Direct screening of herbal blends for new synthetic cannabinoids by MALDI‐TOF MS

Since 2004, a number of herbal blends containing different synthetic compounds mimicking the pharmacological activity of cannabinoids and displaying a high toxicological potential have appeared in the market. Their availability is mainly based on the so‐called “e‐commerce”, being sold as legal alternatives to cannabis and cannabis derivatives. Although highly selective, sensitive, accurate, and quantitative methods based on GC–MS and LC–MS are available, they lack simplicity, rapidity, versatility and throughput, which are required for product monitoring. In this context, matrix‐assisted laser desorption ionization‐time of flight mass spectrometry (MALDI‐TOF MS) offers a simple and rapid operation with high throughput. Thus, the aim of the present work was to develop a MALDI‐TOF MS method for the rapid qualitative direct analysis of herbal blend preparations for synthetic cannabinoids to be used as front screening of confiscated clandestine preparations. The sample preparation was limited to herbal blend leaves finely grinding in a mortar and loading onto the MALDI plate followed by addition of 2 µl of the matrix/surfactant mixture [α‐cyano‐4‐hydroxy‐cinnamic acid/cetyltrimethylammonium bromide (CTAB)]. After drying, the sample plate was introduced into the ion source for analysis. MALDI‐TOF conditions were as follows: mass spectra were analyzed in the range m/z 150–550 by averaging the data from 50 laser shots and using an accelerating voltage of 20 kV. The described method was successfully applied to the screening of 31 commercial herbal blends, previously analyzed by GC–MS. Among the samples analyzed, 21 contained synthetic cannabinoids (namely JWH‐018, JWH‐073, JWH‐081, JWH‐250, JWH‐210, JWH‐019, and AM‐694). All the results were in agreement with GC–MS, which was used as the reference technique. Copyright © 2012 John Wiley & Sons, Ltd.     

Prince Cangrande’s Collagen: Study of Protein Modification on the Mummy of the Lord of Verona,Italy (1291–1329 AD)

The natural mummy of prince Cangrande, Lord of Verona, Italy (1291–1329 AD) was studied. Two samples were taken: rib bone and muscle. These samples were cleaved with trypsin and analysed by liquid chromatographic methods coupled to mass spectrometry (Q-TOF, ion-trap). Special attention was devoted to nonenzymatic protein modification––the deamidation of asparagine and glutamine. A huge amount of collagen was determined in the tissues of the mummy (covering over 80 % of the sequence)––collagen type I was identified in the rib bone and collagen types I and III in the muscle. A high overall percentage of asparaginyl and glutaminyl residues were deamidated (up to 92 %). In agreement with the literature we can suppose that the deamidation of really old samples (at least 100-years-old) is mainly dependent on the burial conditions and/or thermal age and cannot serve as a precise “molecular clock”.

     

On the inter‐instrument and the inter‐laboratory transferability of a tandem mass spectral reference library. 3. Focus on ion trap and upfront CID

Mass spectral libraries represent versatile tools for the identification of small bioorganic molecules. Libraries based on electron impact spectra are rated robust and transferable. Tandem mass spectral libraries are often considered to work properly only on the instrument that has been used to build the library. An exception from that rule is the ‘Wiley Registry of Tandem Mass Spectral Data, MSforID’. In various studies with data sets from different kinds of tandem mass spectrometric instruments, the outstanding sensitivity and robustness of this tandem mass spectral library search approach was demonstrated. The instrumental platforms tested, however, mainly included various tandem‐in‐space instruments. Herein, the results of a multicenter study with a focus on upfront and tandem‐in‐time fragmentation are presented. Five laboratories participated and provided fragment ion mass spectra from the following types of mass spectrometers: time‐of‐flight (TOF), quadrupole–hexapole–TOF, linear ion trap (LIT), 3‐D ion trap and LIT–Orbitrap. A total number of 1231 fragment ion mass spectra were collected from 20 test compounds (amiloride, buphenin, cinchocaine, cyclizine, desipramine, dihydroergotamine, dyxirazine, dosulepin, ergotamine, ethambutol, etofylline, mefruside, metoclopramide, phenazone, phentermine, phenytoin, sulfamethoxazole, sulfamoxole, sulthiame and tetracycline) on seven electrospray ionization instruments using 18 different instrumental configurations for fragmentation. For 1222 spectra (99.3%), the correct compound was retrieved as the best matching compound. Classified matches (matches with ‘relative average match probability’ >40.0) were obtained for 1207 spectra (98.1%). This high percentage of correct identifications clearly supports the hypothesis that the tandem mass spectral library approach tested is a robust and universal identification tool. Copyright © 2012 John Wiley & Sons, Ltd.     

Optimization and validation of a new approach based on CE-HRMS for the screening analysis of novel psychoactive substances (cathinones,phenethylamines, and tryptamines) in urine

The continuous introduction in the market of new psychoactive drugs (NPS) represents a well-known international emergency. Indeed, the European Monitoring Centre for Drugs and Drug Addiction and the United Nations Office on Drugs and Crime are paying great attention to the spread of NPS. In addition to the traditional analytical approaches based on GC-MS and HPLC-MS, also CE coupled with MS has proved to be a precious tool for the toxicological screening of biosamples. On these grounds, the aim of the present work was to test the application of CE-HRMS as a new screening tool for the rapid detection of these novel drugs in urine. Separations were performed in an uncoated fused-silica capillary with id of 75 μm with a total length of 100 cm, by applying a constant voltage of 15 kV. The QTOF-MS was implemented with an electrospray ion source operating in positive ionization full scan mode in the range of 100–1000 m/z. Under these conditions, different NPS has been tested, including eight cathinones, five phenethylamine, and seven tryptamines. The method was validated after optimization of the following analytical parameters: BGE composition and pH, separation voltage, sheath liquid composition, and flow rate and ESI source settings. The applicability of the method was successfully tested by analyzing a series of real urine samples obtained from drug users.     

16+ spin-gap isomer in 96Cd

A β-decaying high-spin isomer in (96)Cd, with a half-life T(1/2)=0.29(-0.10)(+0.11) s, has been established in a stopped beam rare isotope spectroscopic investigations at GSI (RISING) experiment. The nuclei were produced using the fragmentation of a primary beam of (124)Xe on a (9)Be target. From the half-life and the observed γ decays in the daughter nucleus, (96)Ag, we conclude that the β-decaying state is the long predicted 16(+) "spin-gap" isomer. Shell-model calculations, using the Gross-Frenkel interaction and the πν(p(1/2),g(9/2)) model space, show that the isoscalar component of the neutron-proton interaction is essential to explain the origin of the isomer. Core excitations across the N=Z=50 gaps and the Gamow-Teller strength, B(GT) distributions have been studied via large-scale shell-model calculations using the πν(g,d,s) model space to compare with the experimental B(GT) value obtained from the half-life of the isomer.     

Crystallographic characterization of a stable 7‐phosphanorbornadiene‐7‐oxide: 2,3‐benzo‐1,4,5,6,7‐pentaphenyl‐7‐phosphabicyclo[2.2.1] hepta‐2,5‐diene‐7‐oxide

The stable 7‐phosphanorbornadiene derivative, 2,3‐benzo‐1,4,5,6,7‐pentaphenyl‐7‐phosphabicyclo[2.2.1]hepta‐2,5‐diene‐7‐oxide ( 1 ) was synthesized in 45% yield via the Diels‐Alder reaction of pentaphenylphosphole oxide and benzyne. The reaction occurs specifically to give a single isomer, which was characterized by use of X‐ray crystallography and ³¹P NMR spectroscopy. © 2000 John Wiley & Sons, Inc. Heteroatom Chem 11:182–186, 2000