Analysis of organotin compounds by grignard derivatization and gas chromatography-ion trap tandem mass spectrometry

The determination of organotin compounds in water using gas chromatography-tandem mass spectrometry (GC-MS-MS) is described. Several organotin derivatives were synthesized by the reaction of organotin chlorides with Grignard reagents such as methyl-, propyl- and pentylmagnesium halides. After the optimization of the GC-MS-MS conditions, several derivatizations with the Grignard reagents were compared by evaluating the molar responses and volatilities of the derivatives and derivatization yields. As a result, the derivatizing reagent of choice is pentylmagnesium bromide. Calibration curves for the mono-, di- and tributyltins and mono-, di- and triphenyltins with pentylmagnesium bromide were linear in the range of 0.5-100 pg of Sn. The instrumental detection limits of six organotins ranged from 0.20 to 0.35 pg of Sn. The recovery tests from water samples (500 ml) were performed by using sodium diethyldithiocarbamate (DDTC) as a complexing reagent. Except for monophenyltin, the absolute recoveries of organotins from pure water at 200 ng of Sn/l were satisfactory. The recoveries calibrated by surrogate compounds (perdeuterated organotin chlorides) ranged from 71 to 109%. The method detection limits ranged from 0.26 to 0.84 pg of Sn (500-ml sample). This method was applied to the recovery of organotins from river water and seawater. The calibrated recoveries were between 90 and 122%.     

Chemical and biological evaluation on scopadulane-type diterpenoids from Scoparia dulcis of Vietnamese origin

From the aerial parts of Scoparia dulcis L. (Scrophulariaceae) grown in Vietnam, four scopadulane-type diterpenoids (4-7), of which 7 is new and was given the trivial name scopadulcic acid C, together with nine known compounds were isolated. Their structures were elucidated by spectroscopic analyses. The absolute configurations of 4-7 were ascertained by applying the modified Mosher's method to iso-dulcinol (6). The isolation of the lignans nirtetralin and niranthin for the first time from S. dulcis is also of chemotaxonomic interest. The cytotoxic activity in KB cells, inhibitory effect on LPS/IFNgamma-induced NO production, inhibition of multidrug resistance (MDR), and antibacterial and antifungal activities of the scopadulane-type diterpenoids 4-7 were examined in this study.     

Specific ion effects on the electrophoretic mobility of small,highly charged peptides: A modeling study

In this work, we use coarse‐grained modeling to study the free solution electrophoretic mobility of small highly charged peptides (lysine, arginine, and short oligos thereof (up to nonapeptides)) in NaCl and Na₂SO₄ aqueous solutions at neutral pH and room temperature. The experimental data are taken from the literature. A bead modeling methodology that treats the electrostatics at the level of the nonlinear Poisson Boltzmann equation developed previously in our laboratory is able to account for the mobility of all peptides in NaCl, but not Na₂SO₄. The peptide mobilities in Na₂SO₄ can be accounted for by including sulfate binding in the model and this is proposed as one possible explanation for the discrepancy. Oligo arginine peptides bind more sulfate than oligo lysines and sulfate binding increases with the oligo length.     

Turning Tryptophanase into Odor‐Generating Biosensors

An odor‐based sensor system that exploits the metabolic enzyme tryptophanase (TPase) as the key component is reported. This enzyme is able to convert an odorless substrate like S‐methyl‐L ‐cysteine or L ‐tryptophan into the odorous products methyl mercaptan or indole. To make a biosensor, TPase was biotinylated so that it could be coupled with a molecular recognition element, such as an antibody, to develop an ELISA‐like assay. This method was used for the detection of an antibody present in nM concentrations by the human nose. TPase can also be combined with the enzyme pyridoxal kinase (PKase) for use in a coupled assay to detect adenosine 5′‐triphosphate (ATP). When ATP is present in the low μM concentration range, the coupled enzymatic system generates an odor that is easily detectable by the human nose. Biotinylated TPase can be combined with various biotin‐labeled molecular recognition elements, thereby enabling a broad range of applications for this odor‐based reporting system.     

Chemical Probing of the Human Sirtuin 5 Active Site Reveals Its Substrate Acyl Specificity and Peptide‐Based Inhibitors

Sirtuins are NAD⁺‐dependent deacetylases acting as sensors in metabolic pathways and stress response. In mammals there are seven isoforms. The mitochondrial sirtuin 5 is a weak deacetylase but a very efficient demalonylase and desuccinylase; however, its substrate acyl specificity has not been systematically analyzed. Herein, we investigated a carbamoyl phosphate synthetase 1 derived peptide substrate and modified the lysine side chain systematically to determine the acyl specificity of Sirt5. From that point we designed six potent peptide‐based inhibitors that interact with the NAD⁺ binding pocket. To characterize the interaction details causing the different substrate and inhibition properties we report several X‐ray crystal structures of Sirt5 complexed with these peptides. Our results reveal the Sirt5 acyl selectivity and its molecular basis and enable the design of inhibitors for Sirt5.     

New labdane-type diterpenoids from Leonurus heterophyllus SW

Five new natural labdane-type diterpenoids (5-9), designated leoheteronins A-E, together with four known diterpenoids (1-4), two phytosterols as a mixture of beta-sitosterol and stigmasterol, and the flavone genkwanin (10) were isolated from the aerial parts of Leonurus heterophyllus SW. (Lamiaceae) collected in northern Vietnam. Compound 1 was isolated for the first time from a Leonurus species, and 10 is considered to be a chemotaxonomic marker of the Leonurus genus. Their structures were determined using spectroscopic analyses.     

A decision theory for partially consonant belief functions

Partially consonant belief functions (pcb), studied by Walley, are the only class of Dempster-Shafer belief functions that are consistent with the likelihood principle of statistics. Structurally, the set of foci of a pcb is partitioned into non-overlapping groups and within each group, foci are nested. The pcb class includes both probability function and Zadeh’s possibility function as special cases. This paper studies decision making under uncertainty described by pcb. We prove a representation theorem for preference relation over pcb lotteries to satisfy an axiomatic system that is similar in spirit to von Neumann and Morgenstern’s axioms of the linear utility theory. The closed-form expression of utility of a pcb lottery is a combination of linear utility for probabilistic lottery and two-component (binary) utility for possibilistic lottery. In our model, the uncertainty information, risk attitude and ambiguity attitude are separately represented. A tractable technique to extract ambiguity attitude from a decision maker behavior is also discussed.     

Utilization of 2-ethoxymethylene-3-oxobutanenitrile in the synthesis of heterocycles possessing biological activity

2-Ethoxymethylene-3-oxobutanenitrile is a versatile trifunctional reagent that allows the introduction of a three-carbon moiety to amine-substrates. The reaction of the title compound with hydrazines has been studied leading to appropriate substituted pyrazoles 4-11. Reactions with other dinitrogen nucleophiles were studied giving access to a set of fused pyrimidines 13. All types of compounds displayed biological activity against bacteria, filamentous fungi and tumour HeLa cells, but not for yeasts. Pyrazole 10 and pyrimidine 13d have been found to possess the broadest activity.     

Operational Properties of Two Integral Transforms of Fourier Type and their Convolutions

In this paper we present the operational properties of two integral transforms of Fourier type, provide the formulation of convolutions, and obtain eight new convolutions for those transforms. Moreover, we consider applications such as the construction of normed ring structures on L₁(\mathbbR)L_{1}({\mathbb{R}}), further applications to linear partial differential equations and an integral equation with a mixed Toeplitz-Hankel kernel.