β-Cyclodextrin Effect on Micellization of Cetyltrimethyl ammonium Bromide in Aqueous Solution. Probed by Dual Fluorescence of Sodium P-Dimethylaminobenzoate

Effect of p-cyclodextrin (β-CD) on micellization of cetyltrimethylammonium bromide (CTAB) in aqueous solution was investigated by twisted intramolecular charge transfer (TICT) dual fluorescence of sodium p-dimethylaminobenzoate (SDMAB). It was shown that β-CD induces the micellization of CTAB and the aggregation of CTAB below CMC as well. A reduced charge density at CTAB micelle interface in the presence of β-CD, due to the incorporation of 1:1 CTAB-β-CD inclusion complex in micelle, was concluded to be the reason for β-CD induced micellization of CTAB.     

Effects of Ionic Liquids on Fluorescence Characteristics of 17α- and 17β-estradiol

Herein, we report the effects of six different room temperature ionic liquids (RTILs) on fluorescence spectra of 17α-estradiol (EE1) and 17β-estradiol (E2). The selected RTILs belonged to the compound classes of 1-alkyl-3-methylimidazolium tetrafluoroborate ([C_nMIM]BF₄) and 1-alkyl-3-methyl imidazolium hexafluorophosphate ([C_nMIM]PF₆). RTILs had a gradual quenching effect on fluorescence intensity (FI) of EE1 and E2, and the quenching process followed the well-known Stern-Volmer theory. The quenching mechanism of EE1 and E2 by RTILs was demonstrated to be dynamic quenching. Additionally, the overall quenching efficiency by [C_nMIM]BF₄ was higher than [C_nMIM]PF₆. The increased carbon chain length of RTILs did not lead to obvious differences in FI for EE1 and E2. The quenching efficiency showed irregular trend at three different temperatures (25, 35 and 45 °C). RTILs such as [C₄MIM]PF₆ had the different fluorescent effects on organic chemicals with different fluorophores. The enhancing effects of [C₄MIM]PF₆ were observed on strong fluorescence chemicals (dansyl chloride, rhrodamine B, 1,10-phenanthroline, norfloxacin), while quenching effect on weak fluorescence chemicals (EE1 and E2). In theory, these results provide a theoretical foundation for deep insight into their interaction mechanism between RTILs and estradiol.     

Effect of Heavy Metals on Dynamic and Static Quenching of the Fluorescence of the Host-Guest Inclusion Complex Methyl-β-Cyclodextrin by 2,9-Dimethyl-4,7-Diphenyl-1,10-Phenanthroline in Aqueous Media

Journal of Applied Spectroscopy - An inclusion complex was formed with methyl-β-cyclodextrin (Me-β-CD) and the smallest unit of the macrocyclic family of bathocuproine,...     

Fabrication of fucoxanthin/2-hydroxypropyl-β-cyclodextrin inclusion complex assisted by ultrasound procedure to enhance aqueous solubility,stability and antitumor effect of fucoxanthin

Fucoxanthin (Fx) possesses multiple bioactivities such as antitumor, antioxidant and anti-inflammatory activities, but its application is limited due to the poor water solubility, low bioavailability, and instability to some external harsh conditions. In this study, a stable inclusion complex of Fx and 2-hydroxypropyl-β-cyclodextrin (2-HP-β-CD) was prepared with the aid of ultrasound, which was characterized by scanning electron microscope, Fourier transform infrared spectroscopy, powder X-ray diffraction, and differential scanning calorimetry techniques. The phase solubility analysis and absorption spectroscopy results showed that Fx formed stoichiometry 1:2 inclusion complex with 2-HP-β-CD, and this could be well proved by molecular simulation. Structural analyses and molecular docking study indicated that Fx was successfully encapsulated into the cavity of 2-HP-β-CD, promoting it soluble in water and stable against heat, storage and gastrointestinal environments. In addition, Fx/2-HP-β-CD inclusion complex exhibited excellent antitumor activity against HCT116 and Caco-2 cell lines with IC₅₀ values of 12.0 μΜ and 14.86 μΜ, respectively. Therefore, it could be a potentially promising way to promote the application of Fx in pharmaceuticals and functional foods by HP-β-CD encapsulation strategy.     

Study of 124Te by the 122Sn(α,2nγ) reaction and by the decay of 124I

In-beam γ-ray spectroscopy and the decay of ¹²⁴I were used to study the nuclear structure of ¹²⁴Te. On the basis of γγ-coincidences, a level scheme was constructed with over 100 levels and 170 transitions. The use of excitation functions and angular distributions for the (α, 2n) reaction, and the log(ft) values for the decay, allowed spin assignments for a large number of the levels to be made. The resulting level scheme was interpreted in the framework of the interacting boson model and the particle-core coupling model.     

A Preliminary Investigation of the Complexation of Dopamine by p‐Sulfonated Calix[4, 6] Arene and β‐Cyclodextrin Using Fluorescence Spectrometry

The inclusion complexes of p‐sulfonated calix[4, 6] arene and β‐cyclodextrin with dopamine were studied by fluorescence spectrometry in aqueous media. It was found that the fluorescence intensity of dopamine regularly decreased upon the addition of p‐sulfonated calix[4, 6] arene, on the contrary, it increased upon the addition of β‐cyclodextrin. ¹H NMR spectra were applied to verify the formation of the complexes. According to the experimental results, 1:1 stoichiometry for the complexes was established and their association constants at 25°C were calculated by applying a deduced equation. Judging from the magnitude of their inclusion constants, the p‐sulfonated calix[4, 6] arene showed better inclusion capability than β‐cyclodextrin. The probable interaction mechanisms are proposed.     

Spectral energy characteristics of 6,γ- and 7,γ-dimethyl ethers of chlorine 6 in water-alcohol solutions

Absorption spectra and dispersion of optical rotation (DOR) are measured for monomers of 6,γ- and,7,γ-dimethyl ethers of chlorin e₆ (Ch-6,γ-DME and Ch-7,γ-DME) in 96% ethanol and for associates of them that are polymers and colloidal particles. The optical activity of Ch-6,γ-DME monomers is higher than that of Ch-7,γ-DME monomers, which is linked with more pronounced distortion of the molecular macrocycle for Ch-6,γ-DME in the γ-C₆ local region. The structural and energy parameters of dimeric unit cells of Ch-6,γ-DME and Ch-7,γ-DME polymers are discussed from the standpoint of the Davydov-Tinoko exciton theories. Longwave absorption spectra and DOR are resolved into individual components with the aid of a modified Alentsev-Fock method. Institute of Molecular and Atomic Physics of the National Academy of Sciences of Belarus, 68, F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 3, pp. 331–337, May–June, 1999.     

The isomeric ratios in some photonuclear reactions (γ, n), (γ, p), (γ, 2n), and (γ, np) induced by bremsstrahlungs with end-point energies in the Giant Dipole Resonance region

We have determined the isomeric ratios in photonuclear reactions ¹¹⁶Cd(γ, n)^{115m, g} Cd, ¹³⁸Ce(γ, n)^{137m, g} Ce, ¹⁵³Eu(γ, n)^{152m, g} Eu, ⁹⁶Mo(γ, p)^{95m, g} Nb, ¹¹⁸Sn(γ, p)^{117m, g} In, ⁸⁹Y(γ, 2n)^{87m, g} Y, ¹⁰⁶Cd(γ, np)^{104m, g} Ag, and ¹¹²Sn(γ, np)^{110m, g} In induced by bremsstrahlungs with end-point energies in the Giant Dipole Resonance (GDR) region. The targets were irradiated at electron accelerator Microtron MT-25 of the Flerov Laboratory of Nuclear Reactions, Joint Institute for Nuclear Research, Dubna. Gamma spectra of irradiated samples were measured with a spectroscopic system consisting of 8192-channel analyzer and high-energy resolution (180 keV at gamma ray 1332 keV of ⁶⁰Co) semiconductor detector CANBERRA. The results were discussed and compared with those of other authors. The article is published in the original.     

Fluorescence “Switch on” of Conjugates of CdTe@ZnS Quantum Dots with Al, Ni and Zn Tetraamino-Phthalocyanines by Hydrogen Peroxide: Characterization and Applications as Luminescent Nanosensors

In this study, we have developed a novel nanoprobe for H₂O₂ based on the conjugation of CdTe@ZnS quantum dots (QDs) to different metal tetraamino-phthalocyanine (MTAPc): (M?=?(OAc)Al, {OAc?=?acetate}, Ni and Zn). Chemical coordination of the QDs to the MTAPc resulted in the fluorescence “switch off” of the linked QDs which was associated with Förster resonance energy transfer (FRET). In the presence of varying concentration of H₂O₂, the fluorescence of the linked QDs was progressively “switched on” and the FRET mechanism between the QDs and the MTAPc was disrupted. The sensitivity/limit of detection of the nanoprobe followed the order: QDs-ZnTAPc (2.2 μM)?>?QDs-NiTAPc (4.4 μM)?>?QDs-AlTAPc (9.8 μM) while the selectivity followed the order: QDs-NiTAPc?>?QDs-AlTAPc?>?QDs-ZnTAPc. The varying degree of sensitivity/selectivity and mechanism of detection is discussed in detail.     

Determination of Chemical Effect on the Kβ1/Kα, Kβ2/Kα, Kβ2/Kβ1 and Kβ/Kα X-Ray Intensity Ratios of 4d Transition Metals

It is clear that detailed studies performed under identical experimental conditions are desirable to determine the effect of the chemical environment on the value of intensity ratios. To better understand this effect, we conducted measurements on Kβ₁/Kα, Kβ₂/Kα, Kβ₂/Kβ₁ and Kβ/Kα x-ray intensity ratios. The Kα and Kβ_1,2 emission spectra for compounds of 4d transition metals Y, Zr, Nb, and Mo were measured using a Si(Li) solid-state detector. The samples were excited by 22.69 keV x-rays emitted from a ¹⁰⁹Cd radioisotopes source. The experimental results for pure elements are compared with the other experimental and theoretical values.     

The E1 and E2 capture amplitudes in 12C(α,γ0)16O

Excitation functions of the %₀ capture transition in ¹²C(!,%)¹⁶O at /_% = 90^§ were obtained using a 4 2 4' BGO crystal in close geometry (E = 0.94 to 3.39 MeV) and a 2 2 2' BGO crystal in far geometry (E = 1.69 to 3.29 MeV), where the study of the reaction was initiated in inverse kinematics involving a windowless gas target. The small crystal detected essentially the E1 multipole component in the %₀ capture transition, while the large crystal observed approximately the angle-integrated sum of the E1 and E2 multipole components. Analysis of the two data sets together with data from previous work provided strong evidence that both multipoles are of equal importance at the relevant stellar energy E₀ = 0.3 MeV.     

Studies on the Miscibility of Chitosan/Poly(vinyl pyrrolidone) Blend in Solution by Viscometry,Ultrasonic Velocity,Density and Refractometry Techniques at 30, 40, and 50°C

Polymer blends of chitosan (CHI) with poly(vinyl pyrrolidone) (PVP) have been prepared by solution blending, and their miscibility studies were carried out by using physical techniques over an extended range of concentration and composition in buffer solution. The viscosity, ultrasonic velocity, density, and refractive index were measured at 30, 40, and 50°C, respectively. Using viscosity data, the interaction parameter μ and α were computed to probe the miscibility. These values revealed that the blend is miscible when the chitosan content is more than 60% in the blend at all temperatures. The obtained results were further confirmed by the ultrasonic velocity, density, and refractive index measurements.     

Investigation of thermoluminescence in Li_2B_4O_7 phosphors doped with Cu, Ag and Mg

Li_2B_4O_7 (LBO):Cu,Ag,Mg phosphors have been prepared by the sintering technique. The roles of the Ag and Mg dopants in the phosphors have been studied using the methods of thermoluminescence (TL) glow curves and TL 3D spectra. The results indicated that proper concentrations of Ag and Mg can enhance the TL of LBO:Cu. It was also indicated that the intensity of TL peak at ~130℃ is reduced with the in- creasing Ag concentration, and enhanced with the increasing Mg concentration. From the TL 3D spectra, three emission bands (λ1 = 421 nm, λ2 = 380 nm, λ3 = 350 nm) were observed: the intensity of low energy emission band is reduced and that of the high energy is enhanced with the increasing dopant Ag; on the contrary, the intensity of low energy emission band is enhanced and that of the high energy one is reduced with the increasing dopant Mg.     

Synthesis,characteristics and sonocatalytic activities of calcined γ-Fe2O3 and TiO2 nanotubes/γ-Fe2O3 magnetic catalysts in the degradation of Orange G

In this work, γ-Fe₂O₃ and TiO₂ NTs/γ-Fe₂O₃ composites with good magnetism and sonocatalytic activity were prepared by a facile polyol method and utilize the principle of isoelectric point method, respectively. The structural and magnetic features of the prepared calcined γ-Fe₂O₃ and composite catalysts were investigated by transmission electron microscopy (TEM), powder X-ray diffraction (XRD), surface analysis, UV–Vis diffuse reflectance spectra (UV–Vis DRS), vibrating sample magnetometry (VSM) and zeta potential analysis. The effects of calcination temperature on γ-Fe₂O₃ phase variation, physical properties and sonocatalytic properties were investigated. The porosity, specific surface area, band gap energy and sonocatalytic activity of γ-Fe₂O₃ were gradually decreased with calcination temperature increased. TiO₂ NTs/γ-Fe₂O₃ with appropriate composition and specific structural features possess synergetic effects such as efficient separation of charge carriers and hydroxyl radicals produced by heterogeneous fenton and fenton-like reactions. This enhanced the sonocatalytic activity for the degradation of Orange G under ultrasonic irradiation. The sonocatalytic reactions obeyed pseudo first-order kinetics. All these information provide insight into the design and development of high-efficiency catalyst for wastewater treatment.     

Deuteron disintegration, thermonuclear and nuclear fission reactions induced by γ-quanta in D-saturated palladium and dense deuterium gas with synthesis of new structures

The results obtained by investigating the chemical composition and structure of Pd sample sur-faces, chamber components, and a new synthesized object (NSO) are presented. The NSO is produced in the chamber with a high-pressure (about 3 kbar) deuterium gas under irradiation by γ-quanta with an energy of 8.8 MeV. The measured concentrations of chemical elements arisen from nuclear reactions initiated by γ-quanta have made it possible to develop the phenomenological approach to describing the process whereby deuterium atoms are heated by the protons and neutrons of a deuteron photofission reaction, hot D-D fusion, Oppenheimer reactions, and palladium nuclear fission. The coefficient of the process efficiency greatly exceeds unity. A new type of reactors (deuterated nuclear fission reactor) is proposed.     

Spectrophotometric determination of copper(II) in pharmaceutical,biological and water samples by 4-(2′-benzothiazolylazo)-salicylic acid

A highly sensitive method is proposed to determine copper(II) ions by forming a stable complex through their interaction with 4-(2′-benzothiazolylazo)-salicylic acid (BTAS) at room temperature and pH of about 5.0. The complex gave a maximum absorption at λ = 485 nm with a molar absorptivity coefficient of 2.35·10⁴ l/(mol·cm). The linear range for the copper determination is 0.63–5.04 mg/l. The method can be applied to determine copper ions in different biological specimens like some drugs and water samples.     

A Comparison of Complexation of Li<Superscript>+</Superscript> Ion with Macrocyclic Ligands 15-Crown-5 and Benzo-derivatives in Binary Nitromethane–Acetonitrile Mixtures by Using Lithium-7 NMR Technique and Ab Initio Calculation

Abstract  

Lithium-7 nuclear magnetic resonance (NMR) measurements were used to investigate the stoichiometry and stability of Li⁺ complexes with 15-crown-5 (15C5), benzo-15-crown-5 (B15C5) and dibenzo-15-crown-5 (DB15C5) in a number of nitromethane (NM)–acetonitrile (AN) binary mixtures. In all cases, the exchange between the free and complexed lithium ion was fast on the NMR time scale and a single population average resonance was observed. While all crown ethers form 1:1 complexes with Li⁺ ion in the binary mixtures used, stepwise formation constants of the 1:1 (ligand/metal) complexes were evaluated from computer fitting of the NMR-mole ratio data to equations which relate the observed metal ion chemical shifts to formation constants. There is an inverse linear relationship between the logarithms of the stability constants and the mole fraction of AN in the solvent mixtures. The stability order of the 1:1 complexes was observed to be 15C5.Li⁺ > B15C5.Li⁺ > DB15C5.Li⁺. The optimized structures of the free ligands and their 1:1 complexes with the Li⁺ ion were predicted by ab initio theoretical calculations using the Gaussian 98 software. The results of calculations are discussed.     

A DFT study of the mechanism and the regioselectivity of [3 + 2] cycloaddition reactions of nitrile oxides with α,β-acetylenic aldehyde

A DFT study of the (32CA) reaction of a series of some nitrile oxides with electron-deficient alkyne (3-phenylpropionlaldehyde) in gas phase and in toluene has been carried out using B3LYP functional with 6-31G(d) basis set. Two reactive channels 4- and 5-associated with the two regioisomeric modes have been located and characterised. These 32CA reactions are characterised by a low asynchronous one-step mechanism with a low-polar character. Analysis of the DFT reactivity indices indicates that the nucleophilic centre of the different nitrile oxides accounts for the 4-regioselectivity. Our calculations are in a good agreement with the experimental findings.