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.     

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.     

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.     

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.     

Effect of photo-dimerization of coumarins on their interaction with polymeric <Emphasis Type="Italic">β</Emphasis>-cyclodextrin

Coumarin and 7-hydroxycoumarin (7HC) were photo-dimerized in an aqueous solution of polymeric β-cyclodextrin (PβCD) to investigate the effect of the photo-dimerization on the viscosity of PβCD solution. PβCD was prepared by cross-linking β-cyclodextrin (βCD) using epichlorohydrin. The content of βCD residues in PβCD, determined by a colorimetric method using phenolphthalein as an indicator, was 28.8 wt%. The solubility of coumarin increased with increasing concentration of PβCD, because the benzene ring of coumarin was included in the hydrophobic cavity of βCD residue. PβCD also increased the solubility of 7HC, but the solubilizing effect on 7HC was much less than that on coumarin, possibly because the hydroxy group on the benzene ring was likely to suppress the inclusion in the cavity of βCD. And, the photo-dimerization degree of 7HC in an aqueous solution of PβCD was about half than that of coumarin, possibly because the vinyl ether of pyrone group of 7HC could be concealed in the cavity of βCD. The photo-dimerization of coumarin in an aqueous solution of PβCD could significantly increase the viscosity of the solution. One coumarin dimer would hydrophobically interact with two βCD residues so it can act as a cross-linker for PβCD.     

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.     

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.     

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.     

Fed-batch optimization of recombinant <Emphasis Type="Italic">α</Emphasis>-amylase production by <Emphasis Type="Italic">Bacillus subtilis</Emphasis> using a modified Markov chain Monte Carlo technique

A modified Markov Chain Monte Carlo (MCMC) searching procedure was developed to search for an optimal set of decision variables and optimal feed rate trajectories for recombinant α-amylase expression by Bacillus subtilis ATCC 6051a. The bacterium also synthesizes proteases as undesirable products in fed-batch culture that need to be minimized. To maximize α-amylase productivity, a 14th-order fed-batch model was optimized by integrating Pontryagin’s maximum principle with the Luedeking-Piret equation. The number of iterations and simulations of the proposed searching procedure were statistically examined for accuracy and acceptability of the results. It can be concluded that the proposed searching procedure increased the parameter selection opportunity near the tail ends of redefined triangular distribution. By applying a modified MCMC searching procedure with 1,500 iterations, the predicted α-amylase productivity was improved by 18% in comparison with near-optimum experimental results. This productivity was 3.5% higher than predicted by conventional MCMC optimization.     

Multifunctional wool fiber treated with <Emphasis Type="Italic">ɛ</Emphasis>-polylysine

A creative method for fabricating environmentally-benign multifunctional wool fibers was established and reported. Through coating the wool fibers with ɛ-polylysine, the surface morphology and biochemical properties of the fibers were altered, enhancing their antimicrobial, hygroscopic and finished properties. The process of ɛ-polylysine coating was dependent on the solution environment, which influenced the electrostatic interactions between ɛ-polylysine molecules and wool fibers. The results showed that a maximum ɛ-polylysine coating (23.60 mg/g) on the surface of wool fibers was reached when wool fibers were soaked at 50 °C for 2 h in the solution with 10% on weight of fabric (owf) ɛ-polylysine and pH 8.0. The coated wool fiber showed promising antimicrobial rates of 96.98% and 97.93% against Escherichia coli and Micrococcus luteus, respectively. The wool fiber coated with the ɛ-polylysine was more hydrophilic than the uncoated wool fabrics. The functional wool fibers after water scrubbing for two times still have good antibacterial efficiency against Escherichia coli and Micrococcus luteus, and antimicrobial rates were 96.77% and 97.33%, respectively. This study shows that wool fibers modified by the nontoxic ɛ-polylysine have a great potential to be used in constructing multifunctional textiles.     

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.     

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.     

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.     

(11<Emphasis Type="Italic">Z</Emphasis>,13<Emphasis Type="Italic">E</Emphasis>)-Hexadecadien-1-yl Acetate: Sex Pheromone of the Grass Webworm <Emphasis Type="Italic">Herpetogramma licarsisalis</Emphasis>—Identification,Synthesis, and Field Bioassays

The grass webworm Herpetogramma licarsisalis (Lepidoptera: Crambidae), which has recently established in pasture in Northland, New Zealand, is an important pest of many tropical and subtropical grasses. Two pheromone components, (Z)-11-hexadecen-1-yl acetate (Z11–16:Ac) and (11Z,13E)-hexadecadien-1-yl acetate (Z11,E13–16:Ac), were identified in pheromone gland extracts of female moths by gas chromatography (GC), GC-electroantennographic detection, and GC-mass spectrometry in conjunction with microchemical tests (dimethyldisulfide and 4-methyl-1,2,4-triazoline-3,5-dione derivatizations). Z11,E13–16:Ac and its geometric isomer (11E,13Z)-hexadecadien-1-yl acetate (E11,Z13–16:Ac) were synthesized via stereoselective Wittig reactions, and the identity of the diene present in the pheromone glands was confirmed to be Z11,E13–16:Ac. Field bioassays at Indooroopilly in Brisbane, Australia, established that Z11,E13–16:Ac was necessary and sufficient for attraction of male grass webworm moths and that the corresponding alcohol, (11Z,13E)-hexadecadien-1-ol (Z11,E13–16:OH), had a strong inhibitory effect on trap catches at the ratios tested. When mixed with Z11,E13–16:Ac in various ratios, Z11–16:Ac had no effect on the attractiveness of lures. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Investigation of the Meyer-Neldel rule for AC conduction in glassy Se<Subscript>100 − <Emphasis Type="Italic">x</Emphasis></Subscript>Te<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> alloys

In many amorphous and liquid semiconductors and other class of materials, the Meyer-Neldel rule is observed in the dc conductivity, where the preexponential factor (σ₀) is found to increase exponentially with the activation energy (ΔE). In the present paper, we report on the observation of the Meyer-Neldel rule in case of ac conductivity at high temperatures (300–350 K) in bulk samples of glassy Se_{100 − x} Te _x (x = 10, 20, 30) alloys. In this temperature range, the approximate variation in ac conductivity with temperature is found to be exponential and the activation energy is found to vary with frequency. The observation of the Meyer-Neldel rule in the present study is explained in terms of the compensation effect in the relaxation time. The text was submitted by the authors in English.     

Direct-hydrothermal synthesis of LiFe<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>PO<Subscript>4</Subscript> cathode materials

Carbon free LiFe_1−x Mn _x PO₄ (x = 0, 0.05, 0.1, 0.2, 0.4) cathode materials were prepared by a direct-hydrothermal process at 170 °C for 10 h. The structural and electrochemical properties of the samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), charge–discharge experiments, cyclic voltammetry (CV) and alternating current (AC) impedance spectroscopy. The electrochemical performance of LiFePO₄ prepared in this manner showed to be positively affected by Mn²⁺-substitution. Among the Mn²⁺-substitution samples, the LiFe_0.9Mn_0.1PO₄ exhibited an initial discharge capacity of 141.4 mA h g⁻¹ at 0.1 C, and the capacity fading is only 2.7% after 50 cycles.     

Identification and Functional Expression of a Δ9-Fatty Acid Desaturase from <Emphasis Type="Italic">Psychrobacter urativorans</Emphasis> in <Emphasis Type="Italic">Escherichia coli</Emphasis>

The Δ9-fatty acid desaturase is a key enzyme in the synthesis of unsaturated fatty acids. The fatty acid composition of membrane phospholipids in Psychrobacter urativorans is characterized by a high degree of desaturation at Δ9 position. Based on CODEHOP-mediated PCR strategy, a novel gene designated as PuFAD9, putatively encoding a Δ9-fatty acid desaturase (PuFAD9), was isolated from P. urativorans. The gene consists of 1,455 bp and codes for 484 amino acids. Analysis of the amino acid sequence reveals three histidine clusters and a hydropathy profile, typical for membrane-bound desaturases. Activity of the PuFAD9 protein, recombinantly expressed in Escherichia coli was confirmed by GC-MS analysis of the cellular fatty acid composition. It was found that the ratio between palmitoleic and palmitic acid in E. coli cells heterologously expressing the PuFAD9 gene was significantly affected by IPTG induction and the growth temperature.