Evolution of Artificial Arginine Analogues—Fluorescent Guanidiniocarbonyl-Indoles as Efficient Oxo-Anion Binders

In this article, we present fluorescent guanidiniocarbonyl-indoles as versatile oxo-anion binders. Herein, the guanidiniocarbonyl-indole (GCI) and methoxy-guanidiniocarbonyl-indole (MGCI) were investigated as ethylamides and compared with the well-known guanidiniocarbonyl-pyrrole (GCP) concerning their photophysical properties as well as their binding behavior towards oxo-anions. Hence, a variety of anionic species, such as carboxylates, phosphonates and sulfonates, have been studied regarding their binding properties with GCP, GCI and MGCI using UV-Vis titrations, in combination with the determination of the complex stoichiometry using the Job method. The emission properties were studied in relation to the pH value using fluorescence spectroscopy as well as the determination of the photoluminescence quantum yields (PLQY). Density functional theory (DFT) calculations were undertaken to obtain a better understanding of the ground-lying electronic properties of the investigated oxo-anion binders. Additionally, X-ray diffraction of GCP and GCI was conducted. We found that GCI and MGCI efficiently bind carboxylates, phosphonates and sulfonates in buffered aqueous solution and in a similar range as GCP (K_ass ≈ 1000–18,000 M⁻¹, in bis-tris buffer, pH = 6); thus, they could be regarded as promising emissive oxo-anion binders. They also exhibit a visible fluorescence with a sufficient PLQY. Additionally, the excitation and emission wavelength of MGCI was successfully shifted closer to the visible region of the electromagnetic spectrum by introducing a methoxy-group into the core structure, which makes them interesting for biological applications.     

Preparation of nano-hydroxyapatite/poly(<Emphasis Type="SmallCaps">l</Emphasis>-lactide) biocomposite microspheres

Nano-hydroxyapatite (HA)/poly(l-lactide) (PLLA) composite microspheres with relatively uniform size distribution were prepared by a solid-in-oil-in-water (s/o/w) emusion solvent evaporation method. The encapsulation of the HA nanopaticles in microshperes was significantly improved by grafting PLLA on the surface of the HA nanoparticles (p-HA) during emulsion process. This procedure gave a possibility to obtain p-HA/PLLA composite microspheres with uniform morphology and the encapsulated p-HA nanoparticle loading reached up to 40 wt% (33 wt% of pure HA) in the p-HA/PLLA composite microspheres. The microstructure of composite microspheres from core-shell to single phase changed with the variation of p-HA to PLLA ratios. p-HA/PLLA composite microspheres with the diameter range of 2–3 μm were obtained. The entrapment efficiency of p-HA in microspheres could high up to 90 wt% and that of HA was only 13 wt%. Surface and bulk characterizations of the composite microspheres were performed by measurements such as wide angle X-ray diffraction (WAXD), thermal gravimetric analysis (TGA), environmental scanning electron microscope (ESEM) and transmission electron microscopy (TEM).     

Characterizing polymer macrostructures by identifying and locating microstructures along their chains with the kerr effect

In this brief report, we demonstrate that Kerr effect measurements, which determine the excess birefringence contributed by polymer solutes in dilute solutions observed under a strong electric field, are highly sensitive to and capable of determining their microstructures, as well as their locations along the macromolecular backbone. Specifically, using atactic triblock copolymers with the same overall composition of styrene (S) and p-bromostyrene (pBrS) units, but with two different block arrangements, that is, pBrS₉₀-b-S₁₂₀-b-pBrS₉₀ (I) and S₆₀-b-pBrS₁₈₀-b-S₆₀ (II), which are indistinguishable by NMR, we detected a dramatic difference in their molar Kerr constants (_mK), in agreement with those previously estimated. Although similar in magnitude, their Kerr constants differ in sign, with _mK(II) positive and _mK(I) negative. In addition, S/pBrS random and gradient copolymers synthesized by reversible addition-fragmentation chain-transfer (RAFT) polymerization exhibit a heretofore unexpected enhanced enchainment of racemic (r) pBrS-pBrS diads. Comparison of their observed and calculated _mKs suggests that the gradient S/pBrS copolymers possess an unanticipated additional gradient in stereosequence that parallels their comonomer gradient, that is, as the concentration of pBrs units decreases from one end of the copolymer chain to the other, so does the content of r diads. This conclusion could only be reached by comparison of observed and calculated Kerr effects, which access the global properties of macromolecules, and not NMR, which is only sensitive to local polymer structural environments, but not to their locations on the copolymer chains. Molar Kerr constants are characteristic of entire polymer chains and are highly sensitive to their constituent microstructures and their distribution along the chain. They may be used to both identify constituent microstructures and locate them along the polymer chain, thereby enabling, for the first time, characterization of their complete macrostructures. © 2013 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

Analysis of Malathion and its Breakdown Products in Aquaria Containing Golden Shiners (N. CHRYSOLEUCAS)

Abstract

The 1-ethylmonocarboxylic acid of Malathion (MCA) was identified as a metabolite of Malathion in the gut of golden shiners (N. Chrysoleucas) (7.11 × 10²±0.66 × 10² ng/g tissue). As noted in the literature the rate of hydrolysis of Malathion above pH 7 is first order with respect to Malathion and pH dependent. In addition, the rate of hydrolysis of Malathion in aquaria housing these fish was found to be dependent on the concentration of Ca⁺²; sparging the aquaria with air affected the rate. Some of the hydrolysis products of Malathion were identified by gc/ms and found to be pH dependent above pH 7. The half-life of Malathion under different conditions, the identification of some hydrolytic products and a general scheme for the analysis of Malathion, along with some of its metabolic and hydrolytic products are included in this paper.     

Phase Transfer Catalyzed Anomeric Nucleophilic Substitutions with D-Xylopyranosyl Halides

Abstract

Anomeric pairs of per-O-acetylated-D-xylopyranosyl halides were individually treated with a wide variety of nucleophiles under mild PTC conditions. Thus, 2,3,4-tri-O-acetyl-α-D-xylopyranosyl bromide 1 provided exclusively the β-D-xylopyranosyl anomers 2-11 in good to excellent yields (65-95%). Alternatively, under the same PTC conditions, 2,3,4-tri-O-acetyl-β-D-xylopyranosyl chloride 13 afforded solely the inverted α-D-anomers 15 (82%) and 16 (67%) upon treatment with thiophenol and sodium azide, respectively. Similarly, 2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl chloride 19 provided the analogous products 20 (63%) and 21 (31%) upon treatment with thiophenol and sodium azide. In the presence of tetrabutylammonium chloride as PTC catalyst, β-xylopyranosyl chloride 13 was shown to slowly equilibrate to the α-chloride 14. Therefore, care must be taken to avoid PTC catalyst for which counter anions can cause anomerization of the starting glycosyl halides.     

The effect of drying method on the properties and nanoscale structure of cellulose whiskers

Cellulose whiskers were prepared from wood- and cotton-based microcrystalline cellulose and dried by two methods: freeze-drying or air-drying. The effect of drying method on the properties and structure of the whiskers were studied. Furthermore, the influence of the source of cellulose on the nanoscale structure was investigated. Drying method was observed to slightly influence the thermal stability of cellulose whiskers, whereas the char residue varied significantly depending on the drying process performed. Small- and wide-angle X-ray scattering and solid state nuclear magnetic resonance spectroscopy were used to examine the crystallinity and nanoscale structure of the dried whiskers. It was observed that the crystal structure and crystallinity of cellulose whiskers remained during all treatments, whereas their nanoscale structure was significantly influenced by drying method, neutralization, and source of cellulose. Relationships between thermal behavior and nanoscale structure were reported and discussed.     

DSC study of stabilizing effect of antioxidant mixtures in styrene-butadiene rubber

The type of cooperation between antioxidants in the binary mixtures of four substituted diphenylamines and phenotiazine in the stabilization of styrene-butadiene rubber has been tested. Thermooxidation of the samples has been studied by differential scanning calorimetry under non-isothermal conditions. The protection factors of the individual stabilizers and their mixtures were determined. The synergy factors were applied to asses the type of cooperation of antioxidants in the mixtures. From their values it can be concluded that the type of cooperation depends on temperature. The highest synergistic effect has been observed for the mixture of phenotiazine and [4-(1-methyl-1-phenyl-ethyl)-phenyl]-phenylamine.     

Numerical simulation for the temperature changing rule of the crude oil in a storage tank based on the wavelet finite element method

In order to study the temperature changing rule of the crude oil in the storage tank, the wavelet finite element method, the traditional finite element method and the test were used to carry out the numerical simulation. Firstly, the thermal wavelet finite element was put forward established based on thermal finite element theory and the wavelet theory. And the computational model and three boundary conditions were established. And then the temperature changing rule of the crude oil in the storage tank in 24 h for three boundary conditions was obtained by using three methods, and the results showed that the wavelet finite element method had advantages in the numerical analysis of the temperature changing rule of the crude oil in the storage. And then the temperature distribution rule of the crude oil in the storage tank under different conditions in 5 h was obtained. And the temperature changing mechanism of the crude oil was summarized finally.