Seasonal Variability of a Caryophyllane Chemotype Essential Oil of Eugenia patrisii Vahl Occurring in the Brazilian Amazon

Eugenia patrisii Vahl is a native and non-endemic myrtaceous species of the Brazilian Amazon. Due to few botanical and phytochemical reports of this species, the objective of the present work was to evaluate the seasonal variability of their leaf essential oils, performed by GC and GC-MS and chemometric analysis. The results indicated that the variation in oil yields (0.7 ± 0.1%) could be correlated with climatic conditions and rainy (R) and dry seasons (D). (E)-caryophyllene (R = 17.1% ± 16.0, D = 20.2% ± 17.7) and caryophyllene oxide (R = 30.1% ± 18.4, D = 14.1% ± 19.3) are the major constituents and did not display significant differences between the two seasons. However, statistically, a potential correlation between the main constituents of E. patrisii essential oil and the climatic parameters is possible. It was observed that the higher temperature and insolation rates and the lower humidity rate, which are characteristics of the dry season, lead to an increase in the (E)-caryophyllene contents, while lower temperature and insolation and higher humidity, which occur in the rainy season, lead to an increase in the caryophyllene oxide content. The knowledge of variations in the E. patrisii essential oil composition could help choose the best plant chemical profile for medicinal purposes.     

多检测GPC/SEC技术在高分子表征中的应用Ⅳ.氘化高分子的溶液性质

采用体积排斥色谱法／ 示差折光指数／ 直角激光光散射／ 示差粘度三检测联用技术表征了氘化聚苯乙烯、聚苯乙烯和氘化聚苯乙烯－ 聚异戊二烯。结果表明,在θ条件下,虽然氘化聚苯乙烯的化学依赖性常数υＴ,ＤＰＳ比聚苯乙烯的化学依赖性常数υＴ,ＰＳ大,但２５ ℃时在四氢呋喃中,氘化聚苯乙烯的分子尺寸仍小于聚苯乙烯的分子尺寸。由于嵌段共聚物的淋洗体积随组成变化,所以用传统的ＳＥＣ／ＲＩ得不到准确的分子量。经比较膜渗透、小角激光光散射和基质辅助激光脱吸与离子化时间飞行质谱等的实验结果,证明体积排斥色谱法／ 示差折光指数／ 直角激光光散射／ 示差粘度三检测技术能准确地得到氘化二嵌段共聚物的分子量以及其它重要信息。     

Complications in the Use of the Taylor Dispersion Method for Ternary Diffusion Measurements: Methanol + Acetone + Water Mixtures

The Taylor dispersion technique is used to measure the ternary mutual diffusion coefficients of aqueous nonelectrolyte solutions at 25°C. The dispersion of the injected solutes is recorded by a differential refractometer and an ultraviolet-visible detector. The diffusion coefficients are calculated directly by fitting the theoretical dispersion equations to about six experimental curves simultaneously. If the ternary diffusion effects in the measured dispersion profiles are not confused by the inaccuracy of the experimental method or an unfavorable relative detector sensitivity, the diffusion coefficients are precise. For the system methanol + acetone + water, it is shown that the Taylor dispersion method is unsuitable for the determination of all the diffusion coefficients if the methanol mole fraction is less than 0.45 or the acetone mole fraction if more than 0.001.     

New ligands and structural insights into the catalytic asymmetric addition of organozinc reagents to ketones

The catalytic asymmetric addition of alkyl groups to ketones has received considerable attention. Outlined herein is the synthesis of two new ligands based on the C₂-symmetric 11,12-diamino-9,10-dihydro-9,10-ethanoanthracene. The scope of the new ligands has been evaluated in the catalytic asymmetric addition of diethylzinc to a variety of ketones. Enantioselectivities as high as 99% have been achieved. The structures of two of these ligands have been determined by X-ray crystallography and are compared with related structures. Additionally, the structure of a titanium complex bound to a bis(sulfonamide) diol ligand is reported.     

Numerical homogenization of cracking processes in thin fibre-epoxy layers

Discrete microscale fracture processes in thin fibre-epoxy layers are connected to a mesoscale traction-separation law through a numerical homogenization framework. The microscale fracture processes are studied with the finite element method, where cracking within the epoxy and debonding between fibres and epoxy is simulated by placing interface elements furnished with a mixed-mode interface damage model in between the continuum elements modelling the fibres and epoxy. It is demonstrated how the effective traction-separation response and the corresponding microscale fracture patterns under mesoscale tensile conditions depend on the sample size, the fibre volume fraction and the presence of imperfections.     

Production and Digestibility Studies of β-Galactosyl Xylitol Derivatives Using Heterogeneous Catalysts of LacA β-Galactosidase from Lactobacillus Plantarum WCFS1

The synthesis of β-galactosyl xylitol derivatives using immobilized LacA β-galactosidase from Lactobacillus plantarum WCFS1 is presented. These compounds have the potential to replace traditional sugars by their properties as sweetener and taking the advantages of a low digestibility. The enzyme was immobilized on different supports, obtaining immobilized preparations with different activity and stability. The immobilization on agarose-IDA-Zn-CHO in the presence of galactose allowed for the conserving of 78% of the offered activity. This preparation was 3.8 times more stable than soluble. Since the enzyme has polyhistidine tags, this support allowed the immobilization, purification and stabilization in one step. The immobilized preparation was used in synthesis obtaining two main products and a total of around 68 g/L of β-galactosyl xylitol derivatives and improving the synthesis/hydrolysis ratio by around 30% compared to that of the soluble enzyme. The catalyst was recycled 10 times, preserving an activity higher than 50%. The in vitro intestinal digestibility of the main β-galactosyl xylitol derivatives was lower than that of lactose, being around 6 and 15% for the galacto-xylitol derivatives compared to 55% of lactose after 120 min of digestion. The optimal amount immobilized constitutes a very useful tool to synthetize β-galactosyl xylitol derivatives since it can be used as a catalyst with high yield and being recycled for at least 10 more cycles.     

Structural Stability Theory and Phase Transitions Models

Global stability theory is introduced as a tool allowing the classification of mathematical models of phase transitions. The point of view is that a topological structure whose stability controls the transition, can be identified in the process of computation of the partition function. In particular we discuss mean field theories and the two dimensional Ising model. Interesting features are disclosed concerning the classification of the instabilities, such as the number of parameters and possible approximations.     

Pole placement controllers for linear time-delay systems with commensurate point delays

This paper investigates the exact and approximate spectrum assignment properties associated with realizable output-feedback pole-placement type controllers for single-input single-output linear time-invariant time-delay systems with commensurate point delays. The controller synthesis problem is discussed through the solvability of a set of coupled diophantine equations of polynomials. An extra complexity is incorporated to the above design to cancel extra unsuitable dynamics being generated when solving the above diophantine equations. Thus, the complete controller tracks any arbitrary prefixed (either finite or delaydependent) closed-loop spectrum. However, if the controller is simplified by deleting the above mentioned extra complexity, then the robust stability and approximated spectrum assignment are still achievable for a certain sufficiently small amount of delayed dynamics. Finally, the approximate spectrum assignment and robust stability problems are revisited under plant disturbances if the nominal controller is maintained. In the current approach, the finite spectrum assignment is only considered as a particular case to the designer‘s choice of a (delay-dependent) arbitrary spectrum assignment objective.     

Geometric Integration Methods that Preserve Lyapunov Functions

We consider ordinary differential equations (ODEs) with a known Lyapunov function V. To ensure that a numerical integrator reflects the correct dynamical behaviour of the system, the numerical integrator should have V as a discrete Lyapunov function. Only second-order geometric integrators of this type are known for arbitrary Lyapunov functions. In this paper we describe projection-based methods of arbitrary order that preserve any given Lyapunov function. AMS subject classification (2000) 65L05, 65L06, 65L20, 65P40     

Positron trapping in deformed Gd

Positron lifetime and Doppler broadening measurements have been used to study the annealing behaviour of deformed Gd between 290 and 700 K. The observed recovery stage at about 370 K is attributed to dislocations annealing.