Development of a chemical ionization ion trap mass spectrometric method for trace level determination of molecular halogens

An ion trap mass spectrometric technique using negative ion chemical ionization has been developed for the quantitative determination of the molecular halogen species Br(2), Cl(2), and BrCl. The technique utilizes NO(2)(-) as a chemical ionization reagent in an electron-transfer reaction to form the corresponding molecular anions of the halogen species, lending excellent selectivity to the measurement. Reaction rate experiments performed in the ion trap yield a rate constant for Br(2) + NO(2)(-) --> Br(2)(-) + NO(2) of (1.4 +/- 0.6) x 10(-)(9) cm(3) molecule(-)(1) s(-)(1), determined relative to published data for Cl(2) + NO(2)(-) --> Cl(2)(-) + NO(2). This paper describes a mass spectrometer pinhole inlet design and cryogenic preconcentration system for detection of the molecular halogens at atmospherically relevant concentrations. Linear calibration curves were obtained for Cl(2) and Br(2) over 3 orders of magnitude and indicate limits of detection of 50 and 8 pmol for 3.8- and 5.1-L samples, respectively, corresponding to 220 and 50 parts per trillion (mole/mole). Quantitation is based on the total signal at m/z values of 70, 72, and 74 for Cl(2) and 158, 160, and 162 for Br(2). The effects of water vapor on the cryogenic preconcentration step are quantitatively assessed.     

Fluorophilic ionophores for potentiometric pH determinations with fluorous membranes of exceptional selectivity

Ionophore-doped sensor membranes exhibit greater selectivities and wider measuring ranges when they are prepared with noncoordinating matrixes. Since fluorous phases are the least polar and least polarizable liquid phases known, a fluorous phase was used for this work as the membrane matrix for a series of ionophore-based sensors to explore the ultimate limit of selectivity. Fluorous pH electrode membranes, each comprised of perfluoroperhydrophenanthrene, sodium tetrakis[3,5-bis(perfluorohexyl)phenyl]borate, and one of four fluorophilic H(+)-selective ionophores were prepared. All the ionophores are highly fluorinated trialkylamines containing three electron withdrawing perfluoroalkyl groups shielded from the central nitrogen by alkyl spacers of varying lengths: [CF(3)(CF(2))(7)(CH(2))(3)](2)[CF(3)(CF(2))(6)CH(2)]N, [CF(3)(CF(2))(7)(CH(2))(3)](2)(CF(3)CH(2))N, [CF(3)(CF(2))(7)(CH(2))(3)](3)N, and [CF(3)(CF(2))(7)(CH(2))(5)](3)N. Their pKa values in the fluorous matrix are as high as 15.4 +/- 0.3, and the corresponding electrodes exhibit logarithmic selectivity coefficients for H(+) over K(+) as low as <-12.8. The pKa and selectivity follow the trends expected from the degree of shielding and the length of the perfluoroalkyl chains of the ionophores. These electrodes are the first fluorous ionophore-based sensors described in the literature. The selectivities of the sensor containing [CF(3)(CF(2))(7)(CH(2))(5)](3)N are not only greater than those of analogous sensors with nonfluorous membranes but were of the same magnitude as the best ionophore-based pH sensors ever reported.     

Electrospray Ion Chromatography-Tandem Mass Spectrometry of Bromate at Sub-ppb Levels in Water

An electrospray ion chromatography-tandem mass spectrometry (IC-MS/MS) method has been developed for the analysis of bromate ions in water. This IC-MS/MS method improves the limit of detection of bromate ions by a factor of 10. The method consists of solid phase extraction with an ion exchange column and elution of the analyte with water/methanol ammonium sulfate eluent on-line with a negative ion electrospray mass spectrometry detection. SPE requires sample pretreatment to remove any major ions that displace bromate, consisting of eliminating SO(4)(2)(-), Cl(-), and HCO(3)(-) ions respectively with barium-form, silver-form, and acid (H(+)-form) exchange resins. The methanolic sulfate eluent permits IC-MS coupling via an electrospray interface. BrO(3)(-) was selected in the first quadrupole (Q1) at two m/z values, 127 and 129, according to the isotope contributions of (79)Br and (81)Br. After fragmentation in the collision cell (second quadrupole, Q2), the third quadrupole (Q3) analyzes the product ions as (M - O)(-), (M - 2O)(-), and (M - 3O)(-). Among the six recordable transitions, four were selected, the other two yielding high background. A lowered resolution raised sensitivity by a factor of up to 3. The limit of quantitation of this method was 0.1 μg/L.     

Protein-repellent silicon nitride surfaces: UV-induced formation of oligoethylene oxide monolayers

The grafting of polymers and oligomers of ethylene oxide onto surfaces is widely used to prevent nonspecific adsorption of biological material on sensors and membrane surfaces. In this report, we show for the first time the robust covalent attachment of short oligoethylene oxide-terminated alkenes (CH(3)O(CH(2)CH(2)O)(3)(CH(2))(11)-(CH═CH(2)) [EO(3)] and CH(3)O(CH(2)CH(2)O)(6)(CH(2))(11)-(CH═CH(2)) [EO(6)]) from the reaction of alkenes onto silicon-rich silicon nitride surfaces at room temperature using UV light. Reflectometry is used to monitor in situ the nonspecific adsorption of bovine serum albumin (BSA) and fibrinogen (FIB) onto oligoethylene oxide coated silicon-rich silicon nitride surfaces (EO(n)-Si(x)N(4), x > 3) in comparison with plasma-oxidized silicon-rich silicon nitride surfaces (SiO(y)-Si(x)N(4)) and hexadecane-coated Si(x)N(4) surfaces (C(16)-Si(x)N(4)). A significant reduction in protein adsorption on EO(n)-Si(x)N(4) surfaces was achieved, adsorption onto EO(3)-Si(x)N(4) and EO(6)-Si(x)N(4) were 0.22 mg m(-2) and 0.08 mg m(-2), respectively. The performance of the obtained EO(3) and EO(6) layers is comparable to those of similar, highly protein-repellent monolayers formed on gold and silver surfaces. EO(6)-Si(x)N(4) surfaces prevented significantly the adsorption of BSA (0.08 mg m(-2)). Atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), X-ray reflectivity and static water contact angle measurements were employed to characterize the modified surfaces. In addition, the stability of EO(6)-Si(x)N(4) surfaces in phosphate-buffered saline solution (PBS) and alkaline condition (pH 10) was studied. Prolonged exposure of the surfaces to PBS solution for 1 week or alkaline condition for 2 h resulted in only minor degradation of the ethylene oxide moieties and no oxidation of the Si(x)N(4) substrates was observed. Highly stable antifouling coatings on Si(x)N(4) surfaces significantly broaden the application potential of silicon nitride-coated microdevices, and in particular of microfabricated filtration membranes.     

Determination of atmospheric methyl bromide by cryotrapping-gas chromatography and application to soil kinetic studies using a dynamic dilution system

Methyl bromide (CH(3)Br) is considered to be a major source of stratospheric Br, which contributes to the destruction of ozone. It is therefore necessary to understand the natural sinks of this compound and to accurately measure ambient mixing ratios. Methodology is described for the measurement of atmospheric CH(3)Br by cryotrapping-gas chromatography and its application to soil kinetics. A 2-propanol/dry ice cryotrap was used to preconcentrate CH(3)Br in standard and air samples, with subsequent detection using a gas chromatograph equipped with an O(2)-doped electron capture detector (GC-ECD). The GC-ECD cryotrapping method had a detection limit of 0.23 pmol of CH(3)Br. This is equivalent to the amount of CH(3)Br in a 500 mL sample of ambient air at the estimated northern hemisphere atmospheric mixing ratio of 11 parts per trillion by volume (pptv). A dynamic dilution system was developed to produce mixing ratios of CH(3)Br ranging between 4 and 1000 pptv. Calibrated mixing ratios of CH(3)Br produced with the dilution system were used to determine soil uptake kinetics employing a dynamic soil incubation method.     

Secondary ion emission from solutions: time dependence and surface phenomena.

The temporal behavior of FAB mass spectra from glycerol solutions of tetradecyltrimethylammonium bromide (C14H29-N(CH3)3Br, TTAB) and tetraethylammonium iodide (TEAI) was investigated. FAB spectra of the TTAB solution displayed a continuous decrease in TTA+ with time. Spectra obtained from the TEAI solution were initially invariant for several minutes and then displayed a gradual increase in the relative abundance of TEA+ to a maximum, followed by a precipitous drop in ion intensity. Secondary ion images of droplets of TTAB solution showed that emission of both TTA+ and glycerol secondary ions was homogeneous across the sample. Secondary ion images of droplets of TEAI solution showed heterogeneous and segregated emission of both TEA+ and protonated glycerol. Results from the FAB spectra and the secondary ion images were correlated and rationalized on the basis of surface tension-induced mass transport and matrix evaporation.     

Interaction of TEMAHf precursor with OH-terminated Si (001) surface: a first principles study

We performed a first principles study to investigate the interaction of tetrakis-ethylmethylaminohafnium (4[(C2H5)(CH3)N]Hf, TEMAHf) precursors with an OH-terminated Si (001) surface that is the initial stage of atomic layer deposition (ALD). When TEMAHf reacted on the OH-terminated Si surface, there were two reaction mechanisms. One was the reaction with one -OH, and the other was the reaction with two -OH's. When TEMAHf reacted with an -OH on the Si (001) surface, an ethylmethylamine ((C2H5)(CH3)NH, EMA) was produced as a by-product and the trikis-ethylmethylaminohafnium group (3[(C2H5)(CH3)N]Hf) was attached to the O atom of the -OH. There were five reaction sites for TEMAHf to react with two -OH's to form the dikis-ethylmethylaminohafnium group (2[(C2H5)(CH3)N]Hf): Inter-dimer, intra-dimer, inter-row, cross-dimer, and cross-row. The reaction with two -OH's on the inter-dimer, intra-dimer, and inter-row sites were more favorable than the reaction with one -OH. Since the inter-dimer reaction was the most favorable, the energy barrier on the inter-dimer site for the reaction of the trikis-ethylmethylaminohafnium group with -OH to form the dikis-ethylmethylaminohafnium group was calculated, and the result was 0.19 eV. An extra energy of 0.25 eV was needed to remove EMA from the surface. Four TEMAHf's reacted with the surface and these reactions were exothermic by -7.77 eV, and the calculated Hf coverage of the first-half ALD cycle was 1.67 x 10(14)/cm2.     

Surface modification and patterning using low-energy ion beams: Si-O bond formation at the vacuum/adsorbate interface.

Modification of hydroxyl-terminated self-assembled monolayer (HO-SAM) surfaces by collision of low-energy (15 eV) hyperthermal Si(CH3)3+ ions is shown to lead to Si-O bond formation and terminal trimethylsilyl ether formation. Modification was verified by in situ mass spectrometry using chemical sputtering with CF3+ ions (70 eV), ex situ secondary ion mass spectrometric analysis (12 kV Ga+ primary ion beam), and through X-ray photoelectron spectroscopy by monitoring Si (2s). The nature of the surface modification was further established by analysis of synthetic SAM surfaces made up of mixtures of the trimethylsilyl-11-mercapto-1-undecane ether and various proportions of the hydroxyl-terminated mercaptan (11-mercapto-1-undecanol). These mixed surfaces, as well as the spectroscopic data, indicate that ca. 30% of the hydroxyl chains are covalently modified at saturation coverage. Analogous surface transformations are achieved using Si(CH3)2F+ and Si(CH3)2C6H5+.     

对甲基苯乙烯阳离子聚合研究

采用PEC1／SnCl4/CH2Cl2/Bu4N^ Br^-/-15℃体系进行了对甲基苯乙烯阳离子聚合。分别研究了Bu4N^ Br^-浓度、溶剂极性和单体浓度等对聚合的影响。结果表明：对甲基苯乙烯聚合速度非常快，5min即能完成反应；溶剂极性对聚合速度影响较大，溶剂极性降低，反应速度减慢。在 纯的非极性溶剂中，聚合物为多峰分布；在纯CH2Cl2中，Bu4N^ Br^-用量从0.005mol/L到0.05mol/L对对甲基苯乙烯的聚合无影响。在极性较低的体系中，Bu4N^ Br^-对聚合影响很明显，聚合速度显著降低，相对分子质量分布交窄；在本聚合体系中都存在着一定程度向单体的链转移，不是活性聚合。     

Infrared spectroscopy of fluid lipid bilayers

Infrared spectroscopy is a powerful technique for examining lipid bilayers; however, it says little about the fluidity of the bilayer-a key physical aspect. It is shown here that it is possible to both acquire spectroscopic data of supported lipid bilayer samples and make measurements of the membrane fluidity. Attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FT-IR) is used to obtain the spectroscopic information and fluorescence recovery after photobleaching (FRAP) is used to determine the fluidity of the samples. In the infrared spectra of lipid bilayers composed of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine, the following major peaks were observed; nu(as)(CH3) 2954 cm(-1), nu(s)(CH3) 2870 cm(-1), nu(as)(CH2) 2924 cm(-1), nu(s)(CH2) 2852 cm(-1), nu(C=O) 1734 cm(-1), delta(CH2) 1463-1473 cm(-1), nu(as)(PO2-) 1226 cm(-1), nu(s)(PO2-) 1084 cm(-1), and nu(as)(N+(CH3)3) 973 cm(-1). The diffusion coefficient of the same lipid bilayer was measured to be 3.5 +/- 0.5 micom(2)/s with visual recovery also noted through use of epifluorescence microscopy. FRAP and visual data confirm the formation of a uniform, mobile supported lipid bilayer. The combination of ATR-FT-IR and FRAP provides complementary data giving a more complete picture of fully hydrated model membrane systems.     

A chemical ionization mass spectrometry method for the online analysis of organic aerosols

A new technique employing chemical ionization mass spectrometry (CIMS) is described that allows the composition of organic particles to be determined on the time scale of seconds. With this Aerosol CIMS technique, particles are vaporized thermally at temperatures up to 480 degrees C, and the resulting vapor is chemically ionized and detected with a quadrupole mass spectrometer. The separation of the vaporization and ionization steps allows greater control and more flexibility for the detection of condensed phases than with other chemical ionization methods. Consequently, composition can be correlated to volatility, providing an additional dimension of information. The use of a variety of positive and negative reagent ions, such as H(+)(H(2)O)(2), H(+)(CH(3)OH)(2), NO(+), O(2)(+), O(2)(-), F(-), and SF(6)(-), offers flexibility in the detection sensitivity and specificity. Furthermore, the degree of fragmentation of the resulting ion can be controlled, providing more straightforward identification and quantification than with other commonly used methods, such as electron impact ionization. Examples are given of the detection of aerosols consisting of organics with various functionalities, including alkanes, alkenes, alcohols, aldehydes, ketones, and carboxylic acids. Applications of this technique to laboratory studies of atmospherically relevant aerosol reactions are discussed.     

Fourier transform infrared analysis of gas composition in low-volume light bulbs

Fourier transform infrared spectroscopy has been used for in situ analysis of HBr, CH3Br, and CO within light bulbs at different stages of burning time. The interference fringes originated in the quartz walls of the bulbs have been eliminated by different methods. The NIPALS procedure yielded higher S/N ratio than the fringe-elimination method applied. The CO and HBr showed time-dependent concentration changes during the burning period. The maximum CO concentration (approximately 6 ppm) was detected after 30-50 s of burning time, and then it practically burned out after 5 h. The HBr concentration increased in the first 3 min of burning, and then its concentration stabilized at a 10-15 ppm level. After 5 s of illumination, the CH3Br concentration became undetectable.     

Ionic transacetalization with acylium ions: a class-selective and structurally diagnostic reaction for cyclic acetals performed under unique electrospray and atmospheric pressure chemical ionization in-source ion-molecule reaction conditions

Ionic transacetalization of cyclic acetals with the gaseous (CH3)2NCO+ acylium ion has been performed under unique in-source ion-molecule reaction (in-source IMR) conditions of electrospray (ESI) and atmospheric pressure chemical ionization (APCI). In-source IMR under ESI and APCI greatly expands the range of neutral molecules that can be brought to the gas phase to react by ionic transacetalization, a general, class-selective and structurally diagnostic reaction for cyclic acetals (Moraes, L. A. B.; Gozzo, F. C.; Vainiotalo, P.; Eberlin, M. N. J. Org. Chem. 1997, 62, 5096). Heavier, more polar, and less volatile cyclic acetals than those previously employed in quadrupole collision cells are shown to react efficiently by ionic transacetalization under the ESI and APCI in-source IMR conditions. Tetramethylurea (TMU) acts as an efficient dopant, being co-injected with the acetal in either benzene, toluene, methanol, or water/methanol solutions. Under APCI or ESI, the basic TMU dopant is protonated preferentially, and the labile protonated TMU then undergoes dissociation to (CH3)2NCO+, the least acidic and the most transacetalization-reactive acylium ion so far tested. Under the relatively high-pressure, low-energy collision conditions set to favor associative reactions, (CH3)2NCO+ reacts competitively both with TMU to form acylated TMU and with the acetal via ionic transacetalization to form the respective cyclic ionic acetals. Spectrum subtraction removes the ionic products of the dopant (TMU) self-reactions, thus providing clean ion-molecule reaction product ion mass spectra, which are used for the selective, structurally diagnostic detection of cyclic acetals. Information on ring substituents comes from characteristic mass shifts resulting from aldehyde/ketone by acylium ion replacement. Enhanced selectivity in structural characterization or chemical recognition for cyclic acetal monitoring is gained by performing on-line collision-induced dissociation via tandem mass spectrometric experiments. Most cyclic ionic acetals dissociate exclusively or nearly exclusively to re-form the reactant (CH3)2NCO+ acylium ion whereas the presence of additional functional groups with increased structural complexity tends to favor other specific but likewise selective dissociation channels.     

High-Resolution Enabled TMT 8-plexing

Isobaric mass tag-based quantitative proteomics strategies such as iTRAQ and TMT utilize reporter ions in the low-mass range of tandem MS spectra for relative quantification. The number of samples that can be compared in a single experiment (multiplexing) is limited by the number of different reporter ions that can be generated by differential stable isotope incorporation ((15)N, (13)C) across the reporter and the mass balancing parts of the reagents. Here, we demonstrate that a higher multiplexing rate can be achieved by utilizing the 6 mDa mass difference between (15)N- and (13)C-containing reporter fragments, in combination with high-resolution mass spectrometry. Two variants of the TMT127 and TMT129 reagents are available; these are distinguished by the position and the nature of the incorporated stable isotope in the reporter portions of the labels (TMT127L, (12)C(8)H(16)(15)N(1)(+); TMT127H, (12)C(7)(13)C(1)H(16)(14)N(1)(+); TMT129L, (12)C(6)(13)C(2)H(16)(15)N(1)(+); and TMT129H, (12)C(5)(13)C(3)H(16)(14)N(1)(+)). We demonstrate that these variants can be baseline-resolved in Orbitrap Elite higher-energy collision-induced dissociation spectra recorded with a 96 ms transient enabling comparable dynamic range, precision, and accuracy of quantification as 1 Da spaced reporter ions. The increased multiplexing rate enabled determination of inhibitor potencies in chemoproteomic kinase assays covering a wider range of compound concentrations in a single experiment, compared to conventional 6-plex TMT-based assays.     

Brominated tyrosine and polyelectrolyte multilayer analysis by laser desorption vacuum ultraviolet postionization and secondary ion mass spectrometry

The small molecular analyte 3,5-dibromotyrosine (Br(2)Y) and chitosan-alginate polyelectrolyte multilayers (PEM) with and without adsorbed Br(2)Y were analyzed by laser desorption postionization-mass spectrometry (LDPI-MS). LDPI-MS using a 7.87 eV laser and tunable 8-12.5 eV synchrotron vacuum ultraviolet (VUV) radiation found that desorption of clusters from Br(2)Y films allowed detection by ≤8 eV single photon ionization. Thermal desorption and electronic structure calculations determined the ionization energy of Br(2)Y to be ~8.3 ± 0.1 eV and further indicated that the lower ionization energies of clusters permitted their detection at ≤8 eV photon energies. However, single photon ionization could only detect Br(2)Y adsorbed within PEMs when using either higher photon energies or matrix addition to the sample. All samples were also analyzed by 25 keV Bi(3)(+) secondary ion mass spectrometry (SIMS), with the negative ion spectra showing strong parent ion signal which complemented that observed by LDPI-MS. However, the negative ion SIMS appeared strongly dependent on the high electron affinity of this specific analyte and the analyte's condensed phase environment.     

Photocatalytic decomposition of acephate in irradiated TiO2 suspensions

In the present study, the photocatalytic degradation of acephate (O,S-dimethyl acetyl phosphoramidothioate ((CH(3)O)(CH(3)S)P(O)NHCOCH(3))) in aqueous TiO2 suspensions is extensively investigated, pertaining to the concentration of photocatalyst and substrate on degradation rate of acephate. It is found that the acephate can be degradated and mineralized. The high-degradation rate is obtained with 4 g/L concentration of TiO2. Moreover, Langmuir-Hinshelowood rate expression is employed for the degradation of acephate with adsorption constant and rate constant, i.e., 2.0 L/mmol and 0.6 mmol/(min L), respectively. The main target is to identify the products by a number of analytical techniques, such as HPLC, IC, ESR and GC-MS. Under acidic condition, the primary products are phosphorothioic acid, O,O',S-trimethyl ester (CH(3)O(CH(3)S)P(O)OCH(3)) and phosphoramidothioic acid, O,S-dimethyl ester (CH(3)O(CH(3)S)P(O)NH(2)), etc. It indicates that the decomposition of acephate begin from the destruction of C-N and P-N bonds. Subsequently, the P-S, P-O, P-C bonds may be oxidized gradually or simultaneously, and the final products such as CO(2), H(3)PO(4), were formed. About 100% sulfur atoms are transformed into SO(4)(2-) in 180 min, however; only 3% nitrogen atoms and 2% phosphorus atoms were transformed into NO(3)(-) and PO(4)(3-).     

Highly Cooperative Tetrametallic Ruthenium-mu-Oxo-mu-Hydroxo Catalyst for the Alcohol Oxidation Reaction

The tetrametallic ruthenium-oxo-hydroxo-hydride complex {[(PCy(3))(CO)RuH](4)(mu(4)-O)(mu(3)-OH)(mu(2)-OH)} (1) was synthesized in two steps from the monomeric complex (PCy(3))(CO)RuHCl (2). The tetrameric complex 1 was found to be a highly effective catalyst for the transfer dehydrogenation of alcohols. Complex 1 showed a different catalytic activity pattern towards primary and secondary benzyl alcohols, as indicated by the Hammett correlation for the oxidation reaction of p-X-C(6)H(4)CH(2)OH (rho = -0.45) and p-X-C(6)H(4)CH(OH)CH(3) (rho = +0.22) (X = OMe, CH(3), H, Cl, CF(3)). Both a sigmoidal curve from the plot of initial rate vs [PhCH(OH)CH(3)] (K(0.5) = 0.34 M; Hill coefficient, n = 4.2+/-0.1) and the phosphine inhibition kinetics revealed the highly cooperative nature of the complex for the oxidation of secondary alcohols.     

Corona discharge ion mobility spectrometry with orthogonal acceleration time of flight mass spectrometry for monitoring of volatile organic compounds

We demonstrate the application of corona discharge ion mobility spectrometry with orthogonal acceleration time of flight mass spectrometry (CD IMS-oaTOF) for volatile organic compounds (VOCs) monitoring. Two-dimensional (2D) IMS-oaTOF spectra of VOCs were recorded in nearly real time. The corona discharge atmospheric pressure chemical ionization (APCI) source was operated in positive mode in nitrogen and air. The CD ion source generates in air H(3)O(+)(H(2)O)(n) and NO(+). The NO(+) offers additional possibility for selective ionization and for an increase of the sensitivity of monoaromatic compounds. In addition to H(3)O(+)(H(2)O)(n) and NO(+), we have carried out ionization of VOCs using acetone as dopant gas ((CH(3))(2)COH(+)). Sixteen model VOCs (tetrahydrofuran, butanol, n-propanol, iso-propano, acetone, methanol, ethanol, toluene, benzene, amomnia, dioxan, triethylamine, acetonitrile, formaldehyde, m-xylene, 2,2,2-trifluoroethylamine) were tested using these ionization techniques.     

表面改性对纳米蒙脱土/聚酰胺6-66复合材料性能的影响

选取三种不同的纳米蒙脱土（nMMT）（分别为钠基蒙脱土（Na-MMT）、氨基酸改性nMMT（OMMT-A）和CH₃（CH₂）₁₇N（CH₃）[（CH₂CH₂OH）₂]+改性nMMT（OMMT-B））,通过熔融共混法制备了不同改性的纳米蒙脱土/聚酰胺6-66（nMMT/PA6-66）复合材料,研究了不同表面改性对nMMT/PA6-66复合材料的结晶、流变和力学等性能的影响。结果表明,nMMT的加入促进了nMMT/PA6-66复合材料中γ晶的形成,提高了复合材料的结晶温度,但加入OMMT-B后OMMT-B/PA6-66复合材料的异相成核作用效率有一定程度减弱;同时,OMMT-B能更好地改善PA6-66的储能模量,提高PA6-66的流动性。力学性能测试表明,nMMT提高了nMMT/PA6-66复合材料的强度,降低了复合材料的韧性,但效果不同。其中,加入OMMT-B后OMMT-B/PA6-66复合材料的韧性几乎保持不变,拉伸强度和弯曲强度相对于纯PA6-66分别提高了26%和28%,表现出最佳的综合力学性能。综合研究结果表明,不同表面改性nMMT对PA6-66性能的影响主要取决于改性剂和PA6-66分子链之间相互作用的强弱。      

Electrospray ionization high-field asymmetric waveform ion mobility spectrometry-mass spectrometry

High-field asymmetric waveform ion mobility spectrometry (FAIMS) is a new technique that separates gas-phase ions at atmospheric pressure (760 Torr) and room temperature. A FAIMS instrument acts as an ion filter and can be set to continuously transmit one type of ion. Despite the stringent requirement for a flow of clean, dry gas in the FAIMS analyzer region, a method of coupling electrospray to FAIMS has been developed. The identity of the electrospray ions separated by FAIMS was determined using mass spectrometry (FAIMS-MS). The theory of FAIMS is discussed, and electrospray FAIMS-MS spectra of several compounds in modes P1, P2, N1, and N2 are presented. Ions appearing in P1 and N1 modes tend to have mobilities that increase as a function of increasing electric field strength, whereas ions appearing in P2 and N2 modes tend to have mobilities that decrease. In general, low-mass ions are focused in P1 and N1 modes, whereas larger ions (e.g., proteins) are focused in P2 and N2 modes. Short-chain peptides, (Gly)(n) where n = 1-6, are shown to cross over from P1 mode into P2 mode as the chain length increases. The removal of the low-mass solvent cluster ions, combined with a reduction of the background noise in electrospray FAIMS-MS, results in an improved signal-to-noise ratio for mass spectra of larger ions (e.g., cyctochrome c) when compared with conventional electrospray-MS. Preliminary results also suggest that various charge states of cytochrome c can be distinguished by FAIMS, implying that the ion mobility of these species at high electric field strength is sensitive to the structure of the protein ion. The linearity of response of electrospray FAIMS-MS was investigated using leucine enkephalin and shows the calibration curve to be linear for ～3 orders of magnitude.