Spontaneous weathering of natural minerals in charged water microdroplets forms nanomaterials.

In this work, we show that particles of common minerals break down spontaneously to form nanoparticles in charged water microdroplets within milliseconds. We transformed micron-sized natural minerals like quartz and ruby into 5- to 10-nanometer particles when integrated into aqueous microdroplets generated via electrospray. We deposited the droplets on a substrate, which allowed nanoparticle characterization. We determined through simulations that quartz undergoes proton-induced slip, especially when reduced in size and exposed to an electric field. This leads to particle scission and the formation of silicate fragments, which we confirmed with mass spectrometry. This rapid weathering process may be important for soil formation, given the prevalence of charged aerosols in the atmosphere.

Spontaneous α-C-H Carboxylation of Ketones by Gaseous CO2 at the Air-water Interface of Aqueous Microdroplets.

We present a catalyst-free route for the reduction of carbon dioxide integrated with the formation of a carbon-carbon bond at the air/water interface of negatively charged aqueous microdroplets, at ambient temperature. The reactions proceed through carbanion generation at the α-carbon of a ketone followed by nucleophilic addition to CO2. Online mass spectrometry reveals that the product is an α-ketoacid. Several factors, such as the concentration of the reagents, pressure of CO2 gas, and distance traveled by the droplets, control the kinetics of the reaction. Theoretical calculations suggest that water in the microdroplets facilitates this unusual chemistry. Furthermore, such a microdroplet strategy has been extended to seven different ketones. This work demonstrates a green pathway for the reduction of CO2 to useful carboxylated organic products.

Detecting Early-Stage Intermediates of Free-Radical Oxidative Degradation in Charged Aqueous Microdroplets.

We report the detection of early-stage intermediates of spontaneous free-radical oxidation of organic pollutants such as aliphatic amino alcohols and diamines in charged aqueous microdroplets in the ambient atmosphere. We propose that the intrinsic formation of reactive oxygen species at the air-water interface is responsible for the radical oxidation of the sp3 carbon. We suggest that our work will aid the understanding of the degradation mechanisms of organic molecules in the environment.

Spatial reorganization of analytes in charged aqueous microdroplets.

Imprinted charged aqueous droplets of micrometer dimensions containing spherical gold and silver nanoparticles, gold nanorods, proteins and simple molecules were visualized using dark-field and transmission electron microscopies. With such studies, we hoped to understand the unusual chemistry exhibited by microdroplets. These droplets with sizes in the range of 1-100 µm were formed using a home-built electrospray source with nitrogen as the nebulization gas. Several remarkable features such as mass/size-selective segregation and spatial localization of solutes in nanometer-thin regions of microdroplets were visualized, along with the formation of micro-nano vacuoles. Electrospray parameters such as distance between the spray tip and surface, voltage and nebulization gas pressure influenced particle distribution within the droplets. We relate these features to unusual phenomena such as the enhancement of rates of chemical reactions in microdroplets.

Aggregation of molecules is controlled in microdroplets.

Molecular de-aggregation was observed at the air/water interface of aqueous microdroplets. We probed this phenomenon using dyes such as Rhodamine 6G (R6G), Rhodamine B, acridine orange, and fluorescein, which show aggregation-induced shift in fluorescence. The fluorescence micrographs of microdroplets derived from the aqueous solutions of these dyes show that they are monomeric at the air/water interface, but highly aggregated at the core. We propose that rapid evaporation of the solvent influences the de-aggregation of molecules at the air-water interface of the microdroplets.

2D-Molybdenum Disulfide-Derived Ion Source for Mass Spectrometry.

Generation of current or potential at nanostructures using appropriate stimuli is one of the futuristic methods of energy generation. We developed an ambient soft ionization method for mass spectrometry using 2D-MoS2, termed streaming ionization, which eliminates the use of traditional energy sources needed for ion formation. The ionic dissociation-induced electrokinetic effect at the liquid-solid interface is the reason for energy generation. We report the highest figure of merit of current generation of 1.3 A/m2 by flowing protic solvents at 22 µL/min over a 1 × 1 mm2 surface coated with 2D-MoS2, which is adequate to produce continuous ionization of an array of analytes, making mass spectrometry possible. Weakly bound ion clusters and uric acid in urine have been detected. Further, the methodology was used as a self-energized breath alcohol sensor capable of detecting 3% alcohol in the breath.

Microdroplet Impact-Induced Spray Ionization Mass Spectrometry (MISI MS) for Online Reaction Monitoring and Bacteria Discrimination.

Microdroplet impact-induced spray ionization (MISI) is demonstrated involving the impact of microdroplets produced from a paper and their impact on another, leading to the ionization of analytes deposited on the latter. This cascaded process is more advantageous in comparison to standard spray ionization as it performs reactions and ionization simultaneously in the absence of high voltage directly applied on the sample. In MISI, we apply direct current (DC) potential only to the terminal paper, used as the primary ion source. Charge transfer due to microdroplet/ion deposition on the flowing analyte solution on the second surface generates secondary charged microdroplets from it carrying the analytes, which ionize and get detected by a mass spectrometer. In this way, up to three cascaded spray sources could be assembled in series. We show the detection of small molecules and proteins in such ionization events. MISI provides a method to understand chemical reactions by droplet impact. The C-C bond formation reactions catalyzed by palladium and alkali metal ion encapsulation using crown ether were studied as our model reactions. To demonstrate the application of our ion source in a bioanalytical context, we studied the noninvasive in situ discrimination of bacteria samples under ambient conditions.

Accelerated microdroplet synthesis of benzimidazoles by nucleophilic addition to protonated carboxylic acids.

We report a metal-free novel route for the accelerated synthesis of benzimidazole and its derivatives in the ambient atmosphere. The synthetic procedure involves 1,2-aromatic diamines and alkyl or aryl carboxylic acids reacting in electrostatically charged microdroplets generated using a nano-electrospray (nESI) ion source. The reactions are accelerated by orders of magnitude in comparison to the bulk. No other acid, base or catalyst is used. Online analysis of the microdroplet accelerated reaction products is performed by mass spectrometry. We provide evidence for an acid catalyzed reaction mechanism based on identification of the intermediate arylamides. Their dehydration to give benzimidazoles occurs in a subsequent thermally enhanced step. It is suggested that the extraordinary acidity at the droplet surface allows the carboxylic acid to function as a C-centered electrophile. Comparisons of this methodology with data from thin film and bulk synthesis lead to the proposal of three key steps in the reaction: (i) formation of an unusual reagent (protonated carboxylic acid) because of the extraordinary conditions at the droplet interface, (ii) accelerated bimolecular reaction because of limited solvation at the interface and (iii) thermally assisted elimination of water. Eleven examples are shown as evidence of the scope of this chemistry. The accelerated synthesis has been scaled-up to establish the substituent-dependence and to isolate products for NMR characterization.

Ambient electrospray deposition Raman spectroscopy (AESD RS) using soft landed preformed silver nanoparticles for rapid and sensitive analysis.

We introduce a technique called ambient electrospray deposition Raman spectroscopy (AESD RS) for rapid and sensitive surface-enhanced Raman scattering (SERS) based detection of analytes using a miniature Raman spectrometer. Using electrospray, soft landing of preformed silver nanoparticles (AgNPs) was performed for 30-40 seconds for different concentrations of analytes deposited on conducting glass slides. Using AESD RS, SERS signals were collected within 4-6 minutes, including sample preparation. Transmission electron microscopy (TEM) and dark-field microscopy (DFM) were used to characterize the preformed AgNPs before and after electrospray. We achieved the nanomolar and micromolar detection of p-mercaptobenzoic acid (p-MBA) and 2,4-dinitrotoluene (2,4-DNT), respectively. In this work, 0.3 µL of preformed AgNPs were used, which is ∼33 times less in volume than the quantity needed for conventional SERS. Quantitation of unknown concentration of analytes was also possible. A similar amount of electrosprayed AgNPs was utilized to characterize Escherichia coli (E. coli) bacteria of different concentrations. Viability of bacteria was tested using fluorescence microscopic imaging. Besides reduced analysis time and improved reproducibility of the data in every analysis, which is generally difficult in SERS, the amount of AgNPs required is an order of magnitude lower in this method. This method could also be used to probe the real-time changes in molecular and biological species under ambient conditions.

In situ monitoring of electrochemical reactions through CNT-assisted paper cell mass spectrometry.

A novel method of coupling electrochemistry (EC) with mass spectrometry (MS) is illustrated with a paper-based electrochemical cell supported by carbon nanotubes (CNTs). The electrochemically formed ions, created at appropriate electrochemical potentials, are ejected into the gas phase from the modified paper, without the application of additional potential. The electrochemical cell was fabricated by using a rectangular CNT-coated Whatman 42 filter paper with printed electrodes, using silver paste. This was used for studying the electrochemical conversion of thiols to disulfides, and the functionalization of polycyclic aromatic hydrocarbons (PAHs), which involve S-S and C-C bond formations, respectively. We also demonstrate the versatility of the set-up by utilizing it for the detection of radical cations of metallocenes, monitoring the oxidation of sulfides through the detection of reactive intermediates, and the detection of radical cations of PAHs, all of which occur at specific applied potentials. Finally, the applicability of this technique for qualitative and quantitative analyses of environmentally relevant molecules has been demonstrated by studying the electrochemical oxidation of glucose (Glu) to gluconic acid (GlcA) and saccharic acid (SacA).

Sub-Parts-per-Trillion Level Detection of Analytes by Superhydrophobic Preconcentration Paper Spray Ionization Mass Spectrometry (SHPPSI MS).

A new kind of ambient ionization method named superhydrophobic preconcentration paper spray ionization mass spectrometry (SHPPSI MS) is introduced, where superhydrophobicity and paper spray mass spectrometry (PS MS) are coupled. The SHPPSI MS requires only microliter amounts of analyte solutions, allows easy sampling procedure, and provides high sensitivity for a diverse array of analytes. It can be used to detect food adulteration at extremely low concentrations. The experimental methodology involves modifying one of the surfaces of a triangularly cut filter paper to make it acquire low surface energy by drop casting a green and ecofriendly superhydrophobic coating material over it followed by drying. A micrometer scale defect was made at close proximity to one of the tips of the paper using a pin. Preconcentration of the sample was accomplished by allowing a 10 µL droplet of an aqueous solution of the analyte to stand at the defect followed by drying naturally. The dried paper was used as the substrate for paper spray mass spectrometry by eluting the analyte with a suitable solvent. This novel technique was used to detect melamine in adulterated milk, whose detection at the ppt level in milk normally needs sophisticated instruments, a larger amount of sample, and a complex sampling procedure, including further purification and separation. The SHPPSI MS detects melamine directly from milk at the sub-ppb level by simply putting a microdroplet of adulterated milk at the substrate and eluting the sample with methanol. This paper-based technique can be a promising tool for direct sensing of analytes such as drugs in body fluids, pesticides in water and soil, etc.

Preparation of gas phase naked silver cluster cations outside a mass spectrometer from ligand protected clusters in solution.

Gas phase clusters of noble metals prepared by laser desorption from the bulk have been investigated extensively in a vacuum using mass spectrometry. However, such clusters have not been known to exist under ambient conditions to date. In our previous work, we have shown that in-source fragmentation of ligands can be achieved starting from hydride and phosphine co-protected silver clusters leading to naked silver clusters inside a mass spectrometer. In a recent series of experiments, we have found that systematic desorption of ligands of the monolayer protected atomically precise silver cluster can also occur in the atmospheric gas phase. Here, we present the results, wherein the [Ag18H16(TPP)10]2+ (TPP = triphenylphosphine) cluster results in the formation of the naked cluster, Ag17+ along with Ag18H+ without mass selection, outside the mass spectrometer, in air. These cationic naked metal clusters are prepared by passing electrosprayed ligand protected clusters through a heated tube, in the gas phase. Reactions with oxygen suggest Ag17+ to be more reactive than Ag18H+, in agreement with their electronic structures. The more common thiolate protected clusters produce fragments of metal thiolates under identical processing conditions and no naked clusters were observed.

Detection of Hydrocarbons by Laser Assisted Paper Spray Ionization Mass Spectrometry (LAPSI MS).

Here we introduce a new ambient ionization technique named laser assisted paper spray ionization mass spectrometry (LAPSI MS). In it, a 532 ± 10 nm, ≤10 mW laser pointer was shone on a triangularly cut paper along with high voltage, to effect ionization. The analyte solution was continuously pushed through a fused silica capillary, using a syringe pump, at a preferred infusion rate. LAPSI MS promises enhanced ionization with high signal intensity of polycyclic aromatic hydrocarbons (PAHs), which are normally not ionizable with similar ionization methods involving solvent sprays. LAPSI MS works both in positive and negative modes of ionization. A clear enhancement of signal intensity was visualized in the total ion chronogram for most analytes in the presence of the laser. We speculate that the mechanism of ionization is field assisted photoionization. The field-induced distortion of the potential well can be large in paper spray as the fibers comprising the paper are separated at tens of nanometers apart, and consequently, the analyte molecules are subjected to very large electric fields of the order of 107 Vcm-1. Ionization occurs from their distorted electronic states of reduced ionization energy, using the laser. Negative ion detection is also demonstrated, occurring due to the capture of produced photoelectrons. LAPSI MS can be used for monitoring in situ photoassisted reactions like the decarboxylation of mercaptobenzoic acid in the presence of gold and silver nanoparticles and the dehydrogenation reaction of 2,3-dihydro-1 H-isoindole, which were chosen as examples. As an application, we have shown that paraffin oil, which is usually nonionizable by paper spray or by electrospray ionization can be efficiently detected using this technique. Impurities like mineral oils were detected easily in commercially available coconut oil, pointing the way to applications of social relevance.