Development of atmospheric pressure ionization ion mobility spectrometry and ion mobility spectrometry mass spectrometry

This study is focused on the development and evaluation of ion mobility instrumentation with various atmospheric pressure ionization techniques and includes the following work. First, a high-resolution drift tube ion mobility spectrometer (IMS), coupled with a commercial triple quadrupole mass spectrometer (MS), was developed. This drift tube IMS is compatible with the front-end of commercial Sciex mass spectrometers (e.g., Sciex API-300, 365, and 3000) and also allows easy (only minor modifications are needed) installation between the original atmospheric pressure ion source and the triple quadrupole mass spectrometer. Performance haracteristics (e.g.,resolving power, detection limit, transmission efficiency of ions) of this IMS-MS instrument were evaluated. Development of the IMS-MS instrument also led to a study where a proposal was made that tetraalkylammonium ions can be used as chemical standards for ESI-IMS. Second, the same drift tube design was also used to build a standalone ion mobility spectrometer equipped with a Faraday plate detector. For this highresolution (resolving power about 100 shown) IMS device, a multi-ion source platform was built, which allows the use of a range of atmospheric pressure ionization methods, such as: corona discharge chemical ionization (CD-APCI), atmospheric pressure photoionization (APPI), and radioactive atmospheric pressure chemical ionization (R-APCI). The multi-ion source platform provides easy switching between ionization methods and both positive and negative ionization modes can be used. Third, a simple desorpion/ionization on silicon (DIOS) ion source set-up for use with the developed IMS and IMS-MS instruments was built and its operation demonstrated. Fourth, a prototype of a commercial aspiration-type ion mobility spectrometer was mounted in front of a commercial triple quadrupole mass spectrometer. The set-up, which is simple, easy to install, and requires no major modifications to the MS, provides the possibility of gathering fundamental information about aspiration mobility spectrometry.

Electron paramagnetic resonance studies on Mn doped GaSb

We report on the X-band (similar to 9.43 GHz) electron paramagnetic resonance (EPR) investigations carried out on polycrystalline Ga1-xMnxSb (x=0.02). A strong EPR signal with an effective g factor (g(eff)) close to 2.00 was observed, suggesting that the ionic state of Mn which replaces Ga ion in the lattice, is Mn2+ attributable to Delta M=1 transition of the ionized Mn acceptor A(-), Mn (3d(5)). The apparent absence of EPR signal, typical for neutral Mn acceptor at g=2.7 suggests either no such centers are present or the signal broadens beyond detection limit. The temperature dependent EPR studies combined with dc magnetization data suggest the possible coexistence of antiferromagnetic and ferromagnetic phases at very low temperatures. (C) 2011 American Institute of Physics. doi:10.1063/1.3543983]

Recognition of Polycyclic Aromatic Hydrocarbons and Their Derivatives by the 1,3-Dinaphthalimide Conjugate of Calix4]arene: Emission, Absorption, Crystal Structures, and Computational Studies

Polycyclic aromatic hydrocarbons (PAHs) are environmental pollutants as well as well-known carcinogens. Therefore, it is important to develop an effective receptor for the detection and quantification of such molecules in solution. In view of this, a 1,3-dinaphthalimide derivative of calix4]arene (L) has been synthesized and characterized, and the structure has been established by single crystal XRD. In the crystal lattice, intermolecular arm-to-arm pi center dot center dot center dot pi overlap dominates and thus L becomes a promising receptor for providing interactions with the aromatic species in solution, which can be monitored by following the changes that occur in its fluorescence and absorption spectra. On the basis of the solution studies carried out with about 17 derivatives of the aromatic guest molecular systems, it may be concluded that the changes that occur in the fluorescence intensity seem to be proportional to the number of aromatic rings present and thus proportional to the extent of pi center dot center dot center dot pi interaction present between the naphthalimide moieties and the aromatic portion of the guest molecule. Though the nonaromatic portion of the guest species affects the fluorescence quenching, the trend is still based on the number of rings present in these. Four guest aldehydes are bound to L with K-ass of 2000-6000 M-1 and their minimum detection limit is in the range of 8-35 mu M. The crystal structure of a naphthaldehyde complex, L.2b, exhibits intermolecular arm-to-arm as well as arm-to-naphthaldehyde pi center dot center dot center dot pi interactions. Molecular dynamics studies of L carried out in the presence of aromatic aldehydes under vacuum as well as in acetonitrile resulted in exhibiting interactions observed in the solid state and hence the changes observed in the fluorescence and absorption spectra are attributable for such interactions. Complex formation has also been delineated through ESI MS studies. Thus L is a promising receptor that can recognize PAHs by providing spectral changes proportional to the aromatic conjugation of the guest and the extent of aromatic pi center dot center dot center dot pi interactions present between L and the guest.

Enhanced sensitivity for the differential pulse polarographic determination of molybdenum(VI) based on adsorption catalytic current

A differential pulse polarographic (DPP) method based on the adsorption catalytic current in a medium containing chlorate and 8-hydroxyquinoline (oxine) is suggested for the determination of molybdenum(VI). Experimental conditions such as pH and the composition of supporting electrolyte have been optimized to get a linear calibration graph at trace levels of Mo(VI). The sensitivity for molybdenum can be considerably enhanced by this method. The influence of possible interferences on the catalytic current has been investigated. The sensitivity of the method is compared with those obtained for other DPP methods for molybdenum. A detection limit of 1.0 x 10(-8) mol/L has been found.

Electrochemical Determination of L-Dopa in Mucuna pruriens Seeds, Leaves and Commercial Siddha Product Using Gold Modified Pencil Graphite Electrode

In the present work a gold modified pencil graphite electrode (GPGE) was used for the determination of L-dopa present in the aqueous extracts of Mucuna pruriens seeds (MPS), Mucuna pruriens leaves (MPL) and Commercial Siddha Product (CSP). The GPGE shows excellent electrocatalytic activity towards the oxidation of both L-dopa and ascorbic acid (AA), with the separation of peak potential of 98 mV. The differential pulse voltammetric (DPV) results indicated that the detection limit for L-dopa was 1.54 mu M (S/N=3). This method can be successfully applied for the determination of L-dopa in real samples.

Fluorescence and visual sensing of nitroaromatic explosives using electron rich discrete fluorophores

Several pi-electron rich fluorescent aromatic compounds containing trimethylsilylethynyl functionality have been synthesized by employing Sonogashira coupling reaction and they were characterized fully by NMR (H-1, C-13)/IR spectroscopy. Incorporation of bulky trimethylsilylethynyl groups on the peripheral of the fluorophores prevents self-quenching of the initial intensity through pi-pi interaction and thereby maintains the spectroscopic stability in solution. These compounds showed fluorescence behavior in chloroform solution and were used as selective fluorescence sensors for the detection of electron deficient nitroaromatics. All these fluorophores showed the largest quenching response with high selectivity for nitroaromatics among the various electron deficient aromatic compounds tested. Quantitative analysis of the fluorescence titration profile of 9,10-bis(trimethylsilylethynyl) anthracene with picric acid provided evidence that this particular fluorophore detects picric acid even at ppb level. A sharp visual detection of 2,4,6-trinitrotoluene was observed upon subjecting 1,3,6,8-tetrakis (trimethylsilylethynyl) pyrene fluorophore to increasing quantities of 2,4,6-trinitrotoluene in chloroform. Furthermore, thin film of the fluorophores was made by spin coating of a solution of 1.0 x 10(-3) M in chloroform or dichloromethane on a quartz plate and was used for the detection of vapors of nitroaromatics at room temperature. The vapor-phase sensing experiments suggested that the sensing process is reproducible and quite selective for nitroaromatic compounds. Selective fluorescence quenching response including a sharp visual color change for nitroaromatics makes these fluorophores as promising fluorescence sensory materials for nitroaromatic compounds (NAC) with a detection limit of even ppb level as judged with picric acid.

Chemically functionalized glassy carbon spheres: a new covalent bulk modified composite electrode for the simultaneous determination of lead and cadmium

A new type of covalent bulk modified glassy carbon composite electrode has been fabricated and utilized in the simultaneous determination of lead and cadmium ions in aqueous medium. The covalent bulk modification was achieved by the chemical reduction of 2-hydroxybenzoic acid diazonium tetrafluroborate in the presence of hypophosphorous acid as a chemical reducing agent. The covalent attachment of the modifier molecule was examined by studying Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and the surface morphology was examined by scanning electron microscopy images. The electrochemistry of modified glassy carbon spheres was studied by its cyclic voltammetry to decipher the complexing ability of the modifier molecules towards Pb2+ and Cd2+ ions. The developed sensor showed a linear response in the concentration range 1-10 mu M with a detection limit of 0.18 and 0.20 mu M for lead and cadmium, respectively. The applicability of the proposed sensor has been checked by measuring the lead and cadmium levels quantitatively from sewage water and battery effluent samples.

An Exfoliated Graphite-Based Bisphenol A Electrochemical Sensor

The use of an exfoliated graphite (EG) electrode in the square wave voltammetric detection of bisphenol A (a model phenolic pollutant) in water, whereby the phenolic electrode fouling challenge is mitigated, is described. The oxidation peak of BPA was observed at about 0.45 V in phosphate buffer solution at pH 10. The current response exhibited a linear relationship with the concentration over a range from 1.56 mu M-50 mu M. The detection limit was calculated to be 0.76 mu M. The EG electrode surface was renewed after each measurement with excellent reproducibility. A real sample application was also investigated.

Electron rich supramolecular polymers as fluorescent sensors for nitroaromatics

Three pi-electron rich fluorescent supramolecular polymers (1-3) have been synthesized incorporating 2-methyl-3-butyn-2-ol groups in reasonable yield by employing Sonagashira coupling. They were characterized by multinuclear NMR (H-1, C-13), ESI-MS and single crystal X-ray diffraction analyses 1 = 1( 2-methyl-3-butyn-2-ol) pyrene; 2 = 9,10-bis(2-methyl-3-butyn-2-ol) anthracene; 3 = 1,3,6,8-tetrakis(2methyl- 3-butyn-2-ol) pyrene]. Single crystal structures of 1-3 indicated that the incorporation of hydroxy (-OH) groups on the peripheral of the fluorophores helps them to self-associate into an infinite supramolecular polymeric network via intermolecular hydrogen bonding interactions between the adjacent discrete fluorophore units. All these compounds showed fluorescence characteristics in chloroform solution due to the extended pi-conjugation and were used as selective fluorescent sensors for the detection of electron deficient nitroaromatics. The changes in photophysical properties of fluorophores (1-3) upon complex formation with electron deficient nitroaromatic explosives were studied in chloroform solution by using fluorescence spectroscopy. All these fluorophores showed the largest quenching response with moderate selectivity for nitroaromatics over various other electron deficient/ rich aromatic compounds tested (Chart 1). Analysis of the fluorescence titration profile of 9,10-bis(2-methyl-3butyn- 2-ol) anthracene fluorophore (2) with 1,3,5-trinitrotoluene/ 2,4-dinitrotoluene provided evidence that this particular fluorophore detects nitroaromatics in the nanomolar range 2.0 ppb for TNT, 13.7 ppb for DNT]. Moreover, sharp visual color change was observed upon mixing nitroaromatic (DNT) with fluorophores (1-3) both in solution as well as in solid phase. Furthermore, the vapor-phase sensing study of thin film of fluorophores (1-3) showed efficient quenching responses for DNT and this sensing process is reproducible. Selective fluorescence quenching response including a sharp visual color change for nitroaromatics make these tested fluorophores (1-3) as potential sensors for nitroaromatic compounds with a detection limit of ppb level.

Green synthesis of polysaccharide/gold nanoparticle nanocomposite: An efficient ammonia sensor

A low cost eco-friendly method for the synthesis of gold nanoparticles (AuNPs) using guar gum (GG) as a reducing agent is reported. The nanoparticles obtained are characterized by UV-vis spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD). Based on these results, a potential mechanism for this method of AuNPs synthesis is discussed. GG/AuNPs nanocomposite (GG/AuNPs NC) was exploited for optical sensor for detection of aqueous ammonia based on surface plasmon resonance (SPR). It was found to have good reproducibility, response times of similar to 10 s and excellent sensitivity with a detection limit of 1 ppb (parts-per-billion). This system allows the rapid production of an ultra-low-cost GG/AuNPs NC-based aqueous ammonia sensor.

Nanocomposite based flexible ultrasensitive resistive gas sensor for chemical reactions studies

Room temperature operation, low detection limit and fast response time are highly desirable for a wide range of gas sensing applications. However, the available gas sensors suffer mainly from high temperature operation or external stimulation for response/recovery. Here, we report an ultrasensitive-flexible-silver-nanoparticle based nanocomposite resistive sensor for ammonia detection and established the sensing mechanism. We show that the nanocomposite can detect ammonia as low as 500 parts-per-trillion at room temperature in a minute time. Furthermore, the evolution of ammonia from different chemical reactions has been demonstrated using the nanocomposite sensor as an example. Our results demonstrate the proof-of-concept for the new detector to be used in several applications including homeland security, environmental pollution and leak detection in research laboratories and many others.

Non-Enzymatic Electroanalysis of Glucose on Electrodeposited Au-PEDOT Dendrites

Electrodeposition of Au on poly (3,4-ethylenedioxythiophene) (PEDOT) coated carbon paper electrode results in the formation of a stable 3-D urchin-like morphology. Au-PEDOT/C electrode exhibits higher surface area, greater catalytic activity, higher sensitivity and lower detection limit for glucose analysis in an alkaline medium than Au/C electrode. Au-PEDOT/C electrode exhibits a linear current response in glucose concentration ranging up to 10 mu M with sensitivity of 515 mu A cm(-2) mu M-1 (on the basis of geometric area) and a low detection limit of 0.03 mu M with signal to noise ratio of 3. Thus, the PEDOT under-layer improves the property of Au for glucose analysis. (c) 2013 The Electrochemical Society.

Naphthalene Carbohydrazone Based Dizinc(II) Chemosensor for a Pyrophosphate Ion and Its DNA Assessment Application in Polymerase Chain Reaction Products

A new naphthalene carbohydrazone based dizinc(II) complex has been synthesized and investigated to act as a highly selective fluorescence and visual sensor for a pyrophosphate ion with a quite low detection limit of 155 ppb; this has also been used to detect the pyrophosphate ion released from polymerase-chain-reaction.

Pt-6(II) nanoscopic cages with an organometallic backbone as sensors for picric acid

An organometallic building block 1,3,5-tris(4-trans-Pt(PEt3)(2)I(ethynyl)phenyl)benzene (1) incorporating Pt-ethynyl functionality has been synthesized and characterized. 2 + 3] self-assembly of its nitrate analogue 1,3,5-tris(4-trans-Pt(PEt3)(2)(ONO2)(ethynyl)phenyl)benzene (2) with ``clip'' type bidentate donors (L-1-L-3) separately afforded three trigonal prismatic architectures (3a-3c), respectively. All these prisms were characterized and their shapes/sizes are predicted through geometry optimization employing molecular mechanics universal force field (MMUFF) simulation. The extended p-conjugation including the presence of Pt-ethynyl functionality makes them electron rich as well as luminescent in nature. Macrocycles 3b and 3c exhibit fluorescence quenching in solution upon addition of picric acid PA], which is a common constituent of many explosives. Interestingly, the non-responsive nature of fluorescent intensity towards other electron-deficient nitro-aromatic explosives (NAEs) makes them promising selective sensors for PA with a detection limit predicted to be ppb level. Furthermore, solid-state quenching of fluorescent intensity of the thin film of 3b upon exposure to saturated vapor of picric acid has drawn special attention for infield applications.

Anthracene-Containing Conjugated Polymer Showing Four Optical Transitions Upon Doping: A Spectroscopic Study

An anthracene-containing poly(arylene-ethynylene)-alt-poly(arylene-vinylene) (PAE-PAV) of general constitutional unit (PhCCAnthrCCPhCHCHAnthrCHCH)(n) bearing two 2-ethylhexyloxy solubilizing side chains on each phenylene (Ph) unit has been synthesized and characterized. The basic electrochemical characterization was done, showing the existence of two non-reversible oxidation and one reversible reduction peaks. The optical properties, the real and imaginary part of the dielectric function, were probed using spectroscopic ellipsometry (SE). The vibrational structure of the undoped/doped polymer was investigated using Fourier transformed infrared spectroscopy. A strong change in the polaronic absorption was observed during the doping, which after modeling revealed the existence of two separated transitions. The optical changes upon doping were additionally recorded using the SE technique. Similar to the results from FT-IR spectroscopy, two new in-the-gap absorptions were found. Moreover, the electrical conductivity as well as the mobility of positive carriers were measured. In the undoped state, the conductivity of the polymer was found to be below the detection limit (