Fast Heroin and Cocaine Analysis by GC–MS with Cold EI: The Important Role of Flow Programming

A fast GC–MS method was developed based on the use of GC–MS with Cold EI. This new method was applied for the analysis of the street drugs heroin and cocaine and it enabled 2 min chromatography time and 3 min full analysis cycle time. GC–MS with cold EI provides mass spectra with enhanced molecular ions that are library compatible (with increased identification probabilities) and allows the use of short, 5 m 0.25 mm ID columns, which facilitates fast GC–MS. A central ingredient of our unique cold EI-based fast GC–MS analysis method is the use of column flow programming from 1 up to 32 ml min^?1 column flow rate. Column flow programming can reduce the analysis time by about a factor of two and unlike temperature programs of GC ovens the carrier gas flow rate can be raised and lowered very quickly (in a few seconds). The fast GC–MS with Cold EI method is demonstrated by the analysis of heroin in its street drug powder and cocaine on paper money and it can be applied for other drugs of abuse as a general fast drugs analysis method.     

Characterization of an orphan Ra–Be neutron source

Journal of Radioanalytical and Nuclear Chemistry - An orphan radium-beryllium (Ra–Be) neutron source (Nuclear Chicago Corporation) detected inside a scrap metal shipping container, was seized...     

<Emphasis Type="Italic">l</Emphasis><Subscript>1</Subscript>-<Emphasis Type="Italic">l</Emphasis><Subscript>2</Subscript> regularization of split feasibility problems

Numerous problems in signal processing and imaging, statistical learning and data mining, or computer vision can be formulated as optimization problems which consist in minimizing a sum of convex functions, not necessarily differentiable, possibly composed with linear operators and that in turn can be transformed to split feasibility problems (SFP); see for example Censor and Elfving (Numer. Algorithms 8, 221–239 1994). Each function is typically either a data fidelity term or a regularization term enforcing some properties on the solution; see for example Chaux et al. (SIAM J. Imag. Sci. 2, 730–762 2009) and references therein. In this paper, we are interested in split feasibility problems which can be seen as a general form of Q-Lasso introduced in Alghamdi et al. (2013) that extended the well-known Lasso of Tibshirani (J. R. Stat. Soc. Ser. B 58, 267–288 1996). Q is a closed convex subset of a Euclidean m-space, for some integer m ≥ 1, that can be interpreted as the set of errors within given tolerance level when linear measurements are taken to recover a signal/image via the Lasso. Inspired by recent works by Lou and Yan (2016), Xu (IEEE Trans. Neural Netw. Learn. Syst. 23, 1013–1027 2012), we are interested in a nonconvex regularization of SFP and propose three split algorithms for solving this general case. The first one is based on the DC (difference of convex) algorithm (DCA) introduced by Pham Dinh Tao, the second one is nothing else than the celebrate forward-backward algorithm, and the third one uses a method introduced by Mine and Fukushima. It is worth mentioning that the SFP model a number of applied problems arising from signal/image processing and specially optimization problems for intensity-modulated radiation therapy (IMRT) treatment planning; see for example Censor et al. (Phys. Med. Biol. 51, 2353–2365, 2006).     

Algorithms for the Split Variational Inequality Problem

We propose a prototypical Split Inverse Problem (SIP) and a new variational problem, called the Split Variational Inequality Problem (SVIP), which is a SIP. It entails finding a solution of one inverse problem (e.g., a Variational Inequality Problem (VIP)), the image of which under a given bounded linear transformation is a solution of another inverse problem such as a VIP. We construct iterative algorithms that solve such problems, under reasonable conditions, in Hilbert space and then discuss special cases, some of which are new even in Euclidean space.     

Isotope abundance analysis for improved sample identification with tandem mass spectrometry

Tandem mass spectrometry (MS/MS) is widely used for trace level sample analysis in complex mixtures. However, sample identification in MS/MS is challenging and not as trustworthy as with electron ionization (EI) mass spectral libraries. This paper presents a novel method for the combination of isotope abundance analysis (IAA) and EI‐MS/MS for improved sample identification even at trace level in complex matrices. Accordingly, the first quadrupole is scanned in a narrow range around the molecular ion group of isotopomers such as M⁺, [M+1]⁺ and [M+2]⁺, Q2 serves for collision‐induced dissociation to produce product ions while Q3 transfers the major sample product ions with low resolution, thus encompassing and uniformly transmitting all the product ion isotopomers. IAA can then be used to derive elemental formula information from the cleansed experimental data. IAA‐MS/MS was experimentally tested with perfluorotributylamine and a very good matching factor of 995 (out of 1000) was obtained for IAA on m/z 502, 503 and 504 (fragment ion isotopomers) while Q3 transmitted the m/z 264 product ion with a mass window of 6 m/z units. The IAA‐MS/MS method was further tested with the pesticide diazinon on its molecular ions m/z 304, 305 and 306 while Q3 was locked on its m/z 179 product ion with a mass window of 6 m/z units. Again, very good matching factors were obtained, even for 40 pg diazinon on‐column during its GC/MS analysis (match = 981). IAA‐MS/MS combines the traditional benefits of MS/MS in the removal of matrix interferences with the IAA power of elemental analysis. Copyright © 2009 John Wiley & Sons, Ltd.     

Electron impact mass spectrometry of alkanes in supersonic molecular beams

The electron impact mass spectrometry of straight chain alkanes C₈H₁₈-C₄₀H₈₂, squalane, methylstearate, 1-chlorohexadecane, 1-bromohexadecane, and dioctylphthalate was studied by sampling them with supersonic molecular beams. A fly-through Brink-type electron impact ion source was used, utilizing a vacuum background ion filtration technique based on differences between the kinetic energy of the supersonic beam species and that of thermal molecules. The 70-eV electron impact mass spectra of all the alkanes were characterized by a pronounced or dominant molecular weight peak together with all the fragment ions normally exhibited by the standard thermal 70-eV EI mass spectra. In contrast, the NIST library of most of these molecules did not show any molecular weight peak. By eliminating tile intramolecular thermal vibrational energy we gained control over the degree of molecular ion fragmentation by the electron energy. At an electron energy of 18 eV the molecular ion dissociation was further reduced considerably, with only a small absolute reduction in the peak height by less than a factor of 2. The effect of vibrational cooling increased with the molecular size and number of atoms. Pronounced differences were observed between the mass spectra of the straight chain triacontane and its branched isomer squalane. Similar mass spectra of octacosane (C₂₈H₅₈) achieved with 70-eV EI in a supersonic molecular beam were obtained with a magnetic sector mass spectrometer by using an electron energy of 14 eV and an ion source temperature of 150 °C. However, this ion source temperature precluded the gas chromatography-mass spectrometry (GC-MS) of octacosane. The GC-MS of alkanes was studied with an ion trap gas chromatograph-mass spectrometer at an ion source temperature of 230 °C. Thermal peak tailing was observed for C₂₀H₄₂ and heavier alkanes, whereas for C₂₈H₅₈ and heavier alkanes the severe peak tailing made quantitative GC-MS impractical. In contrast, no peak tailing existed even with C₄₀H₈₂ for GC-MS in supersonic molecular beams. The minimum detected amount of eicosane (C₂₀, H₄₂) was shown to be 60 fg. This was demonstrated by using single ion monitoring with the quadrupole mass analyzer tuned to the molecular weight peak of 282 u. The coupling of electron impact mass spectrometry in supersonic molecular beams with hyperthermal surface ionization and a fast GC-MS inlet is briefly discussed.     

Fast analysis of drugs in a single hair

A new method for the fast screening of cocaine and 6-monoacetylmorphine (6-MAM) in a single hair, using gas chromatography/mass spectrometry (GC/MS), is described. The analyses are conducted in less than 10 min with minimal sample preparation. The novel method combines the ChromatoProbe direct sample introduction device for intrainjector thermal extraction, fast GC separation, a supersonic molecular beam GC/MS interface and hyperthermal surface ionization (HSI). The technique has been successfully employed for the detection of cocaine in as little as a 1-mm section of hair using selected ion monitoring (SIM). Unambiguous full scan mass spectra of cocaine and 6-MAM were obtained on a single hair for cocaine and heroin users, respectively. HSI was found to be almost 3 orders of magnitude more selective than electron impact ionization for cocaine compared with the major hair constituents, with a minimum detected concentration of approximately 10 ppb in the SIM mode. Results obtained for 12 drug users showed full qualitative agreement with similar results using rigorous solvent extraction followed by electrospray-liquid chromatography/mass spectrometry analysis. However, quantitative studies showed only partial agreement. No false positives were observed for 10 drug free subjects. This method enables fast drug monitoring along the hair length which permits time correlation studies.     

On the evolution of recombination in haploids and diploids: I. Deterministic models

In population genetic theory, most analytical and numerical studies of the evolution of recombination have focused on diploid genetics. In studies of the foundations and applications of genetic algorithms (GA's), however, the bit-strings are usually treated as haploid genotypes. In this paper and its companion paper (Bergman et al., 1995), we compare results for the evolutionary dynamics of modifiers of recombination in haploids with results derived for diploids. In this paper, we study the evolution of an allele that controls the rate of recombination between two loci subject to directional selection. It is shown analytically that the fate of a recombination modifier in both haploids and diploids is determined in a complicated way by the sign of the epistasis (interaction in fitness) between the loci, the sign of the initial linkage disequilibrium, and the amount of recombination between the modifier and the genes under selection. This theory is deterministic in that the population is regarded as infinite and no sampling occurs to produce offspring from parents. In the companion paper (Bergman et al., Complexity, 1(2) 1995), we expand upon this work by addressing epistatic interactions among several loci in finite populations.     

Identification of novel synthetic organic compounds with supersonic gas chromatography-mass spectrometry

Several novel synthetic organic compounds were successfully analyzed with a unique type of GC-MS titled Supersonic GC-MS following a failure in their analysis with standard GC-MS. Supersonic GC-MS is based on interfacing GC and MS with a supersonic molecular beam (SMB) and on electron ionization of sample compounds as vibrationally cold molecules while in the SMB, or by cluster chemical ionization. The analyses of novel synthetic organic compounds significantly benefited from the extended range of compounds amenable to analyses with the Supersonic GC-MS. The Supersonic GC-MS enabled the analysis of thermally labile compounds that usually degrade in the GC injector, column and/or ion source. Due to the high carrier gas flow rate at the injector liner and column these compounds eluted without degradation at significantly lower elution temperatures and the use of fly-through EI ion source eliminated any sample degradation at the ion source. The cold EI feature of providing trustworthy enhanced molecular ion (M+), complemented by its optional further confirmation with cluster CI was highly valued by the synthetic organic chemists that were served by the Supersonic GC-MS. Furthermore, the provision of extended mass spectral structural, isomer and isotope information combined with short (a few minutes) GC-MS analysis times also proved beneficial for the analysis of unknown synthetic organic compounds. As a result, the synthetic organic chemists were provided with both qualitative and quantitative data on the composition of their synthetic mixture, and could better follow the path of their synthetic chemistry. Ten cases of such analyses are demonstrated in figures and discussed.