Parahydrogen-Induced Hyperpolarization of Unsaturated Phosphoric Acid Derivatives.

Parahydrogen-induced nuclear polarization offers a significant increase in the sensitivity of NMR spectroscopy to create new probes for medical diagnostics by magnetic resonance imaging. As precursors of the biocompatible hyperpolarized probes, unsaturated derivatives of phosphoric acid, propargyl and allyl phosphates, are proposed. The polarization transfer to H and P nuclei of the products of their hydrogenation by parahydrogen under the ALTADENA and PASADENA conditions, and by the PH-ECHO-INEPT+ pulse sequence of NMR spectroscopy, resulted in a very high signal amplification, which is among the largest for parahydrogen-induced nuclear polarization transfer to the P nucleus.

Design of Conjugates Based on Sesquiterpene Lactones with Polyalkoxybenzenes by "Click" Chemistry to Create Potential Anticancer Agents.

Using the methodology of "click" chemistry, a singular method has been developed for the synthesis of unique conjugates based on sesquiterpene lactones: dehydrocostuslactone and alantolactone with polyalkoxybenzenes. To expand the structural range of the resulting conjugates, the length of the 1,2,3-triazole spacer was varied. For all synthesized compounds, the cytotoxic profile was determined on the cell lines of tumor origin (SH-SY5Y, HeLa, Hep-2, A549) and normal Hek 293 cells.

New Approach toward Dual-Emissive Organic-Inorganic Hybrids by Integrating Mn(II) and Cu(I) Emission Centers in Ionic Crystals.

Inorganic-organic hybrid luminescent materials have received great attention for their potential applications in a wide range of clean/renewable energy-related areas, including photovoltaics and solid-state lighting. Herein, we present a unique and general "Mn + Cu" approach by blending two earth-abundant luminogenic metals, manganese and copper, within a single ionic structure to construct a remarkable family of low-cost and multifunctional hybrid materials featuring dual emission, as well as triboluminescence and second-harmonic generation response. The novel hybrid materials are made of diphosphine dioxide-chelated [Mn(O∧O)] cations and various anionic [CuI] clusters, ensuring manifestation of dual phosphorescence streamed from octahedral Mn ions (605-648 nm) and iodocuprate anions (480-728 nm).

Conformational Analysis of -Alkyl--[2-(diphenylphosphoryl)ethyl]amides of Diphenylphosphorylacetic Acid: Dipole Moments, IR Spectroscopy, DFT Study.

Experimental and theoretical conformational analysis of -methyl--[2-(diphenylphosphoryl)ethyl]diphenylphosphorylacetamide, -butyl--[2-(diphenylphosphoryl)ethyl]diphenylphosphorylacetamide, and -octyl--[2-(diphenylphosphoryl)ethyl]diphenylphosphorylacetamide was carried out by the methods of dipole moments, IR spectroscopy, and Density Functional Theory (DFT) B3PW91/6-311++G(df,p) calculations. In solution, these ,-dialkyl substituted bisphosphorylated acetamides exist as a conformational equilibrium of several forms divided into two groups-with - or -configuration of the carbonyl group and alkyl substituent, and or arrangement of the phosphoryl-containing fragments relative to the amide plane. The substituents at the phosphorus atoms have eclipsed - or staggered -orientation relative to the P=O groups, and orientation of the substituents is due to the presence of intramolecular H-contacts P=O.

Synthesis and biological evaluation of indolylglyoxylamide bisphosphonates, antimitotic microtubule-targeting derivatives of indibulin with improved aqueous solubility.

Indibulin (D-24851) derivatives with bisphosphonate fragment connected to the N1 atom of imidazole ring were synthesized by alkylation of (indolyl-3)methylglyoxylates with ethylenebisphosphonate. Biological evaluation of targeted compounds 4a-d using the phenotypic sea urchin embryo assay provided evidence that replacing of p-chlorobenzene ring in indibulin by bisphosphonate group did not eliminate antimitotic microtubule destabilizing activity. The most active molecule, tetraacid 5a, at physiological pH formed tetrasodium salt 6a with aqueous solubility value of at least 10 mg/mL.

Synthesis of Camphecene and Cytisine Conjugates Using Click Chemistry Methodology and Study of Their Antiviral Activity.

A series of camphecene and quinolizidine alkaloid (-)-cytisine conjugates has been obtained for the first time using 'click' chemistry methodology. The cytotoxicity and virus-inhibiting activity of compounds were determined against MDCK cells and influenza virus A/Puerto Rico/8/34 (H1N1), correspondingly, in in vitro tests. Based on the results obtained, values of 50 % cytotoxic dose (CC ), 50 % inhibition dose (IC ) and selectivity index (SI) were determined for each compound.

Synthesis and antitumor activity of daunorubicin conjugates with of 3,4-methylendioxybenzaldehyde.

The design of hybrid (chimeric) molecules containing two different pharmacophores connected via a spacer (linker) is a promising approach to the functionalization of natural compounds and potentially of drug molecules. These are important examples for the use of this approach with anthracycline antibiotics. The use of this methodology may help to eliminate some of the drawbacks of anthracycline drugs, e.

Synthesis of camphecene derivatives using click chemistry methodology and study of their antiviral activity.

A series of seventeen tetrazole derivatives of 1,7,7-trimethyl-[2.2.1]bicycloheptane were synthesized using click chemistry methodology and characterized by spectral data.

Clathrochelates meet phosphorus. New thio- and phosphorylation reactions of an iron(II) dichloroclathrochelate precursor and preparation of its first phosphorus(III)-containing macrobicyclic derivative.

Phosphorylation reactions of an iron(II) dichloroclathrochelate FeBd2(Cl2Gm)(BF)2 (where Bd(2-) and Cl2Gm(2-) are α-benzildioxime and dichloroglyoxime dianions, respectively) with diphenylphosphine oxide and diethyl thiophosphite were performed under phase-transfer conditions. In the case of diethyl thiophosphite as a P-nucleophile, the best yields were obtained in the dichloromethane-50% NaOH aqueous solution-5 mol% triethylbenzylammonium chloride (TEBAC) system. The use of different molar ratios of a macrobicycle precursor and this thiophosphorylating agent allowed us to obtain both the mono- and the diphosphorylated cage complexes.

Clathrochelates meet phosphorus: thiophosphorylation of Fe(II) dichloroclathrochelate precursor, synthesis of N,S-donor macrobicyclic ligands and their Pd(II) complexes as potent catalysts of Suzuki cross-coupling reaction.

Nucleophilic substitution of an iron(ii) dichloroclathrochelate with diphenylphosphine sulfide under PTC afforded a monophosphorylated cage complex. This precursor undergoes further nucleophilic substitution with mono- and diamines giving P,N-substituted mono- and bis-clathrochelates; those with thiophosphoryl and pyridyl groups were used as N,S-donor macrobicyclic ligands toward the palladium(ii) ion. In the resulting Pd,Fe-binuclear 1 : 1 complexes, the clathrochelate moieties retain the geometry, characteristic of low-spin iron(ii) complexes, with a minor distortion caused by intramolecular interactions.

o-Semiquinonic PCP-pincer nickel complexes with alkyl substituents: versatile coordination sphere dynamics.

o-Semiquinonic nickel pincer complexes (R2PCP)Ni(SQ) show a versatile coordination sphere dynamics via "swing" or "fan" oscillations depending on the steric properties of the phosphorus substituents.