Olfactory Responses to Aphid and Host Plant Volatile Releases: (E)-β-Farnesene an Effective Kairomone for the Predator Adalia bipunctata

The volatiles released from several aphid and host plant species, alone or associated, were studied for their infochemical role in prey location. Using a four-arm olfactometer, the attraction of several combinations of three aphid (Myzus persicae, Acyrthosiphon pisum, and Brevicoryne brassicae) and three plant (Vicia faba, Brassica napus, and Sinapis alba) species toward Adalia bipunctata larvae and adults was observed. Both predatory larvae and adults were attracted only by A. pisum and M. persicae when they were crushed, whatever the host plant. (E)-beta-farnesene, the aphid alarm pheromone, was the effective kairomone for the ladybird. Plant leaves alone (V. faba, B. napus, and S. alba) or in association with nonstressed whole aphids (the three species) did not have any attraction for the predator. The B. brassicae specialist aphid is the only prey that was not attracted to A. bipunctata larvae and adults, even if they were crushed. Release of B. brassicae molecules similar to the host plant allelochemicals was demonstrated by GC-MS analysis. The lack of behavioral response of the ladybird at short distance toward the cruciferous specialist aphid was related only to the absence of (E)-beta-farnesene in the aphid prey volatile pattern.     

Apple Fruit Infested with Codling Moth are More Attractive to Neonate Codling Moth Larvae and Possess Increased Amounts of (E,E)-α-Farnesene

Apple fruit artificially infested with codling moth larvae attracted significantly more neonate larvae of the codling moth, Cydia pomonella than uninfested fruit. A greater number of larvae responded to odor in an olfactometer from codling moth-infested cold-stored Red Delicious thinning apples than uninfested apples. Immature Granny Smith, Red Delicious, or Golden Delicious apples that were infested on the tree for five days by codling moth larvae were more attractive to neonate codling moth larvae than similar but uninfested fruit of the same varieties. Apples infested on the tree and sampled five days later also contained significantly greater amounts of the larval attractant (E,E)--farnesene, compared to uninfested apples. Other types of injury to apple fruit did not produce results similar to that from codling moth infestation, either in increased attractiveness to codling moth larvae or in increased quantities of (E,E)--farnesene. These results are consistent with the reported attractiveness of (E,E)--farnesene to neonate codling moth larvae.     

Compatibilizing capability of poly(β-hydroxybutyrate-,co-ε-caprolactone) in the blend of poly(β-hydroxybutyrate) and poly(ε-caprolactone)

In order to increase the miscibility in the blend of poly(β-hydroxybutyrate) [PHB] and poly(ε-caprolactone) [PCL], PHB/PCL copolyesters were used as compatibilizers. These PHB/PCL copolyesters were synthesized by transesterification in solution phase. The melting point [T_m] depression, which was not observed in PHB/PCL blend without compatibilizer, was observed when PHB/PCL copolyesters as compatibilizers were added to the PHB/PCL blend system. As the amount of compatibilizer added to the blend increased, the crystallization temperature [T_c] of PCL in the blend increased and T_c of PHB in the blend decreased. The difference in T_c between PHB and PCL was gradually reduced. When the sequence length of PHB block and PCL block in the PHB/PCL copolyester increased, the miscibility of the blend increased. This is evidenced by the depression in the T_m of PHB and PCL in the blend and by the decrease in the difference of T_c between PHB and PCL. From the polarizing optical micrographs, the phase separation in PHB/PCL blend was observed. However, in the presence of PHB/PCL copolyester, the spherulite of PHB grows in equilibrium with one phase melt. Received: 27 July 1998/Revised version: 12 October 1998/Accepted: 4 November 1998     

Studies on the Dehydrogenative Polymerizations of Monolignol β‐Glycosides. Part 1. Syntheses of Monolignol β‐glycosides, (E)‐Isoconiferin, (E)‐Isosyringin,and (E)‐Triandrin

Abstract

(E)‐4‐O‐Acetyl coniferyl alcohol was synthesized by the reduction of (E)‐4‐O‐acetyl ferulic acid with sodium borohydride and N,N‐dimethylchloromethylenium chloride in 80.2% yield. The glycosylation of (E)‐4‐O‐acetyl coniferyl alcohol with trichloroacetimidoyl 2,3,4,6‐tetra‐O‐pivaloyl‐α‐D‐glucopyranoside in the presence of BF₃-Et₂O in anhydrous CH₂Cl₂, followed by deacylation gave (E)‐isoconiferin in high yield. This synthetic method could be applied to the syntheses of other monolignol β‐glycosides. As a result, (E)‐isoconiferin, (E)‐isosyringin, and (E)‐triandrin were synthesized from vanillin, syringaldehyde, and p‐hydroxybenzaldehyde, respectively, by five reaction steps in high overall yield.     

A new method for the synthesis of tetrahydrothiophene-S,S-dioxide derivatives: the Michael ring closure reaction between halomethyl (E)-β-styryl sulfones and CH-acids

Bromomethyl and chloromethyl (E)-β-styryl sulfones enter a Michael ring closure reaction with sodium enolates prepared from dimethyl malonate, malononitrile and ethyl acetoacetate. The condensation results in formation of substituted tetrahydrothiophene-S,S-dioxides. It is a new instance of α-haloalkyl sulfones transformations, which are not connected with Ramberg–Bäcklund reaction.     

Synthesis of stereoisomers of 6β- and 7β-(benzylthio)-3-(p-tolyl) tropane-2-carboxylic acid methyl ester

To develop new ^99mTc-labelled agents to evaluate dopamine transporters (DAT) involved in Parkinson's disease, by in vivo SPECT imaging, we have synthesized six new sulfur-containing ligands with the tropane skeleton. We have introduced the complexing sulfur atom far from the three sites of recognition by DAT of these tropane derivatives. The 6β-substituted tropinone has been obtained by a double Mannich condensation followed by the introduction of the moieties for molecular interactions at the binding site on C2 and C3, leading to the six stereoisomers.     

β,β'-双取代-(E)-甲酸乙烯酯的选择性合成研究

以廉价易得的各类苯乙酮衍生物为原料,经Wittig-Horner反应得到(E)-β-芳基丙烯酸酯,然后经DIBAL-H还原、MnO_2氧化以及Baeyer-Villiger氧化"一锅法"合成一系列具有全新结构的标题化合物。该产物是一类重要的药物分子和活性产物中间体,其结构通过1HNMR和13CNMR确认。该合成路线简单易行、选择性高,是迄今为止获得该类化合物的首例方法学研究报道。     

Synthesis of polymer having β,β-triketone unit in the main chain and its copper (II) complex

Summary A novel polymer having β,β-triketone unit in the main chain was prepared by polycondensation of triethylene glycol bis(p-butoxycarbonylphenyl) ether (1) with triethylene glycol bis(p-acetylacetophenyl) ether (4). The obtained polymer was soluble in CHCl₃, DMF, and DMSO. The structure of the polymer was confirmed by ¹H-NMR. Insoluble brownish yellow copper (II) chelate was obtained by adding a methanol solution of copper (II) acetate to a chloroform solution of the polymer. The IR analysis and the measurement of copper content by iodometric titration showed the quantitative formation of binuclear copper (II) complex. Received: 20 March 1998/Accepted: 17 April 1998     

Preparation of poly(methyl methacrylate) macromonomer by radical polymerization in the presence of methyl α-(bromomethyl)acrylate and copolymerization of the resultant macromonomer

Radical polymerization of methyl methacrylate (MMA) in the presence of methyl -(bromomethyl) acrylate yielded poly-(MMA) bearing the 2-methoxycarbonylallyl end group through chain reaction involving bimol ecular termination. The molecular weight of the resultant polymer was effectively controlled with a small amount of the bromomethylacrylate added; the chain transfer constant was estimated to be 0.9. The poly (MMA) with the unsaturated end group (

Thermo- and pH-Responsive Polymersomes of Poly(α,β-N-substituted-DL-aspartamide)s

Materials that can respond to multiple stimuli, such as temperature and pH changes, are of considerable interest for applications in drug delivery systems. Notably, α,β-[poly(2-hydroxyethyl)-DL -aspartamide] is a potentially useful material for such applications. This study investigated the temperature and pH responsiveness of polymers structurally similar to α,β-[poly(2-hydroxyethyl)-DL -aspartamide], namely, poly(α,β-N-substituted-DL -aspartamide)s, in aqueous media. These polymers were derived from polysuccinimide (PSI), which was first synthesized via acid-catalyzed bulk polycondensation of L -aspartic acid (L-ASP) in the presence of 85% o-phosphoric acid under N2. Two primary amino alcohols, 4-aminobutanol (4AB) and 6-aminohexanol (6AH), were then respectively utilized to modify PSI to form poly (α,β-N-substituted-DL -aspartamide)s via aminolysis. Different ratios of these two amino alcohols were used to modify the polymer to produce a series of copolymers with lower critical solution temperatures ranging from 53–28°C when dispersed in aqueous media. Moreover, the properties of the poly(α,β-N- substituted-DL -aspartamide)s in aqueous solution were affected by pH changes. The morphology of the particles formed by these amphiphilic polymers was observed using scanning electronic microscopy and transmission electronic microscopy, and the particles were found to be polymersomes with shell and hollow core structures and diameters of 0.5–1 μm. Other properties of this series of self-assembly copolymers were also characterized. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

The effect of chemistry on the polymerization, thermo-mechanical properties and degradation rate of poly(β-amino ester) networks

Poly(β-amino ester) networks are gaining attention as a scaffold material for tissue engineering applications where it is important to have tailorable degradation rate and elastic modulus. The objective of this work is to characterize and understand the relationships between chemical structure, polymerization, thermo-mechanical properties, and degradation in poly(β-amino esters) networks. The networks were synthesized from a primary amine with systematically varied molar ratios and chemical structures of diacrylates. Fundamental trends were established between the chemical structure, conversion during polymerization, macromer molecular weight, rubbery modulus, and degradation rate. The thermo-mechanical properties were dependent upon both polymerization steps. The rubbery modulus was tailorable over a range of several MPa by changing molar ratio and diacrylate molecular weight. The degradation rate ranged from hours to months depending upon the composition. Select chemical structures showed degradation rate independent of modulus. This work provides a basis for designing poly(β-amino esters) networks with specific thermo-mechanical properties and degradation rates for biomedical scaffolds.     

Effect of Yb,Gd, and Nd Substitution at the Sr Site on the Metal–Insulator Transition of the (Bi,Pb)-2212 System

Resistivity measurements in the temperature range (64–300 K) were used to study the metal–insulator transition (MIT) driven by a change in the carrier concentration of the Bi_1.7Pb_0.4Sr₂Ca_1.1Cu_2.1O_y [(Bi,Pb)-2212] system. The carrier-concentration is changed by substituting rare-earth (RE) elements (Nd, Gd, and Yb) at the Sr site of (Bi,Pb)-2212. Results show that at higher levels of RE substitution, MIT occurs in (Bi,Pb)-2212, during which the resistivity becomes minimum at a particular temperature(T_min) for a particular doping level. Below this temperature, resistivity increases with a decrease in the temperature and vice versa, showing an insulating and a metallic nature, respectively. This T_min and the carrier concentration at which MIT occurs depend on the substituted RE.     

Evaluation of the Hydrophilic Complexant N,N,N’,N’-tetraethyldiglycolamide (TEDGA) and its Methyl-substituted Analogues in the Selective Am(III) Separation

ABSTRACT

N,N,N’,N’-tetraethyldiglycolamide (TEDGA) is used in the French EXAm (extraction of americium) process to separate Am(III) from Cm(III) and Ln(III). In this study, the complexation behavior of TEDGA towards actinides(III) and lanthanides(III) was compared to its methyl-substituted derivatives Me-TEDGA and Me₂-TEDGA under experimental conditions applying to the EXAm process. Using the EXAm solvent, 0.6 mol/L N,N’-dimethyl-N,N’-dioctyl-hexylethoxymalonamide (DMDOHEMA) and 0.45 mol/L bis(2-ethylhexyl)-phosphoric acid (HDEHP), An(III) and Ln(III) distribution ratios increase in the order TEDGA < Me-TEDGA < Me₂-TEDGA. This is explained by differences in the strength of complexation in the aqueous phase: Conditional stability constants for the formation of [Cm(DGA)_x]³⁺ complexes decrease in the order TEDGA > Me-TEDGA > Me₂-TEDGA, as shown by time-resolved laser fluorescence spectroscopy (TRLFS). TRLFS measurements verified the exclusive existence of [Cm(DGA)₃]³⁺ complexes in the aqueous phase. Both the homoleptic [Cm(DMDOHEMA)_n]³⁺ and the heteroleptic [Cm(DGA)_x(DMDOHEMA)_y]³⁺ complexes were detected in the organic phase, as postulated in the literature.^[14]     

Effect of sintering conditions and heat treatment on the properties,microstructure and machining performance of α-β-SiAlON ceramics

The properties of SiAlON ceramics are strongly affected by the composition and structure of the intergranular phase, which are controlled by dopants, sintering conditions and starting silicon nitride (Si₃N₄) powder characteristics. In this study, 25α:75β SiAlON compositions were designed with different molar ratios of Y:Sm:Ca (9:0.5:0.5 and 3:6:1). The effects of cation ratios, different cooling profiles (50 °C/min and 5 °C/min) and further heat treatment under different conditions (at 1600 °C for 2, 4 and 6 h) on the final phase composition, the type of the intergranular phase (amorphous or crystalline) formation, the resulting microstructures and the machining performance were studied. It is found that slow cooling and heat treatment have a great influence on crystallisation behaviour and in turn the crystallisation enhance the machining performance of SiAlON materials in cutting tool applications.     

Investigation of Spectroscopic Properties and Spin-Orbit Splitting in the X(2)Π and A(2)Π Electronic States of the SO(+) Cation

The potential energy curves (PECs) of the X(2)Π and A(2)Π electronic states of the SO(+) ion are calculated using the complete active space self-consistent field method, which is followed by the internally contracted multireference configuration interaction (MRCI) approach for internuclear separations from 0.08 to 1.06 nm. The spin-orbit coupling effect on the spectroscopic parameters is included using the Breit-Pauli operator. To improve the quality of PECs and spin-orbit coupling constant (A(0)), core-valence correlation and scalar relativistic corrections are included. To obtain more reliable results, the PECs obtained by the MRCI calculations are corrected for size-extensivity errors by means of the Davidson modification (MRCI+Q). At the MRCI+Q/aug-cc-pV5Z+CV+DK level, the A(0) values of the SO(+)(X(2)Π(1/2, 3/2)) and SO(+)(A(2)Π(1/2, 3/2)) are 362.13 and 58.16 cm(-1) when the aug-cc-pCVTZ basis set is used to calculate the spin-orbit coupling splitting, and the A(0) of the SO(+)(X(2)Π(1/2, 3/2)) and SO(+)(A(2)Π(1/2, 3/2)) are 344.36 and 52.90 cm(-1) when the aug-cc-pVTZ basis set is used to calculate the spin-orbit coupling splitting. The conclusion is drawn that the core-valence correlations correction makes the A(0) slightly larger. The spectroscopic results are obtained and compared with those reported in the literature. Excellent agreement exists between the present results and the measurements. The vibrational manifolds are calculated, and those of the first 30 vibrational states are reported for the J = 0 case. Comparison with the measurements shows that the present vibrational manifolds are both reliable and accurate.