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Lysergic acid diethylamide (LSD) is a hallucinogen, synthesized from ergot alkaloid, and controlled as a narcotic in Japan. Recently, LSD derivatives have appeared as designer drugs, all over the world. In previous study, we reported identification and analysis of four LSD derivatives in four paper sheet products. In this study, we detected three additional LSD derivatives from three paper sheet products, which were obtained from September 2019 to March 2020 in Japan. We extracted the compounds from paper sheet products with methanol for LC-MS, high-resolution MS and GC-MS analyses. The compounds were identified as 4-cyclopropionyl-N,N-diethyl-7-methyl-4,6,6a,7,8,9-hexahydroindolo[4,3-fg]quinoline-9-carboxamide (1cP-LSD), N-methyl-N-isopropyl-7-methyl-4,6,6a,7,8,9-hexahydroindolo-[4,3-fg]quinoline-9-carboxamide (MIPLA), 4-butyryl-N,N-diethyl-7-methyl-4,6,6a,7,8,9-hexahydroindolo[4,3-fg]quinoline-9-carboxamide (1B-LSD), by GC-MS, LC-MS, LC-Q-TOF-MS and NMR analyses. As well as other N1-acylated LSD derivatives, 1cP-LSD and 1B-LSD were easily deacylated to LSD during GC-MS analysis, we have to be careful to analyze these compounds.

To prevent the abuse of new psychoactive substances (NPS), a total of 2372 substances and two plants are controlled as "Designated Substances" in Japan as of September 2019. Although the distribution of these substances has decreased for the past three years, newly-emerged NPS are still being found. In this study, we detected four lysergic acid diethylamide (LSD) derivatives as designer drugs from four paper sheet products, which were obtained from 2014 to 2017 in Japan. The compounds were identified as 4-Acetyl-N,N-diethyl-7-methyl-4,6,6a,7,8,9-hexahydroindolo[4,3-fg]quinoline-9-carboxamide (ALD-52), N,N,7-triethyl-4,6,6a,7,8,9-hexahydroindolo[4,3-fg]quinoline-9-carboxamide (ETH-LAD), 7-Allyl-N,N-diethyl-4,6,6a,7,8,9-hexahydroindolo[4,3-fg]quinoline-9-carboxamide (AL-LAD), N,N-diethyl-7-methyl-4-propionyl-4,6,6a,7,8,9-hexahydroindolo[4,3-fg]quinoline-9-carboxamide (1P-LSD), by GC-MS, LC-MS, LC-Q-TOF-MS and NMR analyses. Further, we studied the extraction methods of LSD derivatives from paper sheet, and the analytical conditions of GC-MS, LC-MS and LC-FL(fluorescence). Among LSD derivatives, 1P-LSD have been controlled as designated substances (Shitei Yakubutsu) under the Pharmaceutical and Medical Device Act in Japan since April 2016. For the legislation of the other derivatives identified in this study, the evaluation of their pharmacological properties are now in progress.

The rapid dispersion of new psychoactive substances (NPS) presents challenges to customs services and analytical laboratories, which are involved in their detection and characterization. When the seized material is limited in quantity or of a complex nature, or when the target substance is present in very small amounts, the need to use advanced analytical techniques, efficient workflows and chemo-informatics tools is essential for the complete identification and elucidation of these substances. The current work describes the application of such a workflow in the analysis of a single blotter paper, seized by Swedish customs, that led to the identification of a lysergic acid diethylamide (LSD) derivative, 1-butyl-lysergic acid diethylamide (1B-LSD). Such blotter paper generally contains an amount in the range of 30&ndash, 100 ug. This substance, which is closely related to 1-propionyl-lysergic acid diethylamide (1P-LSD), seems to have only recently reached the drug street market. Its identification was made possible by comprehensively combining gas chromatography with mass spectrometry detection (GC&ndash, MS), liquid chromatography coupled with high-resolution tandem MS (LC&ndash, HR-MS/MS), Orbitrap-MS and both 1D and 2D nuclear-magnetic-resonance (NMR) spectroscopy. All the obtained data have been managed, assessed, processed and evaluated using a chemo-informatics platform to produce the effective chemical and structural identification of 1B-LSD in the seized material.

© 2020 John Wiley & Sons, Ltd. Drug misuse in prisons contributes to increased disruption and violence and negatively impacts prisoner safety, rehabilitation, and recovery. Synthetic cannabinoid receptor agonists (SCRAs), colloquially known as “spice”, are infused into papers and are of particular concern in a prison setting where they are commonly vaped. Methods for the qualitative and quantitative analysis of SCRA infused papers, including impurity profiling, were developed using gas chromatography–mass spectrometry (GC–MS) with qualitative confirmation by ultra high pressure liquid chromatography with photodiode array and quadrupole time of flight mass spectrometry detection (UPLC-PDA-QToF-MS) and applied to 354 individual seized paper samples originating from 168 seizures from three Scottish prisons. Of these samples, 41% (146 samples from 101 seizures) contained at least one SCRA and multiple SCRAs were detected on 23% of these papers. Concentrations ranged from < 0.05–1.17 mg/cm2 paper, representing the first reported quantitative data for SCRA infused papers. An evolution in the SCRAs detected was demonstrated; 5F-MDMB-PINACA (5F-ADB) predominated until late 2018, after which time 5F-MDMB-PICA and 4F-MDMB-BINACA became increasingly more prevalent, followed by the arrival of MDMB-4en-PINACA in June 2019. Concentration mapping data from two seized paper samples demonstrated that SCRA concentrations across larger papers were highly variable (0.47–2.38 mg/cm2 paper) making consistent dosing by users, and representative sampling by laboratory analysts, difficult. Near real-time qualitative and quantitative information on SCRAs circulating in prisons acts as an early warning system for SCRAs emerging on the wider illicit market, inform the methods used to detect them and limit supply, and provide information to support harm reduction measures.

A new promising rhodamine based colorimetric and fluorometric chemosensor, RDV has been designed and synthesized for specific detection of Hg2+ ion. It acts as highly selective “turn-on” fluorescent chemosensor for Hg2+ ion without interference from other competitive metal ions in aqueous acetonitrile medium. The drastic color change with addition of Hg2+, from colorless to pink, indicates RDV can acts as “naked-eye” indicator for Hg2+. The Hg2+ promoted selective hydrolysis of appended vinyl ether group in RDV followed by Hg2+ chelated complex formation with concomitant opening of spirolactam ring is the plausible sensing mechanism. The detailed absorption, fluorescence, 1H NMR, 13C NMR and mass spectrometry confirms the proposed sensing mechanism. The limit of detection (LOD) of Hg2+ by RDV is 136 nM indicating the high sensitivity towards Hg2+. The RDV shows consistent spectroscopic response in biological pH range 4–10. In addition to explore practical applicability of RDV, its paper strips have been made and used to detect Hg2+ in pure water solution up to 10 ppm level. Furthermore, the potential application of RDV for the sensing of Hg2+ in real water samples (tap water and drinking waters from different sources) were also monitored and demonstrated.

Within this study the mediated detoxification of spent sulphite liquor via laccase from Trametes versicolor was analysed and optimised using an in-situ NMR-spectroscopy method. The enzymatic degradation kinetic was optimised using the degradation rate of aromatic compounds as indirect parameter. Via response surface methodology the impact of the temperature, the pH and the enzyme concentration was analysed and the conditions were optimised focusing on optimal detoxification. The results of the statistical calculation revealed a valid statistical model for the optimal impact on the aromatic degradation with a temperature of 31 °C, a pH of 6 and a laccase concentrations of 179 U g−1 dry matter of spent sulphite liquor. By using these conditions 88.73% of aromatic compounds could be degraded.

Objective: This study explores the potential use of high-resolution magic angle spinning proton magnetic resonance spectroscopy as an ancillary diagnostic technique for papillary thyroid carcinoma in thyroid fine-needle aspiration biopsies. The method has already been shown to be effective in the classification of various other nonthyroid cancers. Study Design: Twenty-six samples (13 paired cytologic and histologic samples) from patients being evaluated for thyroid abnormalities at the Massachusetts General Hospital were spectroscopically analyzed, and included: papillary thyroid carcinomas (n = 4), follicular adenomas (n = 4), and normal thyroid samples (n = 5). Metabolic profiles were statistically generated based on the spectroscopy results, which were then correlated with the final cytologic and histologic diagnoses from the same samples to determine the diagnostic capacity of the profiles. Results: Principal component analysis of the tissue samples revealed statistically significant correlations among principal components and various cytologic and histologic features. Canonical score 1, calculated with principal components in correlation with analyzed pathologies, revealed the ability of the metabolic profile to differentiate all three examined histologic tissue groups (ANOVA, p < 0.0001). Applying coefficients of principal components and canonical scores obtained with tissue samples directly onto spectral results of cytology samples, the calculated canonical score 1 also revealed similar trends among the three fine-needle aspiration biopsy groups. In particular, the papillary thyroid carcinoma group exhibited significant differences from both the adenomatous and normal cytology groups (p < 0.0170). Conclusions: The results indicate the potential of high-resolution magic angle spinning proton magnetic resonance spectroscopy as an ancillary marker for papillary thyroid carcinoma in fine-needle aspiration biopsy specimens.

Assuming dipole–dipole interaction as the dominant relaxation mechanism of protons of water molecules adsorbed onto macromolecule (biopolymer) surfaces we have been able to model the dependences of relaxation rates on temperature and frequency. For adsorbed water molecules the correlation times are of the order of 10 −5 s, for which the dispersion region of spin–lattice relaxation rates in the rotating frame R 1 ρ = 1/ T 1 ρ appears over a range of easily accessible B 1 values. Measurements of T 1 ρ at constant temperature and different B 1 values then give the “dispersion profiles” for biopolymers. Fitting a theoretical relaxation model to these profiles allows for the estimation of correlation times. This way of obtaining the correlation time is easier and faster than approaches involving measurements of the temperature dependence of R 1 = 1/ T 1 . The T 1 ρ dispersion approach, as a tool for molecular dynamics study, has been demonstrated for several hydrated biopolymer systems including crystalline cellulose, starch of different origins (potato, corn, oat, wheat), paper (modern, old) and lyophilized proteins (albumin, lysozyme).

A sequence of treatments consisting of an initial xylanase treatment followed by cold alkaline extraction and a final endoglucanase treatment was investigated as a process for upgrading non-wood paper-grade pulps to dissolving-grade pulps for viscose production. Five commercial dried bleached non-wood soda/AQ paper pulps, from flax, hemp, sisal, abaca, and jute, were studied for this purpose. Commercial dried bleached eucalyptus dissolving pulp was used as reference sample. Sisal pulp showed the highest improvement in Fock's reactivity, reaching levels nearly as high or even higher than that of eucalyptus dissolving pulp (65%), and a low hemicellulose content (3-4%) when was subjected to this sequence of treatments. The viscosity, however, decreased considerably. A uniform and narrow molecular weight distribution was observed by size exclusion chromatography. (13)C nuclear magnetic resonance spectroscopy and Raman microspectroscopy revealed that the cellulose structure consisted of cellulose I.

In this work, pulp mill wastewater was treated using a novel copolymer flocculant with a high water-solubility, which was synthesized through grafting (2-methacryloyloxyethyl) trimethyl ammonium chloride (DMC) onto chitosan initiated by potassium persulphate. The experimental results demonstrate that the two main problems associated with the utilization of chitosan as a flocculant, i.e., low molecular weight and low water-solubility, were concurrently sorted out. The physicochemical properties of this flocculant were characterized with Fourier-transform infrared spectroscopy, 1H nuclear magnetic resonance spectroscopy, X-ray powder diffraction and field emission scanning electron microscopy. Reaction parameters influencing the grafting percentage, such as temperature, reaction time, initiator concentration and monomer concentration, were optimized using an orthogonal array design matrix. With an increase in grafting percentage, the water-solubility of the flocculant was improved, and it became thoroughly soluble in water when the grafting percentage reached 236.4% or higher. Its application for the treatment of pulp mill wastewater indicates that it had an excellent flocculation capacity and that its flocculation efficiency was much better than that of polyacrylamide. The optimal conditions for the flocculation treatment of pulp mill wastewater were also obtained.

International audience; Environmentally friendly and potentially bioactive food packaging based on chitosan-coated papers were elaborated. The morphology and the microstructure of these new materials were characterized by infrared spectroscopy and scanning electron microscopy. These observations suggested that the chitosan penetrated deeply into the paper, embedding the cellulose fibers, instead of forming a layer as expected. Through the barrier properties against moisture, the liquid water sensitivity, and NMR-relaxometry measurements, the water interactions were evaluated on the chitosan films and the chitosan-coated papers. They revealed that the coating by a chitosan film forming solution improved the paper moisture barrier properties but the surface hydrophilicity remained high. Relaxometry studies showed that, due to its hydrophilic character, chitosan controlled the interaction with water, despite the very low amount of deposit. On the other hand, the mechanical properties of papers were unmodified by the chitosan coating, which did not fundamentally affect the solid structure of the papers.

Uptake properties of Ni2+ were examined for unmilled and milled paper sludge calcined at various temperatures to develop a new usage of waste paper sludge. Since paper sludge mainly consists of cellulose ([C6H(10)O5]n) fibers, calcite (CaCO3), kaolinite (Al2Si2O5(OH)4) and talc (Mg3Si(4)O(10)(OH)2), amorphous and crystalline CaO(MgO)-Al(2)O(3)-SiO(2) compounds are formed by calcining paper sludge. Wet and dry milling treatments were performed to accelerate solid-state reaction to form the above mentioned target compounds. The crystalline phases originally present decompose at increasing calcining temperature (up to 800 degrees C) in the order cellulose

Background: The memory deficits in patients with temporal lobe epilepsy (TLE) are associated with epileptogenic lesions of the temporal lobes, especially hippocampal sclerosis. Memory deficits have been extensively studied in TLE, but the presence of pre-existing temporal lobe abnormality has confounded studies on the relationship between memory dysfunction and seizure activity. Idiopathic generalised epilepsy (IGE) is characterised by primary generalised seizures and is found to occur in the absence of any macroscopic brain abnormalities. IGE is therefore ideal for investigations on the effects of seizure activity on memory and cognition. Aim and methods: Magnetic resonance spectroscopy (MRS) and neuropsychological testing were used to investigate the relationship between epileptic seizures, memory performance and neuronal dysfunction in the temporal lobes of a group of patients with IGE. 30 patients and 15 healthy controls participated in the study. Results: Patients with IGE were found to perform worse than controls on tests of speed of information processing, general cognitive performance and a range of memory tests, including face recognition, word recognition, verbal recall and complex figure recall. The performance of the patient group on the visual recognition and verbal recall sections of the Doors and People Test was found to correlate with MRS ratios of N-acetyl aspartate:choline and N-acetyl aspartate:creatine in the temporal lobes. Conclusion: This result supports the hypothesis that memory deficits in epilepsy may be due to neuronal dysfunction secondary to epileptic activity itself in the absence of any macroscopic lesions in the temporal lobes.

Parchment, a biologically based material obtained from the processed hides of animals such as cattle and sheep, has been used for millennia as a writing medium. Although numerous studies have concentrated on the structure and degradation of collagen within parchment, little attention has been paid to noncollagenous components, such as lipids. In this study, we present the results of biochemical and structural analyses of historical and newly manufactured parchment to examine the potential role that lipid plays in parchment stability. The lipid fraction extracted from the parchments displayed different fatty acid compositions between historical and reference materials. Gas chromatography, small-angle X-ray scattering, and solid-state NMR were used to identify and investigate the lipid fraction from parchment samples and to study its contribution to collagen structure and degradation. We hypothesize that the origin of this lipid fraction is either intrinsic, attributable to incomplete fat removal in the manufacturing process, or extrinsic, attributable to microbiological attack on the proteinaceous component of parchments. Furthermore, we consider that the possible formation of protein-lipid complexes in parchment over the course of oxidative degradation may be mediated by reactive oxygen species formed by lipid peroxidation.

13C NMR analyses of hydrophobic dissolved organic matter (DOM) fractions isolated from a landfill leachate contaminated groundwater near Norman, OK; the Colorado River aqueduct near Los Angeles, CA; Anaheim Lake, an infiltration basin for the Santa Ana River in Orange County, CA; and groundwater from the Tomago Sand Beds, near Sydney, Australia, found branched methyl groups and quaternary aliphatic carbon structures that are indicative of terpenoid hydrocarbon precursors. Significant amounts of lignin precursors, commonly postulated to be the major source of DOM, were found only in trace quantities by thermochemolysis/gas chromatography/mass spectrometry of the Norman Landfill and Tomago Sand Bed hydrophobic DOM fractions. Electrospray/tandem mass spectrometry of the Tomago Sand Bed hydrophobic acid DOM found an ion series differing by 14 daltons, which is indicative of aliphatic and aryl-aliphatic polycarboxylic acids. The product obtained from ozonation of the resin acid, abietic acid, gave a similar ion series. Terpenoid precursors of DOM are postulated to be derived from resin acid paper sizing agents in the Norman Landfill, algal and bacterial terpenoids in the Colorado River and Anaheim Lake, and terrestrial plant terpenoids in the Tomago Sand Beds.

Paper fiber was treated in a heterogeneous esterification reaction with four different fatty acids. This fiber was used to strengthen polyethylene (PE) composites. Modified and unmodified cellulose fiber was characterized with inverse gas chromatography. In previous work, characterization was also carried with X-ray photoelectron spectroscopy (XPS), solid-state NMR, differential scanning calorimetry and thermogravimetry. Individual fibers were found to be covered with the corresponding esters (cellulose undecylenate, undecanoate, oleate, stearate) with partial degrees of substitution of the cellulose. Comparison of XPS and NMR results showed that the surface degree of substitution of the cellulose fiber was higher than for the bulk, showing that the esterification reaction was a surface phenomenon. The aim of this work was to acquire information on the surface characteristics of the fiber and to see whether it could be correlated to PE composite mechanical strength results. The conclusions are that polar probes seem to diffuse more into the fibers than the non-polar probes, as the non-polar component of the surface tension of the modified fiber is much lowered towards that of PE, while donor–acceptor characteristics are hardly changed by esterification. The ester with the lowest non-polar component of the surface energy, the oleate, also gives the composite with the best mechanical properties.

© 2015 Elsevier Ireland Ltd. Most spectroscopic studies of the reaction products formed by ninhydrin, 1,2-indanedione-zinc (Ind-Zn) and 1,8-diazafluoren-9-one (DFO) when reacted with amino acids or latent fingermarks on paper substrates are focused on visible absorption or luminescence spectroscopy. In addition, structural elucidation studies are typically limited to solution-based mass spectrometry or liquid nuclear magnetic resonance (NMR) spectroscopy, which does not provide an accurate representation of the fingermark development process on common paper substrates. The research presented in this article demonstrates that solid-state carbon-13 magic angle spinning NMR (13C-MAS-NMR) is a technique that can not only be utilised for structural studies of fingermark enhancement reagents, but is a promising technique for characterising the effect of paper chemistry on fingermark deposition and enhancement. The latter opens up a research area that has been under-explored to date but has the potential to improve our understanding of how fingermark secretions and enhancement reagents interact with paper substrates.

A hybrid technique incorporating a wet oxidation stage and secondary fermentation step was used to process Pinus radiata pulp mill effluent sludge. The effect of hydrothermal oxidation at high temperature and pressure on the hydrolysis of constituents of the waste stream was studied. Biochemical acidogenic potential assays were conducted to assess acid production resulting from anaerobic hydrolysis of the wet oxidised hydrolysate under acidogenic conditions. Significant degradation of the lignin, hemicellulose, suspended solids, carbohydrates and extractives were observed with wet oxidation. In contrast, cellulose showed resistance to degradation under the experimental conditions. Extensive degradation of biologically inhibitory compounds by wet oxidation did not show a beneficial impact on the acidogenic or methanogenic potential compared to untreated samples.

The hornification process of paper pulp was investigated using solid-state (13)C NMR spectroscopy. Nanocrystalline cellulose was used to serve as a model system of the crystalline parts of the fibrils in pulp fibers. Characterization of the nanocrystalline cellulose dimensions was carried out using scanning electron microscopy. The samples were treated by drying and wetting cycles prior to NMR analysis where the hornification phenomenon was recorded by spectral changes of the cellulose C-4 carbon signals. An increase of the crystalline signal and a decrease of the signals corresponding to the accessible amorphous domains were found for both paper pulp and nanocrystalline cellulose. These spectral changes grew stronger with repeating drying and wetting cycles. The results show that cellulose co-crystallization contribute to hornification. Another conclusion is that the surfaces of higher hydrophobicity in cellulose fibrils have an increased preference for aggregation.

This publication reports analytical properties of three new hallucinogenic substances identified in blotter papers seized from the drug market, namely 25D-NBOMe [2-(2,5-dimethoxy-4-methylphenyl)-N-(2-methoxybenzyl)ethanamine], 25E-NBOMe [2-(4-ethyl-2,5-dimethoxyphenyl)-N-(2-methoxybenzyl)ethanamine] and 25G-NBOMe [2-(2,5-dimethoxy-3,4-dimethylphenyl)-N-(2-methoxybenzyl)ethanamine]. These substances are N-(2-methoxy)benzyl derivatives of the 2C-series of phenethylamine drugs. The applied procedure covered a variety of analytical methods, including gas chromatography with electron impact mass spectrometry (GC-EI-MS; without derivatization and after derivatization with trifluoroacetic anhydride (TFAA)), liquid chromatography-electrospray ionization-quadrupole time of flight mass spectrometry (LC-ESI-QTOF-MS), Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR), which made it possible to identify the active components unequivocally. The GC-MS spectra of analyzed compounds were very similar, with dominant ions observed at m/z = 150, 121, and 91. The remaining ions were analogous to those observed for parent substances, namely 2C-D, 2C-E, 2C-G, but their intensities were low. Derivatization allowed determination of molecular masses of the investigated substances. Their exact masses and chemical formulas were confirmed by LC-QTOF-MS experiments and the fragmentation patterns of these compounds following ESI were determined. The tandem mass spectrometry (MS/MS) experiments confirmed that the studied substances were N-(2-methoxy)benzyl derivatives of the 2C-series compounds. Final elucidation of the structures was performed by NMR spectroscopy. The substances were also characterized by FTIR spectroscopy to corroborate the identity of the compounds.

International audience; AMDES (aminopropylmethyldiethoxysilane) was used to investigate the physicochemical and chemical events related to the introduction of aminoalkylalkoxysilanes in cellulosic materials. Using 29Si CP-MAS and 1H NMR to study the reactivity and structural modification of AMDES in the paper it was shown that polymerization occurs in situ. The distribution of the active compound on the surface of the fibers and throughout the fibers’ thickness was visualized by SEM-EDS. A relation between moisture content, fiber swelling, and uptake of AMDES was found. To better represent old and brittle documents, the paper was predegraded by oxidation with sodium hypochlorite. XRD confirmed the advanced destruction of the amorphous areas of cellulose. Adding AMDES in the oxidized paper resulted in improved mechanical properties, a roughly unmodified degree of polymerization of cellulose, but a slight increase in the yellowing, probably due to several possible reaction products such as imines, amine, amides, and Maillard reactions products. The deacidification efficacy was established and the strengthening effect was shown to arise from the interaction of AMDES with the cellulose fibers.

Conventional MRI can provide critical information for care of patients with traumatic brain injury (TBI), but MRI abnormalities rarely correlate to clinical severity and outcome. Previous magnetic resonance spectroscopy studies have reported clinically relevant brain metabolic changes in patients with TBI. However, these changes were often assessed a few to several days after the trauma, with a consequent variation of the metabolic pattern due to temporal changes.Proton magnetic resonance spectroscopic imaging (1H-MRSI) examinations were performed in 10 patients with TBI 48-72 h after the trauma, to obtain early measurements of central brain levels of N-acetylaspartate (NAA), choline (Cho), creatine (Cr) and lactate (La). Metabolite values were expressed as ratios to (1) a metabolic pattern, given by the sum of the resonance intensities of all metabolites detected in the same voxel and (2) intravoxel Cr.NAA ratios were found to be significantly lower in patients with TBI than in normal controls. In contrast, Cho ratios were significantly higher in patients with TBI than in normal controls. Increased La levels were found in 5 of 10 patients with TBI. Both NAA and La values correlated closely with those of the Glasgow Coma Scale at presentation (r = 0.73 and -0.62, respectively; p0.01 for both) and the Glasgow Outcome Scale at 3 months (r = -0.79 and 0.79, respectively; p0.01 for both).Spectroscopic measures of neuro-axonal damage occurring soon after a brain trauma are clinically relevant. Significant increases in cerebral La level also may be detected when 1H-MRSI is performed early after the trauma and, at this stage, can represent a reliable index of injury severity and disease outcome in patients with TBI.

To determine the relationship of cerebral degeneration with survival in amyotrophic lateral sclerosis (ALS).Patients with probable or definite ALS underwent magnetic resonance spectroscopic imaging (MRSI) of the brain between July 1996 and May 2002, and were followed prospectively until March 2004. Creatine (Cr), choline (Cho) and the neuronal marker N-acetylaspartate (NAA) were quantified as ratios in the motor cortex.In 63 patients compared with 18 healthy people, NAA/Cho was reduced by 13% (p0.001), NAA/Cr was reduced by 5% (p = 0.01) and Cho/Cr was increased by 8% (p = 0.01). NAA/Cho was used for survival analysis, given its larger effect size and superior test accuracy (a sensitivity of 67% and a specificity of 83%). Median survival after MRSI was 24 months. Multivariate analysis showed reduced survival for lower NAA/Cho (hazard ratio (HR) 0.24, 95% confidence interval (CI) 0.08 to 0.72, p = 0.01), older age (HR 1.03, 95% CI 1.00 to 1.06, p = 0.04) and shorter symptom duration (HR 0.96, 95% CI 0.93 to 0.99, p = 0.01). Patients with NAA/Cho2.11 had a reduced survival of 19.4 v 31.9 months (HR 2.05, 95% CI 1.12 to 4.03, p = 0.02).Cerebral degeneration is predictive of reduced survival in ALS.

Objective: Abnormal thalamo-cortical oscillations underlie idiopathic generalised epilepsy (IGE). Although thalamic involvement has long been indicated by electrophysiological data, it has only recently become feasible to test this with independent methods. In this magnetic resonance (MR) study, we investigated the metabolic and structural integrity of the thalamus. Possible changes in glutamine and glutamate concentrations and signs of neuronal damage were of particular interest. Method: Forty three IGE patients and 38 age and sex matched healthy controls were investigated. Quantitative single volume MR spectroscopy (MRS, 1.5 T) was used to measure concentrations of glutamate and glutamine (Glx) and N -acetyl aspartate (NAA) in thalamus and occipital cortex. We also measured thalamic volumes on high resolution gradient-echo images and estimated fractions of thalamic grey and white matter with voxel based morphometry (VBM). Results: IGE patients showed elevated Glx and reduced NAA concentrations in the thalamus compared to controls (12.2±2.6 v 8.9±4.1 mM, p = 0.0022 for Glx, and 9.9±1.0 v 10.7±0.9 mM, p = 0.017 for NAA). Thalamic grey matter fraction was reduced in IGE patients, and white matter fraction was increased with the greatest increase in the dorso-medial thalamus. Mean thalamic volume was reduced in patients (6.7±0.7 v 7.2±0.6 ml in controls, p = 0.0001), as was mean cerebral volume (1163±128 v 1250±102 ml, p = 0.0003). Patients’ thalamus/whole brain ratios were normal. Conclusion: Quantitative MRS and VBM provide further evidence for involvement of the thalamus in IGE. The observed elevation of Glx levels together with reductions in NAA levels and grey matter fractions are consistent with epilepsy related excitoxicity as a possible underlying mechanism.

Contamination of foods with trimethyldiphenylmethanes is reported and the origin is shown to be migration from food packaging materials of which the use of recycled carbonless copy paper was found to be the major source. This chemical is one of the solvents used in the carbonless copy paper and its presence in food and the environment has not been previously identified. In this paper we have pursued previous studies on diisopropylnaphthalenes and hydrogenated terphenyls contamination from packaging and now report the identification of this new food contaminant and present evidence of its source. Solid foods such as egg pasta, barley coffee and rice were analysed by GC/MS and a mean concentration of 18 microg/kg of trimethyldiphenylmethanes was found. Extracts from carbonless copy paper were analysed by proton NMR to characterize the trimethyldiphenylmethanes. Since trimethyldiphenylmethanes are found in solid food together with diisopropylnaphthalenes, and considering their similar chemical character, they may follow the same migration pathway as one another.

The nuclear magnetic resonance (NMR) Surface scanner, which provides images of sample surfaces larger than the probe dimension. has been realized using a single-sided device. Although conditioned by distortion effects originated by convolution between the sensitive volume of the probe and the space structures to be imaged. the scanner is able to provide in images with Rood spatial resolution. The images obtained by the surface scanner can be made sensitive to relaxation parameters, magnetization or molecular self-diffusion: also. the dimension perpendicular to the sample surface can be scanned by varying the depth from which the probe detects the sample signal. It may scan Surfaces arbitrarily large and with some degree of curvature. This aspect, together with the noninvasive characteristic of the apparatus. indicates that the surface scanner could be used profitably in the field of cultural heritage. where it could provide NMR maps of frescos. paintings oil wood, marble artifacts, books and others. (C) 2006 Elsevier Inc. All rights reserved.

Newsprint samples collected from 12-16 ft (top layer (TNP)), 20-24 ft (middle layer (MNP)), and 32-36 ft (bottom layer (BNP)) below the surface of the Norman Landfill (NLF) were characterized by infrared (IR) spectroscopy, cross-polarization, magic-angle spinning 13C nuclear magnetic resonance (CP-MAS 13C NMR) spectroscopy, and tetramethylammonium hydroxide (TMAH) thermochemolysis gas chromatography/mass spectrometry (GC/MS). The extent of NLF newsprint degradation was evaluated by comparing the chemical composition of NLF newsprint to that of fresh newsprint (FNP) and newsprint degraded in the laboratory under methanogenic conditions (DNP). The O-alkyl/alkyl, cellulose/lignin, and lignin/resin acid ratios showed that BNP was the most degraded, and that all three NLF newsprint samples were more degraded than DNP. 13C NMR and TMAH thermochemolysis data demonstrated selective enrichment of lignin over cellulose, and TMAH thermochemolysis further exhibited selective enrichment of resin acids over lignin. In addition, the crystallinity of cellulose in NLF newsprint samples was significantly lower relative to that of FNP and DNP as shown by 13C NMR spectra. The yield of lignin monomers from TMAH thermochemolysis suggested that hydroxyl groups were removed from the propyl side chain of lignin during the anaerobic decomposition of newsprint in the NLF. Moreover, the vanillyl acid/aldehyde ratio, which successfully describes aerobic lignin degradation, was not a good indicator of the anaerobic degradation of lignin on the basis of the TMAH data. The toluene sorption capacity increased as the degree of newsprint degradation increased or as the O-alkyl/alkyl ratio of newsprint decreased. The results of this study further verified that the sorbent O-alkyl/ alkyl ratio is useful for predicting sorption capacities of natural organic materials for hydrophobic organic contaminants.

Background: Normal pressure hydrocephalus (NPH) is considered to be a treatable form of dementia, because cerebrospinal fluid (CSF) shunting can lessen symptoms. However, neuroimaging has failed to predict when shunting will be effective. Objective: To investigate whether 1 H (proton) magnetic resonance (MR) spectroscopy could predict functional outcome in patients after shunting. Methods: Neurological state including Hasegawa’s dementia scale, gait, continence, and the modified Rankin scale were evaluated in 21 patients with secondary NPH who underwent ventriculo-peritoneal shunting. Outcomes were measured postoperatively at one and 12 months and were classified as excellent, fair, or poor. MR spectra were obtained from left hemispheric white matter. Results: Significant preoperative differences in N-acetyl aspartate (NAA)/creatine (Cr) and NAA/choline (Cho) were noted between patients with excellent and poor outcome at one month (p = 0.0014 and 0.0036, respectively). Multiple regression analysis linked higher preoperative NAA/Cr ratio, gait score, and modified Rankin scale to better one month outcome. Predictive value, sensitivity, and specificity for excellent outcome following shunting were 95.2%, 100%, and 87.5%. Multiple regression analysis indicated that NAA/Cho had the best predictive value for one year outcome (p = 0.0032); predictive value, sensitivity, and specificity were 89.5%, 90.0%, and 88.9%. Conclusions: MR spectroscopy predicted long term post-shunting outcomes in patients with secondary NPH, and it would be a useful assessment tool before lumbar drainage.

A sequential totally chlorine-free procedure for isolation of cellulose from wheat straw was proposed in this study. The dewaxed straw was pretreated with 0.5 M NaOH in 60% methanol at 60 degrees C for 2.5 h under ultrasonic irradiation for 0-35 min and sequentially posttreated with 2% H(2)O(2)-0.2% TAED at pH 11.8 for 12 h at 48 degrees C, which together solubilized 85.3-86.1% of the original hemicelluloses and 91.7-93.2% of the original lignin, respectively. The yield of crude cellulose ranged between 46.2 and 49.2% on a dry weight basis related to wheat straw, which contained 11.2-12.2% residual hemicelluloses and 2.5-2.9% remaining lignin. Further treatment of the corresponding crude cellulosic preparations with 80% acetic acid-70% nitric acid under the condition given yielded 36.8-37.7% of the purified cellulose, which contained minor amounts of bound hemicelluloses (2.5-2.8%) and was relatively free of associated lignin (0.1-0.2%). The isolated crude and purified cellulose samples were comparatively studied by FT-IR and CP/MAS (13)C NMR spectroscopy, and the relative crystallinity was also estimated. The final stage treatment with 80% acetic acid-70% nitric acid decreased the hemicelluloses and lignin associated in the crude cellulose but led to 3.1-5.4% degradation of the original cellulose; in addition, the purity of the obtained cellulose was high. However, it was found that the final stage treatment is not severe enough to cause decrystallization of cellulose. The thermal stability of the purified cellulose is higher than that of the corresponding crude cellulose.

We performed (1)H-MR spectroscopy ((1)H-MRS) on multiple brain regions to determine the metabolite pattern and diagnostic utility of (1)H-MRS in multiple system atrophy (MSA).Examining single voxels at 3.0 T, we studied metabolic findings of the putamen, pontine base, and cerebral white matter in 24 MSA patients (predominant cerebellar ataxia (MSA-C), n = 13), parkinsonism (MSA-P), n = 11), in 11 age and duration matched Parkinson's disease patients (PD) and in 18 age matched control subjects.The N-acetylaspartate to creatine ratio (NAA/Cr) in MSA patients showed a significant reduction in the pontine base (p0.0001) and putamen (p = 0.02) compared with controls. NAA/Cr in cerebral white matter also tended to decline in long standing cases. NAA/Cr reduction in the pontine base was prominent in both MSA-P (p0.0001) and MSA-C (p0.0001), and putaminal NAA/Cr reduction was significant in MSA-P (p = 0.009). It was also significant in patients who were in an early phase of their disease, and in those who showed no ataxic symptoms or parkinsonism, or did not show any MRI abnormality of the "hot cross bun" sign or hyperintense putaminal rims. NAA/Cr in MSA-P patients was significantly reduced in the pontine base (p = 0.001) and putamen (p = 0.002) compared with PD patients. The combined (1)H-MRS in the putamen and pontine base served to distinguish patients with MSA-P from PD more clearly.(1)H-MRS showed widespread neuronal and axonal involvement in MSA. The NAA/Cr reduction in the pontine base proved highly informative in the early diagnosis of MSA prior to MRI changes and even before any clinical manifestation of symptoms.

The slime-forming bacterium Methylobacterium sp. was isolated from a Finnish paper machine and its exopolysaccharide (EPS) was produced on laboratory scale. Sugar compositional analysis revealed a 100% galactan (EPS). However, FT-IR showed a very strong peak at 1611 cm−1 showing the presence of pyruvate. Analysis of the pyruvate content revealed that, based on the sugar composition, the EPS consists of a trisaccharide repeating unit consisting of d-galactopyranose and [4,6-O-(1-carboxyethylidene)]-d-galactopyranose with a molar ratio of 1:2, respectively. Both linkage analysis and 2D homo- and heteronuclear 1H and 13C NMR spectroscopy revealed the following repeating unit: →3)-[4,6-O-(1-carboxyethylidene)]-α-d-Galp-(1→3)[4,6-O-(1-carboxyethylidene)]-α-d-Galp-(1→3)-α-d-Galp-(1→. By enrichment cultures from various ground and compost heap samples a polysaccharide-degrading culture was obtained that produced an endo acting enzyme able to degrade the EPS described. The enzyme hydrolysed the EPS to a large extent, releasing oligomers that mainly consisted out of two repeating units.

Objectives: To determine whether proton magnetic resonance spectroscopy (MRS), a newer radiographic technology, would be useful in the evaluation of the thalamus of patients in vegetative states resulting from traumatic brain injury. Methods: 14 victims of severe traumatic brain injury who were in the vegetative state and whose magnetic resonance images of the thalamus were normal underwent bilateral thalamic proton (MRS) studies. The N-acetyl aspartate to creatine (NAA:Cr) and choline to creatine (Cho:Cr) ratios were obtained for each patient. The proton thalamic MRS findings of patients who were in a persistent vegetative state (n = 8) and in patients who had regained awareness after being in the vegetative state (n = 6) were compared with proton thalamic MRS findings in five healthy volunteers. Results: While conventional magnetic resonance imaging suggested that each patient had a normal thalamus, proton MRS indicated that the thalamus of each patient in the series was damaged. The NAA:Cr ratio was significantly lower in the thalami of both the patients who remained in a persistent vegetative state for the duration of the study and in those who regained awareness after being in the vegetative state (p < 0.001). In addition, NAA:Cr ratios were lower in the group of patients who remained in a persistent vegetative state than in the group of patients who regained awareness after being in the vegetative state (p < 0.001). Conclusions: Results suggest that the NAA:Cr ratio within the thalamus is significant and that thalamic MRS may be helpful when attempting to determine the degree of severity of neuronal and axonal injury in patients in the vegetative state.

The slime forming bacteria Brevundimonas vesicularis sp. was isolated from a paper mill and its EPS was produced on laboratory scale. After production, the exopolysaccharide (EPS) was purified and analysed for its purity and homogeneity, HPSEC revealed one distinct population with a molecular mass of more than 2,000 kDa. The protein content was around 9 w/w%. The sample was analysed to determine its chemical structure. The EPS was found to consist of rhamnose, glucose, galacturonic acid and glucuronic acid. Due to the presence of uronic acids the molar ratio between the four sugars found varies from 3:5:2:4 by sugar composition analyses after methanolysis to 1:1:1:1 found by NMR. A repeating unit with a molecular mass of 678 Da was confirmed by MALDI-TOF mass spectrometry after mild acid treatment. 13C and 1H hetero- and homonuclear 2D NMR spectroscopy of the native and partial hydrolysed EPS revealed a Download : Download full-size image repeating unit, no non-sugar substituents were present.

The water content of paper and its time dependence are of great importance for the use of paper and cardboard as packaging materials. The physical process of water sorption and the mechanisms of water "binding" in paper, as fundamental principles of the kinetics, are discussed. Water exists in up to four different "states" (i.e. domains of mobility) in paper: the first layer at the primary sites on the surface of the fibers; the multimolecular layers, with less "binding" energy, on these inner surfaces; condensed water in the voids; and dissolved water in the cellulose fibers. All these "states" influence the shape of the sorption isotherm and correspond to a different water content and to different transport mechanisms. The various types of water "binding" on paper were studied by measuring the transversal relaxation rate, T2, using a pulsed Nuclear Magnetic Resonance spectrometer (minispec pc 120). In addition, a non-destructive, fast method of determining the water content in packaging materials with NMR spectroscopy is described.

The principal water-soluble compound formed on incubation of estradiol and glutathione in the presence of horseradish peroxidase has been assigned the structure of S-(3,17β-dihydroxy-9,10-secoestra-1,3,5(10)-trien-9-one-10-yl)-glutathione (II). A side product of the incubation was shown to be estra-l,3,5(10),9(11)-tetraene-3,17β-diol. In addition, non-phenolic metabolites were formed in small amounts and were not fully characterized.

An unknown polyamine isolated from a pseudomonad which contains no spermidine is identified as 2-hydroxyputrescine by comparison of the IR, NMR and mass spectra of its benzoylated derivative with that of the benzoyl derivative of 2-hydroxyputrescine synthesized from 1, 4-diamino butanone.