Ambient desorption ionization mass spectrometry

Ambient desorption ionization mass spectrometry (MS) allows for the direct analysis of ordinary objects in the open atmosphere of the laboratory or in their natural environment. Analyte desorption usually accompanies the ionization step and these processes are often concerted, multi-step processes. Ambient desorption ionization methods typically require little or no sample preparation, offer a much simplified work flow and deliver unprecedented ease of use to MS analyses.

Since the introduction of desorption electrospray ionization (DESI [Z. Takats, J.M. Wiseman, B. Gologan, R.G. Cooks, Science (Washington, D. C.) 306 (2004) 471]) in 2004 and the direct analysis in real time (DART [R.B. Cody, J.A. Laramee, H.D. Durst, Anal. Chem. 77 (2005) 2297]) in 2005, this new field of MS has developed rapidly. Numerous permutations of the various options for analyte desorption and ionization have been demonstrated. Desorption steps, such as momentum transfer, dissolution into ricocheting droplets and thermal desorption, have been combined with ionization steps, including ESI, atmospheric pressure chemical ionization and photo-ionization. The large number of possible combinations of desorption and ionization components that have already been applied is creating a proliferation of techniques and acronyms that is becoming ever more complex.

Here, we provide a logical framework for the classification of these related experiments, based on the desorption and ionization processes involved in each.     

Comparative studies on conventional and microwave synthesis of some benzimidazole, benzothiazole and indole derivatives and testing on inhibition of hyaluronidase

We have synthesized twelve 2-substituted benzimidazole, benzothiazole and indole derivatives using on both microwave irradiation and conventional heating methods. The microwave method was observed to be more beneficial as it provides an increase of yield from 3% to 113% and a 95 to 98 % reduction in time. All compounds were tested by a stains-all assay at pH 7 and by a Morgan-Elson assay at pH 3.5 for hyaluronidase inhibitory activity at a concentration of 100 microM. The most potent compound was 2-(4-hydroxyphenyl)-3-phenylindole (12) with an IC(50) value of 107 microM at both pH 7 and 3.5.     

Rankin-Selberg without unfolding and bounds for spherical Fourier coefficients of Maass forms

We use the uniqueness of various invariant functionals on irreducible unitary representations of in order to deduce the classical Rankin-Selberg identity for the sum of Fourier coefficients of Maass cusp forms and its new anisotropic analog. We deduce from these formulas non-trivial bounds for the corresponding unipotent and spherical Fourier coefficients of Maass forms. As an application we obtain a subconvexity bound for certain -functions. Our main tool is the notion of a Gelfand pair from representation theory.

     

Identifying hexagonal boron nitride monolayers by transmission electron microscopy

Multislice simulations in the transmission electron microscope (TEM) were used to examine changes in annular-dark-field scanning TEM (ADF-STEM) images, conventional bright-field TEM (BF-CTEM) images, and selected-area electron diffraction (SAED) patterns as atomically thin hexagonal boron nitride (h-BN) samples are tilted up to 500 mrad off of the [0001] zone axis. For monolayer h-BN the contrast of ADF-STEM images and SAED patterns does not change with tilt in this range, while the contrast of BF-CTEM images does change; h-BN multilayer contrast varies strongly with tilt for ADF-STEM imaging, BF-CTEM imaging, and SAED. These results indicate that tilt series analysis in ADF-STEM image mode or SAED mode should permit identification of h-BN monolayers from raw TEM data as well as from quantitative post-processing.     

Sonolysis of Escherichia coli and Pichia pastoris in microfluidics

We report on an efficient ultrasound based technique for lysing Escherichia coli and Pichia pastoris with oscillating cavitation bubbles in an integrated microfluidic system. The system consists of a meandering microfluidic channel and four piezoelectric transducers mounted on a glass substrate, with the ultrasound exposure and gas pressure regulated by an automatic control system. Controlled lysis of bacterial and yeast cells expressing green fluorescence protein (GFP) is studied with high-speed photography and fluorescence microscopy, and quantified with real-time polymerase chain reaction (qRT-PCR) and fluorescence intensity. The effectiveness of cell lysis correlates with the duration of ultrasound exposure. Complete lysis can be achieved within one second of ultrasound exposure with a temperature increase of less than 3.3 °C. The rod-shaped E. coli bacteria are disrupted into small fragments in less than 0.4 seconds, while the more robust elliptical P. pastoris yeast cells require around 1.0 second for complete lysis. Fluorescence intensity measurements and qRT-PCR analysis show that functionality of GFP and genomic DNA for downstream analytical assays is maintained.     

Improved surface properties of CTMP fibers with enzymatic pretreatment of wood chips prior to refining

Surface properties of chemithermomechanical pulp (CTMP) fibers produced from enzymatically pretreated eucalyptus wood chips prior to refining were investigated by Field Emission Scanning Electron Microscope (FE-SEM), Transmission Electron Microscope (TEM) and X-ray Photoelectron Spectroscopy (XPS). The results showed that in a traditional CTMP refining process most fiber disruptions occur in the middle lamella (ML) leaving behind a significant amount of hydrophobic materials on the resulting fiber surface. However, in a Bio-CTMP refining process, fiber fractures preferentially take place in the primary (P) and secondary 1 (S1) layers or the S1 and secondary 2 (S2) layers, which results in more fibrillation being generated in the subsequent refining thus improving inter-fiber bonding strength and paper strength. XPS chemical composition analysis together with pulp physical strength property showed that the surfaces of Bio-CTMP fibers become enriched with a greater proportion of carbohydrates in comparison with CTMP fiber surface, which supports FE-SEM and TEM observations.     

Deconstructing Desorption Electrospray Ionization: Independent Optimization of Desorption and Ionization by Spray Desorption Collection

Spray desorption collection (SDC) and reflective electrospray ionization (RESI) were used to independently study the desorption and ionization processes that together comprise desorption electrospray ionization (DESI). Both processes depend on several instrumental parameters, including the nebulizing gas flow rate, applied potential, and source geometries. Each of these parameters was optimized for desorption, as represented by the results obtained by SDC, and ionization, as represented by the results obtained by RESI. The optimized conditions were then compared to the optimization results for DESI. Our results confirm that optimal conditions for desorption and ionization are different and that in some cases the optimized DESI conditions are a compromise between both sets. The respective results for DESI, RESI, and SDC for each parameter were compared across the methods to draw conclusions about the contribution of each parameter to desorption and ionization separately and then combined within DESI. Our results indicate that desorption efficiency is (1) independent of the applied potential and (2) the impact zone to inlet distance, and that (3) gas pressure settings and (4) sprayer to impact zone distances above optimal for DESI are detrimental to desorption but beneficial for ionization. In addition, possible interpretations for the observed trends are presented.     

Investigating the Role of Adducts in Protein Supercharging with Sulfolane

The supercharging effect of sulfolane on cytochrome c (cyt c) during electrospray ionization mass spectrometry (ESI-MS) in the absence of conformational effects was investigated. The addition of sulfolane on the order of 1 mM or greater to denaturing solutions of cyt c results in supercharging independent of protein concentration over the range of 0.1 to 10 μM. While supercharging was observed in the positive mode, no change in the charge state distribution was observed in the negative mode, ruling out polarity-independent factors such as conformational changes or surface tension effects. A series of sulfolane adducts observed with increasing intensity concurrent with increasing charge state suggests that a direct interaction between sulfolane and the charged sites of cyt c plays an important role in supercharging. We propose that charge delocalization occurring through large-scale dipole reordering of the highly polar supercharging reagent reduces the electrostatic barrier for proximal charging along the cyt c amino acid chain. Supporting this claim, supercharging was shown to increase with increasing dipole moment for several supercharging reagents structurally related to sulfolane.     

Students' Accuracy of Measurement Estimation: Context,Units, and Logical Thinking

This study examined students' accuracy of measurement estimation for linear distances, different units of measure, task context, and the relationship between accuracy estimation and logical thinking. Middle school students completed a series of tasks that included estimating the length of various objects in different contexts and completed a test of logical thinking ability. Results found that the students were not able to give accurate estimations for the lengths of familiar objects. Students were also less accurate in estimating in metric units as compared to English or novel units. Estimation accuracy was dependent on the task context. There were significant differences in estimation accuracy for two‐ versus three‐dimensional estimation tasks. There were no significant differences for estimating objects with different orientations or embedded objects. For the tasks requiring the students to estimate in English units, the embedded task and the three‐dimensional tasks were correlated with logical thinking. For estimation tasks with novel units, three‐dimensional and two‐dimensional estimation tasks were significantly correlated with the logical thinking. In order to interact effectively with our environment it is essential to possess an intuitive grasp of both dimension and scale and to be able to manipulate such information. Estimation, approximating and measuring are all components of such intuition ( Forrester, Latham, & Shire, 1990 , p. 283).