Aminosilylene-bridged ansa-zirconocenes for branched polyethylenes with bimodal molecular weight distributions

Reactions of the dilithium salt of aminosilylene-bridged ligands with (Me₂N)₂ZrCl₂(THF)₂ followed by the treatment of Me₃SiCl are found to be an efficient synthetic route to aminosilylene-bridged ansa-zirconocenes, R₂N(Me)Si(η⁵-C₅H₄)₂ZrCl₂ (R = Me (1), Et (2)) and Me₂N(Me)Si(η⁵-C₅H₄)(η⁵-C₅Me₄)ZrCl₂ (3). Crystal structure of 3 determined by X-ray diffraction study reveals the presence of π-bonding interaction between N and Si atoms, which is further supported by DFT calculation results. These complexes are very active (>1 × 10³ Kg/(mol Cat.·atm·h)) for homopolymerization of ethylene in the presence of methylalumoxane (MAO) cocatalyst, generating polyethylenes that contain branches as well as bimodal molecular weight distribution (MWD). Methyl, ethyl, butyl, and other longer branches (n ≥ 6) are observed in the resulting polyethylenes. The polyethylenes from 1, 2 and 3/MAO show a broad MWD range (6.3-42.2, 3.5-4.0 and 2.6-3.4, respectively).     

Chemical constituents from the leaves of Manglietia phuthoensis and their effects on osteoblastic MC3T3-E1 cells

Two new phenyl glycosides, mangliesides A and B (1, 2), a new ionol glycoside, manglieside C (3), two new lignan glycosides, mangliesides D and E (4, 5), were isolated from the leaves of Manglietia phuthoensis, along with two known lignans, 3-methoxymagnolol (6) and obovatol (7). Their structures were established by means of 1D and 2D NMR, electrospray ionization (ESI)-MS and HR-ESI-MS experiments. Among them, compounds 2 and 5 significantly (p<0.05) increased the growth and differentiation of osteoblastic MC3T3-E1 cells in vitro.     

A new tool to assess ceramide bioactivity: 6-bromo-7-hydroxycoumarinyl-caged ceramide

The bioactivity of natural, long-chain ceramides has until now been studied after its delivery to cells in organic solvent mixtures containing dodecane. We have synthesized ceramides conjugated to a (6-bromo-7-hydroxycoumarin-4-yl)methyl group. The photocaged ceramide is efficiently released with 350 nm light in aqueous solution at neutral pH, thus providing a promising new tool to study ceramide's properties.     

Development of a fast spectroscopic enzyme assay for on-site measurement of total polyphenol content in grapes and wine

In recent years interest in polyphenols as a nutrient in vegetables and fruits has increased because of polyphenols’ positive effects on human health. The interest focuses on the sensory properties of polyphenols and their influence on the taste of fruits and derived products. This article presents the development of a bioanalytical measurement technique enabling the determination of the total polyphenol content (TPC) of fresh grapes within a few minutes. Furthermore this technique allows the control of TPC during production processes, e. g. fermentation of wine.     

Formulation variation and in vitro-in vivo correlation for a rapidly swellable three-layered tablet of tamsulosin HCl

In order to develop a preferable once-a-day oral tablet formulation, various formulations of three-layered tablets containing tamsulosin HCl as a hydrophilic model drug were evaluated and compared with a commercial reference, tamsulosin OCAS?. When the test tablet was exposed to a release medium, the medium quickly permeated to the mid-layer and the two barrier layers swelled surrounding the mid-layer rapidly. Volume expansion showed faster and enough swelling of the three-layered tablet up to 2 h. Larger amount of barrier layers caused reduced release kinetics and a high molecular weight polymer showed more resistance against agitation force. A formulation with water-soluble mid-layer showed fast erosion decreasing its volume significantly. On the pharmacokinetic study, the mean ratio of area under the curve (AUC) and C(max) for the test formulation to the reference was 0.69 and 0.84, respectively, showing that the absorption of the drug was less complete than the reference. Plasma concentration at 24 h of the test formulation was higher than the reference. The Wagner-Nelson method showed that decreased initial dissolution rate might be the cause of the less complete absorption. On considering in vitro-in vivo correlation (IVIVC), level A, the reference (R2=0.981) showed more linear relationship than the test (R2=0.918) due to the decreased dissolution and absorption rate of the formulation. This result suggests that the in vitro dissolution profiles and release kinetics might be useful in correlating absorption kinetics as well as overall plasma drug concentration-time profiles for formulation studies.     

Dependence of turbidity oscillations of self-oscillating polymers on the selective recognition of the crown ether receptors contained in the polymer chain

The turbidity oscillations of self-oscillating polymers in the Belousov-Zhabotinsky (BZ) reaction system depending on the crown ether receptors contained in the polymer network have been studied. The three monomers are copolymerized, namely, N-isopropylacrylamide, the metal catalyst monomer for the BZ reaction, and the crown ether receptor monomer, to prepare the self-oscillating polymers used in this study. The turbidity oscillations are characterized by monitoring the transmittance of the polymer solution in the BZ reaction system at a specific wavelength of 570 nm. The oscillations are varied by crown ether receptors used in the polymerization process, i.e., BCAm(6) or BCAm(5), for the selective recognition of specific cations between potassium and sodium ions in the solution. The selective recognition of the BCAm receptors in the polymer chain for the two ions has brought out a variation in the turbidity oscillations by a change in the hydrophilicity of the polymer chain. The oscillations of the polymer solution composed of the BCAm(5) receptor are more influenced by sodium ion, while the polymer solution of BCAm(6) receptor is affected by potassium ion. However, the oscillation patterns of the redox changes obtained by these solution systems look much alike despite the differences in the polymer chain by crown ether receptors and cations of bromate used for the BZ reaction.     

Functionalized methanofullerenes used as n-type materials in bulk-heterojunction polymer solar cells and in field-effect transistors

The synthesis of two well-solubilized [60]methanofullerene derivatives ( p- EHO-PCBM and p- EHO-PCBA) is presented for usage in organic solar cells and in field-effect transistors. The para position of the PCBM's phenyl ring was substituted with a branched alkoxy side chain, which contributes to higher solubility, facilitating synthesis, purification, and processing. We find a small change of the open-circuit voltage ( V oc) as a slight improvement in performance upon application in P3HT/[60]methanofullerene bulk-heterojunction-photovoltaic cells, when compared to PCBM, because of the electron donation of the alkoxy group. In the case of the devices with a TiO x layer, the best power conversion efficiencies (PCE, eta e) is observed in a layered structure of P3HT/ p- EHO-PCBA/TiO x (eta e = 2.6%), which slightly exceeds that of P3HT/PCBM/TiO x (eta e = 2.3%) under conditions reported here. This can be attributed, in part, to the carboxylic acid group in p- EHO-PCBA that leads to an effective interface interaction between the active layer and TiO x phase. In addition, n-channel organic field-effect transistor (OFET) devices were fabricated with thin films of p- EHO-PCBM and p- EHO-PCBA, respectively cast from solution on SiO 2/Si substrates. The values of field-effect mobility (mu) for p- EHO-PCBM and p- EHO-PCBA are 1 x 10 (-2) and 1.6 x 10 (-3) cm (2)/V.s, respectively. The results in this paper demonstrate the effects of a carboxylic acid group and an electron-donating substituent in [60]methanofullerenes as n-type materials with respect to organic solar cells and OFET applications.     

Dye-sensitized solar cells based on composite solid polymer electrolytes

The ionic conductivity of polymer electrolytes and their interfacial contact with dye-attached TiO2 particles were enhanced markedly by the addition of amorphous oligomer into polymer electrolytes, resulting in very high overall energy conversion efficiency.