Chain stiffness and chain conformation of poly(α-methylene-γ-butyrolactone) in dilute solutions

The chain stiffness and local chain conformation of atactic poly(α-methylene-γ-butyrolactone) (PMBL), which is a side chain cyclic structural analog of poly(methyl methacrylate) (PMMA), with a weight-average molecular weight (M_w) ranging from 2.8 × 10³ to 2.6 × 10⁶ in N,N-dimethylformamide (DMF) and γ-butyrolactone (GBL) were characterized by size exclusion chromatography with a multi-angle light-scattering detector (SEC-MALS) and synchrotron radiation small-angle X-ray scattering (SAXS). Based on the Kratky-Porod worm-like chain model, the scattering functions and the M_w dependence of z-average root-mean-square radius of gyration <S²>_z^1/2 yielded the Kuhn segment lengths λ⁻¹, the diameter of the PMBL chains d, and the excluded-volume strengths in DMF and GBL. The local conformation of atactic PMBL in DMF and GBL were slightly larger than those of atactic PMMA, due to the presence of the conformationally rigid lactone ring structure.     

Influence of metal ion concentration in the glycol mediated synthesis of Gd2O3:Eu nanophosphor

The solvothermal synthesis of highly luminescent and homogeneous Gd₂O₃:Eu³⁺ nanophosphor using diethylene glycol as medium, followed by controlled combustion with citric acid as fuel is reported. The influence of concentrations of carboxylic acid and metal cations on the structure, morphology and luminescence properties are investigated in detail. The microscopic investigations indicate the nanocrystalline nature and the strong influence of cation concentration on the size, shape and agglomeration of the particles. It is found that increase in concentration of metal cations lead to the reduction in agglomeration of nanophosphors. The large value of intensity parameter Ω_2, suggested that Eu³⁺ ions reside in a more asymmetric environment, resulted in intense emission due to ⁵D₀–⁷F₂ electric dipole transition. Emission decay analysis of the samples exhibited one exponential nature. The samples prepared under optimum conditions showed a quantum efficiency of 78.63% and a moderately high life time of 1.217 ms.     

Mechanical properties of drawn poly(methyl methacrylate) filled with ultrafine particles

The elastic and yield properties of drawn poly(methyl methacrylate) (PMMA) filled with ultrafine SiO₂ are described as functions of filler content and size. The drawn PMMA composites were made by uniaxially drawing to x4.0 at 100°C and at a rate of 20 mm/min. Four compliance values, i.e., S₃₃, S₁₁, S₁₃, and S₄₄ were determined. These values decreased with filler content and decreasing filler size. The relative compliance values S^de/S^do(S^de is the compliance of drawn PMMA composites and S^do is that of drawn unfilled PMMA) are almost equivalently changed with changes in filler content. The elastic properties of drawn PMMA composites are thus reinforced isotopically. This is characteristic of PMMA which has a large side group. The yield behavior of drawn PMMA composites have similar filler size and content dependence to those of elastic properties except that the transverse yield stresses become more brittle with filler content. The anisotropy in yield stress is relatively larger than that of elastic properties. This is probably because the anti-reiforcing effect, such as fibrillation becomes prominent with increasing filler content in the perpendicular direction.     

Treatment of Chronic Kidney Disease with Extracellular Vesicles from Mesenchymal Stem Cells and CD133+ Expanded Cells: A Comparative Preclinical Analysis

Chronic kidney disease (CKD) is characterized by structural abnormalities and the progressive loss of kidney function. Extracellular vesicles (EVs) from human umbilical cord tissue (hUCT)-derived mesenchymal stem cells (MSCs) and expanded human umbilical cord blood (hUCB)-derived CD133⁺ cells (eCD133⁺) maintain the characteristics of the parent cells, providing a new form of cell-free treatment. We evaluated the effects of EVs from hUCT-derived MSCs and hUCB-derived CD133⁺ cells on rats with CDK induced by an adenine-enriched diet. EVs were isolated by ultracentrifugation and characterized by nanoparticle tracking analysis (NTA) and electron microscopy. The animals were randomized and divided into the MSC-EV group, eEPC-EV group and control group. Infusions occurred on the seventh and 14th days after CKD induction. Evaluations of kidney function were carried out by biochemical and histological analyses. Intense labeling of the α-SMA protein was observed when comparing the control with MSC-EVs. In both groups treated with EVs, a significant increase in serum albumin was observed, and the increase in cystatin C was inhibited. The results indicated improvements in renal function in CKD, demonstrating the therapeutic potential of EVs derived from MSCs and eCD133⁺ cells and suggesting the possibility that in the future, more than one type of EV will be used concurrently.     

Am1 MO Study of Benzene Nitro Derivatives

Molecular properties of benzene nitro derivatives were investigated by using semi-empirical MO calculations. As the results, the molecular structures and the rotational barrier of the nitro group calculated by AM1 showed a good agreement with the experimental values. The heats of formation in gaseous and condensed phases were obtained by considering isodesmic reactions. By this procedure, the heat of formation of hexanitrobenzene in solid phase was calculated to be +22.7 kcal/mol. The detonation parameters were also calculated by using four equations of state. The predicted detonation velocities showed a good agreement with the experimental values.     

Dielectric study of β-relaxation in some cellulosic substances

6-(2-Cyanoethylamino)-6-deoxycellulose (Cell-CEA) as a novel cellulose derivative was prepared from 6-bromo-6-deoxycellulose. The influence of the reaction conditions on the degree of substitution was studied in detail. The dielectric characteristics of a Cell-CEA sample having degree of substitution of 0.86, together with those of microcrystalline and regenerated celluloses, have been investigated in the temperature range from −60 to 120°C, and frequency range 30 Hz to 100kHz. One relaxation process, designated as β, was recognised, which was attributed to side-group motions, probably −CH₂X (X = OH or NHCH₂CH₂CN). The higher activation energy of this process and the shift to higher temperature in Cell-CEA, compared with microcrystalline and regenerated celluloses, reflects the enhanced steric constraints involved in the motion of the bulkier, −CH₂NHCH₂CH₂CN, side groups. The results obtained are discussed in terms of the dielectric parameters ϵ″_max′ β and Δϵ.     

Vitamin E reduces cholesterol esterification and uptake of acetylated low density lipoprotein in macrophages

The effects of vitamin E on cholesteryl ester (CE) metabolism in 1774 cells were examined. Pretreatment of 1774 cells with vitamin E at concentrations above 50 μM significantly decreased acetylated low density lipoprotein (LDL)-induced incorporation of [¹⁴C]oleate into CF in cells in a dose-dependent manner. This was partly due to vitamin E Also significantly inhibiting the uptake of [³H]CE-labeled acetylated LDL by 1774 cells. A trend existed toward suppression of acyl-CoA:cholesterol acyltransferase (ACAT) activity in the cell lysate at high vitamin E concentration, but there was no effect on hydrolysis of CE. These data indicate that vitamin E reduces the uptake of modified LDL and suppresses ACAT activity, resulting in less cholesterol esterification in macrophages; a novel mechanism underlying the antiatherogenic properties of vitamin E.     

Poly(sulfonated phenylene)-block-poly(arylene ether sulfone) copolymer for polymer electrolyte fuel cell application

Novel poly(2-(3-sulfo)benzoyl-1,4-phenylene)-block-poly(arylene ether sulfone) copolymers (PSP-b-PAESs) were successfully synthesized by Ni(0)-catalyzed copolymerization of 2,5-dichloro-3′-sulfo-benzophenone (DCSB) and chlorobenzophenone-endcapped oligo(arylene ether sulfone). Their physical property, morphology and polymer electrolyte fuel cell (PEFC) performance were investigated compared to those of the DCSB-based random copolymers and Nafion112. PSP-b-PAES with a measured ion exchange capacity (IEC) of 1.82 meq g^?1, of which the hydrophilic/hydrophobic block lengths were evaluated as 17/8.4, showed the relatively small number of water molecules sorbed per sulfonic acid group (λ = 15) in water and the anisotropic membrane swelling with 2.4 times larger through-plane swelling than in-plane one, whereas it showed the almost isotropic proton conductivity. The PSP-b-PAES exhibited a microphase-separated structure composed of hydrophobic and hydrophilic domains, whereas the random copolymers exhibited a homogenous morphology. The PSP-b-PAES had the larger proton conductivity than the random copolymer with an IEC of 2.01 meq g^?1, especially under the low relative humidities. Even at a low humidification of 17% RH at 90 °C and 0.2 MPa, the PSP-b-PAES exhibited the high PEFC performance; namely, cell voltage of 0.69 V at load current density of 0.5 A cm^?2 and maximum output of 0.73 W cm^?2, which were much higher than those at 30% RH for the random copolymer (0.65 V and 0.51 W cm^?2) and Nafion112 (0.70 V and 0.61 W cm^?2). The PSP-b-PAES showed the fairly high durability of 750 h under PEFC operation at 90 °C in spite of the relatively low molecular weight. PSP-b-PAESs have the high potential as polymer electrolyte membrane for PEFC applications.     

Thermal behaviors and flame‐retardancy of styrene–ethylene–butadiene–styrene–block copolymer containing various additives

The thermal behaviors and the flame‐retardancy of styrene–ethylene–butadiene–styrene–block copolymer containing various additives were studied. The combustion was measured by the Underwriter laboratory (UL) test and cone calorimeter test and thermogravimetric analysis and program‐mass spectroscopy were applied to analyze the thermal behaviors. The blend with halogen additives showed the best result in the UL test. However, the blend with red‐phosphorous was the best in the cone calorimeter test. As the styrene sequence in the copolymer tended to degradate at a lower temperature, the major scission products spouted out from the polymer surface originated from polystyrene. The shorter the ignition times of the blends with red‐phosphorous were, the lower the peak heat release rates were. It was an interesting phenomenon because it suggested that the chemical structure of the residue changed to more stable polymers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 156–161, 2007     

A Multiple‐Labeling Strategy for Nonribosomal Peptide Synthetases Using Active‐Site‐Directed Proteomic Probes for Adenylation Domains

Genetic approaches have greatly contributed to our understanding of nonribosomal peptide biosynthetic machinery; however, proteomic investigations are limited. Here, we developed a highly sensitive detection strategy for multidomain nonribosomal peptide synthetases (NRPSs) by using a multiple‐labeling technique with active‐site‐directed probes for adenylation domains. When applied to gramicidin S‐producing and ‐nonproducing strains of Aneurinibacillus migulanus (DSM 5759 and DSM 2895, respectively), the multiple technique sensitively detected an active multidomain NRPS (GrsB) in lysates obtained from the organisms. This functional proteomics method revealed an unknown inactive precursor (or other inactive form) of GrsB in the nonproducing strain. This method provides a new option for the direct detection, functional analysis, and high‐resolution identification of low‐abundance active NRPS enzymes in native proteomic environments.