Comprehensive profiling and quantitation of amine group containing metabolites

Primary and secondary amines, including amino acids, biogenic amines, hormones, neurotransmitters, and plant siderophores, are readily derivatized with 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate using easily performed experimental methodology. Complex mixtures of these amine derivatives can be fractionated and quantified using liquid chromatography–electrospray ionization-mass spectrometry (LC–ESI-MS). Upon collision induced dissociation (CID) in a quadrupole collision cell, all derivatized compounds lose the aminoquinoline tag. With the use of untargeted fragmentation scan functions, such as precursor ion scanning, the loss of the aminoquinoline tag (Amq) can be monitored to identify derivatized species; and the use of targeted fragmentation scans, such as multiple reaction monitoring, can be exploited to quantitate amine-containing molecules. Further, with the use of accurate mass, charge state, and retention time, identification of unknown amines is facilitated. The stability of derivatized amines was found to be variable with oxidatively labile derivatives rapidly degrading. With the inclusion of antioxidant and reducing agents, tris(2-carboxyethyl)-phosphine (TCEP) and ascorbic acid, into both extraction solvents and reaction buffers, degradation was significantly decreased, allowing reproducible identification and quantification of amine compounds in large sample sets.

Probing the effect of charge transfer enhancement in off resonance mode SERS via conjugation of the probe dye between silver nanoparticles and metal substrates

The charge transfer-mediated surface enhanced Raman scattering (SERS) of crystal violet (CV) molecules that were chemically conjugated between partially polarized silver nanoparticles and optically smooth gold and silver substrates has been studied under off-resonant conditions. Tyrosine molecules were used as a reducing agent to convert silver ions into silver nanoparticles where oxidised tyrosine caps the silver nanoparticle surface with its semiquinone group. This binding through the quinone group facilitates charge transfer and results in partially oxidised silver. This establishes a chemical link between the silver nanoparticles and the CV molecules, where the positively charged central carbon of CV molecules can bind to the terminal carboxylate anion of the oxidised tyrosine molecules. After drop casting Ag nanoparticles bound with CV molecules it was found that the free terminal amine groups tend to bind with the underlying substrates. Significantly, only those CV molecules that were chemically conjugated between the partially polarised silver nanoparticles and the underlying gold or silver substrates were found to show SERS under off-resonant conditions. The importance of partial charge transfer at the nanoparticle/capping agent interface and the resultant conjugation of CV molecules to off resonant SERS effects was confirmed by using gold nanoparticles prepared in a similar manner. In this case the capping agent binds to the nanoparticle through the amine group which does not facilitate charge transfer from the gold nanoparticle and under these conditions SERS enhancement in the sandwich configuration was not observed.

The three-dimensional hydrogen-bonded structures in the ammonium and sodium salt hydrates of 4-aminophenylarsonic acid

The structures of two hydrated salts of 4-aminophenylarsonic acid (p-arsanilic acid), namely ammonium 4-aminophenylarsonate monohydrate, NH4(+)·C6H7AsNO3(-)·H2O, (I), and the one-dimensional coordination polymer catena-poly[[(4-aminophenylarsonato-κO)diaquasodium]-μ-aqua], [Na(C6H7AsNO3)(H2O)3]n, (II), have been determined. In the structure of the ammonium salt, (I), the ammonium cations, arsonate anions and water molecules interact through inter-species N-H...O and arsonate and water O-H...O hydrogen bonds, giving the common two-dimensional layers lying parallel to (010). These layers are extended into three dimensions through bridging hydrogen-bonding interactions involving the para-amine group acting both as a donor and an acceptor. In the structure of the sodium salt, (II), the Na(+) cation is coordinated by five O-atom donors, one from a single monodentate arsonate ligand, two from monodentate water molecules and two from bridging water molecules, giving a very distorted square-pyramidal coordination environment. The water bridges generate one-dimensional chains extending along c and extensive interchain O-H...O and N-H...O hydrogen-bonding interactions link these chains, giving an overall three-dimensional structure. The two structures reported here are the first reported examples of salts of p-arsanilic acid.

Two- and three-dimensional lead-1H-imidazole-4,5-dicarboxylates

Reaction of lead nitrate and 1H-imidazole-4,5-dicarboxylic acid under hydrothermal conditions carried out at different temperatures and pH yields a hybrid Compound Pb-2(1H-imidazole-4,5-dicarboxylate)2, 1, and a three-dimensional coordination polymer Pb(1H-imidazole-4,5-dicarboxylate), It. The two-dimensional double-layered compound, 1, with two-dimensional inorganic connectivities and one-dimensional organic connectivity is novel since hybrid compounds formed by 1H-imidazole-4,5-dicarboxylic acid are uncommon. The lead atoms in I have holodirectional geometry, while those in II show hemidirectionality. In both I and II, 1H-imidazole-4,5-dicarboxylic acid acts as a multi-dentate ligand with both the carboxylic groups and the amine group taking part in coordination. (C) 2009 Elsevier B.V. All rights reserved.

Tribology of soot suspension in hexadecane as distinguished by the physical structure and chemistry of soot particles

Ethylene gas is burnt to generate soot which is collected thermophoretically from different locations of the flame. Tribological performance of the collected soot in hexadecane suspension is compared with that of carbon black and diesel soot. The soots are analysed to yield a range of mechanical properties, physical structures and chemistry. The paper correlates these property variations with the corresponding variations in friction and wear when the soot suspended in hexadecane is used to lubricate a steel on steel sliding interaction. The particles are dispersed in hexadecane by a non-ionic surfactant, poly-isobutylene succinimide (PIBS), which is mono-functional with no free amine group. The grafting of the surfactant on the soot particles is found to have a profound effect on the dispersion of the soot, in general, while, between the different soot types, the tribology is differentiated by the physical structure and chemistry.

Grafting of Dispersants on MoS2 Nanoparticles in Base Oil Lubrication of Steel

Solid lubricant nanoparticles in suspension in oil are good lubricating options for practical machinery. In this article, we select a range of dispersants, based on their polar moieties, to suspend 50-nm molybdenum disulfide particles in an industrial base oil. The suspension is used to lubricate a steel on steel sliding contact. A nitrogen-based polymeric dispersant (aminopropyl trimethoxy silane) with a free amine group and an oxygen-based polymeric dispersant (sorbital monooleate) when grafted on the particle charge the particle negatively and yield an agglomerate size which is almost the same as that of the original particle. Lubrication of the contact by these suspensions gives a coefficient of friction in the similar to 0.03 range. The grafting of these surfactants on the particle is shown here to be of a chemical nature and strong as the grafts survive mechanical shear stress in tribology. Such grafts are superior to those of other silane-based test surfactants which have weak functional groups. In the latter case, the particles bereft of strong grafts agglomerate easily in the lubricant and give a coefficient of friction in the 0.08-0.12 range. This article investigates the mechanism of frictional energy dissipation as influenced by the chemistry of the surfactant molecule.

Determination of isocyanates by capillary electrophoresis with tris(2,2 '-bipyridine) ruthenium(II) electrochemiluminescence

CE with tris(2,2'-bipyridyl) ruthenium(II) (Ru(bpy)(3)(2+)) electrochemiluminescence (ECL) detection for the quantitative determination of isocyanates was first reported. Hexamethylene diisocyanate (HDI) and hexyl isocyanate (HI) were used as the model analytes. Commercially available N,N-diethyl-N'-methylethylenediamine was used as the derivatization reagent. It has both a secondary amine group and a tertiary amine group. The secondary amine group can quantitatively react with isocyanate group, and the tertiary amine group can react with Ru(bpy)(3)(2+) to produce strong ECL signal for sensitive detection. The derivatization reaction was almost instantaneous and is much faster than other reported derivative reactions using other derivative reagents.

Bonding quartz wafers by the atom transfer radical polymerization of the glycidyl methacrylate at mild temperature

In this paper, we presented a novel covalent bonding process between two quartz wafers at 300 degrees C. High-quality wafer bonding was formed by the hydroxylization, aminosilylation and atom transfer radical polymerization (ATRP) of glycidyl methacrylate (GMA), respectively, on quartz wafer surfaces, followed by close contact of the GMA functional wafer and the aminosilylation wafer, the epoxy group opening ring reaction was catalyzed by the amino and solidified to form the covalent bonding of the quartz wafers. The shear force between two wafers in all bonding samples was higher than 1.5 MPa. Microfluidic chips bonded by the above procedures had high transparency and the present procedure avoided the adhesive to block or flow into the channel.

Synthesis, crystal structure, spectroscopy and electroluminescence of zinc(II) complexes containing bidentate 2-(2-pyridyl)quinoline derivative ligands

Three bidentate ligands, 4-phenyl-2-(2-pyridyl)-quinoline (ppq), 6-(carbazol-9-yl)-4-phenyl-2-(2-pyridyl)-quinoline (cpq) and 6-diphenylamino-4-phenyl-2-(2-pyridyl)-quinoline (dpq) and their zinc(II) complexes, have been designed and synthesized. The crystal structure of [Zn(ppq)(2)Cl]PF6 shows that the central zinc atom is coordinated with one chloride and four nitrogen atoms from two ligands. The introduction of an electron-donating substituent such as carbazole or an aromatic amine group at the 6-position of the quinoline moiety can generate colored tunable Zn complexes, and the photoluminescence (PL) wavelength was modulated from 418 nm for [Zn(ppq)(2)Cl]PF6 to 591 nm for [Zn(cpq)(2)Cl]PF6 and 638 nm for [Zn(dpq)(2)Cl]PF6 in CH2Cl2 solution. The electroluminescence spectrum of [Zn(dpq)(2)Cl]PF6 exhibits pure red light emission with the Commission Internationale de L'Eclairage (CIE) coordinates (0.63, 0.36) and a maximum at 648 nm.

The electrochemical oxidation of catechol and dopamine on platinum in 1-Ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C(2)mim][NTf2]) and 1-Butyl-3-methylimidazolium tetrafluoroborate ([C(4)mim][BF4]): Adsorption effects in ionic liquid voltammetry

The electrochemical oxidation of catechol and dopamine has been studied at a platinum micro-electrode (10 pm diameter) in two room temperature ionic liquids (RTILs): 1-Ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C(2)mim][NTf2]) and 1-Butyl-3-methylimidazolium tetrafluoroborate ([C(4)mim][BE4]). For catechol in [C(2)mim][NTf2], an electrochemically quasi-reversible oxidation peak was observed at 1.1 V vs. Pt with a back peak at 0.4 V vs. Pt. This is assigned to the two-electron oxidation of catechol to doubly protonated o-benzoquinone. Double-step chronoamperometry gave a diffusion coefficient for the catechol and the oxidised species which is 3.8 x 10(-11) m(2) s(-1) for both. For catechol in [C(4)mim][BF4], a two-electron oxidation wave was observed at 1.0 V vs. Pt with no back peak. Another peak at less positive potential was also observed at 0.6 V vs. Pt in [C(4)mim][BF4] but not in [C(2)mim][NTf2] which is assigned to the adsorption of electrochemically formed neutral o-benzoquinone on the platinum electrode. The oxidised protonated o-benzoquinone is suggested to be deprotonated by the [BF4](-) anion, but not by the [NTf2](-) anion: hence adsorption of the neutral species at the platinum electrode, not the charged species. For dopamine in both RTILs, two chemically irreversible oxidation peaks were observed at 0.75 V and 1.1 V vs. Pt, and assigned to the oxidation of dopamine to the corresponding semi-quinone and the quinone. Potential-step chronoamperometry was carried out on the oxidation waves of dopamine in [C(2)mim][NTf2] and the diffusion coefficient of species in solution was calculated to be 6.85 x 10(-12) m(2) s(-1) and confirmed that the waves corresponded to one and two electron processes. A third wave was observed at 1.8 V vs. Pt which is attributed to the oxidation of the amine group to a radical cation with likely subsequent follow up chemistry. In [C(4)mim][BF4] a peak at less positive potential was observed for dopamine, similar to catechol which is assigned to the adsorption of the neutral quinone species on the platinum electrode formed by the reaction of the removal of protons from the oxidised dopamine with the [BF4](-) anion. (C) 2009 Elsevier B.V. All rights reserved.

Path-selective photoinduced electron transfer (PET) in a membrane-associated system studied by pH-dependent fluorescence

The pH-dependent fluorescence behavior of two regioisomeric 'receptor(1)-spacer(1)-fluorophore-spacer(2)-receptor(2)' systems 1 and 2 in micellar solutions of sodium dodecyl sulfate show that photoinduced electron transfer (PET) only occurs from the amine group connected to the 4-amino position of the aminonaphthalimide fluorophore in both cases. This demonstrates the directing influence of the photogenerated electric field within the aminonaphthalimide excited state on the electron transfer process. Since path-selectivity of PET is also known within the membrane-bound photosynthetic reaction center in bacteria, its origins may be illuminated by the simple experiments described here. (C) 2011 Elsevier B. V. All rights reserved.

Oxidation and glycoxidation of phosphatidylserine and their effect in immune response : a lipidomic approach

Phosphatidylserine (PS) is a member of the class of phospholipids, and is distributed among all cells of mammalians, playing important roles in diverse biological processes, including blood clotting and apoptosis. When externalized, PS is a ligand that is recognized on apoptotic cells. It has been considered that before externalization PS is oxidized and oxPS enhance the recognition by macrophages receptors, however the knowledge about oxidation of PS is still limited. PS, like others phospholipids, has two fatty acyl chains and one polar head group, in this case is the amino acid serine. The modifications in PS structure can occur by oxidation of the unsaturated fatty acyl chains and by glycation of the polar head group, due to free amine group, thus increasing the susceptibility to oxidative events. The main goal of this work was to characterize and identify oxidized and glycoxidized PS, contributing to the knowledge of the biological role of oxidation products of PS, as well as of glycated PS, in immune and inflammatory processes. To achieve this goal, PS standards (1-palmitoyl-2-oleoyl-sn-glycero-3-phospho- L-serine (POPS), 1,2-dipalmitoyl-sn-glycero-3-phospho-L-serine (DPPS), 1- palmitoyl-2-linoleoyl-sn-glycero-3-phospho-L-serine (PLPS) and 1-palmitoyl-2- arachidonoyl-sn-glycero-3-phospho-L-serine (PAPS)) and glycated PS (PAPS and POPS) were induced to oxidize in model systems, using different oxidant reagents: HO• and 2,2'-azobis-2-methyl-propanimidamide dihydrochloride (AAPH) . The detailed structural characterization of the oxidative products was performed by ESI-MS and MS/MS coupled to separation techniques such as off line TLC-MS and on line LC-MS, in order to obtained better characterization of the larger number of PS and glycated PS oxidation products. The results obtained in this work allowed to identify several oxidation products of PS and glycated PS with modifications in unsaturated fatty acyl chain. Also, oxidation products formed due to structural changes in the serine polar head with formation of terminal acetamide, terminal hydroperoxyacetaldehyde.and terminal acetic acid (glycerophosphacetic acid, GPAA) were identified. The mass spectrometric specific fragmentation pathway of each type of oxidation product was determined using different mass spectrometry approaches. Based on the identified fragmentation pathways, targeted lipidomic analysis was performed to detect oxidation products modified in serine polar head in HaCaT cell line treated with AAPH. The GPAA was detected in HaCaT cells treated with AAPH to induce oxidative stress, thus confirming that modifications in PS polar head is possible to occur in biological systems. Furthermore, it was found that glycated PS species are more prone to oxidative modifications when compared with non glycated PS. During oxidation of glycated PS, besides the oxidation in acyl chains, new oxidation products due to oxidation of the glucose moiety were identified, including PS advanced glycation end products (PSAGES). To investigate if UVA oxidative stress exerted changes in the lipidome of melanoma cell lines, particularly in PS profile, a lipidomic analysis was performed. The lipid profile was obtained using HILIC-LC-MS and GC-MS analysis of the total lipid extracts obtained from human melanoma cell line (SKMEL- 28) after UVA irradiation at 0, 2 and 24 hours. The results did not showed significant differences in PS content. At molecular level, only PS (18:0:18:1) decreased at the moment of irradiation. The most significant changes in phospholipids content occurred in phosphatidylcholines (PC) and phosphatidylinositol (PI) classes, with an increase of mono-unsaturated fatty acid (MUFA), similarly as observed for the fatty acid analysis. Overall, these data indicate that the observed membrane lipid changes associated with lipogenesis after UVA exposure may be correlated with malignant transformations associated with cancer development and progression. Despite of UVA radiation is associated with oxidative damage, in this work was not possible observe oxidation phospholipids. The anti/pro-inflammatory properties of the oxidized PLPS (oxPLPS) versus non-oxidized PLPS were tested on LPS stimulated RAW 264.7 macrophages. The modulation of intracellular signaling pathways such as NF-kB and MAPK cascades by oxPLPS and PS was also examined in this study. The results obtained from evaluation of anti/pro-inflammatory properties showed that neither PLPS or oxPLPS species activated the macrophages. Moreover only oxidized PLS were found to significantly inhibit NO production and iNOS and il1β gene transcription induced by LPS. The analysis at molecular level showed that this was the result of the attenuation of LPS-induced c-Jun-N-terminal kinase (JNK) and p65 NF-kB nuclear translocation. Overall these data suggest that oxPLPS, but not native PLPS, mitigates pro-inflammatory signaling in macrophages, contributing to containment of inflammation during apoptotic cell engulfment. The results obtained in this work provides new information on the modifications of PS, facilitating the identification of oxidized species in complex samples, namely under physiopathologic conditions and also contributes to a better understanding of the role of oxPS and PS in the inflammatory response, in the apoptotic process and other biological functions.

GABA and 5-HT chitosan nanoparticles enhanced liver cell proliferation and neuronal survival in partially hepatectomised rats: GABAB and 5-HT2A receptors functional

Nanoparticulate drug delivery systems provide wide opportunities for solving problems associated with drug stability or disease states and create great expectations in the area of drug delivery (Bosselmann & Williams, 2012). Nanotechnology, in a simple way, explains the technology that deals with one billionth of a meter scale (Ochekpe, et al., 2009). Fewer side effects, poor bioavailability, absorption at intestine, solubility, specific delivery to site of action with good pharmacological efficiency, slow release, degradation of drug and effective therapeutic outcome, are the major challenges faced by most of the drug delivery systems. To a great extent, biopolymer coated drug delivery systems coupled with nanotechnology alleviate the major drawbacks of the common delivery methods. Chitosan, deacetylated chitin, is a copolymer of β-(1, 4) linked glucosamine (deacetylated unit) and N- acetyl glucosamine (acetylated unit) (Radhakumary et al., 2005). Chitosan is biodegradable, non-toxic and bio compatible. Owing to the removal of acetyl moieties that are present in the amine functional groups of chitin, chitosan is readily soluble in aqueous acidic solution. The solubilisation occurs through the protonation of amino groups on the C-2 position of D-glucosamine residues whereby polysaccharide is converted into polycation in acidic media. Chitosan interacts with many active compounds due to the presence of amine group in it. The presence of this active amine group in chitosan was exploited for the interaction with the active molecules in the present study. Nanoparticles of chitosan coupled drugs are utilized for drug delivery in eye, brain, liver, cancer tissues, treatment of spinal cord injury and infections (Sharma et al., 2007; Li, et a., 2009; Paolicelli et al., 2009; Cho et al., 2010). To deliver drugs directly to the intended site of action and to improve pharmacological efficiency by minimizing undesired side effects elsewhere in the body and decrease the long-term use of many drugs, polymeric drug delivery systems can be used (Thatte et al., 2005).

A ferromagnetic methoxido-bridged Mn(III) dimer and a spin-canted metamagnetic μ1,3-azido-bridged chain

Two new Mn(III) complexes of formulas [MnL1(N-3)(OMe)](2) (1) and [MnL2(N-3)(2)](n) (2) have been synthesized by using two tridentate NNO-donor Schiff base ligands HL1{(2-[(3-methylaminoethylimino)-methyl]-phenol)} and HL2 {(2-[1-(2-dimethylaminoethylimino)methyl]-phenol)}, respectively. Substitution of the H atom on the secondary amine group of the N-methyldiamine fragment of the Schiff base by a methyl group leads to a drastic structural change from a methoxido-bridged dimer (1) to a single mu(1,3)-azido-bridged 1D helical polymer (2). Both complexes were characterized by single-crystal X-ray structural analyses and variable-temperature magnetic susceptibility measurements. The magnetic properties of compound I show the presence of weak ferromagnetic exchange interactions mediated by double methoiddo bridges (J = 0.95 cm(-1)). Compound 2 shows the existence of a weak antiferromangetic coupling along the chain (J = -8.5 cm(-1)) through the single mu(1,3)-N-3 bridge with a spin canting that leads to a long-range antiferromagnetic order at T-c approximate to 9.3 K and a canting leading to a weak ferromagnetic long-range order at T-c approximate to 8.5 K. It also exibits metamagnetic behavior at low temperatures with a critical field of ca.1.2 T due to the weak antiferromagnetic interchain interactions that appear in the canted ordered phase.

Azide photochemistry for facile modification of graphitic surfaces : preparation of DNA-coated carbon nanotubes for biosensing

A facile, two-step method for chemically attaching single-stranded DNA to graphitic surfaces, represented here by carbon nanotubes, is reported. In the first step, an azide-containing compound, N-5-azido-nitrobenzoyloxy succinimide (ANB-NOS), is used to form photo-adducts on the graphitic surfaces in a solid-state photochemical reaction, resulting in active ester groups being oriented for the subsequent reactions. In the second step, pre-synthesized DNA strands bearing a terminal amine group are coupled in an aqueous solution with the active esters on the photo-adducts. The versatility of the method is demonstrated by attaching pre-synthesized DNA to surfaces of carbon nanotubes in two platforms—as vertically-aligned multi-walled carbon nanotubes on a solid support and as tangled single-walled carbon nanotubes in mats. The reaction products at various stages were characterized by x-ray photoelectron spectroscopy. Two different assays were used to check that the DNA strands attached to the carbon nanotubes were able to bind their partner strands with complementary base sequences. The first assay, using partner DNA strands tethered to gold nanoparticles, enabled the sites of DNA attachment to the carbon nanotubes to be identified in TEM images. The second assay, using radioactively labelled partner DNA strands, quantified the density of functional DNA strands attached to the carbon nanotubes. The diversity of potential applications for these DNA-modified carbon-nanotube platforms is exemplified here by the successful use of a DNA-modified single-walled carbon-nanotube mat as an electrode for the specific detection of metal ions.