Search results for "Epoxy Compounds"
showing 10 items of 77 documents
Epoxidation of benzo[a]pyrene-7,8-dihydrodiol by human CYP1A1 in reconstituted membranes. Effects of charge and nonbilayer phase propensity of the me…
2002
Human cytochrome P4501A1 (CYP1A1) is one of the key enzymes in the bioactivation of environmental pollutants such as benzo[a]pyrene (B[a]P) and other polycyclic aromatic hydrocarbons. To evaluate the effect of membrane properties and distinct phospholipids on the activity of human CYP1A1 purified insect cell-expressed human CYP1A1 and of human NADPH-P450 reductase were reconstituted into phospholipid vesicle membranes. Conversion rates of up to 36 pmol x min(-1) x pmol(-1) CYP1A1 of the enantiomeric promutagens (-)- and (+)-trans-7,8-dihydroxy-7,8-dihydro-B[a]P (7,8-diol) to the genotoxic diolepoxides were achieved. The highest rates were obtained when negatively charged lipids such as phos…
Controlled Synthesis of Multi-Arm Star Polyether-Polycarbonate Polyols Based on Propylene Oxide and CO2
2013
Multi-arm star copolymers based on a hyperbranched poly(propylene oxide) polyether-polyol (hbPPO) as a core and poly(propylene carbonate) (PPC) arms are synthesized in two steps from propylene oxide (PO), a small amount of glycidol and CO2 . The PPC arms are prepared via carbon dioxide (CO2 )/PO copolymerization, using hbPPO as a multifunctional macroinitiator and the (R,R)-(salcy)CoOBzF5 catalyst. Star copolymers with 14 and 28 PPC arms, respectively, and controlled molecular weights in the range of 2700-8800 g mol(-1) are prepared (Mw /Mn = 1.23-1.61). Thermal analysis reveals lowered glass transition temperatures in the range of -8 to 10 °C for the PPC star polymers compared with linear …
Aminal Protection of Epoxide Monomer Permits the Introduction of Multiple Secondary Amine Moieties at Poly(ethylene glycol).
2019
In contrast to acetal groups, aminal moieties are almost unknown in polymer chemistry. The aminal-protected isopropyl-hexahydro-pyrimidine glycidyl amine (PyGA) for the anionic ring-opening polymerization (AROP) is introduced. The monomer is prepared in a two-step synthesis and can be polymerized in a well-controlled manner under AROP conditions. Several poly(ethylene glycol) block and triblock copolymers are synthesized in a molecular weight range from 2 700 to 11 400 g mol-1 with up to 11 mol% PyGA. The molecular weight distributions are monomodal with low dispersity (Đ = Mw /Mn ) below 1.2. After the polymerization, the acid-labile hexahydro-pyrimidine rings can be conveniently cleaved i…
Maleimide Glycidyl Ether: A Bifunctional Monomer for Orthogonal Cationic and Radical Polymerizations.
2015
A novel bifunctional monomer, namely maleimide glycidyl ether (MalGE), prepared in a four-step reaction sequence is introduced. This monomer allows for selective (co)polymerization of the epoxide group via cationic ring-opening polymerization, preserving the maleimide functionality. On the other hand, the maleimide functionality can be copolymerized via radical techniques, preserving the epoxide moiety. Cationic ring-opening multibranching copolymerization of MalGE with glycidol was performed, and a MalGE content of up to 24 mol% could be incorporated into the hyperbranched polymer backbone (Mn = 1000-3000 g mol(-1)). Preservation of the maleimide functionality during cationic copolymerizat…
Universal Concept for the Implementation of a Single Cleavable Unit at Tunable Position in Functional Poly(ethylene glycol)s
2013
Poly(ethylene glycol) (PEG) with acid-sensitive moieties gained attention particularly for various biomedical applications, such as the covalent attachment of PEG (PEGylation) to protein therapeutics, the synthesis of stealth liposomes, and polymeric carriers for low-molecular-weight drugs. Cleavable PEGs are favored over their inert analogues because of superior pharmacodynamic and/or pharmacokinetic properties of their formulations. However, synthetic routes to acetal-containing PEGs published up to date either require enormous efforts or result in ill-defined materials with a lack of control over the molecular weight. Herein, we describe a novel methodology to implement a single acetalde…
Multifunctional Fe(III)-Binding Polyethers from Hydroxamic Acid-Based Epoxide Monomers.
2019
Multiple hydroxamic acids are introduced at poly(ethylene glycol) (PEG) via copolymerization of ethylene oxide with a novel epoxide monomer containing a 1,4,2-dioxazole-protected hydroxamic acid (HAAGE). AB- and ABA-type di- and triblock copolymers as well as statistical copolymers of HAAGE and ethylene oxide are prepared in a molecular weight range between 2600 and 12 000 g mol-1 with low dispersities (Ð < 1.2). Cleavage of the acetal protecting group after the polymerization is achieved by mild acidic treatment, releasing multiple free hydroxamic acids tethered to the polyether backbone. The chelation properties of different polymer architectures (statistical versus diblock and ABA triblo…
Cationic Copolymerization of 3,3-Bis(hydroxymethyl)oxetane and Glycidol: Biocompatible Hyperbranched Polyether Polyols with High Content of Primary H…
2015
The cationic ring-opening copolymerization of 3,3-bis(hydroxymethyl)oxetane (BHMO) with glycidol using different comonomer ratios (BHMO content from 25 to 90%) and BF3OEt2 as an initiator has been studied. Apparent molecular weights of the resulting hyperbranched polyether copolymers ranged from 1400 to 3300 g mol(-1) (PDI: 1.21-1.48; method: SEC, linear PEG standards). Incorporation of both comonomers is evidenced by MALDI-TOF mass spectroscopy. All hyperbranched polyether polyols with high content of primary hydroxyl groups portray good solubility in water, which correlates with an increasing content of glycerol units. Detailed NMR characterization was employed to elucidate the copolymer …
Influence of the polymerization step alone on oxygen affinity and cooperativity during production of hyperpolymers from native hemoglobins with cross…
1994
The aim of this study was to find out how the polymerization per se changes oxygen affinity (P50) and cooperativity (n50) of various soluble huge hyperpolymers prepared from native hemoglobins by crosslinking. Increase of cooperativity would be expected considering natural hemoglobin networks. Those hyperpolymers with molecular weights of some 10(6) g/mol are candidates for artificial oxygen-carrying blood additives rather than volume substitutes. Human and bovine hemoglobin reacted with several crosslinkers (2,5-diisothiocyanatobenzenesulfonate (DIBS); 4,4'-diisothiocyanatostilbene-2, 2'-disulfonate (DIDS); 1,3-butadiene diepoxide (BUDE); glutaraldehyde (GDA)) in concentrated (case 1) and …
Some substrates and inhibitors of cytosolic epoxide hydrolase induce sister-chromatid exchanges in mammalian cells, but do not induce gene mutations …
1993
Abstract Trans -stilbene oxide, trans -β-methylstyrene, 7,8-oxide, trans -β-ethylstyrene, 7,8-oxide, trans -β-propylstyrene 7,8-oxide and 4-fluorochalcone oxide were investigated for genotoxic activity in bacterial and mammalian cells, in the absence of external xenobiotic-metabolising systems. All compounds strongly enhanced the frequency of sister-chromatid exchanges (SCE) in cultured human lymphocytes. None of them was mutagenic in Salmonella typhimurium (reversion of the his − strains TA98, TA100 and TA104). The limit of detection was 1 20,000 to 1 10 6 of the activity of the positive control, benzo[ a ]pyrene 4,5-oxide, depending on the compound and the bacterial strain. Trans -β-methy…
Synthesis, Absolute Configuration, and Bacterial Mutagenicity of the 8 Stereoisomeric Vicinal Diol Epoxides at the Terminal Benzo Ring of Carcinogeni…
2011
The synthesis of the 8 possible stereoisomeric diol epoxides (DEs) at the terminal benzo ring of carcinogenic dibenz[a,h]anthracene (DBA) is reported. trans-3,4-Dihydroxy-3,4-dihydro-DBA (1) afforded the 4 bay region DEs: the enantiomeric pairs of the anti diastereomers (+)-3/(-)-3 and of the syn diastereomers (-)-4/(+)-4, respectively. trans-1,2-Dihydroxy-1,2-dihydro-DBA (2) served as precursor of the 4 reverse DEs: the enantiomeric pairs of the anti diastereomers (+)-5/(-)-5 and of the syn diastereomers (-)-6/(+)-6, respectively. The transformation of the olefinic double bond in the enantiomeric trans-dihydrodiols to epoxides was achieved by either (i) oxidation with m-chloroperoxybenzoic…