Ratiometric Detection of ATP by Fluorescent Cyclophanes with Bellows-Type Sensing Mechanism

Pyrene-based cyclophanes have been synthesized with the aim to realize a bellows-type sensing mechanism for the ratiometric detection of nucleotide concentrations in a buffered aqueous solution. The sensing mechanism involves the encapsulation of a nucleobase between two pyrene rings, which affects the monomer-excimer equilibrium of the receptor in the excited state. The nature of the spacer and its connection pattern to pyrene rings have been varied to achieve high selectivity for ATP. The 1,8-substituted pyrene-based cyclophane with the 2,2’-diaminodiethylamine spacer demonstrates the best selectivity for ATP showing a 50-fold increase in the monomer-excimer emission ratio upon saturation with the nucleotide. The receptor can detect ATP within the biological concentrations range over a wide pH range. NMR and spectroscopic studies have revealed the importance of hydrogen bonding and stacking interactions for achieving a required receptor selectivity. The probe has been successfully applied for the real-time monitoring of creatine kinase activity.     

Probing the Roughness of Porphyrin Thin Films with X-ray Photoelectron Spectroscopy

Thin-film growth of molecular systems is of interest for many applications, such as for instance organic electronics. In this study, we demonstrate how X-ray photoelectron spectroscopy (XPS) can be used to study the growth behavior of such molecular systems. In XPS, coverages are often calculated assuming a uniform thickness across a surface. This results in an error for rough films, and the magnitude of this error depends on the kinetic energy of the photoelectrons analyzed. We have used this kinetic-energy dependency to estimate the roughnesses of thin porphyrin films grown on rutile TiO₂(110). We used two different molecules: cobalt (II) monocarboxyphenyl-10,15,20-triphenylporphyrin (CoMCTPP), with carboxylic-acid anchor groups, and cobalt (II) tetraphenylporphyrin (CoTPP), without anchor groups. We find CoMCTPP to grow as rough films at room temperature across the studied coverage range, whereas for CoTPP the first two layers remain smooth and even; depositing additional CoTPP results in rough films. Although, XPS is not a common technique for measuring roughness, it is fast and provides information of both roughness and thickness in one measurement.     

First macrocycle based on chlorin and isosteviol structural elements

Acylation by suberic acid chloride of chlorin with two oximated isosteviol groups on its periphery produced for the first time a macrocyclic system containing a porphyrin ring and two tetracyclic ent-beyerane frameworks.     

An unusual reaction of cyclopropenylphosphonium bromide with sodium polyphosphides – A novel approach to sodium 3,4,5-triphenyl-1,2-diphosphacyclopentadienide

1,2,3-Triphenylcyclopropenylphosphonium bromide reacts with sodium polyphosphides to give sodium 3,4,5-triphenyl-1,2-diphosphacyclopentadienide in high yield.     

Spin gap in the zigzag spin-1/2 chain cuprate Sr(0.9)Ca(0.1)CuO(2)

We report a comparative study of (63)Cu nuclear magnetic resonance spin lattice relaxation rates T(1)(-1) on undoped SrCuO(2) and Ca-doped Sr(0.9)Ca(0.1)CuO(2) spin chain compounds. A temperature independent T(1)(-1) is observed for SrCuO(2) as expected for an S=1/2 Heisenberg chain. Surprisingly, we observe an exponential decrease of T(1)(-1) for T<90 K in the Ca-doped sample evidencing the opening of a spin gap. The data analysis within the J(1)-J(2) Heisenberg model employing density-matrix renormalization group calculations suggests an impurity driven small alternation of the J(2)-exchange coupling as a possible cause of the spin gap.     

The reaction of selenium with phenylacetylene

The reaction of selenium with phenylacetylene in the presence of sodium ethoxide in boiling dioxane has given 2, 5-diphenyl-1, 4-diselenacyclohexa-2, 5-diene, whose molecules have the boat conformation.     

First conjugate of glucuronic acid with triterpenoid dihydrobetulin

Russian Journal of General Chemistry - 3β-O-Acetyl-28-O-succinyl-(2,3,4-tri-O-acetyl-5-methoxycarbonyl-β-D-glucopyranosyl)dihydrobetulin was synthesized.     

The Inclusion Properties of a New Watersoluble Sulfonated Calix[4]resorcinarene towards Alkylammonium and N-Methylpyridinium Cations

The inclusion behaviour of a new water-soluble sulfonated calix[4]resorcinarene towards alkylammonium and N-methylpyridinium cations has been investigated on the basis of ¹H NMR spectroscopy and pH-potentiometry data. The inclusion of the N-methylpyridinium cation has been found to be dependent on pH with the preferable inclusion of the methyl substituent in alkaline and the aromatic ring in neutral aqueous media.     

Synthesis and antituberculosis activity of derivatives of the diterpenoid isosteviol with azine,hydrazide, and hydrazone moieties

Derivatives of the diterpenoid isosteviol (16-oxo-ent-beyeran-19-oic acid) with azine, hydrazone, and hydrazide moieties were synthesized. They exhibited high tuberculostatic activity in vitro against the strain Mycobacterium tuberculosis H₃₇R_V (minimum inhibiting concentration in the range 6.3–1.7 μg/mL).