New Triphenylphosphonium Salts of Spiropyrans: Synthesis and Photochromic Properties.

The most important area of modern pharmacology is the targeted delivery of drugs, and one of the most promising classes of chemical compounds for creating drugs of this kind are the photochromic spiropyrans, capable of light-controlled biological activity. This work is devoted to the synthesis and study of the photochromic properties of new triphenylphosphonium salts of spiropyrans. It was found that all the synthesized cationic spiropyrans have high photosensitivity, increased resistance to photodegradation and the ability for photoluminescence.

Single-Bubble Sonoluminescence of Colloidal Suspensions of Europium(II) Salt Nanoparticles.

Colloidal suspensions of EuCl2, EuBr2, and EuSO4 nanoparticles (<50 nm) in dodecane and EuSO4 in 70% H2SO4 were synthesized. Moving single-bubble sonoluminescence (m-SBSL) spectra were obtained for a bubble performing radial oscillations in these suspensions and translational motions at the antinode of a standing ultrasonic wave with a frequency of about 27 kHz. In these spectra (at a spectral resolution of 10 nm), the sono-excited luminescence bands of the Eu2+ ion were detected for the first time, coinciding in the shape and position of the maxima (404, 413, and 377 nm for EuCl2, EuBr2, and EuSO4, respectively) with the bands of Eu2+ located in a crystalline environment in the photoluminescence spectra of nanoparticles of europium salts in suspensions. The detected sonoluminescence of Eu2+ arises due to the injection of nanoparticles into a bubble deformed during motion and excitation of a lanthanide ion at the periphery of the bubble volume during collisions of nanoparticles with charged particles, mainly electrons, coming from a hot nonequilibrium plasma, which periodically arises during bubble compression. Evidence for the excitation of the europium ion in the bubble is the absence of its luminescence bands in the SBSL spectra of the translationally immobile bubble, in which nanoparticles are unlikely to enter. The nanoparticles that enter the bubble also undergo decomposition in the plasma into fragments, in particular, with the formation of Eu, Eu+ in the excited state. The atomic lines of these fragments were recorded for the first time in the m-SBSL spectrum with a resolution of 1 nm for a suspension of EuSO4 nanoparticles in 70% H2SO4. The resulting m-SBSL spectra will add to the library of characteristic spectra of objects of sonoluminescent spectroscopic analysis and will make it possible to identify and determine the content of Eu or Eu2+ in these objects.

Application of Sonotriboluminescence to Determine Arene Molecules in Hydrocarbons.

The sonotriboluminescence of suspensions of terbium(III) and europium(III) sulfates in decane without and in the presence of benzene, toluene and p-xylene was studied. The choice of crystals of these lanthanides is due to the fact that they have intense luminescence during mechanical action, and also do not dissolve in hydrocarbon solvents. During ultrasonic exposure to suspensions in pure alkanes, bands of Ln3+ ions and N2 in the UV region are recorded in the luminescence spectrum. When aromatic hydrocarbon molecules are added, bands of benzene, toluene and p-xylene molecules, coinciding with their photoluminescence spectra, are recorded in the sonotriboluminescence spectra in the UV region. The high sensitivity of the luminescence of suspensions to arene additives made it possible to obtain the dependence of the characteristic fluorescence of arene molecules in the sonotriboluminescence spectra on their concentration in suspensions. The limits of detection of benzene, toluene and p-xylene in the composition of this suspension were established. The lower limits of detection from the sonotriboluminescence spectra for xylene, toluene and benzene are 0.1, 3 and 50 ppmv, respectively. Fluorescence bands of these molecules were also recorded in the sonotriboluminescence spectra of suspensions in commercial dodecane and heptane with additives of commercial gasoline (up to 1%). The results obtained can be used for luminescent detection of aromatic compounds in saturated hydrocarbons.

Photochromic and Luminescent Properties of a Salt of a Hybrid Molecule Based on C60 Fullerene and Spiropyran-A Promising Approach to the Creation of Anticancer Drugs.

For the first time a pyrrolidinofullerene salt containing a spiropyran group and an ammonium group, capable of reversibly reacting to UV radiation, has been synthesized. Photoinduced reactions of the synthesized compounds were studied using absorption and luminescence spectroscopies, spectral and kinetic characteristics were measured. The hybrid molecule was found to exhibit intrinsic fluorescence even in the spirocyclic form. The C60 derivative showed a higher stability and better spectral and luminescent properties than the precursor.

Synthesis, Photochromic and Luminescent Properties of Ammonium Salts of Spiropyrans.

New salts of photochromic indoline spiropyrans capable of reversibly responding to UV radiation were synthesized to develop light-controlled materials. Photoinduced reactions of the synthesized compounds were studied using absorption and luminescence spectroscopies, and the quantum yields of photoisomerization and other spectral and kinetic characteristics were measured. It was shown that the light sensitivity and photostability of the synthesized compounds are considerably influenced by the length of the spacer between the indole and ammonium nitrogen atoms.

New sonochemiluminescence involving solvated electron in Ce(III)/Ce(IV) solutions.

The moving single-bubble sonoluminescence of Ce3+ in water and ethylene glycol solutions of CeCl3 and (NH4)2Ce(NO3)6 was studied. As found, a significant part of intensity of the luminescence (100% with cerium concentration less than 10-4 M) is due to the sonochemiluminescence. A key reaction of sonochemiluminescence is the Ce4+ reduction by a solvated (or hydrated in water) electron: Ce4+ + es (eaq) â†’ *Ce3+. Solvated electrons are formed in a solution via electrons ejection from a low-temperature plasma periodically generated in deformable moving bubble at acoustic vibrations. Reactions of heterolytic dissociation of solvents make up the source of electrons in the plasma. In aqueous CeCl3 solutions, the Ce4+ ion is formed at the oxidation of Ce3+ by OH radical. The latter species originates from homolytic dissociation of water in the plasma of the bubble, also penetrating from the moving bubble into the solution. The sonochemiluminescence in cerium trichloride solutions are quenched by the Br- (acceptor of OH) and H+ ions (acceptor of eaq). In water and ethylene glycol solutions of (NH4)2Ce(NO3)6, the sonochemiluminescence also quenched by the H+ ion. The sonochemiluminescence in CeCl3 solutions is registered at [Ce3+] ≥ 10-5 M. Then the sonochemiluminescence intensity increases with the cerium ion concentration and reaches the saturation plateau at 10-2 M. It was shown that sonophotoluminescence (re-emission of light of bubble plasma emitters by cerium ions) also contributes to the luminescence of Ce3+ in solutions with [Ce3+] ≥ 10-4 M. If the cerium concentration is more than 10-2 M, a third source contributes to luminescence, viz., the collisional excitation of Ce3+ ions penetrating into the moving bubble.