Electrospray ionization using wooden tips

Electrospray ionization (ESI) is a mass spectrometric technique widely used in various fields including chemistry, biology, medicine, pharmaceutical industry, clinical assessment, and forensic science. In this study, we report a simple and economical ESI-mass spectrometry (MS) technique, which makes use of disposable wooden tips (wooden toothpicks) for loading and ionization of samples. Samples could be loaded by normal pipetting onto the tip or simply dipping the tip into sample solutions. The hydrophilic and porous nature of wood allows effective adhesion of the sample solution for durable ion signals. The tip can be directly connected to nano-ESI ion sources of various mass spectrometers. Upon application of high voltage to the tip, desirable mass spectra could be obtained. We demostrated that this new technique is applicable for analysis of various samples, including organic compounds, organometallic compounds, peptides, proteins, and samples that cannot be directly analyzed by conventional ESI techniques, e.g., slurry samples and powder samples. The slim and hard properties of the wooden tip enable sampling from specific locations such as corners and small openings, indicating potential applications of the new technique in forensic investigations. The observation of electrospray ionization from wooden materials also allows us to get new insights into the materials that can be directly ionized for mass spectrometric analysis.     

Dual-wavelength superfluorescent fiber emitter

The feasibility of constructing a dual-wavelength, spatially single-mode, superfluorescent fiber emitter on the basis of erbium optical fibers with pumping by multimode semiconductor lasers is demonstrated. The emitter is fabricated by all-fiber technology and has a power output in excess of 10 mW, an average emission wavelength of 1.54 μm, and a spectral resolution of 27.5 nm at component linewidths of 3 nm and 9 nm. The depolarization of the radiation from the emitter as it propagates in an anisotropic, single-mode fiber waveguide is investigated. Pis’ma Zh. Tekh. Fiz. 23, 37–42 (October 26, 1997)     

Field electron emitter for air ionization in a supersonic flow

It is suggested to use a field electron emitter based on liquid gallium for the ionization of molecules in a supersonic air flow.     

Electrospray ionization high-resolution ion mobility spectrometry-mass spectrometry

A hybrid atmospheric pressure ion mobility spectrometer is described which exhibits resolving power approaching the diffusion limit for singly and multiply charged ions (over 200 for the most favorable case). Using an electrospray ionization source and a downstream quadrupole mass spectrometer with electron multiplier as detector, this ESI-IMS-MS instrument demonstrates the potential of IMS for rapid analytical separations with a resolving power similar to liquid chromatography. The first measurements of gas-phase mobility spectra of mass-identified multiply charged ions migrating at atmospheric pressure are reported. These spectra confirm that collision cross sections are strongly affected by charge state. Baseline separations of multiply charged states of cytochrome c and ubiquitin demonstrate the improved resolving power of this instrument compared with previous atmospheric pressure ion mobility spectrometers. The effects of electric potential, initial pulse duration, ion-molecule reactions, ion desolvation, Coulombic repulsion, electric field homogeneity, ion collection, and charge on the resolving power of this ion mobility spectrometer are discussed.     

Electrospray ionization of protein mixtures at low pH

Solutions composed of single proteins and mixtures of proteins are subjected to electrospray ionization to study the influence of protein components on the responses of one another. Protein matrix effects in electrospray ionization are particularly relevant to the development of top-down protein identification methodologies involving protein mixtures, whereby whole protein ions are subjected to tandem mass spectrometry. Emphasis is placed largely on solutions composed of equal parts methanol and water and 1% acetic acid. The results, therefore, are relevant to low-pH solutions with significant organic content, a commonly used set of conditions in electrospray ionization mass spectrometry that tends to denature proteins. Under these conditions, very similar response curves are measured for a variety of proteins after charge normalization. That is, when the data are plotted in terms of the concentration of charge sites, rather than in terms of the concentration of protein molecules, the slopes of the response curves as well as the point at which response becomes less than linear with concentration are similar. Charge normalization is made on the basis of the weighted average charge of a protein, as reflected in the electrospray ionization mass spectrum. When proteins can be regarded as a collection of equivalent charge sites, the signal response from one protein can be used to predict the responses for other proteins. Furthermore, it is also possible to predict the dependence of the signal response for a particular protein in a mixture on the concentration of other proteins in the mixture. Examining signal response on a weighted average charge basis appears to be an effective means for identifying situations in which the protein does not behave as a collection of equivalent charge sites.     

Ionization vacuum gauge with a carbon nanotube field electron emitter combined with a shield electrode

The applicability of carbon nanotubes to an electron source for a Bayard-Alpert type vacuum gauge has been investigated. Three gauge configurations are designed to optimize the gauge performance. The optimized gauge, in which an additional shield electrode is fixed on a gate electrode, exhibits good measurement of linearity between ion current and system pressure from 10⁻⁷ to 10⁻² Pa. A gauge sensitivity of 0.05 Pa⁻¹ has been achieved under 100 μA emission current for nitrogen, comparable with 0.07 Pa⁻¹ of commercial ionization gauges.     

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.     

Microfluidic dual emitter electrospray ionization source for accurate mass measurements

A glass microfluidic device with two independent electrospray ionization (ESI) emitters has been designed to sequentially generate ions from different solutions for mass analysis. Rapid modulation between the emitters is accomplished by turning on and off the voltage that simultaneously generates the fluid flow rate and ESI potential. The time required to switch between the two electrospray signals is less than 70 ms. Using the second emitter to introduce a reference compound for internal calibration, accurate mass measurements (less than 3 ppm mass error) were obtained with a time-of-flight mass spectrometer.     

New-type planar field emission display with superaligned carbon nanotube yarn emitter

With the superaligned carbon nanotube yarn as emitter, we have fabricated a 16 × 16 pixel field emission display prototype by adopting screen printing and laser cutting technologies. A planar diode field emission structure has been adopted. A very sharp carbon nanotube yarn tip emitter can be formed by laser cutting. Low voltage phosphor was coated on the anode electrodes also by screen printing. With a specially designed circuit, we have demonstrated the dynamic character display with the field emission display prototype. The emitter material and fabrication technologies in this paper are both easy to scale up to large areas.     

Electrospray ionization mass spectrometry of semduramicin and other polyether ionophores.

Pneumatically assisted electrospray mass spectrometry of polyether ionophores yields several molecular ions. A single metal adduct molecular ion can be obtained by the addition of a neutral salt to the HPLC mobile phase. This approach may be useful in structural studies of unknown ionophores and in the development of specific methods for their analysis in complex matrices. Collision-induced dissociation of the molecular ions provides additional structural information and enhanced specificity for trace analysis. HPLC mobile-phase composition and flow rates have been optimized for on-line analysis. Best response and lowest background noise were obtained at the flow rate of 40 microL/min of a mobile phase containing a 20/80 mixture of water and acetonitrile. The development of a specific confirmatory assay for the new ionophore semduramicin in chicken liver demonstrates the usefulness of on-line HPLC pneumatically assisted electrospray mass spectrometry.     

The Ni-plated carbon fiber as a tracer for observation of the fiber orientation in the carbon fiber reinforced plastic with X-ray CT

Microfocus X-ray computed tomography (XCT) is effective to evaluate the 3-dimensional (3D) structure (position and orientation) of the fillers in the composites. However, the observation of the carbon fiber (CF) in resin by XCT is not easy due to the small difference between X-ray attenuation coefficient of CF and that of resin. We conducted XCT scanning of carbon fiber reinforced plastics (CFRPs) containing Ni-plated CF. The fiber orientation can be clearly observed in CT images due to a large X-ray attenuation coefficient of Ni-plating. Ni-plated CF essentially showed the same fiber orientation as that of normal CF. We also carried out the 3D characterization of the fiber orientation in an injection-molded dumbbell specimen with weld line. The fibers around the weld line are oriented perpendicular to the longitudinal direction of the specimen.     

Launching propagating surface plasmon polaritons by a single carbon nanotube dipolar emitter

We report on the excitation of propagating surface plasmon polaritons in thin metal films by a single emitter. Upon excitation in the visible regime, individual semiconducting single-walled carbon nanotubes are shown to act as directional near-infrared point dipole sources launching propagating surface plasmons mainly along the direction of the nanotube axis. Plasmon excitation and propagation is monitored in Fourier and real space by leakage radiation microscopy and is modeled by rigorous theoretical calculations. Coupling to plasmons almost completely reshapes the emission of nanotubes both spatially and with respect to polarization as compared to photoluminescence on a dielectric substrate.     

Fabrication and characterization of a 3D-structured field emitter using carbon nanotube

Carbon nanotube has good electrical properties and a high aspect ratio, which enable it to obtain a high current at a low voltage due to its high field. Due to the life and uniformity of their emission tips, carbon nanotube field emitters are hard to commercialize. A field emitter with a three-dimensional (3D) structure was fabricated in this study to overcome such problems. In the 3D-structured field emitter, the field emission tips are located only at the vertical plane, where an enlarged field emission area can be attained. To fabricate the tip of the 3D-structured field emitter, carbon nanotube/silver nanocomposite powders were fabricated via molecular-level mixing and were sprayed at a substrate with good attachment and homogeneous dispersion between the CNT tips and the silver. The field emission properties of the 3D-structured field emitter were then determined and compared with those of a flat field emitter. The field emission area of the 3D-structured field emitter was found to be 4.5 times larger than that of the flat field emitter, with six times higher current density. Moreover, the 3D-structured field emitter had better stability than the flat field emitter. At a high gate field, the emission images of the 3D-structured field emitter showed light spots expanded towards the gate direction.     

碳纳米管接枝炭纤维对环氧树脂浸润性能的影响

以乙炔为碳源、二茂铁为催化剂,通过雾化辅助化学气相沉积法(AACVD)制备多尺度杂化材料CNT/CF.利用扫描电镜(SEM)、透射电镜(TEM)表征所制CNr/CF的形貌及其微观结构.结果表明:在反应温度750℃～800℃、沉积30min的条件下,碳纳米管(CNTs)能够以较高的密度均匀生长在炭纤维表面形成多尺度杂化材料CNr/CF.单纤维拉伸测试表明:在700℃～800℃、沉积30min的条件下所制CNT/CF的单纤维拉伸强度降低幅度小于13％;在反应温度750℃、沉积40 min的条件下、单纤维拉伸强度降低幅度小于10％.纤维悬挂液滴法研究表明:所制CNT/CF比原始炭纤维对环氧树脂有更好的浸润性能.     

苎麻短纤维层间增韧碳纤维/环氧树脂复合材料

采用热压机层压成型工艺制备了苎麻短纤维(SRF)层间增韧碳纤维/环氧树脂(CF/EP)复合材料层压板,研究了SRF的长度、面密度及其表面偶联处理对CF/EP复合材料层间断裂韧性的影响,并进一步研究了SRF的铺入对复合材料弯曲、拉伸性能的影响。研究结果表明,层间SRF的铺入明显改善了CF/EP复合材料的I型和II型层间断裂韧性(G_(IC)和G_(IIC)),当表面偶联处理的纤维长度为6mm、面密度为12g·m~(-2)时,增韧效果最佳,GIC由497.48J·m~(-2)增加到667.54J·m~(-2),提高了34.24%;GIIC由508.52J·m~(-2)增加到862.11J·m~(-2),提高了69.54%。此外,铺入SRF对复合材料的弯曲、拉伸性能也有一定程度的提高。通过SEM观察发现,SRF的增韧机制与其层间桥联以及裂纹扩展过程中从基体中拔出与劈裂等现象有关。     

碳纤维截面特性对碳纤维/环氧树脂复合材料压缩强度的影响

基于压拉平衡为特征的新一代先进复合材料的需求,开展了碳纤维截面形状和尺寸对碳纤维/环氧树脂复合材料压缩强度的影响研究。有限元模拟和试验结果均表明,增大碳纤维直径可以提高复合材料压缩强度。另外碳纤维截面形状也对复合材料压缩强度有影响,圆形截面优于椭圆形截面。      

炭毡传感特性研究

通过对炭毡进行拉伸、循环加载等试验,研究了其电阻随变形而改变的规律.结果表明:在弹性范围内,拉伸加载时,电阻值呈可逆性增加;卸载时,电阻值则为可逆性减小.炭毡具有良好的电阻-变形敏感性,且有满意的线性度和良好的重复性.炭毡通电处理后,其电阻值更加稳定,在循环载荷下,重复性比未通电前好.炭毡作为一种新型的传感元件,可用于监测工程结构的服役状况.     

A colloidal graphite-coated emitter for sheathless capillary electrophoresis/nanoelectrospray ionization mass spectrometry

A colloidal graphite-coated emitter is introduced for sheathless capillary electrophoresis/nanoelectrospray ionization time-of-flight mass spectrometry (CE/ESI-TOFMS). The conductive coating can be produced by brushing the capillary tip to construct a fine layer of 2-propanol-based colloidal graphite. The fabrication involves a single step and requires less than 2 min. Full cure properties develop in approximately 2 h at room temperature and then the tip is ready for use. The coated capillary tip is applied as a sheathless electrospray emitter. The emitter has proven to bear stable electrospray and excellent performance for 50 microm i.d. x 360 microm o.d. and 20 microm i.d. x 360 microm o.d. capillaries within the flow rate of 80-500 nL/min; continuous electrospray can last for over 200 h in positive mode. Baseline separation and structure elucidation of two clinically interesting basic drugs, risperidone and 9-hydroxyrisperidone, are achieved by coupling pressure-assisted CE to ESI-TOFMS using the described sheathless electrospray emitter with a bare fused-silica capillary at pH 6.7. It is found that the signal intensity of m/z in sheathless CE/ESI-TOFMS at pH 6.7 is approximately 50 times higher than that at pH 9.0 for the two analytes, although the electroosmotic flow (EOF) at pH 9.0 provides sufficient flow rate (approximately 150 nL/min) to maintain electrospray.     

Electrospray ionization and collision induced dissociation mass spectrometry of primary fatty acid amides

Primary fatty acid amides are a group of bioactive lipids that have been linked with a variety of biological processes such as sleep regulation and modulation of monoaminergic systems. As novel forms of these molecules continue to be discovered, more emphasis will be placed on selective, trace detection. Currently, there is no published experimental determination of collision induced dissociation of PFAMs. A select group of PFAM standards, 12 to 22 length carbon chains, were directly infused into an electrospray ionization source Quadrupole Time of Flight Mass Spectrometer. All standards were monitored in positive mode using the [M + H](+) peak. Mass Hunter Qualitative Analysis software was used to calculate empirical formulas of the product ions. All PFAMs showed losses of 14 m/z indicative of an acyl chain, while the monounsaturated group displayed neutral losses corresponding to H(2)O and NH(3). The resulting spectra were used to propose fragmentation mechanisms. Isotopically labeled PFAMs were used to validate the proposed mechanisms. Patterns of saturated versus unsaturated standards were distinctive, allowing for simple differentiation. This determination will allow for fast, qualitative identification of PFAMs. Additionally, it will provide a method development tool for selection of unique product ions when analyzed in multiple reaction monitoring mode.