Sensing the wavefront of x-ray free-electron lasers using aerosol spheres.

Characterizing intense, focused x-ray free electron laser (FEL) pulses is crucial for their use in diffractive imaging. We describe how the distribution of average phase tilts and intensities on hard x-ray pulses with peak intensities of 10(21) W/m(2) can be retrieved from an ensemble of diffraction patterns produced by 70 nm-radius polystyrene spheres, in a manner that mimics wavefront sensors. Besides showing that an adaptive geometric correction may be necessary for diffraction data from randomly injected sample sources, our paper demonstrates the possibility of collecting statistics on structured pulses using only the diffraction patterns they generate and highlights the imperative to study its impact on single-particle diffractive imaging.

Toward unsupervised single-shot diffractive imaging of heterogeneous particles using X-ray free-electron lasers.

Single shot diffraction imaging experiments via X-ray free-electron lasers can generate as many as hundreds of thousands of diffraction patterns of scattering objects. Recovering the real space contrast of a scattering object from these patterns currently requires a reconstruction process with user guidance in a number of steps, introducing severe bottlenecks in data processing. We present a series of measures that replace user guidance with algorithms that reconstruct contrasts in an unsupervised fashion. We demonstrate the feasibility of automating the reconstruction process by generating hundreds of contrasts obtained from soot particle diffraction experiments.

Design and optimization of a light-emitting diode projection micro-stereolithography three-dimensional manufacturing system.

The rapid manufacture of complex three-dimensional micro-scale components has eluded researchers for decades. Several additive manufacturing options have been limited by either speed or the ability to fabricate true three-dimensional structures. Projection micro-stereolithography (PµSL) is a low cost, high throughput additive fabrication technique capable of generating three-dimensional microstructures in a bottom-up, layer by layer fashion. The PµSL system is reliable and capable of manufacturing a variety of highly complex, three-dimensional structures from micro- to meso-scales with micro-scale architecture and submicron precision. Our PµSL system utilizes a reconfigurable digital mask and a 395 nm light-emitting diode (LED) array to polymerize a liquid monomer in a layer-by-layer manufacturing process. This paper discusses the critical process parameters that influence polymerization depth and structure quality. Experimental characterization and performance of the LED-based PµSL system for fabricating highly complex three-dimensional structures for a large range of applications is presented.

Detecting trace pesticides in real time using single particle aerosol mass spectrometry.

Pesticides are toxic substances and may cause unintentional harm if improperly used. The ubiquitous nature of pesticides, with frequent use in agriculture and the household, and the potential for harm that pesticides pose to non-target organisms such as wildlife, humans, and pets, demonstrate the need for rapid and effective detection and identification of these compounds. In this study, single particle aerosol mass spectrometry (SPAMS) was used to rapidly detect compounds from four classes of pesticides commonly used in agricultural and household applications. These include permethrin (pyrethroid class), malathion and dichlorvos (organophosphate class), imidacloprid (chloronicotinyl class), and carbaryl (carbamate class). Analytical standards of each compound were diluted and aerosolized using a nebulizer to create particles for analysis in the SPAMS instrument. The resultant dual-polarity time-of-flight mass spectra were then analyzed to identify the characteristic peaks of the compound in each sample. In addition, samples of commercial products containing pesticides, a commercial insecticide spray, containing permethrin, and a canine flea collar, containing carbaryl, were analyzed in their original form using SPAMS without any significant sample preparation. The characteristic mass spectral peaks of the active pesticides in these samples were identified using the mass spectra obtained earlier from the pesticide analytical standards. By successfully identifying pesticides in analytical standards and in commercial products, it is demonstrated herein that the SPAMS system may be capable of pesticide detection in numerous environmental and agricultural situations.

Human breath analysis: methods for sample collection and reduction of localized background effects.

Solid-phase microextraction (SPME) was applied, in conjunction with gas chromatography-mass spectrometry, to the analysis of volatile organic compounds (VOCs) in human breath samples without requiring exhaled breath condensate collection. A new procedure, exhaled breath vapor (EBV) collection, involving the active sampling and preconcentration of a breath sample with a SPME fiber fitted inside a modified commercial breath-collection device, the RTube, is described. Immediately after sample collection, compounds are desorbed from the SPME fiber at 250 degrees C in the GC-MS injector. Experiments were performed using EBV collected at -80 degrees C and at room temperature, and the results compared to the traditional method of collecting exhaled breath condensate at -80 degrees C followed by passive SPME sampling of the collected condensate. Methods are compared in terms of portability, ease-of-use, speed of analysis, and detection limits. The need for a clean air supply for the study subjects is demonstrated using several localized sources of VOC contaminants including nail polish, lemonade, and gasoline. Various simple methods to supply clean inhaled air to a subject are presented. Chemical exposures are used to demonstrate the importance of providing cleaned air (organic vapor respirator) or an external air source (tubing stretched to a separate room). These techniques allow for facile data interpretation by minimizing background contaminants. It is demonstrated herein that this active SPME breath-sampling device provides advantages in the forms of faster sample collection and data analysis, apparatus portability and avoidance of power or cooling requirements, and performance for sample collection in a contaminated environment.

Use of single particle aerosol mass spectrometry for the automated nondestructive identification of drugs in multicomponent samples.

In this work, single particle aerosol mass spectrometry (SPAMS) was used to identify the active drug ingredients in samples of multicomponent over-the-counter (OTC) drug tablets with minimal damage to the tablets. OTC drug tablets in various formulations were analyzed including single active ingredient tablets and multi-ingredient tablets. Using a sampling apparatus developed in-house, micrometer-sized particles were simultaneously dislodged from tablets and introduced to the SPAMS, where dual-polarity mass spectra were obtained from individual particles. Active ingredients were identified from the parent ions and fragment ions formed from each sample, and alarm files were developed for each active ingredient, allowing successful automated identification of each compound in a mixture. The alarm algorithm developed for SPAMS correctly identified all drug compounds in all single-ingredient and multi-ingredient tablets studied. A further study demonstrated the ability of this technique to identify the active ingredient in a single tablet analyzed in the presence of several other nonidentical tablets. In situ measurements were also made by sampling directly from a drug sample in its original bottle. A single tablet embedded in 11 identical tablets of different composition was detected in this manner. Overall, this work demonstrates the ability of the SPAMS technique to detect a target drug compound both in complex tablets, i.e., multidrug ingredient tablets, and complex sampling environments, i.e., multitablet sampling sources. The technique is practically nondestructive, leaving the characteristic shape, color, and imprint of a tablet intact for further analysis. Applications of this technique may include forensic and pharmaceutical analysis.

Autonomous, broad-spectrum detection of hazardous aerosols in seconds.

Actual or surrogate chemical, biological, radiological, nuclear, and explosive materials and illicit drug precursors can be rapidly detected and identified when in aerosol form by a Single-Particle Aerosol Mass Spectrometry (SPAMS) system. This entails not only the sampling of such particles but also the physical analysis and subsequent data analysis leading to a highly reliable alarm state. SPAMS hardware is briefly reviewed. SPAMS software algorithms are discussed in greater detail. A laboratory experiment involving actual threat and surrogate releases mixed with ambient background aerosols demonstrates broad-spectrum detection within seconds. Data from a field test at the San Francisco International Airport demonstrate extended field operation with an ultralow false alarm rate. Together these data sets demonstrate a significant and important advance in rapid aerosol threat detection.

The non-destructive identification of solid over-the-counter medications using single particle aerosol mass spectrometry.

Single over-the-counter medication tablets were analyzed in real time using Single Particle Aerosol Mass Spectrometry (SPAMS). Dual-polarity time-of-flight mass spectra were obtained for micrometer-sized single particles dislodged from a single tablet without destroying the shape or markings of each tablet. The solid tablet was placed in a modified-top glass vial and shaken to dislodge and introduce micrometer-sized particles into the SPAMS system. Unique spectra from these particles were obtained in less than 1 s for single tablets of aspirin, ibuprofen, pseudoephedrine, phenylephrine, loratadine, or diphenhydramine. The signals obtained allowed the non-destructive identification of an individual tablet in seconds. SPAMS presents an ideal system for high-throughput analysis of solid drugs.

Single-particle aerosol mass spectrometry for the detection and identification of chemical warfare agent simulants.

Single-particle aerosol mass spectrometry (SPAMS) was used for the real-time detection of liquid nerve agent simulants. A total of 1000 dual-polarity time-of-flight mass spectra were obtained for micrometer-sized single particles each of dimethyl methyl phosphonate, diethyl ethyl phosphonate, diethyl phosphoramidate, and diethyl phthalate using laser fluences between 0.58 and 7.83 nJ/microm2, and mass spectral variation with laser fluence was studied. The mass spectra obtained allowed identification of single particles of the chemical warfare agent (CWA) simulants at each laser fluence used although lower laser fluences allowed more facile identification. SPAMS is presented as a promising real-time detection system for the presence of CWAs.

Identification of high explosives using single-particle aerosol mass spectrometry.

The application of single-particle aerosol mass spectrometry (SPAMS) to the real-time detection of micrometer-sized single particles of high explosives is described. Dual-polarity time-of-flight mass spectra from 1000 single particles each of 2,4,6-trinitrotoluene (TNT), 1,3,5-trinitro-1,3,5-triazinane (RDX), and pentaerythritol tetranitrate (PETN), as well as those of complex explosives, Composition B, Semtex 1A, and Semtex 1H, were obtained over a range of desorption/ionization laser fluences between 0.50 and 8.01 nJ/microm2. Mass spectral variability with laser fluence for each explosive is discussed. The ability of the SPAMS system to identify explosive components in a single complex explosive particle ( approximately 1 pg) without the need for consumables is demonstrated.

An infrared and X-ray spectroscopic study of the reactions of 2-chlorophenol, 1,2-dichlorobenzene, and chlorobenzene with model cuO/silica fly ash surfaces.

The surface-mediated reactions of 2-chlorophenol, 1,2-dichlorobenzene, and chlorobenzene were studied using CuO/ SiO2 as a fly ash surrogate. These compounds served as model precursors that have been implicated in the formation of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs). With FTIR, we determined that reactions of the model precursors with a substrate composed of CuO dispersed on silica result in the formation of a mixture of surface-bound phenolate and carboxylate partial oxidation products from 200 to 500 degrees C. Chemisorption of 2-chlorophenol and 1,2-dichlorobenzene resulted in the formation of identical surface-bound species. Using X-ray absorption near-edge structure spectroscopy, we measured the time- and temperature-dependent reduction of Cu(II) in a fly ash surrogate during reaction with each precursor. It was demonstrated that CuI2O is the major reduction product in each case. The rate of Cu(II) reduction could be described using pseudo-first-order reaction kinetics with Arrhenius activation energies for reduction of Cu(II) of 112, 101, and 88 kJ mol(-1) for 2-chlorophenol, 1,2-dichlorobenzene, and chlorobenzene, respectively. We demonstrate that chlorinated phenol and chlorinated benzene both chemisorb to form chlorophenolate. Although chlorinated phenols chemisorb at a faster rate, chlorinated benzenes are found at much higher concentrations in incinerator effluents. The implication is that chlorinated benzenes may form 10 times more chlorophenolate precursors to PCDD/Fs than chlorinated phenols in combustion systems.

X-ray spectroscopic studies of the high temperature reduction of Cu(II)O by 2-chlorophenol on a simulated fly ash surface.

The reaction of 2-chlorophenol on Cu(II)O at 375 degrees C is studied using X-ray absorption near edge structure (XANES) spectroscopy. A mixture of copper(II) oxide and silica is prepared to serve as a surrogate for fly ash in combustion systems. 2-Chlorophenol is utilized as a model precursor for formation of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/F). The Cu K-edge spectra shiftto lower binding energy, reflecting the reduction of the copper. The substrate is found to form a mixture of Cu(II), Cu(I), and Cu(O), with the dominant species being Cu(I). The data are fitted well with a first-order reaction scheme, with a time constant at 375 degrees C of 76 s. This is the first application of XANES spectroscopy for studying the kinetics and mechanism of heterogeneous reactions relevant to combustion processes, and the results demonstrate the utility and desirability of such X-ray spectroscopic studies.