Maya blue: a computational and spectroscopic study

Maya Blue pigment, used in pre-Colombian America by the ancient Mayas, is a complex between the clay palygorskite and the indigo dye. The pigment can be manufactured by mixing palygorskite and indigo and heating to T > 120 degrees C. The most quoted hypothesis states that the dye molecules enter the microchannels which permeate the clay structure, thus creating a stable complex. Maya Blue shows a remarkable chemical stability, presumably caused by interactions formed between indigo and clay surfaces. This work aims at studying the nature of these interactions by means of computational and spectroscopic techniques. The encapsulation of indigo inside the clay framework was tested by means of molecular modeling techniques. The calculation of the reaction energies confirmed that the formation of the clay-organic complex can occur only if palygorskite is heated at temperatures well above the water desorption step, when the release of water is entropically favored. H-bonds between the clay framework and the indigo were detected by means of spectroscopic methods. FTIR spectroscopy on outgassed palygorskite and freshly synthesized Maya Blue samples showed that the presence of indigo modifies the spectroscopic features of both structural and zeolitic water, although no clear bands of the dye groups could be observed, presumably due to its very low concentration. The positions and intensities of delta(H2O) and nu(H2O) modes showed that part of the structural water molecules interact via a hydrogen bond with the C=O or N-H groups of indigo. Micro-Raman spectra clearly evidenced the presence of indigo both in original and in freshly synthesized Maya Blue. The nu(C=O) symmetric mode of Maya Blue red-shifts with respect to pure indigo, as the result of the formation of H-bonds with the nearest clay structural water. Ab initio quantum methods were applied on the indigo molecule, both isolated and linked through H-bonds with water, to calculate the magnitude of the expected vibrational shifts. Calculated and experimental vibrational shifts appeared to be in good agreement. The presence of a peak at 17.8 ppm and the shift of the N-H signal in the 1H MAS NMR spectrum of Maya Blue provide evidence of hydrogen bond interactions between indigo and palygorskite in agreement with IR and ab initio methods.     

Electrochemical determination of heparin using methylene blue probe and study on competition of Ba with methylene blue for binding heparin

Cyclic voltammetric investigation of the interaction of methylene blue (MB) with heparin (hep) at a gold electrode is presented. The combination of MB with heparin formed a nonelectroactive complex MB-hep, which resulted in the peak current decrease of MB. The anodic peak current difference of MB was found to be proportional to the concentration of heparin in the range of 0.666-64.5 μg mL⁻¹ with a detection limit of 270 ng mL⁻¹ and a satisfactory result was obtained for the determination of heparin in injection samples. The equilibrium constant for MB-hep complex was calculated to be 7.32 × 10⁵. The dynamic process of competition of Ba²⁺ with methylene blue for binding heparin was monitored using quartz crystal microbalance (QCM) technique. The reaction rate constant between Ba²⁺ and MB-hep was estimated to be 0.0022 s⁻¹.     

Self-assembled film based on carboxymethyl-beta-cyclodextrin and diazoresin and its binding properties for methylene blue

Polyelectrolyte-layered films containing beta-cyclodextrin (beta-CD) were fabricated by a layer-by-layer deposition of carboxymethyl-beta-cyclodextrin (CM-beta-CD) as a polyanion and cationic photosensitive diazoresin (DR) on a solid surface. Under UV irradiation, following the decomposition of diazonium group between the adjacent interfaces of the multilayers, the ionic bonds of the self-assembly film convert to covalent bonds and the film become stable toward many common organic solvent. When a high-ionic-strength buffer is employed as a bathing solution, the film is thicker than that deposited from water solution. And the deposition increases with the increase of the carboxymethylated degree of CM-beta-CD. The CM-beta-CD/DR film can bind methylene blue (MB), and the durability of MB-adsorbing films to reductive glucose indicates that MB molecules not only diffuse into the film, but also load to the cavity of beta-CD through a host-guest complexation assisted by electrostatic interactions. The binding quantity of MB increases linearly with increasing the number of bilayers, and is influenced obviously by the pH value of MB aqueous solution. MB molecules can desorb from the 12-bilayer MB-absorbing CM-beta-CD/DR films when being immersed in water/ethanol mixture, and the released quantity of MB increases a little with increasing the concentration of water when it is below 30%, while decreases evidently over 30%.     

trans-Parinaric acid as a versatile spectroscopic label to study ligand binding properties of bovine beta-lactoglobulin

Advantageous spectroscopic properties of the plant derived polyunsaturated trans-parinaric acid (tPnA) was demonstrated in obtaining valuable data on the ligand binding characteristics of the lipocalin member bovine beta-lactoglobulin A (BLG-A). Titration of the protein with tPnA resulted in the appearance of an intense negative induced circular dichroism (CD) band and bathochromic shift of the ultraviolet (UV) peak of the ligand. The extrinsic optical activity was interpreted by the chiral contribution of the allylic axial CH bonds of tPnA to the pi-pi(*) transition of the planar tetraene chromophore. Analysis of the series of induced CD curves obtained by CD titration experiment indicated the complexation of a single ligand molecule to a uniform protein binding site. Additionally, the dramatic increase of fluorescence intensity of the lactoglobulin bound ligand suggested the hydrophobic nature of the binding site. CD and fluorescence titration data were utilized to calculate the binding constant (K(a)) of which high value ( approximately 10(6)M(-1)) refers to strong protein association of tPnA. pH dependent reversible dis- and reappearance of the induced CD signal unambigously proved the inclusion of tPnA into the central hydrophobic cavity of the lactoglobulin governed by the protonation induced conformational movement of the EF loop at the opening of the calyx. This conclusion was supported and complemented by molecular docking calculations.     

Photoacoustic spectroscopic studies of methylene blue and malachite green adsorbed on silica

Spectra and calibration curves of methylene blue and malachite green adsorbed on silica show that photoacoustic spectroscopy can be used for the determination of these compounds. The problem of the existence of an equilibrium between monomer and dimer for methylene blue is considered.     

The crystalline state of methylene blue: a zoo of hydrates

A re-investigation of the crystalline state of methylene blue has led to the identification of five different hydrates with clearly distinct structures. These include the already known pentahydrate, a hydrate with 2.2-2.3 equivalents of water, two dihydrates, and a monohydrate. Contrary to older reports, no trihydrate was found. The preparation and characterization of the hydrates as well as the transformations between them are reported. The applied analytical methods include X-ray powder diffraction (XRPD), infrared spectroscopy (ATR-IR), thermogravimetry (TGA), differential scanning calorimetry (DSC), dynamic water vapor sorption (DVS) and solution calorimetry (SolCal). A phase diagram of temperature vs. composition has been established, and the stability domains of the different hydrates as a function of water activity and temperature have been determined based on data from DSC, SolCal and suspension equilibration experiments. Four out of the five hydrates are thermodynamically stable within a certain range of temperature and humidity.     

Multiplex binding modes of toluidine blue with calf thymus DNA and conformational transition of DNA revealed by spectroscopic studies

It is noteworthy to understand the details of interactions between antitumor drugs and DNA because the binding modes and affinities affect their antitumor activities. Here, The interaction of toluidine blue (TB), a potential antitumor drug for photodynamic therapy of tumor, with calf thymus DNA (ctDNA) was explored by UV–vis, fluorescence, circular dichroism (CD) spectroscopy, UV-melting method and surface-enhance Raman spectroscopy (SERS). The experimental results suggest that TB could bind to ctDNA via both electrostatic interaction and partial intercalation. The fluorescence quenching of TB by ctDNA was static and due to electron transfer from bases to the excited singlet state of TB. At low [TB]/[DNA] ratio, TB mainly partially intercalated into ctDNA resulting in the slight increase of base stacking degree; at high [TB]/[DNA] ratio, excessive TB externally stacked along the helix surface via coupling with partially intercalated ones, thereby inducing B-A transition of ctDNA. The conformational transition of DNA was confirmed by the obvious improvement of the thermal stability of ctDNA. The SERS spectra suggest that TB could partially intercalate into DNA basepairs with its ring C₁NC_1′ side buried.     

Mapping the formation areas of giant molybdenum blue clusters: a spectroscopic study

The self-assembly of soluble molybdenum blue species from simple molybdate solutions has primarily been associated with giant mixed-valent wheel-shaped cluster anions, derived from the {Mo(V/VI)(154/176)} archetypes, and a {Mo(V/VI)(368)} lemon-shaped cluster. The combined use of Raman spectroscopy and kinetic precipitation as self-assembly monitoring techniques and single-crystal X-ray diffraction is key to mapping the realm of molybdenum blue species by establishing spherical {Mo(V/VI)(102)}-type Keplerates as an important giant molybdenum blue-type species. We additionally rationalize the empirical effect of reducing agent concentration on the formation of all three relevant skeletal types: wheel, lemon and spheres. Whereas both wheels and the lemon-shaped {Mo(V/VI)(368)} cluster are obtained from weakly reduced molybdenum blue solutions, considerably higher reduced solutions lead to {Mo(V/VI)(102)}-type Keplerates.     

Determination of adsorptive properties of clay/water system: methylene blue sorption

In this study, adsorption of methylene blue onto clay was investigated. The effect of adsorption time and temperature on the adsorption process was studied. To reveal the adsorptive characteristics of the clay studied, porosity and BET surface area measurements were made. It was observed that the adsorption capacity decreases with increasing temperature, and adsorption equilibrium was attained within 1 h. It was found that the data fit well to Langmuir, Halsey, Henderson, and Harkins-Jura models but experimental data deviate significantly from BET and Freundlich models at especially high concentrations. Furthermore, isosteric adsorption enthalpy and entropy are calculated as -7.99 kJ mol(-1) and 25.41 JK(-1)mol(-1), respectively.     

Scanning electrochemical microscopy imaging of DNA microarrays using methylene blue as a redox-active intercalator

Scanning electrochemical microscopy (SECM) has been employed in the imaging of DNA microarrays fabricated on gold substrates using methylene blue (MB) as a redox-active intercalator and ferrocyanide as the SECM mediator in solution. MB intercalated between base pairs of immobilized ds-DNA is electrochemically reduced via electron transfer from the underlying gold substrate, and the product is reoxidized in solution by SECM tip-generated ferricyanide. The resulting feedback current allows a heterogeneous electron-transfer rate constant for the MB-intercalated DNA to be deduced. Moreover, DNA microarray spots can be imaged at a detection level of 14 fmol/spot for ds-DNA consisting of 15 base pairs. Microarrays prepared using 20 microM DNA solutions are easily visualized, and the feasibility of detecting base pair mismatches is also demonstrated.     

Synchronous fluorescence determination of DNA based on the interaction between methylene blue and DNA

The fluorescence intensity of methylene blue (MB) quenched by DNA in the pH range of 6.5-8.0 was studied with synchronous fluorescence technology. A novel method for detecting single-stranded and double-stranded DNA was developed. The decreased fluorescence intensity at 664 nm is in proportion to the concentration of DNA in the range of 0.28-11.0 μmol L⁻¹ for ctDNA, 0.14-8.25 μmol L⁻¹ for thermally denatured ctDNA and 0.28-8.25 μmol L⁻¹ for hsDNA. The detection limits (S/N = 3) are 0.11, 0.04 and 0.04 μmol L⁻¹, respectively. The method is rapid, selective, and the reagents are lower toxic. It has been used for the determination of DNA in synthetic samples with good satisfaction. In addition, the interaction modes between MB and ctDNA and the mechanism of the fluorescence quenching were also discussed in detail. The experimental results from absorption spectra and fluorescence polarization indicate that the possible interaction modes between MB and DNA are the electrostatic binding and the intercalation binding.     

Protein-DNA interaction: impedance study of MutS binding to a DNA mismatch

MutS binding to a double-stranded DNA containing a single nucleotide mismatch can be conveniently monitored by impedance spectroscopy and represents the first step in developing an electrochemical binding essay for single nucleotide mismatch detection.     

Microcalorimetry and spectroscopic studies on the binding of dye janus green blue to deoxyribonucleic acid

The interaction of the phenazinium dye janus green blue (JGB) with deoxyribonucleic acid was investigated using isothermal titration calorimetry and thermal melting experiments. The calorimetric data were supplemented by spectroscopic studies. Calorimetry results suggested the binding affinity of the dye to DNA to be of the order of 10⁵ M^?1. The binding was predominantly entropy driven with a small negative favorable enthalpy contribution to the standard molar Gibbs energy change. The binding became weaker as the temperature and salt concentration was raised. The temperature dependence of the standard molar enthalpy changes yielded negative values of standard molar heat capacity change for the complexation revealing substantial hydrophobic contribution in the DNA binding. An enthalpy–entropy compensation behavior was also observed in the system. The salt dependence of the binding yielded the release of 0.69 number of cations on binding of each dye molecule. The non-polyelectrolytic contribution was found to be the predominant force in the binding interaction. Thermal melting studies revealed that the DNA helix was stabilized against denaturation by the dye. The binding was also characterized by absorbance, resonance light scattering and circular dichroism spectral measurements. The binding constants from the spectral results were close to those obtained from the calorimetric data. The energetic aspects of the interaction of the dye JGB to double-stranded DNA are supported by strong binding revealed from the spectral data.     

Electrochemical genosensor for the detection of interaction between methylene blue and DNA

Described here are the chronocoulometric and voltammetric parameters for methylene blue [3,7-bis(dimethylamino)phenothiazin-5-ium chloride, MB] on binding to DNA at carbon paste electrode (CPE) surface. MB, which interacts with the immobilized calf thymus DNA was detected by using single stranded DNA modified CPE (ssDNA modified CPE), bare CPE and double stranded DNA modified CPE (dsDNA modified CPE) in combination with chronocoulometry and differential pulse voltammetry (DPV) techniques. The effect of ionic strength to the behavior of MB with dsDNA and ssDNA was also studied by means of voltammetry. These results demonstrated that MB could be used as an effective electroactive hybridization indicator for DNA biosensors. Performance characteristics of the sensor are described, along with future prospects.     

Modeling of DNA hybridization detection using methylene blue as an electroactive label

Mathematical modeling of methylene blue (MB) signal in ssDNA and dsDNA on pencil graphite electrode is described. A DNA biosensor was developed based on MB signal. The probe and target DNAs were 20 mer oligonucleotides corresponding to consensus sequence of HPV major capsid protein L1 gene. Hybrids of various complementary and non-complementary oligonucleotides with the probe were considered as dsDNA with different hybridization degrees. Modeling was developed by incorporation of only the stable forms of dsDNA hybrids. Effect of hybridization degree on current signal in various forms was studied. A factor named AHP (Average Hybridization Percentage) for verifying the hybridization events was defined. Results showed that there is a significant mathematical relation between the calculated AHP and MB signals.     

Chlorobenzylidine-herring sperm DNA interaction: binding mode and thermodynamic studies

The interaction of chlorobenzylidine with herring sperm DNA has been investigated by fluorescence, absorption, DNA melting experiment and differential scanning calorimetry (DSC). When bound to DNA, chlorobenzylidine shows hypochromism and red shift in absorption spectra, fluorescence quenching and polarization increasing in fluorescence spectra and increasing in DNA melting temperature. These spectral characteristics strongly support intercalation of chlorobenzylidine into herring sperm DNA. Scatchard plots constructed from fluorescence titration data give a binding constant of 3.2 x 10(4) M(-1) and a binding site size of six base pairs per bound drug molecule. The intercalative interaction is exothermic with a van't Hoff enthalpy of -30.6 kJ mol(-1). This result is obtained from DSC experiment. In addition, DeltaG degrees =-28.5 kJ mol(-1), and DeltaS degrees =-7.1 J mol(-1) K(-1). These results show that the binding of chlorobenzylidine to herring sperm DNA is exothermic.     

The removal of methylene blue as a remedy of dye-based marine pollution: a photocatalytic perspective

Research on Chemical Intermediates - The effluents containing the discarded water from the textile industry are graded as one of the foremost pollutants in all industrial sectors. The wide...     

Side chain-dependent binding of antitumor indoloquinoxaline derivatives to DNA: comparative spectroscopic and viscometric measurements

NCA0424 (1) and its side chain positional isomer, NCA0465 (2), are indoloquinoxaline derivatives with potent antitumor activity. To investigate the effect of side chain position for binding with DNA, the interactions of 2 with various B-form DNAs were studied by spectroscopic (circular dichroism (CD), fluorescence and UV) and viscosity measurements and were compared with those of 1. The binding preference for the base sequence was different in each case. The CD spectra showed that 2 formed an asymmetric binding of indoloquinoxaline ring with adenine in DNA, whereas such a base selectivity was not found with 1. The binding features are discussed based on association constants and thermodynamic parameters, indicating the importance of the side chain position for binding specificity for DNA.