.) were packed with modified 2 μm nonporous carbon clad zirconia. Addition of the latex particles after the initial packing produced almost double the efficiency for the system compared to adding the latexes before packing. The optimized system could separate mixtures of common inorganic anions with efficiencies greater than of 41,000 plates/m and retention reproducibility of <2% RSD.