Synthesis and Stereochemistry of α-Aryl-β-Nitroalkylphosphinate

Abstract

Twenty-three new α -aryl-β -nitroalkylphosphinates 3a - g were synthesized in high yields under very mild conditions. Compounds 3 consist of two pairs of diastereomeric isomers (A) and (B)     

Rates of Sulfonation of Bead Copolymers of Styrene Cross - Linked with Mixtures of m- and p-Divinylbenzene

Abstract

The rate of sulfonation of bead copolymers of styrene cross-linked with 8 mole % divinylbenzene (mixed isomers) is remarkably sensitive to the isomeric (para/meta) composition of the mixture of divinylbenzenes. The rate is enhanced by a factor of 4 for compositions containing 20–40% para isomer.     

Palladium-Catalyzed Arylation and Vinylation of 2,3-Dihydrofuran with Hypervalent Iodonium Salts

The palladium-catalyzed arylation and vinylation of 2,3-dihydrofuran with aryl and alkenyl iodonium salts afforded 2-phenyl- or 2-alkenyl-2,5-dihydrofurans at room temperature in an aqueous medium.     

5′-O-TBDMS-3′-O--(1H-Imidazole-1-Thiocarbonyl)thymidine: A Novel Intermediate for the Synthesis of 2,3′-Anhydrothymidine

Thermal or base-promoted conversion of 5′-O-TBDMS-3′-O-(1H-imidazole-1-thiocarbonyl)thymidine (1) afforded 5′-O-TBDMS-2,3′-anhydro-thymidine (2), a pivotal intermediate for the transformation of the 3′-hydroxy group of 2′-deoxyribonucleosides, in high yield.     

Synthesis and characterisation of photopolymerisable liquid crystals based on the π-extended fluorene core and their corresponding non-reactive analogues

We have synthesised a series of new reactive mesogens with photopolymerisable di-acrylates and their corresponding non-reactive analogues based on the π-conjugated aromatic core, fluorene (F)-di-[thiophene (T)-benzene (B)], using the Stille and Suzuki coupling reaction. The effect of lateral alkyl chains on the 9-position of the central fluorene moiety as well as α, ω- side alkyl chains attached to the π-conjugated aromatic core on the mesomorphism was investigated by utilising differential scanning calorimetry (DSC) and polarising optical microscopy (POM). A wide angle X-ray scattering (WAXS) study at the various temperatures was also carried out to reveal phase structures. Photopolymerisable di-acrylates connected directly to the rigid aromatic core showed higher phase transition temperatures, probably due to the induced dipole moment in comparison with those of a non-reactive methyl–ether counterpart.     

Substrate interaction effects on order to disorder transition behavior in block copolymer films

We present an overview of the recent progress on the phase transition in the block copolymer (BCP) films in terms of the interfacial interactions effects of the substrates and the χ (Flory-Huggins segmental interaction parameter) effects between the two blocks. For the BCP films thinner than a critical thickness (L_c) above which the transition is independent of film thickness, the order-to-disorder transition (ODT) increased or decreased with decreasing film thickness depending on the interfacial interaction types. The rapid and slow changes in the ODT were attributed to the relative magnitude of enthalpic contribution to χ between two blocks. Interestingly, a periodic amplification in the block composition for the BCP films suppressed the compositional fluctuation in the film geometry, resulting in the ODT shifts from the bulk ODTs above L_c. This effect of the BCP films was more illustrated by the ODT shift effects depending on the strength of the preferential interactions on the substrates. © 2013 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

The influence of alkaline reserve on the aging behavior of book papers

Degradation of cellulose under alkaline conditions is involved either involuntarily or deliberately in many different cellulose processing steps, such as pulping, bleaching, or aging within the viscose process, and the underlying chemistry has been the topic of numerous studies. When it comes to aging under alkaline conditions—either natural or accelerated (artificial)—the degradation processes are by far less investigated and understood. A prominent example of moderately alkaline cellulosic material is deacidified book paper from libraries which had undergone a mass-deacidification treatment. We studied their aging behavior under accelerated conditions in comparison to non-deacidified duplicates in order to better understand how the alkaline reserve, which was introduced by the deacidification treatment, affects the stability of the books on the long run. GPC analysis of cellulose and determination of carbonyl functionalities were performed, which were critical parameters to achieve a deeper insight into hydrolytic and oxidative changes of cellulose structure upon deacidification treatment and subsequent aging. Also, model book papers impregnated with different amounts of alkaline reserve were used to support the findings from the original book samples. Hydrolytic degradation rates of the original book papers were significantly reduced after mass deacidification compared to the non-deacidified duplicates. The beneficial effect of mass deacidification on cellulose stability was found to be strongly related to the amount of alkaline reserve deposited, independent of varying parameters of book papers. Although some indication of alkali-induced β-elimination was found (a minor decrease of the along-chain carbonyl content in the original deacidified book papers during aging), it did not occur to an extent that significantly influenced the molar mass of cellulose. The beneficial effect of retarded hydrolytic degradation by mass deacidification thus clearly outweighed possible negative alkalinity effects of the deposited alkaline reserve.     

Prenylated Flavonoid Glycosides with PCSK9 mRNA Expression Inhibitory Activity from the Aerial Parts of Epimedium koreanum

Phytochemical investigation on the n-BuOH-soluble fraction of the aerial parts of Epimedium koreanum using the PCSK9 mRNA monitoring assay led to the identification of four previously undescribed acylated flavonoid glycosides and 18 known compounds. The structures of new compounds were elucidated by NMR, MS, and other chemical methods. All isolated compounds were tested for their inhibitory activity against PCSK9 mRNA expression in HepG2 cells. Of the isolates, compounds 6, 7, 10, 15, and 17–22 were found to significantly inhibit PCSK9 mRNA expression. In particular, compound 7 was shown to increase LDLR mRNA expression. Thus, compound 7 may potentially increase LDL uptake and lower cholesterol levels in the blood.