Nucleic acid related compounds. 114. Synthesis of 2,6‐(disubstituted)purine 2′,3′‐dideoxynucleosides and selected cytotoxic,anti‐hepatitis b,and adenosine deaminase substrate activities

Selected 2,6‐(disubstituted)purine 2′,3′‐didehydro‐2′,3′‐dideoxynucleosides and 2′,3′‐dideoxynucleosides were prepared and evaluated. Treatment of 5′‐protected ribonucleosides with phenoxythiocarbonyl chloride and 4‐(dimethylamino)pyridine, or under Schotten‐Baumann conditions, gave high yields of 2′,3′‐O‐thiono‐carbonates that underwent Corey‐Winter elimination. Treatment of unprotected ribonucleosides with α‐ace‐toxyisobutyryl bromide in “moist” acetonitrile gave trans 2′,3′‐bromohydrin acetate mixtures that underwent reductive elimination with zinc‐copper couple or zinc/acetic acid. Catalytic hydrogenation of the resulting 2′,3′‐enes gave 2′,3′‐dideoxynucleosides. Treatment of the 2‐amino‐6‐chloropurine and 6‐amino‐2‐fluoro‐purine derivatives with nucleophiles gave 2,6‐(disubstituted)purine 2′,3′‐dideoxynucleosides. 2′,3′‐Dideoxyguanosine and the 2‐amino‐6‐[amino ( 16d ), methoxy ( 16b ), ethoxy ( 16c ), and methylamino ( 16j )]purine 2′,3′‐dideoxynucleosides showed good anti‐hepatitis B activity with infected primary duck hepatocytes. Cytotoxic effects with selected analogues were evaluated in human T‐lymphoblastic and promyelocytic leukemia cell lines. The 2‐amino‐6‐fluoro derivative 16m was the most cytotoxic of the 2‐amino‐6‐(substituted)purine 2′,3′‐dideoxynucleosides, and 2‐fluoro‐2′,3′‐dideoxyadenosine ( 21a ) was the most cytotoxic compound. The order of efficiency of hydrolysis of the 6‐substituent from 2‐amino‐6‐(sub‐stituted)purine 2′,3′‐dideoxynucleosides (V_max/K_m) with adenosine deaminase from calf intestine was: 2‐amino‐6‐[amino ( 16d ) > methoxy ( 16b ) > ethoxy ( 16c )], all of which were ≤3% of the efficiency with adenosine. The 6‐methylamino derivative 16j , as well as 16b , 16c , and 16d were readily converted into 2′,3′‐dideoxyguanosine by duck cell supernatants.     

Effect of Ester Moiety on Structural Properties of Binary Mixed Monolayers of Alpha-Tocopherol Derivatives with DPPC

Phospholipid membranes are ubiquitous components of cells involved in physiological processes; thus, knowledge regarding their interactions with other molecules, including tocopherol ester derivatives, is of great importance. The surface pressure–area isotherms of pure α-tocopherol (Toc) and its derivatives (oxalate (OT), malonate (MT), succinate (ST), and carbo analog (CT)) were studied in Langmuir monolayers in order to evaluate phase formation, compressibility, packing, and ordering. The isotherms and compressibility results indicate that, under pressure, the ester derivatives and CT are able to form two-dimensional liquid-condensed (LC) ordered structures with collapse pressures ranging from 27 mN/m for CT to 44 mN/m for OT. Next, the effect of length of ester moiety on the surface behavior of DPPC/Toc derivatives’ binary monolayers at air–water interface was investigated. The average molecular area, elastic modulus, compressibility, and miscibility were calculated as a function of molar fraction of derivatives. Increasing the presence of Toc derivatives in DPPC monolayer induces expansion of isotherms, increased monolayer elasticity, interrupted packing, and lowered ordering in monolayer, leading to its fluidization. Decreasing collapse pressure with increasing molar ratio of derivatives indicates on the miscibility of Toc esters in DPPC monolayer. The interactions between components were analyzed using additivity rule and thermodynamic calculations of excess and total Gibbs energy of mixing. Calculated excess area and Gibbs energy indicated repulsion between components, confirming their partial mixing. In summary, the mechanism of the observed phenomena is mainly connected with interactions of ionized carboxyl groups of ester moieties with DPPC headgroup moieties where formed conformations perturb alignment of acyl chains, resulting in increasing mean area per molecule, leading to disordering and fluidization of mixed monolayer.     

Polycondensation of diglycerol with H3PO4. Reversibly degradable gels giving multireactive,highly branched macromolecules

Polycondensation of H₃PO₄ with diglycerol (DGL) involves biobased, commercial products and leads, via hydrolyzable gels, to highly branched reactive macromolecules. These reactive macromolecules have been applied as multiacidic catalysts with hydroxyl groups in polymerization of l ‐lactide, consuming entirely the starting highly branched macromolecules. Polycondensation was performed in bulk, at 110–120 °C with efficient elimination of water under vacuum. The process with DGL differs substantially from the previously studied polycondensation with ethylene glycol and glycerol. Formation of pyrophosphoric acid (PY) constitutes the rate determining step: the rate of PY formation is the same in the absence and presence of DGL. Kinetic studies explained why the rate of monoesters (M) accumulation may be the same as the rate of accumulation of di‐ (D), and triesters (T). This is because the rate of M formation is relatively low when compared with rates of further reactions of M, leading to D and T. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3303–3317     

S-adenosylhomocysteine analogues with the carbon-5' and sulfur atoms replaced by a vinyl unit

Cross-metathesis of suitably protected 5'-deoxy-5'-methyleneadenosines with racemic and chiral N-Boc-protected six-carbon amino acids bearing a terminal double bond in the presence of the Hoveyda-Grubbs catalyst gave adenosylhomocysteine analogues with the C5'-C6' double bond. Bromination with pyridinium tribromide and dehydrobromination with DBU followed by standard deprotections yielded the 5'-(bromo)vinyl analogue. [structure: see text]     

Polymer Nano- and Microparticle Based Systems for Medical Diagnostics

Summary: Synthesis, properties and medical diagnostic applications of hydrophilic nano- and microspheres with carboxyl, aldehyde and hydroxyl groups on their surface are described. The particles were obtained by emulsion copolymerization of styrene, acrolein, methyl methacrylate, methacrylic acid, and 2-hydroxyethyl methacrylate carried on in water media and initiated with potassium persulfate. Stabilization of particles' suspensions was provided by addition of sodium dodecyl sulfate to polymerizing mixture or by formation of surfactants in situ in copolymerization involving acrolein or α-tert-butoxy-ω-vinylbenzyl-polyglycidol macromonomer (PGL). Relations between interfacial properties of these particles and their ability for covalent immobilization of proteins, with eliminated or at least reduced nonspecific adsorption of these species were investigated. The particles with covalently attached proteins (antigens or antibodies) were used for preparation of diagnostic tests based on visual or turbidimetric observation of particles' aggregation or by monitoring changes in their electrophoretic mobility accompanying specific antigen (or antibody) binding. The later test was directed toward determination of antibodies against Helicobacter pylori. Principle of a new type of diagnostic test based on photonic crystals of microspheres are described.     

Benchtop 19F NMR spectroscopy as a practical tool for testing of remedial technologies for the degradation of perfluorooctanoic acid,a persistent organic pollutant

The development of effective remedial technologies for the destruction of environmental pollutants requires the ability to clearly monitor degradation processes. Nuclear magnetic resonance (NMR) spectroscopy is a powerful tool for understanding reaction progress; however, practical considerations often restrict the application of NMR spectroscopy as a tool to better understand the degradation of environmental pollutants. Chief among these restrictions is the limited access smaller environmental research labs and remediation companies have to suitable NMR facilities. Benchtop NMR spectroscopy is a low-cost and user-friendly approach to acquire much of the same information as conventional nuclear magnetic resonance (NMR) spectroscopy, albeit with reduced sensitivity and resolution. This paper explores the practical application of benchtop NMR spectroscopy to understand the degradation of perfluorooctanoic acid using sodium persulfate, a common reagent for the destruction of groundwater contaminants. It is found that Benchtop ¹⁹F NMR spectroscopy is able to monitor the complete degradation of perfluorooctanoic acid into fluoride; however, the observation of intermediate degradation products formed, which can be observed using a conventional NMR spectrometer, cannot be readily distinguished from the parent compound when measurements are performed using the benchtop instrument. Under certain reaction conditions, the formation of fluorinated structures that are resistant to further degradation is readily observed. Overall, it is shown that benchtop ¹⁹F NMR spectroscopy has potential as a quick and reliable tool to assist in the development of remedial technologies for the degradation of fluorinated contaminants.     

Complexes of heteroscorpionate trispyrazolylborate ligands. Part XI. Weak CH/π interactions in crystals of hydrotris(3-phenylpyrazolyl)boratothallium(I) and hydrobis(5-methyl-3-phenylpyrazolyl)(3,5-dimethylpyrazol-yl)boratothallium(I) studied by X-ray crystallography

Thallium(I) complexes of heteroscorpionate hydrobis(3-phenyl-5-methylpyrazolyl)(3,5-dimethylpyrazol-yl)borate and hydrotris(3-phenylpyrazol-1-yl)borate were studied crystallographically. Both ligands were coordinated in κ³ fashion via N₂ atoms of pyrazol-1-yl moieties. Both compounds crystallize as centrosymmetric dimers in which weak CH/π intra- and interdimer interactions are responsible for arrangement in crystal structure.     

Carbon-mineral adsorbents prepared by pyrolysis of waste materials in the presence of tetrachloromethane

Natural bentonite spent in the process of plant oil bleaching was used as an initial material for preparation of carbon-mineral adsorbents. The spent bleaching earth was treated using four procedures: T (thermal treatment); H (hydrothermal treatment); C (thermal treatment with addition of CCl4 vapor); M (modification of porous structure). Raw bentonite, RB (raw bleaching earth), and carbon materials prepared using plant oil were compared. The physicochemical characteristics of the adsorbents were determined using different methods: nitrogen adsorption/desorption, XRD, TEM, and MS-TPD. Carbon-mineral adsorbents contain from 5.23 to 19.92% C (w/w) and carbon adsorbents include from 84.2 to 91.18% C (w/w). Parallel processes of organic substance carbonization, porous structure modification, sublimation or evaporation of metal chlorides, and removal of hydrogen chloride take place during pyrolysis of waste mineral materials in the CCl4 atmosphere.     

The influence of side branches on the structure of crystalline phase in ethylene-1-alkene copolymers

The influence of side branches on the unit cell dimensions in ethylene-1-alkene copolymers was investigated both at room temperature as well as during heating of the samples up to melting. Time resolved X-ray diffraction investigations revealed that in the case of ethylene-1-octene copolymers with low and moderate comonomer content, the transversal expansion of the unit cell occurs due to the limited thickness of lamellae, however the samples with higher comonomer content (above 5 mol %) exhibit distinctly larger expansion resulting from the stresses imparted on the basal surfaces of crystals by the excluded branches. At high temperatures, independently on the thermal expansion, an additional increase of the unit cell volume occurs, caused probably by a penetration of the end-parts of side branches, residing near the crystals surface, into the surface cells. Similar phenomenon is observed for ethylene-1-butene copolymer. On contrary, the ratio of the average unit cell volume in ethylene-1-propene copolymer to the unit cell volume in linear polyethylene at the same temperature, decreases starting from about 50 °C. Such a behavior is a new confirmation of a partial inclusion of methyl branches into the crystalline phase. Most probably, when the temperature increases, the volume of included branch becomes a decreasing fraction of the thermally expanding unit cell volume.