Electrochemical study of mono-6-thio-β-cyclodextrin/ferrocene capped on gold nanoparticles: Characterization and application to the design of glucose amperometric biosensor

A novel amperometric glucose sensor based on inclusion complex of mono-6-thio-β-cyclodextrin/ferrocene capped on gold nanoparticles (GNPs/CD-Fc) and glucose oxidase (GOD) was described. The inclusion complex of mono-6-thio-β-cyclodextrin/ferrocene capped on gold nanoparticles played an effective role of an electron shuttle and allowed the detection of glucose at 0.25 V (versus SCE), with dramatically reduced interference from easily oxidizable constituents. The sensor (GNPs/CD-Fc/GOD) showed a relatively fast response time (5 s), low detection limit (15 μM, S/N = 3), and high sensitivity (ca. 18.2 mA M⁻¹ cm⁻²) with a linear range of 0.08-11.5 mM of glucose. The excellent sensitivity was possibly attributed to the presence of the GNPs/CD-Fc film that can provide a convenient electron tunneling between the protein and the electrode. In addition, the biosensor demonstrated high anti-interference ability, stability and natural life. The good stability and natural life can be attributed to the following two aspects: on the one hand, the fabrication process was mild and no damage was made on the enzyme molecule, on the other hand, the GNPs possessed good biocompatibility that could retain the bioactivity of the enzyme molecules immobilized on the electrode.     

A convenient and economic method for the synthesis of mono-2-tosyl-β-cyclodextrin

A convenient and economic method for the regioselective synthesis of mono-2-tosyl-β-cyclodextrin was achieved by using the combination of N-tosylimidazole and carbonate buffer in DMF, the reaction does not require strict anhydrous or specific basic catalysts. Correspondence: Run-Hua Lu, Chinese Academy of Sciences, Chengdu Institute of Biology, Chengdu 610041, China.     

Spectroscopic investigation of interaction of 6-methoxyflavanone and its β-cyclodextrin inclusion complex with calf thymus DNA

The interaction of 6-methoxyflavanone (6MF, 6-methoxy-2-phenyl-4H-1-benzopyran-4-one) with calf thymus DNA (ctDNA) was investigated by absorption spectroscopy, fluorescence spectroscopy, and cyclic voltammetry in the presence and absence of ??-cyclodextrin (??-CD) acting as capping agent. Molecular modelling was used to optimise the study of 6MF-??-CD and 6MF-DNA interactions. Enhancement in the fluorescence intensity of 6MF was observed due to the formation of 1 : 1 complex with ??-CD. In the presence and absence of DNA, 6MF showed different characteristics such as hyperchromic effect, red shift of absorption spectra and fluorescence quenching of 6MF due to binding between 6MF and ctDNA. The nature of the binding group was found to be different for the 6MF-ctDNA and 6MF-ctDNA-??-CD systems. An increase in fluorescence intensity was observed for the 6MF-ctDNA system while varying the concentration of ??-CD due to encapsulation of a part of 6MF in cyclodextrin. The results are compatible with the possibility of the interaction of dihydrobenzopyran-4-one moiety of 6MF with ctDNA as well as with ??-CD. Cyclic voltammetric studies confirmed the binding interaction between 6MF and ctDNA in the absence and presence of ??-CD and molecular modelling explains the site of the interaction of 6MF with cyclodextrin and ctDNA.     

Inclusion of (aminostyryl)-1-methylpyridinium dyes byβ-cyclodextrin and its use for fluorescent-probe studies on association of cationic and neutral molecules withβ-cyclodextrin

An inclusion complex between TRIMEB and (S)-naproxen has been crystallised and characterised by physicochemical methods including X-ray analysis. The complex crystallises in the orthorhombic crystal system, space groupP2₁2₁2₁, witha=15.179(4),b=21.407(5),c=27.67(1) Å andZ=4. The structure was solved using published coordinates for the skeleton atoms of TRIMEB in an isomorphous complex. Refinement by full-matrix least-squares analysis yieldedR=0.0571 for 6573 unique observed reflections. Hydrophobic forces are responsible for the inclusion of the drug, which has its methoxy group buried in the cavity of the host and its propionic acid moiety protruding from the O(2), O(3) side of the TRIMEB molecule. Both host and guest undergo conformational changes on complexation relative to their conformations observed in the TRIMEB monohydrate and naproxen crystal structures respectively. Complex units pack in a screw-channel mode in a head-to-tail fashion with their axes almost parallel to theb-axis.     

Investigation of the interaction of DNA and neutral red by fluorescence spectroscopic analysis

The binding characteristics of neutral red (NR) with DNA were investigated by fluorescence spectrometry. Chemometrics approach as singular value decomposition (SVD) was used to evaluate the number of spectral species in the drug-DNA binding process, and then the intrinsic binding constant of 1.6 × 104 in base pairs and the binding site number of 0.97 were obtained from the Scatchard plot.     

The interaction of biliar acids with 2-hydroxypropyl-β-cyclodextrin in solution and in the solid state

The interaction of two biliar acids (chenodeoxycholic acid and cholic acid) with 2-hydroxypropyl--cyclodextrin (HPCD) in solution and in the solid state was studied using different techniques. The formation of an inclusion complex with a 1:1 stoichiometry was suggested by the phase solubility studies. Both differential scanning calorimetry and X-ray diffractometry exhibited the amorphous state of the complex. The inclusion of both biliar acids into the HPCD cavity was confirmed by the¹³C-NMR studies. Cholic acid showed a weaker affinity with respect to chenodeoxycholic acid probably owing to the presence of a hydroxyl group onC(12) (12) close to the complexation site.     

Investigation of the interaction of DNA and neutral red by?uorescence spectroscopic analysis

The binding characteristics of neutral red (NR) with DNA were investigated by fluorescence spectrometry. Chemometrics approach as singular value decomposition (SVD) was used to evaluate the number of spectral species in the drug-DNA binding process, and then the intrinsic binding constant of 1.6 104 in base pairs and the binding site number of 0.97 were obtained from the Scatchard plot.     

The effect of phosphate buffer solutions on uniconazole complexation with hydroxypropyl-β-cyclodextrin and methyl-β-cyclodextrin

The inclusion complexes of uniconazole [(E)-1-(4-chlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-lyl)-1-penten-3-ol, UCZ] with two cyclodextrin derivatives, hydroxypropyl-β-cyclodextrin (HP-β-CD) and methylated-β-cyclodextrin (Me-β-CD), were prepared and characterized by ¹H NMR and FT-IR. The phase solubility of UCZ and HP-β-CD, UCZ and Me-β-CD, which displays the ability of CDs complexation and solubilization, was studied in aqueous solutions and phosphate buffer solutions (PBS) with different property pH values (6.2, 7.2, 8.0). The solubility results indicated that the pH of PBS showed more enhancement on the interaction of HP-β-CD and UCZ than Me-β-CD with the increasing pH value, and the optimal pH value for complexation of UCZ and HP-β-CD, UCZ and Me-β-CD was at 8.0 and at 7.2, respectively. These were also determined by UCZ release behavior and dissolution studies of the complexes in solid state.     

Electrochemical study of indapamide and its complexation with ��-cyclodextrin

Electrochemical oxidation of indapamide has been investigated at glassy carbon electrode using cyclic and differential pulse voltammetry (DPV). Indapamide exhibited two well resolved signals which attributed to the oxidation of indoline ring and benzamide moiety in phosphate buffers in the pH range of 2.7?C10.1. The oxidation processes have been shown to be irreversible and diffusion controlled. The formation of an inclusion complex of indapamide with ??-cyclodextrin (??-CD) has been investigated by cyclic, differential pulse voltammetry as well as UV?CVis spectrophotometry. The stability constant of the complex was determined to be 6199 and 2717 M^?1 using differential pulse voltammetry and UV?CVis spectrophotometry, respectively.     

Theoretical Studies on the Conformation of mono-6-O-p-nitrobenzoyl-β-cyclodextrin in Aqueous Solution

It is well known that a substituted cyclodextrin (CD) can often form a self-included complex, in which the substituent group is incarcerated into the CD cavity1. The phenomenon is interesting, as the self-inclusion is a nice model of protein folding2 and it has also been successfully used in the construction of various molecular devices3. Studies have showed that van der Waals force, hydrophobic effect, and electrostatic interaction are the major driving forces leading to the self-inclusion4…     

Electrochemical and associated techniques for the study of the inclusion complexes of thymol and β-cyclodextrin and its interaction with DNA

Journal of Solid State Electrochemistry - Thymol, a potent agent for microbial, fungal, and bacterial disease, has low aqueous solubility and it is genotoxic, i.e., is capable of damaging...     

Inclusion complexes of sulfanilamide with β-cyclodextrin and 2-hydroxypropyl-β-cyclodextrin

Sulfanilamide belongs to the group of drugs that have a bacteriostatic effect on different pathogenic microorganisms. This activity originates from the competitive antagonism with p-aminobenzoic acid, which is an integral part of folic acid. The safe use of sulfanilamide is limited due to poor solubility in the aqueous medium. Therefore, the aim of this paper is the synthesis of sulfanilamide, as well as preparing and structural characterization of its inclusion complexes with cyclodextrins. The crude sulfanilamide was obtained in the synthesis between acetanilide and chlorosulfonic acid according to the standard procedure. The synthesized sulfanilamide was recrystallized from water in order to obtain the satisfactory purity of the substance. Sufanilamide was complexed with β-cyclodextrin and 2-hydroxypropyl-β-cyclodextrin by the co-precipitation method. A molecular encapsulation of sulfanilamide was confirmed by using FTIR, ¹H-NMR, XRD and DSC methods. Phase-solubility techniques were used to assess the formation of the inclusion complex between sulfanilamide and cyclodextrins. The photostability of sulfanilamide and its inclusion complexes was estimated by UVB irradiation in a photochemical reactor by applying the UV–Vis method. Based on the UV–Vis analysis, sulfanilamide:2-hydroxypropyl-β-cyclodextrin complex was presented as more photostable than sulfanilamide:β-cyclodextrin complex and sulfanilamide. The obtained results enable the potential use of these inclusion complexes for the preparation of oral formulations due to the enhanced solubility of sulfanilamide.     

The effect of inclusion inβ-cyclodextrin on the chemistry of peroxides: Reactions of radicals withβ-cyclodextrin

Studies by electron paramagnetic resonance (EPR), differential scanning calorimetry, thermogravimetric analysis, HPLC and NMR showed that radicals produced by thermolysis and photolysis of benzoyl peroxide,t-butyl peroxide and cumene hydroperoxide included in-cyclodextrin (-CD), undergo significant reaction with the-CD. The formation of-CD radicals was observed by EPR. Products formed by addition of radicals to-CD were also observed. Such host:guest radical reactions explain the reported stabilization of peroxides, found with-CD inclusion, as being primarily due to the interruption of chain reactions by trapping of the chain carriers. A small increase in activation barrier for cleavage of the included peroxide in-CD was also observed.     

The structure of interlocked helical supramolecule formed by the self-assembly of mono-6-(4-cyano-phenyl)-β-cyclodextrin

The supramolecular self-assembly formed by newly synthesized mono-6-(4-cyano-phenyl)-β-cyclodextrin through the molecular interpenetration has been investigated and compared in both solution and the solid state, which was characterized by X-ray crystallography, fourier transform infrared spectroscopy, NMR spectroscopy and atomic force microscopy. The crystal structure clearly revealed that the benzonitrile group is consecutively inserted into the adjacent cyclodextrin cavity from the second side, thus giving rise to an unusual interlocked helical supramolecular self-assembly in which the benzonitrile group acts as bridge between the cyclodextrin units. As compared with crystal, the conformation in aqueous solution indicates that the benzonitrile group prefer to be self-assembled included into another cavity from the second side of cyclodextrin to form the self-assembly.     

The synthesis of pillared nickel-substituted saponite and its hydroisomerization activity

Nickel-substituted saponite clays (NiS) were synthesized. The pillared clays notedPNiS were prepared from the NiS intercalated with large inorganic cations such as [Al_(13)O_4(OH)_(24).(H_2O)_(12)]~(7+). It is found that the pillar density is correlative with aluminium content in the tetra-hedral sheet of NiS. The results from TPR indicate that the palladium loaded on samples promotesthe reduction of the nickel ion in the octahedral sheet. The pillared clays impregnated with Pd~(2+)noted PdPNiS show excellent hydroisomerization property which is much better than that of nickelsubstituted mica-montmorillonite pillared with silicon oxide oligomer noted PdPSMM. The hexaneconversion increases with the content of aluminium ion in the tetrahedral sheet, whereas the changeof the selectivity of isomerization is not obvious.     

Study on inclusion interaction of hydrophilic 2-chloromandelic acid with hydroxypropyl-β-cyclodextrin

The inclusion interaction between hydroxypropyl-β-cyclodextrin (HP-β-CD) and hydrophilic 2-chloromandelic acid (CMA) was studied by ultraviolet (UV) absorption spectrophotometer. A reliable determination of the complex stoichiometry was provided by the continuous variation technique. ¹H NMR spectrum and Thermo-gravimetric/differential thermal analyzer (TG/DTA) techniques were explored to further characterize the inclusion complex, and molecular modeling was used to investigate the mechanism of inclusion interaction. The results showed that HP-β-CD reacted with R,S-CMA to form inclusion complexes, with 1:1 stoichiometry and inclusion stability constants K_R and K_S were 24 and 39 L/mol determined from UV data by the method of Benesi-Hildebrand’s. Molecular modeling confirmed experimental observation and indicated that the hydrogen bonding interaction plays an important role in the interactive inclusion between HP-β-CD and CMA. Besides, compared with the HP-β-CD, molecular modeling showed R, S-CMA interact with β-CD through different binding modes, in which Vander Waals is the main intermolecular force between β-CD and R-CMA (or S-CMA) while without obvious hydrogen bonding interaction.     

Syntheses and characterization of η-hexamethylbenzeneruthenium(II)-β-diketone complexes: their reactions with mono- and bidentate neutral ligands

The complex [(η⁶-C₆Me₆)Ru(μ-Cl)Cl]₂1 react with sodium salts of β-diketonato ligands in methanol to afford the oxygen bonded neutral complexes of the type [(η⁶-C₆Me₆)Ru(κ²-O,O′-R¹COCHCOR²)Cl] {R¹, R² = CH₃ (2), CH₃, C₆H₅ (3), C₆H₅ (4), OCH₃ (5), OC₂H₅ (6)}. Complex 4 with AgBF₄ yields the γ-carbon bonded ruthenium dimeric complex 7. Complex 4 also reacts with tertiary phosphines and bridging ligands to yield complexes of the type [(η⁶-C₆Me₆)Ru(κ²-O,O′-C₆H₅COCHCOC₆H₅)(L)]⁺ (L = PPh₃ (8), PMe₂Ph (9)) and [{η⁶-C₆Me₆)Ru(κ²-O,O′-C₆H₅COCHCOC₆H₅)}₂(μ-L)] L = 4,4′-bipyridine (4,4′-bipy) (11), 1,4-dicyanobenzene (DCB) (12) and pyrazine (Pz) (13). Complexes 2-4 react with sodium azide to yield neutral complexes [(η⁶-C₆Me₆)Ru(κ²-O,O′-R¹COCHCOR²)N₃] {R¹, R² = CH₃ (10a), CH₃, C₆H₅ (10b), C₆H₅ (10c). All these complexes were characterized by FT-IR and FT-NMR spectroscopy as well as analytical data. The molecular structures of complexes [(η⁶-C₆Me₆)Ru(κ²-O,O′CH₃COCH-COC₆H₅)Cl] (3) and [(η⁶-C₆Me₆)Ru(κ²-O,O′-C₆H₅COCHCOC₆H₅] (4) were established by single crystal X-ray diffraction studies. The complex 3 crystallizes in the triclinic space group, [a = 7.9517(4), b = 9.0582(4) and c = 14.2373(8) Å, α = 88.442(3)°, β = 76.6.8(3)° and γ = 81.715(3)°. V = 987.17(9) ų, Z = 2]. Complex 4 crystallizes in the monoclinic space group, P2₁/c [a = 7.5894(8), b = 20.708(2) and c = 29.208(3) Å,β = 92.059(3)° V = 4587.5(9) ų, Z = 8].     

UV absorption of n-alkyl 1-thio-β-d-glucopyranosides and its utilization in chromatographic separation

The UV absorption of n-alkyl β-d-glucopyranosides has not been utilized so far for their detection which is usually performed by means of the refractive index detector. In this paper, we demonstrate the HPLC separation of several n-alkyl β-d-glucopyranosides with linear gradient by using UV detector and support our findings with time-dependent density functional theory calculations.