Mechanische und thermische Eigenschaften von mit Borax vernetztem Polyvinylalkohol

Ohne Zusammenfassung     

Stoichiometric and catalytic oxidations with hypervalent organo-lambda3-iodanes

Isolation, characterization, and reaction of the activated iodosylbenzene monomer, hydroxy(phenyl)iodonium ion, as a complex with 18-crown-6 (18C6) are reported. The reaction of iodosylbenzene with HBF(4) in the presence of 18C6 afforded the hydroxy-lambda(3)-iodane complex PhI(OH)BF(4).18C6 as stable yellow prisms. X-ray structure analysis indicated that the close contacts between the iodine(III) and the three adjacent oxygen atoms of 18C6 will be responsible for the increased stability of the complex compared to the uncomplexed PhI(OH)BF(4). The aqua complex of the activated iodosylbenzene, PhI(OH)OTf.18C6.H(2)O, with a water molecule coordinated to iodine(III) was also prepared. These crown ether complexes are highly reactive and serve as versatile stoichiometric oxidants, especially in water. Thus, the complexes undergo oxidative transformations of a variety of functional groups such as olefins, alkynes, enones, silyl enol ethers, sulfides, and phenols under mild conditions. The latter part reports on the iodobenzene-catalyzed alpha-oxidation of ketones, in which diacyloxy(phenyl)-lambda(3)-iodanes generated in situ act as real oxidants of ketones and m-chloroperbenzoic acid (m-CPBA) serves as a terminal oxidant. The oxidation of a ketone with m-CPBA in acetic acid in the presence of a catalytic amount of iodobenzene, BF(3)-Et(2)O, and water at room temperature affords an alpha-acetoxy ketone in good yield. It is noted that the use of water and BF(3)-Et(2)O is crucial to the success of this alpha-acetoxylation.     

Development of 14-epi-19-nortachysterol and its unprecedented binding configuration for the human vitamin D receptor

In the study of the synthesis of 14-epi-19-norprevitamin D(3), we found 14-epi-19-nortachysterol derivatives through C6,7-cis/trans isomerization. We also succeeded in their chemical synthesis and revealed their marked stability and potent VDR binding affinity. To the best of our knowledge, this is the first isolation of stable tachysterol analogues. Surprisingly, 14-epi-19-nortachysterol derivatives exhibited an unprecedented binding configurations for the ligand binding pocket in hVDR, C5,6-s-trans and C7,8-s-trans triene configurations, which were opposite the natural C7,8-ene-configuration of 1α,25(OH)(2)D(3).     

Chemoenzymatic synthesis and Fcγ receptor binding of homogeneous glycoforms of antibody Fc domain. Presence of a bisecting sugar moiety enhances the affinity of Fc to FcγIIIa receptor

Structurally well-defined IgG-Fc glycoforms are highly demanded for understanding the effects of glycosylation on an antibody's effector functions. We report in this paper chemoenzymatic synthesis and Fcγ receptor binding of an array of homogeneous IgG-Fc glycoforms. The chemoenzymatic approach consists of the chemical synthesis of defined N-glycan oxazolines as donor substrates, the expression of the Fc domain in a CHO cell line in the presence of an α-mannosidase inhibitor kifunensine, and an endoglycosidase-catalyzed glycosylation of the deglycosylated Fc domain (GlcNAc-Fc homodimer) with the synthetic glycan oxazolines. The enzyme from Arthrobacter protophormiae (Endo-A) was found to be remarkably efficient to take various modified N-glycan core oxazolines, including the bisecting sugar-containing derivatives, for Fc glycosylation remodeling, resulting in the formation of the corresponding homogeneous Fc glycoforms. Nevertheless, neither Endo-A nor the Mucor hiemalis endoglycosidase mutants (EndoM-N175A and EndoM-N175Q) were able to transfer full-length complex-type N-glycan to the Fc domain, implicating the limitations of these two enzymes in Fc glycosylation remodeling. Surface plasmon resonance (SPR) binding studies with the synthetic IgG-Fc glycoforms unambiguously proved that the presence of a bisecting GlcNAc moiety could significantly enhance the binding of Fc to FcγRIIIa, the activating Fcγ receptor, independent of Fc core-fucosylation. Interestingly, the Fc glycoforms carrying an unusual bisecting sugar moiety such as a mannose or a LacNAc moiety also demonstrated enhanced affinity to FcγRIIIa. On the orther hand, the presence of a bisecting GlcNAc or core-fucosylation had little effect on the affinity of Fc to the inhibitory Fcγ receptor, FcγRIIb. Our experimental data also showed that the α-linked mannose residues in the pentasaccharide Man3GlcNAc2 core was essential to maintain a high affinity of Fc to both FcγRIIIa and FcγRIIb. The synthetic homogeneous Fc glycoforms thus provide a useful tool for elucidating how a fine Fc N-glycan structure precisely affects the function of the Fc domain.     

Weakly nucleophilic conjugate bases of superacids as powerful nucleophiles in vinylic bimolecular nucleophilic substitutions of simple β-alkylvinyl(aryl)-λ3-bromanes

We report herein, for the first time, the stereoselective synthesis of simple (E)-β-alkylvinyl(aryl)-λ(3)-bromanes via a boron-λ(3)-bromane exchange reaction and their unique bimolecular nucleophilic substitutions at the vinylic ipso carbon atom under mild conditions. Interestingly, even weakly nucleophilic anions such as conjugate bases of superacids (HBF(4), TfOH, Tf(2)CH(2), Tf(3)CH, Tf(2)NH, etc.) function as nucleophiles toward the vinyl-λ(3)-bromanes. For instance, the vinylic S(N)2 reaction of (E)-vinyl-λ(3)-bromanes with potassium bis(triflyl)methanide stereoselectively produced (Z)-vinyloxy oxosulfonium ylides with exclusive inversion of configuration via oxygen attack, while that with potassium bis(triflyl)imide afforded predominantly (Z)-vinyloxysulfoximines. In marked contrast, (E)-β-alkylvinyl-λ(3)-iodanes do not undergo the vinylic S(N)2 reaction with these conjugate bases of superacids. The differences between the nucleofugalities of aryl-λ(3)-iodanyl and aryl-λ(3)-bromanyl groups (the latter being greater) probably play a pivotal role in these unique reactions.     

Environmental analysis of chlorinated and brominated polycyclic aromatic hydrocarbons by comprehensive two-dimensional gas chromatography coupled to high-resolution time-of-flight mass spectrometry

A method for the analysis of chlorinated and brominated polycyclic aromatic hydrocarbon (Cl-/Br-PAHs) congeners in environmental samples, such as a soil extract, by comprehensive two-dimensional gas chromatography coupled to a high resolution time-of-flight mass spectrometry (GC×GC-HRTOF-MS) is described. The GC×GC-HRTOF-MS method allowed highly selective group type analysis in the two-dimensional (2D) mass chromatograms with a very narrow mass window (e.g. 0.02Da), accurate mass measurements for the full mass range (m/z 35-600) in GC×GC mode, and the calculation of the elemental composition for the detected Cl-/Br-PAH congeners in the real-world sample. Thirty Cl-/Br-PAHs including higher chlorinated 10 PAHs (e.g. penta, hexa and hepta substitution) and ClBr-PAHs (without analytical standards) were identified with high probability in the soil extract. To our knowledge, highly chlorinated PAHs, such as C(14)H(3)Cl(7) and C(16)H(3)Cl(7), and ClBr-PAHs, such as C(14)H(7)Cl(2)Br and C(16)H(8)ClBr, were found in the environmental samples for the first time. Other organohalogen compounds; e.g. polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCNs), and polychlorinated dibenzofurans (PCDFs) were also detected. This technique provides exhaustive analysis and powerful identification for the unknown and unconfirmed Cl-/Br-PAH congeners in environmental samples.     

Selectable one-dimensional or two-dimensional gas chromatography-olfactometry/mass spectrometry with preparative fraction collection for analysis of ultra-trace amounts of odor compounds

A novel selectable one-dimensional ((1)D) or two-dimensional ((2)D) gas chromatography-olfactometry/mass spectrometry with preparative fraction collection (selectable (1)D/(2)D GC-O/MS with PFC) system was developed. The main advantages of this system are the simple and fast selection of (1)D GC-O/MS or (2)D GC-O/MS or (1)D GC-PFC or (2)D GC-PFC operation with a mouse click (without any instrumental set-up change), and total transfer of enriched compounds with thermal desorption (TD) on the same system for identification with (2)D GC-O/MS analysis. Recovery of PFC enrichment with 20 injection cycles of 15 model compounds at 500pg each (e.g. alcohol, aldehyde, ester, lactone, and phenol) was very good with recoveries in the range of 98-116%. The feasibility and benefit of the proposed system was demonstrated with an identification of off-flavor compounds (e.g. 2,4,6-trichloroanisole (TCA), 2-isobutyl-3-methoxypyrazine (IBMP), and geosmin) in spiked wine at odor perception threshold level (5-50ngL(-1)). After parallel stir bar sorptive extraction (SBSE) for 20 aliquots of a sample and subsequent PFC enrichment for the odor-active fractions from the 20 stir bars, three off-flavor compounds were clearly resolved and detected with TD-(2)D GC-O/MS in scan mode. The good efficiency of SBSE-PFC enrichment in the range of 71-78% shows that all analytical steps, e.g. SBSE, TD, (1)D/(2)D GC-O/MS, and PFC, are quantitative and identification of off-flavor compounds at ngL(-1) level in wine is possible.     

A model for the dynamic behavior of financial assets affected by news: The case of Tohoku-Kanto earthquake

The prices of financial products in markets are determined by the behavior of investors, who are influenced by positive and negative news. Here, we present a mathematical model to reproduce the price movements in real financial markets affected by news. The model has both positive and negative feed-back mechanisms. Furthermore, the behavior of the model is examined by considering two types of noise. Our results show that the dynamic balance of positive and negative feed-back mechanisms with the noise effect determines the asset price movement.     

Isotopic compositions of transuranic nuclides released by the Fukushima Dai-ichi Nuclear Power Plant accident: with emphasis on Cm isotopes

Isotopic composition of transuranic nuclides, with emphasis on Cm isotopes, were measured for environmental samples such as dust samples (black substances) from the roadsides and litter samples heavily contaminated by the Fukushima Dai-ichi Nuclear Power Plant (FDNPP) accident. Low levels of ²³⁸Pu, ^239,240Pu, ²⁴¹Am, ²⁴²Cm and ^243,244Cm were determined by α-spectrometry after radiochemical separation. These results, including radioactive Cs, provided an isotopic data set. When the activity ratios among these transuranic nuclides were compared with those of core inventories (Units 1–3) in the FDNPP estimated by the JAEA group, fairly good agreement was found, indicating that traces of transuranic nuclides, probably in the forms of fine particles, were released into the environment without their large fractionations. The obtained data may lead to more accurate information about the on-site situation (e.g., burn-up, conditions of fuel during the release phase, etc.), which would be difficult to receive otherwise, and on the dispersion and deposition processes of transuranic nuclides and the behavior of these nuclides in the environment.     

Reactivity of Hydroxy‐ and Aquo(hydroxy)‐λ3‐iodane–Crown Ether Complexes

We have designed a series of hydroxy(aryl)‐λ³‐iodane–[18]crown‐6 complexes, prepared from the corresponding iodosylbenzene derivatives and superacids in the presence of [18]crown‐6, and have investigated their reactivities in aqueous media. These activated iodosylbenzene monomers are all non‐hygroscopic shelf‐storable reagents, but they maintain high oxidizing ability in water. The complexes are effective for the oxidation of phenols, sulfides, olefins, silyl enol ethers, and alkyl(trifluoro)borates under mild conditions. Furthermore, hydroxy‐λ³‐iodane–[18]crown‐6 complexes serve as efficient progenitors for the synthesis of diaryl‐, vinyl‐, and alkynyl‐λ³‐iodanes in water. Other less polar organic solvents, such as methanol, acetonitrile, and dichloromethane, are also usable in some cases.