Case Study: Doping Substances in Equestrian Food Supplements

In the course of investigations on equestrian supplemental products for the presence of doping substances, two products were found to contain forbidden substances. As reported earlier a plant extract (Mexican cactus extract) named “Energy 5” contained the anabolic androgenic steroids (AAS) stanozolol, 17β-hydroxy-17α-methyl-5α-androstane-3β-ol (3β,5α-THMT) as well as mestanolone not declared on the label. In the present study, a product called “Super Kalm Paste” was tested. Analysis by gas chromatography - mass spectrometry (GC-MS) revealed that the preparation contained the class I anti-arrhythmics quinine (trade names Kinidin^TM, Durules) and cinchonine. The samples were prepared according to a sample preparation procedure established for anabolic steroids in nutritional supplements for humans. The sample treatment comprised the extraction and purification of the analytes as well as the chemical conversion with N-methyl-N-trimethylsilyl-trifluoracetamide (MSTFA) to yield the trimethylsilyl (TMS)-derivatives. To verify whether the administration of such products could lead to positive doping tests, a pilot excretion study on “Energy 5” was conducted with two geldings, and urine samples were collected. Gas chromatography - high resolution mass spectrometry (GC-HRMS) after solid phase extraction and mixed derivatisation has demonstrated the presence of the stanozolol metabolite 16β-hydroxy-stanozolol in urine samples after “Energy 5” application.     

Two organometallic fragments inclusioned in a 1,3-alternate calix[4]arene tetraphosphane: evidence for transition metal-arene interaction through the cavity

The preparation of an 1,3-alternate calix[4]arene tetraphosphane ligand, 25,26,27,28-tetrakis{2-(diphenylphosphino)ethoxy}calix[4]arene (4), is described. Ligand 4 is obtained in four steps in 17% overall yield. Reaction of 4 with AgBF4 produced the encapsulated two silver complex [Ag2{(P,P,P,P)-tetraphencalix[4]arene}](BF4)2. The solid-state structure shows that the encapsulated silver undergoes a substantial pi-interaction by two opposite arene rings. Rhodation of 4 employing [Rh(cot)2]BF4 yielded the encapsulated complex with a bent coordination mode. Two organometallic fragments inclusioned inside a 1,3-alternate calix[4]arene tetraphosphane was also achieved by the reaction of 4 with [PtH(PPh3)2 (thf)]+. Full characterization includes X-ray structural studies of compounds 4-6.     

A benzothiazole-based receptor-immobilised silica nanoparticle as chemosensor for Hg2+

Fluorogenic benzothiazole-based receptor has been easily immobilised onto filter paper and silica nanoparticle by sol-gel reaction. The sensing ability of the benzothiazole-immobilised thin layer filter paper chromatography (TLC-1) was evaluated on the basis of fluorescent changes caused by metal ions that were dropped onto the TLC plate. The TLC-1 exhibited a high affinity and selectivity for Hg²⁺ over other competing metal ions. Therefore, the TLC-1 holds promise as a portable sensor for the detection of Hg²⁺ in aqueous solution. Furthermore, the adsorption capacity of a column packed with SiO₂-1 was evaluated by the application of metal ions under various experimental conditions, such as pH, flow rate and concentration. The SiO2-1 column removed 98% of Hg²⁺ from drinking water containing 10 ppb of Hg²⁺. The adsorption capacity of the SiO₂-1 column was not strongly affected by pH and flow rates.     

Polycondensation of Sebacic Acid with Primary and Secondary Hydroxyl Groups Containing Diols Catalyzed by Candida antarctica Lipase B

Abstract

The aliphatic polyesters are normally synthesized by ester interchange reactions or direct esterification of hydroxyacids or diacid/diol combinations. Biotransformation, utilizing the enzymes as catalysts, was accepted as an alternative route for the synthesis of aliphatic polyesters and offers various advantages compared with the conventional, metal-catalyzed polymerization reactions. Previous studies indicated that lipase-catalyzed polycondensation reactions between diols and diacids occurred preferentially at primary hydroxyl groups of diols, when diols contained both primary and secondary hydroxyl groups. In this work, we investigated lipase-catalyzed polycondensation of diacids and secondary hydroxyl group–containing diols, and successfully synthesized polyesters by polycondensation with secondary hydroxyl groups as well as primary hydroxyl groups. Various diols, glycerol, 1,2-propanediol, 1,3-butanediol, 2,3-butanediol, and 2,4-pentanediol were tested for the polycondensation. The polymerization was achieved by heating a mixture of lipase B, sebacic acid, and the diols in anhydrous toluene at 100 °C for 72 h. The resulting polymers were characterized by ¹H and ¹³C NMR spectroscopy, Fourier transform–infrared spectroscopy, thermogravimetric analysis, and gel permeation chromatography.     

Naphthocrown‐Strapped Calix[4]pyrroles: Formation of Self‐Assembled Structures by Ion‐Pair Recognition

A new approach to the construction of self‐assembled structures is reported that is based on ion‐pair recognition. Towards this end, the calix[4]pyrrole naphthocrown‐4 hybrid structures 2 and 3 were prepared. These multitopic receptors contain recognition sites for both anions and cations. On the basis of solution‐phase ¹H NMR spectroscopic analysis and solid‐state single‐crystal X‐ray diffraction structural studies, it was established that receptors 2 and 3 are able to bind specific ion pairs with high selectivity via different binding modes. In the case of CsF and CsCl, the ion‐pair complexes formed from receptors 2 and 3 were found to self‐assemble to produce either linear supramolecular polymeric crystalline solids or nanotube‐like cyclic hexamers depending on the specific choice of ion pairs and crystallization solvents. Proton NMR studies provided evidence for solution‐phase self‐association in organic media.     

Effect of conformational heterogeneity on excitation energy transfer efficiency in directly meso-meso linked Zn(II) porphyrin arrays

We have investigated the overall excitation energy relaxation dynamics in linear porphyrin arrays as well as the energy transport phenomena by attaching an energy acceptor to one end of a linear porphyrin array by using steady state and time-resolved spectroscopic measurements. We have revealed that the solvation dynamics as well as the conformational dynamics contributes significantly to the energy relaxation processes of linear porphyrin arrays. Consequently, long porphyrin arrays no longer serve as good energy transmission elements in donor-acceptor linked systems due to conformational heterogeneities which provide the non-radiative deactivation channels as energy quenchers.     

Surface functionalization of multi‐walled carbon nanotubes through surface‐initiated atom transfer radical polymerization of glycidyl methacrylate

Herein, we report the fabrication of glycidyl methacrylate (GMA) polymeric conjugates of shortened multi‐walled carbon nanotubes (sMWCNT). The synthesis method involves the attachment of initiator on the surface of nanotubes followed by surface initiated atom transfer radical polymerization (SI‐ATRP) of GMA from the initiator‐bound sMWCNT surface. This is achieved by the procedure consisting of three important steps: introduction of amino groups onto the sMWCNT and attachment of polymerization initiator, 2‐bromo‐2‐methylpropinonyl bromide, and polymerization of GMA. The structure and properties of the resultant polymeric conjugates were characterized by Fourier transform infrared (FT‐IR) spectroscopy, Thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), X‐ray diffraction (XRD), atomic force microscopy (AFM), transmission electron microscopy (TEM) and SEM. The FT‐IR analysis of polymeric conjugates shows infrared (IR) peaks characteristic of GMA. AFM, TEM and SEM images clearly show the formation of poly(glycidyl methacrylate)(PGMA) polymer on sMWCNT surface. Copyright © 2009 John Wiley & Sons, Ltd.