Density-fluctuation-induced swelling of polymer thin films in carbon dioxide

We report an anomalous swelling of polymer thin films in carbon dioxide (CO(2)) which is associated (in both locus and form) with the density fluctuation ridge that forms along the extension of the coexistence curve of gas and liquid in the P-T phase diagram. Neutron reflectivity results showed that CO(2) could be sorbed to a large extent ( approximately 60%) in thin polymer films even when the bulk miscibility of the polymer with CO(2) is very poor. The anomalous swelling is found to scale with the polymer radius of gyration (R(g)) and extends to a distance approximately 10 R(g).     

Studies on the chemical constituents of stem bark of Millettia leucantha: isolation of new chalcones with cytotoxic,anti-herpes simplex virus and anti-inflammatory activities

Four new chalcone derivatives (1, 4, 7, 10) were isolated from the stem bark of Millettia leucantha KURZ (Leguminosae) along with two known ones (2, 6) and five known flavones (3, 5, 8, 9, 11). Structure elucidation and unambiguous assignment of the isolates were achieved with the aid of 1D and 2D NMR extensive studies. Correlation of 10 to 4 was successfully done by reduction with Et(3)SiH/CF(3)CO(2)H. Moderate cytotoxic activity was observed in chalcones (1, 10), whereas dihydrochalcones (4, 6) showed moderate anti-Herpes Simplex Virus (HSV) activity. Interestingly, flavone 8 showed significant anti-inflammatory effects inhibiting both cyclooxygenase (COX)-1 and -2.     

Regioselective allylmetalation of allenes with tetraallylmanganate or allylmagnesium chloride under MnCl2 catalysis

[reaction: see text] Treatment of allenes with tetraallylmanganate provides allylated products with high regioselectivity. A catalytic amount of MnCl(2) combined with allylmagnesium chloride also achieves efficient allylmetalation of allenes. The resulting alkenylmagnesium species react with various electrophiles. In the presence of molecular oxygen, the alkenylmagnesium undergoes diallylation reaction. A cyclization reaction of 1,2,6-heptatriene with tetraallylmanganate is also described.     

Heterogeneity in oscillator networks: are smaller worlds easier to synchronize?

Small-world and scale-free networks are known to be more easily synchronized than regular lattices, which is usually attributed to the smaller network distance between oscillators. Surprisingly, we find that networks with a homogeneous distribution of connectivity are more synchronizable than heterogeneous ones, even though the average network distance is larger. We present numerical computations and analytical estimates on synchronizability of the network in terms of its heterogeneity parameters. Our results suggest that some degree of homogeneity is expected in naturally evolved structures, such as neural networks, where synchronizability is desirable.     

Concentration and degradation of hyaluronic acid in knee synovial fluid from carrageenin-induced rabbit arthritis

The concentration and degradation of hyaluronic acid in the synovial fluid of carrageenin-induced arthritic joints of rabbits was studied. A 0.5-ml volume of 1% lambda-carrageenin was intra-articularly injected three times into a right knee joint, and saline into a left. After 5 d from the last injection, inflammatory changes were observed in the synovial membrane and synovial fluid, but not in the articular cartilage. In the inflammatory synovial fluid, lipid peroxide content, phosphatase activity and cell counts were significantly increased, but the copper concentration was not changed. Concentration of polymeric hyaluronic acid and total hyaluronic acid were determined by high-performance liquid chromatography using gel-permeation columns. Total hyaluronic acid was appreciably decreased in the inflammatory fluid. The polymeric hyaluronic acid determined was 38% of the total hyaluronic acid in the inflammatory fluid and 74% in the control fluid. This suggests that in the inflammatory fluid, molecular weights of hyaluronic acid are distributed in the broader range. The concentration of chondroitin sulphates was similar in both the inflammatory fluid and the control fluid, but the content ratio of chondroitin sulphates to hyaluronic acid was higher in the inflammatory fluid. In the inflamed synovial membrane, synthesis of hyaluronic acid as measured by incorporation of [14C]glucosamine into glycoconjugates was increased by about twice that in the control membrane.     

Synthesis and antiallergic activity of N-[4-(4-diphenylmethyl-1-piperazinyl)butyl]-1,4-dihydro-4-oxopyridine-3 - carboxamides

A new series of oxopyridinecarboxamide derivatives 3a--g and 5a were synthesized and evaluated for their antiallergic activity. 1,4-Dihydro-7-methyl-4-oxo-1,8-naphthyridine-3-carboxamides 3a and 5a exhibited potent antiallergic activity (inhibitory rates of 80.7 and 88.3%, respectively, at 20 mg/kg, p.o.) in the rat passive cutaneous anaphylaxis (PCA) test and also exhibited much more potent in vitro inhibitory activity than caffeic acid against the enzyme 5-lipoxygenase (5-LO). Their in vitro antihistamine activity, however, was weaker than that of ketotifen. Compounds 3a and 5a are viewed as promising candidates for antiallergic agents.     

Fully automated liquid chromatography-mass spectrometry determination of 17beta-estradiol in river water

Surface modified molecularly imprinted polymers (SM-MIPs) for 17beta-estradiol (E2), utilizing 6-ketoecradiol as a pseudo template were prepared. MIPs for E2 were synthesized using 4-vinyl pyridine and ethylene dimethacrylate as a functional monomer and cross-linking agent, respectively. MIPs selectively retained E2 and provided excellent chromatographic resolution from interfering compounds inherent in river water sample matrices. Therefore, freshly prepared MIPs were applied to quantitative mass spectrometric (negative electrospray ionization mode) detection of low levels of E2 in river water sample. In order to pre-concentrate the target compound for HPLC analysis, column switching was coupled with a pretreatment column packed with the MIPs. The repeatability of actual determinations of river water sample, in which background E2 was not detected, spiked with 50 ng/L of E2 was 2.2% RSD with a detection limit and qualification limit of 1.8 and 5.4 ng/L, respectively. Surface modification of MIP particlefs packed in the pretreatment column provided selective affinity and on-line concentration of low levels of E2 while simultaneously eliminating sample matrix interference, resulting in a significant increase in sensitivity and reproducibility for liquid chromatography-mass spectrometry analysis of E2 in river water sample.     

Synthesis of inorganic-organic hybrids by incorporation of inorganic components into organic polymer using metal alkoxides

Inorganic-organic hybrids have been synthesized by incorporation of the inorganic component of Ti(OC₂H₅)₄ into the organic polymer of ethyl cellulose. The inorganic-organic hybrids did not dissolve in toluene used as a solvent for the starting materials. The ethanol was formed as a by-product of the alcoholysis condensation reaction between Ti(OC₂H₅)₄ and ethyl cellulose. These results suggest that ethoxy groups of Ti(OC₂H₅)₄ react with hydroxy groups of ethyl cellulose to form cross-linking bonds of –O–Ti–O–. The reaction of Ti(OC₂H₅)₄ with ethyl cellulose was further investigated by Fourier transform infrared (FT-IR) spectroscopy. The FT-IR spectroscopic experiments revealed that the Ti–O bond state of Ti(OC₂H₅)₄ was changed by refluxing a toluene solution of Ti(OC₂H₅)₄ with ethyl cellulose. The inorganic-organic hybrids have an interesting dielectric property; their dielectric constant is higher than that of ethyl cellulose and that of a simple mixture of TiO₂ and ethyl cellulose.