Design and Synthesis of Highly Photostable Yellow–Green Emitting 1,8-Naphthalimides as Fluorescent Sensors for Metal Cations and Protons

Two highly photostable yellow–green emitting 1,8-naphthalimides 5 and 6, containing both N-linked hindered amine moiety and a secondary or tertiary cation receptor, were synthesized for the first time. Novel compounds were configured as “fluorophore–spacer–receptor” systems based on photoinduced electron transfer. Photophysical characteristics of the dyes were investigated in DMF and water/DMF (4:1, v/v) solution. The ability of the new compounds to detect cations was evaluated by the changes in their fluorescence intensity in the presence of metal ions (Cu²⁺, Pb²⁺, Zn²⁺, Ni²⁺, Co²⁺) and protons. The presence of metal ions and protons was found to disallow a photoinduced electron transfer leading to an enhancement in the dye fluorescence intensity. Compound 5, containing secondary amine receptor, displayed a good sensor activity towards metal ions and protons. However the sensor activity of dye 6, containing a tertiary amine receptor and a shorter hydrocarbon spacer, was substantially higher. The results obtained indicate the potential of the novel compounds as highly photostable and efficient “off–on” pH switchers and fluorescent detectors for metal ions with pronounced selectivity towards Cu²⁺ ions.     

Effect of charge exchange on the energy distribution of fast multiply charged ions propagating through matter

A technique for calculating, in the diffusion approximation, energy distributions of multiply-charged ions with an arbitrary number of charge states propagating through matter has been suggested. Examples of numerical solutions of kinetic equations taking into account charge exchange between ions and matter are given. A compact solution for the special case of two charge states has been found. The calculations are compared to experimental data. Zh. éksp. Teor. Fiz. 111, 2226–2236 (June 1997)     

A New Fluorescent Sensor for the Determination of Iron(III) in Semi-Aqueous Solution

A simple fluorescent sensor 1 has been developed for the recognition of Fe(III) in semi-aqueous solution at pH 7.0. The sensor, containing two Schiff base type receptors directly connected to naphthalene fluorophores, shows a concentration dependent decrease in emission intensity upon Fe(III) addition. The sensor was selective for Fe(III) over other metal ions and can measure Fe(III) ion concentration between 0.05 and 0.12 mM. The binding stoichiometry was established as 1:1 (host: guest) with a binding constant (Logβ) of 4.01. Furthermore, the addition of Fe(III) to a solution of 1 caused a colour change from light yellow to colourless meaning 1 is also capable of detecting Fe(III) by the naked eye.     

Self-consistent mechanism for sustaining ionization waves in a low-pressure discharge

The possibility of constructing a self-consistent model for the sustaining of ionization waves is demonstrated for a low-pressure discharge in an inert gas. The model is based on the combined solution of the kinetic equation of the electrons and the equation of motion of the ions in a spatially periodic field. The distribution function is constructed in an experimentally measured field and then used to calculate the spatial distributions of the plasma density and the ionization rate. The solution of the equation of motion of the ions makes it possible to reconstruct a field similar to the original one. One specific feature of the mechanism considered is the pronounced nonlocal character of the formation of the electron distribution function by the entire nonuniform potential profile of the ionization wave. Zh. Tekh. Fiz. 67, 24–30 (February 1997)     

Calculation of the ranges of slow, heavy ions in an amorphous medium

The low-energy range corresponding to reduced energies ɛ⩽0.1 is investigated. A method is developed for calculating the ranges of heavy ions in an amorphous medium. Analytical expressions for calculating the projective range of ions and the standard deviation of the projective ranges are obtained. The computational results are in good agreement with experiment. Zh. Tekh. Fiz. 67, 16–20 (October 1997)     

Sulfide passivation of III-V semiconductor surfaces: role of the sulfur ionic charge and of the reaction potential of the solution

A model is proposed for describing the effect of a solution on the electronic properties of sulfided surfaces of III-V semiconductors which treats the adsorption of sulfur in terms of a Lewis oxide-base interaction. According to this model, the density of states on a sulfided surface, which pin the Fermi level, decreases as the global hardness of the electron shell of the adsorbed sulfide ions is increased. The Thomas-Fermi-Dirac method is used to calculate the global hardness of sulfide ions with different charges as a function of the dielectric constant of the medium. It is shown that the hardness of a sulfur ion is greater when its charge is lower and the dielectric constant of the solvent is lower. Zh. Tekh. Fiz. 68, 116–119 (August 1998)     

Ranges of low-energy heavy ions in beryllium, boron, carbon, and silicon

Based on a theory of the passage of low-energy, heavy ions through matter, simple analytical expressions are obtained for calculating the average projected ranges of the ions and the rms deviations of the projected ranges. The theoretical and experimental ranges of heavy ions with atomic numbers 29⩽Z ₁⩽83 in targets of Be, B, C, and Si are compared. The theory is found to be in good agreement with experiment. Zh. Tekh. Fiz. 68, 33–36 (September 1998)     

Superhyperfine structure of the EPR spectra of Ce<Superscript>3+</Superscript> ions in Li<Emphasis Type="Italic">R</Emphasis>F<Subscript>4</Subscript> (<Emphasis Type="Italic">R</Emphasis> = Y,Lu, Tm) double fluorides

The EPR spectra of Ce³⁺ impurity ions in LiYF₄, LiLuF₄, and LiTmF₄ double-fluoride single crystals have been investigated at a frequency of ∼9.3 GHz in the temperature range 5–25 K. The effective g factors of the ground Kramers doublet of the cerium ions in three crystals are close to each other (g _‖ = 2.737, g _⊥ = 1.475 for LiYF₄:Ce³⁺). A superhyperfine structure of the EPR spectrum of Ce³⁺ ions in the LiTmF₄ Van Vleck paramagnet has been observed in the external magnetic field B oriented along the crystallographic axis c (B ‖ c). The superhyperfine structure of the EPR soectra of the Ce³⁺ ions in the LiYF₄ and LiLuF₄ diamagnetic matrices is resolved for B ⊥ c. Possible factors responsible for this pronounced difference in the properties of the systems studied have been discussed.     

X-ray spectra of multiply-charged hollow ions in the emission from a femtosecond laser plasma

A new type of quasicontinuous emission spectrum from a femtosecond laser plasma near the Ly_α line of H-like ions is obtained and interpreted. It is shown that these spectra are emitted by multiply charged hollow ions, which are present in the plasma on account of its ultrahigh density, which, in turn, is due to the use of high-contrast laser pulses for producing the plasma. A new spectroscopic approach based on analysis of the composition of spectral complexes of hollow ions is discussed. Pis’ma Zh. éksp. Teor. Fiz. 67, No. 7, 467–472 (10 April 1998)     

Neutralization of H− ions in collisions with fast, multiply charged ions

The neutralization of H⁻ ions in collisions with fast, multiply charged ions is considered in the parameter region where the Born approximation applies. An analytical formula is obtained for the H⁻ neutralization cross section in such collisions. Zh. Tekh. Fiz. 69, 1–4 (July 1999)     

Synthesis of Highly Selective Indole-Based Sensors for Mercuric Ion

Two indole-based fluorescent chemosensors 1 and 2 were prepared and investigated characteristic features with transition metal ions. Sensors 1 and 2 were selective for Hg²⁺ ion, among a series of metal ions, in aqueous ethanol (H₂O–EtOH, 1:2, v/v) with association constants of 5.74 × 10³ and 4.46 × 10³ M⁻¹ and detection limits of 7.4 and 6.8 μM, respectively. Computational results revealed that sensor 1 or 2 with Hg²⁺ ion formed 1:1 complex with a central, sandwich-coordinated Hg²⁺ ion. Computational calculations provided evidence that a sandwich-coordinated Hg²⁺ ion center was formed and the polyoxyethylene spacer acted as a scaffold for bringing functional ligands into a suitable geometry.     

Effect of free electrons on growth of “cancers” in mixed electronic-ionic conductors

The reasons for the anomalously rapid (for solids) growth of “cancers” (filamentary crystals, hills, pores, and other formations) on the surface of samples of superionic conductors with mixed electronic-ionic conductivity (of the type Cu_2−x Se and Ag₂Te) are discussed. The effects are attributed to the acceleration of mobile ions and activated ions in the “core” of the superionic by free electrons in the joint “chemical” diffusion of ions and electrons in the samples. Pis’ma Zh. éksp. Teor. Fiz. 64, No. 2, 97–100 (25 July 1996)     

Measurement of the transverse kinetic energies of argon recoil ions produced in 120 MeV -Ar collisions

Measurements were carried out to deduce the transverse kinetic energies of highly charged argon recoil ions produced in single collisions of 120 MeV ions with argon atoms in which the post collision charge states of the projectiles were not determined. A time of flight spectrometer was designed and fabricated to detect the charge states of recoils. Experimental procedures for optimizing the spectrometer for extraction, transmission and detection of recoils are described. A simple approach for determining the transverse kinetic energy of the recoil ions from FWHM of the peaks is reported. This method is shown to be independent of the choice of collision partners and requires only the knowledge of the physical values of “optimized parameters” of time-of-flight spectrometer used in the experiment. The transverse kinetic energy of the recoil ions determined from the present approach is found to vary from 0.03 eV for to 4.02 eV for Ar¹⁰⁺. These values are compared with the results reported by earlier workers and are shown to follow a q²-behaviour up to a charge state q =8+ of the recoil ions. Received: 5 February 1998 / Revised: 8 June 1998 / Accepted: 11 June 1998     

Effect of Mo3+ ions on Nd3+ spin-lattice relaxation in Y3Al5O12

The content of Mo³⁺ ions in YAG:Nd garnet samples prepared by different technologies has been studied, and the spin-lattice relaxation rate of these ions at temperatures of 4–5 K measured. It is concluded is drawn that Mo³⁺ ions can play the part of rapidly relaxing centers mediating the Nd³⁺ spin-lattice relaxation at liquid-helium temperatures. This may account for a number of features in the spin-lattice relaxation of rare-earth ions in garnets, observed earlier at low temperatures. Fiz. Tverd. Tela (St. Petersburg) 40, 2026–2028 (November 1998)     

Cylindrical cumulation of fast ions in a ring focus of a high-power subpicosecond laser

A new method of cylindrical cumulation of fast ions undergoing ponderomotive acceleration at the focus of a high-power subpicosecond laser is proposed. When a laser beam is focused in a preionized gas at a ring focus, radial acceleration of ions by the ponderomotive force occurs. The ions accelerated from the inner side of the ring form a cylindrical shock wave converging toward the axis. As the shock wave cumulates, the ion density increases rapidly and the ion-ion collision probability increases along with it. A numerical simulation for a ~100 TW subpicosecond laser pulse predicts the generation of up to 200 keV ions and up to 100-fold volume compression of the plasma in a cylinder ~1 μm in diameter. The lifetime of the dense plasma filament over the length of the laser caustic is several picoseconds. It is suggested that laser cumulation of ions be used for the production of a bright and compact subpicosecond source of fast neutrons, media for x-and γ-ray lasers, and multiply-charged ions and for the initiation of nuclear reactions. Pis’ma Zh. éksp. Teor. Fiz. 69, No. 1, 20–25 (10 January 1999)     

Lattice dynamics of ionic crystals in a model of “breathing” and polarizable ions

An expression is written down for the dynamic matrix of ionic crystals in terms of a microscopic, parameterless model of “breathing” and polarizable ions. Results from a calculation of the complete spectrum of the lattice vibrations of ionic crystals having an NaCl structure are presented as an illustration. Fiz. Tverd. Tela (St. Petersburg) 40, 350–354 (February 1998)     

Photo-induced reactions of hemin (DMSO) n clusters (n = 0-3) produced with electrospray ionization

Photo-induced reaction of [Fe(III)-protoporphyrin]⁺ (hemin⁺) ions solvated with dimethylsulfoxide (DMSO) is investigated by using a tandem mass spectrometer with electrospray ionization. We measure the photodissociation yields of mass-selected hemin⁺(DMSO)_n clusters for n = 0-3 in the energy region of 15 800-28 200 cm^-1. The mass spectra of the fragment ions show the β-cleavage of carboxymethyl groups in addition to the evaporation of solvent molecules. Yield of the β-cleavage reaction is found to depend strongly on the excitation energy and the number of solvent molecules. We also examine the metastable decomposition of the clusters following primary mass selection and determine the incremental solvent binding energies and internal energies for the clusters using evaporative ensemble model. From these results, we investigate the reaction mechanism of β-cleavage of hemin⁺ ion.     

Parameters of the discharge plasmas of surface-plasma sources of negative hydrogen ions

The main parameters of the plasma of high-current hydrogen-cesium glow discharges of surface-plasma (planotron and Penning) sources of negative hydrogen ions are determined using contact-free spectroscopic methods and compared for identical discharge current densities. The elemental and charge composition of the plasma is established. The temperature of the hydrogen atoms and the energy of the visible-range radiation of the plasma discharge are measured and estimates of the electron density in the plasma are made. The dynamics of the change in the parameters of the discharge plasma of a Penning source — the densities of hydrogen atoms, cesium atoms and ions, and molybdenum atoms — is tracked during a discharge pulse with spatial resolution along two coordinates. It is observed that cesium atoms and ions and molybdenum atoms are pent up near the cathode surface. Zh. Tekh. Fiz. 68, 32–38 (October 1998)     

Luminescence of biologically active 24-epicastasterone and a model compound

Biologically active brassinosteroid 24-epicastasterone, ring B of which contains a C=O group and has the nπ*-configuration for a low-lying electronic excited state, exhibits rapid fluorescence. The wavelengths of the fluorescence maxima of the steroid dissolved in hexane and acetonitrile are equal to 332 and 394 nm, respectively. The fluorescence lifetime of the steroid dissolved in acetonitrile is τ = 9.9 nsec. Solutions of 24-epibrassinolide do not luminesce. The long-wavelength electronic absorption band λ_max^abs = 340 nm in the absorption spectrum of an ethanol solution of model compound 2, ring D of which contains a C=O group π*-conjugated with the C=C double bond of ring C, like in the spectrum of the steroid, has a low extinction coefficient. An ethanol solution of 2 does not fluoresce. 24-Epicastasterone at 77 K in ethanol solution exhibits phosphorescence with λ_max^phos = 447 nm. The phosphorescence decay is exponential with τ = 0.79 msec. Compound 2 also phosphoresces. The phosphorescence spectrum of its ethanol solution has a maximum at 490 nm. The phosphorescence decay is nonexponential in the early stage. The phosphorescence lifetime is 25 msec in the exponential decay region. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 2, pp. 182–186, March–April, 2008.     

Multi-electron transitions in -Ne and -Ne collisions

The ratios of the multiple ionization cross-section to those of the single ionization of neon are measured for 2.0-8.0 MeV and ( q = 2-5) ions bombardment. By means of the coincidence beween the charge state-selected scattered projectiles and recoil ions the contribution of the electron capture is separated from the total multiple ionization. A theoretical method is proposed to exclude the Auger transitions from the considered multiple ionization processes in the present work. The (q / v) dependence of the obtained ratios of the “pure” direct multiple ionization to those of the single ionization is discussed. The electronic structure dependence of the electron transition occurring in ion-neon collisions is studied and discussed for the symmetrical collision systems - and -. Received: 4 June 1998 / Received in final form: 24 August 1998