Photochemical syn-anti isomerization reactions in N2-hydroxyisocytosines--an experimental matrix isolation and theoretical study

N2-hydroxyisocytosine and 1-methyl-N2-hydroxyisocytosine were studied using a matrix isolation technique combined with infrared absorption spectroscopy. For N2-hydroxyisocytosine isolated in an Ar matrix (at 10 K), two imino-oxo isomers, one with the hydroxyimino =N-OH group directed toward the N1-H group (the form called further anti) and the second with the =N-OH group directed toward N3-H (syn), were observed in the ratio 1.4:1. The syn isomer is converted totally to the anti form after UV (lambda > 295 nm) irradiation of the matrix. A small amount of the N(3)H-hydroxy-amino tautomer of N2-hydroxyisocytosine was also detected in the matrix. This form did not react photochemically. For 1-methyl-N2-hydroxyisocytosine, only the syn form of the imino-oxo tautomer was observed after deposition of the matrix. UV (lambda > 295 nm) irradiation induced a photoreaction converting this isomer into the anti form. After 15% of the starting material had been converted into the product, a photostationary state was achieved, and no further progress of the reaction was observed. Subsequent UV irradiation (lambda > 335 nm) caused a back reaction, leading to a disappearance of the anti form and to the recovery of the initial syn isomer. All isomers were identified by comparing their experimental IR spectra with the spectra theoretically calculated at the DFT(B3LYP)/6-31G(d,p) level, where DFT is the density functional theory. Good agreement between the observed and predicted patterns of the spectral lines allowed for reliable identification. The experimental IR spectra were interpreted and discussed. The relative energies of the 12 isomers of N2-hydroxyisocytosine were calculated at the MP2/6-31G(d,p) and MP4//MP2/6-31G(d,p) levels. For six isomers of 1-methyl-N2-hydroxyisocytosine, the calculations were carried out at the MP2/6-31G(d,p) level. The anti form of the imino-oxo tautomer of N-hydroxyisocytosine and the syn form of the imino-oxo tautomer of 1-methyl-N2-hydroxyisocytosine were predicted to be the most stable.     

Solvatochromism of 3-[2-(aryl)benzoxazol-5-yl]alanine derivatives

The photophysical properties of N-Boc-3-[2-(9-anthryl)benzoxazol-5-yl]-l-alanine methyl ester (BoxAnt) and N-Boc-3-[2-[4-(9′-(10′-butyl)anthryl)phenyl]benzoxazol-5-yl]-l-alanine methyl ester (BoxPhAnt) were studied in a series of solvents. Their absorption spectra are less sensitive to the solvent polarity than the corresponding fluorescence spectra which show a pronounced solvatochromic effect leading to large Stokes shifts. Using an efficient solvatochromic method, based on the empirical solvent polarity parameter , a large change of the dipole moment on excitation for BoxPhAnt has been found. From an analysis of the solvatochromic behaviour of the absorption and fluorescence spectra in terms of bulk solvent polarity functions, f(_r, n) and g(n), a larger excited-state dipole moment (about 8 D, ψ = 56) was obtained for BoxPhAnt than for BoxAnt (about 3 D, ψ = 0). Both applied methods gave similar values of the excited-state dipole moments for both compounds studied.     

Discrete dynamical equations in Minkowski space

Discrete difference equations in Minkowski space are obtained and the discrete Minkowski force is shown to be a four-vector. A transformation from a discrete dynamical equation in Minkowski space to a Lorentz-invariant difference equation in one-dimensional space is given.     

High-spin levels in138Ce and140Nd Observed in the (α, 4n γ) reactions

Levels of¹³⁸Ce and¹⁴⁰Nd have been studied using the¹³⁸Ba(α,4nγ)¹³⁸Ce and¹⁴⁰Ce(α, 4nγ)¹⁴⁰Nd reactions. Singleγ-ray spectra,γ-γ coincidence spectra, angular and time distributions with respect to the beam bursts have been measured. A number of higher excited states with excitation energies up to about 5 MeV and with spin value up to 12 are populated in both nuclei. The lower states with spins and parities 7^?, 5^?, 6^? and 10⁺ can be explained by two-quasiparticle neutron configurations of the types (h _11/2 ^?1 ,d _3/2 ^?1 ) 7^? , (h _11/2 ^?1 ,S _1/2 ^?1 ) 5^?, 6^? and (h _11/2 ^?2 ) 10⁺. Several high-spin states observed in¹³⁸Ce and¹⁴⁰Nd can be explained qualitatively as four-quasiparticle states with two-proton-two-neutron configurations. The 3^? state at an energy of 2,137.4 keV is observed in¹³⁸Ce. The evidence for the existence of the low-lying 3^? states in¹⁴⁰Nd at 2,124.0 keV is discussed. Beside the known 9.6 ms (7^?) isomeric state in¹³⁸Ce another state at 3,538.5keV (10⁺) with a half life of about 200 ns has been observed. The observed levels in the¹³⁸Ce and¹⁴⁰Nd nuclei are compared with theoretical predictions using delta force interaction.     

A Simple Method for the Synthesis of the Sterically Hindered Chloramines

A simple route to the hindered chloramines, starting from the corresponding hindered amines is reported. Sodium dichlorisocyanurate is the chlorinating agent.     

Synthesis and Reactivity of Metallophosphanes

Abstract

Aspects of the reactivity of metallophosphanes are presented along with the synthesis and structure determinations for new aluminophosphanes.     

First application of CE-ICP-MS for monitoring the formation of cisplatin targeting delivery systems with gold nanocarriers

Cisplatin is a drug frequently used in chemotherapy of various types of tumors due to its strong cytostatic activity against cancer cells. However, this therapy is not free from severe side effects related to the nonselective action of the drug. The solution to this problem could be the application of drug-targeted delivery systems (DTDSs). Gold nanoparticles can be used in such systems as selective drug carriers, ensuring its transportation through the bloodstream to destination tissue. The method of DTDSs analysis providing qualitative and quantitative information about the formation of this conjugation is crucial to establish the kinetics of reaction and stoichiometry of reagents, which ensures the best drug binding rate. Moreover, the status of so far proposed techniques/methods dedicated to elaborating the course of DTDSs formation is preliminary and in majority guarantee only the confirmation of drug‒carrier conjugate formation. In this paper, we demonstrate the procedures of reagents’ preparation and cisplatin‒gold nanoparticles DTDS formation, which have a significant influence on the rate and stoichiometry of the reaction. We also present the novel application of CE-ICP-MS hyphenation for effective separation and online monitoring of all components of the reaction mixture.