Simultaneous determination of ascorbic acid and dehydroascorbic acid by HPLC with postcolumn derivatisation and fluorometric detection

Summary A reproducible method is described for the separation and simultaneous and specific quantitation of ascorbic acid and dehydroascorbic acid by ion-pairing reversed-phase HPLC with fluorometric detection. Copper sulphate and copper acetate were compared as oxidizing reagents for ascorbic acid and 1,2-diaminobenzene dihydrochloride and 1,2-diamino-3,4-dimethylbenzene dihydrochloride as derivatising reagents. The HPLC-method was applied to human plasma. The detection limit reaches 16 ng for ascorbic acid and 3 ng for dehydroascorbic acid. Sample preparation is carried out by solid phase extraction with a recovery of 98%; it is compared with conventional precipitation of plasma proteins by metaphosphoric acid.     

Ab initio SCF structure investigation of β-hydroxypropionic acid and 3-aminopropionamide

The potential energy surfaces of β-hydroxypropionic acid and 3-aminopropionamide have been investigated by means of RHF /4-31G calculations. Structures, reaction paths for internal rotations, and the respective energy barriers are reported. The influence of the various intramolecular interactions on structural and energetical properties is shown and compared to the results previously obtained for β-alanine. © 1996 John Wiley & Sons, Inc.     

Formation of coordination compounds with aniline in the interlayer space of Ca<Superscript>2+</Superscript>-, Cu<Superscript>2+</Superscript>- and Fe<Superscript>3+</Superscript>-exchanged montmorillonite

The influence of Ca²⁺-, Cu²⁺- and Fe³⁺-exchanged montmorillonite (MMT) on the type of interaction with aniline in the interlayer space of MMT has been studied by means of X-ray powder diffraction and infrared spectra. Results of X-ray diffraction showed that aniline was successfully intercalated into the interlayer space of MMT. Based on IR spectra evaluation, aniline was indirectly coordinated through a water-bridge in Ca²⁺- and Fe³⁺-MMT and it was indirectly coordinated through a water-bridge as well as protonated in Cu²⁺-MMT (the spectrum of protonated aniline showed deformation and changes in the NH ₃ ⁺ absorption at approximately 1521 cm^?1). It is important to point out that Cu²⁺-MMT indirect coordination and protonation occur simultaneously.     

The protective role of melanin against UV damage in human skin

Human skin is repeatedly exposed to UVR that influences the function and survival of many cell types and is regarded as the main causative factor in the induction of skin cancer. It has been traditionally believed that skin pigmentation is the most important photoprotective factor, as melanin, besides functioning as a broadband UV absorbent, has antioxidant and radical scavenging properties. Besides, many epidemiological studies have shown a lower incidence for skin cancer in individuals with darker skin compared to those with fair skin. Skin pigmentation is of great cultural and cosmetic importance, yet the role of melanin in photoprotection is still controversial. This article outlines the major acute and chronic effects of UVR on human skin, the properties of melanin, the regulation of pigmentation and its effect on skin cancer prevention.     

Phenylene-Bridged Perylene Monoimides as Acceptors for Organic Solar Cells: A Study on the Structure–Property Relationship

A series of non-fullerene acceptors based on perylene monoimides coupled in the peri position through phenylene linkers were synthesized via Suzuki-coupling reactions. Various substitution patterns were investigated using density functional theory (DFT) calculations in combination with experimental data to elucidate the geometry and their optical and electrochemical properties. Further investigations of the bulk properties with grazing incidence wide angle X-ray scattering (GIWAXS) gave insight into the stacking behavior of the acceptor thin films. Electrochemical and morphological properties correlate with the photovoltaic performance of devices with the polymeric donor PBDB-T and a maximum efficiency of 3.17 % was reached. The study gives detailed information about structure–property relationships of perylene-linker-perylene compounds.     

Extract from the Marine Seaweed Padina pavonica Protects Mitochondrial Biomembranes from Damage by Amyloidogenic Peptides

The identification of compounds which protect the double-membrane of mitochondrial organelles from disruption by toxic confomers of amyloid proteins may offer a therapeutic strategy to combat human neurodegenerative diseases. Here, we exploited an extract from the marine brown seaweed Padina pavonica (PPE) as a vital source of natural bioactive compounds to protect mitochondrial membranes against insult by oligomeric aggregates of the amyloidogenic proteins amyloid-β (Aβ), α-synuclein (α-syn) and tau, which are currently considered to be major targets for drug discovery in Alzheimer’s disease (AD) and Parkinson’s disease (PD). We show that PPE manifested a significant inhibitory effect against swelling of isolated mitochondria exposed to the amyloid oligomers, and attenuated the release of cytochrome c from the mitochondria. Using cardiolipin-enriched synthetic lipid membranes, we also show that dye leakage from fluorophore-loaded vesicles and formation of channel-like pores in planar bilayer membranes are largely prevented by incubating the oligomeric aggregates with PPE. Lastly, we demonstrate that PPE curtails the ability of Aβ42 and α-syn monomers to self-assemble into larger β-aggregate structures, as well as potently disrupts their respective amyloid fibrils. In conclusion, the mito-protective and anti-aggregator biological activities of Padina pavonica extract may be of therapeutic value in neurodegenerative proteinopathies, such as AD and PD.     

Strong Electronic Communication in Linearly Elongated Rylenes Featuring Tunable Bridges

A modified synthetic pathway towards perylene-perylene dimers and a facile purification method to obtain the regioisomerically pure syn- and anti-isomers are reported. In addition, a novel perylene-naphthalene heterodimer with 30 conjugated π-electron pairs was designed and synthesized on the basis of a previously described precursor and the resulting regioisomers were separated from each other. Thereby, the opto-electronic properties of the linearly elongated chromophores could be investigated regarding the differences in length of their aromatic system and the configuration of the isomers. Further tuning of their energy gaps was realized via protonation and methylation of the dibenzimidazole-bridging unit. Extraordinary red-shifts of the absorption maxima of 62 nm for the methylated and 92 nm for the protonated perylene-perylene anti-isomer could be achieved. Moreover, the maxima for the syn-isomer could be shifted bathochromically by 87 and 113 nm, respectively.     

Silylanions: inversion barriers and NMR chemical shifts

Alpha-substituent effects on inversion barriers and NMR chemical shifts have been studied on a set of silyl anions, [X(3-n)Y(n)Si](-) (X, Y=H, CH(3), and SiH(3)). The MP2/6-31+G* optimized structures show a pattern of increasing inversion barriers with augmenting numbers of methyl substituents. The highest barrier of 48.5 kcalmol(-1) is obtained for the (CH(3))(3)Si(-) ion. The silyl group displays the opposite effect by decreasing the inversion barrier to a minimum of 16.3 kcalmol(-1) in (SiH(3))(3)Si(-). The influence of counterions on these barriers is probed by addition of a lithium or potassium cation. In most cases, a decrease of the energy barriers with respect to the bare anions is observed. The (29)Si NMR chemical shifts calculated at the IGLO-DFT and GIAO-MP2 level of theory are also analyzed in view of the substituents and counterions.