Online CE-MALDI-TOF MS using a rotating ball interface

We report on the construction and performance of a rotating ball interface for online coupling of capillary electrophoresis (CE) to matrix-assisted laser desorption ionization (MALDI) mass spectrometry with a time-of-flight (TOF) mass analyzer. The interface is based on a rotating stainless steel ball that transports samples from atmospheric pressure to the high vacuum of the mass spectrometer for desorption and ionization. The sample is deposited directly from a 50-microm-i.d. separation capillary onto the 19-mm ball that is rotating at 0.03 to 0.3 rpm. The sample is mixed online with matrix flowing from a separate 50-microm-i.d. capillary. The sample deposit dries before it is rotated past a polymer gasket and into the laser ionization region. Cleaning of the interface is accomplished using solvent-saturated felt, which cleans the ball surface after it rotates out of the ionization chamber. On-line CE-MALDI is demonstrated, and the performance is evaluated with the analysis of a mixture of three peptides: [Lsy8] vasopressin, substance P, and neurotensin. The rotating ball interface to MALDI-TOF MS demonstrated mass detection limit in the high femtomole range. The interface has negligible memory effect and shows no significant electrophoretic peak broadening when operated under optimized conditions.     

Impact Testing and Analysis of Composites for Aircraft Engine Fan Cases

The fan case in a jet engine is a heavy structure because of its size and because of the requirement that it contain a blade released during engine operation. Composite materials offer the potential for reducing the weight of the case. Efficient design, test, and analysis methods are needed to efficiently evaluate the large number of potential composite materials and design concepts. The type of damage expected in a composite case under blade-out conditions was evaluated using a subscale test in which a glass/epoxy composite half-ring target was impacted with a wedge-shaped titanium projectile. Fiber shearing occurred near points of contact between the projectile and target. Delamination and tearing occurred on a larger scale. These damage modes were reproduced in a simpler test in which flat glass/epoxy composites were impacted with a blunt cylindrical projectile. A surface layer of ceramic eliminated fiber shear fracture but did not reduce delamination. Tests on 3D woven carbon/epoxy composites indicated that transverse reinforcement is effective in reducing delamination. A 91-cm (36 in.) diameter full-ring subcomponent was proposed for larger scale testing of these and other composite concepts. Explicit, transient, finite-element analyses indicated that a full-ring test is needed to simulate complete impact dynamics, but simpler tests using smaller ring sections are adequate when the evaluation of initial impact damage is the primary concern.     

Stereoscopic Fractography of Crack Propagation Phenomena in a TiB2—AIN Composite

Microstructural defects identified in a TiB₂–AIN composite were poorly bonded agglomerates, foreign inclusions, and highly strained regions. There were also surface flaws. Fracture surfaces produced in air were highly irregular, suggesting that microcracking caused the composite to behave differently from classical brittle ceramics. Fracture at elevated temperature in Ar or in liquid Al produced the only crack branching observed. No fractographic evidence of slow crack growth in liquid Al was found. Fractographic observations support a proposed explanation of the R -curve behavior which involves grain bridging across the crack.     

Multichannel microchip electrophoresis device fabricated in polycarbonate with an integrated contact conductivity sensor array

A 16-channel microfluidic chip with an integrated contact conductivity sensor array is presented. The microfluidic network consisted of 16 separation channels that were hot-embossed into polycarbonate (PC) using a high-precision micromilled metal master. All channels were 40 microm deep and 60 microm wide with an effective separation length of 40 mm. A gold (Au) sensor array was lithographically patterned onto a PC cover plate and assembled to the fluidic chip via thermal bonding in such a way that a pair of Au microelectrodes (60 microm wide with a 5 microm spacing) was incorporated into each of the 16 channels and served as independent contact conductivity detectors. The spacing between the corresponding fluidic reservoirs for each separation channel was set to 9 mm, which allowed for loading samples and buffers to all 40 reservoirs situated on the microchip in only five pipetting steps using an 8-channel pipettor. A printed circuit board (PCB) with platinum (Pt) wires was used to distribute the electrophoresis high-voltage to all reservoirs situated on the fluidic chip. Another PCB was used for collecting the conductivity signals from the patterned Au microelectrodes. The device performance was evaluated using microchip capillary zone electrophoresis (mu-CZE) of amino acid, peptide, and protein mixtures as well as oligonucleotides that were separated via microchip capillary electrochromatography (mu-CEC). The separations were performed with an electric field (E) of 90 V/cm and were completed in less than 4 min in all cases. The conductivity detection was carried out using a bipolar pulse voltage waveform with a pulse amplitude of +/-0.6 V and a frequency of 6.0 kHz. The conductivity sensor array concentration limit of detection (SNR = 3) was determined to be 7.1 microM for alanine. The separation efficiency was found to be 6.4 x 10(4), 2.0 x 10(3), 4.8 x 10(3), and 3.4 x 10(2) plates for the mu-CEC of the oligonucleotides and mu-CZE of the amino acids, peptides, and proteins, respectively, with an average channel-to-channel migration time reproducibility of 2.8%. The average resolution obtained for mu-CEC of the oligonucleotides and mu-CZE of the amino acids, peptides, and proteins was 4.6, 1.0, 0.9, and 1.0, respectively. To the best of our knowledge, this report is the first to describe a multichannel microchip electrophoresis device with integrated contact conductivity sensor array.     

Effects of some purified alfalfa (Medic ago sativa) saponins on transmural potential difference in mammalian small intestine

The effect of a range of structurally divergent alfalfa saponins on the potential difference (PD) across the rat small intestine has been examined in vitro Typically, there was an immediate reduction in PD, although there was considerable variation in response to particular compounds. Among the glycosides of medicagenic acid, bisdesmosides containing four sugar moieties had activities equal to the monodesmoside and to medicagenic acid itself. The exception was 3Glc, 28Glc-medicagenic acid, which did not affect the membrane potential. Zanhic acid glycosides reduced the PD to a much greater extent than medicagenic acid derived compounds. The tridesmoside of zanhic acid was the most active compound tested. This compound is however not precipitated by cholesterol and hence would not have been present in the ‘biologically active’ fractions used in previous studies. The present data show that both the lipophilic aglyconc portion of saponins, and the sugar composition can influence the ability of these compounds to depolarized the intestinal mucosa. The observations are discussed in the light of anti nutritional properties of alfalfa saponins when fed to monogastric animals.     

Alkanosulfonylated Starches

Syntheses of alkanosulfonylated starches are presented with alkane moiety being 1-propyl-, 1-butyl-, 1-octyl, 1-decyl- and 1-octadecyl. Some properties of these compounds are described and results of their biological screening against Escherichia coli, Bacillus subtilis, Aspergillus niger and Aspergillus flavus are given.     

Upconversion luminescence of Gd2O3:Er3+ and Gd2O3:Er3+/silica nanophosphors fabricated by EDTA combustion method

Gd_2O_3:Er~(3+) nanophosphors were fabricated by the combustion method in presence of Na_2 ethylene diamine tetra acetic acid(EDTA-Na_2) as fuel at not high temperature(≤350℃) within a very short time of 5 min.The added concentration of Er~(3+)ions in Gd_2O_3 matrix was changed from 0.5 mol% to 5.0 mol%.The X-ray diffraction pattern of samples indicates the monoclinic structure of Gd_2O_3:Er3+.The morphology and chemical composition analysis of the Gd_2O_3:Er~(3+) samples are characterized by a field emission scanning electron microscope(FESEM) and a Fourier-transform infrared spectrometer(FTIR).The photoluminescence(PL),photo luminescence excitation(PLE) and upconversion(UC) at room temperature of the prepared materials with different concentrations of Er~(3+) were investigated.The PL of Gd_2O_3:Er~(3+)nanomaterials are shown in visible at 545,594,623,648,688 nm under excitation at 275 nm.The emission bands from transitions of Er~(3+) from ~2P_(3/2) to ~4F_(9/2) are observed,UC luminescent spectra of the Gd_2O_3:Er~(3+)/silica nanocomposites under 976 nm excitation show the bands at 548 and 670 nm.The influence of excitation power at 980 nm for transitions were measured and calculated.The results indicate that the upconversion process of Gd_2O_3:Er~(3+)/silica is two photons absorption mechanism.The low temperature dependence of UC luminescent intensities of the main bands of Gd_2O_3:Er~(3+)was investigated towards development of a nanotemperature sensor in the range of 10-300 K.