Moderate Signal Enhancement in Electrospray Ionization Mass Spectrometry by Focusing Electrospray Plume with a Dielectric Layer around the Mass Spectrometer's Orifice.

Electrospray ionization (ESI) is among the commonly used atmospheric pressure ionization techniques in mass spectrometry (MS). One of the drawbacks of ESI is the formation of divergent plumes composed of polydisperse microdroplets, which lead to low transmission efficiency. Here, we propose a new method to potentially improve the transmission efficiency of ESI, which does not require additional electrical components and complex interface modification. A dielectric plate-made of ceramic-was used in place of a regular metallic sampling cone. Due to the charge accumulation on the dielectric surface, the dielectric layer around the MS orifice distorts the electric field, focusing the charged electrospray cloud towards the MS inlet. The concept was first verified using charge measurement on the dielectric material surface and computational simulation; then, online experiments were carried out to demonstrate the potential of this method in MS applications. In the online experiment, signal enhancements were observed for dielectric plates with different geometries, distances of the electrospray needle axis from the MS inlet, and various compounds. For example, in the case of acetaminophen (15 µM), the signal enhancement was up to 1.82 times (plate B) using the default distance of the electrospray needle axis from the MS inlet (d = 1.5 mm) and 12.18 times (plate C) using a longer distance (d = 7 mm).

High-Speed Schlieren Imaging of Vapor Formation in Electrospray Plume.

Previous mechanistic descriptions of electrosprays mostly focused on the dynamics of Taylor cones, initial droplets, and progeny droplets. However, vapor formation during droplet desolvation in an electrospray plume has not been discussed to a great extent. Here, we implement a double-pass on-axis schlieren high-speed imaging system to observe generation and propagation of vapors in an offline electrospray source under different conditions. Switching between turbulent and laminar vapor flow was observed for all of the scanned conditions, which may be attributed to randomly occurring disturbances in the sample flow inside the electrospray emitter. Calculation of mean vapor flow velocity and analysis of vapor flow patterns were performed using in-house developed image processing programs. Experiments performed at different electrospray voltages (0-6 kV), solvent flow rates (100-600 µL min-1), and methanol concentrations (50-100%), indicate only a weak dependency between electrospray voltage and mean vapor velocity, implying that the vapor is mostly neutral; thus, the vapor is not accelerated by electric field. On the other hand, electrospraying solutions of analytes (with mass 151 Da or 12 kDa) did not remarkably increase the overall vapor flow velocity. The source of vapor's velocity is attributed to the inertia of the electrospray droplets. Although there are some differences between a modern electrospray ionization (ESI) setup and the setup used in our experiment (e.g., using a higher flow rate and larger emitter), we believe the findings of our study can be projected to a modern ESI setup.

Are Most Micrometer Droplets (>10 µm) Wasted in Electrospray Ionization? An Insight from Real-Time High-Speed Imaging.

Electrospray ionization (ESI) is one of the main techniques used in mass spectrometry (MS) of nonvolatile compounds. ESI is a disordered process, in which a large number of polydisperse droplets are projected from a fluctuating Taylor cone and jet protruding ESI emitter. Here, we disclose a system for sectioning electrospray plumes to discrete packets with millisecond and submillisecond lifetime, which are introduced to the MS orifice, one at a time. A high-speed camera was triggered at 10,000 frames per second to capture consecutive images of the electrospray packets transmitted to the mass spectrometer. We further correlated the high-speed images of electrospray packets with MS signals of a test analyte (acetaminophen). Following computational treatment of the images, we determined the number of droplet observations (<300), average diameter of droplets (∼10-20 µm), and average volume of droplets (few tens of picoliters) in the individual electrospray packets. The result shows that most micrometer droplets (>10 µm) do not have any significant contribution to the MS signals. This finding is in agreement with the prior conjecture that most of the MS signals are mainly attributed to nanodroplets. Based on this finding, one can deduce that only a small number of the initial microdroplets effectively carry analyte molecules that undergo ionization. We discuss that, in future, one may propose a way to "recharge" the emitted initial micrometer droplets to increase the efficiency of conventional ESI setups.

Hydrogel-enzyme micropatch array format for chemical mapping: A proof of concept.

Conventional sensing methods report on concentrations of analytes in a single point of sampled medium or provide an average value. However, distributions of substances on surfaces of sampled objects often exhibit intricate inhomogeneities. In order to obtain snapshots of the chemical distributions on surfaces, we have developed enzyme-loaded hydrogel arrays (5 × 5 and 10 × 10). The acrylic 10 × 10 array base contains 100 holes, which are filled with agarose hydrogel containing assay enzymes and substrates. Such arrays can be exposed to the analyzed surfaces to collect minute amounts of analytes. Following a brief incubation, they are subsequently visualized in a custom-built array reader device. The reader incorporates a light-emitting diode-based light source, miniature camera, and Raspberry Pi single-board computer. Two Python programs capture and analyze the images of the array to extract pixel saturation values corresponding to individual hydrogel micropatches. The method has been thoroughly optimized for mapping of glucose and lactic acid. The optimized parameters were: contact time, agarose concentration, substrate concentration, enzyme concentration ratio, and enzyme concentration. The array biosensor was further tested by mapping glucose distribution in fruit/vegetable cross-sections (apple, guava, and cucumber) and lactic acid distribution in cheese. We think that this new hydrogel-based chemical mapping method can find applications in studies related to food science, plant physiology, clinical chemistry, and forensics; wherever the distributions of analytes on the tested surfaces need to be assessed.

An economical setup for atmospheric pressure chemical ionization drift tube ion-mobility mass spectrometry.

Ion-mobility (IM) separations-performed in conjunction with mass spectrometry (MS)-increase selectivity of MS analyses. However, IM-MS instruments are costly, and many laboratories are only equipped with standard MS instruments without an IM separation stage. Therefore, it is appealing to upgrade the existing mass spectrometers with low-cost IM separation devices. Such devices can be constructed using widely available materials such as printed-circuit boards (PCBs). We demonstrate coupling of an economical PCB-based IM spectrometer (disclosed previously) with a commercial triple quadrupole (QQQ) mass spectrometer. The presented PCB-IM-QQQ-MS system incorporates an atmospheric pressure chemical ionization (APCI) source, drift tube comprising desolvation and drift regions, ion gates, and transfer line to the mass spectrometer. The ion gating is accomplished with the aid of two floated pulsers. The separated ions are divided into packets, which are sequentially introduced to the mass spectrometer. Volatile organic compounds (VOCs) are transferred with the aid of nitrogen gas flow from the sample chamber to the APCI source. The operation of the system has been demonstrated using standard compounds. The limits of detection for 2,4-lutidine, (-)-nicotine, and pyridine are 2.02 × 10-7 M, 1.54 × 10-9 mol, and 4.79 × 10-10 mol, respectively. The system was also used to monitor VOCs emitted from the porcine skin after exposure to nicotine patches, and VOCs released from meat undergoing the spoilage process. We believe this simple APCI-PCB-IM-QQQ-MS platform can be reproduced by others to augment the capabilities of the existing MS instrumentation.