Influence of the molecular weight of ionenes on the cobaltphthalocyanine-catalysed autoxidation of mercaptoethanol

In order to study the promoting effect of polycations on the cobalt(II)phthalocyanine-tetrasodiumsulphonate (CoPc(NaSO₃)₄)-catalysed autoxidation of thiols, it is imperative to know the molecular weight dependence of the polymer. Monodisperse oligomers can often supply a lot of information. To elecidate the mechanism of the promoting effect of 2,4-ionene, a poly(quaternary ammonium)salt, on the CoPc(NaSO₃)₄-catalysed autoxidation of 2-mercaptoethanol, a series of monodisperse 2,4-ionene oligomers were prepared. Trimeric 2,4-ionenes, containing two quaternary ammonium groups separated by four methylene groups, showed a high co-catalytic activity, and active Co-aggregates were detected with visible light spectroscopy. The spectroscopic behaviour was in close agreement with that of high molecular 2,4-ionene/CoPc(NaSO₃)₄ complexes. In order to achieve this aggregation several oligomeric ionenes have to act concertedly. If the distance between the ionic sites is short the trimer acts as a simple salt in stablizing the aggregates. With respect to the catalytic activity the optimum polycation/catalyst ratio, expressed as the N⁺/Co ratio, decreased with increasing chain lenght and reached a constant level of 50 at a 2,4-ionene nonamer. For the trimers and pentamers this ratio is affected by the type of end-group. All synthesized 2,4-ionene oligomers exhibited excellent co-catalytic properties at the optimum N⁺/Co ratio, with maximum turnover frequencies of 4600 mol thiol/(mol Co s), i.e. 50 times higher than those obtained for the polymer-free system. In the case of monodisperse 2,4-ionene pentamer with bromo end-groups, double Michaelis–Menten kinetics were observed, as also was exhibited by high molecular weight ionene.     

COLLOIDS IN GLASS1

A discussion of the various elements and compounds found in a colloidal state in glass. Attention is called to the similarity of colloidal behavior in vitreous and aqueous media. Theories and experimental evidence are furnished to account for the formation and destruction of the colloidal state.     

Ru-Containing Polymeric Catalysts for Cellulose Conversion to Polyols

In this paper Ru-containing catalysts based on hypercrosslinked polystyrene (MN-270) and its functional analogues (MN-100 and MN-500) were studied for the first time in cellulose hydrolytic hydrogenation. The catalysts were characterized using transmission electron microscopy (TEM), high resolution TEM, and porosity measurements. Catalytic studies demonstrated that the catalyst containing 1.0 % Ru and based on MN-270 is the most active. The total yield of sorbitol and mannitol was 50 % on the average at 85 % cellulose conversion.     

Clinical Evaluation of Extracellular ADMA Concentrations in Human Blood and Adipose Tissue

Circulating asymmetrical dimethylarginine (ADMA), an endogenous inhibitor of nitric oxide synthesis, has been proposed as a biomarker for clinical outcome. Dimethylarginine dimethylaminohydrolase (DDAH) is the main enzyme responsible for ADMA metabolism and elimination. Adipose tissue ADMA concentrations and DDAH activity and their role in diabetes and obesity have not yet been investigated. In this study, we evaluated clinical microdialysis in combination with a sensitive analytical method (GC-MS/MS) to measure ADMA concentrations in extracellular fluid. Adipose tissue ADMA concentrations were assessed before and during an oral glucose tolerance test in lean healthy subjects and subjects with diabetes (n = 4 each), and in morbidly obese subjects before and after weight loss of 30 kg (n = 7). DDAH activity was determined in subcutaneous and visceral adipose tissue obtained during laparoscopic surgery (n = 5 paired samples). Mean interstitial ADMA concentrations did not differ between study populations (healthy 0.17 ± 0.03 μM; diabetic 0.21 ± 0.03 μM; morbidly obese 0.16 ± 0.01 and 0.17 ± 0.01 μM before and after weight loss, respectively). We did not observe any response of interstitial ADMA concentrations to the oral glucose challenge. Adipose tissue DDAH activity was negligible compared to liver tissue. Thus, adipose tissue ADMA plays a minor role in NO-dependent regulation of adipose tissue blood flow and metabolism.     

Cellular Scent of Influenza Virus Infection.

Volatile organic compounds (VOCs) emanating from humans have the potential to revolutionize non‐invasive diagnostics. Yet, little is known about how these compounds are generated by complex biological systems, and even less is known about how these compounds are reflective of a particular physiological state. In this proof‐of‐concept study, we examined VOCs produced directly at the cellular level from B lymphoblastoid cells upon infection with three live influenza virus subtypes: H9N2 (avian), H6N2 (avian), and H1N1 (human). Using a single cell line helped to alleviate some of the complexity and variability when studying VOC production by an entire organism, and it allowed us to discern marked differences in VOC production upon infection of the cells. The patterns of VOCs produced in response to infection were unique for each virus subtype, while several other non‐specific VOCs were produced after infections with all three strains. Also, there was a specific time course of VOC release post infection. Among emitted VOCs, production of esters and other oxygenated compounds was particularly notable, and these may be attributed to increased oxidative stress resulting from infection. Elucidating VOC signatures that result from the host cells response to infection may yield an avenue for non‐invasive diagnostics and therapy of influenza and other viral infections.