Aliphatic Hydroxyl Research Articles

Inhibitory effects of lignin on enzymatic hydrolysis: The role of lignin chemistry and molecular weight

Abstract Lignocellulose is a promising feedstock for biofuel production, while lignin poses a grand challenge on the entire process, especially enzymatic hydrolysis. In this study, different types of lignin inhibited enzymatic hydrolysis by different mechanisms. Organosolv lignin from Loblolly pine adsorbed enzyme nonproductively and reduced the available enzyme for cellulose, therefore decreasing hydrolysis rate and ultimate sugar yield. Kraft pine lignin precipitated on the surface of cellulose, preventing it from contacting with enzyme. The molecular weight influenced the inhibition effect of lignin. Lignin of lower molecular weight could bind enzyme nonproductively and when the molecular weight increased, the steric repulsion caused by lignin deposition on cellulose became more significant. The NMR analysis revealed that lignin structural features, e.g., functional groups, S/G ratio, determined the behaviors of lignin in enzymatic hydrolysis. High content of aliphatic hydroxyl groups, or low content of carboxylic groups led to high surface hydrophobicity, increasing the adsorption between lignin and enzyme. In addition, the substrate reactivity is also an important factor that affects enzymatic hydrolysis. Cellulose with higher crystallinity exhibited slower hydrolysis rate and lower conversion. When the crystallinity index increased from 0.43 to 0.72 and 0.81, the ultimate conversion decreased from 80 to 68% and 57%, respectively.

Elucidation of structure-inhibition relationship of monosaccharides derived pseudo-lignin in enzymatic hydrolysis

Pseudo-lignin is defined as aromatic material, which could be formed through dehydration synthesis and aromatisation of carbohydrate. In this work, dilute sulfuric acid was carried out to treat monosaccharides and holocellulose to generate pseudo-lignin and the residual lignin (RL) in acid-pretreated bamboo was isolated. The structural informations of pseudo-lignin were assayed by nondestructive techniques (SEM, FTIR, and 31P NMR). Meanwhile, the nonproductive adsorption performance of pseudo-lignin and cellulase was evaluated, taking RL as the comparison. Results showed that pseudo-lignin represented sensible droplets and was consist of aliphatics, carbonyl and aromatic structures. The amounts of aliphatic hydroxyl groups and carboxylic acid in pseudo-lignin were 0.61–0.79 mmol/g and 0.64–0.68 mmol/g, respectively. Total OH content of RL (3.51 mmol/g) was higher than pseudo-lignins (2.52–3.05 mmol/g). Due to the lower negative surface charge, hydrophobic nature, Langmuir constant (K) and binding strength (R) of pseudo-lignin, it represented weaker negative impact on enzymes than RL.

Lignosulfonate/APP IFR and its flame retardancy in lignosulfonate-based rigid polyurethane foams

Lignin containing substantial aromatic rings and high content of carbon has been employed as carbonizing agent to investigate the flame retardancy in the lignin/ammonium polyphosphate (APP) intumescent flame retardant (IFR) system. In addition, owing to the abundant phenolic and aliphatic hydroxyl groups, lignosulfonate, which is considered as a renewable aromatic macropolyols, substituted part of diethylene glycol (DEG) and copolymerized with isocyanate to produce lignosulfonate-based rigid polyurethane (LRPU) foams. Thermal stability was characterized by thermogravimetric analysis (TGA), and flame retardancy was investigated by limiting oxygen index (LOI) and cone calorimetry testing (CCT). Lignosulfonate increases thermal stability of LRPU foams and LRPU containing 15 wt% of lignosulfonate based on DEG (L15RPU) give rise to the best thermal stability. When 15% of lignosulfonate incorporated in the LRPU, reduced the heat release rate (HRR) and total heat release (THR) value 21 kW/m2 and 13 MJ/m2, respectively, and postponed 96 s time-to-peak carbon monoxide production than that of pure DEG rigid polyurethane (RPU) foam, the LOI values increased progressively with lignosulfonate content increasing. These results showed that lignosulfonate polyol may substitute polyol to produce lignosulfonate-based RPU foam and the presence of lignosulfonate could improve the flame retardancy. The mass loss gradually decreases with increasing APP addition, and the highest char yield was obtained from LRPU5 foam which at the lignosulfonate-to-APP ratio is 1:5. At the lignosulfonate-to-APP ratio of 1:5, the LOI value increased over 30%, and the HRR value reduced and the time-to-peak HRR postponed significantly. In addition, LRPU5 foams give rise to the lowest effect heat combustion (EHC) value, less smoke, and carbon monoxide (CO) production. Lignosulfonate acts as carbonizing agent in the lignosulfonate/APP IFR system, and the best fire retardancy is obtained at 1:5 of lignosulfonate-to–APP ratio.

Oxygen consumption and chemisorption in low-temperature oxidation of sub-bituminous pulverized coal

ABSTRACTStudying the effect of oxygen in coal oxidation is very important for understanding and controlling coal spontaneous combustion. However, the oxygen effect is not very easy to determine clearly due to the large effect of heat source on coal oxidation in temperature rising experiments. Here, focused on sub-bituminous coal, the oxygen effect was separated from coal oxidation by continuously measuring FTIR spectra of coal with respect to varying temperatures and under oxygen and nitrogen. The active groups’ real-time changes of coal oxidation, thermal treatment and oxygen effect were measured. The carboxylic ester and carboxyl units are the main functional groups that increase with temperatures increasing under oxygen and nitrogen, while the other functional groups decrease in quantity. The oxygen effect promoted the consumption of aliphatic hydrocarbons and hydroxyl groups and also promoted the formation of oxygen-containing groups (except hydroxyl). Four characteristic temperature stages involved in the oxygen effect and their key functional groups were identified. Simultaneously, the relationship of oxygen consumption and chemisorption in oxygen effect was analyzed. The starting temperature of oxygen chemisorption is between 50 and 60°C. The maximum contribution of oxygen effect was observed in methyl and methylene groups. These results are important for chemical control of coal spontaneous combustion. The oxidation of aliphatic hydrocarbon should be controlled before oxygen chemisorption. The value of oxygen consumption between 70 and 80°C can be measured accurately due to the constant chemisorption rate, which help to identify the tendency for spontaneous combustion. These results will help in better understanding of the reaction mechanism of coal oxidation, especially the oxygen effect.

Evaluation of Ligno Boost™ softwood kraft lignin epoxidation as an approach for its application in cured epoxy resins

In this study, modification of LignoBoost™ softwood kraft lignin with epichlorhydrin in water-organic solvents media was realized. Lignin-based epoxy resins were obtained by two ways: acetone extraction of glycidylated lignin or glycidylation of the acetone soluble lignin fraction. The effect of glycidylation regimes on the yields of acetone soluble fractions, their functional composition and physical-chemical characteristics was investigated using wet chemistry methods, FTIR spectroscopy, size exclusion chromatography (SEC) and differential scanning calorimetry (DSC). The positive effect of the biphasic phase transfer catalytic system – KOH/quaternary ammonium salt – on glycidylation of both phenolic and aliphatic hydroxyl groups was testified, exemplified using a lignin-like model compound – 4-hydroxy-3-methoxylbenzyl alcohol (vanillyl alcohol). The partial substitution (up to 10%) of commercial epoxy resin on the basis of bisphenol A (Araldite® LY1564) by lignin-based epoxy resin significantly increased the viscosity of resin. Therefore, the possible practical application of lignin-containing epoxies as adhesive, mastic or crack filler instead of binder for fiber reinforced composites was considered. A tendency towards increasing Young’s modulus of cured lignin-containing epoxies, compared with the case of the reference composition, was observed. The lignin chemically incorporated into the matrix of cured commercial epoxy resin acts as a charcoal formation promoter in high temperature treatment.

GABAA receptor activity modulating piperine analogs: In vitro metabolic stability, metabolite identification, CYP450 reaction phenotyping, and protein binding.

In a screening of natural products for allosteric modulators of GABAA receptors (γ-aminobutyric acid type A receptor), piperine was identified as a compound targeting a benzodiazepine-independent binding site. Given that piperine is also an activator of TRPV1 (transient receptor potential vanilloid type 1) receptors involved in pain signaling and thermoregulation, a series of piperine analogs were prepared in several cycles of structural optimization, with the aim of separating GABAA and TRPV1 activating properties. We here investigated the metabolism of piperine and selected analogs in view of further cycles of lead optimization. Metabolic stability of the compounds was evaluated by incubation with pooled human liver microsomes, and metabolites were analyzed by UHPLC-Q-TOF-MS. CYP450 isoenzymes involved in metabolism of compounds were identified by reaction phenotyping with Silensomes™. Unbound fraction in whole blood was determined by rapid equilibrium dialysis. Piperine was the metabolically most stable compound. Aliphatic hydroxylation, and N- and O-dealkylation were the major routes of oxidative metabolism. Piperine was exclusively metabolized by CYP1A2, whereas CYP2C9 contributed significantly in the oxidative metabolism of all analogs. Extensive binding to blood constituents was observed for all compounds.

Benzodioxinone Photochemistry in Macromolecular Science: Progress, Challenges, and Opportunities.

This paper reviews the photoinduced reactions of benzodioxinones and how they function in polymer synthesis and UV curing applications. The mechanistic characteristics of the ketene and benzophenone production from the photolysis of benzodioxinone indicate that, under certain conditions, each intermediate may undergo further reactions expedient for the formation of various polymeric structures. While ketenes are efficient contributors to step-growth polymerization when subjected to reaction with the compounds possessing hydroxyl or amine groups, the released benzophenone can be utilized as a photoinitiator in both the free radical and cationic polymerizations. It has been shown that the photolysis of heterobifunctional monomers equipped with benzodioxinone and aliphatic hydroxyl groups leads to the formation of oligoesters with a narrow molecular weight distribution. We also validated the photochemical ability of benzodioxinone to induce the synthesis of block and graft copolymers, hybrid and branched polymers, and cross-linked monofunctional vinyl monomers or hydroxyl group-containing linear polymers.

Biodegradation of Cosmetics Products: A Computational Study of Cytochrome P450 Metabolism of Phthalates

Cytochrome P450s are a broad class of enzymes in the human body with important functions for human health, which include the metabolism and detoxification of compounds in the liver. Thus, in their catalytic cycle, the P450s form a high-valent iron(IV)-oxo heme cation radical as the active species (called Compound I) that reacts with substrates through oxygen atom transfer. This work discusses the possible degradation mechanisms of phthalates by cytochrome P450s in the liver, through computational modelling, using 2-ethylhexyl-phthalate as a model substrate. Phthalates are a type of compound commonly found in the environment from cosmetics usage, but their biodegradation in the liver may lead to toxic metabolites. Experimental studies revealed a multitude of products and varying product distributions among P450 isozymes. To understand the regio- and chemoselectivity of phthalate activation by P450 isozymes, we focus here on the mechanisms of phthalate activation by Compound I leading to O-dealkylation, aliphatic hydroxylation and aromatic hydroxylation processes. We set up model complexes of Compound I with the substrate and investigated the reaction mechanisms for products using the density functional theory on models and did a molecular mechanics study on enzymatic structures. The work shows that several reaction barriers in the gas-phase are close in energy, leading to a mixture of products. However, when we tried to dock the substrate into a P450 isozyme, some of the channels were inaccessible due to unfavorable substrate positions. Product distributions are discussed under various reaction conditions and rationalized with valence bond and thermodynamic models.

Structural characterization of birch lignin isolated from a pressurized hot water extraction and mild alkali pulped biorefinery process

In this work we have characterized a mild soda pulped birch (betula pendula) lignin after a novel pressurized hot water extraction pilot process. In the process hemicelluloses are first isolated from woods chips with hot water at oxygen-starved conditions, followed by mild alkali pulping at oxygen-starved conditions to remove lignin from the cellulose. Lignin was precipitated, washed and fractionated from the black liquor and characterized by quantitative 13C NMR, 13C DEPT experiments, 31P NMR, 2D HSQC, FTIR, size exclusion chromatography (SEC), elemental analysis, pyrolysis-gas chromatography-mass spectrometry (py-GC–MS), methoxyl group quantification and residual carbohydrate analysis after methanolysis. The structure was compared to a MWL of birch obtained from the same wood chips and the differences were an increase in phenolic hydroxyl groups, carboxylic groups, polydispersity index, and reduction of aliphatic hydroxyl groups. The process resulted in β-O-4 cleavage and condensation of the structure. This lignin is therefore suitable to be used in its polymeric form, rather than for degradation of the structure to small building blocks.

Selective aminolysis of acetylated lignin: Toward simultaneously improving thermal-oxidative stability and maintaining mechanical properties of polypropylene

Even with outstanding radical capturing ability, the utilization of lignin as a natural antioxidant in polypropylene (PP) still has been pended. Usually, the compatibility of its blends is improved based on the reaction of hydroxyl content, thus leading to the decreasing content of phenolic hydroxyl (Ph-OH) group and inferior thermal-oxidative stability of lignin blends. Here, the selective aminolysis of acetylated Kraft lignin (pyr-KL) was investigated, which structures were characterized using FTIR, 31P-NMR and GPC. The Ph-OH group of acetylated KL could be released by the addition of pyrrolidine; however the aliphatic hydroxyl group is still blocked. With the control of reaction conditions, the highest oxidation induction time of pyr-KL/PP (0.5wt% loading) reaches up to 22.6min, almost 2.6 times than that of pure PP. More importantly, the mechanical properties of PP were also maintained under the loading of pyr-KL, which is much better than that of curde KL/PP.

Comparison of different cyclic organic carbonates in the oxyalkylation of various types of lignin

The synthetic versatility and the low toxicity of cyclic alkyl carbonates has driven a wider interest in their use to access new biobased and environmentally friendly polymer building blocks, especially as alkylating reagents. Here, we report for the first time, the synthesis of biobased polyols from lignins of different sources (hardwood, softwood, annual plants) and pulping processes (organosolv, kraft, soda) by oxyalkylation with ethylene (EC), propylene (PC), butylene (BC) and glycerol carbonate (GC). The synthesis of lignin polyols was performed using optimized conditions regarding catalysts, catalyst-to-biomass ratio, reaction time, temperature and amount of cyclic carbonates. To better understand the oxyalkylation of the various types of lignins using different cyclic organic carbonates, the generated polyols were comprehensively characterized by FTIR, 1H, 13C, and 31P NMR spectroscopy as well as size exclusion chromatography (SEC). Emphasis was set on the hydroxyl amount, the degree of substitution (DS) and the alkyl chain. This oxyalkylation strongly facilitates the generation of a uniform lignin polyol equipped with two alkyl units on the aliphatic and phenolic hydroxyl groups. Higher degrees of substitution were achieved using cyclic organic carbonates in the following order EC>GC>PC>BC, reaching a maximum of DS 0.96 for a hardwood kraft lignin. Additionally, the influence of ash, sulfur and polysaccharide impurities as well as lignins molar masses was elucidated.

Potential of producing carbon fiber from biorefinery corn stover lignin with high ash content

ABSTRACTThe possibility of producing carbon fiber from an industrial corn stover lignin was investigated in the present study. As‐received, high‐ash containing lignin was subjected to methanol fractionation, acetylation, and thermal treatment prior to melt spinning and the changes in physiochemical and thermal properties were evaluated. Methanol fractionation removed most of the impurities in the raw lignin and also selectively removed the molecules with high melting points. However, neither methanol fractionation nor thermal treatment rendered melt‐spinnable precursors. The precursors were highly viscous and decomposed easily at low temperatures, attributed to the presence of H, G phenolic units, and abundant hydroxycinnamate groups in herbaceous lignin. A two‐step acetylation of methanol fractionated lignin greatly improved the mobility of lignin, while enhancing the thermal stability of the precursor during melt‐spinning. Fourier Transform Infrared and 2D‐NMR analysis showed that the contents of phenolic and aliphatic hydroxyls, as well as the hydroxycinnamates, decreased in the acetylated precursors. The optimum precursor was a partially acetylated lignin with a glass transition temperature of 85 °C. Upon oxidative stabilization and carbonization, the carbon fibers with an average tensile strength of 454 MPa and modulus of 62 GPa were obtained. The Raman spectroscopy showed the ID/IG ratio of the carbon fiber was 2.53. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45736.

Fractionation and Biotransformation of Lignocelluloses-Based Wastes for Bioethanol, Xylose and Vanillin Production

In this study combined NaOH/H2SO4 pretreatment of lignocellulosic biomasses (palm fronds, eucalyptus chips, almond shells and Aleppo pine cones) were used to separate hemicellulose and lignin and improve enzymatic digestibility of cellulose. The recovered celluloses were hydrolyzed using Cellic C-Tec2 or Cellic H-Tech2. The optimal saccharification yields 95.8, 94, 73.3 and 80.5% were obtained from the recovered celluloses of palm fronds, eucalyptus chips, almond shells and Aleppo pine cones respectively using Cellic H-Tec2. The highest ethanol yield [42.6 (±0.8 g) ethanol per 100 g glucose] was obtained from pretreated palm fronds which were hydrolyzed with Cellic H-Tech2. Hemicellulosic fractions obtained after ethanol precipitation were hydrolyzed using diluted acid (10%). These fractions were essentially composed of 38% xylose. Lignins, isolated from lignocellulosic biomasses were analyzed by FT-IR, the major bands characterize the aliphatic and phenolic hydroxyl groups as well as the ketones and aliphatic esters groups. This aromatic character makes it possible to use these lignins as precursor for vanillin production. The highest vanillin production of 162 µg mL−1 was obtained after 96 h of Aleppo pine cone lignin biotransformation by isolated white rot fungi.

Esterification Mechanism of Bagasse Modified with Glutaric Anhydride in 1-Allyl-3-methylimidazolium Chloride.

The esterification of bagasse with glutaric anhydride could increase surface adhesion compatibility and the surface of derived polymers has the potential of immobilizing peptides or proteins for biomedical application. Due to its complicated components, the esterification mechanism of bagasse esterified with glutaric anhydride in ionic liquids has not been studied. In this paper, the homogenous esterification of bagasse with glutaric anhydride was comparatively investigated with the isolated cellulose, hemicelluloses, and lignin in 1-allyl-3-methylimidazolium chloride (AmimCl) to reveal the reaction mechanism. Fourier transform infrared (FT-IR) indicated that the three components (cellulose, hemicelluloses, and lignin) were all involved in the esterification. The percentage of substitution (PS) of bagasse was gradually improved with the increased dosage of glutaric anhydride (10–40 mmol/g), which was primarily attributed to the increased esterification of cellulose and hemicelluloses. However, the PS fluctuation of lignin led to a decrease in the PS of bagasse at high glutaric anhydride dosage (50 mmol/g). The esterification reactivity of bagasse components followed the order of lignin > hemicelluloses > cellulose. The esterification mechanism was proposed as a nucleophilic substitution reaction. Nuclear magnetic resonance (NMR) analysis indicated that lignin aliphatic hydroxyls were prior to be esterified, and primary hydroxyls were more reactive than secondary hydroxyls in cellulose and hemicelluloses.

Adsorption of cellobiohydrolases I onto lignin fractions from dilute acid pretreated Broussonetia papyrifera

Broussonetia papyrifera, known as paper mulberry, is a potential feed stock for bioethanol production because of its cellulose-rich composition. Lignin in dilute acid pretreated Broussonetia papyrifera was fractionated to three different fractions, and their physiochemical properties were determined by FT-IR, GPC and NMR analyses. Different structural characteristics were observed from each lignin fraction. Cellobiohydrolases I (CBH) adsorption to each lignin was understood by the lignin properties. The results showed that aliphatic hydroxyl groups in lignin showed positive correlations with the maximum binding ability of CBH onto lignin samples. Also, the contents of phenolic compounds such as p-hydroxyphenyl benzoate (PB), syringyl (S) and guaiacyl (G) units in the lignin influenced their CBH binding.

Polyimides from an asymmetric hydroxyl‐containing aliphatic‐aromatic diamine synthesized via henry reaction

ABSTRACTAn aliphatic amino and an aliphatic hydroxyl group have been incorporated via Henry reaction highly efficiently toward the synthesis of a novel asymmetric aliphatic–aromatic diamine 2‐amino‐1‐[4‐(5‐aminopyridyloxy)phenyl]‐1‐ethanol (AAPyPhE) in three steps. AAPyPhE shows good copolymerization reactivity with 4,4′‐oxydianiline (ODA) toward different aromatic dianhydrides, especially 4,4′‐oxydiphthalic anhydride (ODPA). TGA measurement and mechanical test results show that all polymers maintain the inherent thermal performance and tensile properties, while the glass transition temperatures (Tg's) by DMA show moderate decrease ranging from 185.5 to 253.3 °C due to the presence of aliphatic segments. The introduction of AAPyPhE is found to improve the solubility of the polymers, and the polymer films' optical transparency with decreased cutoff wavelength (λ0) ranging from 328 to 370 nm. Comparative studies reveal that the pendent aliphatic hydroxyls in the polymer chains would lead to interchain cross‐linking via condensation and secondary weak cross‐linking by hydrogen bond depending on different loading of AAPyPhE, which result in a fluctuation of hydrophilic–hydrophobic properties, DMA tan δ and dielectric constant of the copolymer films. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 3413–3423

Identification of three new phase II metabolites of a designer drug methylone formed in rats by N-demethylation followed by conjugation with dicarboxylic acids

1. Methylone (3,4-methylenedioxy-N-methylcathinone, MDMC), which appeared on the illicit drug market in 2004, is a frequently abused synthetic cathinone derivative. Known metabolic pathways of MDMC include N-demethylation to normethylone (3,4-methylenedioxycathinone, MDC), aliphatic chain hydroxylation and oxidative demethylenation followed by monomethylation and conjugation with glucuronic acid and/or sulphate.2. Three new phase II metabolites, amidic conjugates of MDC with succinic, glutaric and adipic acid, were identified in the urine of rats dosed subcutaneously with MDMC.HCl (20 mg/kg body weight) by LC-ESI-HRMS using synthetic reference standards to support identification.3. The main portion of administered MDMC was excreted unchanged. Normethylone, was a major urinary metabolite, of which a minor part was conjugated with dicarboxylic acids.4. Previously identified ring-opened metabolites 4-hydroxy-3-methoxymethcathinone (4-OH-3-MeO-MC), 3-hydroxy-4-methoxymeth-cathinone (3-OH-4-MeO-MC) and 3,4-dihydroxymethcathinone (3,4-di-OH-MC) mostly in conjugated form with glucuronic and/or sulphuric acids were also detected.5. Also, ring-opened metabolites derived from MDC, namely, 4-hydroxy-3-methoxycathinone (4-OH-3-MeO-C), 3-hydroxy-4-methoxycathinone (3-OH-4-MeO-C) and 3,4-dihydroxycathinone (3,4-di-OH-C) were identified for the first time in vivo.

Two-dimensional correlation spectroscopic analysis on the interaction between humic acids and aluminum coagulant

In this study, two-dimensional correlation spectroscopy integrated with synchronous fluorescence and infrared absorption spectroscopy was employed to investigate the interaction between humic acids and aluminum coagulant at slightly acidic and neutral pH. Higher fluorescence quenching was produced for fulvic-like and humic-like fractions at pH5. At pH5, the humic-like fractions originating from the carboxylic acid, carboxyl and polysaccharide compounds were bound to aluminum first, followed by the fulvic-like fractions originating from the carboxyl and polysaccharide compounds. This finding also demonstrated that the activated functional groups of HA were involved in forming the Al-HA complex, which was accompanied by the removal of other groups by co-precipitation. Meanwhile, at pH7, almost no fluorescence quenching occurred, and surface complexation was observed to occur, in which the activated functional groups were absorbed on the amorphous Al(OH)3. Two-dimensional FT-IR correlation spectroscopy indicated the sequence of HA structural change during coagulation with aluminum, with IR bands affected in the order of COOH>COO−>NH deformation of amide II>aliphatic hydroxyl COH at pH5, and COO−>aliphatic hydroxyl COH at pH7. This study provides a promising pathway for analysis and insight into the priority of functional groups in the interaction between organic matters and metal coagulants.

New Psychoactive Substances 3-Methoxyphencyclidine (3-MeO-PCP) and 3-Methoxyrolicyclidine (3-MeO-PCPy): Metabolic Fate Elucidated with Rat Urine and Human Liver Preparations and their Detectability in Urine by GC-MS, "LC-(High Resolution)-MSn" and "LC-(High Resolution)-MS/MS".

Background:3-Methoxyphencyclidine (3-MeO-PCP) and 3-methoxyrolicyclidine (3-MeO-PCPy) are two new psychoactive substances (NPS). The aims of the present study were the elucidation of their metabolic fate in rat and pooled human liver microsomes (pHLM) the identification of the cytochrome P450 (CYP) isoenzymes involved and the detectability using standard urine screening approaches (SUSA) after intake of common users’ doses using gas chromatography-mass spectrometry (GC-MS) liquid chromatography-multi-stage mass spectrometry (LC-MSn) and liquid chromatography-high-resolution tandem mass spectrometry (LC-HR-MS/MS)Methods:For metabolism studies rat urine samples were treated by solid phase extraction or simple precipitation with or without previous enzymatic conjugate cleavage. After analyses via LC-HR-MSn the phase I and II metabolites were identifiedResults:Both drugs showed multiple aliphatic hydroxylations at the cyclohexyl ring and the heterocyclic ring single aromatic hydroxylation carboxylation after ring opening O-demethylation and glucuronidation. The transferability from rat to human was investigated by pHLM incubations where O-demethylation and hydroxylation were observed. The involvement of the individual CYP enzymes in the initial metabolic steps was investigated after single CYP incubations. For 3-MeO-PCP CYP 2B6 was responsible for aliphatic hydroxylations and CYP 2C19 and CYP 2D6 for O-demethylation. For 3-MeO-PCPy aliphatic hydroxylation was again catalyzed by CYP 2B6 and O-demethylation by CYP 2C9 and CYP 2D6 Conclusions:As only polymorphically expressed enzymes were involved pharmacogenomic variations might occur but clinical data are needed to confirm the relevance. The detectability studies showed that the authors’ SUSAs were suitable for monitoring the intake of both drugs using the identified metabolites

Analysis of the Cross-Linking Reaction of Lignin with Triethyl Phosphate by MALDI-TOF and 13C NMR.

The reaction of condensation and cross-linking of desulfurized kraft lignin with triethyl phosphate (TEP) was explored. Catechol, a simple model of the aromatic ring of lignin, and glycerol, a model compound of the aliphatic hydroyl groups of the side chain of lignin, were employed under similar reaction conditions. Solid state cross-polarisation/magic-angle spinning (CP-MAS) 13C NMR and matrix assisted laser desorption ionization time-of-flight (MALDI-TOF) spectroscopy studies showed that polycondensation occurs on phenolic hydroxyl groups of lignin, as well as on aliphatic hydroxyls groups of its side chain. The reactions appear to be favoured by higher temperatures and in the presence of ammonia. Preliminary adhesion tests on wood shown good hydrophobicity properties of the surface treated with lignin-TEP-based resin. Initial application tests carried out at high temperature demonstrated as good performance as metallic coating.