Macrocyclic Dioxopolyamine Research Articles

Rational design of an “on-off-on” fluorescent switch for Cu2+ and histidine based on chiral macrocyclic dioxopolyamine

A novel chemosensor 1 having a chiral macrocyclic dioxopolyamine of C2 symmetry as a receptor and anthracene as a signal unit has been designed and synthesized for cations and α-amino acids recognition in DMSO-HEPES buffer (1:9, v/v, pH 7.2). The ligand exhibited selective response to Cu2+ even in the presence of other metal ions with a fluorescence “switch-off” behavior. Additionally, the in situ generated 1-Cu2+ ensemble displayed specific recognition to histidine by a “switch-on” fluorescence response. For this dual functional switch, its sensing behavior via a displacement mode was confirmed by 1H NMR titration and ESI mass spectroscopy. Sequential “on-off-on” fluorescence responses of 1 to Cu2+ and histidine are successfully applied in HeLa cells.

Harmonic and anharmonic analysis of the IR and Raman spectrum of macrocyclic dioxopolyamine

A detailed analysis of the vibrational spectra of 8,8a,9,10,11,12,12a,13-octahydrodibenzo[b,h][1,4,7,10] dioxadiazacyclododecine-7,14 (6H,15H)-dione has been conducted in harmonic and anharmonic approximation. B3LYP and B3LYP-D3 functionals and 6-31G(d), 6-31+G(d,p) and TZVP basis set were employed. The calculated frequencies were compared with experimental fundamentals and the error distribution was analysis by Root Mean Square Deviation (RMSD). When a relatively large basis set (6-31+G(d,p)) is adopted, anharmonic approximation presents a overall advantage than empirical scaling factor method, when a medium basis set (6-31G(d)) is adopted, empirical scaling factor method provides a better accuracy than anharmonic approximation, except for ν(CH2) and ν(CH) mode. Anharmonic approximation cannot reduce the large errors of ν(NH), δ(NH) and ν(CO) modes. The bimolecular model reveals that these errors mainly arise from intermolecular hydrogen bonds. Van der Waals correction on DFT makes a significant improvement on prediction of ν(CH2) and ν(CH) modes but a negligible change on the other modes.

Synthesis of Novel L‐Proline Derived Macrocyclic Dioxopolyamines of C2 Symmetry.

Abstract A short and convenient synthesis for four novel chiral L‐proline derived macrocyclic dioxopolyamines of C2 symmetry, by condensation of appropriate diester intermediates and polyamines, is reported. These macrocyclic dioxopolyamines may be applied as chiral solvating agents for enantiomeric recognition, and the work also provided a simple and convenient way for the synthesis of the diester intermediates.

Synthesis of Spirobenzopyrans Bearing Macrocyclic Dioxopolyamine

ABSTRACT Six novel spirobenzopyrans bearing macrocyclic dioxopolyamine were synthesized. Their photochromic, transition metal cations–induced photochromic properties were investigated.

Synthesis of Novel L‐Proline Derived Macrocyclic Dioxopolyamines of C2 Symmetry

A short and convenient synthesis for four novel chiral L‐proline derived macrocyclic dioxopolyamines of C2 symmetry, by condensation of appropriate diester intermediates and polyamines, is reported. These macrocyclic dioxopolyamines may be applied as chiral solvating agents for enantiomeric recognition, and the work also provided a simple and convenient way for the synthesis of the diester intermediates.

Novel rigid chiral macrocyclic dioxopolyamines derived from l-proline as chiral solvating agents for carboxylic acids

1H NMR was employed to investigate the chiral recognition ability of two novel l-proline derived rigid chiral macrocyclic dioxopolyamines, (12 S)-1,4,7,10-tetraazadicyclo[10.3.0]pentadecane-3,11-dione 1 and (8 S,18 S)-1,4,10,13,16-pentaazatricyclo[16.3.0.0 4,8]heneicosane-9,17-dione 2, the latter of which is newly synthesized. The crystal structures of the two macrocyclic compounds were determined by X-ray single crystal structure analysis. The Job plots indicate that compound 1 forms a 1:1 instantaneous complex with ( R)- or ( S)-mandelic acid while compound 2 forms a 1:2 instantaneous complex with each of the two guests above. Association constants of compound 1 with ( R)- and ( S)-mandelic acids were determined by a nonlinear least-squares fitting method. Both of the macrocycles exhibited good chiral recognition toward the enantiomers of the racemic carboxylic acids we chose. It was shown that the macrocyclic dioxopolyamine of C 2 symmetry had a better enantiomeric discriminating ability than that of C 1 symmetry.

Synthesis of New Spirobenzopyrans Bearing Macrocyclic Dioxopolyamine and Their Selective Coloration for Transition Metal Cations

Three new spirobenzopyrans bearing macrocyclic dioxopolyamine were synthesized. Sensitive and selective coloration of the spirobenzopyrans for transition metal cations were observed.

Synthesis of New Spirobenzopyrans Bearing a Macrocyclic Dioxopolyamine and Their Selective Coloration for Transition Metal Cations

Three new spirobenzopyrans bearing a macrocyclic dioxipolyamine were synthesized. Sensitive and selective coloration of the spirobenzopyrans for transition metal cations were observed.

A Short Synthesis of Chiral Macrocyclic Dioxopolyamines Derived from L‐Proline.

AbstractFor Abstract see ChemInform Abstract in Full Text.

A SHORT SYNTHESIS OF CHIRAL MACROCYCLIC DIOXOPOLYAMINES DERIVED FROM l-PROLINE

ABSTRACT A convenient and effective synthesis of enantiomerically pure macrocyclic dioxopolyamine 3 and its derivatives 4–9 is presented. Macrocyle 3, derived from l-proline, was prepared in high overall yield and easily modified. 8 and 9 were prepared by modified Mannich reaction in good yields.

Use of the sol-gel technique to prepare capillary columns coated with a macrocyclic dioxopolyamine for open-tubular capillary electrochromatography

Columns for open-tubular (OT) capillary electrochromatography (CEC), coated with 1,4,7,10-tetraazacyclotridecane-11,13-dione (dioxo[13]aneN4) by use of the sol-gel technique, have been investigated for the first time. Dioxol[13]aneN4 was reacted with 3-(2-cyclooxypropoxy)propyltrimethoxysilane and the product was then mixed with tetraethoxysilane (TEOS) and water to form a glass matrix as a network in which the stationary phase (dioxo[13]aneN4) was incorporated. In comparison with OTCEC columns prepared by the sol-gel process with TEOS only, the sol-gel-derived macrocyclic dioxopolyamine columns enabled better separations of a mixture of isomeric nitrophenols and benzenediols, a mixture of isomeric aminophenols and diaminobenzenes, and a mixture of four biogenic monoamine neurotransmitters. High efficiencies (60 000—340 000 plates m−1) were achieved for isomeric benzenediols, aminophenols, nitrophenols, and diaminobenzenes. Migration time and theoretical plate number reproducibility was satisfactory;RSD was <2% for one column and <8.5% from column to column.

Open tubular capillary electrochromatography in fused-silica capillaries chemically bonded with macrocyclic dioxopolyamine

In this paper, the macrocyclic dioxopolyamine compound: 1,4,7,10-tetraazacyclotridecane-11,13-dione was used as stationary phases with the aid of 3-(2-cyclooxypropoxyl)propyl-trimethoxy silane as bridge in open-tubular capillary electrochromatography (OTCEC). To increase the surface area and produce radial extensions from the surface, the capillaries were etched by aqueous sodium hydroxide before being coated. A comparison was made of the properties of capillary modified with the macrocyclic dioxopolyamine with those of the bare capillary by electroosmotic flow measurements and its dependence on pH. The direction of EOF on the capillaries modified with dioxo[13]aneN4 is reversed at somewhat lower pH (pH<5.23). These modified capillaries had shown improved separations of neurotransmitters, isomeric nitrophenols, isomeric dihydroxybenzenes and isomeric aminophenols, in comparison with untreated capillaries. The plate numbers of the isomeric nitrophenols and dihydroxybenzenes were greater than 20,000/m and the reproducibility of migration time and the plate number was pretty good (R.S.D.<2.5%).

Synthesis and properties of some novel ferrocene macrocyclic dioxopolyamines

A series of novel ferrocene macrocyclic dioxopolyamines ( 1– 4) bearing an iminodiacetamide fragment in their framework were designed and synthesized, and two such new ligands ( 2 and 4) and some of their complexes are reported. The coordination behavior and electrochemical properties of these compounds were systematically examined by cyclic voltammetry (CV) and electronic absorption spectroscopy. Host–guest complexation stoichiometries (1:1) have been confirmed by fast atom bombardment mass spectroscopy (FAB MS) and UV–vis titration of cobalt ion and ligands 3 and 4. Additionally the stability constants for the equilibrium of cobalt ion and ligands 3 and 4 have been evaluated. The coordination of the ligands with transition metal ions (Cu 2+, Ni 2+ and Co 2+) causes anodic shifts of the ferrocene redox couple to various extents. The uncommon oxidation state of nickel(III) and copper(III) can be selectively stabilized by tetra-azamacrocycle 1 and penta-azamacrocycles, 3 and 4, respectively.

Capillary electrophoretic separation enhanced by a macrocyclic dioxopolyamine additive

Macrocyclic polyamines, or in particular dioxopolyamines, are strong receptors for analytes such as metal ions, catechol and catecholamine derivatives. In this paper, based on their interaction with a dioxopolyamine compound: 1,4,7,10-tetraazacyclotridecane-11,13-dione (or dioxo[13]aneN 4), we report its use as an additive in capillary electrophoresis (CE) to improve the separation resolution and selectivity of various model analytes. Using an imidazole–acetic acid electrolyte with dioxo[13]aneN 4 as the only additive, alkali metal, alkaline earth metal and NH 4 + ions can be effectively separated and detected by using CE with indirect UV detection, as opposed to the use of crown ether in which another additive, such as α-hydroxyisobutyric acid, is needed. The host–guest interaction between dioxo[13]aneN 4 and metal and NH 4 + ions can modify their electrophoretic mobilities, and therefore can be used to differentiate the various cations, especially between K + and NH 4 +, and between Sr 2+ and Ca 2+. We have also found that dioxo[13]aneN 4 is an effective additive in CE to resolve nitrophenols and, in particular, dihydroxybenzenes. Moreover, unlike previous reports, the separation of various biogenic monoamine neurotransmitters can be achieved at neutral or physiological pH. This work demonstrates that one of the macrocyclic dioxopolyamine derivatives: dioxo[13]aneN 4 is a promising additive in CE separations for any chemical species: cationic, anionic and neutral.

A Convenient Method for Synthesis of Novel Ferrocene Macrocyclic Dioxopolyamines

Two novel ferrocene macrocyclic dioxopolyamines were synthesized by condensation of dimethyl ferrocenylmethyliminodiacetate and appropriate polyamines. This method provides a simple way for synthesis of mono N—functionalized macrocyclic polyamines.

Potentiometric discrimination between planar and octahedral anionic metal cyano complexes by liquid membrane electrodes based on lipophilic macrocyclic dioxopolyamines

AbstractA novel type of poly(vinyl chloride) matrix liquid membrane electrodes that are capable of discriminating between planar and octahedral anionic metal cyano complexes has been developed by exploiting as the sensory elements lipophilic derivatives of macrocyclic dioxopolyamines (13‐hexadecyl‐1,4,8,11‐tetraaza‐12,14‐dioxocyclotetradecane, 15‐hexadecyl‐1,4,7,10,13‐pentaaza‐14,16‐dioxocyclohexadecane). Potentiometric response behaviors of these electrodes for a series of anionic metal cyano complexes were compared with those of the electrodes based on the corresponding nondioxo macrocyclic pentaamine (15‐hexadecyl‐1,4,7,10,13‐pentaazacyclohexadecane) as well as a conventional anion exchanger (Capriquat®). The electrodes based on the dioxopolyamines displayed strong potentiometric responses at pH 4.0 to the metal cyano complexes having a planar structure ([Ni(CN)4]2−, [Pt(CN)4]2−). In contrast, the responses to the metal cyano complexes having an octahedral structure ([Fe(CN)6]3−, [Fe(CN)6]4−) were only negligible. On the other hand, for all of the guests tested, the electrodes based on the nondioxo macrocyclic pentaamine or the anion exchanger showed strong linear responses to both planar and octahedral complexes. These results represent a new mode of potentiometric discrimination displayed by dioxo‐type macrocyclic polyamines having both amine and amide moieties.

Identification of macrocyclic polyamines and macrocyclic dioxopolyamines by thin-layer chromatography, gas chromatography, and electrophoresis

Identification of macrocyclic polyamines and macrocyclic dioxopolyamines by thin-layer chromatography, gas chromatography, and electrophoresis