Post-irradiation thermal degradation of PA6 and PA6,6

PA 6 and PA6,6 sheets irradiated with electron beam were investigated in relation to their thermal stability in various environments (air, distilled water and NaCl 5% solution) at 70 °C. The preexposure doses were 100, 200, 400 and 600 kGy at a dose rate of 22.4 kGy/s. The FTIR spectra allowed the evaluation of the progress of sample oxidation by elucidating the contributions of each environment to the ageing of polyamides. The increases in the absorbance at 1652 cm^?1 placed the surrounding aggressive attack in the following sequence: air<water<NaCl solution. A scheme of degradation mechanism is proposed for the explanation on the involvement of amidic units.     

Determinations of geniposide using LC/MS/MS methods via forming ammonium and acetate adducts

In this paper, we report method development work to determine geniposide using LC/MS/MS via the formation of positive and negative ion adducts. Geniposide, which has been recognized to have choleretic effects, is the major iridoid glycoside component of Gardenia herbs. To enhance the sensitivity of LC/MS detection of geniposide, a small amount of volatile additives such as ammonium acetate and acetic acid are added into mobile phase solvents to form positive and negative adducts, which can then ionize via electrospray processes. The formation of positive adducts is due to the complexation between geniposide and ammonium ions ([M + NH₄]⁺). The formation of anionic adducts [M + CH₃COO]⁻ is believed to occur via hydrogen bonds bridging acetate ions and glucose groups on the geniposide molecule. Mobile phase solvents containing acetonitrile and aqueous solution (0.2 mM ammonium acetate or 0.1% acetic acid) at the ratio 15: 85 are employed to elute geniposide using C8 reverse phase liquid chromatography columns with electrospray tandem mass spectrometry determinations. Using geniposide standards, the methods are validated at the concentration ranges of 5 to 1000 ng/mL and 20 to 5000 ng/mL using ammonium and acetate adducts respectively. The correlation coefficients of the standard curves are 0.9999 using both ammonium and acetate adducts. The detection limits of using ammonium and acetate adducts are 1 and 5 ng/mL respectively. The measurement accuracy and precision of using ammonium adducts are within 12% and 3% respectively, whereas the accuracy and precision are within 6 and 11% respectively using acetate adducts. When the validated calibration curves of the ammonium adduct of geniposide are used to determine spiked control samples in rat blood dialysates, the determination errors of accuracy and precision are within 12% and 10% respectively.     

Investigation of the pyrolysis behaviour of brown algae before and after pre-treatment using PY-GC/MS and TGA

The pyrolysis behaviour of a number of brown macroalgae (seaweeds) collected in the UK such as Laminaria hyperborea and Fucus vesticulosus, are compared with the tropical algae Macrocystis pyrifera. Macroalgae contain a significant amount of alkali earth metals, halogens and a range of trace heavy metals. Pre-treatment of the algae has been performed to remove mineral matter in both water and weak acid. The pyrolysis behaviour of the residues has been investigated and the effect of processing on ash content and mineral composition has been determined. The pyrolysis behaviour of the raw samples and the residues from processing has been studied using thermal gravimetric analysis (TGA) and pyrolysis-GC/MS (Py-GC/MS). Total mineral matter has been determined using inductively coupled plasma-optical emission spectroscopy (ICP-OES) before and after pre-treatment. The Py-GC/MS pyrograms at 500 °C indicate the presence of a range of ketones, pentosans, nitrogen containing compounds and phenols. The residues from pre-treatment have different pyrolysis behaviours, particularly after acid treatment. The pre-treatment schemes investigated can remove a significant proportion of the mineral matter and halogens although they also selectively extract polymeric material. The residues have lower ash content and lower nitrogen content. Results for pre-treatment in water are consistent with the removal of mannitol, while results for pre-treatment in acid are consistent with the removal of fucoidan, mannitol and the partial removal of laminarin. Py-GC/MS of the residue from pre-treatment in acid produces a similar pyrogram to alginic acid in which furfural is a dominant product. There appears to be potential for the production of fuels and chemicals from brown algae by pyrolysis although the reduction of mineral matter and halogens by pre-treatment is advantageous.     

Development and validation of a sensitive assay for the quantification of imatinib using LC/LC‐MS/MS in human whole blood and cell culture

We developed and validated a semi‐automated LC/LC‐MS/MS assay for the quantification of imatinib in human whole blood and leukemia cells. After protein precipitation, samples were injected into the HPLC system and trapped onto the enrichment column (flow 5 mL/min); extracts were back‐flushed onto the analytical column. Ion transitions [M + H]⁺ of imatinib (m/z = 494.3 → 394.3) and its internal standard trazodone (372.5 → 176.3) were monitored. The range of reliable response was 0.03–75 ng/mL. The inter‐day precisions were: 8.4% (0.03 ng/mL), 7.2% (0.1 ng/mL), 6.5% (1 ng/mL), 8.2% (10 ng/mL) and 4.3% (75 ng/mL) with no interference from ion suppression. Autosampler stability was 24 hs and samples were stable over three freeze–thaw cycles. This semi‐automated method is simple with only one manual step, uses a commercially available internal standard, and has proven to be robust in larger studies. Copyright © 2009 John Wiley & Sons, Ltd.     

Discrimination of Thermoplastic Polyesters by MALDI-TOF MS and Py-GC/MS

The aim of this work is to discriminate thermoplastic polyester-polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polytrimethylene terephthalate (PTT), which cannot be easily identified by many methods. Both matrix-assisted laser desorption/ionization-time of flight mass spectrometry (MALDI-TOF MS) and pyrolysis gas chromatography/mass spectrometry (Py-GC/MS) were applied to identify these polyesters owing to their analytical ability to determining polymers' chemical structure. The three thermoplastic polyesters can be easily distinguished by MALDI-TOF MS according to their different repeated units. Py-GC/MS was used to analyze their specific pyrolyzates. The three polyesters can be identified through their characteristic pyrolysis products as well.     

Evaluation of the engineering performance of different bio-based aliphatic homopolyamide tubes prepared by profile extrusion

In the present study, three different commercial bio-based polyamides (bio-PAs), namely polyamide 610 (PA610), polyamide 1010 (PA1010), and polyamide 1012 (PA1012), were processed by profile extrusion with an annular die. These aliphatic homopolyamides, also known as “green nylons”, are industrially produced by polycondensation reaction of diamines and dicarboxylic acids that are partially or fully obtained from naturally occurring castor oil. The profile-extruded bio-PA tubes were characterized and compared in terms of their thermal, thermomechanical, and mechanical properties and also water uptake. Resultant comparative evaluation indicated that both the methylene-to-amide (CH₂/CONH) ratio and the crystallinity degree of the bio-PAs played the main role in determining the performance of the tubes. Due to significant differences in their CH₂/CONH ratio, the PA610 tubes showed the highest thermal properties while the tubes made of PA1012 presented the highest flexibility and lowest water uptake. Interestingly, the fully bio-based PA1010 tubes offered the most balanced and enhanced engineering performance, which was ascribed to the high crystallinity achieved during profile extrusion. The here-developed bio-PA tubes can fulfil demanding technical requirements and these also certainly represent a sustainable answer to the rising demand for new high-performance biopolymers for engineering applications.     

Second hydrogen atom abstraction by molecular ions

We report the observation of a new physical phenomenon of the addition of 2 hydrogen atoms to molecular ions thus forming [M + 2H]⁺ ions. We demonstrate such second hydrogen atom abstraction onto the molecular ions of pentaerythritol and trinitrotoluene (TNT). We used both gas chromatography mass spectrometry (GC‐MS) with supersonic molecular beam (SMB) with methanol added into its make‐up gas and electron ionization (EI) liquid chromatography mass spectrometry (LC‐MS) with SMB with methanol as the LC solvent. We found that the formation of methanol clusters resulted upon EI in the formation of dominant protonated pentaerythritol ion at m/z = 137 plus about 70% relative abundance of pentaerythritol molecular ion with 2 additional hydrogen atoms at m/z = 138 which is well above the 5.7% natural C¹³ isotope abundance of protonated pentaerythritol. Similarly, we found an abundant protonated TNT ion at m/z = 228 and a similar abundance of TNT molecular ion with 2 additional hydrogen atoms at m/z = 229. Upon the use of deuterated methanol (CD₃OD) as the solvent, we observed an abundant m/z = 231 (M + 2D)⁺ of TNT with 2 deuterium atoms. We found such abundant second hydrogen atom abstraction with butylglycolate and at low abundances in dioctylphthalate, Vitamin K3, phenazine, and RDX. At this time, we are unable to report the magnitude and frequency of occurrence of this phenomenon in standard electrospray LC‐MS. This observation could have important implications on the provision of elemental formula from mass spectra that are involved with protonated molecules. Accordingly, while accurate mass measurements can serve for the generation of elemental formula, their further support and improvement via isotope abundance analysis are questionable. Consequently, if a given compound can be analyzed by both GC‐MS and LC‐MS, its GC‐MS analysis can be superior for the provision of accurate elemental formulae if its EI mass spectrum exhibits abundant molecular ions such as with GC‐MS with SMB (also known as cold EI).     

Synthesis of transition metal complexes containing a Schiff base ligand derived from 1,10-phenanthroline-2,9-dicarboxaldehyde and 2-aminobenzenethiol

The synthesis of a new Schiff base containing 1,10-phenanthroline-2,9-dicarboxaldehyde and 2-aminobenzenethiol subunits is described. The reaction of 1,10-phenanthroline-2,9-dicarboxaldehyde with 2-aminobenzenethiol leads to the isolation of 2,9-bis(2-benzothiazolinyl)-1,10-phenanthroline (I) which undergoes rearrangement when reacted with cobalt, nickel, copper or zinc ions to produce complexes of the tautomeric Schiff base 2,9-bis[2-(2-mercaptophenyl)-2-azaethene]-1,10-phenanthroline (L). The [Cu(L)ClO₄][ClO₄] and [M(L)X₂] complexes (where M = Co(II), Ni(II) and Zn(II) and X = Br) were characterized by physical and spectroscopic measurements which indicated that the ligand is acting probably as a tetradentate N₄ chelating agent.     

Novel heteroligand complexes of Co(II), Cu(II), Ni(II) and Mn(II) formed by 2,2′-dipyridyl or 1,10-phenanthroline and phosphortriamide ligands: Synthesis and structure

This paper presents examples of mixed-ligand Co(II), Cu(II), Ni(II) and Mn(II) complexes, with a distorted octahedral coordination geometry, with 2,2′-dipyridyl or 1,10-phenanthroline and phosphortriamide ligands. The complexes of the general type ML₂·Lig (where M = Co(II), Cu(II), Ni(II), Mn(II); L⁻ = {Cl₃C(O)NP(O)R₂}⁻ (R = NHBz, NHCH₂CHCH₂, NEt₂); Lig = 2,2′-dipyridyl or 1,10-phenanthroline) were synthesised and characterised by means of X-ray diffraction, IR and UV–Vis spectroscopy. The phosphortriamide ligands are coordinated via oxygen atoms of phosphoryl and carbonyl groups involved in six-membered metal cycles. The additional ligands 2,2′-dipyridyl or 1,10-phenanthroline are coordinated to the central atom, forming five-membered cycles.     

New matrix of MALDI-TOF MS for analysis of small molecules

New matrix, metal-phthalocyanine (MPc), of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) was used for analysis of small molecules (usually <500 Da). By using MPcs as matrices, small molecular samples were moved to high mass-to-charge region where there was no interference caused by the traditional matrices. The mass of the target analyte was obtained by simple calculation.     

Spectroscopic investigation on europium complexation with humic acid and its model compounds

Time resolved fluorescence spectroscopy (TRFS) of Eu(III) (an analogue of trivalent actinides) complexation with humic acid (HA) and its model compounds, namely phthalic acid (PA), mandelic acid (MA) and succinic acid (SA) has been carried out at varying concentration ratios of ligand to metal ion. The emission spectra were recorded in the range of 550–650 nm by exciting at an appropriate wavelength. The intensity of the 616 nm peak of Eu(III) was found to be sensitive to complexation. The ratio of the intensities of 616 and 592 nm peaks was used to determine the stability constants of Eu-phthalate, Eu-mandelate and Eu-succinate complexes. In the case of model compounds, the life-time was found to increase with increasing ligand to metal ratio (L/M) indicating the decrease in quenching of the fluorescence by coordinated water molecules with increasing complexation. On the other hand in the case of HA, the life-time was found to be constant at least up to L/M of 5, indicating the formation of outer sphere complex. Beyond L/M = 5 the life-time value was found to increase which can be attributed to the binding of the metal ion to the higher affinity sites in the HA macromolecule.     

Application of matrix-assisted laser desorption and ionization time-of-flight mass spectrometry for the characterization of the substrate specificity of neutrophil phospholipase A2

Matrix-assisted laser desorption and ionization time-of-flight mass spectrometry (MALDI-TOF MS) was successfully applied for the analysis of various lipid classes. It can also be used for monitoring the digestion of phosphatidylcholine (PC) with phospholipase A₂ (PLA₂) and it was shown that MALDI-TOF MS possesses a number of advantages over well established methods for this purpose. In this work, we use MALDI-TOF MS for determination of the substrate specificity of neutrophil PLA₂. For the comparison of the selectivity of the enzyme to various phospholipid (PL) classes, the intensities of the signals arising from the product of the reaction (Sp) and the signal intensity of the residual substrate (Ss) were compared and the resulting Sp/Ss ratio was used as the measure. This approach was first tested with a model system pancreatic PLA₂ and afterwards two sources of the neutrophil PLA₂—the enzyme extracted from the neutrophils and the enzyme released from these cells—were tested for their substrate specificity. We will show that the neutrophil-secreted PLA₂ possesses high preferences for digestion of phosphatidic acid (PA) over other phospholipids. The method applied here is simple and much information can be obtained from a single mass spectrum. Moreover, this approach works well also with a crude biological systems, i.e. no prior purification of the enzyme is required for means of characterisation.     

利用MALDI-TOF MS鉴定芽苗菜中解鸟氨酸拉乌尔菌和肺炎克雷伯菌的研究

应用基质解析电离飞行时间质谱(MALDI-TOF MS)方法对芽苗菜中检出率较高的2种微生物进行鉴定,结果为解鸟氨酸拉乌尔菌(33.3%)和肺炎克雷伯菌(43.5%)。应用SARAMIS Premium软件对这2种微生物的蛋白质图谱进行分析,获得解鸟氨酸拉乌尔菌特征标识峰16组,肺炎克雷伯菌特征标识峰10组;对分离微生物进行全标识峰和加权特征峰相关性分析,结果表明特征峰的加权会影响微生物鉴定结果间的相关关系,增强微生物的辨识度;对两种微生物进行多方面比较,发现两种微生物生化特性比较接近,但16Sr DNA分辨率较高,质谱相关分析虽有相交但可辨识。实验结果表明MALDI-TOF MS具有检测芽苗菜中微生物的能力并在其特征分析及溯源研究上具有一定的优势,MALDI-TOF MS为开放平台,对农产品微生物蛋白质特征图谱的收集与优化可提高其鉴定准确性。     

Liquid-liquid extraction coupled with LC/MS/MS for monitoring of malonyl-CoA in rat brain tissue

The formation of malonyl-CoA is catalyzed by acetyl-CoA carboxylase (ACC), the rate-limiting enzyme of de novo fatty acid synthesis. Monitoring the changes of malonyl-CoA concentration in the brain in response to treatments such as pharmaceutical intervention (via ACC inhibitors) or different dietary conditions (such as varied feeding regimes) is of great interest and could help increase the understanding of how this molecule contributes to feeding behavior and overall energy balance. We have developed a sensitive analytical method for the determination of malonyl-CoA levels in rat brain tissue. The assay involved removal of tissue lipids by liquid-liquid extraction followed by LC/MS/MS analysis of the aqueous layer for malonyl-CoA. The method was sensitive enough (limit of quantitation = 50 ng/mL, or approximately 0.018 nmol/g brain tissue) to determine malonyl-CoA in individual rat brain preparations. The assay performance was sufficiently rugged to support drug discovery screening efforts and provided an additional analytical tool for monitoring brain malonyl-CoA levels.     

Synthesis,crystal structures,magnetic and luminescent properties of nickel(II) and cadmium(II) coordination polymers bearing 5-(2′-carboxylphenyl) nicotate ligands

Two coordination polymers, namely [M(cpna)(phen)(H₂O)] _n (M = Ni, 1; Cd, 2, H₂cpna = 5-(2′-carboxylphenyl) nicotic acid, phen = 1,10-phenanthroline), have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction, magnetic and luminescence measurements. Single-crystal X-ray diffraction studies show that the two complexes are isostructural polymers. They have 1D step-like chain structures, which are further extended into 3D metal–organic supramolecular frameworks by π–π stacking interactions. Magnetic studies for complex 1 show antiferromagnetic coupling between the adjacent Ni(II) centers, with g = 2.10 and J = −4.30 cm⁻¹. Complex 2 displays strong green fluorescent emission at room temperature.     

MALDI-TOF MS analysis of native and permethylated or benzimidazole-derivatized polysaccharides

MALDI-TOF MS provides rapid and sensitive analyses of larger biomolecules. However, MS analyses of polysaccharide have been reported to have lower sensitivity compared to peptides and proteins. Here, we investigated some polysaccharides chemically derivatized by permethylation and ortho-phenylene diamine (OPD) tagging. Methylated glycan is obviously able to improve the sensitivity for mass spectrometry detection. Oxidative condensation by UV-activation tagging to saccharides by OPD and peptide-OPD also improve the sensitivity of MALDI-TOF MS analyses. Polysaccharides including dextran, glucomannan, arabinoxylan, arabinogalactan and beta-1,3-glucan, isolated from nutritional supplements of Ganoderma lucidum and Saccharomyces pastorianus were measured using MALDI-TOF MS with 2,5-dihydroxybenzoic acid (2,5-DHB) as the matrix. These glycans were also derivatized to methylated and benzimidazole-tagged glycans by chemical transformation for molecular weight analysis. The derivatized polysaccharides showed excellent MALDI-TOF MS signal enhancement in the molecular weight range from 1 to 5 kDa. Here, we demonstrate an efficient method to give glycan-benzimidazole (glycan-BIM) derivatives for polysaccharide determination in MALDI-TOF MS. Therefore, permethylated or benzimidazole-derivatized polysaccharides provide a new option for polysaccharide analysis using MALDI-TOF MS.     

Derivatization of chiral carboxylic acids with (S)‐anabasine for increasing detectability and enantiomeric separation in LC/ESI‐MS/MS

A simple and practical derivatization procedure for increasing the detectability and enantiomeric separation of chiral carboxylic acids in LC/ESI‐MS/MS has been developed. (S)‐Anabasine (ANA) was used as the derivatization reagent and rapidly reacted with carboxylic acids [3‐hydroxypalmitic acid (3‐OH‐PA), 2‐(β‐carboxyethyl)‐6‐hydroxy‐2,7,8‐trimethylchroman (γ‐CEHC), and etodolac] in the presence of 4‐(4,6‐dimethoxy‐1,3,5‐triazin‐2‐yl)‐4‐methylmorpholium chloride. The resulting ANA‐derivatives were highly responsive in ESI‐MS operating in the positive‐ion mode and gave characteristic product ions during MS/MS, which enabled sensitive detection using selected reaction monitoring; the detection responses of the ANA‐derivatives were increased by 20–160‐fold over those of the intact carboxylic acids and the limits of detection were in the low femtomole range (1.8–11 fmol on the column). The ANA‐derivatization was also effective for the enatiomeric separation of the chiral carboxylic acids; the resolution was 1.92, 1.75, and 2.03 for 3‐OH‐PA, γ‐CHEC, and etodolac, respectively. The derivatization procedure was successfully applied to a biological sample analysis; the derivatization followed by LC/ESI‐MS/MS enabled the separation and detection of trace amounts of 3‐OH‐PA in neonatal dried blood spot and γ‐CEHC in human saliva with a simple pretreatment and small sample volume.     

Thermal properties of PA 6 and PA 6 modified with copolyamides and layered silicates

This article focuses on the thermal properties of PA 6 and additives, i.e. ternary copolyamides, concentrates consisting of binary or ternary copolyamides + nanoadditive montmorillonite Bentonite 11958 or Cloisite 15A and PA 6 fibres modified with Bentonite, copolyamide and concentrate. The copolyamides are prepared from ε-caprolactam as a major comonomer and nylon salts AN2 from adipic acid + 1-(2-aminoethyl)piperazine and ADETA from adipic acid + diethylenetriamine. All copolyamides and concentrates exhibit lower melting temperatures T _m and lower melting enthalpies ΔH _m compared to neat PA 6. PA 6 fibres modified with 0.25–2.5 wt% MMT exhibit higher melting enthalpies in comparison with unmodified PA 6 fibres. PA 6 fibres modified with 10 wt% of ternary copolyamide containing 21.4 wt% of comonomers AN2 and ADETA have higher melting enthalpy as well. PA 6 fibres modified with 10 and 20 wt% of concentrate containing the same ternary copolyamide + 5 wt% of MMT have higher melting enthalpies and higher tensile strength in comparison with these characteristics of unmodified PA 6 fibres.     

GC/MS and LC-MS/MS phytochemical evaluation of the essential oil and selected secondary metabolites of Ajuga orientalis from Jordan and its antioxidant activity

The current investigation aimed to shed light in the volatile and non-volatile secondary metabolites of Ajuga orientalis L. from Jordan. GC/MS and GC/FID analysis of the hydrodistilled essential oil obtained from aerial parts of the plant revealed tiglic acid (18.90 %) as main constituent. Each of the methanol and butanol fractions of A. orientalis were screened for their total phenol content (TPC), total flavonoid content (TFC), and antioxidant activity determined by DDPH and ABTS methods. The extracts were then analyzed by LC-ESI-MS/MS to unveil their chemical constituents, especially phenols and flavonoids. Results showed that the AO-B extract had the highest TPC (217.63 ± 2.65 mg gallic acid/g dry extract), TFC (944.41 ± 4.77 mg quercetin /g dry extract), highest DPPH and ABTS antioxidant activity ((4.00 ± 0.20) × 10^-2; (3.00 ± 0.20) × 10^-2 mg/mL, respectively) as compared to the AO-M extract. LC-ESI-MS/MS analysis of both extracts revealed the presence of several phenolics, flavonoids and nonphenolic acids.     

Effect of Ca,Mg-ions on the properties of LiCo0.9M0.1PO4/graphitic carbon composites

LiCo_0.9M_0.1PO₄ (M = Co²⁺, Mg²⁺, Ca²⁺)/graphitic carbon composites are synthesized by Pechini-assisted sol–gel process and annealed by the 2-steps annealing process (300 °C for 5 min in air, then at 730 °C for 12 h in nitrogen). The structural investigation, performed on powders, reveals the presence of LiCoPO₄ as the major crystalline phase and of CoP₂O₇ (M = Co), of Co₂P (M = Mg), of Co₂P, Li₃PO₄, (Ca,Co)₃(PO₄)₂ (M = Ca) as impurities. The morphological investigation of the composites shows the formation of crystalline “islands-like” structures with acicular crystallites with different dimensions (typically 5–50 μm) on the top of them. The voltammetric analysis shows a very good reversibility of the (de)intercalation processes and the presence of two mean peak maxima in the cathodic region at ∼5.01 V and ∼5.05 V respectively. The discharge specific capacities, at a discharge rate of C/10 and room temperature, were 100 mAh g⁻¹ for M = Co, 68 mAh g⁻¹ for M = Mg and 104 mAh g⁻¹ for M = Ca respectively. The electrochemical impedance spectroscopy data reveal a decrease of the electrical resistance and the improvement of the Li-ion conductivity in the Ca and Mg ions containing composites.