Peptidehelicenes in solution and gel: chiral discrimination through interactions between two types of helixes

Helical [5]thiaheterohelicene 5HM, which rapidly interconverts between P and M enantiomers in solution, was connected to helical l-phenylalanine oligomers with an ester linkage to give peptidehelicenes (5Fn, where n: number of bonded phenylalanines). The characteristics of 5F4 and 5F5 with two types of helixes in a molecule were investigated, particularly in comparison with those of 5F1–5F3 with an incomplete coil of a peptide moiety. l-Phenylalanine peptide chains induced a shift in the equilibrium between the P and M helixes of 5HM toward the P side for all the 5Fns examined. The enantiomeric excess (ee) of the P form increased with a decrease in temperature, together with an elongation of the peptide chains. 5F4 and 5F5 in hot solutions of some solvents formed a gel at room temperature, whereas 5F1–5F3 showed no such behavior. In this gel, the stable helical form of the 5HM moiety in 5F4 and 5F5 was observed to be the M form in contrast to that in their solutions.     

Preconcentration and determination of cadmium by GFAAS after solid-phase extraction with synthetic zeolite.

The solid-phase extraction (SPE) method for the preconcentration of trace amounts of cadmium using synthetic zeolite A-4 and its determination by graphite furnace atomic absorption spectrometry (GFAAS) was investigated. The preconcentration conditions, such as the optimum pH range of the sample solution for the adsorption of cadmium and the kind of acid solution for dissolving the cadmium-adsorbed synthetic zeolite A-4, as well as the measurement conditions for the determination of cadmium by GFAAS, e.g., the ashing and atomizing temperature, were investigated. Quantitative recovery of cadmium onto zeolite A-4 from the sample solution over the pH range 2.0 - 9.0 was achieved by the batch method. After the solid-phase (cadmium-adsorbed zeolite A-4) was separated from the sample solution by a membrane filter, it was dissolved in 2.0 cm(3) of 2.0 mol dm(-3) nitric acid. An aliquot of the resulting solution was injected into the graphite furnace. In GFAAS measurements an alternate gas (Ar, 90%; O(2), 10%) was used as a sheath gas, and the ashing temperature and atomizing temperature were 400 degrees C and 1600 degrees C, respectively. The detection limit (3 sigma) for cadmium was 0.002 microg dm(-3). The relative standard deviation at 0.010 microg dm(-3) was 3.5 - 4.5% (n = 5). The proposed method has been successfully applied to the analysis of trace cadmium in environmental water samples.     

Design and stereoselective synthesis of four peptide nucleic acid monomers with cyclic structures in backbone

Four isomers of the monomer of peptide nucleic acid (PNA) were derived from (2S,4R)‐4‐hydroxyproline; they had different stereochemistries at the C² and C⁴ positions in the pyrrolidine ring. These different backbone conformations corresponding to four different stereochemistries were realized through a combination of inversions at the C² and the C⁴ positions in pyrrolidine ring. The obtained backbone frameworks were reacted with N‐benzoyl thymine to give the corresponding PNA monomers. Spectroscopic comparison of the resultant monomers confirmed their stereochemistries. J. Heterocyclic Chem., (2011).     

Fibrin glue increases the cell survival and the transduced gene product secretion of the ceiling culture-derived adipocytes transplanted in mice

The development of clinically applicable scaffolds is important for the application of cell transplantation in various human diseases. The aims of this study are to evaluate fibrin glue in a novel protein replacement therapy using proliferative adipocytes and to develop a mouse model system to monitor the delivery of the transgene product into the blood and the fate of the transduced cells after transplantation. Proliferative adipocytes from mouse adipose tissue were transduced by a retroviral vector harboring the human lecithin-cholesterol acyltransferase (lcat) gene, and were subcutaneously transplanted into mice combined with fibrin glue. The lcat gene transduction efficiency and the subsequent secretion of the product in mouse adipocytes were enhanced using a protamine concentration of 500 μg/ml. Adipogenesis induction did not significantly affect the lcat gene-transduced cell survival after transplantation. Immunohistochemistry showed the ectopic enzyme production to persist for 28 days in the subcutaneously transplanted gene- transduced adipocytes. The increased viability of transplanted cells with fibrin glue was accompanied with the decrease in apoptotic cell death. The immunodetectable serum LCAT levels in mice implanted with the fibrin glue were comparable with those observed in mice implanted with Matrigel, indicating that the transplanted lcat gene-transduced adipocytes survived and functioned in the transplanted spaces with fibrin glue as well as with Matrigel for 28 days. Thus, this in vivo system using fibrin is expected to serve as a good model to further improve the transplanted cell/scaffold conditions for the stable and durable cell-based replacement of defective proteins in patients with LCAT deficiency.     

Influence of halogen substituents on the catalytic oxidation of 2,4,6-halogenated phenols by Fe(III)-tetrakis(p-hydroxyphenyl) porphyrins and potassium monopersulfate

The influence of halogen substituents on the catalytic oxidation of 2,4,6-trihalogenated phenols (TrXPs) by iron(III)-porphyrin/KHSO? catalytic systems was investigated. Iron(III)-5,10,15,20-tetrakis(p-hydroxyphenyl)porphyrin (FeTHP) and its supported variants were employed, where the supported catalysts were synthesized by introducing FeTHP into hydroquinone-derived humic acids via formaldehyde poly-condensation. F (TrFP), Cl (TrCP), Br (TrBP) and I (TrIP) were examined as halogen substituents for TrXPs. Although the supported catalysts significantly enhanced the degradation and dehalogenation of TrFP and TrCP, the oxidation of TrBP and TrIP was not enhanced, compared to the FeTHP catalytic system. These results indicate that the degree of oxidation of TrXPs is strongly dependent on the types of halogen substituent. The order of dehalogenation levels for halogen substituents in TrXPs was F > Cl > Br > I, consistent with their order of electronegativity. The electronegativity of a halogen substituent affects the nucleophilicity of the carbon to which it is attached. The levels of oxidation products in the reaction mixtures were analyzed by GC/MS after extraction with n-hexane. The most abundant dimer product from TrFP via 2,6-difluoroquinone is consistent with a scenario where TrXP, with a more electronegative halogen substituent, is readily oxidized, while less electronegative halogen substituents are oxidized less readily by iron(III)-porphyrin/KHSO? catalytic systems.     

Living cationic polymerization of vinyl ethers by electrophile/lewis acid initiating systems. XII. Phosphoric and phosphinic acids/zinc chloride initiating systems for isobutyl vinyl ether

Phosphoric and phosphinic acid derivatives (R¹R²PO₂H; R¹, R² = OPh, OPh; OnBu, OnBu; Ph, Ph; Ph, H) in conjunction with zinc chloride (ZnCl₂) led to living cationic polymerization of isobutyl vinyl ether (IBVE) in toluene below 0°C. The number-average molecular weights (M?_n) of the polymers (M?_n > 2 × 10⁴) were directly proportional to monomer conversion and in excellent agreement with the calculated values assuming that one polymer chain forms per R¹R²PO₂H molecule. Throughout the reaction, the molecular weight distributions (MWDs) stayed narrow (M?_w/M?_n ? 1.1). A dibasic acid, PhOP (O) (OH)₂, coupled with ZnCl₂, also induced living cationic polymerization of IBVE where one molecule of the acid generated two living polymer chains. The polymerization by (PhO)₂PO₂H/ZnCl₂ and its model reactions were directly analyzed by ³¹P and ¹H-NMR spectroscopy. The analysis showed that the acid initially forms the adduct [CH₃CH(OiBu)OP(O)(OPh)₂], the phosphate linkage of which is in turn activated by ZnCl₂ so as to initiate living propagation. The finding thus indicates that (PhO)₂PO₂H indeed acts as an initiator in the living polymerization. The NMR analysis also suggested that an exchange reaction occurs between the phosphate group at the polymer terminal and the chlorine in ZnCl₂. The occurrence of living IBVE polymerization with these various R¹R²PO₂H/ZnCl₂ systems shows that phosphoric and phosphinic acids are another general class of protonic acids which are effective initiators for the living cationic polymerization assisted by Lewis acids. © 1993 John Wiley & Sons, Inc.     

Crystal structure of 7,8-dihydroxy-4-methylcoumarin.

The structure of 7,8-dihydroxy-4-methylcoumarin was determined by an X-ray diffraction method. The compound crystallized in the triclinic space group P1, Z = 2, with a = 7.631(2), b = 9.456(5), c = 7.075(3)A, alpha = 103.13(3), beta = 91.84(3), gamma= 68.21(3) degrees, and V= 460.9(3)A3. The X-ray crystal structure was also compared with those of 5,7-dihydroxy-4-methylcoumarin and 7-hydroxy-4-methylcoumarin.     

Reaction of O6-methylguanosine with nitrite in the presence of carboxylic acid: synthesis of the purin-2-yl carboxylate

O6-Methylguanosine derivative was treated with sodium nitrite or isoamylnitrite in the presence of carboxylic acid to give the purin-2-yl carboxylate, an unusual product bearing a carboxylic group at the 2-position of the purine moiety.