Interaction of bacterial acidic polysaccharide with cationic dyes

The interaction of acidic capsular polysaccharide isolated fromKlebsiella K26 with cationic dyes pinacyanol chloride, acridine orange and phenosafranin has been studied by spectral measurements. The polymer induces metachromasy in pinacyanol chloride dye, indicating a blue shift in the visibly absorption spectrum of the dye from 600 to 500 nm. The stoichiometry of polymer/dye in the metachromatic compound, thermodynamic parameters of interaction, and effects of different cosolvents on the stability of the complex have been studied. Spectrophotometric and spectrofluorometric properties of the interaction between the polymer and all three dyes are presented. The chromotropic property of the polymer has been established.     

Heteroassociates of singly- and doubly-charged anions of alizarin red S with the pinacyanol cation

The formation of heteroassociates of singly- and doubly-charged anions of alizarin red S with the cation of the cyanine dye pinacyanol in an aqueous solution was considered. The most probable structure of the heteroassociates was proposed on the basis of the data of spectrophotometry and theoretical calculations (quantum chemical methods of determination of the geometry of the structures and the enthalpy of formation). The destructive effect of the ionic surfactants on the heteroassociates was established, and the kinetics of their destruction was studied.     

Effect of surfactants on homo- and heteroassociation of pinacyanol cation in aqueous solution

The aggregative properties of pinacyanol in aqueous solution and the capability of its ionic associates to interact with surfactants were studied. The possibility of using pinacyanol associates for quantitative determination of cationic surfactants in aqueous solution and for estimation of the critical micelle concentration of anionic surfactants was examined.     

Effect of Cationic Surfactants on Association of Pinacyanol with Organic Counterions

The absorption spectra of aqueous solutions containing associates of pinacyanol and organic counterions (tetraphenylborate, sulfophthalein, and oxyxanthene) were studied as influenced by cationic surfactants. The possibility of developing sensitive procedures for quantitative evaluation (test control) of the content of cationic surfactants in aqueous solutions using pinacyanol associates was analyzed.     

Density Functional Theory Calculations on Rhodamine B and Pinacyanol Chloride. Optimized Ground State,Dipole Moment,Vertical Ionization Potential,Adiabatic Electron Affinity and Lowest Excited Triplet State

The ground state configuration of the gas phase cationic dyes pinacyanol chloride and rhodamine B are optimized with HF/6–311 + G(2d,2p) method and basis set. B3PW91/6–311 + G(2df,2p) functional and basis set is used to calculate the Mulliken atom charge distribution, total molecular energy, the dipole moment, the vertical ionization potential, the adiabatic electron affinity and the lowest excited triplet state, the last three as an energy difference between separately calculated open shell and ground states. The triplet and extra electron states are optimized to find the relaxation energy. In the ground state optimization of both dyes the chloride anion migrates to a position near the center of the chromophore. For rhodamine B the benzoidal group turns perpendicular to the chromophore plane. For both dyes, the LUMO is mostly of π character associated with the aromatic part of the molecule containing the chromophore. The highest occupied MOs consist of three almost degenerate eigenvectors involving the chloride anion coordinated with σ electrons in the molecular framework. The fourth highest MO is of π character. For both molecules in the gas phase ionization process the chloride anion loses the significant fraction of electric charge. In electron capture, the excess charge goes mainly on the dye cation.     

Calculation of the viscosity dependence of the excited-state lifetime in pinacyanol solution

The viscosity dependence of the S₁ lifetime of pinacyanol in solutions is calculated by solving the appropriate Fokker-Planck equation considering     

Association of anions of phenolsulfonephthalein and its alkyl-substituted derivatives with single-charged cations of polymethines

The interaction of single- and double-charged anions (HAn⁻, An²⁻) of sulfonephthaleins (phenolsulfonephthaleins and its alkyl-substituted derivatives, viz., o-cresolsulfonephthalein and thymolsulfonephthalein) with single-charged cations (Ct⁺) of polymethines (pinacyanol, quinaldine red) was studied. The interaction in an aqueous solution affords heteroassociates of stoichiometric composition (Ct⁺)·HAn⁻ and (Ct⁺)₂·An²⁻. The association constants were estimated from the spectrophotometric data. The enthalpies of formation of dye and heteroassociate ions were calculated and the most probable structure of the heteroassociates was deter- mined using the semiempirical methods.     

Circular dichroism and theoretical calculations of pinacyanol dimer inclusion in γ-cyclodextrin

Aggregation of pinacyanol chloride is strongly enhanced through inclusion into γ-cyclodextrin, which was studied using both UV/Visible, derivative and Circular Dichroism (CD) spectroscopy. The intensities at 546 and at 507 nm were increased with the growing ratio of γ-cyclodextrin to dye. Both aggregates were shown to be optically active. CD spectra with two and three oppositely signed excitonic bands were shown. The structures of the aggregates have been analysed and discussed in terms of qualitative H-type aggregation and quantitative based on OSCI program. Applying eight different parameter sets aggregates of pinacyanol chloride ranging in size from 2 to 20 dye molecules were considered. The calculated energy splitting was adjusted, via the transition dipole length, to the experimentally observed band shift. Rotational strengths associated with the CD absorptions were calculated and used to obtain an estimate of the inherent twist of the dimer aggregate inside the γ-cyclodextrin cavity.     

Photochemical isomerization in the absence of a potential barrier

The photoisomerization dynamics of the dyes pinacyanol, 1,1'-diethyl-4,4'-eyanine and t-stilbene in n-alcohol solutions has been studied by picosecond absorption spectroscopy. The dyes are found to isomerize without any potential barrier in the excited state. The viscosity and temperature dependence of the relaxation rates of pinacyanol and t-stilbene agree with predictions of theoretical models, whereas for 1,1'-4,4'-cyanine more complex behaviour is observed and possible reasons discussed. An excitation wavelength dependence of the isomerization rate for 1,1'-4,4'-cyanine was also observed; the isomerization lifetime varies by a factor 2–3 over the absorption band. Such a dependence is predicted from the theoretical models.     

Experimental and Computational Studies on the Formation of Three para‐Benzyne Analogues in the Gas Phase

Experimental and computational studies on the formation of three gaseous, positively‐charged para‐benzyne analogues in a Fourier transform ion cyclotron resonance (FT‐ICR) mass spectrometer are reported. The structures of the cations were examined by isolating them and allowing them to react with various neutral reagents whose reactions with aromatic carbon‐centered σ‐type mono‐ and biradicals are well understood. Cleavage of two iodine–carbon bonds in N‐deuterated 1,4‐diiodoisoquinolinium cation by collision‐activated dissociation (CAD) produced a long‐lived cation that showed nonradical reactivity, which was unexpected for a para‐benzyne. However, the reactivity closely resembles that of an isomeric enediyne, N‐deuterated 2‐ethynylbenzonitrilium cation. A theoretical study on possible rearrangement reactions occurring during CAD revealed that the cation formed upon the first iodine atom loss undergoes ring‐opening before the second iodine atom loss to form an enediyne instead of a para‐benzyne. Similar results were obtained for the 5,8‐didehydroisoquinolinium cation and the 2,5‐didehydropyridinium cation. The findings for the 5,8‐didehydroisoquinolinium cation are in contradiction with an earlier report on this cation. The cation described in the literature was regenerated by using the literature method and demonstrated to be the isomeric 5,7‐didehydro‐isoquinolinium cation and not the expected 5,8‐isomer.     

Dual reactivity of an intermediate cation formed in the photolysis of dihydroquinolines in methanol

Photolysis of 2,2,4,6-tetramethyl- (1) and 1,2,2,4,6-pentamethyl-1,2-dihydroquinoline (2) in methanolic alkali yields only 4-methoxy-2,2,4,6-tetramethyl-1,2,3,4-tetrahydroquinoline in the former case and a mixture of 4-methoxy- and 4-hydroxy-1,2,2,4,6-pentamethyl-1,2,3,4-tetrahydroquinoline in the latter case. This result was rationalized by the existence of two resonance structures of an intermediate cation, viz., carbocationic and ortho-quinomethaneiminium species. The cation from 1 reacts with an alkali in the ortho-quinomethaneiminium form, and the cation generated from 2 reacts in the carbocationic form.     

Effects of ion pairing on the capillary electrophoretic separation and ultraviolet‐absorption detection of quaternary ammonium cations using meso‐octamethylcalix[4]pyrrole as the background electrolyte additive

Five quaternary ammonium cations, including tetramethylammonium, tetraethylammonium, hexadecyltrimethylammonium, benzyltrimethylammonium, and 1‐butyl‐3‐methylimidazolium, have been separated by capillary electrophoresis. A direct ultraviolet method has been achieved when tetrabutylammonium fluoride was the background electrolyte and meso‐octamethylcalix[4]pyrrole was the background electrolyte additive. The ultraviolet spectra of meso‐octamethylcalix[4]pyrrole and cation mixtures showed that redshifts can be attributed to the size of cations, and the maximum absorption wavelength shifted from 218 to 230 nm when tetrabutylammonium cation was substituted with tetramethylammonium cation or tetraethylammonium cation. Conductivity measurements were performed to evaluate the ion‐pairing effect of tetrabutylammonium fluoride in a mixture of acetonitrile/ethanol (80:20, v/v), and the ion‐pairing formation constant, K_ip, was calculated (K_ip = 14.8 ± 0.3 L/mol) using the Fuoss extended model. Ion pairing also occurs between cations of the analytes and counterion, a fluoride complex of meso‐octamethylcalix[4]pyrrole. The tetramethylammonium cations associate more strongly with this counterion than the tetraethylammonium cation that contributes to the change of selectivity in capillary electrophoresis separation. The effective mobilities of the cations with trimethyl groups, such as tetramethylammonium cation, benzyltrimethylammonium cation, and hexadecyltrimethylammonium cation, decreased faster than others with the increase of meso‐octamethylcalix[4]pyrrole concentration, highlighting the fact that the ion‐pairing effect played an important role in this method.     

Extraction,Partial Characterization,and Studies of Some Spectroscopic Properties of the Anionic Polysaccharide from Colocasia Antiquorum

Abstract

The natural anionic polysaccharide (Ps-A) isolated from arum (Colocasia antiquorum) tubers contains 56% neutral sugars as galactose, mannose, rhamnose, and arabinose, and 40% anionic components as galacturonic acid and mannuronic acid. The equivalent weight of Ps-A estimated by conductometric and spectrophotometric titrations is rather high, 1510 ± 5, which on saponification is reduced to 479. This indicates that about two-thirds of the carboxylic groups of Ps-A exist in the esterified form. Ps-A and its saponified product (Ps-B) induce strong metachromasia in the dyes 1,9-dimethyl methylene blue and pinacyanol chloride (PCYN). Ps-A, with its lower charge density, induces relatively sharp and single banded metachrotnatic spectra, but the spectra induced by Ps-B, with its higher charge density, is broad and multiple banded. Ps-A induces weak dichroism in PCYN, indicating a bit of helical asymmetry in its conformation; Ps-B does not induce dichroism in this dye. The failure of Ps-B to induce dichroism presumably indicates that Ps-B has a nonhelical conformation.     

Radical cation of hydrogen sulfide and reactions of cyclization of 1,5-Diketones with its participation

Radical cation of hydrogen sulfide is generated electrochemically by γ-irradiating a Freon matrix, under the action of single-electron oxidants (sterically hinderedo-benzoquinones). It is shown that the radical cation exhibits properties of a superacid. The possibility of obtaining thiopyrans and salts of thiopyrilium from substituted 1,5-diketones during an anodic oxidation of molecular hydrogen sulfide to radical cation in acetonitrile is studied.     

The temperature dependence of the fluorescence lifetime of pinacyanol iodide

The fluorescence decay time of pinacyanol (1,1′-diethyl-2,2′-carbocyanine) iodide has been measured in the temperature range 95–225 K. The results indicate that two separate internal-conversion processes are operative. One of these involves torsional relaxation and is viscosity dependent.     

High Pressure Study of NH4Pb2Br5 Type Compounds. I Structural Parameters and Their Evolution under High Pressure

We have investigated the nature of the interactions of ns²‐cations and the possible structure‐determining role of the ns²electron pair at ambient and high pressure in several AB₂X₅ (A = K, Rb, Cs, In, Tl; B = Sn, Pb, Sr; X = Cl, Br, I) compounds. Structural parameters are obtained by high pressure x‐ray diffraction as well as by quantum mechanical methods (DFT‐GGA‐calculations). The structural parameters at ambient and high pressure are discussed and compared to those of Tl₅Se₂I crystallising in the antitype structure. Short cation—cation distances in the NH₄Pb₂Br₅ type structure enable direct cation—cation interactions and the existence of an ns²‐cation in the B‐position is crucial for the stability of these structures. The effect of pressure on the structural parameters of these compounds gives new insights into the interactions of lone pair cations. The pronounced decrease of the cation—cation distances with pressure points to strongly increasing bonding interactions between the lone pair cations.     

A nonelectrocyclic path from the cyclobutene cation radical to the 1,3-butadiene cation radical

The conversion of the cyclobutene cation radical to the 1,3-butadiene cation radical has been studied using MINDO /3 and ab initio SCF MO methods. Not only smooth electrocyclic but also stepwise, non-electrocyclic routes were considered. Both calculational methods agree that the preferred reaction path is a novel nonelectrocyclic one proceeding through an intermediate “cyclopropylcarbinyl cation radical.” The quantitative agreement in the activation parameters calculated by the two methods is excellent. The proposed intermediate also provides an attractive explanation for the mass spectrometric fragmentation patterns of the cyclobutene and butadiene cation radicals.     

Metal cation-induced multifluorescence of azacrown-substituted (tetrafluorophenyl)imidazo[1,2-a]pyridine

ortho-Azacrown-substituted (tetrafluorophenyl)imidazo[1,2-a]pyridine (2) in an acetonitrile solution emits 380 nm light in the presence of Li⁺ cation and emits 460 nm light in the presence of Zn²⁺, Mg²⁺ or H⁺ cation. In contrast, para-azacrown-substituted analogue (1) emits three different fluorescent lights responding to Li⁺, Zn²⁺ or H⁺ cation, respectively; 388 nm light to Li⁺ cation, 433 nm light to Zn²⁺ cation or 469 nm light to H⁺ cation.     

Electrophilic Reaction of Phenyl Bis(Phenylthio) Sulfonium Cation as an Active Species for the Oxidative Polymerization of Diphenyl Disulfide

Computer modeling predicts that the methyl bis(methylthio) sulfonium cation can act as an efficient electrophile for sulfide bond formation in which the sulfur atoms at the side position of the cation react with the phenyl ring of an aromatic molecule. The electrophilic reaction mechanism of phenyl bis-(phenylthio) sulfonium cation with anisole was examined using computer simulation. The reaction between phenyl bis- (phenylthio) sulfonium cation, which is a homogeneous structure of thecation, and anisole shows the efficient formation of 4-phenylthioanisole with diphenyl disulfide as a by-product. In the oxidative polymerization of diphenyl disulfide, the formation process of polyp-phenylene sulfide) includes an elementary reaction between the phenylthio group at each side position of the phenyl bis(phenylthio) sulfonium cation and the carbon at the para position of the phenyl ring.