Investigation of the reaction impurities associated with methylamphetamine synthesized using the Nagai method

The synthesis of methylamphetamine hydrochloride from l-ephedrine or d-pseudoephedrine hydrochloride via reduction with hydriodic acid and red phosphorus was investigated. Eighteen batches of methylamphetamine hydrochloride were synthesized in six replicate batches using three different reaction times. This allowed the investigation of the variation of impurities in the final product with reaction time. The results obtained have resolved previously conflicting impurity profile data reported in the literature for this synthesis route. The impurity profile was shown to change with reaction time, and all previously reported impurity components were identified but not in all batches. Additionally, 20 batches of methylamphetamine hydrochloride were synthesized from either from l-ephedrine or d-pseudoephedrine hydrochloride in reactions which were allowed to proceed for 24 h. The impurities present in the resulting batches were investigated, and route-specific impurities present in all batches were identified. Batch-to-batch fluctuations in the resultant chromatographic impurity profile, despite careful synthetic monitoring and control, were also noted.     

Determination of origin of ephedrine used as precursor for illicit methamphetamine by carbon and nitrogen stable isotope ratio analysis

The sale of ephedrine, one of the precursors of methamphetamine, is strictly controlled and monitored in various countries to prevent the production of illicit methamphetamine. There are three kinds of production scheme for ephedrine manufacture, and it is very useful for precursor control to investigate the origin of ephedrine used for the synthesis of illicit methamphetamine. By means of stable isotope ratio mass spectrometry (IR-MS), we investigated the origin of ephedrine based on the delta(13)C and delta(15)N values. The various origins of ephedrine (biosynthetic, semisynthetic, or synthetic) could be discriminated clearly by using these values. The delta(15)N values of synthetic ephedrine were more negative than those of ephedrine from other sources. By the repeated distillation of methylamine in our laboratory, we confirmed that this could be due to isotope separation during distillation for the purification of methylamine used for ephedrine synthesis. The values for ephedrine used as the precursor were well-correlated with those for methamphetamine synthesized from it. This drug characterization analysis should be useful to illuminate the origin of the precursors used for clandestine methamphetamine and to trace the diversion of medicinal ephedrine for illicit manufacture of methamphetamine.     

Determination of the synthetic origin of methamphetamine samples by 2H NMR spectroscopy

Samples of methamphetamine, prepared according to the most common synthetic pathways, were submitted to natural-abundance 2H NMR spectroscopy. The deuterium content at the various sites of the molecule was found to depend on its synthetic history. The technique provides a chemical fingerprint of methamphetamine samples and can give hints to trace back the starting materials and the synthetic procedures.     

Exploring the analytical potential of NMR spectroscopy in chiral anisotropic media for the study of the natural abundance deuterium distribution in organic molecules

The deuterium/hydrogen (D/H)(i) ratio measurement by quantitative (2)H NMR spectroscopy is a method of choice for the analysis of kinetic isotopic effects associated with enzyme-catalyzed reactions during a biosynthetic pathway. However, the efficiency of the current isotropic (2)H-[(1)H] NMR can be limited by the rather small chemical shift dispersion of deuterium nuclei. In addition, this method does not allow the enantiotopic deuterons in prochiral molecules to be spectrally discriminated, hence precluding the quantification of isotopic fractionation on methylene prostereogenic sites. In this work, we explore another analytical strategy able to circumvent these disadvantages. This approach is based on the use of natural abundance (2)H 2D NMR experiments on solutes embedded in polypeptidic, chiral liquid crystalline solvent. Thus, we show that NMR in these oriented phases is a powerful way to separate deuterium signals on the basis of the quadrupolar interactions, providing a promising alternative to overcrowded (2)H NMR spectra obtained in liquid state. To illustrate our purpose, we have experimentally investigated the case of 1,1'-bis(phenylthio)hexane derived by cleavage from methyl linoleate of safflower. The (2)H NMR results in chiral liquid crystals are presented and discussed. We show, for the first time, that (D/H)(pro-R) and (D/H)(pro-S) can be measured at the same methylene position of a fatty acid chain.     

In vitro quantification of hydrolysis-induced racemization of amino acid enantiomers in environmental samples using deuterium labeling and electron-impact ionization mass spectrometry

D-amino acids indicate aging, bacterial origin, and pathogenic properties of peptides in the environment, but the reliable assessment of D-enantiomers must account for a yet unknown formation during hydrolyses. Here, we introduce a method for the in vitro determination of the hydrolysis-induced racemization (HIR) of amino acids in environmental samples. It involves hydrolyses with hydro- and deuteriochloric acid (6 M, 12 h, 105 degrees C), desalting, and selective detection of chiral mass fragments of amino acid-N-pentafluoropropionyl derivatives. D-Amino acids formed in 2HCl incorporated deuterium into their C(alpha) position. This resulted in a relative signal loss of the nondeuterated fragment compared with the 1HCl hydrolysate. Mathematically evaluating the relative target signal intensities of both hydrolysates allowed the quantification of the proportion of D-amino acids formed during sample processing. Side-chain incorporations of deuterium were no limitations for this method as they could be estimated from that of the respective L-enantiomers. In soil and litter samples, between 0 (D-glutamic acid) and 85% (D-alloisoleucine) of the detected D-amino acids were formed upon hydrolysis (standard error, 5-11%). For a given amino acid, the HIR varied by a factor of 2-10 between samples, thereby confirming that HIR must be individually assessed for samples from different environments.     

Quantitative analysis of deuterium using laser-induced plasma at low pressure of helium

It was proved that the analysis of deuterium can be conducted using laser-induced plasma spectroscopy. By selecting the appropriate surrounding gas, its pressure, and gating time of the detection system, it was shown that the emission lines of both hydrogen (H(alpha)) and deuterium (D(alpha)), separated by only 0.179 nm, can be fully resolved. A linear calibration curve was also obtained, indicating that this technique has the potential for quantitative analysis of deuterium. The minimum detection limit achieved in this stage of research was estimated to be 50 ppm. We have also shown that this technique can be used as a simple and rapid method for D and H analysis in solid samples.     

Glass-type hydrogen and deuterium absorption cells developed for D/H ratio measurements in the Martian atmosphere

Hydrogen and deuterium absorption cells of a new glass type have been developed for the D/H ratio measurements on the Japanese Mars mission PLANET-B. The H/D cells work as narrow-band rejection filters for the H/D Lyman-alpha line, respectively, when the H or D atoms are produced at a heated filament inside the cells. The absorption profiles of the cells were successfully measured with a high-resolution vacuum ultraviolet spectrometer with a wavelength resolution of 6.6 x 10(-4) nm. The derived optical thickness was found to be ~7 and ~14 for the hydrogen and deuterium cells, respectively. It was also found that the derived temperature of atomic gas ranges between the temperature of the cell wall and that of the heated filament, and it increases with increasing filament temperature. The measured profiles showed that the absorption efficiencies of the developed absorption cells are sufficient to observe the D/H ratios of the Martian atmosphere.     

Phase Identification of La-Doped Hard Magnetic Barium Ferrite Using Artificial Neural Network

A model based on an artificial neural network (ANN) was designed for the simulation and estimation of 2 theta and intensity values obtained by X-Ray Diffraction (XRD) of pure and La-doped barium ferrite powders which have been synthesized in ammonium nitrate melt. Its performance is evaluated by the influences of different La content, sintering temperature, Fe/Ba ratio, and washed in HCl (or not washed in HCl) samples. The XRD patterns of samples estimated by the ANN agree well with the experimental values, indicating that the model is reliable and adequate.     

含辣素衍生结构单体及其聚合物的合成、抑菌与抑藻性能

以取代芳烃和N-羟甲基丙烯酰胺为原料,采用傅克烷基化反应合成了四种含辣素衍生结构单体:4-羟基-2-甲基-5-甲硫基苄基丙烯酰胺(A)、2-羟基-4-丙烯酰胺甲基-5-甲硫基-6-甲基苄基丙烯酰胺(B)、3-丙烯酰胺甲基-2-羟基苯甲酰胺(C)和1-丙烯酰胺甲基-2-萘酚(D),并通过红外光谱(IR)和核磁氢谱(1H NMR)对其结构进行了表征.抑菌实验结果表明化合物D对两种受试菌(金黄色葡萄球菌和大肠杆菌)的抑制活性最高,最小抑菌浓度均可达到0.187 5 mg/mL,且D对两种受试藻(三角褐指藻和新月菱形藻)的抑制活性也最高.以四种化合物为功能单体合成出树脂,树脂对受试藻均具有较高的抑制活性,含化合物D的树脂的抑制活性最高,72 h后抑制率均可达到50％以上.     

含辣素衍生结构单体及其聚合物的合成、抑菌与抑藻性能

以取代芳烃和N-羟甲基丙烯酰胺为原料,采用傅克烷基化反应合成了四种含辣素衍生结构单体:4-羟基-2-甲基-5-甲硫基苄基丙烯酰胺(A)、2-羟基-4-丙烯酰胺甲基-5-甲硫基-6-甲基苄基丙烯酰胺(B)、3-丙烯酰胺甲基-2-羟基苯甲酰胺(C)和1-丙烯酰胺甲基-2-萘酚(D),并通过红外光谱(IR)和核磁氢谱(1 H NMR)对其结构进行了表征。抑菌实验结果表明化合物D对两种受试菌(金黄色葡萄球菌和大肠杆菌)的抑制活性最高,最小抑菌浓度均可达到0.187 5mg/mL,且D对两种受试藻(三角褐指藻和新月菱形藻)的抑制活性也最高。以四种化合物为功能单体合成出树脂,树脂对受试藻均具有较高的抑制活性,含化合物D的树脂的抑制活性最高,72h后抑制率均可达到50%以上。     

Emerging use of isotope ratio mass spectrometry as a tool for discrimination of 3,4-methylenedioxymethamphetamine by synthetic route

Drug profiling, or the ability to link batches of illicit drugs to a common source or synthetic route, has long been a goal of law enforcement agencies. Research in the past decade has explored drug profiling with isotope ratio mass spectrometry (IRMS). This type of research can be limited by the use of substances seized by police, of which the provenance is unknown. Fortunately, however, some studies in recent years have been carried out on drugs synthesized in-house and therefore of known history. In this study, 18 MDMA samples were synthesized in-house from aliquots of the same precursor by three common reductive amination routes and analyzed for 13C, 15N, and 2H isotope abundance using IRMS. For these three preparative methods, results indicate that 2H isotope abundance data is necessary for discrimination by synthetic route. Furthermore, hierarchical cluster analysis using 2H data on its own or combined with 13C and/or 15N provides a statistical means for accurate discrimination by synthetic route.     

Study of hydrogen and deuterium emission characteristics in laser-induced low-pressure helium plasma for the suppression of surface water contamination

An experimental study was conducted in search of the experimental condition required for the much needed suppression of spectral interference caused by surface water in hydrogen analysis using laser-induced low-pressure helium plasma spectroscopy. The problem arising from the difficulty in distinguishing hydrogen emission from hydrogen impurity inside the sample and that coming from the water molecules was overcome by taking advantage of similar emission characteristics shared by hydrogen and deuterium demonstrated in this experiment by the distinct time-dependent and pressure-dependent variations of the D and H emission intensities from the D-doped zircaloy-4 samples. This similarity allows the study of H impurity emission in terms of D emission from the D-doped samples and thereby separating it from the H emission originating from the water molecules. Employing this strategy has allowed us to achieve the large suppression of water induced spectral interference from the previous minimum of 400 microg/g to the current value of 30 microg/g when a laser beam of 34 mJ under tight focusing condition was employed. Along with this favorable result, this experimental condition has also provided a much better (about 6-fold higher) spatial resolution, although these results were achieved at the expense of reducing the linear calibration range from the previous 4 300 microg/g to the present 200 microg/g.     

Deuterated H3+ as a probe of isotope fractionation in star-forming regions

Observations of molecular D/H ratios in the interstellar medium are used to probe the physical conditions, such as temperature, ionization fraction and the importance of gas-grain reactions. In cold, dense regions, such as cores which are collapsing to form stars, the level of deuterium fractionation depends on the conversion of H3+ into its deuterated isotopologues (H2D+, D2H+ and D3+). The relative abundances of these molecules uniquely probe the centres of these cores where other, heavier, species have frozen onto dust grains. We present models of the deuterium chemistry close to the centre of a pre-stellar core, in the last stage before the star forms, showing the dependence of the observable molecular D/H ratios on the physical parameters and rate coefficients that are assumed. We compare model predictions with the latest observations of these regions.     

Fe2o3 shell growth on Pt nanoparticles

Fe2O3 shells have been synthesized around Pt cores to create Pt@Fe2O3 core-shell nanoparticles. The synthesis conditions allow control of the shell shape and allow the preparation of both hexagonal shells and spherical shells. 2D cross-sectional TEM images show that the cores are not positioned at the centers of the shells. By rotating the nanoparticles and monitoring the apparent motions of the cores in the 2D cross-sectional images, it is possible to determine quantitatively the radial position of the Pt core with respect to the center of the Fe2O3 shell. The distribution of core positions within the core-shell structures is bimodal. These observations suggest that the Fe2O3 shells grow on the Pt cores by a nucleation process, rather than layer-by-layer growth.     

Magnetic Resonance Studies of Impurity-Helium Solids Containing Hydrogen and Deuterium Impurities

Impurity-Helium Solids (Im-He) produced by injecting a mixed beam of helium and impurity gases into superfluid ⁴He have been investigated by electron spin resonance (ESR) and nuclear magnetic resonance (NMR) techniques. NMR signals from deuterium molecules in a D₂-He solid have been studied. Only samples prepared from gaseous mixtures containing high concentrations of D₂ molecules gave observable signals. The ESR experiments were performed on H and/or D atomic impurities in Im-He solids containing H, D, H₂, and D₂ in various combinations. The exchange tunneling reactions D+H₂HD+H and D+HDD₂+H were used to generate high concentrations of H atoms (10¹⁷/cm³) in Im-He samples.     

Deuterium enhancement in H3+ in pre-stellar cores

Deuterium enhancement of monodeuterated species has been recognized for more than 30 years as a result of chemical fractionation that results from the difference in zero-point energies of deuterated and hydrogenated molecules. The key reaction is the deuteron exchange in the reaction between HD, the reservoir of deuterium in dark interstellar clouds, and the H3+ molecular ion, leading to the production of H2D+ molecule, and the low temperature in dark interstellar clouds favours this production. Furthermore, the presence of multiply deuterated species have incited our group to proceed further and consider the subsequent reaction of H2D+ with HD, leading to D2H+, which can further react with HD to produce D3+. In pre-stellar cores, where CO was found to be depleted, this production should be increased as CO would normally destroy H3+. The first model including D2H+ and D3+ predicted that these molecules should be as abundant as H2D+. The first detection of the D2H+ was made possible by the recent laboratory measurement for the frequency of the fundamental line of para-D2H+. Here, we present observations of H2D+ and D2H+ towards a sample of dark clouds and pre-stellar cores and show how the distribution of ortho-H2D+ (1(1,0)-1(1,1)) can trace the deuterium factory in pre-stellar cores. We also present how future instrumentation will improve our knowledge concerning the deuterium enhancement of H3+.     

Quantification of deuterium isotopomers of tree-ring cellulose using nuclear magnetic resonance

Stable isotopes in tree rings are important tools for reconstruction of past climate. Deuterium (D) is of particular interest since it may contain climate signals and report on tree physiology. Measurements of the D/H ratio of tree-ring cellulose have proven difficult to interpret, presumably because the D/H ratio of the whole molecule blends the abundances of the seven D isotopomers of cellulose. Here we present a method to measure the abundance of the D isotopomers of tree-ring cellulose by nuclear magnetic resonance spectroscopy (NMR). The method transforms tree-ring cellulose into a glucose derivative that gives highly resolved, quantifiable deuterium NMR spectra. General guidelines for measurement of D isotopomers by NMR are described. The transformation was optimized for yield and did not alter the original D isotopomer abundances, thus, conserving the original signals recorded in wood cellulose. In the tree-ring samples tested, the abundances of D isotopomers varied by approximately +/-10% (2% standard error). This large variability can only be caused by biochemistry processes and shows that more information is present in D isotopomer abundances, compared to the D/H ratio. Therefore, measurements of the D isotopomer distribution of tree rings may be used to obtain information on long-term adaptations to environmental changes and past climate change.     

Sensitivity of peak positions to flight-path parameters in a deep-inelastic scattering neutron TOF spectrometer

The effects of small changes in flight-path parameters (primary and secondary flight paths, detector angles), and of displacement of the sample along the beam axis away from its ideal position, are examined for an inelastic time-of-flight (TOF) neutron spectrometer, emphasising the deep-inelastic regime. The aim was to develop a rational basis for deciding what measured shifts in the positions of spectral peaks could be regarded as reliable in the light of the uncertainties in the calibrated flight-path parameters. Uncertainty in the length of the primary or secondary flight path has the least effect on the positions of the peaks of H, D and He, which are dominated by the accuracy of the calibration of the detector angles. This aspect of the calibration of a TOF spectrometer therefore demands close attention to achieve reliable outcomes where the position of the peaks is of significant scientific interest and is discussed in detail. The corresponding sensitivities of the position of peak of the Compton profile, J(y), to flight-path parameters and sample position are also examined, focusing on the comparability across experiments of results for H, D and He. We show that positioning the sample to within a few mm of the ideal position is required to ensure good comparability between experiments if data from detectors at high forward angles are to be reliably interpreted.     

Hydrothermal synthesis and effects of pH values on properties of CdWO4 powders

Cadmium tungstate (CdWO₄) powders were synthesized by a hydrothermal method at different pH values. The samples show a pure monoclinic phase with the wolframite structure when they are synthesized at higher pH values. And the sample shows the highest crystallinity at a pH value of 7. All of the CdWO₄ samples show the characteristic band at 788 cm^?1 corresponding to symmetrical stretching vibration of W–O–W bond in WO₄ ^2? group in Fourier transform infrared absorption spectra. The transmission electron microscope results show that the particle sizes increase with the increase of pH value, according with the results of X-ray diffraction. All synthesized CdWO₄ samples show a broad blue–green emission at 350–550 nm. The emission intensity of sample synthesized at a pH value of 4 is nearly five times of that synthesized at a pH value of 1. These results indicate that the pH values have obvious influence on properties of CdWO₄ crystal in the hydrothermal synthesis.     

Synthesis of MCM-41 from coal fly ash by a green approach: influence of synthesis pH

The present study reports a green synthesis method for preparing pure (free of fly ash) and ordered MCM-41 materials from coal fly ash at room temperature (25 degrees C) during 24 h of reaction. It was shown that the impurities in the coal fly ash were not detrimental to the formation of MCM-41 at the tested conditions. The influence of initial synthesis pH on material properties of calcined MCM-41 samples was investigated by various techniques such as XRF, XPS, XRD, FTIR, DR-UV-vis, solid state NMR, N2 physisorption, TG-DTA, SEM and TEM. The experimental results showed that the amount of trace elements such as Al, Na, Ti and Fe incorporated into the sample increased with synthesis pH value. More aluminum species were incorporated with tetrahedral coordination in the framework under a high pH value. The particle size of the sample decreased with the synthesis pH value. Samples synthesized at high pH values had a larger pore size and were more hydrothermally stable than those at low pH values. From thermal analysis, it was observed that the synthesized MCM-41 samples showed a high thermal stability. These properties made the synthesized MCM-41 suitable for further processing into more useful materials in a wide range of applications.