Interfacial Growth of Large Area Single-Crystalline Silver Sheets Through Ambient Microdroplets.

The creation of micrometer-sized sheets of silver at the air-water interface by direct deposition of electrospray-generated silver ions (Ag+) on an aqueous dispersion of reduced graphene oxide (RGO), in ambient conditions, is reported. In the process of electrospray deposition (ESD), an electrohydrodynamic flow is created in the aqueous dispersion, and the graphene sheets assemble, forming a thin film at the air-water interface. The deposited Ag+ coalesce to make single-crystalline Ag sheets on top of this assembled graphene layer. Fast neutralization of Ag+ forming atomic Ag, combined with their enhanced mobility on graphene surfaces, presumably facilitates the growth of larger Ag clusters. Moreover, restrictions imposed by the interface drive the crystal growth in 2D. By controlling the precursor salt concentration, RGO concentration, deposition time, and ion current, the dimensionality of the Ag sheets can be tuned. These Ag sheets are effective substrates for surface-enhanced Raman spectroscopy (SERS), as demonstrated by the successful detection of methylene blue at nanomolar concentrations.

Paper Spray Ionization Ion Mobility Mass Spectrometry of Sebum Classifies Biomarker Classes for the Diagnosis of Parkinson's Disease.

Parkinson's disease (PD) is the second most common neurodegenerative disorder, and identification of robust biomarkers to complement clinical diagnosis will accelerate treatment options. Here, we demonstrate the use of direct infusion of sebum from skin swabs using paper spray ionization coupled with ion mobility mass spectrometry (PS-IM-MS) to determine the regulation of molecular classes of lipids in sebum that are diagnostic of PD. A PS-IM-MS method for sebum samples that takes 3 min per swab was developed and optimized. The method was applied to skin swabs collected from 150 people and elucidates ∼4200 features from each subject, which were independently analyzed. The data included high molecular weight lipids (>600 Da) that differ significantly in the sebum of people with PD. Putative metabolite annotations of several lipid classes, predominantly triglycerides and larger acyl glycerides, were obtained using accurate mass, tandem mass spectrometry, and collision cross section measurements.

Metabolomics of sebum reveals lipid dysregulation in Parkinson's disease.

Parkinson's disease (PD) is a progressive neurodegenerative disorder, which is characterised by degeneration of distinct neuronal populations, including dopaminergic neurons of the substantia nigra. Here, we use a metabolomics profiling approach to identify changes to lipids in PD observed in sebum, a non-invasively available biofluid. We used liquid chromatography-mass spectrometry (LC-MS) to analyse 274 samples from participants (80 drug naïve PD, 138 medicated PD and 56 well matched control subjects) and detected metabolites that could predict PD phenotype. Pathway enrichment analysis shows alterations in lipid metabolism related to the carnitine shuttle, sphingolipid metabolism, arachidonic acid metabolism and fatty acid biosynthesis. This study shows sebum can be used to identify potential biomarkers for PD.

Validating Differential Volatilome Profiles in Parkinson's Disease.

Parkinson's disease (PD) is a progressive neurodegenerative disorder that does not currently have a robust clinical diagnostic test. Nonmotor symptoms such as skin disorders have long since been associated with the disease, and more recently a characteristic odor emanating from the skin of people with Parkinson's has been identified. Here, dynamic head space (DHS) thermal desorption (TD) gas chromatography-mass spectrometry (GC-MS) is implemented to directly measure the volatile components of sebum on swabs sampled from people with Parkinson's-both drug naïve and those on PD medications (n = 100) and control subjects (n = 29). Supervised multivariate analyses of data showed 84.4% correct classification of PD cases using all detected volatile compounds. Variable importance in projection (VIP) scores were generated from these data, which revealed eight features with VIP > 1 and p < 0.05 which all presented a downregulation within the control cohorts. Purified standards based on previously annotated analytes of interest eicosane and octadecanal did not match to patient sample data, although multiple metabolite features are annotated with these compounds all with high spectral matches indicating the presence of a series of similar structured species. DHS-TD-GC-MS analysis of a range of lipid standards has revealed the presence of common hydrocarbon species rather than differentiated intact compounds which are hypothesized to be breakdown products of lipids. This replication study validates that a differential volatile profile between control and PD cohorts can be measured using an analytical method that measures volatile compounds directly from skin swabs.

Discovery of Volatile Biomarkers of Parkinson's Disease from Sebum.

Parkinson's disease (PD) is a progressive, neurodegenerative disease that presents with significant motor symptoms, for which there is no diagnostic chemical test. We have serendipitously identified a hyperosmic individual, a "Super Smeller" who can detect PD by odor alone, and our early pilot studies have indicated that the odor was present in the sebum from the skin of PD subjects. Here, we have employed an unbiased approach to investigate the volatile metabolites of sebum samples obtained noninvasively from the upper back of 64 participants in total (21 controls and 43 PD subjects). Our results, validated by an independent cohort (n=31), identified a distinct volatiles-associated signature of PD, including altered levels of perillic aldehyde and eicosane, the smell of which was then described as being highly similar to the scent of PD by our "Super Smeller".

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.

Holey MoS2 Nanosheets with Photocatalytic Metal Rich Edges by Ambient Electrospray Deposition for Solar Water Disinfection.

A new method for creating nanopores in single-layer molybdenum disulfide (MoS2) nanosheets (NSs) by the electrospray deposition of silver ions on a water suspension of the former is introduced. Electrospray-deposited silver ions react with the MoS2 NSs at the liquid-air interface, resulting in Ag2S nanoparticles which enter the solution, leaving the NSs with holes of 3-5 nm diameter. Specific reaction with the S of MoS2 NSs leads to Mo-rich edges. Such Mo-rich defects are highly efficient for the generation of active oxygen species such as H2O2 under visible light which causes efficient disinfection of water. 105 times higher efficiency in disinfection for the holey MoS2 NSs in comparison to normal MoS2 NSs is shown. Experiments are performed with multiple bacterial strains and a virus strain, demonstrating the utility of the method for practical applications. A conceptual prototype is also presented.

Catalytic Paper Spray Ionization Mass Spectrometry with Metal Nanotubes and the Detection of 2,4,6-Trinitrotoluene.

Materials are making inroads into mass spectrometry, and an example is the use of advanced materials for enhanced ionization by transformation of a less-ionizable molecule to an easily ionizable one. Here we show the use of Pt nanoparticle-decorated nanotubes as highly active catalysts for the reduction of 2,4,6-trinitrotoluene to 2,4,6-triaminotoluene and subsequent easy detection of the product by in situ ambient ionization mass spectrometry.

Ultra-high sensitivity infra-red detection and temperature effects in a graphene-tellurium nanowire binary hybrid.

The optoelectronic performance of hybrid devices from graphene and optically sensitive semiconductors exceeds conventional photodetectors due to a large in-built optical gain. Tellurium nanowire (TeNW), being a narrow direct band gap semiconductor (∼0.65 eV), is as an excellent potential candidate for near infra-red (NIR) detection. Here we demonstrate a new graphene-TeNW binary hybrid that exhibits a maximum photoresponsivity of ∼106 A W-1 at 175 K in the NIR regime (920 nm-1720 nm), which exceeds the photoresponsivity of the most common NIR photodetectors. The resulting noise-equivalent power (NEP) is as low as 2 × 10-18 W Hz-1/2, and the specific detectivity (D*) exceeds 5 × 1013 cm Hz1/2 W-1 (Jones). The temperature range of optimal operation, which extends up to ≈220 K and ≈260 K for 1720 nm and 920 nm excitation, respectively, is primarily limited by the electrical conductivity of the TeNW layer, and can further be improved by lowering of the defect density as well as inter-wire electronic coupling.

Unusual reactivity of MoS2 nanosheets.

The reactivity of the 2D nanosheets of MoS2 with silver ions in solution, leading to their spontaneous morphological and chemical transformations, is reported. This unique reactivity of the nanoscale form of MoS2 was in stark contrast to its bulk counterpart. While the gradual morphological transformation involving several steps has been captured with an electron microscope, precise chemical identification of the species involved was achieved by electron spectroscopy and mass spectrometry. The energetics of the system investigated supports the observed chemical transformation. The reaction with mercury and gold ions shows similar and dissimilar reaction products, respectively and points to the stability of the metal-sulphur bond in determining the chemical compositions of the final products.

Metallic Nanobrushes Made using Ambient Droplet Sprays.

An ambient solution-state method for making uniform nanobrushes composed of oriented 1D silver nanowires (NWs) with aspect ratios of 10(2) -10(4) is reported. These structures are grown over cm(2) areas on conducting surfaces. Assemblies of NWs form uniform nanobrush structures, which can capture micrometer-sized objects, such as bacteria and particulate matter. Variation in composition produces unique structures with catalytic properties.

Anisotropic Molecular Ionization at 1 V from Tellurium Nanowires (Te NWs).

Ionization of molecular species from one-dimensional (1D) tellurium nanowires (Te NWs) has been achieved at 1 V. Molecules with a range of chemical functional groups gave quality mass spectra with high signal/noise ratios and no fragment ions. Experiments suggest the possibility of emission of microdroplets of solution due to the intense fields at the ends or interfaces of nanostructures. It appears that electrolytic conduction of the solution wetting of the nanostructures and not the electronic conduction of the nanostructures themselves is involved in the ionization event. Anisotropy was seen when two-dimensionally aligned Te NWs were used for ionization. The orientation effect of aligned Te NWs on molecular ion intensity is demonstrated for many analytes including organic molecules and amino acids with experiments done using a silicon substrate having aligned Te NWs. These measurements suggest the possibility of creating a MS source that extends the applicability of mass spectrometry. Analysis of a variety of analytes, including amino acids, pesticides, and drugs, in pure form and in complex mixtures, is reported. These experiments suggest that 1D nanostructures in general could be excellent ionization sources.

Ambient preparation and reactions of gas phase silver cluster cations and anions.

Electrospray ionization of metal salt solutions followed by ambient heating transforms the resulting salt clusters into new species, primarily naked ionic metal clusters. The experiment is done by passing the clusters through a heated coiled loop outside the mass spectrometer which releases the counter-anion while generating the anionic or cationic naked metal cluster. The nature of the anion in the starting salt determines the type of metal cluster observed. For example, silver acetate upon heating generates only positive silver clusters, Ag(n)(+), but silver fluoride generates both positive and negative silver clusters, Ag(n)(+/-) (3 < n < 20). Both unheated and heated metal salt sprays yield ions with characteristic geometric and electronic magic numbers. There is also a strong odd/even effect in the cationic and anionic silver clusters. Thermochemical control is suggested as the basis for favored formation of the observed clusters, with anhydride elimination occurring from the acetates and fluorine elimination from the fluorides to give cationic and anionic clusters, respectively. Data on the intermediates observed as the temperature is ramped support this. The naked metal clusters react with gaseous reagents in the open air, including methyl substituted pyridines, hydrocarbons, common organic solvents, ozone, ethylene, and propylene. Argentation of hydrocarbons, including saturated hydrocarbons, is shown to occur and serves as a useful analytical ionization method. The new cluster formation methodology allows investigation of ligand-metal binding including in reactions of industrial importance, such as olefin epoxidation. These reactions provide insight into the physicochemical properties of silver cluster anions and cations. The potential use of the ion source in ion soft landing is demonstrated by reproducing the mass spectra of salts heated in air using a custom surface science instrument.

Zero Volt Paper Spray Ionization and Its Mechanism.

The analytical performance and a suggested mechanism for zero volt paper spray using chromatography paper are presented. A spray is generated by the action of the pneumatic force of the mass spectrometer (MS) vacuum at the inlet. Positive and negative ion signals are observed, and comparisons are made with standard kV paper spray (PS) ionization and nanoelectrospray ionization (nESI). While the range of analytes to which zero volt PS is applicable is very similar to kV PS and nESI, differences in the mass spectra of mixtures are interpreted in terms of the more significant effects of analyte surface activity in the gentler zero volt experiment than in the other methods due to the significantly lower charge. The signal intensity of zero volt PS is also lower than in the other methods. A Monte Carlo simulation based on statistical fluctuation of positive and negative ions in solution has been implemented to explain the production of ions from initially uncharged droplets. Uncharged droplets first break up due to aerodynamics forces until they are in the 2-4 µm size range and then undergo Coulombic fission. A model involving statistical charge fluctuations in both phases predicts detection limits similar to those observed experimentally and explains the effects of binary mixture components on relative ionization efficiencies. The proposed mechanism may also play a role in ionization by other voltage-free methods.

Using ambient ion beams to write nanostructured patterns for surface enhanced Raman spectroscopy.

Electrolytic spray deposition was used to pattern surfaces with 2D metallic nanostructures. Spots that contain silver nanoparticles (AgNP) were created by landing solvated silver ions at desired locations using electrically floated masks to focus the metal ions to an area as little as 20 µm in diameter. The AgNPs formed are unprotected and their aggregates can be used for surface-enhanced Raman spectroscopy (SERS). The morphology and SERS activity of the NP structures were controlled by the surface coverage of landed silver ions. The NP structures created could be used as substrates onto which SERS samples were deposited or prepared directly on top of predeposited samples of interest. The evenly distributed hot spots in the micron-sized aggregates had an average SERS enhancement factor of 10(8) . The surfaces showed SERS activity when using lasers of different wavelengths (532, 633, and 785 nm) and were stable in air.

Molecular ionization from carbon nanotube paper.

Ambient ionization is achieved by spraying from a carbon nanotube (CNT)-impregnated paper surface under the influence of small voltages (≥3 V). Organic molecules give simple high-quality mass spectra without fragmentation in the positive or negative ion modes. Conventional field ionization is ruled out, and it appears that field emission of microdroplets occurs. Microscopic examination of the CNT paper confirms that the nanoscale features at the paper surface are responsible for the high electric fields. Raman spectra imply substantial current flows in the nanotubes. The performance of this analytical method was demonstrated for a range of volatile and nonvolatile compounds and a variety of matrices.

Studying reaction intermediates formed at graphenic surfaces.

We report in-situ production and detection of intermediates at graphenic surfaces, especially during alcohol oxidation. Alcohol oxidation to acid occurs on graphene oxide-coated paper surface, driven by an electrical potential, in a paper spray mass spectrometry experiment. As paper spray ionization is a fast process and the time scale matches with the reaction time scale, we were able to detect the intermediate, acetal. This is the first observation of acetal formed in surface oxidation. The process is not limited to alcohols and the reaction has been extended to aldehydes, amines, phosphenes, sugars, etc., where reaction products were detected instantaneously. By combining surface reactions with ambient ionization and mass spectrometry, we show that new insights into chemical reactions become feasible. We suggest that several other chemical transformations may be studied this way. This work opens up a new pathway for different industrially and energetically important reactions using different metal catalysts and modified substrate.

Rapid identification of molecular changes in tulsi (Ocimum sanctum Linn) upon ageing using leaf spray ionization mass spectrometry.

Tulsi or Holy Basil (Ocimum sanctum Linn) is a medicinally important plant. Ursolic acid (UA) and oleanolic acid (OA) are among its major constituents which account for many medicinal activities of the plant. In the present work, we deployed a new ambient ionization method, leaf spray ionization, for rapid detection of UA, OA and their oxidation products from tulsi leaves. Tandem electrospray ionization mass spectrometry (ESI-MS) has been performed on tulsi leaf extracts in methanol to establish the identity of the compounds. We probed changes occurring in the relative amounts of the parent compounds (UA and OA) with their oxidized products and the latter show an increasing trend upon ageing. The findings are verified by ESI-MS analysis of tulsi leaf extracts, which shows the same trend proving the reliability of the leaf spray method.