Nystatin Interferes with the Effects of <Emphasis Type="Italic">N</Emphasis>-Methyl-<Emphasis Type="Italic">N</Emphasis>′-nitro-<Emphasis Type="Italic">N</Emphasis>-nitrosoguanidine on Sphingolipid Metabolism in Human FL Cells

Previously we have shown that an alkylating agent N-methyl-N'-nitro-N- nitrosoguanidine (MNNG) can induce receptor clustering and the activation of a downstream signal molecule NF-kappaB, and that the receptor clustering is associated with changes in sphingolipids metabolism. On the other hand, the polyene antibiotic nystatin can block MNNG-induced receptor clustering. In this study, using a lipidomic approach, we further evaluated whether nystatin influenced the effects of MNNG on sphingolipids metabolism. It was found that nystatin itself induced changes in the sphingolipids profile in human amnion FL cells to a certain extent, including an increase or decrease of some sphingolipid species. Interestingly, nystatin can block, at least partially, the changes of sphingolipids-induced by MNNG. In addition, nystatin can also partially inhibit the activation of NF-kappaB induced by MNNG. Neither MNNG nor nystatin affects the mRNA levels of serine palmitoyltransferase, acid sphingomyelinase (ASM), and sphingomyelin synthase, key enzymes in the sphingolipids biosynthesis pathway. However, MNNG can activate ASM and neutral sphingomyelinase, while nystatin preincubation inhibits the activation. Taken together, these data suggested that nystatin interferes with the effects of MNNG, and might elicit its function through altered sphingolipids metabolism.     

Cellulose–<Emphasis Type="Italic">co</Emphasis>-polyacrylonitrile blends: Properties of combined solutions in <Emphasis Type="Italic">N</Emphasis>-metylmorpholine-<Emphasis Type="Italic">N</Emphasis>-oxide and the formation and thermolysis of composite fibers

Combined solutions of cellulose and an acrylonitrile-based copolymer in N-methylmorpholine-N-oxide have been prepared for the first time, new composite fibers have been formed, and the properties of the solutions and fibers under standard conditions and during thermal treatment have been studied. On the basis of studying the phase state and morphological peculiarities of combined cellulose solutions with polyacrylonitrile additives, it has been shown that the completed solutions make emulsions in the entire range of investigated concentrations. The rheological behavior of combined solutions changes with temperature. With the use of IR spectroscopy methods, it has been found that the addition of polyacrylonitrile to cellulose results in the association of nitrile groups with hydroxyl groups of cellulose, which favors the cyclization of CN groups during heating and the appearance of polyconjugated bonds in polyacrylonitrile chains. Thermal transformations of cellulose and polyacrylonitrile in the course of mixed-fiber carbonization have been studied via DSC and TGA. It has been shown that polyacrylonitrile inhibits the dehydration processes in cellulose and reduces the intensity of the peak due to the first stage of the structural rearrangement, i.e., acts as a “catalyst” of pyrolysis.     

Syntheses and optical properties of <Emphasis Type="Italic">α</Emphasis>- and <Emphasis Type="Italic">β</Emphasis>-cyano-poly(<Emphasis Type="Italic">p</Emphasis>-phenylene vinylene) derivatives

Two light emitting molecules with the cyano group at different positions on the vinylene i.e., 2,5-bis(2-thienyl-1-cyanovinyl)-1-(2_-ethylhexyloxy)-4-methoxybenzene (-TPT) and 2,5-bis(2-thienyl-2-cyanovinyl)-1-(2-ethylhexyloxy)-4-methoxybenzene (-TPT), and corresponding polymers, i.e., poly[2,5-bis(2-thienyl-1-cyanovinyl)-1-(2-ethylhexyloxy)-4-methoxybenzene] (denoted as P1) and poly[2,5-bis(2-ethienyl-2-cyanovinyl)-1-(2-ethylhexyloxy)-4-methoxybenzene] (denoted as P2) were synthesized. -TPT and -TPT, respectively, were blended into two host polymers, poly(methyl methacrylate (PMMA) and poly(9-vinylcarbazole) (PVK), to study the optical properties of the dopants in different host polymer matrices. Although -TPT and -TPT have the same backbone structure, their optical properties are much different. The PL emission maximum ( _max) of -TPT was found blue-shifted, compared with that of -TPT, while the PL intensity of -TPT was stronger than that of -TPT. Concentration effect in the optical properties was found, 1 wt% of -TPT in PVK had the maximum fluorescent emission.The PL maximum peak wavelengths for polymer films (P1 and P2) were found red-shifted; while their PL intensities were weaker when compared with those of blends.     

Dynamic-mechanical behavior of polyethylenes and ethene/<Emphasis Type="Italic">α</Emphasis>-olefin-copolymers: Part II. <Emphasis Type="Italic">α</Emphasis>- and <Emphasis Type="Italic">β</Emphasis>-relaxation

Several ethylene homopolymers and ethene/ α-olefin-copolymers with crystallinities ranging between 85 and 12% were characterized by dynamic-mechanical measurements. The occurring relaxations were correlated to the crystallinity of the polymeric materials and to morphology. The α-relaxation, being attributed to interlamellar shear, was found to be around 60 °C with activation energies of about 120 kJ/mol in samples with more than 42% crystallinity. The β-transition shows a much greater variety among the different samples characterized. Its relaxation temperatures vary between −40 and 10 °C with activation energies between 200 and 400 kJ/mol. The α- and β-relaxation of several quenched samples with crystallinities between 63 and 42% were found to overlap, thus producing bimodal maxima and different activation energies from the Arrhenius plots. A separation of these overlapping relaxations was only possible by measuring the relaxations over a frequency range of more than three orders of magnitude.     

Enhanced <Emphasis Type="Italic">β</Emphasis>-carotene production by <Emphasis Type="Italic">Rhodotorula glutinis</Emphasis> using high hydrostatic pressure

High hydrostatic pressure (HHP) technology was used for improving the ability of β-carotene biosynthesis of Rhodotorula glutinis R68. After the treatments of five repeated cycles at 300 MPa for 15 min, the barotolerant mutant PR68 was obtained. After 72 h of culture, the biomass of mutant PR68 was 21.6 g/L, decreased by 8.5% compared to the parent strain R68, but its β-carotene production reached 19.4 mg/L, increased by 52.8% compared to the parent strain R68. The result of restriction fragment length polymorphism analysis suggested that mutant strain PR68 was likely to change in nucleic acid level, and thus enhanced β-carotene production in this strain was a result of gene mutation induced by HHP treatment. HHP technology seems a promising approach for improving industrial microbes.     

A novel ∈-lysine acylase from <Emphasis Type="Italic">Streptomyces mobaraensis</Emphasis> for synthesis of <Emphasis Type="Italic">N∈</Emphasis>-acyl-<Emphasis Type="SmallCaps">l</Emphasis>-lysines

A novel ∈-lysine acylase (N ₆-acyl-l-lysine amidohydrolase; EC 3.5.1.17) was isolated from Streptomyces mobaraensis and purified to homogeneity by SDS-PAGE from the culture broth. The purified enzyme was monomeric, with a molecular mass of approximately 60 kDa. The enzyme was inactivated by the presence of 1,10-phenanthroline and activated in the presence of Co²⁺ and Zn²⁺. The enzyme showed a pH optimum of 8.0 and was stable at temperatures of up to 50°C for 1 h at pH 8.0. The enzyme specifically catalyzed the hydrolysis of the amide bond of various N∈-acyl-l-lysines. Furthermore, the enzyme efficiently catalyzed the synthesis of N∈-acyl-l-lysines with fatty and aromatic acyl groups in an aqueous buffer. In the syntheses of N∈-decanoyl-l-lysine, N∈-lauroyl-l-lysine, and N∈-myristoyl-l-lysine, the product precipitated and the yield was 90% or higher using 10 mM FA and 0.5 M l-lysine as the substrate.     

Living Anionic Polymerization of <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>–Dimethylacrylamide and Copolymerization with Methyl Methacrylate in the presence of Bulky Aluminum Phenoxide

Summary Anionic polymerization of N,N–dimethylacrylamide (DMAAm) was examined in toluene with tert–butyllithium (t–BuLi)/bis(2,6–di–tert–butylphenoxy)ethylaluminum [EtA1(ODBP)₂]. In the presence of excess amounts of the aluminum compound over t–BuLi, the polymerization proceeded in a living manner. Sequential block copolymerization of DMAAm and methyl methacrylate (MMA) with the same initiator underwent smoothly in both directions, that is, polymerization of MMA by poly(DMAAm) living anions and vice versa. Moreover, the copolymerization of an equimolar mixture of DMAAm and MMA proceeded in a monomer–selective manner to give a block–like copolymer; DMAAm was polymerized first followed by MMA polymerization through selective activation of DMAAm by the coordination of EtA1(ODBP)₂.     

Synthesis and Properties of Alkyl <Emphasis Type="Italic">β</Emphasis>-<Emphasis Type="SmallCaps">d</Emphasis>-Galactopyranoside

A series of alkyl β-d-galactopyranosides were prepared by the trichloroacetimidate method with d-galactose and alcohols with different chain lengths as raw materials. Their solubility, surface tension, emulsification, foaming, wettability, thermotropic liquid crystalline properties, and thermal stability were investigated. Alkyl β-d-galactopyranosides are soluble in water and ethanol, and the solubility decreases with increasing alkyl chain length. Decyl β-d-galactopyranoside was insoluble in water, but soluble in ethanol. Dissolution of alkyl β-d-galactopyranoside in water is an endothermic process with dissolution enthalpies greater than zero. Nonyl β-d-galactopyranoside had an excellent emulsifying property, better foaming ability and the best foam stability. The CMC values of alkyl β-d-galactopyranosides decrease with increasing of alkyl chain length. Alkyl β-d-galactopyranosides are thermally stable up to 270 °C. Alkyl β-d-galactopyranosides show the distinctive optical texture of a thermotropic liquid crystal smectic A type phase. Decyl β-d-galactopyranoside showed the strongest wettability.     

Dynamic-mechanical behavior of polyethylenes and ethene-/<Emphasis Type="Italic">α</Emphasis>-olefin-copolymers: Part III. <Emphasis Type="Italic">γ</Emphasis>-relaxation

The temperature- and frequency-dependent dynamic-mechanical properties in the temperature regime of the γ-transition were determined for a number of polyethylenes and ethylene/α-olefin-copolymers differing in their crystallinity and crystal morphology. The temperature dependence of the γ-transition was found to obey the Arrhenius law for thermally activated processes. The γ-transition temperature determined at a frequency of 1 Hz and the corresponding activation energy were analyzed as a function of the crystallinity. As an overall trend, both quantities are found to decrease with decreasing crystallinity, which is explained by the increase in free volume due to the incorporation of short-chain branches or the thermal pretreatment (e.g., quenching). Taking into account that the crystal morphology of polyethylenes can be classified into four different groups, a more detailed picture appears. Within one type of morphology both quantities, namely the transition temperature and the activation energy, increase with decreasing crystallinity independent of the α-olefin used as the comonomer. These findings can be explained by partial orientations of the molecule segments in the interlamellar amorphous space in the case of HDPE or by the increased steric hindrance of the crankshaft motion by the short-chain branches. From the findings of this series of studies, it was concluded that the glass transition in polyethylene and polyethylene/α-olefin-copolymers is the β- and not the γ-transition.     

Effect of <Emphasis Type="Italic">β</Emphasis>-Cyclodextrin on <Emphasis Type="Italic">trans</Emphasis> Fats,CLA, PUFA and Phospholipids of Milk Fat

The aim of this study was to evaluate the effect of β-cyclodextrin (β-CD) on trans C18:1 fatty acid isomers, conjugated linoleic acid (CLA), polyunsaturated fatty acids (PUFA) and phospholipids in pasteurized milk. The individual trans C18:1 isomers were not significantly affected by the β-CD. trans-11 C18:1 (vaccenic acid) was found to be the major isomer (1.31 ± 0.12%) followed by trans-15 C18:1 (0.35 ± 0.06%). Individual trans linoleic acids did not show differences from the effect of β-CD, representing the high amount of the isomer trans-11 cis-15 C18:2 (0.433 ± 0.087%). The main CLA isomer cis-9 trans-11 C18:2 (rumenic acid) did not show differences between the control milk (0.672 ± 0.080%) and β-CD milk (0.663 ± 0.074%). PUFA and omega-3 and -6 fatty acids were not also significant by the effect of β-CD. Total phospholipids were not significantly affected by effect of the β-CD (0.023 ± 0.001% vs. 0.022 ± 0.001%). β-CD is a effective oligosaccharide for cholesterol removal from pasteurized milk and does not significantly affect the lipid components of the milk fat.     

Variation of Insect Attracting Odor in Endophytic <Emphasis Type="Italic">Epichloë</Emphasis> Fungi: Phylogenetic Constrains <Emphasis Type="Italic">Versus</Emphasis> Host Influence

Odor is a key trait for pollinator attraction in flowering plants, and many studies have investigated odor evolution in the light of pollinator selection by emphasizing the importance of the plant phylogenetic history. By contrast, little is known on the evolution of odors in fungus–insect interactions. In this study, profiles of three volatile compounds that are emitted by grass-inhabiting Epichloë fungi (Clavicipitaceae, Ascomycota) and that have a confirmed or likely role in the attraction of gamete-transferring Botanophila flies were investigated. We collected headspace samples from stromata of six European Epichloë species (including various host races) that originated from different locations in Switzerland, France, Poland, and UK for conducting gas chromatography analyses. Odor profiles exhibited considerable variation, but profiles of most species overlapped and did not discriminate at the species level. The exception was Epichloë festucae, which had a profile dominated by methyl (Z)-3-methyldodec-2-enoate. Based on an Epichloë phylogeny, there was some hierarchical structuring regarding levels of chokol K, another confirmed Botanophila attractant. However, patterns of odor profiles appeared to be largely dependant on particular Epichloë–host associations. The observed variation may be the result of complex selective pressures imposed by Botanophila gametic vectors, local environment, and mycoparasites.     

Dual stimuli-responsive supramolecular polymeric nanoparticles based on poly(<Emphasis Type="Italic">α</Emphasis>-cyclodextrin) and acetal-modified <Emphasis Type="Italic">β</Emphasis>-cyclodextrin-azobenzene

To aim at pH environment in tumor tissue and light-controlled drug release, UV and pH dual-responsive supramolecular polymeric nanoparticles mediated by host-guest interactions of poly(α-cyclodextrin) and acetal-modified β-cyclodextrin-azobenzene were developed in this work. The host molecule was poly(α-cyclodextrin) and the guest molecule was composed of acetal-modified β-cyclodextrin with one azobenzene linked. The inclusion of α-cyclodextrin and azobenzene leaded to amphiphilic supramolecular polymer, which further self-assembled to form supramolecular polymeric nanoparticles in aqueous medium. UV and pH responsiveness of supramolecular polymeric nanoparticles attributed to azobenzene and acetal, respectively. Supramolecular polymeric nanoparticles based on poly(α-cyclodextrin) and acetal-modified β-cyclodextrin-azobenzene with the average diameter of sub-100 nm were controllable to release the drugs regulated by pH and UV.     

Vaccenic acid (<Emphasis Type="Italic">t</Emphasis>11–18∶1) is converted to <Emphasis Type="Italic">c</Emphasis>9,<Emphasis Type="Italic">t</Emphasis>11-CLA in MCF-7 and SW480 cancer cells

The aims of this study were to determine whether vaccenic acid (VA; t11–18∶1) is converted to c9,t11-CLA in human mammary (MCF-7) and colon (SW480) cancer cell lines and whether VA influences cell viability and other CLA-bioresponsive markers. When cells were incubated in the presence of VA at concentrations of 5 to 20 μg/mL, both VA and c9,t11-CLA increased in cellular lipids in a dose-dependent manner. After 4 d of incubation of SW480 and MCF-7 cells with VA (20 μg/mL), c9,t11-CLA increased from undetectable levels to 8.57 and 12.14 g/100 g FAME in cellular lipids, respectively. VA supplementation for 4 d at 5, 10, and 15 μg/mL had no effect on cell growth, whereas 20 μg/mL significantly (P<0.05) reduced cell growth in both cell lines. VA (20 μg/mL) treatment induced DNA fragmentation and significantly (P<0.05) depeleted cytosolic GSH levels in the SW480 cell line after 4 d of incubation, suggesting that apoptosis was the mode of cell death induced by VA. Both VA and c9,t11-CLA reduced (P<0.05) total ras expression in SW480 cells. ¹⁴C-Arachidonic acid uptake into the MG fraction was significantly increased (P<0.05) in both cell lines while uptake into the phospholipid fraction decreased in response to VA. VA treatment significantly (P<0.05) increased 8-epi-prostaglandin F_2α in both cell lines. The data indicate that growth suppression and cellular responses of both cells lines are likely mediated by VA desaturation to c9,t11-CLA via Δ⁹-desaturase.     

Hepatic Lipase Gene −514<Emphasis Type="Italic">C</Emphasis>/<Emphasis Type="Italic">T</Emphasis> Polymorphism in the Guangxi Hei Yi Zhuang and Han Populations

Hei Yi Zhuang is an isolated subgroup of the Zhuang minority in China. This study was designed to compare the difference in the hepatic lipase gene (LIPC) -514C/T polymorphism and its association with lipid profiles between the Guangxi Hei Yi Zhuang and Han populations. Genotyping of the LIPC -514C/T was performed in 873 subjects of Hei Yi Zhuang and 867 participants of Han Chinese. The frequency of -514T allele was 43.47% in Hei Yi Zhuang, and 36.10% in Han (P < 0.001). The frequencies of CC, CT and TT genotypes were 30.01, 53.04 and 16.95% in Hei Yi Zhuang, and 40.95, 45.91 and 13.14% in Han (P < 0.001); respectively. Serum high-density lipoprotein cholesterol (HDL-C) and apolipoprotein B levels in both ethnic groups were higher in LIPC -514T carriers than in C carriers. In addition, serum triglyceride levels in Han were higher in TT genotype individuals than in CC genotype subjects (P < 0.05). Serum HDL-C levels were positively correlated with age, alcohol consumption and LIPC -514C/T genotypes, and negatively associated with hypertension and cigarette smoking in Hei Yi Zhuang (P < 0.05-0.01), whereas HDL-C levels were positively correlated with age, alcohol consumption and LIPC -514C/T genotypes, and negatively associated with body mass index and cigarette smoking in Han (P < 0.05-0.001). The differences in serum HDL-C levels between the two ethnic groups might partially attribute to the differences in the LIPC -514C/T polymorphism.     

Synthesis and characterization of amphiphilic triblock-graft PEG-(<Emphasis Type="Italic">b</Emphasis>-PαN<Subscript>3</Subscript>CL-<Emphasis Type="Italic">g</Emphasis>-Alkyne)<Subscript>2</Subscript> degradable copolymers

The study proposes a straightforward strategy for synthesizing novel, amphiphilic triblock-graft PEG-(b-PαN₃CL-g-Alkyne)₂ degradable copolymers. First, this investigation performs copolymerization of α-chloro-ε-caprolactone (αClCL) using α,ω-dihydroxyl-terminated macroinitiator poly(ethylene glycol) (PEG) and stannous octoate as the catalyst. In a second step, the current work converts pendent chlorides into azides by reacting with sodium azide. Finally, various kinds of terminal alkynes react with pendent azides by copper-catalyzed Huisgen’s 1,3-dipolar cycloaddition, thus a “click” reaction. These copolymers are characterized by differential scanning calorimetry (DSC), ¹H NMR, IR and gel permeation chromatography. The resulting triblock-graft copolymers exhibit lower crystallinity and melting temperature with respect to the original PEG. The triblock-graft copolymers form micelles in the aqueous phase with critical micelle concentrations (CMCs) in the range of 1.58–8.62 mg L⁻¹, depending on polymer composition. The ¹H NMR spectrum of micelles in D₂O demonstrate only the PEG signal and thus confirm the PCL-g-Alkyne blocks constitute the micelle core, while the central PEG block constitutes the micelle shell. The hydrophilic segment lengths influence the micelle shape. The mean hydrodynamic diameters of micelles from DLS range from 90–200 nm. The work describes drug entrapment efficiency and drug loading content of micelles depending on the composition of triblock-graft polymers.      

Bulky <Emphasis Type="Italic">N</Emphasis>-acyl-pyridylbenzamidine Ligands for Palladium Catalyzed Suzuki–Miyaura Reaction

Abstract  

In this letter, a series of bulky N-acyl-pyridylbenzamidine ligands were synthesized and characterized. Under the optimized reaction conditions, these bulky ligands were applied to catalyze Suzuki–Miyaura reactions of various aryl bromides and chlorides. The desired biaryl products were obtained in good to high yields.     

Photoelectrochemical Properties of NiO Coupled with TiO<Subscript>2−<Emphasis Type="Italic">x</Emphasis></Subscript>N<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> Thin Film Prepared by Magnetron Sputtering Method

TiO_2−x N _x films were deposited on ITO glass by reactive dc magnetron sputtering method under different O₂/N₂ flow ratios. A NiO film was deposited by chemical bath deposition onto the as-prepared ITO/TiO_2−x N _x film to form an ITO/TiO_2−x N _x /NiO composite electrode. The morphology, crystal structure and composition of the TiO_2−x N _x films were characterized by SEM, XRD and XPS. The photoelectrochemical properties of the TiO_2−x N _x films were investigated by means of UV–Vis absorption spectra and photocurrent measurements. The results showed that the TiO_2−x N _x film sputtered under O₂/N₂ flow ratio of 1:2 exhibited a higher photocurrent response than the others. Correspondingly, the TiO_2−x N _x /NiO electrode consisting of the sputtered TiO_2−x N _x film under O₂/N₂ flow ratio of 1:2 also showed the best photoelectrochromic feature.     

Distribution of nonequilibrium carriers in the region of a <Emphasis Type="Italic">p</Emphasis>–<Emphasis Type="Italic">n</Emphasis> junction under various photogeneration conditions

A model is described, which makes it possible to calculate the distribution of nonequilibrium carriers and an electric field near the p–n junction, which arose as a result of the internal photoeffect. Using laser illumination, the possibilities to control the properties of nanolayered structures sensitive to the concentration of free carriers are analyzed. The mutual location of the region of the intense absorption of radiation and the p–n junction itself is varied and the linear and square mechanisms of carrier recombination are analyzed.     

Properties of perovskite-like phases <Emphasis Type="Italic">Ln</Emphasis>BaCuFeO<Subscript>5 + δ</Subscript> (<Emphasis Type="Italic">Ln</Emphasis> = La,Pr)

The influence of the oxygen content on the crystal chemical parameters of the LnBaCuFeO_{5 + δ} (Ln = La, Pr) ferrocuprates is investigated using X-ray powder diffraction and IR spectroscopy. The electrical conductivity of these phases is studied. The chemical expansion coefficients α_δ and the activation energies E _a for electrical conduction are calculated. It is demonstrated that, for the LnBaCuFeO_{5 + δ} (Ln = La, Pr) phases, the chemical expansion coefficients ad depend on both the ionic radius of Ln ³⁺ cations and the oxygen nonstoichiometry of the ferrocuprate, whereas the activation energies E _a for electrical conduction are predominantly determined by the oxygen content in the samples.