The effect of methyl jasmonate and light irradiation treatments on the stilbenoid biosynthetic pathway in Vitis vinifera cell suspension cultures

Grape stilbenes are a well-known family of plant polyphenolics that have been confirmed to have many biological activities in relation to health benefits. In the present study, we investigated the effect of methyl jasmonate (MeJA) elicitor at four different concentrations (25, 50, 100 and 200 μM) in combination or not with high-level light irradiation (10,000 LUX) on a cell line obtained from the pulp of Vitis vinifera cv. Shahani. Our results showed that the stilbene synthesis pathway is inhibited by high-light conditions. A concentration of 50 μM MeJA was optimum for efficient production and high accumulation of total phenolics and total flavonoids as well as total stilbenoids. Furthermore, we showed that there is a significant negative correlation between the production of these metabolites and cell growth. These data provide valuable information for the future scale-up of cell cultures for the production of these very high value compounds in bioreactor system.     

On construction ofk-wise independent random variables

A 0–1probability space is a probability space (, 2,P), where the sample space -{0, 1} ⁿ for somen. A probability space isk-wise independent if, whenY _i is defined to be theith coordinate or the randomn-vector, then any subset ofk of theY _i 's is (mutually) independent, and it is said to be a probability spacefor p ₁,p ₂, ...,p _n ifP[Y _i =1]=p _i .We study constructions ofk-wise independent 0–1 probability spaces in which thep _i 's are arbitrary. It was known that for anyp ₁,p ₂, ...,p _n , ak-wise independent probability space of size always exists. We prove that for somep ₁,p ₂, ...,p _n [0,1],m(n,k) is a lower bound on the size of anyk-wise independent 0–1 probability space. For each fixedk, we prove that everyk-wise independent 0–1 probability space when eachp _i =k/n has size (n _k ). For a very large degree of independence —k=[n], for >1/2- and allp _i =1/2, we prove a lower bound on the size of . We also give explicit constructions ofk-wise independent 0–1 probability spaces.This author was supported in part by NSF grant CCR 9107349.This research was supported in part by the Israel Science Foundation administered by the lsrael Academy of Science and Humanities and by a grant of the Israeli Ministry of Science and Technology.     

Steric,Electronic and Conformational Synergistic Effects in the Gold(I)-catalyzed α-C−H Bond Functionalization of Tertiary Amines**

Direct C−H bond functionalization is a useful strategy for the straightforward formation of C−C and C−Heteroatom bonds. In the present work, a unique approach for the challenging electrophilic Au-catalyzed α-C−H bond functionalization of tertiary amines is presented. Electronic, steric and conformational synergistic effects exerted by the use of a malonate unit in the substrate were key to the success of this transformation. This new reactivity was applied to the synthesis of tetrahydro-γ-carboline products which, under oxidative conditions, could be converted into valuable structural motifs found in bioactive alkaloid natural products.     

Potentiometric Sensing of Aspirin Metabolite in Human Plasma and Pharmaceutical Preparations Using Co(III)‐complex Based Electrodes: Experimental and Quantum Chemical Calculations

Three novel poly vinyl chloride (PVC) ( A ), carbon paste (CP) ( B ), and coated glassy carbon‐MWCNT (CGC) ( C ) salicylate (sal^?) sensors based on new synthesized [Co(L^2Cl)Cl₃(H₂O)] ? H₂O complex (L^2Cl=(1H‐benzimidazol‐2‐ylmethyl)‐N‐(2‐chloro‐phenyl)‐ amine)), o‐nitrophenyloctyl ether as a mediator and tridodecylmethylammonium chloride as a cationic additive were successfully used for determination of sal^? in human plasma and pharmaceutical formulations. The sal^?‐sensors exhibited enhanced sensitivity with slope of ?63.5, ?60.5 and ?58.9 mV/decade and detection limit of 1.0×10^?5, 4.0×10^?7, and 1.0×10^?6 mol L^?1 for A – C sensors respectively. Quantum chemical calculations were carried out by HF and DFT/B3LYP methods to explore and investigate the interaction between the receptor and the different anions. The intermolecular H‐bond created between the uncoordinated C?O of salicylate group and the secondary amino group in the complex is the key factor of the selectivity of the proposed sensor. A linear relation is established between the natural charge on the Co center and the value of the binding energy, where the decrease in positive charge is associated by an increase in the anion binding energy.     

The dual reciprocity boundary elements method for the linear and nonlinear two‐dimensional time‐fractional partial differential equations

In this paper, we apply the dual reciprocity boundary elements method for the numerical solution of two‐dimensional linear and nonlinear time‐fractional modified anomalous subdiffusion equations and time‐fractional convection–diffusion equation. The fractional derivative of problems is described in the Riemann–Liouville and Caputo senses. We employ the linear radial basis function for interpolation of the nonlinear, inhomogeneous and time derivative terms. This method is improved by using a predictor–corrector scheme to overcome the nonlinearity which appears in the nonlinear problems under consideration. The accuracy and efficiency of the proposed schemes are checked by five test problems. The proposed method is employed for solving some examples in two dimensions on unit square and also in complex regions to demonstrate the efficiency of the new technique. Copyright © 2016 John Wiley & Sons, Ltd.     

1,1-dioxonaphtho[1,2-b]thiophene-2-methyloxycarbonyl (alpha-Nsmoc) and 3,3-dioxonaphtho[2,1-b]thiophene-2-methyloxycarbonyl (beta-Nsmoc) amino-protecting groups

Of the three theoretically possible, Bsmoc-related, naphthothiophene sulfone-based amino-protecting groups, the two most readily available derivatives, the alpha- and beta-Nsmoc analogues, have been examined as substitutes for the Bsmoc residue in cases where the latter lead to oily protected amino acids or amino acid fluorides. All of the naphtho systems gave easily handled solid amino acid derivatives. The intermediate sulfone alcohol 11 used as the key reagent for introduction of the alpha-Nsmoc protecting group was readily made from alpha-tetralone (Scheme 1). The corresponding beta-analogue 17 was made similarly on a small scale, but due to the high cost of beta-tetralone, an alternate route involving reaction of rhodanine with alpha-naphthaldehyde was used for large-scale work (Scheme 2). All proteinogenic amino acids were converted to their alpha- and beta-Nsmoc derivatives. Deblocking studies showed that the reactivity toward deblocking by piperidine followed the order alpha-Nsmoc > Bsmoc > beta-Nsmoc. 1H NMR experiments showed that deblocking of the two new systems was mechanistically similar to that previously established for the Bsmoc derivative in that the reaction is initiated by Michael addition to the beta-carbon atom of the alpha,beta-unsaturated sulfone system. Application of alpha- and beta-Nsmoc amino acids to the solid-phase synthesis of two model peptides was examined. An advantage of the alpha-Nsmoc system over the long-known Bsmoc system proved to be the milder conditions needed for the deblocking step relative to the Bsmoc case, which is itself more readily deblocked than the classic Fmoc analogue.     

Relationships between equilibrium spreading pressure and phase equilibria of phospholipid bilayers and monolayers at the air-water interface

The intricate interplay between the bilayer and monolayer properties of phosphatidylcholine (PC), phosphatidylglycerol (PG), and phosphatidylethanolamine (PE) phospholipids, in relation to their polar headgroup properties, and the effects of chain permutations on those polar headgroup properties have been demonstrated for the first time with a set of time-independent bilayer-monolayer equilibria studies. Bilayer and monolayer phase behavior for PE is quite different than that observed for PC and PG. This difference is attributed to the characteristic biophysical PE polar headgroup property of favorable intermolecular hydrogen-bonding and electrostatic interactions in both the bilayer and monolayer states. This characteristic hydrogen-bonding ability of the PE polar headgroup is reflected in the condensed nature of PE monolayers and a decrease in equilibrium monolayer collapse pressure at temperatures below the monolayer critical temperature, T(c) (whether above or below the monolayer triple point temperature, T(t)). This interesting phenomena is compared to equilibrated PC and PG monolayers which collapse to form bilayers at 45 mN/m at temperatures both above and below monolayer T(c). Additionally, it has been demonstrated by measurements of the equilibrium spreading pressure, pie, that at temperatures above the bilayer main gel-to-liquid-crystalline phase-transition temperature, T(m), all liquid-crystalline phospholipid bilayers spread to form monolayers with pie around 45 mN/m, and spread liquid-expanded equilibrated monolayers collapse at 45 mN/m to form their respective thermodynamically stable liquid-crystalline bilayers. At temperatures below bilayer T(m), PC and PG gel bilayers exhibit a drop in bilayer pi(e) values < or =0.2 mN/m forming gaseous monolayers, whereas the value of pic of spread monolayers remains around 45 mN/m. This suggests that spread equilibrated PC and PG monolayers collapse to a metastable liquid-crystalline bilayer structure at temperatures below bilayer T(m) (where the thermodynamically stable bilayer liquid-crystalline phase does not exist) and with a surface pressure of 45 mN/m, a surface chemical property characteristically observed at temperatures above bilayer T(m) (monolayer T(c)). In contrast, PE gel bilayers, which exist at temperatures below bilayer T(m) but above bilayer T(s) (bilayer crystal-to-gel phase-transition temperature), exhibit gel bilayer spreading to form equilibrated monolayers with intermediate pie values in the range of 30-40 mN/m; however, bilayer pie and monolayer pic values remain equal in value to one another. Contrastingly, at temperatures below bilayer T(s), PE crystalline bilayers exhibit bilayer pie values < or =0.2 mN/m forming equilibrated gaseous monolayers, whereas spread monolayers collapse at a value of pic remaining around 30 mN/m, indicative of metastable gel bilayer formation.     

活体肝胵Fasciola hepatica及其高氯酸萃取物的31P及13C NMR研究

本工作报道了用³¹P NMR谱定量分析活体肝胵Fasiciola hepatica中含磷化合物的实验方法及一些初步结果,测定了活体肝胵体内含磷化合物的弛豫时间T₁,观察了无灌注循环系统时肝胵体内pH值变化。利用高氯酸萃取物测得的³¹P NMR谱,定出了各谱峰的归属,观察了用含糖及缺糖培养液培养的肝胵糖类养料的代谢变化,并利用¹³C NMR谱肯定了肝胵体内主要含磷化合物之一的α-甘油磷酰胆碱³¹P NMR谱峰的归属。